CN102527241B - Gas separation membrane module and gas separating method - Google Patents

Gas separation membrane module and gas separating method Download PDF

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Publication number
CN102527241B
CN102527241B CN201110345156.XA CN201110345156A CN102527241B CN 102527241 B CN102527241 B CN 102527241B CN 201110345156 A CN201110345156 A CN 201110345156A CN 102527241 B CN102527241 B CN 102527241B
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China
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gas
tube sheet
mentioned
hollow
separation membrane
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CN201110345156.XA
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CN102527241A (en
Inventor
金筑丰
福田叙彦
谷原望
中村智英
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Ube Corp
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Ube Industries Ltd
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Priority claimed from JP2010247931A external-priority patent/JP6067205B2/en
Priority claimed from JP2010274619A external-priority patent/JP5740952B2/en
Priority claimed from JP2011207647A external-priority patent/JP5825008B2/en
Priority claimed from JP2011207538A external-priority patent/JP5825007B2/en
Priority claimed from JP2011227101A external-priority patent/JP5825032B2/en
Priority claimed from JP2011239388A external-priority patent/JP5794110B2/en
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Publication of CN102527241A publication Critical patent/CN102527241A/en
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Abstract

The invention provides a kind of high temperature air by more than 150 DEG C and be supplied to air separation membrane module to manufacture the method for nitrogen-rich air.

Description

Gas separation membrane module and gas separating method
Technical field
The present application relates to gas separation membrane module and the gas separating method that many hollow cortina that a kind of utilization has a selective penetrated property carries out gas separaion.
Background technology
As the separating film module using the diffusion barrier with selective penetrated property to carry out gas separaion (such as oxygen separating, nitrogen separation, hydrogen separation, steam separation, carbon dioxide separation, organic vapor separation etc.), there are template and frame-type, cast, hollow fiber type etc.Wherein, the gas separation membrane module of hollow fiber type not only has the maximum advantage of the membrane area of per unit volume, and also excellent in resistance to pressure, self-supporting, therefore, is industrially favourable, can uses by wide region.
Summary of the invention
The present application is described in detail in following part A ~ G, also comprises the invention that combination has invention illustrated in two or more each several part.About the background technology involved by the invention disclosed in various piece and problem etc., be described in each several part.
Accompanying drawing explanation
Fig. 1 represents the embodiment 1 of part A and the measurement result of comparative example 2;
Fig. 2 represents the embodiment 1 of part A and the measurement result of embodiment 2;
Fig. 3 is the sketch of the example representing gas separation membrane module;
Fig. 4 is the sketch of the preparation method representing the separatory tube sheet of mist;
Fig. 5 is the sectional view of the basic comprising of the separating film module of the 1st embodiment schematically showing part C;
In Fig. 6, Fig. 6 (a) represents an example of the structure of assembly end, and Fig. 6 (b) represents the structure of existing type;
Fig. 7 is the figure of other structure representing tube sheet periphery;
Fig. 8 represents an example of the structure of the assembly end of the 2nd embodiment of part C, and Fig. 8 (a) represents state during normal temperature, and Fig. 8 (b) represents state during high temperature;
Fig. 9 represents an example of the structure of the assembly end of the 3rd embodiment of part C;
Figure 10 is the figure of the example representing other embodiment;
In Figure 11, Figure 11 (a) is the sectional view of other example another representing separating film module, and Figure 11 (b) is the figure after a part of Figure 11 (a) being amplified;
Figure 12 is the figure of an example of the configuration representing O ring;
Figure 13 is the sectional view of the gas separation membrane module that a mode of part D relates to;
Figure 14 is the sectional view of the cylindrical member of the assembly of Figure 13;
Figure 15 is front elevation and the side cross-sectional views of the cap component of the assembly of Figure 13, and Figure 15 (A) is the sectional view of the X-X line along Figure 15 (B);
Figure 16 is the schematic diagram of the cap component of example for representing the radical changing fixed bar;
Figure 17 is the sectional view of the basic comprising of the gas separation membrane module that the mode schematically showing part E relates to;
Figure 18 is the magnified partial view of Figure 17;
Figure 19 is the sectional view of an example of the casing represented in the assembly of Figure 17;
Figure 20 is the sectional view of the basic comprising of the gas separation membrane module of the embodiment schematically showing part F;
Figure 21 (A) is the magnified partial view of Figure 20, and (B) is the enlarged drawing representing its part further;
Figure 22 (A) is the sectional view of the gas separation membrane module representing other embodiment, and (B) is magnified partial view;
Figure 23 is the sectional view of the gas separation membrane module representing other embodiment further;
Figure 24 is the sectional view of the gas separation membrane module representing other embodiment;
Figure 25 is the sectional view of the basic comprising of the gas separation membrane module of the embodiment schematically showing part G.
