CN102527241A - Gas separation membrane assembly and gas separation method - Google Patents

Gas separation membrane assembly and gas separation method Download PDF

Info

Publication number
CN102527241A
CN102527241A CN201110345156XA CN201110345156A CN102527241A CN 102527241 A CN102527241 A CN 102527241A CN 201110345156X A CN201110345156X A CN 201110345156XA CN 201110345156 A CN201110345156 A CN 201110345156A CN 102527241 A CN102527241 A CN 102527241A
Authority
CN
China
Prior art keywords
gas
tube sheet
hollow
mentioned
separation membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201110345156XA
Other languages
Chinese (zh)
Other versions
CN102527241B (en
Inventor
金筑丰
福田叙彦
谷原望
中村智英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2010247931A external-priority patent/JP6067205B2/en
Priority claimed from JP2010274619A external-priority patent/JP5740952B2/en
Priority claimed from JP2011207538A external-priority patent/JP5825007B2/en
Priority claimed from JP2011207647A external-priority patent/JP5825008B2/en
Priority claimed from JP2011227101A external-priority patent/JP5825032B2/en
Priority claimed from JP2011239388A external-priority patent/JP5794110B2/en
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Publication of CN102527241A publication Critical patent/CN102527241A/en
Application granted granted Critical
Publication of CN102527241B publication Critical patent/CN102527241B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The prevent invention provides a method for preparing nitrogen-rich gas through supplying high-temperature gas with a temperature above 150 DEG C to a gas separation membrane assembly.

Description

Gas separation membrane assembly and gas separating method
Technical field
The application invention relates to a kind of utilization to have and selects the many hollow cortina of permeability to carry out gas gas separated separating film module and gas separating method.
Background technology
Have the diffusion barrier of selecting permeability as use and carry out the separating film module that gas separates (for example oxygen separation, nitrogen separation, hydrogen separation, steam separation, carbon dioxide separation, organic vapor separation etc.), template and frame-type, cast, hollow fiber type etc. are arranged.Wherein, the gas separation membrane assembly of hollow fiber type not only has the membrane area biggest advantage of per unit volume, and in resistance to pressure, from also excellent aspect the supporting, therefore, is favourable in industry, can use by wide region.
Summary of the invention
The application's invention is specified in following part A～G, and also comprising combination has the invention of illustrated invention in the each several part more than 2 kinds.About the related background technology of the disclosed invention of various piece and problem etc., in each several part, describe.
Description of drawings
Fig. 1 representes the mensuration result of the embodiment 1 and the comparative example 2 of part A;
Fig. 2 representes the mensuration result of the embodiment 1 and the embodiment 2 of part A;
Fig. 3 is the sketch of an example of expression gas separation membrane assembly;
Fig. 4 is the sketch of the preparation method of the separatory tube sheet of expression mist;
Fig. 5 is the sectional view of basic comprising of separating film module that schematically shows the 1st embodiment of portion C;
One example of the structure of Fig. 6 among Fig. 6 (a) expression assembly end, the structure of the existing type of Fig. 6 (b) expression;
Fig. 7 is the figure of other structure of expression tube sheet periphery;
Fig. 8 representes the example of structure of assembly end of the 2nd embodiment of portion C, the state during Fig. 8 (a) expression normal temperature, the state during Fig. 8 (b) expression high temperature;
Fig. 9 representes the example of structure of assembly end of the 3rd embodiment of portion C;
Figure 10 is the figure of the example of other embodiment of expression;
Figure 11 among Figure 11 (a) is another other routine sectional view of expression separating film module, and Figure 11 (b) is the figure after the part of Figure 11 (a) is amplified;
Figure 12 is the figure of an example of the configuration of expression O ring;
Figure 13 is the sectional view of the gas separation membrane assembly that relates to of the mode of part D;
Figure 14 is the sectional view of cylindrical member of the assembly of Figure 13;
Figure 15 is the front elevation and the side cross-sectional views of cap member of the assembly of Figure 13, and Figure 15 (A) is the sectional view along the X-X line of Figure 15 (B);
Figure 16 is the sketch map of cap member of example that is used to have represented to change the radical of fixed bar;
Figure 17 is the sectional view that schematically shows the basic comprising of the gas separation membrane assembly that the mode of part E relates to;
Figure 18 is the part enlarged drawing of Figure 17;
Figure 19 be the expression Figure 17 assembly in casing one the example sectional view;
Figure 20 is the sectional view of basic comprising of gas separation membrane assembly that schematically shows the embodiment of part F;
Figure 21 (A) is the part enlarged drawing of Figure 20, (B) is the enlarged drawing of representing that further it is a part of;
Figure 22 (A) is the sectional view of the gas separation membrane assembly of other embodiment of expression, (B) is the part enlarged drawing;
Figure 23 is a sectional view of further representing the gas separation membrane assembly of other embodiment;
Figure 24 is the sectional view of the gas separation membrane assembly of other embodiment of expression;
Figure 25 is the sectional view of basic comprising of gas separation membrane assembly that schematically shows the embodiment of part G.
Figure 26 is a part of enlarged drawing of Figure 25.
Figure 27 is the sectional view among the A-A of Figure 26.
Symbol description
1,1 ', 101 separating film modules
10,110,110 ' cylindrical container
10a container inner peripheral surface
The 10f flange part
The 10h peristome
The 10s stage portion
The 10t stage portion
The 110g groove
111 tubing
112 end members
12,112h sees through gas discharge outlet
The 112f flange part
14 hollow cortinas
15,115 hollow tow
17 annular seal members
18,118,119 O ring
20,21,26,27,120,121,127 caps
The 20h peristome
The 120f flange part
The 120s stage portion
22A mist introducing port
The non-gas discharge outlet that sees through of 22B
The 27f flange part
The 127f flange part
The 127g groove
30,30 ', 38,130A, 130B, 530 tube sheets
30s, 530s stage portion
30 ' t stage portion
41 discharge pipes
42 hold-down screws
43 fixtures
201 gas separation membrane assemblies
210 boxes
211 cylindrical containers
212 peristomes
214 hollow cortinas
215 hollow tow
217,218 internal circle grooves
219 circumferential groove
220,221 cap members
The 220A end face
The 220B cylindrical portion
The 220f par
The 220g par
The 220h through hole
223 outlets
227a, 227b internal circle groove
230,231 tube sheets
R1, R2 elastic ring member
245 fixed bars
246 nuts
The P1 gas introduction port
The non-gas discharge outlet that sees through of P2
The P3 gas flow path
601 gas separation membrane assemblies
610 casings
610a mist inlet
610b does not see through gas vent
610c sees through gas vent
611 cylindrical members
612,613 caps
614 hollow cortinas
615 hollow tow
618 seal cavities
619a mist space
619b does not see through the gas compartment
621,622 tube sheets
631 film structural components
631a, 631b end
801 gas separation membrane assemblies
810,910 casings
810a, 910a mist inlet
810b, 910b do not see through gas vent
810c, 910c see through gas vent
910d Purge gas inlet
811 cylindrical members
813 tube sheet retaining members
The 813a line part
The 813b large-diameter portion
The 813c tapered portion
814,914 hollow cortinas
815,915 hollow tow
818,918 seal cavities
819a mist space
819b does not see through the gas compartment
821,822,921,922 tube sheets
The hollow cortina of 822a is buried portion underground
The 822b tube sheet does not have dirty portion
831 film structural components
831a, 831b end
850,950 hermetically-sealed constructions
851,853 bands
855 fixation adhesive tapes
857 fixtures
891,893 packing materials
971 core pipes
The 971a hole
The A1 exposed portions serve
The A31 clearance portion
1001 gas separation membrane assemblies
1010 casings
1010a mist inlet
1010b does not see through gas vent
1010c sees through gas vent
1011 cylindrical structural members
1011a, 1011b heavy section
The 1011d recess
1012 cap members
1014 hollow cortinas
1015 hollow tow
1018 seal cavities
1019a mist space
1019b does not see through the gas compartment
1021,1022 tube sheets
1021s rank portion
1060 containment members
The groove of C1 ring-type
B11 mist inlet
B12 sees through gas discharge outlet
The non-gas discharge outlet that sees through of B13
The hollow cortina of B14
The B15 casing
B16a, 16b tube sheet
The B21 mould
The B22 casing
The B23 tube sheet
The hollow cortina of B24
The specific embodiment
Below, about embodiment of the present invention, part A～part G is described.
[part A: the method for making nitrogen-rich air by high-temperature gas]
(background technology)
As far as airborne vehicle, one of the explosion-proof method of jar that acts as a fuel has the method for using mounting type inert gas generating system (OBIGGS:on board inert gas generating system).For the danger that prevents to explode, the oxygen concentration of the vapor phase areas in the tanks need be lower than the concentration of regulation.Therefore, OBIGGS separated oxygen and make the high nitrogen-rich air of nitrogen concentration from air offers tanks with it.
OBIGGS for example utilizes the air separation membrane module to make nitrogen-rich air.About air separation membrane, because the gas that is supplied to is got over high pressure, high temperature, treating capacity just increases more usually, and therefore, the extraction gas of engine or ambient air etc. are with being provided for the air separation membrane module after the compressions such as compressor reducer.Gas after this compression is generally 149～260 ℃.
Existing air separation membrane module is worked under about 82 ℃～about 93 ℃ effectively, and under aforesaid high temperature, separating property significantly reduces, and therefore can't use.Therefore, usually, through using heat exchanger or will mixing with the air of low temperature etc., the gas after the compression is cooled to this temperature after, offer air separation membrane module (TOHKEMY 2010-142801 communique).
(problem that the invention of part A will solve)
The purpose of the invention of part A is, provides a kind of high temperature compressed air more than 150 ℃ is offered the method that the air separation membrane module is made nitrogen-rich air.
The disclosed main invention main points of this part are described below.
1, a kind of method of using the air separation membrane module by air manufacturing nitrogen-rich air is characterized in that,
Air more than 150 ℃ is offered the air separation membrane module.
(effect of the invention of part A)
According to the method for the invention of part A, can be with high temperature, for example the air more than 150 ℃ offers the air separation membrane module, the nitrogen-rich air of the nitrogen concentration that has been improved.The invention of this part is characterised in that the use air separation membrane, and the above-mentioned air separation membrane at high temperature separating property of transmission rates and the oxygen and the nitrogen of oxygen is high, and then, even at high temperature long-time use also can be kept its performance.The invention of this part for example is suitable for the explosion protection system of the tanks of airborne vehicle.When in this explosion protection system, using the invention of this part, when air was offered the air separation membrane module, the heat exchanger etc. that is used for the cooling down high-temperature air can lightweight.In addition, as far as air separation membrane, the air that is supplied to is got over high temperature, and transmission rates is fast more, therefore, according to the method for the invention of this part that can handle high temperature air, also can dwindle membrane area effectively.Therefore, can carry out simplification, the lightweight of the equipment in the airborne vehicle.
(embodiment in the part A)
The disclosed invention of this part is a kind of method of using the air separation membrane module by air generation nitrogen-rich air, it is characterized in that, the high temperature air more than 150 ℃ is offered the air separation membrane module.In this part, short of special instruction, " high temperature " be meant more than 150 ℃, and is preferred more than 175 ℃, more preferably more than 200 ℃.
The air separation membrane module for example can obtain as follows: about 100～1000000 of the hollow cortinas of harness suitable length; At least one end that makes air silk is the state that maintains open state; Use the both ends of this hollow tow of tube sheet set that constitutes by thermosetting resin etc.; At least possessing the air supply port, seeing through gas discharge outlet and non-seeing through in the container of gas discharge outlet; Take in and install the air silk membrane component that constitutes by the hollow tow of gained and tube sheet etc. so that to feed the inboard space of hollow cortina isolated with the space of leading to the hollow cortina outside, obtain therefrom.In such air separation membrane module; The space air supply that joins to the inboard or the outside from the air supply port with hollow cortina; And hollow cortina join and flow periods between airborne oxygen selective permeation film; See through gas (oxygen-enriched air) and discharge from seeing through gas discharge outlet, the non-gas (nitrogen-rich air) that sees through that does not see through film is discharged from the non-gas discharge outlet that sees through, and carries out gas thus and separates.
As air separation membrane; Not special the qualification for example can be enumerated and had by the asymmetric air separation membrane of the compacted zone as thin as a wafer of mainly undertaking the air separation performance (preferred thickness is 0.001～5 μ m) with the unsymmetric structure of thicker porous layer (preferred thickness is 10～2000 μ m) formation that supports this compacted zone.Preferred internal diameter is that 10～3000 μ m and external diameter are the hollow cortina about 30～7000 μ m.
Air separation membrane preferably at high temperature has the characteristic that is described below.
The transmission rates of the preferred oxygen at high temperature of air separation membrane is high.For example, 175 ℃ oxygen transmission rates (P ' O2) be 20 * 10 -5Cm 3(STP)/cm 2More than the seccmHg, be preferably 25 * 10 -5Cm 3(STP)/cm 2More than the seccmHg, more preferably 30 * 10 -5Cm 3(STP)/cm 2More than the seccmHg.And then at high temperature separating property is also high even air separation membrane is preferred, for example, and under 175 ℃, the oxygen transmission rates of the separating property of demonstration film and the ratio of nitrogen transmission rates (P ' O2/ P ' N2) be more than 1.8, be preferably more than 2.0, more preferably more than 2.5.Need to prove that the ratio of transmission rates is bigger value usually at low temperatures.The transmission rates ratio is separating property when high, and the rate of recovery of target nitrogen-rich air raises.
In addition, at high temperature use for a long time even air separation membrane is preferred, the transmission rates of oxygen and the separating property of film do not reduce greatly yet.For example, when under 175 ℃, having used 140 hours, the oxygen transmission rates (P ' O2) and the ratio of the transmission rates of the transmission rates of oxygen and nitrogen (P ' O2/ P ' N2) be preferably and use preceding P ' O2And P ' O2/ P ' N2Separately more than 75%, more preferably more than 80%, further be preferably more than 90%.
And then, even if air separation membrane preferably also keeps shape on the degree of not damaging its function under the condition of high temperature.For example, the glass transition temperature (Tg) that constitutes the material of air separation membrane preferably is higher than 225 ℃ (promptly not showing below 225 ℃), more preferably more than 250 ℃, further is preferably more than 300 ℃ and (comprises the unmeasured situation of glass transition temperature).And then, preferably at high temperature keeping shape for a long time, the shape conservation rate when having placed 2 hours for 175 ℃ is preferably more than 95%, more preferably more than 99%.At this, in this part, so-called shape conservation rate, expression is used in the ratio of the original length of length before divided by heat treatment of the silk of 175 ℃ of heat treatments after 2 hours.
As glass transition temperature be higher than 225 ℃ and in diffusion barrier preferable material, can enumerate polyimides, polyether sulfone, polyamide, polyether-ether-ketone etc., especially preferably enumerate polyimides.
As forming the material that asymmetric gas separates hollow cortina (following also abbreviate as hollow cortina), not special the qualification describes being preferably used as the example of composition that air separation membrane and glass transition temperature be higher than 225 ℃ polyimides.The polyimides of below forming is the aromatic polyimide shown in the repetitive of formula (1), and glass transition temperature is generally more than 250 ℃, is preferably more than 300 ℃ (to comprise the unmeasured situation of glass transition temperature).
[changing 1]
Figure BDA0000105556110000101
general formula (1)
In the above-mentioned formula, B results from 4 valency unit of tetrabasic carboxylic acid composition, and A results from the divalent unit of two amine components.Below, the unit that constitutes aromatic polyimide is described in detail.
Unit B is for resulting from tetrabasic carboxylic acid composition 4 valency unit; Comprise the unit B with biphenyl structural 2 shown in the formula (B2) of the unit B 1 shown in the formula (B1) of 10～70 moles of %, preferred 20～60 moles of % and 90～30 moles of %, preferred 80～40 moles of %, preferably have unit B 1 and unit B 2 in fact with diphenyl HFC-236fa structure.When diphenyl HFC-236fa structure was lower than 10 moles of % and biphenyl structural and surpasses 90 moles of %, the gas separating property of the polyimides of gained reduced, and is difficult to obtain the high performance gas diffusion barrier.On the other hand, when diphenyl HFC-236fa structure surpassed 70 moles of % and biphenyl structural and is lower than 30 moles of %, the mechanical strength of the polyimides of gained reduced sometimes.
In addition, unit B also can contain the 4 valency unit based on the phenyl structure shown in the following formula (B3).4 valency unit based on the phenyl structure shown in the formula (B3) are 0～30 mole of %, are preferably 10～20 moles of %.
And then unit B can contain the 4 valency unit B 4 that result from other tetrabasic carboxylic acid beyond the unit B 1, B2, B3.
[changing 2]
Figure BDA0000105556110000111
Unit A results from the divalent unit of two amine components, comprises from by the unit A1 that selects formula (A1a), (A1b) and the group that (A1c) constitutes with from by the unit A2 that selects formula (A2a) and the group that (A2b) constitutes.And then unit A can contain the divalent unit A3 that results from other two amine component beyond the unit A1, A2.
Unit A1a is the divalent unit based on biphenyl structural shown in the formula (A1a), and unit A1b and A1c contain the hexafluoro shown in formula (A1b) and the formula (A1c) and replace structure, and is more detailed, has the construction unit that contains 2 trifluoromethyls.
[changing 3]
Figure BDA0000105556110000121
(in the formula, X is chlorine atom or bromine atoms, and n is 1～3.)
[changing 4]
Figure BDA0000105556110000122
(in the formula, r is 0 or 1, and benzyl ring can be replaced by the OH base.)
[changing 5]
(in the formula, Y representes O or singly-bound.)
When unit A1 has the unit shown in the formula (A1a), be 30～70 moles of % in unit A, be preferably 30～60 moles of %.This diphenyl amine helps to improve separating degree, but it measures when too much, and polymer becomes insoluble and is difficult to make film, and when it was very few, separating degree reduced, so not preferred.
When unit A1 had the unit shown in formula (A1b) and/or the formula (A1c), these unit were contained 10～50 moles of %, preferred 20～40 moles of % in unit A.
Unit A2 is selected from by the sulfur heterocyclic ring structure, particularly, is selected from the group that the unit class shown in reaching (A2b) by formula (A2a) constitutes.
[changing 6]
Figure BDA0000105556110000131
(in the formula, R and R ' are hydrogen atom or organic group, and n is 0,1 or 2.)
[changing 7]
Figure BDA0000105556110000132
(in the formula, R and R ' are hydrogen atom or organic group, and X is-CH 2-or-CO-.)
Unit A2 is contained 90～30 moles of % in unit A, preferred 90～40 moles of %, more preferably 90～50 moles of %, further preferred 80～60 moles of %.
Unit A3 in unit A with 50 moles below the %, preferred 40 moles below the %, more preferably 20 moles of amounts below the % contain.
Below, the monomer component of above-mentioned each unit of constituting aromatic polyimide is described.
The unit with diphenyl HFC-236fa structure shown in the above-mentioned general formula (B1) becomes to assign to obtain as tetrabasic carboxylic acid through using (hexafluoro isopropylidene) two phthalic acids, its dicarboxylic anhydride or its carboxylate.As above-mentioned (hexafluoro isopropylidene) two O-phthalic acids; Can suitably use 4; 4 '-(hexafluoro isopropylidene) two phthalic acids, 3,3 '-(hexafluoro isopropylidene) two phthalic acids, 3,4 '-(hexafluoro isopropylidene) two phthalic acids, their dicarboxylic anhydride or their carboxylate; But preferred especially 4,4 '-(hexafluoro isopropylidene) two phthalic acids, its dicarboxylic anhydride or its carboxylate.
The unit with biphenyl structural shown in the above-mentioned general formula (B2) becomes to assign to obtain as tetrabasic carboxylic acid through using biphenyltetracarboxyacid acid classes such as biphenyltetracarboxyacid acid, its dicarboxylic anhydride or its carboxylate.As above-mentioned biphenyltetracarboxyacid acid class, can suitably use 3,3 ', 4; 4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2; 2 ', 3,3 '-biphenyltetracarboxyacid acid, their dicarboxylic anhydride or their carboxylate, but preferred especially 3; 3 ', 4,4 '-biphenyltetracarboxyacid acid, its dicarboxylic anhydride or its carboxylate.
4 valency unit based on the phenyl structure shown in the above-mentioned general formula (B3) obtain through using PMA classes such as PMA and acid anhydrides thereof.This PMA class is improving aspect the engineering properties preferably, but it measures when too much, and the polymer solution when causing the system film solidifies etc., becomes unstable, is difficult to form air silk.
Other tetrabasic carboxylic acid composition of unit B 4 is provided, is the tetracarboxylic acid acids beyond the compound shown in above-mentioned, select not damage this part the invention effect and can be according to circumstances the further compound of improved performance.For example can enumerate: diphenyl ether tetracarboxylic acid acids, benzophenone tetracarboxylic acid acids, diphenyl sulfone tetracarboxylic acid acids, naphthalene tetracarboxylic acid class, diphenyl methane tetracarboxylic acid acids, diphenyl propane tetracarboxylic acid acids etc.
The divalent unit based on biphenyl structural shown in the above-mentioned general formula (A1a) obtains as two amine components through using the halogen substituted biphenyl amine shown in the general formula (A1a-M).
[changing 8]
Figure BDA0000105556110000141
(in the formula, X is chlorine atom or bromine atoms, n=1～3.)
As halogen substituted biphenyl amine, can enumerate: dichloro-benzidine (diaminourea DCBP) class, tetrachloro benzidine (diaminourea tetrachloro biphenyl) class, chlordene diphenyl amine, tetrabromo diphenyl amine, '-dibromobiphenyl amine, hexabromobiphenyl amine etc.As above-mentioned DCBP amine, can enumerate 3,3 '-dichloro-benzidine (DCB) as the tetrachloro biphenyl amine, can enumerate 2,2 ', 5,5 '-tetrachloro benzidine (TCB) etc.
Divalent unit shown in the general formula (A1b) obtains as two amine components through using the hexafluoro substituted compound class shown in the general formula (A1b-M).
[changing 9]
Figure BDA0000105556110000142
(in the formula, r is 0 or 1, and benzyl ring can be replaced by the OH base.)
The preferred compound of the hexafluoro substituted compound class (A1b-M) is represented by general formula (A1b-M1)～(A1b-M3).
[changing 10]
Figure BDA0000105556110000151
As two [(amino-benzene oxygen) phenyl] the HFC-236fa classes shown in the general formula (A1b-M1), for example can enumerate: 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 2 of 2-, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fas of 2-.As two (aminophenyl) HFC-236fa classes shown in the general formula (A1b-M2), for example can enumerate 2, two (4-aminophenyl) HFC-236fas of 2-.Replace two (aminophenyl) HFC-236fa classes as the hydroxyl shown in the general formula (A1b-M3), for example can enumerate 2, two (3-amino-4-hydroxy) HFC-236fas of 2-.
In addition, the divalent unit shown in the general formula (A1c) obtains as two amine components through using the hexafluoro substituted compound class shown in the general formula (A1c-M).
[changing 11]
Figure BDA0000105556110000152
(in the formula, Y representes O or singly-bound.)
As the diamine compound class shown in the general formula (A1c-M), for example can enumerate: 2,2 '-two (trifluoromethyl)-4,4 '-diamino-diphenyl ether, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine etc.
In addition, have the unit of the structure shown in above-mentioned general formula (A2a) or the above-mentioned general formula (A2b), obtain as two amine components through using the aromatic diamine shown in formula (A2a-M) and the general formula (A2b-M) respectively.
[changing 12]
Figure BDA0000105556110000161
(in the formula, R and R ' are hydrogen atom or organic group, and n is 0,1 or 2.)
[changing 13]
(in the formula, R and R ' are hydrogen atom or organic group, and X is-CH 2-or-CO-.)
As the aromatic diamine shown in the above-mentioned general formula (A2a-M); The n that can suitably enumerate general formula (A2a-M) is that the n of diaminourea dibenzothiophenes class shown in 0 the formula (A2a-M1) or general formula (A2a-M) is diaminourea dibenzothiophenes=5 shown in 2 the formula (A2a-M2), 5-dioxide class.
[changing 14]
Figure BDA0000105556110000163
(in the formula, R and R ' are hydrogen atom or organic group.)
[changing 15]
Figure BDA0000105556110000171
(in the formula, R and R ' are hydrogen atom or organic group.)
As above-mentioned diaminourea dibenzothiophenes class (general formula (A2a-M1)), for example can enumerate: 3,7-diaminourea-2,8-dimethyl Dibenzothiophene, 3,7-diaminourea-2; 6-dimethyl Dibenzothiophene, 3,7-diaminourea-4,6-dimethyl Dibenzothiophene, 2,8-diaminourea-3,7-dimethyl Dibenzothiophene, 3; 7-diaminourea-2,8-diethyl dibenzothiophenes, 3,7-diaminourea-2,6-diethyl dibenzothiophenes, 3,7-diaminourea-4; 6-diethyl dibenzothiophenes, 3,7-diaminourea-2,8-dipropyl dibenzothiophenes, 3,7-diaminourea-2,6-dipropyl dibenzothiophenes, 3; 7-diaminourea-4,6-dipropyl dibenzothiophenes, 3,7-diaminourea-2,8-dimethoxy dibenzothiophenes, 3; 7-diaminourea-2,6-dimethoxy dibenzothiophenes, 3,7-diaminourea-4,6-dimethoxy dibenzothiophenes etc.
As above-mentioned diaminourea dibenzothiophenes=5,5-dioxide class (general formula (A2a-M2)), for example can enumerate: 3,7-diaminourea-2,8-dimethyl Dibenzothiophene=5,5-dioxide, 3; 7-diaminourea-2,6-dimethyl Dibenzothiophene=5,5-dioxide, 3,7-diaminourea-4,6-dimethyl Dibenzothiophene=5,5-dioxide, 2; 8-diaminourea-3,7-dimethyl Dibenzothiophene=5,5-dioxide, 3,7-diaminourea-2,8-diethyl dibenzothiophenes=5; 5-dioxide, 3,7-diaminourea-2,6-diethyl dibenzothiophenes=5,5-dioxide, 3,7-diaminourea-4; 6-diethyl dibenzothiophenes=5,5-dioxide, 3,7-diaminourea-2,8-dipropyl dibenzothiophenes=5,5-dioxide, 3; 7-diaminourea-2,6-dipropyl dibenzothiophenes=5,5-dioxide, 3,7-diaminourea-4,6-dipropyl dibenzothiophenes=5; 5-dioxide, 3,7-diaminourea-2,8-dimethoxy dibenzothiophenes=5,5-dioxide, 3,7-diaminourea-2; 6-dimethoxy dibenzothiophenes=5,5-dioxide, 3,7-diaminourea-4,6-dimethoxy dibenzothiophenes=5,5-dioxide etc.
In above-mentioned general formula (A2b-M), be-CH as X 2-diaminourea thioxanthene-10,10-two ketones, for example can enumerate: 3,6-diaminourea thioxanthene-10,10-diketone, 2; 7-diaminourea thioxanthene-10,10-diketone, 3,6-diaminourea-2,7-dimethyl thioxanthene-10,10-diketone, 3; 6-diaminourea-2,8-diethyl-thioxanthene-10,10-diketone, 3,6-diaminourea-2,8-dipropyl thioxanthene-10; 10-diketone, 3,6-diaminourea-2,8-dimethoxy thioxanthene-10,10-diketone etc.
In above-mentioned general formula (A2b-M), as X be-the diaminourea thioxanthene-9,10 of CO-, the 10-three ketones, for example can enumerate: 3,6-diaminourea-thioxanthene-9,10,10-triketone, 2,7-diaminourea-thioxanthene-9,10,10-triketone etc.
Other two amine component of unit A3 is provided, is the diamine compound beyond the compound shown in above-mentioned, select not damage this part invention effect and can be according to circumstances the further compound of improved performance.
For example can enumerate: 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminourea-3, diamino diphenyl sulfone classes such as 3 '-dimethyl diphenyl sulfone;
4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,3 '-dimethyl-4,4 '-diamino-diphenyl ether, 3,3 '-diethoxy-4, diamino-diphenyl ethers such as 4 '-diamino-diphenyl ether;
4,4 '-diaminodiphenyl-methane, 3, diaminodiphenyl-methane classes such as 3 '-diaminodiphenyl-methane;
2, two (3-aminophenyl) propane, 2 of 2-, two (4-aminophenyl) propane of 2-etc. 2, two (aminophenyl) propane classes of 2-;
2, two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-etc. 2, two (amino-benzene oxygen phenyl) the propane classes of 2-;
4,4 '-diaminobenzophenone, 3, diaminobenzophenone classes such as 3 '-diaminobenzophenone;
3, diaminobenzoic acid classes such as 5-diaminobenzoic acid;
1,3-phenylenediamine, 1, phenylenediamines such as 4-phenylenediamine;
2,2 '-two chloro-4, dichloro diamino-diphenyl ethers such as 4 '-diamino-diphenyl ether;
Ditolyl amines such as o-tolidine, a tolidine;
2,2 '-dihydroxy-4, dihydroxy benzidine classes such as 4 '-benzidine etc.
Wherein, be preferably diamino diphenyl sulfone class, diamino-diphenyl ethers, diaminobenzoic acid class, dichloro diamino-diphenyl ethers, dihydroxy benzidine class.
In asymmetric air separation membrane, use under the situation of the aromatic polyimide shown in the repetitive of general formula (1), for example, above-mentioned tetrabasic carboxylic acid composition preferred compositions is used as 4 of the carboxylic acid that unit B 1 is provided; 4 '-(hexafluoro isopropylidene-two (phthalic anhydride), as provide unit B 2 carboxylic acid 3,3 ', 4; 4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, conduct provide the PMA dicarboxylic anhydride of the carboxylic acid of unit B 3, and above-mentioned two amine component preferred compositions are used as 2,2 ' of the diamines that unit A1 is provided; 5; 5 '-tetrachloro benzidine, as provide unit A2 diamines 3,7-diaminourea-dimethyl Dibenzothiophene=5,5-dioxide.3,7-diaminourea-dimethyl Dibenzothiophene=5, the 5-dioxide is meant with 3; 7-diaminourea-2,8-dimethyl Dibenzothiophene=5, the 5-dioxide is main component, comprise the different isomers 3 in position of methyl; 7-diaminourea-2,6-dimethyl Dibenzothiophene=5,5-dioxide, 3; 7-diaminourea-4,6-dimethyl Dibenzothiophene=5, the mixture of 5-dioxide.
The preparation of above-mentioned aromatic polyimide solution; Preferably utilize two-step method or one-step method to carry out; Above-mentioned two-step method is that the ratio of components with regulation adds tetrabasic carboxylic acid composition and two amine components in organic polar solvent; Under the low temperature about room temperature, carry out polymerisation and generate polyamic acid, then heat and add hot-imide or add pyridine etc. and carry out chemical imidizate; Above-mentioned one-step method is that the ratio of components with regulation adds tetrabasic carboxylic acid composition and two amine components in organic polar solvent, under 100～250 ℃, preferred about 130～200 ℃ high temperature, carries out the polymerization imidization reaction.When carrying out imidization reaction through heating, carry out on water or pure limit that disengaging is removed on preferred limit.With respect to regard to the use amount of organic polar solvent, the concentration that preferably makes the polyimides in the solvent is about 5～50 weight %, preferred 5～40 weight % with regard to tetrabasic carboxylic acid composition and two amine components.
The aromatic polyimide solution that carries out the polymerization imidizate and obtain also can directly be used for spinning.In addition; Also can for example in the solvent that with respect to aromatic polyimide is non-solubility, drop into the aromatic polyimide solution of gained; Aromatic polyimide is separated out and after separating; Mode to become normal concentration is dissolved in organic polar solvent again, and preparation aromatic polyimide solution is used it for spinning.
With regard to the aromatic polyimide solution that is used for spinning; The concentration that preferably makes polyimides is 5～40 weight %, further is preferably 8～25 weight %, and solution viscosity (rotary viscosity) is 100～15000 pools at 100 ℃ preferably; More preferably 200～10000 pools are preferably 300～5000 pools especially.When solution viscosity is lower than 100 pools, might obtains homogeneous membrane (film), but be difficult to obtain the big anisotropic membrane of mechanical strength.In addition, when surpassing 15000 pools, be difficult for from spinning-nozzle, extruding, therefore, be difficult to obtain the asymmetric hollow cortina of target shape.
As above-mentioned organic polar solvent; So long as it is just unqualified suitably to dissolve the solvent of aromatic polyimide of gained; But for example can suitably enumerate by the pyrocatechol of the catechol that directly has 2 hydroxyls on the phenol of phenol, cresols, xylenols and so on, the phenyl ring, resorcinol and so on, 3-chlorophenol, 4-chlorophenol (with after the parachlorophenol stated identical), the phenol series solvent that constitutes such as halo phenols such as 3-bromophenol, 4-bromophenol, 2-chloro-5-hydroxy-methylbenzene or by N-N-methyl-2-2-pyrrolidone N-, 1; 3-dimethyl-2-imidazolone, N; Dinethylformamide, N; N-DEF, N, N-dimethylacetylamide, N, acid amides series solvent that amide-types such as N-diethyl acetamide constitute or their mixed solvent etc.
Hollow cortina can be through using above-mentioned aromatic polyimide solution etc., utilizing the spinning (dry-and wet-type spin processes) based on the dry-and wet-type method to come suitably to obtain.The dry-and wet-type method is the compacted zone (separating layer) that the solvent evaporation on the surface of the polymer solution of making the air silk shape formed approach, further impregnated in solidification liquid (mix with the solvent of polymer solution, polymer is insoluble solvent); Utilize the phenomenon of phase separation that produces this moment; The method (phase inversion) that forms minute aperture and porous layer (supporting course) is formed, this method are that Loeb etc. proposes the method for (for example No. 3133132, United States Patent (USP)).
The dry-and wet-type spin processes utilizes the dry-and wet-type method to form the method for hollow cortina for using spinning with nozzle, for example is recorded in japanese kokai publication sho 61-133106 communique or the japanese kokai publication hei 3-267130 communique etc.
Manufacturing approach comprises spinning process (spinning slurry ejection operation) usually, solidifies operation, matting, drying process and heat treatment step.
At first, in spinning process (spinning slurry ejection operation), be used to spray the spinning-nozzle of spinning pulp feed liquid so long as the spinning-nozzle that the spinning pulp feed liquid is extruded into hollow filamentous get final product preferred Guan Zaikong medium-sized (tube-in-orifice type) nozzle etc.Usually, the temperature range of the aromatic polyimide solution when extruding preferably is about 20 ℃～150 ℃, is preferably 30 ℃～120 ℃ especially.Preferred temperature range is according to the solvent species of liquid, viscosity etc. and different.In addition, spinning is carried out to the internal feed gas or the liquid limit of the hollow filamentous of extruding from nozzle in the limit.
From continuous the solidifying the operation of spinning process, from the hollow filamentous of nozzle ejection temporarily be squeezed in the atmosphere or inert gas atmosphere such as nitrogen medium, then import to coagulating bath and impregnated in the solidification liquid.Solidification liquid does not preferably dissolve the aromatic polyimide composition in fact and has the liquid of intermiscibility with the solvent of aromatic polyimide solution.Not special the qualification, but preferably make lower alcohols such as water, methyl alcohol, ethanol, propyl alcohol or acetone, diethyl ketone, methyl ethyl ketone etc. have the ketone etc. of low alkyl group or their mixture.In addition, when the solvent of aromatic polyimide solution is the acid amides series solvent, the also aqueous solution of preferred amide series solvent.
In following matting; Clean with cleaning solvents such as ethanol as required, then use aliphatic hydrocarbons such as replacement solvent, for example isopentane, n-hexane, isooctane, normal heptane to replace the outside and the inboard solidification liquid and/or the cleaning solvent of air silk.
In following drying process, the air silk that will contain replacement solvent carries out drying under suitable temperature.And, in heat treatment step, preferably under the temperature of softening point that is lower than employed aromatic polyimide or second order transition point, heat-treat, obtain asymmetric gas thus and separate hollow cortina.
(utilizability in the industry)
According to the invention of this part, can with high temperature for example the air more than 150 ℃ offer the air separation membrane module, the nitrogen-rich air of the nitrogen concentration that has been improved.The method of the invention of this part for example can be applied to the explosion protection system of the tanks of airborne vehicle.
(summary of the invention)
The invention that relates to part A is described below.
1. a method of using the air separation membrane module by air manufacturing nitrogen-rich air is characterized in that,
Air more than 150 ℃ is offered the air separation membrane module.
2. as above-mentioned 1 described method, it is characterized in that, above-mentioned air separation membrane module when bringing into use, 175 ℃ oxygen transmission rates (P ' O2) be 20 * 10 -5Cm 3(STP)/cm 2More than the seccmHg, and 175 ℃ oxygen transmission rates and the ratio of nitrogen transmission rates (P ' O2/ P ' N2) be more than 1.8, and
P ' when under 175 ℃, having used 140 hours O2And P ' O2/ P ' N2Keep the above-mentioned preceding P ' that brings into use O2And P ' O2/ P ' N2Separately more than 90%.
3. like above-mentioned 1 or 2 described methods, it is characterized in that the air separation membrane in the above-mentioned air separation membrane module is by forming at the material that does not show glass transition temperature below 225 ℃.
4. like above-mentioned 1 described method, it is characterized in that above-mentioned air separation membrane shows the shape conservation rate more than 95% when having placed 2 hours for 175 ℃.
5. the explosion-proof method of an airborne vehicle is characterized in that, utilizes each described manufacturing approach manufacturing nitrogen-rich air in above-mentioned 1～4, offers airborne vehicle and uses tanks.
[part B: under high temperature, high pressure, have sufficient hear resistance and resistance to pressure etc. and the gas separation membrane assembly in crack do not occur]
(technical field)