Figure 26 is a part of enlarged drawing of Figure 25.
Figure 27 is the sectional view in the A-A of Figure 26.
Symbol description
1,1 ', 101 separating film modules
10,110,110 ' cylindrical container
10a container inner peripheral surface
10f flange part
10h opening portion
10s stage portion
10t stage portion
110g groove
111 tubing
112 end members
12,112h is through gas discharge outlet
112f flange part
14 hollow cortinas
15,115 hollow tow
17 annular seal components
18,118,119 O rings
20,21,26,27,120,121,127 caps
20h opening portion
120f flange part
120s stage portion
22A mist introducing port
22B is non-through gas discharge outlet
27f flange part
127f flange part
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 module
210 boxes
211 cylindrical containers
212 opening portions
214 hollow cortinas
215 hollow tow
217,218 internal circle grooves
219 circumferential groove
220,221 cap components
220A end face
220B cylindrical portion
220f par
220g par
220h through hole
223 outlets
227a, 227b internal circle groove
230,231 tube sheets
R1, R2 elastic ring component
245 fixed bars
246 nuts
P1 gas introduction port
P2 is non-through gas discharge outlet
P3 gas flow path
601 gas separation membrane module
610 casings
610a mist entrance
610b is not through gas vent
610c is through gas vent
611 cylindrical members
612,613 caps
614 hollow cortinas
615 hollow tow
618 seal cavities
619a mist space
619b is not through the gas compartment
621,622 tube sheets
631 film structural components
631a, 631b end
801 gas separation membrane module
810,910 casings
810a, 910a mist entrance
810b, 910b be not through gas vent
810c, 910c are through gas vent
910d Purge gas entrance
811 cylindrical members
813 tube sheet retaining members
813a line part
813b large-diameter portion
813c tapered portion
814,914 hollow cortinas
815,915 hollow tow
818,918 seal cavities
819a mist space
819b is not through the gas compartment
821,822,921,922 tube sheets
The hollow cortina embedded portion of 822a
822b tube sheet is without 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
971a hole
A1 exposed portion
A31 clearance portion
1001 gas separation membrane module
1010 casings
1010a mist entrance
1010b is not through gas vent
1010c is through gas vent
1011 cylindrical structural members
1011a, 1011b heavy section
1011d recess
1012 cap components
1014 hollow cortinas
1015 hollow tow
1018 seal cavities
1019a mist space
1019b is not through the gas compartment
1021,1022 tube sheets
1021s rank portion
1060 containment members
The groove of C1 ring-type
B11 mist entrance
B12 is through gas discharge outlet
B13 is non-through gas discharge outlet
The hollow cortina of B14
B15 casing
B16a, 16b tube sheet
B21 mould
B22 casing
B23 tube sheet
The hollow cortina of B24
Detailed description of the invention
Below, about embodiments of the present invention, part A ~ part G is described.
[part A: the method being manufactured nitrogen-rich air by high-temperature gas]
(background technology)
For airborne vehicle, as one of the explosion-proof method of fuel tank, there is the method using mounting type inert gas generating system (OBIGGS:on board inert gas generating system).In order to prevent the danger of exploding, the oxygen concentration of the vapor phase areas in fuel tank needs the concentration lower than regulation.Therefore, OBIGGS separated oxygen and manufacture the high nitrogen-rich air of nitrogen concentration from air, provides it to fuel tank.
OBIGGS such as utilizes air separation membrane module to manufacture nitrogen-rich air.About air separation membrane, the gas usually owing to being supplied to gets over high pressure, high temperature, and treating capacity more increases, and therefore, the extraction gas of engine or ambient air etc. are provided to air separation membrane module with after the compressions such as compressor reducer.Gas after this compression is generally 149 ~ 260 DEG C.
Existing air separation membrane module effectively works at about 82 DEG C ~ about 93 DEG C, and under high temperature as above, separating property significantly reduces, and therefore cannot use.Therefore, typically, by using heat exchanger or mixing with the air of low temperature, after the gas after compression is cooled to this temperature, air separation membrane module (Japanese Unexamined Patent Publication 2010-142801 publication) is supplied to.
(problem that the invention of part A will solve)
The object of the invention of part A is, provides a kind of high temperature compressed air by more than 150 DEG C to be supplied to air separation membrane module to manufacture the method for nitrogen-rich air.
Main inventive main points disclosed in this part are as described below.
1, use air separation membrane module to make a method for nitrogen-rich air by air-making, it is characterized in that,
The air of more than 150 DEG C is supplied to air separation membrane module.
(effect of the invention of part A)
According to the method for the invention of part A, air more than high temperature, such as 150 DEG C can be supplied to air separation membrane module, be improved the nitrogen-rich air of nitrogen concentration.The feature of the invention of this part is to use air separation membrane, above-mentioned air separation membrane at high temperature the transmission rates of oxygen and the separating property of oxygen and nitrogen high, and then, even if at high temperature long-time use also can maintain its performance.The example of this part is as be suitable for the explosion protection system of the fuel tank of airborne vehicle.When using the invention of this part in this explosion protection system, when air being supplied to air separation membrane module, the heat exchanger etc. for cooling down high-temperature air can lightweight.In addition, for air separation membrane, the air be supplied to gets over high temperature, and transmission rates is faster, therefore, according to the method for invention of this part that can process high temperature air, also effectively can reduce membrane area.Therefore, simplification, the lightweight of the equipment in airborne vehicle can be carried out.
(embodiment in part A)
Invention disclosed in this part is that a kind of air separation membrane module that uses generates the method for nitrogen-rich air by air, it is characterized in that, the high temperature air of more than 150 DEG C is supplied to air separation membrane module.In this part, unless otherwise specified, " high temperature " refers to more than 150 DEG C, preferably more than 175 DEG C, more preferably more than 200 DEG C.
Air separation membrane module such as can obtain as follows: the hollow cortina of harness suitable length about 100 ~ 1000000, at least one end of air silk is made to be the state maintaining open state, with the both ends of this hollow tow of tube sheet set be made up of thermosetting resin etc., at least possessing air supply port, through gas discharge outlet and non-through in the container of gas discharge outlet, receive and the air silk membrane component be made up of the hollow tow of gained and tube sheet etc. is installed and completely cut off with the space led to outside hollow cortina to make the space passed into inside hollow cortina, obtain therefrom.In such air separation membrane module, from air supply port to the space air supply connected with the inner side or outside of hollow cortina, at the oxygen selective also between flow periods in air that connects with hollow cortina through film, discharge from through gas discharge outlet through gas (oxygen-enriched air), do not discharge through gas discharge outlet from non-through gas (nitrogen-rich air) through the non-of film, carry out gas separaion thus.
As air separation membrane, be not particularly limited, such as, can enumerate the asymmetric air separation membrane with the unsymmetric structure be made up of the thicker porous layer (preferred thickness is 10 ~ 2000 μm) of the very thin compacted zone (preferred thickness is 0.001 ~ 5 μm) and this compacted zone of support of mainly undertaking air separation performance.Preferred internal diameter is 10 ~ 3000 μm and external diameter is the hollow cortina of about 30 ~ 7000 μm.
Air separation membrane preferably at high temperature has characteristic as described below.
Preferably at high temperature the transmission rates of oxygen is high for air separation membrane.Such as, 175 DEG C oxygen transmission rates (P ' o2) be 20 × 10 -5cm 3(STP)/cm 2more than seccmHg, is preferably 25 × 10 -5cm 3(STP)/cm 2more than seccmHg, is more preferably 30 × 10 -5cm 3(STP)/cm 2more than seccmHg.And then, even if air separation membrane preferably at high temperature separating property is also high, such as, at 175 DEG C, the ratio of the Oxygen Transmission Rate of the separating property of display film and nitrogen transmission rates (P ' o2/ P ' n2) be more than 1.8, be preferably more than 2.0, be more preferably more than 2.5.It should be noted that, the ratio of transmission rates is larger value usually at low temperatures.When transmission rates ratio and separating property height, the rate of recovery of target nitrogen-rich air raises.
In addition, even if air separation membrane preferably at high temperature uses for a long time, the transmission rates of oxygen and the separating property of film also do not reduce greatly.Such as, employ 140 constantly little at 175 DEG C, oxygen transmission rates (P ' o2) and the transmission rates of oxygen and the transmission rates of nitrogen ratio (P ' o2/ P ' n2) be preferably the P ' before using o2and P ' o2/ P ' n2respective more than 75%, be more preferably more than 80%, more preferably more than 90%.
And then, even if air separation membrane preferably also keeps shape at high operating temperatures in the degree not damaging its function.Such as, form the glass transition temperature (Tg) of the material of air separation membrane preferably higher than 225 DEG C (namely not showing below 225 DEG C), be more preferably more than 250 DEG C, more preferably more than 300 DEG C (comprising the unmeasured situation of glass transition temperature).And then, preferably at high temperature keep shape for a long time, placed 2 little form trait rates constantly at 175 DEG C and be preferably more than 95%, be more preferably more than 99%.At this, in this part, so-called form trait rate, represents that the length being used in the silk of 175 DEG C of heat treatments after 2 hours is divided by the ratio of the original length before heat treatment.