The invention of this part relates to the separatory gas separation membrane assembly of a kind of mist, and it will use the tube sheet set integratedly after specific composition epoxy resin solidifies by the tow that the many hollow cortina with selection permeability constitutes.
(background technology)
The gas separation membrane assembly of hollow fiber type; Be cured plate (tube sheet) at the resin that will use through casting mold by at least one end with tow that the many hollow cortina of selecting permeability constitute tie together integratedly and the state of set under, be accommodated in and have the mist introducing port at least, see through gas discharge outlet and the non-assembly that sees through the casing of gas discharge outlet.Tube sheet has inner space and the bubble-tight effect of space outerpace, maintenance inner space and space outerpace through completely cut off hollow cortina between sealing air silk and the air silk and between air silk and the casing except the effect with set tow integratedly.When the gas separation membrane assembly of hollow fiber type is lost the air-tightness that above-mentioned tube sheet causes, the separation that is not fit to.
In the gas separating method that has used diffusion barrier, accomplish suitable gas through supply gas mixture under the state of high temperature, high pressure sometimes and separate.At this moment, with regard to tube sheet material, demanding hear resistance, resistance to pressure, its glass transition temperature or heat distortion temperature must be than the tens of at least degree of the operating temperature height of gas separation membrane assembly.
Realize high hear resistance, the tube sheet material of resistance to pressure as being used to, generally use the thermohardening type resin, but when tube sheet is shaped, accomplish, under significantly high temperature, handle for the curing reaction that makes the thermohardening type resin.This be because, use when not accomplishing the tube sheet of curing reaction, make separating film module at high temperature be cured reaction between on-stream period and tube sheet shrinks, the sealing property between tube sheet and the casing is insufficient.The hear resistance of the remarkable high temperature when therefore, tube sheet material also being required to be shaped with respect to tube sheet.
As the gas separated separating film module of the mist that can be used for high temperature, high pressure, for example record in japanese kokai publication sho 62-74434 communique that the aqueous polybutadiene that makes phenol aldehyde type epoxy resin and end have reactive functional groups reacts and air silk element that the modified epoxy that obtains is processed.
(problem that the invention of part B will solve)
But there is following problem in existing tube sheet material: cure shrinkage is big when the tube sheet moulding, produces crack or tube sheet destruction etc.And have following problem: only paying attention under resistance to pressure and the stable on heating situation, therefore the flexible deficiency of tube sheet material, for example receives when impacting in the running, on tube sheet, produces crack or tube sheet destruction etc.The purpose of the invention of this part is, a kind of tube sheet of gas separation membrane assembly is provided, and it keeps sufficient hear resistance and resistance to pressure under high temperature, high pressure, the crack can not occur.
The disclosed main invention main points of this part are described below.
1. gas separation membrane assembly, it has:
The tow that constitutes by the many hollow cortina with gas separating property,
Have mist inlet, see through gas discharge outlet and non-see through gas discharge outlet and said hollow tow be configured in inner casing and
The tube sheet of at least one end of fixing said hollow tow,
Wherein, Said tube sheet is formed by the curable epoxide thing that the castable resin composition is solidified into, and this castable resin composition comprises: (a) phenolic epoxy compound and (b) end are had the modified epoxy that can react with the hycar of the functional group of epoxy reaction and obtain, and (c) curing agent.
(the invention effect of part B)
Tube sheet in the gas separation membrane assembly of the invention of this part can be made with the hycar of the functional group of epoxy reaction through using end to have, and compares with existing tube sheet, has flexible.And, when being exposed to the gas of high temperature, high pressure when tube sheet is shaped or during the running of gas separation membrane assembly, on tube sheet, do not produce the crack, and the airtight performance between the adaptation of air silk or tube sheet and the casing is also no problem.
(embodiment among the part B)
Form the curable epoxide thing of the tube sheet of the air silk element of inventing this part; Can obtain through heat-treating and make it to solidify to the castable resin composition, this castable resin composition comprises at least: (a) phenolic epoxy compound and (b) end are had the modified epoxy that can obtain with the hycar reaction of the functional group of epoxy reaction, and (c) curing agent.Below, at length describe.
< modified epoxy >
Modified epoxy can make the phenolic epoxy compound below; Sometimes also be recited as epoxide (a) } and terminal have and can obtain with the hycar of the functional group of epoxy reaction { below, also be recited as compound (b) sometimes } reaction.
The phenolic epoxy compound (a) that is used for the invention of this part is the compound of formula (a) expression.
[changing 16]
Figure BDA0000105556110000241
(in the formula, R " expression carbon number 1～3 alkyl or hydrogen atom, n representes 0～500, preferred 0～20 integer.)
In the formula (a), R " be preferably methyl or hydrogen atom.With regard to the epoxide (a) of above-mentioned general formula (a) expression, molecular weight is preferably 300～2000, and in addition, epoxide equivalent is preferably 150～250.As epoxide (a), can enumerate: jER152, the jER154 of Mitsubishi Chemical's (strain) system; The EPICLON-N740 of DIC (strain) system, N-770, N-775 etc.; Dongdu changes into the YDPN-638, YDCN-700 series etc. of (strain) system; The D.E.N.438 of Dow Chemical's system etc.
The end of the invention that is used for this part have can with the hycar { compound (b) } of the functional group of epoxy reaction, as can with the functional group of epoxy reaction, can enumerate for example carboxyl, amino, hydroxyl etc., preferred especially carboxyl.Through containing compound (b), can give flexible to formed tube sheet.
As end have can with the hycar of the functional group of epoxy reaction, the carboxyl terminal hycar (CTBN) of for example preferred formula (b) expression.
[changing 17]
Figure BDA0000105556110000242
In the formula (b), m representes the total of the repeat number of butadiene monomer unit, and n representes the total of the repeat number of acrylonitrile monemer unit; There are 2 in structure in [] when above, and m, n represent the summation of the repeat number of unit separately, no matter exist as block; Still exist with random, which can.
The molecular weight of the CTBN of above-mentioned general formula (b) expression is preferred 2000～4000, for example among the CTBN, preferably contains the acrylonitrile monemer unit of 5～50 weight %.As commercially available article, can enumerate for example Emerald functional material system Hypro TMCTBN1300 * 8, CTBN1300 * 13, CTBN1300 * 31 etc.
About modified epoxy, through relative epoxide (a) 100 weight portions, with preferred 5～50 weight portions, further preferred 5～20 weight portions mode mixing cpd (b) and it is reacted obtain.When the content that uses each compound was the modified epoxy in the above-mentioned scope, formed tube sheet did not produce the crack under high temperature, high pressure, in addition, did not produce that glass transition temperature reduces greatly and the problem of being out of shape yet.In addition, only otherwise the goal of the invention of infringement this part also can be mixed other compound.Reaction condition when preparing this modified epoxy is not special to be limited, but reaction temperature is preferably 100～200 ℃, and the reaction time is preferably 2～5 hours.
< curing agent >
The curing agent that is used for the invention of this part, so long as the thermal curing agents of epoxy resin, just not special the qualification can be enumerated amine, phenols, acid anhydrides etc., more preferably uses acid anhydrides.As acid anhydrides, for example can enumerate: phthalic anhydride, pyromellitic acid anhydride, methyl-5-ENB-2,3-dicarboxylic anhydride (methyl carbic anhydride), benzophenone tetracarboxylic dianhydride etc., special preferable methyl-5-ENB-2,3-dicarboxylic anhydride.
< curing accelerator >
The castable resin composition that is used for the invention of this part can contain curing accelerator as required, as curing accelerator, can enumerate for example imidazolium compounds.As imidazolium compounds; For example can enumerate: glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole etc., preferred especially 2-ethyl-4-methylimidazole.
< curable epoxide thing >
The curable epoxide thing of the tube sheet of the invention of formation this part; Castable resin composition that can be through will being mixed with above-mentioned modified epoxy, curing agent and curing accelerator as required (below, also be recited as the castable resin composition sometimes) is heat-treated and is made it to solidify and obtains.The mixed proportion of modified epoxy in the castable resin preparation of compositions and curing agent etc. can be according to functional group's number of the epoxy-functional number of modified epoxy and curing agent, simultaneously according to the suitably adjustment such as viscosity of castable resin composition.Need to prove that with respect to modified epoxy 100 weight portions, curing accelerator is preferably 0～5 weight portion, more preferably 0.1～3 weight portion.
With regard to heat treatment, for example preferably the castable resin composition is heated and the degree of the flowability forfeiture of one-step solidification to castable resin composition, then, the resin of one-step solidification is further at high temperature carried out back curing.Carry out the back when solidifying, preferably mode that rerum natura changes does not take place with the temperature more than the final operating temperature of castable resin composition at assembly, for example preferred 100 ℃～250 ℃, more preferably heat treatment 2～10 hours more than 120 ℃ with tube sheet material in the assembly running.In addition, do not limit, for example preferably be lower than 100 ℃, more preferably under 50～85 ℃, carrying out 2～24 hours one-step solidification is special.Need to prove when the resin of one-step solidification is heated to the back solidification temperature with the programming rate below the 5 ℃/min, do not have because the problem of the reaction heat generation thermal runaway that produces sharp in castable resin composition inside is preferred.State after the preparation method of tube sheet carried out.
< gas separation membrane assembly >
Below, the structure of the gas separation membrane assembly of the invention of this part is described.
As by the film formed gas separation membrane assembly of air silk, known have so-called Bore Feed type and a shell feed type.For example; In the gas separation membrane assembly of Bore Feed type; Shown in Fig. 3 (A); With many (for example hundreds of～hundreds thousand of) boundlings of hollow cortina B14 and make hollow tow; This hollow tow is accommodated in has mist inlet B11 at least, see through in gas discharge outlet B12 and the non-casing B15 of gas discharge outlet B13 of seeing through; The mode that is open state with hollow cortina B14 in two ends of this hollow tow is bonded to casing B15, constitutes tube sheet B16a and B16b, with from mist inlet B11 supply gas and through leading to the space (the non-side that sees through) of the non-gas discharge outlet B13 of seeing through and the isolated mode in space (seeing through side) of leading to through gas discharge outlet B12 from the outside of hollow cortina B14 constitutes in the inboard of hollow cortina B14.Casing B15 makes with for example materials such as stainless steel and other metal materials, plastic material, fibre reinforced plastics material and pottery.In shell feed type gas separation membrane assembly; For example; Shown in Fig. 3 (B); End at hollow tow constitutes tube sheet, is the outside of hollow cortina B14 from mist inlet B11 supply gas and the non-space that sees through side of leading to the non-gas discharge outlet B13 of seeing through, and the space of leading to through gas discharge outlet B12 that sees through side constitutes in the inboard of hollow cortina B14.
At Fig. 3 (A) and (B); The hollow cortina B14 of mist in the gas separation membrane assembly that supplies with from the mist of gas separation membrane assembly inlet B11 joins and between flow periods; Height sees through the hollow cortina B14 of gas penetrated preferably, is separated into the gas (seeing through gas) and the less height that contains that contain height in a large number and see through gas and sees through residual gas gas, that do not see through (non-through gas).See through gas and discharge from seeing through gas discharge outlet B12, the non-gas that sees through is discharged from the non-gas discharge outlet B13 of seeing through.Non-ly see through gas and see through gas from what the gas separation membrane assembly was discharged, according to purposes, only a side is recovered or both sides are recovered.
As the air silk that is used for gas separation membrane, the many air silks that thin thickness and diameter are little even if midget plant also forms high membrane area, can improve separative efficiency, and also are preferred at economic aspect.Above-mentioned air silk for example can enumerate that thickness is that 10～500 μ m and external diameter are the air silk of 50～2000 μ m, not special the qualification.In addition, gas separation membrane can be homogenieity, also can be inhomogeneities such as composite membrane or anisotropic membrane, can also be little porous or imporosity.
Gas separation membrane can be enumerated the gas separation membrane that is formed by for example ceramic materials such as polymeric materials such as polyimides, PEI, polyamide, polyamidoimide, polysulfones, Merlon, silicone resin, cellulose-based polymer, zeolite etc.As the gas separation membrane that forms by polyimides, preference such as aromatic polyimide air silk diffusion barrier, the more preferably asymmetric air silk diffusion barrier of aromatic polyimide.
As the wire distribution form of hollow tow, can enumerate: be arranged in parallel, cross arrangement, textile-like, helical form etc.In addition, hollow tow can have the core pipe in approximate centre portion, at the peripheral part of the hollow tow film of can reeling.And the form of hollow tow can be cylindric, tabular, corner post shape etc., can be in casing directly with above-mentioned form or bend to U word shape or be wound into helical form and take in.
Below, the manufacturing approach of the gas separation membrane assembly of the invention of this part is described.
At first, to hollow cortina is described as the method that hollow tow carries out boundling.
As the hocket method of mode boundling of cross arrangement of the angle that makes hollow cortina have 5～30 degree, can enumerate for example following method with relative direction of principal axis.The direction of principal axis that 1～100 hollow cortina is utilized in the tube (core pipe) that becomes core carries out wire distribution with the wire distribution guider that certain speed comes and goes on the core pipe, simultaneously, the core pipe rotates with certain speed.Therefore, hollow cortina does not carry out wire distribution with axle abreast, has relative direction of principal axis and only rotates the angle of core pipe and carry out wire distribution.During wire distribution to end, be fixed at this hollow cortina, the wire distribution guider turns back to contrary direction, further carries out wire distribution.The core pipe continues to equidirectional rotation, therefore, have specifically relative direction of principal axis with last time angle identical and carry out wire distribution for the angle of just in time opposite direction.When it is repeated, submitted for cross arrangement at the hollow cortina that carries out wire distribution with opposite angle by the hollow cortina of wire distribution, boundling becomes hollow tow.
Below, the method for the tube sheet in the invention that forms this part is described.As the method that forms tube sheet, can enumerate flospinning and leave standstill forming process, but leave standstill forming process owing to installing easy and can boosting productivity, therefore preferred.Below, an example that leaves standstill forming process is described.
The hollow tow of hollow cortina B24 that boundling is had specific length and radical with said method etc. is with after removing the core pipe or the state that core pipe the approximate centre portion at bundle of remaining untouched has being accommodated in casing B22; Be arranged at the assigned position in the mould B21 of end formed tube sheet, above-mentioned hollow tow is basically kept vertical with the end for following with columned casing B22.Fig. 4 b representes the sketch map of this state.
In mould B21, inject the castable resin composition that is used to form tube sheet B23 of ormal weight.Fig. 4 c representes to inject the sketch map of the state of castable resin composition.The method for implanting of castable resin composition is not special to be limited, but owing to easy and uniform in mould B21 and between the hollow cortina B24 is injected the castable resin composition, therefore preferably uses syringe to inject from the mould bottom.When the injection rate of castable resin composition is too fast, be difficult to inject equably, therefore, preferably inject with the sufficient time at position that should the filling cast resin combination.During the castable resin composition flow into mould B21, the temperature of preferred suitably control mould B21.Likewise, preferably control the temperature of castable resin composition.
With regard to the castable resin composition before solidifying, consider from the mouldability aspect, preferably be liquid under the temperature when resin injects.
To the not special restriction of the viscosity of castable resin composition, but the viscosity during 70～90 ℃ of common employed temperature preferably is lower than 120poise when resin injects, and especially preferably is lower than 20poise.At this, the viscosity of resin combination uses rotation viscometer suitably to measure.
Have following problem: the viscosity during 70～90 ℃ of castable resin composition is that 120poise is when above; Resin injection during the tube sheet moulding needs long-time; And the bubble that when resin injects, produces is difficult for disappearing, and resin soaks in air silk intermembranous and produce the space deficiently.
After in mould B21, injecting the castable resin composition, make the castable resin composition carry out one-step solidification, form tube sheet B23 through mould B21 and hollow tow are remained on uniform temperature.The temperature of this moment is lower than 100 ℃, preferred 50～85 ℃.When the temperature in this stage was high, it is fierce that the curing reaction of castable resin composition becomes, and the intensity of the tube sheet that finally obtains is exerted an influence, therefore not preferred.
Make aspect the durability of tube sheet, the mechanical property raising, preferably after the castable resin composition solidifies, the castable resin composition is further being heated, carrying out back curing thus.Preferred 100 ℃～250 ℃ of temperature when solidify the back.When the temperature when solidify the back was lower than 100 ℃, the curing of castable resin composition was insufficient, and is therefore not preferred.In addition, when the temperature when solidify the back was too high, it is fierce that the curing reaction of castable resin composition becomes, and going wrong aspect the intensity of tube sheet, therefore not preferred.Making the castable resin composition carry out the back when solidifying, can be divided into repeatedly, heat in separately temperature respectively.
After making the castable resin composition carry out back curing, through tube sheet being cut off and making hollow cortina open-ended, air silk keeps open state in the end, makes the air silk element with the tube sheet set.
At this, form under the situation of tube sheet at the both ends of hollow tow, carry out through utilizing above-mentioned steps after an end of hollow tow forms tube sheet, in another end, to utilize same step to form tube sheet.So-called after an end forms tube sheet, can be with after the tube sheet cut-out, making hollow cortina opening.In addition, also preferably be arranged at an end in the mould and injecting the castable resin composition, carrying out behind the one-step solidification and carry out forming tube sheet in another end before the back solidifies, carrying out the back at both ends simultaneously and solidify later step.
In the method that the gas separation membrane assembly of the invention that will use this part separates mist, the mist of separation is so long as the admixture of gas more than 2 kinds, just not special restriction.The gas separation membrane assembly of the invention of this part for example can suitably be used for from the separation of the hydrogen of the mist that separates, comes self-contained hydrogen of the nitrogen-rich gas of air and oxygen rich gas, from the separating of the steam of the mixed vapour of steam and organic vapor (dehydration of organic vapor) etc.
(technical scheme)
The invention that part B relates to is described below.
1. gas separation membrane assembly, it has:
The tow that constitutes by the many hollow cortina with gas separating property,
Have mist inlet, see through gas discharge outlet and non-see through gas discharge outlet and said hollow tow be configured in inner casing and
The tube sheet of at least one end of fixing said hollow tow,
Wherein, Said tube sheet is formed by the curable epoxide thing that the castable resin composition is solidified into, and this castable resin composition comprises: (a) phenolic epoxy compound and (b) end are had the modified epoxy that can obtain with the hycar reaction of the functional group of epoxy reaction, and (c) curing agent.
2. like above-mentioned 1 described gas separation membrane assembly, wherein, said castable resin composition also contains curing accelerator.
3. like above-mentioned 1 or 2 described gas separation membrane assemblies, wherein, said can be carboxyl with the functional group of epoxy reaction.
As above-mentioned 1～3 in each described gas separation membrane assembly, wherein, said curing agent is an acid anhydrides.
As above-mentioned 2～4 in each described gas separation membrane assembly, wherein, said curing accelerator is an imidazolium compounds.
[portion C :] even the separating film module that at high temperature also can work well etc.
(technical field)
The disclosed invention of this part relates to a kind of separating film module, and above-mentioned separating film module has the air silk element of the hollow tow that is made up of the many hollow cortina with selection permeability being used the tube sheet set integratedly after specific epoxy resin component solidifies.Even be particularly related to separating film module that influence that a kind of thermal expansion that suppresses tube sheet produces at high temperature also can work well etc.
(background technology)
The gas separation membrane assembly of hollow fiber type possesses air silk element with the tow that is made up of the many hollow cortina with selection permeability and the hollow container of accommodating this element usually.The hollow tow of air silk element, its one or both ends utilize the cured plate (tube sheet) of resin to be fixed in the end of container.In addition, in container, be provided with at least the unstrpped gas introducing port, see through gas discharge outlet and the non-gas discharge outlet that sees through.
With regard to gas separation membrane, generally speaking, institute's gas supplied is HTHP more, and the transmission rates of gas is big more.Therefore, under the situation of using gases separating film module, study sometimes with compressor reducer etc. and offer assembly after with the unstrpped gas compression.Gas after this compression according to circumstances is supplied under 149 ℃～260 ℃ very high temperature sometimes.
But; When under aforesaid hot conditions, using separating film module; For example might concentrate, perhaps, produce because of resulting from the crack of this concentrated tube sheet and lose the problems such as air-tightness of separating film module because of tube sheet generation thermal expansion has produced stress in the tube sheet member.Therefore, generally speaking, will specially cool off with the gas of the high temperature after the compressions such as compressor reducer and offer the gas separation membrane assembly.About the use under the high temperature, existing separating film module is also residual to have room for improvement (for example, based on parts efficient design of the specific condition of high temperature etc.).And then, no matter whether be the separating film module that high temperature is used, seeking to develop a kind of structure of the structure of separating film module further being simplified and can be helped miniaturization.
The invention of this part is accomplished in view of above-mentioned problem, and its purpose is to provide a kind of separating film module, and above-mentioned separating film module suppresses the influence of the thermal expansion generation of tube sheet, even at high temperature also can work well.In addition, other purpose is, a kind of the seek simplification of the structure of separating film module, the structure favourable to miniaturization/lightweight are provided.
The disclosed main invention main points of this part are described below.
1. separating film module possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of selecting permeability;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and have above-mentioned cylindrical container is fixed in the end of this bundle the end simultaneously with the tube sheet of the inside and outside isolated function of above-mentioned cylindrical container; With
The annular seal member that seals between the inner peripheral surface with the outer peripheral face of above-mentioned tube sheet and above-mentioned cylindrical container;
Said separating film module uses under hot conditions, wherein,
At the periphery that above-mentioned annular seal member is installed, stage portion is not set on above-mentioned tube sheet.
According to such formation; Because the periphery in that ring-type containment member (following in detail) is installed is not provided with stage portion on tube sheet; Therefore, dispose the existing structure of O ring with stage portion at tube sheet and compare, the stress when suppressing at high temperature to use is concentrated the influence that produces.
" annular seal member " in this part is meant the containment member with the ring-type that seals between tube sheet outer peripheral face and the cylindrical container inner peripheral surface, and its cross sectional shape is not special to be limited.As the annular seal member, can be for example O ring (cross sectional shape is a circular), maybe can be respectively that cross sectional shape is roughly V-type, roughly the V-seal spare, U type seal etc. of U type.And then, also comprise the situation of ellipse, rectangle, polygonal, X type prismatic shapes.
" under the hot conditions " is meant in 80 ℃～300 ℃ scope.
" cylindrical container " is not limited to the container of both ends open, also comprises the only container of an end opening.
The gas separation membrane assembly can be used for the purposes of for example oxygen separation, nitrogen separation, hydrogen separation, steam separation, carbon dioxide separation, organic vapor separation.
(the 1st embodiment in the portion C)
Fig. 5 is the sketch map of the basic comprising of expression gas separation membrane assembly.Need to prove, in following explanation, the illustration plurality of embodiments, but each embodiment is not independent respectively, the content of each embodiment can suit to make up.
As shown in Figure 5, this gas separation membrane assembly 1 possesses the hollow tow 15 and the container 10 of accommodating the roughly cartridge type of this hollow tow 15 as the bundle with many hollow cortina 14 of selecting permeability.As an example, cylindrical container 10 is a metal system, its both ends opening.Cylindrical container 10 can be circular cross-section, also can be elliptic cross-section, can also be polygonal cross section.In following explanation, be that example describes with the situation of circular cross-section (be container 10 for cylindric).
Hollow cortina 14 can utilize known hollow cortina at present, just can be the hollow cortina of any material as long as have gas separating property.Good by for example macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. in the gas separating property of the following hollow cortina that forms for glass macromolecular material of normal temperature (23 ℃), so preferred.
Hollow tow 15 is tow that the for example hollow cortina boundling about 100～1000000 is become.The not special restriction of the shape of the hollow tow that boundling becomes, but consider that from the viewpoint of the resistance to pressure of the easness made and container preferred boundling is columned hollow tow.In addition, illustration has the form that hollow cortina is arranged in parallel in fact in Fig. 5, but also can be the form of each hollow cortina cross arrangement.
With reference to Fig. 5, each end at container 10 is provided with tube sheet 30 in the end of hollow tow 15, disposes annular seal member 17 at its peripheral part once more.As annular seal member 17, for example can encircle (cross sectional shape is a circular) for O, or also can be respectively that cross sectional shape is roughly V-type, roughly the V-seal spare, U type seal etc. of U type.In following explanation, situation about encircling with O is that example describes.
As an example, tube sheet 30 is formed by the solidfied material (following in detail) of epoxy resin component, forms such roughly discoid in the end that is embedded in container 10.A plurality of hollow cortinas 14 run through this tube sheet 30 at its thickness direction, and the end of each hollow cortina 14 is at the lateral surface opening of tube sheet 30.Tube sheet has the function of the many hollow cortinas of one set.In addition, tube sheet through and annular seal member association is moving seals hollow cortina and reach each other between hollow cortina and the container inner peripheral surface, have isolated hollow cortina inner space and space outerpace, keep bubble-tight function.
As the cured resin that forms tube sheet 30, as long as for possessing thermo-tolerance, can keeping the airtight material in the air silk assembly, just not special restriction.Under the situation of dehydration purposes that is used for organic vapor or humidification purposes, preferably possesses durability simultaneously to steam.Usually the preferred thermosetting resins such as polyurethane, epoxy resin that use.Consider from thermo-tolerance and intensity aspect, especially preferably use epoxy resin.As far as epoxy resin, for example under the situation of nitrogen membrane module, can utilize the epoxy resin of being put down in writing among the special fair 2-36287 of Japan etc., in addition, under the situation of organic vapor separation assembly, can utilize the epoxy resin of being put down in writing among the WO2009/044711 etc.
As shown in Figure 5, in this separating film module 1, be respectively arranged with cap 20,21 at the two ends of cylindrical container 10.On cap 20, be formed with mist introducing port 22A, on cap 21, be formed with the non-gas discharge outlet 22B of seeing through.On the part of the perisporium of container 10, be formed with outlet 12 through gas.Need to prove that of the back, the principal character portion of the invention of this part is the peripheral structure of tube sheet 30, as long as can adopt such structure, the type of separating film module just has no qualification.
Below, with reference to Fig. 6 the peripheral structure of tube sheet is described.One example of the structure of the assembly end that the invention of Fig. 6 (a) expression this part relates to, Fig. 6 (b) representes other structure.
With regard to the gas separation membrane assembly shown in Fig. 6 (b), between the outer peripheral face of the inner peripheral surface of cylindrical container 10 and tube sheet 530, be provided with O ring 18, guarantee the air-tightness between two members thus.Particularly, on the part of the peripheral part of tube sheet 530, form stage portion 530s, chimeric on this stage portion 530s have an O ring 18.Under the situation of such structure, at high temperature during using gases separating film module 101, might be created in according to condition and stress take place near this stage portion 530s of tube sheet 530 and concentrate, tube sheet is damaged or follows this breakage and damage bubble-tight unfavorable condition.
For corresponding, shown in Fig. 6 (a), in the structure of this embodiment, use the tube sheet 30 that stage portion is not set at outer peripheral face with it.As far as the diameter of tube sheet 30, in this example, its total length certain (, stating after carrying out with reference to Fig. 7) about alternate manner.Be provided with the 10s of rank portion in the end of cylindrical container 10, thus, be formed for the groove of chimeric O ring 18 at this step part.As an example, the cross sectional shape of groove is a rectangle.O ring 18 is embedded in this groove, guarantees the air-tightness between the inner peripheral surface of outer peripheral face and cylindrical container of tube sheet.
In addition, O ring 18 also with the inner face driving fit of cap 20, thus, also can guarantee the air-tightness of container end portion and cap inner face.According to such formation, carry out between (i) tube sheet and the cylindrical container and (ii) both sealings between cap and the cylindrical container with 1 O ring 18, therefore, the O ring that need not append.
Need to prove that the device that cap 20 is fixed in cylindrical container 10 does not have special the qualification, can adopt present known variety of way (for example, utilizing bonding fixing, use that fixing of fixture etc. arranged).
In the gas separation membrane assembly 1 of this embodiment that as above constitutes, the periphery in that O ring 18 is installed is not provided with stage portion on tube sheet 30.Therefore, compare with the existing structure that Fig. 6 (b) is such, the stress when not being vulnerable at high temperature use is concentrated the influence that causes.Its result can improve thermo-tolerance and reliability as gas separation membrane assembly 1 integral body.
Such advantage is not limited to Fig. 6 (a), even under the situation of the such structure of Fig. 7, also can likewise obtain.That is, in the form of Fig. 6 (a), become simple, the axial mobile device that limits tube sheet 30 is not had specified otherwise, but in the formation of Fig. 7, be provided with this device in order to make explanation.
As shown in Figure 7, in this gas separation membrane assembly 1 ', getting into inboard formation step 10t from the end of container 10 with predetermined distance.For corresponding, also be provided with step 30 ' t in the end of tube sheet 30 ' with it.About other structure, identical with Fig. 6 (a).According to such formation, axial moving limited in the end of tube sheet 30 ' (diagram right side) with this step 10t butt, and therefore, tube sheet can not get into its above inside.
Need to prove that the gas separation membrane assembly of more than enumerating Fig. 5 is that example is illustrated, certainly, the invention of this part also can be applied to other formation.For example, also can be preferably applied to the assembly of shell feed type (shell feed type) or on cylindrical container, further be provided with the assembly of the type that purifies of Purge gas introducing port.
(the 2nd embodiment in the portion C)
Fig. 8 representes an example of the structure of the assembly end that the 2nd embodiment relates to, the state during Fig. 8 (a) expression normal temperature, the state when Fig. 8 (b) expression is used during high temperature.
The gas separation membrane assembly of Fig. 8 is identical with above-mentioned embodiment, possesses harness hollow tow 15 with many hollow cortinas of selecting permeability and the cylindrical container 10 of accommodating this hollow tow are arranged.In addition, possess tube sheet 38 that is provided with in the end of hollow tow 15 and the cap of installing in the end of cylindrical container 10 20.The additional symbol identical with above-mentioned accompanying drawing of structural portion same with above-mentioned embodiment omits repeat specification.
Shown in Fig. 8 (a), in this gas separation membrane assembly, the mode of internal diameter that the diameter of the tube sheet 38 during with normal temperature is slightly less than the inner peripheral surface 10a of cylindrical container 10 forms, and between the inner peripheral surface 10a of the outer peripheral face of tube sheet 38 and cylindrical container, produces the gap.Need to prove that the material of tube sheet 38 is identical with above-mentioned embodiment, be resin materials such as epoxy resin, be the big material of thermal coefficient of expansion than the material (is metal as an example) of cylindrical container 10.
This gas separation membrane assembly uses in for example 80 ℃～300 ℃ scope.Shown in Fig. 8 (b), constitute in use that tube sheet 38 is heated to set point of temperature, carry out hole enlargement through thermal expansion, thus the inner peripheral surface 10a driving fit of its outer peripheral face and cylindrical container.Utilize this driving fit, can guarantee the air-tightness between two members.
When using this gas separation membrane assembly, assembly is fully heated up, guarantee the air-tightness of tube sheet 38 and cylindrical container 10 after, carry out the supply of mist.
In above-mentioned formation, between tube sheet and cylindrical container, bring into play sealing effectiveness through making tube sheet 38 that thermal expansion take place.Therefore, for sealing between two members, do not need to be provided with in addition the O ring or carry out the outer peripheral face of tube sheet and the inner peripheral surface of cylindrical container bonding.In addition, when making tube sheet 38 carry out thermal expansion, the stress that puts on cylindrical container 10 also diminishes, and therefore, also is favourable at the aspects such as breakage that can prevent cylindrical container 10.
Need to prove, in above explanation, suppose that tube sheet is that epoxy resin and cylindrical container are that the situation of metal is illustrated, but about the material of cylindrical container, so long as thermal coefficient of expansion just is not limited to metal than the little material of tube sheet.In addition, in Fig. 8, do not illustrate, but can be provided for sealing device yet sealing between cap 20 and the cylindrical container 10.The annular seal member that for example, can be utilized in the annular seal member that disposes between the outer peripheral face of inner peripheral surface and cylindrical container 10 of cap 20 or between the end face of the inner face of cap 20 and cylindrical container 10, dispose.
(the 3rd embodiment in the portion C)
Fig. 9 representes an example of the structure of the assembly end that the 3rd embodiment relates to.Need to prove that the assembly intention of the 1st and the 2nd embodiment is at high temperature used,, do not limit serviceability temperature is special about the gas separation membrane assembly of Fig. 9.
The gas separation membrane assembly of Fig. 9 and above-mentioned 2 embodiments are same, possess: harness has the hollow tow 15 with many hollow cortinas of selecting permeability; Accommodate the cylindrical container 10 of said air silk bundle; Tube sheet 30 that is provided with and the cap 20 that is installed on the end of cylindrical container 10 in the end of hollow tow 15.In addition, also be provided with the O ring 18 that seals between tube sheet and the cylindrical container.The additional symbol identical with above-mentioned accompanying drawing of structural portion same with above-mentioned embodiment omits repeat specification.
In the formation of Fig. 9,, be formed for the gas that sees through that sees through hollow cortina is discharged to the outer peristome 10h of this cylindrical container in the part of the perisporium of cylindrical container 10.In addition, the part at the perisporium of cap 20 also is formed with peristome 20h in position corresponding with it.Mode with through two peristome 10h, 20h is equipped with hollow discharge pipe 41.In the gas separation membrane assembly of Fig. 9, this discharge pipe 41 plays the effect that sees through gas discharge outlet 12 as Fig. 5, therefore, be not provided with Fig. 5 such see through gas discharge outlet 12.
This discharge pipe 41 also has as the function with cap 20 and cylindrical container 10 stationary devices in addition.That is, lead to two peristome 10h, 20h through making discharge pipe 41, axial the moving between restriction cap 20 and the cylindrical container 10 reaches moving of direction of rotation.
In order to fix two members 10,20 more firmly, can utilize the hold-down screw that appends 42 shown in Figure 9.This hold-down screw 42 is communicated with the screwed hole that forms at the perisporium of cap 20, the part of the perisporium of its front end entering cylindrical container 10.The negative thread that hold-down screw 42 is fixed can form on cap 20, also can on cylindrical container, form.Need to prove, also can utilize steady pin to replace hold-down screw.
Need to prove, also can be provided for the annular seal member (not shown) that seals between the outer peripheral face with the inner peripheral surface of the perisporium of cap 20 and cylindrical container 10.Thus, can guarantee air-tightness between cap 20 and the cylindrical container 10 more fully.Fully carrying out between tube sheet-cylindrical container with 1 O ring 18 and between cap-cylindrical container during both sealing, can omit the sealing member.
In the such formation of above explanation, be used to form and be used to discharge member 41 through the stream of gas, also have both the effect of locking cap 20 and cylindrical container 10.Therefore, the designs simplification of assembly, and then can seek lightweight, the miniaturization of assembly.
Need to prove, in the example of Fig. 9, be that example is illustrated with the discharge pipe 41 that is discharged to outside the cylindrical container through gas that will see through hollow cortina.But, also can use formation that other tubular element of the stream of the inside and outside connection of cylindrical container is replaced this discharge pipe 41.
In addition, also can adopt following formation: omit peristome 10h, the 20h of discharge pipe 41, only cap 20 is fixed in cylindrical container 10 with fixed components such as hold-down screw 42 or steady pins through container and cap.Under the situation of such formation, with carry out with reference to Figure 10 (b) with after the flange part formation fixed to one another stated when comparing, flange part need be set, therefore, favourable to the miniaturization of assembly.
This fixed component can be merely 1, also can be for more than 2, but under the situation more than 2, the preferred immobilization member disposes in a circumferential direction equably.
(other embodiment in the portion C)
Except that above-mentioned embodiment, the invention of this part also can be mode such shown in Figure 10 (a) and (b).These gas separation membrane assemblies and above-mentioned embodiment are same, possess: harness has the hollow tow 15 of hollow cortina; Accommodate the cylindrical container 10 of this hollow tow; The tube sheet 30 that is provided with in the end of hollow tow 15; The cap of installing in the end of cylindrical container 26,27.In addition, also possesses the O ring 18 that seals between the inner peripheral surface with the outer peripheral face of tube sheet and cylindrical container.
In the formation of Figure 10 (a), cap 26 is fixed in cylindrical container 10 with the mode of being screwed into.That is the outer screw section engaging that, constitutes negative thread portion that the part at the inner peripheral surface of cap 26 forms and form in the part of the outer peripheral face of cylindrical container 10.Rotate at cap 26 under the state of fixed position of regulation (with reference to Figure 10 (a)), the part of O ring 18 and the inner face butt of cap 26 thus, can be guaranteed the air-tightness of cylindrical container end and cap inner face.Same with above-mentioned embodiment, O ring 18 is also guaranteed the air-tightness between the inner peripheral surface of outer peripheral face and cylindrical container of tube sheet.
In the formation of Figure 10 (b), on cap 27, form flange part 27f, simultaneously, on cylindrical container 10, also be formed with flange part 10f corresponding with it.Fixing of cap 27 and cylindrical container 10 through carrying out with fixture 43 fixing these flanges 27f, 10f.As fixture 43, for example can use bolt and nut.In addition, also can use screwed hole and the bolt that forms at flange 10f.Do not limit with fixture 43 fastening flange part places each other are special, but fastening place preferably relates to the circumferencial direction of flange part, and equally spaced be provided with.
(another other embodiment in the portion C)
The gas separation membrane assembly of the invention of this part also can be the formation of that kind shown in Figure 11.Figure 11 (a) is the sectional view of an example of expression gas separation membrane assembly, and Figure 11 (b) is the figure after the part of Figure 11 (a) is amplified.
The gas separation membrane assembly of Figure 11 possesses: harness has the hollow tow 115 of hollow cortina; Accommodate the cylindrical container 110 of hollow tow; The tube sheet 130A, the 130A that are provided with at the both ends of hollow tow 115; The cap of installing in the end of cylindrical container 110 120,121.In addition, also possesses the O ring 118 that is provided with at the outer peripheral face of each tube sheet 130A.
In this example, cylindrical container 110 has along the length direction of assembly tubing 111 that extends and the end member 112,112 that is installed on its two ends.On the perisporium of the end member 112 of (gas importing side) on the left of the diagram, be formed with outlet 112h through gas (example).
On each end member 112, be formed with flange part 112f.On the other hand, on each cap 120,121, also be formed with flange part 120f, 121f.Flange part 112f through making end member and the flange part 120f of cap butt joint, same with the mode of Figure 10, use for example bolt and nut etc. (in Figure 11, omitting diagram), can cap 120 be fixed in end member 112 (about cap 121, also identical).
Shown in Figure 11 (b), in this example, tube sheet 130A is configured with the mode with a part of driving fit of the inner peripheral surface of the part of the inner peripheral surface of cap 120 and cylindrical container 110.The tube sheet 30 ' of each tube sheet 130A and Fig. 7 is same, and its outer peripheral face forms the rank shape, the rank portion butt of the rank portion of tube sheet outer peripheral face and cylindrical container inner peripheral surface, the position of limiting the axis direction (diagram transverse direction) of tube sheet 130A thus.
At the radially inner side of the flange part 120f of cap 120, stage portion 120s forms ring-type.In the groove (cross sectional shape is a rectangle) of the ring-type that the part by the flange part 112f of this stage portion 120s and end member 112 forms, dispose O ring 118.The air-tightness that O ring 118 is guaranteed between tube sheet 130A and the cap 120 is guaranteed the air-tightness between cap 120 and the end member 112 simultaneously.
Structure with cap 120 is an example, the peripheral structure of O ring 118 is illustrated, and about cap 121 sides, also be same structure.As the device of holding flange portion, be not limited to utilize the device of screw bolt and nut, for example, can be for be screwed into the formation of bolt front end with respect to the screwed hole that on any of flange part 112f, 120f, forms.
In the such formation of above-mentioned Figure 11, same with the 1st embodiment, the periphery in that O ring 118 is installed is not provided with stage portion on tube sheet 130A.Therefore, compare with the existing structure shown in Fig. 6 (b), the stress when not being vulnerable at high temperature use is concentrated the influence that produces.Its result can improve as gas separation membrane assembly whole thermo-tolerance and reliability.
In addition, in the formation of Figure 11, cylindrical container 110 is made up of tubing 111 and end member 112,112, according to such formation, is being favourable aspect the material of each member of selection that can suit according to the proterties of each member.Need to prove that the invention of this part does not limit therewith, also can utilize single cylindrical container tubing 111 and end member 112 integrated that kind.
The gas separation membrane assembly of the invention of this part can also be assembly shown in Figure 12.This assembly is same with the formation of Figure 10 (b) basically, so that the mode of the flange part 110f of the flange part 127f of cap 127 and cylindrical container 110 ' butt joint is fixed in cylindrical container 110 ' with cap 127.O number of rings and allocation position etc. are different with the assembly of Figure 10 (b).The assembly of tube sheet 130B and Figure 11 is same, with a part of driving fit of the inner peripheral surface of the part of the inner peripheral surface of cap 127 and cylindrical container 110 '.
The one O ring 118 is disposed in the groove 127g of formed ring-type on the inner peripheral surface of cap 127, guarantees the air-tightness between tube sheet 130B and the cap 127.Groove 127g to ring-type is unqualified, but in the inner peripheral surface of cap 127, the position that gets into inboard (diagram left side) at the end face from flange part 127f side slightly forms.
The 2nd O ring 119 is configured between flange part 110f and the flange part 127f.In this example, on the groove 110g of formed ring-type on the flange part 110f of cylindrical container 110, dispose O ring 119.Such O encircles 119 optional formations, utilizes this O ring 119, can prevent that gas is through leaking into the outside between flange part 110f, 127f.
Need to prove that certainly, the formation of such O ring 118,119 is not only the described form of Figure 12, but also can utilize with the suitable combination of above-mentioned embodiment.In addition, the groove that disposes the 2nd O ring 119 also can be formed at the flange part 127f of cap 127.
(summary of the invention)
The invention that relates to portion C is described below.
1. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of selecting permeability;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and have the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously are fixed in the end of this bundle; With
Seal the annular seal member between the inner peripheral surface of outer peripheral face and above-mentioned cylindrical container of above-mentioned tube sheet;
Said gas separation membrane assembly uses under hot conditions, wherein,
At the periphery that above-mentioned annular seal member is installed, stage portion is not set on above-mentioned tube sheet.
2. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of selecting permeability;
Accommodate the cylindrical container of this hollow tow; With
Be arranged at the end of above-mentioned hollow tow and have the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously are fixed in the end of this bundle;
Said gas separation membrane assembly uses under hot conditions, wherein,
Above-mentioned tube sheet is formed by the big material of thermal coefficient of expansion than the material of above-mentioned cylindrical container, and
At normal temperatures, between the inner peripheral surface of the outer peripheral face of above-mentioned tube sheet and above-mentioned cylindrical container, produce the gap, when being warming up to set point of temperature, above-mentioned tube sheet expands, the inner peripheral surface driving fit of its outer peripheral face and above-mentioned cylindrical container and bring into play sealing effectiveness.
3. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of selecting permeability;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and have the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously are fixed in the end of this bundle; With
Cap in the end that above-mentioned cylindrical container is installed; Wherein,
The tubular element that form to be communicated with the inside and outside stream of above-mentioned cylindrical container, (diametrically) run through above-mentioned cylindrical container a part and above-mentioned cap a part and be provided with.
4. as above-mentioned 3 above-mentioned gas separation membrane assemblies, it also possesses:
Be communicated with and play the fixed component of the effect of fixing this cap and above-mentioned cylindrical container with the part of the perisporium of above-mentioned cap.
5. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of selecting permeability;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and have the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously are fixed in the end of this bundle; With
The cap of installing in the end of above-mentioned cylindrical container; Wherein,
Possesses the fixed component that is communicated with and plays the effect of fixing this cap and above-mentioned cylindrical container with the part of the perisporium of above-mentioned cap.
6. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of selecting permeability;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and have the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously are fixed in the end of this bundle;
Be installed on the cap of the end of above-mentioned cylindrical container; With
Seal the annular seal member between the inner peripheral surface of outer peripheral face and above-mentioned cylindrical container of above-mentioned tube sheet;
Wherein, it is following above-mentioned cap to be fixed in the mode of above-mentioned cylindrical container:
(i) mode that is utilized in threaded portion that the part of the inner peripheral surface of above-mentioned cap forms and fixes in the threaded portion that the part of the outer peripheral face of opposed above-mentioned cylindrical container with it forms; Or
(ii) the flange part of opposed above-mentioned cylindrical container links with fixture and the mode of fixing with the flange part of above-mentioned cap with it.
As above-mentioned 3～6 in each described gas separation membrane assembly, wherein, above-mentioned annular seal member also seals between above-mentioned cap and the above-mentioned cylindrical container.
[part D: can control the cost when changing, the gas separation membrane assembly also favourable] to the simplification of structure
(technical field)
The disclosed invention of this part relates to a kind of utilization to have and selects the many hollow cortina of permeability to carry out gas gas separated separating film module.Be particularly related to a kind of cost and the separating film module also favourable that can control when changing to the simplification of structure.
(background technology)
The gas separation membrane assembly of hollow fiber type possesses air silk element with the tow that is made up of the many hollow cortina with selection permeability and the cylindrical container of accommodating this element usually.The hollow tow of air silk element, its one or both ends utilize the cured plate (tube sheet) of resin to be fixed in the end of container.In the end of cylindrical container the cap member is installed, thus with airtight in the container.
In existing gas separation membrane assembly, as stated, the cap member is installed in the end of cylindrical container, these cap members form 1 main body as a whole, and therefore, when changing separating film module, it is whole to need to change assembly.Therefore, have following problem: the cap member that originally need not change etc. are also changed together, and the cost of changing parts raises.
On the other hand, also can consider only to change the air silk element in the main body, but this moment, for example need be in main body the built-in structure that makes the loading and unloading of air silk element etc., cause the complicated of modular construction, also unfavorable to lightweight.
The invention of this part is accomplished in view of above-mentioned problem, and its purpose is, provide a kind of can control when changing cost and also to the simplification of structure also favourable and miniaturization and is easy to the gas separation membrane assembly.
The main disclosed main invention main points of this part are described below.
1. gas separation membrane assembly possesses:
To be contained in the box (cartridge) in the cylindrical container by the hollow tow that many hollow cortinas constitute;
The cap member of installing at the both ends of this box;
With the containment member that seals between above-mentioned each cap member and the above-mentioned box; With
The fixture that above-mentioned cap member is interfixed;
Wherein, above-mentioned box constitutes at above-mentioned cap member and installs with the mode that can change each other.
According to such formation, provide a kind of can control when changing cost and also to the simplification of structure also favourable and miniaturization and is easy to the gas separation membrane assembly.
(embodiment among the part D)
Below, with reference to accompanying drawing, an embodiment of the invention of this part is described.Need to prove that the invention of this part is not limited to the formation shown in the following form, can carry out appending or the change of omission, shape etc. of parts as required.
Shown in figure 13, this gas separation membrane assembly 201 (below, also abbreviate separating film module as) possess: the box 210 that contains the tubular of hollow tow 215 in inside; The cap member of installing at its both ends 220,221; With fixed bar 245 that these cap members 220,221 are fixing etc.
Box 210 has the cylindrical container 211 of both ends open, hollow tow 215 and the tube sheet 230,231 taken in of portion within it.The end that tube sheet 230,231 keeps hollow tow 215, isolated cylindrical container 211 is inside and outside simultaneously.
Hollow tow 215 can utilize known hollow tow at present.The hollow tow that hollow tow 215 for example can become about 100～1000000 hollow cortina 214 boundlings.As long as hollow cortina 214 has gas separating property, just can be the hollow tow of any material.For example, by the hollow cortina that macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. form for glass macromolecular material down at normal temperature (23 ℃), its gas separating property is good, so preferred.The not special restriction of shape of the hollow tow that boundling is become is considered from the viewpoint of the resistance to pressure of the easness made and container, can become columned hollow tow for boundling.Need to prove that illustration has the form that hollow cortina 214 is arranged in parallel in fact in Figure 13, but also can be the form of each hollow cortina cross arrangement.
The cross sectional shape of cylindrical container 211 can be arbitrary shapes such as circle, ellipse or polygonal.In following explanation, the example of circle is described.As an example, cylindrical container 211 can be made through 1 metal pipe is processed.In this embodiment,, preferably on cylindrical container 211, be not provided for cap member 220,221 is fixed in the device (that is, on cylindrical container, there not being the structure of locking cap member) of cylindrical container 211 as the box side as an example.Thus, need be to the processing of cylindrical container 211, the making of for example flange, the formation of screwed hole, the configuration of steady pin etc.
Shown in figure 14, be formed with internal circle groove 217 near the end in the inside of cylindrical container 211, it is big that inner-diameter portion whose becomes.Of the back, the part of embedding tube sheet 230,231 on internal circle groove 217.Vacate the interval of regulation from this internal circle groove 217, further be formed with another internal circle groove 218 in inboard (away from the direction of end).About each internal circle groove 217,218, the cross sectional shape that digs the groove that forms for example can be rectangle type, essentially rectangular type, trapezoidal type or roughly trapezoidal type.
Be formed with a plurality of peristomes 212 that are used for the gas in the container is discharged to the outside in the part that is formed with internal circle groove 218.Split the not special qualification of number and position of oral area 212.As an example, can be uniformly-spaced to form a plurality of openings 212 around cylindrical container 211.Shown in figure 14, the periphery of cylindrical member 211 and than internal circle groove 218 a little in the inner part (away from the direction of tube end) be formed with the circumferential groove 219 of the elastic ring member R2 that is used for stating after chimeric.
As far as the tube sheet 230 and 231 (with reference to Figure 13) of box 210, be epoxy resin as an example, form such roughly discoid in the end that embeds container 211.Because tube sheet 230 is essentially same structure with tube sheet 231, therefore, below only a tube sheet 230 is described.Each hollow cortina 214 runs through this tube sheet 230 along its thickness direction, each hollow cortina 214 open-ended in the outside of tube sheet 230.Tube sheet 230 in addition, completely cuts off the inside and outside of cylindrical container 211 with the set integratedly of many hollow cortinas 214.As long as forming the cured resin of tube sheet possesses sufficient durability and can keep airtight in the air silk assembly, just not special restriction.Under the situation of purposes or humidification purposes that is used to dewater, preferably possesses durability simultaneously to steam.Usually the preferred thermosetting resins such as polyurethane, epoxy resin that use.From the durability aspect and the intensity aspect consider, especially preferably use epoxy resin.Epoxy resin is for example under the situation of nitrogen membrane module; Can utilize the middle epoxy resin of putting down in writing that kind such as the special fair 2-36287 of Japan; In addition, under the situation of organic vapor separation assembly, can utilize the middle epoxy resin of putting down in writing that kind such as WO2009/044711.Tube sheet preferably utilizes centrifugal forming, leave standstill known method such as moulding forms.
Need to prove that in above-mentioned, tube sheet " completely cuts off " inside and outside being meant of cylindrical container and utilizes tube sheet to carry out substantial isolated getting final product, the peripheral part of tube sheet may not be adhered to the inner face of cylindrical container.
Shown in figure 13, the part of tube sheet 230 is outstanding a little from the end of cylindrical container 211, forms fillet surface (taper surface) along the periphery of the end of tube sheet 230.As the operation of making tube sheet 230, as an example, at first, and the hollow tow 215 of configuration in cylindrical container 211, not shown mould (example) is installed in the end at cylindrical container 211 under this state.Then, injection resin and make its curing in this mould and in the cylindrical container 211.Behind the resin solidification, take mould, the end of the resin after cut off solidifying forms the end face of tube sheet 230 thus, makes hollow cortina 214 open-ended simultaneously.The fillet surface of tube sheet 230 can utilize mould to form, and also can form through the secondary operations behind the resin solidification.
Owing in cylindrical container 211, be formed with internal circle groove 217, therefore, the resin of tube sheet 230 also is filled in this groove 217.Its result, the part of tube sheet 230 engages with internal circle groove 217, carries out the axial location of tube sheet 230 with respect to cylindrical container 211.Usually, when using separating film module 201, the pressure that it is squeezed into the direction in the cylindrical container 211 is worked with respect to tube sheet 230.According to the formation of this embodiment, because the part of tube sheet 230 engages with internal circle groove 217, therefore, the pressure during not because of use is squeezed into tube sheet 230 in the cylindrical container 211.
Then, with reference to Figure 13, Figure 15, the structure of cap member 220,221 is described.In this example, because cap member 220,221 is essentially same structure, therefore, below only a cap member 220 is described, only the different piece to cap member 221 describes.Do not limit the material of cap member 220,221 is special, for example can be metal system yet.Need to prove that certainly, each cap member 220,221 can have different shapes, the shape of each cap member 220,221 can be according to the purposes or the suitable change of specification of separating film module.
Like Figure 13, shown in Figure 15, cap member 220 has the shape that the round-ended cylinder shape is arranged.Particularly, shown in Figure 15 (A), have the end face 220A of the peristome that covers cylindrical container 211 and the cylindrical portion 220B that extends from its circumference.
On end face 220A, be formed with the gas introduction port P1 that is used to import mist.Be formed with internal circle groove 227a, 227b in the inboard of cylindrical portion 220B.Shown in figure 13, on internal circle groove 227a, embed the elastic ring member R1 (detailed content is described below) that is used to seal.When cap member 220 was embedded in cylindrical container 211, another internal circle groove 227b was used to form the gas flow path P3 in a reciprocal week in cylindrical container 211.Need to prove, on another cap member 221, be formed with the non-gas discharge outlet P2 of seeing through.
Gas flow path P3 (Figure 13) is communicated with a plurality of peristomes 212 of cylindrical container 211, and the gas of internal tank flow among the gas flow path P3 through each peristome 212.This gas is discharged to the outside from last formed 1 outlet 223 of the cylindrical portion 220B of cap.Need to prove in the form of Figure 13, on cap member 221, do not have to form the structure (peristome) that is equivalent to outlet 223.But, according to purposes of assembly etc., peristome is set on cap member 221, corresponding with it simultaneously, one or more peristomes 212 can be set on cylindrical container 211.
When referring again to Figure 15, on cylindrical portion 220B, be formed with and be used to make fixed bar 245 (Figure 13, following in detail) to insert logical a plurality of through hole 220h.In this example, 6 through hole 220h are in a circumferential direction with uniformly-spaced configuration.Like this, be formed with through hole 220h on the cylindrical portion 220B and therein under the situation of the formation through fixed bar 245, favourable aspect following.That is,, keep fixed bar 245, therefore, need on cap member 220, not be provided for keeping the special structure of fixed bar in addition as the cylindrical portion 220B of the part of cap 220 according to such formation.Therefore, can seek the miniaturization of cap member 220 and then separating film module 201, also help the lightweight of assembly.
Need to prove that the radical of fixed bar 245 is not limited to 6, also can be for more than 1～5 or 7.As an example, shown in figure 16, also can be 3,4 or 8 etc.The material of fixed bar 245 is not special to be limited, and as an example, can be metal system.
Shown in Figure 15 (B), in cylindrical portion 220B, in the part of outlet 223 openings, the part of cylindrical portion 220B is cut, and forms par 220f.In addition, in the bottom of cylindrical portion 220B,, be formed with the par 220g that is used to prevent the separating film module rolling as an example.
Shown in figure 13, embedding the flexible sealing component R1 that has between sealing tube sheet 230 and the cap member 220 on the internal circle groove 227a of cap member.Elastic ring member R1 constitutes when changing and when cap member 220 is taken above-mentioned box 210, all to residue in cap member 220 sides.As elastic ring member R1, for example also can encircle (cross sectional shape is a circular) for O.Perhaps, can be respectively that cross sectional shape is the V-seal spare of roughly V-type, the U type seal that cross sectional shape is roughly U font etc.And then cross sectional shape also can be ellipse, rectangle, polygonal, X-shaped etc.
Between cylindrical container 211 and cylindrical portion 220B, other elastic ring member R2 is configured to be embedded in the circumferential groove 219 of cylindrical container 211, is sealed between two members thus.This elastic ring member R2 also with above-mentioned same, can utilize various seals such as O ring, V-seal spare or U type seal.
Like Figure 13, shown in Figure 15, cap member 220,221 utilizes 6 (example) fixed bars 245 to reach the nut of installing at its two ends 246 each other and interfixes.In this embodiment, as stated, be to utilize the interfix structure of cap member 220,221 of the fixture of preparing as other parts with respect to box 210.Therefore, need not be provided at the fixing flange of box 210 sides (particularly cylindrical member 211) etc., can be with the designs simplification of box 210.
Need to prove that the fixture that is used for fixing cap member 220,221 is not limited thereto, and can utilize various fixtures.For example, an end that can be fixed bar is large diameter head, at the other end nut is installed.Perhaps, can be at interior all screw cuttings of the through hole 220h of cap member 220, corresponding with it simultaneously, at boom end also screw cutting, boom end is screwed in the through hole 220h.Perhaps, can utilize mechanical link locking cap member other mechanical device each other, for example carry out the fixed mechanical device with the mode at the two ends (cap member 220,221) of using the anchor clamps clamp assemblies.
And then; Be not limited to be fixed in cap member 220,221 mechanical device each other, also can be utilized as with each cap member 220,221 be fixed in regulation the fixed position mechanical device and at 220,221 mechanical devices that box 210 is set with the mode that can load and unload of cap member.For example, be equipped with the device of separating film module or the part of equipment and work, can utilize each cap member 220,221 relative its basic component such formation that is fixed as base member (not shown).
In the separating film module 201 of this embodiment, carry out for example following gas and separate: the air of pressurized state is directed to internal tank through gas introduction port P1, and this air is fed to its inside from the open end of hollow cortina 214.In hollow cortina 214 between flow periods, oxygen-enriched air optionally penetrates into outside the film at forced air, and the oxygen-enriched air that has seen through moves in the space of taking in the hollow tow between tube sheet and (sees through the side space).Should see through gas from being discharged to the outside as the peristome 212 and the peristome 223 that see through gas discharge outlet.On the other hand, the nitrogen-rich air that does not see through via another opening of hollow cortina 214 from being discharged to the outside as the non-non-gas discharge outlet P2 of seeing through that sees through gas discharge outlet.
In the gas separation membrane assembly 201 of above explanation, the box 210 that contains hollow tow 215 constitute with removable mode be installed on cap member 220, between 221.Therefore, when changing, only replace box and get final product, need not change assembly integral body, therefore, can control the cost of changing parts.
On the other hand, also can consider only to change the such structure of element that is equivalent to inner air silk element 215, but this moment, need be in the cylindrical container 211 built-in structure that these replacings parts load and unload etc. that makes.Relative with it, in assembly 201, directly work as the main bodys of assembly 201 as the cylindrical container 211 of the part of box 210, therefore, do not need complicated structure.It is favourable to the whole lightweight of separating film module 201, particularly can be in the light-weighted field of expectation assemblies such as for example aviation field special advantageous applications.
And then above-mentioned formation is to use to link cap member 220,221 with the fixture (245,246) of box 210 various parts and form.Therefore, need on cylindrical container 211, not be formed for linking the structural portion (for example flange part etc.) of cap member.Therefore, the structure of box 210 can be simplified, in addition, also manufacturing cost can be controlled.
In addition, above-mentioned being constructed as follows: elastic ring member R1 remains on the interior week of cap member 220,221, and ring element R1 all residues in the cap member side when when changing, taking box 210.Such formation with in box 210 sides ring element R1 is set and compares, favourable to the manufacturing cost of control box 210.
Shown in figure 13, in the formation of this embodiment, owing to be formed with fillet surface (taper surface) along the periphery of the end of tube sheet 230, and therefore, the end that can in elastic ring member R1, successfully insert tube sheet 230.
More than, be illustrated with reference to the working of an invention mode of accompanying drawing, but the invention of this part is not limited to illustrated form this part, can carry out various changes.For example, about being used to seal the containment member between each member, its shape and allocation position can suitably change.Except that elastic ring member R1, R2, also the containment member that appends can be set.
Shown in figure 13; In the above-described embodiment; Illustration on the periphery of cylindrical container 211 formation of chimeric flexible ring element R2; But the invention of this part is not limited thereto, and can adopt following formation: this elastic ring member R2 residues in cap member 220,221 sides when being provided with elastic ring member R2 and the replacing at box on the interior week of cap member 220,221.At this moment, owing to need on the cylindrical container 211 of box 210, not form circumferential groove 219, therefore, the further manufacturing cost of control box 211.
In the above-described embodiment, illustration constitute the example of the separating film module of so-called boring feed type (Bore Feed type), but the invention of this part also can be applied to constitute the separating film module of shell feed type (shell feed Type).At this moment, constituting the such mode changing of above-mentioned explanation with the corresponding box of shell feed type (shell feed Type) is installed on the cap member and gets final product each other.
(technical scheme)
The invention that relates to part D is described below.
1. gas separation membrane assembly possesses:
To be contained in the box in the cylindrical container by the hollow tow that many hollow cortinas constitute;
Be installed on the cap member at the both ends of this box;
Seal the containment member between above-mentioned each cap member and the above-mentioned box; With
The fixture that above-mentioned cap member is interfixed;
Wherein, above-mentioned box constitutes with the mode that can change and is installed on above-mentioned cap member each other.
2. like above-mentioned 1 described gas separation membrane assembly, wherein,, have the above-mentioned cap member of binding at least 1 fixed bar each other as the said fixing device,
On each cap member, be formed with the said fixing bar and insert logical through hole.
3. as above-mentioned 1 or 2 described gas separation membrane assemblies, wherein, above-mentioned cap member is installed with the mode of the end that is covered in above-mentioned cylindrical container,
Above-mentioned containment member is the elastic ring member that between the interior week of the periphery of above-mentioned box and above-mentioned cap member, disposes.
4. like above-mentioned 3 described gas separation membrane assemblies, wherein, above-mentioned elastic ring member remains on the interior week of above-mentioned cap member, constitutes with the mode that when changing, when above-mentioned cap member is taken above-mentioned box, all residues in above-mentioned cap member side.