As glass transition temperature preferred material higher than 225 DEG C and in diffusion barrier, polyimides, polyether sulfone, polyamide, polyether-ether-ketone etc. can be enumerated, particularly preferably enumerate polyimides.
As the material forming the hollow cortina of asymmetric gas separaion (hereinafter also referred to as hollow cortina), be not particularly limited, to being preferably used as air separation membrane and glass transition temperature is described higher than the example of the composition of the polyimides of 225 DEG C.The polyimides below formed is the aromatic polyimide shown in the repetitive of following general formula (1), glass transition temperature is generally more than 250 DEG C, is preferably more than 300 DEG C (comprising the unmeasured situation of glass transition temperature).
[changing 1]
general formula (1)
In above-mentioned formula, B results from 4 valency unit of tetrabasic carboxylic acid composition, and A results from the divalent unit of diamine component.Below, the unit forming aromatic polyimide is described in detail.
Unit B is for resulting from tetrabasic carboxylic acid composition 4 valency unit, comprise 10 ~ 70 % by mole, the unit B 2 with biphenyl structural shown in following general formula (B2) of the preferably unit B 1 with diphenyl HFC-236fa structure shown in following general formula (B1) of 20 ~ 60 % by mole and 90 ~ 30 % by mole, preferably 80 ~ 40 % by mole, preferably there is in fact unit B 1 and unit B 2.Diphenyl HFC-236fa structure lower than 10 % by mole and biphenyl structural more than 90 % by mole time, the gas separating property of the polyimides of gained reduces, and is difficult to obtain high performance gas diffusion barrier.On the other hand, diphenyl HFC-236fa structure more than 70 % by mole and biphenyl structural lower than 30 % by mole time, sometimes the polyimides of gained mechanical strength reduce.
In addition, unit B also can contain the 4 valency unit based on phenyl structure shown in following formula (B3).The 4 valency unit based on phenyl structure shown in formula (B3) are 0 ~ 30 % by mole, are preferably 10 ~ 20 % by mole.
And then unit B can contain the 4 valency unit B 4 resulting from other tetrabasic carboxylic acid beyond unit B 1, B2, B3.
[changing 2]
Unit A results from the divalent unit of diamine component, comprises the unit A1 selected from the group be made up of following general formula (A1a), (A1b) and (A1c) and the unit A2 selected from the group be made up of following general formula (A2a) and (A2b).And then unit A can containing the divalent unit A3 resulting from other diamine component beyond unit A1, A2.
Unit A1a is the divalent unit based on biphenyl structural shown in formula (A1a), unit A1b and A1c contains formula (A1b) and the hexafluoro shown in formula (A1c) replaces structure, more specifically, there is the construction unit containing 2 trifluoromethyls.
[changing 3]
(in formula, X is chlorine atom or bromine atoms, and n is 1 ~ 3.)
[changing 4]
(in formula, r is 0 or 1, and benzyl ring can be replaced by OH base.)
[changing 5]
(in formula, Y represents O or singly-bound.)
When unit A1 has the unit shown in formula (A1a), in unit A, be 30 ~ 70 % by mole, be preferably 30 ~ 60 % by mole.This diphenyl amine contributes to improving separating degree, but when its amount is too much, polymer becomes insoluble and is difficult to masking, and when it is very few, separating degree reduces, therefore not preferred.
When unit A1 has formula (A1b) and/or the unit shown in formula (A1c), these unit are contained 10 ~ 50 % by mole, preferably 20 ~ 40 % by mole in unit A.
Unit A2 is selected from by sulfur heterocyclic ring structure, specifically, is selected from the group be made up of the unit class shown in following general formula (A2a) and (A2b).
[changing 6]
(in formula, R and R ' is hydrogen atom or organic group, and n is 0,1 or 2.)
[changing 7]
(in formula, R and R ' for hydrogen atom or organic group, X be-CH 2-or-CO-.)
Unit A2 in unit A by containing 90 ~ 30 % by mole, preferably 90 ~ 40 % by mole, more preferably 90 ~ 50 % by mole, preferably 80 ~ 60 % by mole further.
Unit A3 in unit A with below less than 50 % by mole, preferably 40 % by mole, more preferably the amount of less than 20 % by mole contain.
Below, the monomer component of the above-mentioned each unit forming aromatic polyimide is described.
The unit with diphenyl HFC-236fa structure shown in above-mentioned general formula (B1), becomes to assign to obtain as tetrabasic carboxylic acid by use (hexafluoroisopropylidenyl) two phthalic acid, its dicarboxylic anhydride or its carboxylate.As above-mentioned (hexafluoroisopropylidenyl) two O-phthalic acids, suitably can use 4,4 '-(hexafluoroisopropylidenyl) two phthalic acid, 3,3 '-(hexafluoroisopropylidenyl) two phthalic acid, 3,4 '-(hexafluoroisopropylidenyl) two phthalic acid, their dicarboxylic anhydride or their carboxylate, but particularly preferably 4,4 '-(hexafluoroisopropylidenyl) two phthalic acid, its dicarboxylic anhydride or its carboxylate.