5. each described gas separation membrane assembly as in above-mentioned 1～4, wherein, above-mentioned box has the end inside and outside tube sheet of isolated above-mentioned cylindrical container simultaneously that is used to keep above-mentioned hollow tow,
Form internal circle groove in the inside of above-mentioned cylindrical container and towards the zone of above-mentioned tube sheet,
The part of above-mentioned tube sheet engages with this internal circle groove.
[part E: can implement gas gas separated separating film module efficiently]
(technical field)
The invention of this part relates to and a kind ofly utilizes hollow cortina to carry out gas gas separated separating film module, particularly a kind ofly in the assembly of so-called boring feed type (bore feed type), can implement gas gas separated separating film module efficiently.
(background technology)
The gas separation membrane assembly of hollow fiber type possesses usually: air silk element and the hollow casing of accommodating this hollow tow with the hollow tow that is made up of the many hollow cortina with selection permeability.The hollow tow of air silk element, its one or both ends utilize the cured plate (tube sheet) of resin to be fixed.In addition, on casing, being provided with mist enters the mouth, sees through gas vent and see through gas vent etc.
With effective divided gas flow is purpose; For example in TOHKEMY 2000-262838, disclose a kind of gas separation membrane assembly; Said gas separation membrane assembly constitutes as follows: in the assembly that mist is offered the so-called boring feed type (bore feed Type) in the hollow cortina; With the be covered part of hollow tow of film structural component, forming with the hollow cortina of mobile clamping with mist of flowing of carrier gas is convection current.
In the gas separation membrane assembly of above-mentioned patent documentation 1; Flow direction through the restriction carrier gas; Can seek the validation that gas separates; But be boring feed type (bore feed Type) and do not utilizing in the gas separation membrane assembly of carrier gas (Purge gas) that the efficient of improving the gas separation also is important.The invention of this part is accomplished in view of above-mentioned problem, and its purpose is to provide a kind of can implement gas gas separated separating film module efficiently in the assembly of boring feed type (bore feed Type).
The disclosed main invention main points of this part are described below.
1. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of gas separating property;
Have the mist inlet, see through gas vent reaches has above-mentioned hollow tow through gas vent and in internal configurations casing; With
2 tube sheets that the both ends of above-mentioned hollow tow are fixing;
Said gas separation membrane assembly will offer in the above-mentioned hollow cortina from the mist that above-mentioned mist inlet imports, and see through through a part that makes this mist and carry out the gas separation, wherein,
(i) be not provided for supplying with and be used to discharge the structure that sees through gas cleaning gas that sees through above-mentioned hollow cortina,
(ii) also possesses a kind of film structural component; It is the film structural component of the gas impermeability (also comprising the film structural component of gas impermeability in fact) that is wound in the outer peripheral face of above-mentioned hollow tow; Wherein, dispose from the mode that the above-mentioned tube sheet of mist direction of the supply upstream side leaves with the above-mentioned tube sheet butt in mist direction of the supply downstream, the other end in fact with the one of which end.
Invention according to this part; The film structural component control that utilization is wound in hollow tow sees through the gas flow direction; With the reverse flows of the direction of the supply of mist (detailed content is of the back); Therefore, can in the assembly of boring feed type (bore feed Type), implement gas efficiently separates.
(embodiment among the part E)
Below, with reference to accompanying drawing, an embodiment of the invention of this part is described.Figure 17 is the sectional view of basic comprising that schematically shows the gas separation membrane assembly of this embodiment.
Gas separation membrane assembly 601 shown in Figure 17 is the gas separation membrane assembly of boring feed type (bore feed Type), possesses: with the hollow tow 615 of many hollow cortina 614 boundlings one-tenth; Accommodate the casing 610 of this hollow tow; With tube sheet 621,622 in the setting of the both ends of hollow tow 615.
Hollow cortina 614 can utilize known hollow cortina at present, as long as have gas separating property, just can be the hollow cortina of any material.As an example, by the hollow cortina that macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. form for glass macromolecular material down at normal temperature (23 ℃), its gas separating property is good, so preferred.
Hollow tow 615 is hollow tow that for example hollow cortina 614 boundlings about 100～1000000 are become.The not special restriction of the shape of the hollow tow 615 that boundling becomes, but consider from the viewpoint of the resistance to pressure of the easness made and casing, as an example, preferably cylindric.Illustration has the form that hollow cortina 614 is arranged in parallel in fact in Figure 17, but also can be the form of each hollow cortina cross arrangement.
The mist that utilizes hollow cortina 614 to separate is not special to be limited, for example, and also can be for comprising the admixture of gas that ratio with respect to the transmission rates of diffusion barrier is the little gas of big gas of permeability more than 2 and permeability.The gas separation membrane assembly 601 of this embodiment can be used for separating the specific gas composition from mist in every way.For example, can carry out the dehumidifying of all gases, the humidification of all gases, rich nitrogen or oxygen enrichment etc.
Tube sheet 621,622 corresponding with the casing cross sectional shape and be arranged to discoid, the end of the hollow tow 615 of set under the state of the opening that has kept each hollow cortina 614.Tube sheet 621,622 can perhaps contain the thermosetting resin of epoxy resin or polyurethane resin etc. for thermoplastic resins such as polyethylene or polypropylene.Tube sheet 621,622 plays the effect of the many hollow cortinas 614 of set integratedly.In addition, play the hollow cortina 614 of sealing and reach the effect between the inner face of hollow tow 615 and casing 610 each other.Shown in figure 17, form 1 confined space 618 (of the back, as to have) by casing 610 and 2 tube sheets 621,622 through gas discharge outlet 610c, in this confined space 618, import the gas that sees through that has seen through hollow cortina 614.And then, form mist space 619a by casing 610 and tube sheet 621, form by casing 610 and tube sheet 622 and do not see through gas compartment 619b.Need to prove, between the inner face that seals tube sheet 621,622 and casing 610, other sealing device can be set.
Need to prove; As the epoxy resin that is used for tube sheet 621,622; For example under the situation of nitrogen membrane module, can utilize the middle epoxy resin of putting down in writing that kind such as the special fair 2-36287 of Japan, in addition; Under the situation of organic vapor separation assembly, can utilize the middle epoxy resin of putting down in writing that kind such as WO2009/044711.
Shown in figure 17, casing 610 is arranged to roughly cylindric as a whole.Casing 610 has the mist inlet 610a that is used for mist imported in the casing 610 at upstream side (left side of figure), and (right side of figure) has and do not see through gas vent 610b in the downstream, has through gas vent 610c at side wall portion.The number that sees through gas vent 610c can be 1, also can be for a plurality of.A plurality of gas vent 610c that see through can be along the side wall portion of casing 610 with uniformly-spaced configuration.In this example, see through gas vent 610c and be formed at the position approaching (position of the exposed portions serve A1 of the hollow tow 615 that the film structural component of particularly, stating after not having 631 exists) with the tube sheet of upstream side 621.
From the mist that mist inlet 610a imports, in each hollow cortina 614 of end face entering of tube sheet 621, portion flows towards the downstream within it.At this moment, the part in the mist penetrates into outside the hollow cortina 614, should see through gas and be admitted in the confined space 618, then, is discharged to outside the casing via seeing through gas vent 610c.On the other hand, the gas that sees through that sees through hollow cortina directly flows towards the downstream hollow cortina 614 in, passed out to outside the film from the end face in downstream, then, via not being discharged to outside the casing through gas vent 610b.
Need to prove that Figure 17 schematically shows casing 610, particularly, can be the formation of the such casing of Figure 19.In this example, casing 610 has the cylindrical structural member 611 and the cap 612,613 that is installed on its both ends of both ends opening.Cylindrical member 611 and cap 612,613 can be metal system, plastics system or pottery system as an example.On each cap 612,613, be formed with mist inlet 610a respectively, do not see through gas vent 610b.As an example, mist inlet 610a reaches and sees through the central part (being seen as central part from the cap frontal) that gas vent 610b can be formed at cap 612,613.
Like Figure 17, shown in Figure 180, in the gas separation membrane assembly 601 of this embodiment, be wound with film structural component 631 in the periphery of hollow tow 615.Film structural component 631 is configured from the mode that tube sheet 621 leaves the distance of regulation with tube sheet 622 butts, the other end 631b in fact with one of which end 631a.In Figure 17, the zone of the hollow tow 615 that film structural component 631 of no use covers is represented with symbol A1 (exposed portions serve).Film structural component 631 can constitute with 50%～95%, preferred 75%～92% mode of the outer surface that covers hollow tow.In addition, film structural component 631 also can constitute as follows: both ends and each tube sheet are being opened one or more holes near the whole outer surface of also covering hollow tow admittedly on film structural component 631 near the tube sheet 621.
Need to prove that the end of film structural component " butt in fact " is meant: (i) the film end fully and the situation of tube sheet butt; (ii) for example, according to the situation on making etc., film end and the approaching situation of tube sheet under the state that produces slit a little between film end and the tube sheet.On the other hand, be under the situation of epoxy resin etc. at tube sheet, when the film end gets in the tube sheet (for example, make the film end be embedded in tube sheet and make situation that tube sheet solidifies etc.), might be starting point with this part, tube sheet breaks or produces damage.Therefore, preferably not getting into the inner mode of tube sheet with the film end sometimes constitutes.
Film structural component 631 is so long as the material of gas impermeability in fact just can be any material.Need to prove that " gas impermeability in fact " is meant: the gas permeation of film structural component 631 is enough little, can limit the stream of gas.For example can be plastic foils such as polyimides, polyethylene, polypropylene, polyamide, polyester.Wherein, aspect hear resistance, solvent resistance, processability, preferred polyimides.Except that plastic foil, also can be metal formings such as aluminium or stainless steel.The thickness of film can be in the scope of tens of μ m～number mm.Film structural component 631 can form tubular each other through the lateral margin of a film of set, maybe can use the cylindrical member that does not have seam.As set film device each other, can utilize for example bonding agent, adhesive tape etc.
Supposing under the situation that does not dispose film structural component 631, shown in the arrow f3 of Figure 18, is cross flow direction (direction of promptly intersecting with hollow cortina 614) from the direction of advance that sees through gas of hollow cortina 614.On the other hand, as this embodiment, on hollow tow 615, be wound with under the situation of film structural component 631, prevent to see through scattering and disappearing of gas, shown in arrow f2, seeing through gas is that the direction of adverse current flows at the direction of the supply f1 of mist relatively.
Below, an example of the method for using of the separating film module of this embodiment of as above constituting is described.Need to prove that the method for using of the assembly of this embodiment is not limited to following method.
At first, mist is imported to the mist space 619a in the casing 610 from mist inlet 610a.This mist that is imported from the end face of tube sheet 621 enter in each hollow cortina 614 and within it portion move towards the downstream.At this moment, the pressure in the preferred hollow cortina 614 are higher than the pressure of confined space 618, for example, and preferably with the pressure feed mist of 0.01MPaG～10MPaG; Making confined space 618 is decompression state etc.At this moment, the part of mist optionally sees through hollow cortina 614, passes out to the confined space 618 outside the hollow cortina 614.On the other hand, the gas that does not see through directly flows to the downstream in hollow cortina 614, from the end face in downstream pass out to hollow cortina 614 outside not through gas compartment 619b.
The gas that has seen through hollow cortina 614 is directed in the confined space 618 in the casing 610.Shown in figure 18, particularly in the zone that is wound with film structural component 631, utilize the effect of film structural component 631, can prevent to see through scattering and disappearing of gas, see through gas and flowing with the reverse arrow f2 direction of the direction of the supply f1 of mist.Then, see through gas via seeing through the outside that gas vent 610c (with reference to Figure 17) is discharged to casing 610.After the gas that does not see through is seen off from the end of downstream side of hollow cortina 614, be discharged to the outside via not seeing through gas vent 610b.
In the separating film module 601 of above explanation, utilize film structural component 631 to prevent to see through scattering and disappearing of gas, simultaneously, the direction that is adverse current in the relative mist direction of the supply through gas flows.Therefore, can seek to improve the separative efficiency of gas.
(summary of the invention)
The invention that relates to part E is described below.
1. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of gas separating property;
Have the mist inlet, see through gas vent reaches has above-mentioned hollow tow through gas vent and in internal configurations casing; With
2 tube sheets at the both ends of fixing above-mentioned hollow tow;
To offer in the above-mentioned hollow cortina from the mist that above-mentioned mist inlet imports, see through through a part that makes this mist and carry out the gas separation, wherein,
(i) be not provided for supplying with the structure of Purge gas, said Purge gas is used to discharge the gas that sees through that sees through above-mentioned hollow cortina,
(ii) also possesses a kind of film structural component; It is the film structural component of gas impermeability that is wound in the outer peripheral face of above-mentioned hollow tow; Wherein, be configured away from the mode of the above-mentioned tube sheet of mist direction of the supply upstream side with above-mentioned tube sheet butt, the other end in mist direction of the supply downstream in fact with the one of which end.
2. as above-mentioned 1 described gas separation membrane assembly, wherein, the mode that does not get into the inside of above-mentioned tube sheet with the above-mentioned end of film structural component constitutes.
3. as above-mentioned 1 or 2 described gas separation membrane assemblies, wherein, above-mentionedly see through the part that gas vent is arranged at the above-mentioned casing that surrounds the exposed portions serve that does not have the above-mentioned hollow tow that above-mentioned film structural component exists.
As above-mentioned 1～3 in each described gas separation membrane assembly, wherein, above-mentioned film structural component constitute from above-mentioned tube sheet to another tube sheet the zone in the covering above-mentioned hollow tow outer surface 50%～95%.
As above-mentioned 1～4 in each described gas separation membrane assembly, wherein, the material of above-mentioned film structural component is a polyimides.
[part F: prevent the gas separation membrane assembly that gas spills from the clearance portion between film end and the tube sheet]
(technical field)
The invention of this part relates to and a kind ofly utilizes hollow cortina to carry out gas gas separated separating film module; Be particularly related to a kind ofly in the assembly of boring feed type (bore feed Type), prevent that gas from spilling and can implement gas gas separated separating film module efficiently from the clearance portion between film end and the tube sheet.
(background technology)
The gas separation membrane assembly of hollow fiber type possesses usually: air silk element and the hollow casing of accommodating this air silk element with the hollow tow that is made up of the many hollow cortina with selection permeability.The hollow tow of air silk element, its one or both ends utilize the cured plate (tube sheet) of resin to be fixed.In addition, on casing, being provided with mist enters the mouth, sees through gas vent and see through gas vent etc.
With divided gas flow effectively is purpose; For example in TOHKEMY 2000-262838, disclose a kind of gas separation membrane assembly; Said gas separation membrane assembly in the assembly that mist is offered the what is called boring feed type (bore feed Type) in the hollow cortina, uses film structural component be covered hollow tow a part and with carrier gas flow and mode that the hollow cortina of mobile clamping of mist forms to convection current constitutes.
In the gas separation membrane assembly of above-mentioned document, can seek the validation that gas separates through the flow direction of restriction carrier gas, but in the gas separation membrane assembly that does not utilize carrier gas (Purge gas), the efficient of improving the gas separation also is important.On the other hand, utilize Purge gas,, prevent that gas from spilling from the clearance portion between film end and the tube sheet (detailed content is of the back) is effective in order to seek the further validation that gas separates no matter have or not.
The invention of this part is to accomplish in view of above-mentioned problem; Its purpose is to provide a kind of gas separation membrane assembly; Said gas separation membrane assembly is in the assembly of boring feed type (bore feed Type); Prevent that gas from spilling from the clearance portion between film end and the tube sheet, can implement gas efficiently and separate.
The disclosed main invention main points of this part are described below.
1. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of gas separating property;
Have the mist inlet, see through gas vent reaches has above-mentioned hollow tow through gas vent and in internal configurations casing;
2 tube sheets at the both ends of fixing above-mentioned hollow tow;
Be wound in the film structural component of the gas impermeability (also comprising the film structural component of gas impermeability in fact) of the outer peripheral face of above-mentioned hollow tow, said film structural component with the above-mentioned tube sheet in one of which end and mist direction of the supply downstream near and the other end from the above-mentioned tube sheet of mist direction of the supply upstream side away from mode be configured; With
An above-mentioned end of diaphragm seal member and the hermetically-sealed construction of the clearance portion between the above-mentioned tube sheet.
Invention according to this part; A kind of gas separation membrane assembly can be provided; Said gas separation membrane assembly prevents that gas from spilling from the clearance portion between film end and the tube sheet in the assembly of boring feed type (bore feed Type), can implement gas efficiently and separate.
(embodiment among the part F)
Below, describe with reference to the embodiment of accompanying drawing the invention of this part.Need to prove, in Figure 21,, more specifically show the shape of casing (detailed content is described below) as an example.
Figure 20, gas separation membrane assembly shown in Figure 21 (below, abbreviate assembly as) 801 possesses: the hollow tow 815 that many hollow cortina 814 boundlings become, accommodate the casing 810 of this hollow tow and be arranged at the tube sheet 821,822 at the both ends of hollow tow 815.This assembly 801 is the assembly of so-called boring feed type (bore feed Type), and mist (unstrpped gas) is provided for the inboard of hollow cortina 814.
Hollow cortina 814 can utilize known hollow cortina at present, as long as have gas separating property, just can be any material.As an example, by the hollow cortina that macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. form for glass macromolecular material down at normal temperature (23 ℃), its gas separating property is good, so preferred.
Hollow tow 815 is hollow tow that for example hollow cortina 814 boundlings about 100～1000000 are become.The not special restriction of the shape of the hollow tow that boundling becomes, but consider from the viewpoint of the resistance to pressure of the easness made and container, as an example, preferably cylindric.In addition, illustration has the form that hollow cortina 814 is arranged in parallel in fact in Figure 20, but can be the form of each hollow cortina cross arrangement.
The mist that utilizes hollow cortina 814 to separate is not special to be limited, for example, and can be for comprising the admixture of gas that ratio with respect to the transmission rates of diffusion barrier is the little gas of big gas of permeability more than 2 and permeability.The gas separation membrane assembly 801 of this embodiment can be used for separating the specific gas composition from mist in every way.For example, can carry out the dehumidifying of all gases, the humidification of all gases, rich nitrogen or oxygen enrichment etc.
Tube sheet 821,822 corresponding with the shape of casing 810 and be set to roughly discoid, the end of fixation hollow tow 815 under the state of the opening that has kept each hollow cortina 814.Tube sheet 821,822 can perhaps contain the thermosetting resin of epoxy resin or polyurethane resin etc. for thermoplastic resins such as polyethylene or polypropylene.Tube sheet 821,822 plays the effect of the many hollow cortinas 814 of set integratedly.In addition, play the hollow cortina 814 of sealing and reach the effect between the inner face of hollow tow 815 and casing 810 each other.Shown in figure 20, form 1 confined space 818 (of the back, as to have) by casing 810 and 2 tube sheets 821,822 through gas discharge outlet 810c, in this confined space 818, import the gas that sees through that has seen through hollow cortina 814.And then, form mist space 819a by casing 810 and tube sheet 821, form by casing 810 and tube sheet 822 and do not see through gas compartment 819b.Need to prove, between the inner face that seals tube sheet 821,822 and casing 810, also other sealing device can be set.
Need to prove; As the epoxy resin that is used for tube sheet 821,822; For example under the situation of nitrogen membrane module, can utilize the middle epoxy resin of putting down in writing that kind such as the special fair 2-36287 of Japan, in addition; Under the situation of organic vapor separation assembly, can utilize the middle epoxy resin of putting down in writing that kind such as WO2009/044711.
Shown in figure 20, casing 810 is set to roughly cylindric as a whole.Casing 810 has the mist inlet 810a that is used for mist imported in the casing 810 at upstream side (left side of figure), and (right side of figure) has and do not see through gas vent 810b in the downstream, has through gas vent 810c at side wall portion.The number that sees through gas vent 810c can be 1, also can be for a plurality of.A plurality of gas vent 810c that see through can be along the side wall portion of casing 810 with uniformly-spaced configuration.In this example, see through gas vent 810c and be formed at the position approaching (position of the exposed portions serve A1 of the hollow tow 815 that the film structural component of particularly, stating after not having 831 exists) with the tube sheet of upstream side 821.
The mist that imports from mist inlet 810a, from the end face of tube sheet 821 get in each hollow cortina 814 and within it portion flow towards the downstream.At this moment, the part in the mist penetrates into outside the hollow cortina 814, should see through gas and be fed in the confined space 818, then, is discharged to outside the casing via seeing through gas vent 810c.On the other hand, the gas that sees through that sees through hollow cortina directly flows towards the downstream hollow cortina 814 in, passed out to outside the film from the end face in downstream, then, via not being discharged to outside the casing through gas vent 810b.
Need to prove, mist inlet 810a and/or see through gas vent 810b, it is consistent with the central shaft (being the central shaft of hollow tow 815) of casing 810 to be configured to its central shaft.In addition, shown in the example of Figure 21 (A), casing 810 can have cylindrical structural member 811 and the tube sheet retaining member 813 (is not shown) that is installed on its both ends.The connecting portion of cylindrical member 811 and tube sheet retaining member 813 can weld.As an example, the inner peripheral surface of tube sheet retaining member 813 comprises diameter dimension tapered portion 813c that to be certain line part 813a, diameter dimension slowly diminish greater than large-diameter portion 813b and the diameter dimension of this line part 813a.Need to prove that shown in Figure 21 (A), tube sheet 822 has the nothing dirt 822b of portion that does not have hollow cortina 814 to exist that the hollow cortina that has hollow cortina 814 is buried the 822a of portion and its periphery underground.
Like Figure 20, shown in Figure 21, in the gas separation membrane assembly 801 of this embodiment, be wound with film structural component 831 at the outer peripheral face of hollow tow 815.Film structural component 831 is 822 approaching with one of which end 831a (being also referred to as film end 831a) and tube sheet, the other end 831b is configured from the mode that tube sheet 821 leaves the distance of regulation.In Figure 20, the zone of the hollow tow 815 of film structural component 831 linings of no use is represented by symbol A1 (exposed portions serve).Film structural component 831 can constitute with 50%～95%, preferred 70%～92% mode of the outer surface of the hollow tow that is covered.In addition, film structural component 831 can constitute as follows: both ends and each tube sheet near and cover the whole outer surface of hollow tow, near tube sheet 821, on film structural component 831, open one or more holes.
Film structural component 831 just can be any material as long as be the material of gas impermeability in fact.Need to prove that " gas impermeability in fact " is meant that the gas permeation of film structural component is enough little, can limit the stream of gas.For example can be plastic foils such as polyimides, polyethylene, polypropylene, polyamide, polyester.Wherein, aspect hear resistance, solvent resistance, processability, preferred polyimides.Except that plastic foil, also can be metal formings such as aluminium or stainless steel.The thickness of film can be in the scope of tens of μ m～number mm.
Film structural component 831 can form tubular each other through the lateral margin of a film of set, or also can use the cylindrical member that does not have seam.Lateral margin device each other as the set film can utilize for example bonding agent, adhesive tape etc.
Need to prove, be under the situation of epoxy resin at tube sheet for example, (for example, makes the film end be embedded in tube sheet material and situation about being cured etc.) when the film end gets in the tube sheet, might be starting point with this part, and tube sheet breaks or produces damage.Therefore, in this embodiment, the film end constitutes with the mode that is not embedded in the tube sheet.On the other hand, shown in figure 21 under the situation that is such formation, might between film end 831a and tube sheet 822, produce clearance portion A31 (in order to explain, the size of exaggerative clearance portion A31 is described).
Like Figure 20, shown in Figure 21, in this embodiment, be provided with the hermetically-sealed construction 850 of the clearance portion A31 between diaphragm seal end 831a and the tube sheet 822.In this example, hermetically-sealed construction 850 is configured in the film two sides with the mode of clamping film 831a, and has 2 bands 851,853 (with reference to Figure 21) that form tubular with the mode of surrounding hollow tow 815.
Band 851,853 forms by the material of saturable liquid resin material (is epoxy as an example), in other words, is formed by the material of the capillary force with regulation.Band 851,853 just can be any material so long as have such materials with function, for example, and can be for enrolling the mesh material (for example cloth shape or netted material) that fiber is made.Fiber for example can be chemical fibre or natural fiber, also can utilize glass fibre or carbon fiber etc.
Shown in figure 21, the 1st band 851 is configured in the outer peripheral face of film structural component 831, and the 2nd band 853 is configured in the inner peripheral surface of film structural component 831.Each band 851,853 disposes with the mode that the 831a from the film end extends to tube sheet 822 sides.The extended part of each band 851,853 is embedded in the nothing dirt 822b of portion in the tube sheet 822.
Shown in Figure 21 (A), on the 1st band 851, be pasted with the fixation adhesive tape 855 that sealing band 851 is fixed in film structural component 831.As an example, fixation adhesive tape 855 can attach with the mode in a reciprocal week of the peripheral part of hollow tow 815.Can fixation adhesive tape 855 be reeled more than two circles, or can be only attach fixation adhesive tape 855 in the part of peripheral part.
Shown in Figure 21 (B), can use fixture 857 fixing for overlapping of 2 bands 851,853.As fixture 857, as an example, can be the device of mechanical fixation two members, also can be the pin of for example stapler.In addition, for example also can utilize silk or wire etc.
Of the back, band 851,853 has and prevents to see through the function that gas spills from clearance portion A31.Spill in order to prevent efficiently, in the band 851,853 is the state that resin material soaks into and solidifies towards the zone of clearance portion A31 at least.Thus, give the gas impermeability to band 851,853, its result can further prevent spilling of gas.Need to prove that aforesaid processing can be only to an enforcement in 2 bands 851,853.
Film structural component 831 and hermetically-sealed construction 850 for example can be made as follows.Need to prove that following operation is a simple example, the invention of this part does not receive any qualifications such as this process sequence.
At first, prepare hollow tow 815 and casing (the for example material of Figure 21).In addition, prepare to form 1 film structural component 831 of the size of regulation, simultaneously, with near the mode the 831a of its end of clamping on the film two sides lap seal band 851,853, with the overlapping portion of stapler (example) fixing seal band 851,853.
Then, the film structural component 831 of this state is wound in hollow tow 815 and fixes with for example adhesive tape (not shown).Then, the hollow tow 815 of configuration on the assigned position in casing 810 forms tube sheet 821,822 at the both ends of hollow tow 815.Tube sheet 821,822 can form through epoxy material being filled in the end of hollow tow 815 and it being solidified.
Example with Figure 21 specifies.As an example, being filled under the following state of epoxy material carried out: the casing 810 that will have hollow tow 815 to get into remains on vertical direction and mould (not shown) is installed in the casing bottom.At this moment, shown in Figure 21 (A), the front end that the liquid level of the epoxy material of being filled is set in band 851,853 is embedded in the tube sheet 822 but does not bury the such position of end 831a underground.When the end of band 851,853 impregnated in epoxy material, utilize capillary force, in band 851,853 (comprising at least), soak into epoxy material towards the zone of the part of clearance portion A31.
Then, the tube sheet 822 through after cutting off the curing that makes tube sheet material curing on the assigned position makes hollow cortina 814 openings.Then, as required, carry out the assembling procedure same (for example be used to make operation that casing 810 accomplishes etc.), assembly is accomplished with existing operation.
Need to prove, can be with following arranged in order film structural component 831 and band 851,853: at first, the 2nd band 853 is wound in hollow tow 815, then, coiling film structural component 831, then, the 1st band 851 of reeling.
Below, an example of the method for using of the separating film module of this embodiment of as above constituting is described.Need to prove that the method for using of the assembly of this embodiment is not limited to following method.
At first, mist is imported to the mist space 819a in the casing 810 from mist inlet 810a.This mist that is imported from the end face of tube sheet 821 enter in each hollow cortina 814 and within it portion move towards the downstream.At this moment, the pressure in the preferred hollow cortina 814 are higher than the pressure of confined space 818, for example, and preferably with the pressure feed mist of 0.01MPaG～10MPaG; Making confined space 818 is decompression state etc.At this moment, the part of mist optionally sees through hollow cortina 814, is passed out to the confined space 818 outside the hollow cortina 814.On the other hand, the gas that does not see through directly flows towards the downstream in hollow cortina 814, from the end face in downstream be released to hollow cortina 814 outside not through gas compartment 819b.
Supposing under the situation that does not dispose film structural component 831, shown in the arrow f3 of Figure 21 (B), is cross flow direction (direction of promptly intersecting with hollow cortina 814) from the direction of advance that sees through gas of hollow cortina 814.Perhaps, shown in f4, the direction of advance that sees through gas be the mobile that kind opposite with f2 and flow path direction, and, be such mobile of f3.On the other hand, as this embodiment, on hollow tow 815, be wound with under the situation of film structural component 831; Can prevent to see through scattering and disappearing of gas; Seeing through gas is that the direction of the arrow f2 of adverse current flows at the direction of the supply f1 of mist relatively, and its result can improve the efficient that gas separates.Particularly in this embodiment, be provided with the hermetically-sealed construction 850 that clearance portion A31 is sealed, can prevent to see through gas and escape to the outside through this clearance portion A31.Therefore, can prevent more reliably to see through scattering and disappearing of gas, can carry out the validation that gas separates more well.
Prevent to see through gas and spill and can soil realize, at this moment, might as above-mentioned, produce the breaking or damage of tube sheet 822 near the 831a of film end to be starting point through the structures of processing film end 831a and directly being embedded in the tube sheet 822.Relative with it, in this embodiment, therefore the formation for the band 851,853 of burying the member different with film structural component 831 underground, through the suitable material of selecting band, can prevent the generation of breaking or damaging of such tube sheet 822.
As stated,, compare, also can suppress to see through spilling of gas with the situation that any band is not set even band 851,85 is a mesh material.But in this embodiment, and then resin material soaks into band 851,853 and in this curing, therefore, can prevent to see through spilling of gas more reliably.
(other embodiment)
More than, a mode of the invention of this part is illustrated, but the invention of this part is not limited to foregoing, can carry out various changes.
For example, can be for only having any one the mode in the 1st and the 2nd band 851,853.In addition, the fixation adhesive tape 855 that the 1st band 851 is fixed in film structural component 831 also can omit.In addition, overlapping the fixture 857 (with reference to Figure 21 (B)) of fixing 2 bands 851,853 also can be omitted.
Figure 22 representes other seal ring structure, and Figure 22 (A) is the whole schematic sectional view of assembly, and Figure 22 (B) is its part enlarged drawing.In this example, as far as hermetically-sealed construction, the packing material 891 that illustration has the mode with the clearance portion A31 between landfill film structural component 831 and the tube sheet 822 to dispose.As far as packing material 891,, can be the resin material (is heat-resisting silicone as an example) that injects with the mode of surrounding film structural component 831 as an example.Utilize such packing material 891, also can prevent to see through gas and spill from clearance portion A31, its result can obtain implementing the assembly of effective gas separation.Packing material 891 for example can form through following method: after in casing, forming tube sheet 822, on wall box, form one or more holes, from the hole, inject packing material 891 and make its curing.
The place that such packing material 891 is set is not limited to position shown in Figure 22.For example shown in Figure 23, between film structural component 831 and casing 810 and from the position that clearance portion A31 leaves predetermined distance, can dispose packing material 893.Shown in figure 23, packing material 893 also can be configured in the place on the length direction of film structural component 831.Such packing material 893 disposes with the mode that can block gas flow and with the mode in a reciprocal week of the periphery of film structural component 831, as far as its width, and as an example, can be for more than (for example 0.5% of the outer surface of film) about 3mm～5mm.
Perhaps; At the periphery of film structural component 831 packing material in a reciprocal week; Can spread all over the mode in the slit between landfill film structural component 831 and the casing 810 in broader (length) scope and fill, for example, can account for the scope more than 10% of the outer surface of coverlay member.
In addition, shown in figure 24, the gas separation membrane assembly of the invention of this part can have the structure that is used to make Purge gas to flow.This gas separation membrane assembly possess the both ends of hollow tow 915, casing 910, fixation hollow tow 915 2 tube sheets 921,922, be wound in film structural component 931 and the end of diaphragm seal member 931 and the hermetically-sealed construction 950 of the clearance portion between the tube sheet 922 of gas impermeability of the outer peripheral face of hollow tow.This gas separation membrane assembly also possesses the core pipe 971 that is used for delivery of purge gas.
Same with the assembly of Figure 20, casing 910 has mist inlet 910a at upstream side (left side of figure), has through gas vent 910c at side wall portion.More lean on the structure in downstream slightly different than tube sheet 922, form at the side wall portion of casing 910 and see through gas vent 910b, pass through core pipe 971 at the central part of casing 910 with the assembly of Figure 20.
Core pipe 971 is the member of the obturation of one in the two ends and another person's opening, and peristome is becoming the direction configuration in downstream (tube sheet 922 sides).Core pipe 971 runs through tube sheet 922 and extends, and its fore-end is embedded in the tube sheet 921 of upstream side.Core pipe 971 become 2 tube sheets 921, zone between 922 has hole 971a.
As far as the assembly that as above constitutes, the principle that basic gas separates is identical with the assembly of Figure 20.Supply with Purge gas from the peristome (Purge gas inlet 910d) of core pipe 971, this Purge gas is released in the confined space 918 in the casing 910 through hole 971a.This Purge gas flows in f2 direction (the mist direction of the supply is the direction of adverse current relatively) between hollow cortina 914, and the gas that sees through that is released in the isospace is expressed to the side through gas vent 910c, promotes to see through the discharge of gas thus.
In the assembly that utilizes such Purge gas, the hermetically-sealed construction 950 of the clearance portion between diaphragm seal member 931 and the tube sheet 922 is set preferably also.Hermetically-sealed construction 950 also can use any in the above-mentioned various structures.Thus, prevent to spill from clearance portion through gas and Purge gas, make through gas and Purge gas and flow well in the f2 direction, its result can seek the further validation that gas separates.
(summary of the invention)
The invention that relates to part F is described below.
1. gas separation membrane assembly possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of gas separating property;
Have the mist inlet, see through gas vent reaches has above-mentioned hollow tow through gas vent and in internal configurations casing;
2 tube sheets at the both ends of fixing above-mentioned hollow tow;
Be wound in the film structural component of gas impermeability of the outer peripheral face of above-mentioned hollow tow, said film structural component with the above-mentioned tube sheet in one of which end and mist direction of the supply downstream near and the other end be configured from the mode that the above-mentioned tube sheet of mist direction of the supply upstream side leaves; With
The hermetically-sealed construction that an above-mentioned end and the clearance portion between the above-mentioned tube sheet of film structural component sealed.
2. like above-mentioned 1 described gas separation membrane assembly; Wherein, Above-mentioned hermetically-sealed construction has band; Said band is wound in the radially inner side or the outside of above-mentioned film structural component in an above-mentioned end of film structural component, and extends from this end towards above-mentioned tube sheet side, and an extended part is embedded in the above-mentioned tube sheet.
3. like above-mentioned 2 described gas separation membrane assemblies, wherein,, have the 1st band and the 2nd band as above-mentioned band,
Said the 1st band is formed by the saturable material of aqueous resin material, is wound in the radial outside of above-mentioned film structural component;
Said the 2nd band is formed by the saturable material of aqueous resin material, is wound in the radially inner side of above-mentioned film structural component.
4. like above-mentioned 2 or 3 described gas separation membrane assemblies, wherein, above-mentioned band is a mesh material.
5. as above-mentioned 3 or 4 described gas separation membrane assemblies, wherein, in above-mentioned band at least in the zone of above-mentioned clearance portion, resin material soaks into and solidifies, and seals above-mentioned clearance portion thus.
6. like above-mentioned 3 described gas separation membrane assemblies, wherein, above-mentioned hermetically-sealed construction also has the fixation adhesive tape that above-mentioned the 1st band is fixed in above-mentioned film structural component.
7. like above-mentioned 3 described gas separation membrane assemblies; Wherein, Above-mentioned hermetically-sealed construction also has fixture, and said fixture is used for fixing from the extension of extended above-mentioned the 1st band in an above-mentioned end of film structural component with from the extension of extended above-mentioned the 2nd band in an above-mentioned end of film structural component.
8. as above-mentioned 1 described gas separation membrane assembly, wherein, above-mentioned hermetically-sealed construction has the packing material that the mode with an above-mentioned end of landfill film structural component and the above-mentioned clearance portion between the above-mentioned tube sheet disposes.
As above-mentioned 1～8 in each described gas separation membrane assembly, it constitutes with the mode that an above-mentioned end of film structural component does not get into the inside of above-mentioned tube sheet.
As above-mentioned 1～9 in each described gas separation membrane assembly, wherein, the material of above-mentioned film structural component is a polyimides.
[part G: the gas separation membrane assembly of fully guaranteeing the sealing property of tube sheet periphery]
(technical field)
The present invention relates to a kind ofly utilize hollow cortina to carry out gas gas separated separating film module; Be particularly related to a kind of gas separation membrane assembly etc.; Even said gas separation membrane assembly is using cure shrinkage to be relatively easy under the situation of tube sheet material; Also can guarantee the sealing property of tube sheet periphery fully, and then can at high temperature use well.
(background technology)
The gas separation membrane assembly of hollow fiber type possesses usually: air silk element and the hollow casing of accommodating this air silk element with the hollow tow that is made up of the many hollow cortina with selection permeability.The one or both ends of hollow tow utilize the cured plate (tube sheet) of resin to be fixed.
The common institute of gas separation membrane gas supplied is HTHP more, and the transmission rates of gas is big more.Therefore, under the situation of using gases separating film module, study sometimes unstrpped gas is offered assembly after with compressions such as compressor reducers.Gas after this compression according to circumstances is about 149 ℃～260 ℃ sometimes.
But; There is following problem: under the situation of the assembly of the separation of the mist that carries out aforesaid high temperature; Need to use and have stable on heating tube sheet material; But such tube sheet material is easy cure shrinkage when being cured usually, its result, and the sealing property of tube sheet periphery might be insufficient.The invention of this part is accomplished in view of this aspect; Its purpose is to provide a kind of separating film module etc.; Even said separating film module is using cure shrinkage to be relatively easy under the situation of tube sheet material; Also can guarantee the sealing property of tube sheet periphery fully, and then can at high temperature use well.
The disclosed main invention main points of this part are described below.
The gas separation membrane assembly of a mode of the invention of this part possesses:
The hollow tow that will have the many hollow cortina boundling one-tenth of gas separating property;
The casing that above-mentioned hollow tow is arranged in internal configurations; With
The tube sheet of at least one end of fixing above-mentioned hollow tow;
Said gas separation membrane assembly does not constitute with the bonding mode of the inner peripheral surface of above-mentioned casing with the outer peripheral face of above-mentioned tube sheet,
Wherein, said gas separation membrane assembly also possesses the containment member that seals between the inner peripheral surface with the outer peripheral face of above-mentioned tube sheet and above-mentioned casing.
In addition; The manufacturing approach of the gas separation membrane assembly of a mode of the invention of this part; Said gas separation membrane assembly possesses: will have hollow tow that the many hollow cortina boundling of gas separating property becomes, the tube sheet of at least one end of casing and the fixing above-mentioned hollow tow of above-mentioned hollow tow is arranged in internal configurations; Wherein, said manufacturing approach comprises following steps:
The step of the part release agent application that the above-mentioned at least tube sheet in the inner peripheral surface of above-mentioned casing joins,
The step of a part of filled thermoset resin in above-mentioned casing,
Through make the above-mentioned thermosetting resin cured step that forms above-mentioned tube sheet and
The step of containment member is set between the inner peripheral surface of the outer peripheral face of above-mentioned tube sheet and above-mentioned casing in above-mentioned thermosetting resin cured back.
Need to prove that the definition of the term in this specification is described below.
" hot conditions " or " high temperature " is meant in for example 80 ℃～300 ℃ the scope.
" cylindrical container " is not limited to the container of both ends open, also comprises the only container of an end opening.
According to the invention of this part, a kind of gas separation membrane assembly etc. can be provided, even said gas separation membrane assembly is using cure shrinkage to be relatively easy under the situation of tube sheet material; Also can fully guarantee the sealing property of tube sheet periphery; And, even at high temperature, also can use well.
(embodiment among the part G)
Below, describe with reference to the embodiment of accompanying drawing the invention of this part.Need to prove, in Figure 25,, more specifically show the shape of casing (following in detail) as an example.In addition, the formation of following explanation is the formation of expression one example after all, and gas separation membrane assembly of the present invention is not limited to these formations.
Figure 25, gas separation membrane assembly shown in Figure 26 (below, also abbreviate assembly as) 1001 possesses: hollow tow 1015, casing 1010 of accommodating this hollow tow that many hollow cortina 1014 boundlings are become and the tube sheet 1021,1022 that is provided with at the both ends of hollow tow 1015.As an example, this assembly 1001 is the assembly of so-called boring feed type (bore feed Type), and mist (unstrpped gas) is provided for the inboard of hollow cortina 1014.
Hollow cortina 1014 can utilize known hollow cortina at present, as long as have gas separating property, just can be the hollow cortina of any material.As an example, by the hollow cortina that macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. form for glass macromolecular material down at normal temperature (23 ℃), gas separating property is good, so preferred.
Hollow tow 1015 is hollow tow that for example hollow cortina 1014 boundlings about 100～1000000 are become.The not special restriction of the shape of the hollow tow 1015 that boundling becomes, but consider from the viewpoint of the resistance to pressure of the easness made and container, as an example, preferably cylindric.In addition, illustration has the form that hollow cortina 1014 is arranged in parallel in fact in Figure 25, but can be the form of each hollow cortina cross arrangement.
The mist that utilizes hollow cortina 1014 to separate is not special to be limited, for example, and can be for comprising the admixture of gas that ratio with respect to the transmission rates of diffusion barrier is the little gas of big gas of permeability more than 2 and permeability.The gas separation membrane assembly 1001 of this embodiment can be used for separating the specific gas composition from mist in every way.For example, can carry out the dehumidifying of all gases, the humidification of all gases, rich nitrogen or oxygen enrichment etc.
Tube sheet 1021,1022 is corresponding with the shape of casing 1010 and form roughly discoid (detailed content is described below), the end of fixation hollow tow 1015 under the state of the opening that has kept each hollow cortina 1014.Tube sheet plays the effect each other of the hollow cortina of sealing in this example.Tube sheet can also perhaps contain the thermosetting resin of epoxy resin or polyurethane resin etc. for thermoplastic resins such as polyethylene or polypropylene.Below, be that the example of thermosetting resin describes to tube sheet.
Need to prove; As the epoxy resin that is used for tube sheet 1021,1022; For example under the situation of nitrogen membrane module, can utilize the middle epoxy resin of putting down in writing that kind such as the special fair 2-36287 of Japan, in addition; Under the situation of organic vapor separation assembly, can utilize the middle epoxy resin of putting down in writing that kind such as WO2009/044711.
Shown in figure 25; In this embodiment; Form 1 confined space 1018 (of the back, as to have) by casing 1010 and 2 tube sheets 1021,1022, in this confined space 1018, import the gas that sees through that has seen through hollow cortina 1014 through gas discharge outlet 1010c.And then, form mist space 1019a by casing 1010 and tube sheet 1021, form by casing 1010 and tube sheet 1022 and do not see through gas compartment 1019b.
Shown in figure 25, casing 1010 is set to roughly cylindric as a whole.Casing 1010 has the mist inlet 1010a that is used in casing 1010, importing mist at upstream side (left side of figure), and (right side of figure) has not through gas vent 1010b in the downstream, has through gas vent 1010c at side wall portion.The number that sees through gas vent 1010c can be 1, also can be for a plurality of.A plurality of gas vent 1010c that see through can be along the sidewall of casing 1010 with uniformly-spaced configuration.
From the mist that mist inlet 1010a imports, in each hollow cortina 1014 of end face entering of tube sheet 1021, portion flows towards the downstream within it.At this moment, the part in the mist should see through gas and be admitted in the confined space 1018 for penetrating into the gas that sees through outside the hollow cortina 1014, then, and via being discharged to outside the casing through gas vent 1010c.On the other hand, the gas that sees through that sees through hollow cortina directly flows to the downstream hollow cortina 1014 in, passed out to outside the film from the end face in downstream, then, via not being discharged to outside the casing through gas vent 1010b.
Need to prove mist inlet 1010a and/or see through gas vent 1010b can be configured to its central shaft consistent with the central shaft (being the central shaft of hollow tow 1015) of casing 1010.In addition, shown in the example of Figure 26, casing 1010 can have cylindrical structural member 1011 and the cap member 1012 (is not shown) that is installed on its both ends.Cylindrical member 1011 and cap member 1012 can be metal system as an example.
Particularly, cylindrical structural member 1011 is that internal diameter is d 0Hollow unit and form heavy section 1011a, 1011b in its end.The 1st heavy section 1011a is arranged near the end face of cylindrical structural member 1011, and the internal diameter of this part forms and compares inner diameter d 0Little.The 2nd heavy section 1011b is arranged at than the 1st heavy section 1011a and more leans on direction of principal axis inboard, and the internal diameter of this part also forms and compares inner diameter d 0Little.The internal diameter of the part between heavy section 1011a and the heavy section 1011b can be d greater than the internal diameter of two heavy section 1011a, 1011b as an example 0
Corresponding with such structure of cylindrical structural member 1011, tube sheet 1021 forms following shape.That is, shown in figure 26, tube sheet 1021 broadly has 3 different parts of diameter (being followed successively by part 1 1021a, part 2 1021b and the 3rd part 1021c from the outside), wherein, is that the mode of maximum is provided with the diameter of mid portion 1021b.In this example, the boundary of part 1 1021a and part 2 1021b is a taper surface.In addition, the boundary of part 2 1021b and the 3rd part 1021c for face directly (with the face of the direction expansion of the orthogonality of center shaft of cylindrical structural member).
When using separating film module 1001, utilize the pressure of mist, on tube sheet 1021, apply the power that this tube sheet is squeezed into the direction in the cylindrical structural member 1011.But, the formation such according to Figure 26, the part of tube sheet 1021 and heavy section 1011b butt can limit moving of tube sheet 1021 thus, and therefore, tube sheet 1021 can not be squeezed into inside.
Need to prove, unqualified, but can be provided with the R shape at the part 2 1021b of tube sheet and the connecting portion 1021f of the 3rd part 1021c.Thus, can relax the breakage etc. that tube sheet was concentrated and prevented to stress in this part.
The example of Figure 26 representes that tube sheet 1021 shrinks some states for thermosetting resin and because of cure shrinkage makes the diameter of tube sheet 1021.Under the situation of such formation, can not fully guarantee the sealing between tube sheet 1021 and the cylindrical structural member 1011, therefore, in this embodiment, be provided with the containment member 1060 that is used for the ring-type that seals between two members.
Shown in figure 26, be formed with the 1021s of rank portion of ring-type at the peripheral part of the part 1 1021a of tube sheet.The inner peripheral surface association of this 1021s of rank portion and cylindrical structural member 1011 is moving, integrally forms the groove C1 of ring-type, in this groove C1, disposes the containment member 1060 of ring-type.
Containment member 1060 is the annular element that is formed by elastic component, also can be for being embedded in part in the groove C1 (for example O ring etc.).Perhaps, can be filled in the groove C1 for the resin material that will seal usefulness and pass through this resin material and solidify as the acting part of containment member.The cross sectional shape of O ring can be circle, also can be ellipse.As " part of the ring-type that constitutes by elastic component ", except that the O ring, can be the V-seal spare of roughly V-type, the U type seal etc. of U type roughly for cross sectional shape.And then, for example can be the part of rectangle, polygonal or X type prismatic shapes.Need to prove, in the example of Figure 26, seal between 1060 pairs of tube sheets 1021 of containment member and the casing 1010, simultaneously also to sealing between tube sheet 1021 and the cap member 1012.
In addition, structure shown in Figure 26 is an example after all, and the invention of this part is had no qualification.For example, the diameter of the part 1 1021a of tube sheet and the 3rd part 1021c can be identical.Perhaps, can use the tube sheet that constitutes that kind by part 1 1021a and the 3rd part 1021c.In addition, the face between part 1 1021a and the part 2 1021b can not be the such taper surface of Figure 26 but face directly.Equally, the face between part 2 1021b and the 3rd part 1021c can not be such the facing directly but taper surface of Figure 26.And then, seal between 1060 pairs of tube sheets 1021 of containment member, casing 1010 and the cap member 1012, but also can be different with the containment member between tube sheet 1021 and the casing 1010, the containment member between casing 1010 and the cap member 1012 possessed in addition.
Figure 27 is the sectional view in the A-A line of Figure 26.As shown in the drawing, also can be formed with recess 1011d, 1011d at two places of the inner peripheral surface of cylindrical structural member 1011.At this moment, the tube sheet member enters into this recess 1011d, 1011d and is cured (detailed content is described below), and its result can prevent the rotation of tube sheet 1021.Need to prove, do not limit, can be merely 1 the number of recess 1011d is special, also can be for more than 3.
Make the method for the gas separation membrane assembly 1001 that constitutes as stated, can be the method that is described below as an example.That is, the manufacturing approach of this embodiment comprises following steps:
The step of the part release agent application of (a) in the inner peripheral surface of casing, joining at tube sheet at least;
(b) part in casing is filled the step of the thermosetting resin before solidifying;
(c) through making the thermosetting resin cured step that forms tube sheet after being filled; With
(d) step of the containment member of ring-type is set between the inner peripheral surface of the outer peripheral face of tube sheet and casing in thermosetting resin cured back.
Through release agent application as the step of above-mentioned (a), in the curing process of step (c), tube sheet (is epoxy resin as an example) demoulding well from the casing (as an example for metal).Suppose under the situation of not using releasing agent, when resin solidification, might not leave by tube sheet, according to circumstances on tube sheet, produce crack etc. from main body.
In the step of above-mentioned (b), can not shown mould be installed on the end of cylindrical structural member 1011, the injection of enforcement tube sheet resin under this state.At this moment, mould has the protuberance with the corresponding ring-type of the 1021s of rank portion (with reference to Figure 26) of tube sheet, utilizes this protuberance, can on tube sheet, form the 1021s of rank portion.
In the step of above-mentioned (d), as stated, for example can in groove C1, embed annular resilient members such as O ring, perhaps in groove C1, inject resin and make its curing, can form containment member 1060 thus.
Gas separation membrane assembly 1001 according to this such embodiment of above explanation; Even can not guarantee because of the cure shrinkage of tube sheet 1021 under the situation of the sealing between tube sheet outer peripheral face and the casing inner peripheral surface; Also be provided with containment member 1060 separately; Therefore, can guarantee the sealing between two members fully.
It is to particularly at high temperature the situation of the gas separation membrane assembly of use is favourable.That is, generally speaking, the material that is difficult for cure shrinkage has and has elasticity and glass transition temperature is low, lack stable on heating trend.On the other hand, the tube sheet material of excellent heat resistance has the trend of easy cure shrinkage.Suppose under the situation of the formation of using stable on heating like this material and tube sheet and the bonding that kind of casing, might apply extension stress, on tube sheet, produce the crack because of the cure shrinkage of tube sheet material.Relative with it, according to this embodiment, prevent the bonding of tube sheet material through release agent application in casing, simultaneously, utilize the annular seal member to guarantee the sealing between tube sheet and the casing.Therefore, a kind of gas separation membrane assembly that prevents on tube sheet, to produce the crack and also guarantee sealing property fully can be provided.
Need to prove in above-mentioned explanation, mainly the tube sheet 1021 (Figure 26) in 2 tube sheets 1021,1022 is illustrated, but two tube sheets 1021,1022 can have same formation.Perhaps, the such structure of Figure 26 can only be set on a tube sheet.And then; The structure of tube sheet, annular seal member and casing that this embodiment is such is not limited to the assembly of boring feed type (bore feed Type); Also can be applicable to the assembly of shell feed type (shell feed Type), can also be applied to the assembly of other type.
(summary of the invention)
The invention that part G relates to is described below.
1. gas separation membrane assembly possesses:
To have hollow tow that the many hollow cortina boundling of gas separating property becomes,
Internal configurations have above-mentioned hollow tow casing and
The tube sheet of at least one end of fixing above-mentioned hollow tow;
Said gas separation membrane assembly does not constitute with the bonding mode of the inner peripheral surface of above-mentioned casing with the outer peripheral face of above-mentioned tube sheet,
Wherein, said gas separation membrane assembly also possesses the containment member that seals between the inner peripheral surface to the outer peripheral face of above-mentioned tube sheet and above-mentioned casing.
2. as above-mentioned 1 described gas separation membrane assembly, wherein, above-mentioned tube sheet has with the inner peripheral surface association of above-mentioned casing moving and form the rank portion of the groove of ring-type.
3. like above-mentioned 1 or 2 described gas separation membrane assemblies, wherein, above-mentioned casing has cylindrical member that surrounds above-mentioned hollow tow and the cap member that is provided with in the end of this cylindrical member,
On above-mentioned cylindrical member, be formed with the heavy section that inner-diameter portion whose diminishes, above-mentioned tube sheet and this heavy section butt prevent that thus above-mentioned tube sheet from upwards stating inboard the moving of direction of principal axis of cylindrical member.
As above-mentioned 1～3 in each described gas separation membrane assembly, wherein, above-mentioned containment member is the annular resilient member that is embedded in the groove of above-mentioned ring-type.
5. the manufacturing approach of a gas separation membrane assembly; Said gas separation membrane assembly possesses: will have hollow tow that the many hollow cortina boundling of gas separating property becomes, the tube sheet of at least one end of casing and the fixing above-mentioned hollow tow of above-mentioned hollow tow is arranged in internal configurations; Wherein, said gas separation membrane assembly comprises following steps:
The step of the part release agent application that the above-mentioned at least tube sheet in the inner peripheral surface of above-mentioned casing joins,
The step of a part of filled thermoset resin in above-mentioned casing,
Through make the above-mentioned thermosetting resin cured step that forms above-mentioned tube sheet and
The step of containment member is set between the inner peripheral surface of the outer peripheral face of above-mentioned tube sheet and above-mentioned casing in above-mentioned thermosetting resin cured back.
[embodiment]
[embodiment that relates to part A]
Below, utilize embodiment that the invention of part A is further specified.Need to prove that the invention of part A is not limited to following embodiment.
< assay method of the glass transition temperature of hollow cortina (Tg) >
Change the assay method of initial temperature according to the extrapolation glass of JIS K7121, use the DSC50 of Shimadzu Seisakusho Ltd. device, under sample size 2mg, blanket of nitrogen gas, ℃ implement the mensuration of glass transition temperature (Tg) from room temperature to 400 with 10 ℃/min.
< assay method of the shape conservation rate of hollow cortina >
In the mensuration of shape conservation rate, in 175 ℃ hot air type thermostat, kept the length of 2 hours heat treatment front and back to measure to air silk with 200mm length.The ratio of the length of the script of the length after the heat treatment before with respect to heat treatment is made as the shape conservation rate.
< assay method of solution viscosity >
The solution viscosity of polyimide solution uses rotation viscometer (the shear rate 1.75sec of rotor -1) under 100 ℃ of temperature, measure.
< making example 1 >
In the removable flask of mixer and nitrogen ingress pipe was installed, 1882g added 4 with solvent 4-chlorophenol, 4 '-(hexafluoro isopropylidene)-two (phthalic anhydride) 200 mMs, 3; 3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 225 mMs, PMA dicarboxylic anhydride 75 mMs, 2; 2 ', 5,5 '-tetrachloro benzidine, 250 mMs and 3; 7-diaminourea-dimethyl Dibenzothiophene=5; 5-dioxide 250 mMs, limit feed the nitrogen limit and under agitation under 190 ℃ of reaction temperatures, carried out the polymerization imidization reaction 20 hours in flask, preparation polyimides concentration is the aromatic polyimide solution of 17 weight %.Solution viscosity during 100 ℃ of this aromatic polyimide solution is 1940 pools.
The wire netting of the above-mentioned aromatic polyimide solution that is prepared into 400 meshes filtered; It as doping liquid, is used to possess the device for spinning of air silk spinning with nozzle, from the circular open portion ejection doping liquid of air silk spinning with nozzle (circular open portion external diameter 1000 μ m, circular open portion slit width 200 μ m, core peristome external diameter 400 μ m); Simultaneously from core peristome ejection nitrogen; Form hollow filamentous, after it is passed through in blanket of nitrogen, impregnated in solidification liquid it is solidified; Utilize carry-over pinch rolls to draw, obtained moistening hollow cortina.Then, dry this hollow cortina further 250 ℃ of following heat treated 30 minutes, has obtained hollow cortina 1.
The hollow cortina 1 of gained roughly external diameter is 410 μ m, and internal diameter is 280 μ m.Form the tow element by hollow cortina, then, the tow element of each hollow cortina forms the gas separation membrane assembly by these.
Below in embodiment 1,2, use the air separation membrane module 1 of the hollow cortina 1 adopted above-mentioned manufacturing, in comparative example 1,2, use the air separation membrane module 3 that has adopted the air separation membrane module 2 of following hollow cortina 2 or adopted hollow cortina 3.
To be shown in table 1 about characteristic of each hollow cortina etc.Glass transition temperature, shape conservation rate utilize said method to measure.
[table 1]
Figure BDA0000105556110000711
*1: hollow cortina 1 is not exist below 300 degree at glass transition temperature, can not measure with said method.
*2:P ' O2Oxygen transmission rates when representing 40 ℃.
To be shown in table 2 about the various situation of each air separation membrane module.
[table 2]
Figure BDA0000105556110000721
< embodiment 1 of part A >
With pressure 0.2MPaG 175 ℃ air being offered air separation membrane module 1, is that oxygen concentration in the nitrogen-rich air is that 12% mode is adjusted the air quantity delivered, running continuously under this condition with the non-gas that sees through.In each elapsed time after entry into service, measure the flow of made nitrogen-rich air.To measure the result and be shown in Fig. 1.In addition, according to measuring the result, calculate from running begin through the air separation membrane after 0 hour, 140 hours, 2069 hours the oxygen transmission rates (P ' O2), show the oxygen transmission rates of separating property and the ratio of nitrogen transmission rates (P ' O2/ P ' N2).Its result is shown in table 3.
At the moment (0 hour) of entry into service, P ' O2Be 35.4 * 10 -5Cm 3(STP)/cm 2SeccmHg, the flow of the nitrogen-rich air that is obtained by air separation membrane module 1 is 0.748Nm 3/ h.After running beginning during through 140 hours, P ' O2Be 33.4 * 10 -5Cm 3(STP)/cm 2SeccmHg has only reduced by 5.6% during than the running beginning.After the running beginning through the P ' after 2069 hours O2Be 31.4 * 10 -5Cm 3(STP)/cm 2SeccmHg has reduced by 11% during than the running beginning.Flow by the nitrogen-rich air that obtains through the air separation membrane module 1 after 2069 hours after the running beginning is 0.65Nm 3/ h, the moment that begins than running has only reduced 13%.Can know that by this result even 175 ℃ of runnings 2000 hours, air separation membrane module 1 is also kept the gas separation membrane ability.
< comparative example 1 of part A >
Use air separation membrane module 2, attempt the mensuration same with embodiment 1, but violent in the contraction of 175 ℃ of hollow cortinas, can not obtain nitrogen-rich air.In remaining in 175 ℃ air separation membrane module 2, observe deformation of hollow fragmentation, broken string, tube sheet etc.
< comparative example 2 of part A >
Except using air separation membrane module 3, with the same condition of embodiment 1 under turn round, measure the flow of the nitrogen-rich air in each elapsed time.To measure the result and be shown in Fig. 1.The P ' in the moment of entry into service O2Be 19.3 * 10 -5Cm 3(STP)/cm 2SeccmHg, the flow of the nitrogen-rich air that is obtained by the air separation membrane module is 0.625Nm 3/ h.After running beginning through 140 hours after, the P ' of diffusion barrier O2Be 11.3 * 10 -5Cm 3(STP)/cm 2SeccmHg has reduced 41% when bringing into use, and the flow of the nitrogen-rich air that is obtained by the air separation membrane module is 0.419Nm 3/ h has reduced 35% when bringing into use.
< embodiment 2 of part A >
With the oxygen concentration in the nitrogen-rich air of manufacturing is that 5% mode is adjusted the air quantity delivered, in addition, likewise measures with embodiment 1.To measure the result and be shown in Fig. 2.The flow of the nitrogen-rich air in the moment of entry into service is 0.18Nm 3/ h.Flow through the nitrogen-rich air after 2069 hours after the running beginning is 0.15Nm 3/ h terminates in and reduces 16%.Can know by this result, same with embodiment 1, even 175 ℃ through 2000 hours, air separation membrane module 1 is also kept the gas separation membrane ability.
Figure BDA0000105556110000741
[embodiment that relates to part B]
Below, utilize embodiment that the invention of part B is described, but the present invention is not limited to embodiment.
< embodiment 1 >
(manufacturing of castable resin composition)
Polyglycidyl ether 100 weight portions of mixed phenol Novolac and carboxyl terminal hycar (molecular weight 3100) 10 weight portions heated 3～4 hours down at 150 ℃, the preparation modified epoxy.Mixed prepared modified epoxy 100 weight portions, methyl-5-ENB-2,3-dicarboxylic anhydride 80 weight portions and 2-ethyl-4-methylimidazole 0.3 weight portion stir and have prepared the castable resin composition.
(evaluation of the formability of tube sheet)
Such in the mould of
Figure BDA0000105556110000751
, disposing shown in Fig. 4 b with 12000 hollow cortinas of polyimides (length: 100cm, external diameter: the tow of boundling one-tenth 500 μ m).The front end that makes tow is upright in fact for down, will slowly be injected into insulation through the castable resin composition of above-mentioned gimmick preparation and be in 70 ℃ the mould.It is about 90mm that the amount of castable resin composition is controlled so as to thickness.After the injection, after carrying out 12 hours one-step solidifications under 70 ℃, be heated to 142 ℃ and carry out solidifying after 4 hours, carry out the shaping of tube sheet thus.After the curing, from casing, take out the air silk element and observe through visual, so with tube sheet cut for two halves roughly and to the state of central part also through carrying out visualization.
Its result does not observe the crack on the tube sheet after the shaping.
[embodiment that relates to part E]
Below, expression is to the situation that is wound with film structural component and not have the replying of gas separation membrane assembly of the situation of coiling to carry out Simulation result.Replying of table 1 expression assembly, " pattern A (cross flow) " is the situation of the film structural component of not reeling, " pattern B (adverse current) " is for being wound with the situation of film structural component.Temperature is made as t=25 ℃, the supply pressure of mist and is made as PF=0.7MPaG and calculates.Need to prove, at this, be that the separating film module that goods obtain is simulated to supplying with as the air of mist, with the nitrogen-rich air.This nitrogen-rich air is as being removed through the gas that do not see through of discharging from its end of downstream side in the hollow cortina.Supply pressure in the table and supply flow rate represent to be respectively the supply pressure and the flow of the air of mist; Goods concentration and flow of articles scale show respectively nitrogen concentration and the flow as the nitrogen-rich air that sees through the goods that gas obtains, and the rate of recovery is illustrated in the mist of supply and does not see through the ratio ((goods flow/supply flow rate) * 100) that gas obtains as goods.
[table 4]
Figure BDA0000105556110000761
As shown in table 4, with regard to identical supply flow rate FF (with reference to main body 1,2), the situation that is wound with the main body 2 of film structural component can improve goods concentration XR.On the other hand, with regard to identical goods concentration XR (with reference to main body 1,3), the situation that is wound with the main body 3 of film structural component can improve the goods flow FR and the rate of recovery.That is, can know that the coiling film structural component is effective to the efficient activity that gas separates by these results.