The unit with biphenyl structural shown in above-mentioned general formula (B2), becomes to assign to obtain as tetrabasic carboxylic acid by using the biphenyltetracarboxyacid acid classes such as biphenyltetracarboxyacid acid, its dicarboxylic anhydride or its carboxylate.As above-mentioned biphenyltetracarboxyacid acid class, suitably 3 can be used, 3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid, their dicarboxylic anhydride or their carboxylate, but particularly preferably 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, its dicarboxylic anhydride or its carboxylate.
The 4 valency unit based on phenyl structure shown in above-mentioned general formula (B3), obtain by using the PMA such as PMA and acid anhydrides thereof class.This PMA class is preferred in raising engineering properties, but when its amount is too much, causes polymer solution during masking to solidify, and becomes unstable, is difficult to form air silk.
Other tetrabasic carboxylic acid composition of providing unit B4, be above-mentioned shown in compound beyond tetracarboxylic acid acids, select not damage this part invention effect and can the compound of according to circumstances further improved performance.Such as 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 above-mentioned general formula (A1a), obtains as diamine component by using the halogen substiuted diphenyl amine shown in general formula (A1a-M).
[changing 8]
(in formula, X is chlorine atom or bromine atoms, n=1 ~ 3.)
As halogen substiuted diphenyl amine, can enumerate: dichloro-benzidine (diamino dichloro biphenyl) class, tetrachloro benzidine (diaminourea tetrachloro biphenyl) class, chlordene diphenyl amine, tetrabromo diphenyl amine, '-dibromobiphenyl amine, hexabromobiphenyl amine etc.As above-mentioned DCBP amine, can 3 be enumerated, 3 '-dichloro-benzidine (DCB), as tetrachloro biphenyl amine, can 2 be enumerated, 2 ', 5,5 '-tetrachloro benzidine (TCB) etc.
Divalent unit shown in general formula (A1b), obtains as diamine component by using the hexafluoro substituted compound class shown in general formula (A1b-M).
[changing 9]
(in formula, r is 0 or 1, and benzyl ring can be replaced by OH base.)
(A1b-M) preferred compound of the hexafluoro substituted compound class shown in, is represented by general formula (A1b-M1) ~ (A1b-M3).
[changing 10]
As two [(amino-benzene oxygen) phenyl] the HFC-236fa classes shown in general formula (A1b-M1), such as can enumerate: 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2,2-two [4-(3-amino-benzene oxygen) phenyl] HFC-236fas.As two (aminophenyl) HFC-236fa classes shown in general formula (A1b-M2), such as, can enumerate two (4-aminophenyl) HFC-236fa of 2,2-.Replace two (aminophenyl) HFC-236fa class as the hydroxyl shown in general formula (A1b-M3), such as, can enumerate two (3-amino-4-hydroxy) HFC-236fa of 2,2-.
In addition, the divalent unit shown in general formula (A1c), obtains as diamine component by using the hexafluoro substituted compound class shown in general formula (A1c-M).
[changing 11]
(in formula, Y represents O or singly-bound.)
As the diamine compound class shown in general formula (A1c-M), such as, can enumerate: 2,2 '-bis-(trifluoromethyl)-4,4 '-diamino-diphenyl ether, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine etc.
In addition, there is the unit of above-mentioned general formula (A2a) or the structure shown in above-mentioned general formula (A2b), obtaining as diamine component by using the aromatic diamine shown in following general formula (A2a-M) and general formula (A2b-M) respectively.
[changing 12]
(in formula, R and R ' is hydrogen atom or organic group, and n is 0,1 or 2.)
[changing 13]
(in formula, R and R ' for hydrogen atom or organic group, X be-CH 2-or-CO-.)
As the aromatic diamine shown in above-mentioned general formula (A2a-M), the diaminourea dibenzothiophenes class shown in following general formula (A2a-M1) that the n that suitably can enumerate general formula (A2a-M) is 0 or diaminourea dibenzothiophenes=5 shown in following general formula (A2a-M2) that the n of general formula (A2a-M) is 2,5-dioxide class.
[changing 14]
(in formula, R and R ' is hydrogen atom or organic group.)
[changing 15]
(in formula, R and R ' is hydrogen atom or organic group.)
As above-mentioned diaminourea dibenzothiophenes class (general formula (A2a-M1)), can enumerate such as: 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)), can enumerate such as: 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-diones, such as 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 diaminourea thioxanthene-9,10, the 10-three ketones that X is-CO-, such as, can enumerate: 3,6-diaminourea-thioxanthene-9,10,10-triketone, 2,7-diaminourea-thioxanthene-9,10,10-triketone etc.
Other diamine component of providing unit A3, be above-mentioned shown in compound beyond diamine compound, select not damage the invention of this part effect and can the compound of according to circumstances further improved performance.
Such as can enumerate: 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 4, the diamino diphenyl sulfone classes such as 4 '-diaminourea-3,3 '-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, the diamino-diphenyl ethers such as 3 '-diethoxy-4,4 '-diamino-diphenyl ether;
4,4 '-diaminodiphenyl-methane, 3, the diaminodiphenyl-methane classes such as 3 '-diaminodiphenyl-methane;
2,2-two (aminophenyl) propane classes such as two (3-aminophenyl) propane of 2,2-, 2,2-two (4-aminophenyl) propane;
2,2-two (aminophenoxy phenyl) propane classes such as two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, 2,2-two [4-(3-amino-benzene oxygen) phenyl] propane;
4,4 '-diaminobenzophenone, 3, the diaminobenzophenone classes such as 3 '-diaminobenzophenone;
The diaminobenzoic acid classes such as 3,5-diaminobenzoic acid;
The phenylenediamines such as 1,3-phenylenediamine, Isosorbide-5-Nitrae-phenylenediamine;
2,2 '-two chloro-4, the dichloro diamino-diphenyl ethers such as 4 '-diamino-diphenyl ether;
The ditolyl amines such as o-tolidine, a tolidine;
2, the dihydroxy benzidine classes etc. such as 2 '-dihydroxy-4,4 '-benzidine.
Wherein, diamino diphenyl sulfone class, diamino-diphenyl ethers, diaminobenzoic acid class, dichloro diamino-diphenyl ethers, dihydroxy benzidine class is preferably.
When using the aromatic polyimide shown in repetitive of general formula (1) in asymmetric air separation membrane, such as, above-mentioned tetrabasic carboxylic acid composition preferred compositions is used as 4 of the carboxylic acid of providing unit B1, 4 '-(hexafluoroisopropylidenyl-bis-(phthalic anhydride), as 3 of the carboxylic acid of providing unit B2, 3 ', 4, 4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, as the PMA dicarboxylic anhydride of the carboxylic acid of providing unit B3, above-mentioned diamine component preferred compositions is used as 2 of the diamines of providing unit A1, 2 ', 5, 5 '-tetrachloro benzidine, as 3 of the diamines of providing unit A2, 7-diaminourea-dimethyl Dibenzothiophene=5, 5-dioxide.3,7-diaminourea-dimethyl Dibenzothiophene=5,5-dioxide refers to 3,7-diaminourea-2,8-dimethyl Dibenzothiophene=5,5-dioxide is main component, wraps different isomers 3,7-diaminourea-2,6-dimethyl Dibenzothiophene=5, methylic position, 5-dioxide, 3,7-diaminourea-4,6-dimethyl Dibenzothiophene=5, the mixture of 5-dioxide.
The preparation of above-mentioned aromatic polyimide solution, two-step method or one-step method is preferably utilized to carry out, above-mentioned two-step method adds tetrabasic carboxylic acid composition and diamine component with the ratio of components of regulation in organic polar solvent, under the low temperature of room temperature, carry out polymerisation and generate polyamic acid, then carrying out heating and carrying out adding hot-imide or adding pyridine etc. carrying out chemical imidization; Above-mentioned one-step method adds tetrabasic carboxylic acid composition and diamine component with the ratio of components of regulation in organic polar solvent, under the high temperature about 100 ~ 250 DEG C, preferably 130 ~ 200 DEG C, carry out polymerization imidization reaction.When carrying out imidization reaction by heating, the water that the removing of preferred limit departs from or alcohol limit are carried out.With regard to tetrabasic carboxylic acid composition and diamine component relative to organic polar solvent use amount with regard to, preferably make the concentration of the polyimides in solvent be 5 ~ 50 about % by weight, preferably 5 ~ 40 % by weight.
Carry out being polymerized imidizate and the aromatic polyimide solution that obtains, also can be directly used in spinning.In addition, also the aromatic polyimide solution of gained such as can be dropped in the solvent relative to aromatic polyimide being non-solubility, make aromatic polyimide separate out and be separated after, again organic polar solvent is dissolved in the mode becoming normal concentration, prepare aromatic polyimide solution, use it for spinning.