Claims (5)

1. a method of using the air separation membrane module by air manufacturing nitrogen-rich air is characterized in that,
Air more than 150 ℃ is offered the air separation membrane module.
2. the method for claim 1 is characterized in that,
Said air separation membrane module when bringing into use, 175 ℃ oxygen transmission rates (P ' O2) be 20 * 10 -5Cm 3(STP)/cm 2More than the seccmHg, and 175 ℃ oxygen transmission rates and the ratio of nitrogen transmission rates (P ' O2/ P ' N2) be more than 1.8, and
P ' when having used 140 hours for 175 ℃ O2And P ' O2/ P ' N2Keep the said preceding P ' that brings into use O2And P ' O2/ P ' N2Separately more than 90%.
3. the method for claim 1 is characterized in that,
Air separation membrane in the said air separation membrane module is by forming at the material that does not show glass transition temperature below 225 ℃.
4. the method for claim 1 is characterized in that,
Said air separation membrane shows the shape conservation rate more than 95% when having placed 2 hours for 175 ℃.
5. the explosion-proof method of an airborne vehicle is characterized in that,
Utilize the described manufacturing approach of claim 1 to make nitrogen-rich air, offer airborne vehicle and use tanks.
CN201110345156.XA 2010-11-04 2011-11-04 Gas separation membrane module and gas separating method Active CN102527241B (en)