With regard to the aromatic polyimide solution for spinning, the concentration of polyimides is preferably made to be 5 ~ 40 % by weight, more preferably 8 ~ 25 % by weight, solution viscosity (rotary viscosity) preferably 100 DEG C be 100 ~ 15000 pool, more preferably 200 ~ 10000 pools, are particularly preferably 300 ~ 5000 pools.When solution viscosity is lower than 100 pool, likely obtains homogeneous membrane (film), but be difficult to obtain the large anisotropic membrane of mechanical strength.In addition, during more than 15000 pool, not easily extrude from spinning-nozzle, therefore, be difficult to the asymmetric hollow cortina obtaining target shape.
As above-mentioned organic polar solvent, as long as the solvent that suitably can dissolve the aromatic polyimide of gained does not just limit, but can suitably enumerate such as by phenol, cresols, the phenol of xylenols and so on, phenyl ring directly has the catechol of 2 hydroxyls, the pyrocatechol of resorcinol and so on, 3-chlorophenol, 4-chlorophenol (identical with parachlorophenol described later), 3-bromophenol, 4-bromophenol, the phenol series solvent that the halo phenols such as the chloro-5-hydroxy-methylbenzene of 2-etc. are formed, or by METHYLPYRROLIDONE, 1, 3-dimethyl-2-imidazolinone, N, dinethylformamide, N, N-DEF, N, N-dimethylacetylamide, N, the acid amides series solvent that the amide-types such as N-diethyl acetamide are formed or their mixed solvent etc.
Hollow cortina can by using above-mentioned aromatic polyimide solution etc., utilizing the spinning (dry-and wet-type spin processes) based on dry-and wet-type method suitably to obtain.Dry-and wet-type method is make the evaporation of the solvent on the surface of the polymer solution making air silk shape form thin compacted zone (separating layer), impregnated in solidification liquid (mix with the solvent of polymer solution, polymer is insoluble solvent) further, utilize the phenomenon of phase separation now produced, form minute aperture and method (phase inversion) that porous layer (supporting course) is formed, the method is the method that Loeb etc. proposes (such as No. 3133132, United States Patent (USP)).
Dry-and wet-type spin processes is use spinning nozzle to utilize dry-and wet-type method to form the method for hollow cortina, is recorded in such as Japanese Laid-Open Patent Publication 61-133106 publication or Japanese Unexamined Patent Publication 3-267130 publication etc.
Manufacture method usually comprises spinning process (spinning slurry ejection operation), solidifies operation, matting, drying process and heat treatment step.
First, in spinning process (spinning slurry ejection operation), as long as spinning pulp feed liquid to be extruded into the spinning-nozzle of hollow filamentous by the spinning-nozzle for spraying spinning pulp feed liquid, preferred Guan Kong medium-sized (tube-in-orifice type) nozzle etc.Usually, the temperature range of aromatic polyimide solution when extruding preferably is about 20 DEG C ~ 150 DEG C, is particularly preferably 30 DEG C ~ 120 DEG C.Preferred temperature range is different according to the solvent kind, viscosity etc. of liquid.In addition, while carry out spinning to the inside supply gas of the hollow filamentous extruded from nozzle or liquid limit.
Solidifying in operation from spinning process continuous print, from the hollow filamentous of nozzle ejection be temporarily squeezed in air or the inert gas atmosphere such as nitrogen medium, then import to coagulating bath and impregnated in solidification liquid.Solidification liquid does not preferably dissolve aromatic polyimide composition in fact and has the liquid of intermiscibility with the solvent of aromatic polyimide solution.Be not particularly limited, but preferably use the lower alcohols such as water, methyl alcohol, ethanol, propyl alcohol or acetone, diethyl ketone, methyl ethyl ketone etc. to have ketone of low alkyl group etc. or their mixture.In addition, when the solvent of aromatic polyimide solution is 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 the aliphatic hydrocarbon such as replacement solvent, such as isopentane, n-hexane, isooctane, normal heptane to the solidification liquid in the outside and inner side of replacing air silk and/or cleaning solvent.
In following drying process, the air silk containing replacement solvent is carried out drying at a proper temperature.And, in heat treatment step, preferably heat-treat under lower than the softening point of used aromatic polyimide or the temperature of second order transition point, obtain the hollow cortina of asymmetric gas separaion thus.
(industrial utilizability)
According to the invention of this part, the air of high temperature such as more than 150 DEG C can be supplied to air separation membrane module, be improved the nitrogen-rich air of nitrogen concentration.The method of the invention of this part such as can be applied to the explosion protection system of the fuel tank of airborne vehicle.
(summary of the invention)
The invention relating to part A is as described below.
1. use air separation membrane module to make a method for nitrogen-rich air by air-making, it is characterized in that,
The air of more than 150 DEG C is supplied to air separation membrane module.