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
JP2010247931A JP6067205B2 (en) 2010-11-04 2010-11-04 Method for producing nitrogen-enriched air from hot gas
JP2010-247779 2010-11-04
JP2010-247931 2010-11-04
JP2010247779 2010-11-04
JP2010274619A JP5740952B2 (en) 2010-11-04 2010-12-09 Separation membrane module
JP2010-274619 2010-12-09
JP2011-122285 2011-05-31
JP2011122285 2011-05-31
JP2011-207538 2011-09-22
JP2011-207647 2011-09-22
JP2011207538A JP5825007B2 (en) 2011-09-22 2011-09-22 Gas separation membrane module
JP2011207647A JP5825008B2 (en) 2011-09-22 2011-09-22 Gas separation membrane module
JP2011-227101 2011-10-14
JP2011227101A JP5825032B2 (en) 2011-10-14 2011-10-14 Gas separation membrane module
JP2011-239388 2011-10-31
JP2011239388A JP5794110B2 (en) 2011-10-31 2011-10-31 Gas separation membrane module

Publications (2)

Publication Number Publication Date
CN102527241A true CN102527241A (en) 2012-07-04
CN102527241B CN102527241B (en) 2015-11-04

Family

ID=46336000

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110345156.XA Active CN102527241B (en) 2010-11-04 2011-11-04 Gas separation membrane module and gas separating method

Country Status (1)

Country Link
CN (1) CN102527241B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104703674A (en) * 2012-08-10 2015-06-10 宇部兴产株式会社 Gas-separating membrane module
CN105636670A (en) * 2013-10-09 2016-06-01 乔治洛德方法研究和开发液化空气有限公司 Air-separation device, inerting device and aircraft comprising such a device
CN106132522A (en) * 2014-03-27 2016-11-16 宇部兴产株式会社 Asymmetric gas separation membrane and the method for separation and recovery gas
CN113813800A (en) * 2021-10-19 2021-12-21 中国科学院山西煤炭化学研究所 Preparation of polyimide membrane containing chlorine polar group and gas separation application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5051114A (en) * 1989-06-15 1991-09-24 Du Pont Canada Inc. Perfluorodioxole membranes
US6491739B1 (en) * 1999-11-09 2002-12-10 Litton Systems, Inc. Air separation module using a fast start valve for fast warm up of a permeable membrane air separation module
CN101450792A (en) * 2007-12-06 2009-06-10 中国科学院大连化学物理研究所 Method for preparing oxygen and nitrogen by air separation
WO2010038810A1 (en) * 2008-09-30 2010-04-08 宇部興産株式会社 Asymmetric gas separation membrane, and gas separation method
US20100155046A1 (en) * 2008-12-18 2010-06-24 Eric Surawski Temperature control system for an on board inert gas generation systems

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5051114A (en) * 1989-06-15 1991-09-24 Du Pont Canada Inc. Perfluorodioxole membranes
US5051114B1 (en) * 1989-06-15 1995-05-02 Du Pont Canada Perfluorodioxole membranes.
US5051114B2 (en) * 1989-06-15 1996-01-16 Du Pont Canada Perfluorodioxole membranes
US6491739B1 (en) * 1999-11-09 2002-12-10 Litton Systems, Inc. Air separation module using a fast start valve for fast warm up of a permeable membrane air separation module
CN101450792A (en) * 2007-12-06 2009-06-10 中国科学院大连化学物理研究所 Method for preparing oxygen and nitrogen by air separation
WO2010038810A1 (en) * 2008-09-30 2010-04-08 宇部興産株式会社 Asymmetric gas separation membrane, and gas separation method
US20100155046A1 (en) * 2008-12-18 2010-06-24 Eric Surawski Temperature control system for an on board inert gas generation systems

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104703674A (en) * 2012-08-10 2015-06-10 宇部兴产株式会社 Gas-separating membrane module
CN104703674B (en) * 2012-08-10 2017-08-15 宇部兴产株式会社 Gas separation membrane module
CN105636670A (en) * 2013-10-09 2016-06-01 乔治洛德方法研究和开发液化空气有限公司 Air-separation device, inerting device and aircraft comprising such a device
CN106132522A (en) * 2014-03-27 2016-11-16 宇部兴产株式会社 Asymmetric gas separation membrane and the method for separation and recovery gas
CN113813800A (en) * 2021-10-19 2021-12-21 中国科学院山西煤炭化学研究所 Preparation of polyimide membrane containing chlorine polar group and gas separation application thereof

Also Published As

Publication number Publication date
CN102527241B (en) 2015-11-04

Similar Documents

Publication Publication Date Title
US10369515B2 (en) Gas separation membrane module and method for gas separation
EP0623072B1 (en) Method of forming tube sheet for hollow fibers
CN102527241A (en) Gas separation membrane assembly and gas separation method
RU2715650C2 (en) Flexibly adaptable membrane cartridges for the separation of fluids
CN1059106A (en) The hollow fiber membrane fluid separator(-ter) that contains a plurality of coaxial layers that is fit to the charging of thorax wall
CN104703674B (en) Gas separation membrane module
JP2009082842A (en) Hollow fiber element for organic vapor separation
JP2002543959A (en) Hollow fiber membrane device and assembly method
CN104772041A (en) Hollow fiber membrane module and filtering method
US20180169584A1 (en) Hollow fibre membrane cartridge and module for the separation of fluids
Wang et al. Exploring the spinning and operations of multibore hollow fiber membranes for vacuum membrane distillation
JP6094678B2 (en) Potting material for membrane module and hollow fiber membrane module using the same
JP4963695B2 (en) Hollow fiber element for organic vapor separation
JPS6274434A (en) Yarn bundle element for separating gas
US20190184341A1 (en) Method for preparation of hollow fiber membrane devices and the use thereof
US4842910A (en) Assembly of water wet hollow fibers and a tubesheet derived from a diglycidyl ether of a dihydroxy benzene
JP5794110B2 (en) Gas separation membrane module
JPH01289884A (en) Adhesive for binding hollow fiber
JPH02218714A (en) Sealing medium for separation membrane
JPH0557152A (en) Membrane separation module and production thereof
JP6035859B2 (en) Hollow fiber element for organic vapor separation
CN104741008A (en) Desulfuration film and application thereof in natural gas or petrochemical engineering gas purification
JPS61220711A (en) Bonding method for bundled hollow yarn at end part
JPH01171604A (en) Semipermeable membrane and its production
JP5825008B2 (en) Gas separation membrane module

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: Yamaguchi Prefecture, Japan

Patentee after: Ube Co.,Ltd.

Address before: Yamaguchi Japan

Patentee before: UBE INDUSTRIES, Ltd.