2. the method as described in above-mentioned 1, is characterized in that, above-mentioned air separation membrane module when bringing into use, the Oxygen Transmission Rate of 175 DEG C (P ' o2) be 20 × 10 -5cm 3(STP)/cm 2more than seccmHg, and the Oxygen Transmission Rate of 175 DEG C and nitrogen transmission rates ratio (P ' o2/ P ' n2) be more than 1.8, and
140 little P ' are constantly employed at 175 DEG C o2and P ' o2/ P ' n2keep the P ' before above-mentioned bringing into use o2and P ' o2/ P ' n2respective more than 90%.
3. the method as described in above-mentioned 1 or 2, is characterized in that, the air separation membrane in above-mentioned air separation membrane module is formed by the material not showing glass transition temperature below 225 DEG C.
4. the method as described in above-mentioned 1, is characterized in that, above-mentioned air separation membrane placed 2 constantly little at 175 DEG C, the form trait rate of display more than 95%.
5. an explosion-proof method for airborne vehicle, is characterized in that, utilizes the manufacture method according to any one of above-mentioned 1 ~ 4 to manufacture nitrogen-rich air, is supplied to airborne vehicle fuel tank.
[part B: under high temperature, high pressure, there are sufficient heat resistance and resistance to pressure etc. and do not occur the gas separation membrane module in crack]
(technical field)
The invention of this part relates to the separatory gas separation membrane module of a kind of mist, its tube sheet of tow after specific epoxy resin composition set integratedly will be made up of the many hollow cortina with selective penetrated property.
(background technology)
The gas separation membrane module of hollow fiber type, the at least one end of the tow be made up of the many hollow cortina with selective penetrated property is being tied together integratedly by the cured plate (tube sheet) of the resin of casting mold and under the state of set, is being accommodated in and at least there is mist introducing port, assembly through gas discharge outlet and the non-casing through gas discharge outlet.Tube sheet, except having the effect of set tow integratedly, has by between sealing air silk and air silk and carry out the bubble-tight effect of the inner space of isolated hollow cortina and space outerpace, maintenance inner space and space outerpace between air silk and casing.When the gas separation membrane module of hollow fiber type loses the air-tightness that above-mentioned tube sheet causes, do not carry out the separation be applicable to.
In the gas separating method employing diffusion barrier, sometimes complete applicable gas separaion by supply gas mixture under the state of high temperature, high pressure.Now, with regard to tube sheet material, require high heat resistance, resistance to pressure, its glass transition temperature or heat distortion temperature must degree at least more tens of than the operating temperature height of gas separation membrane module.
As for realizing high heat resistance, the tube sheet material of resistance to pressure, generally using thermohardening type resin, but when tube sheet is shaped, in order to make the curing reaction of thermohardening type resin complete, processing at significantly high temperature.This is because when use does not complete the tube sheet of curing reaction, make separating film module at high temperature be cured between on-stream period and react and tube sheet contraction, the sealing property between tube sheet and casing is insufficient.Therefore, tube sheet material is also required to the heat resistance of significantly high temperature when being shaped relative to tube sheet.
As the gas separation membrane module of separation of mist that may be used for high temperature, high pressure, such as, in Japanese Laid-Open Patent Publication 62-74434 publication, record the aqueous polybutadiene making phenol aldehyde type epoxy resin and end have reactive functional groups react and the air silk element made of the modified epoxy obtained.
(problem that the invention of part B will solve)
But there are the following problems for existing tube sheet material: cure shrinkage is large when tube sheet is shaping, produce crack or tube sheet destruction etc.And there are the following problems: when only paying attention to resistance to pressure and heat resistance, the flexibility of tube sheet material is not enough, therefore, such as, when being subject in the running impacting, tube sheet produces crack or tube sheet destruction etc.The object of the invention of this part is, provides a kind of tube sheet of gas separation membrane module, and it keeps sufficient heat resistance and resistance to pressure under high temperature, high pressure, there will not be crack.
Main inventive main points disclosed in this part are as described below.
1. a gas separation membrane module, it has:
The tow be made up of the many hollow cortina with gas separating property,
Have mist entrance, through gas discharge outlet and non-through gas discharge outlet and described hollow tow be configured in inner casing and
The tube sheet of at least one end of fixing described hollow tow,
Wherein, the curable epoxide thing that described tube sheet is solidified into by castable resin composition is formed, and this castable resin composition comprises: (a) novolak type epoxy compound and (b) end had and can react with the hycar of the functional group of epoxy reaction and the modified epoxy that obtains and (c) curing agent.
(the invention effect of part B)
Tube sheet in the gas separation membrane module of the invention of this part, by use end have can with the hycar of the functional group of epoxy reaction and manufacturing, compared with existing tube sheet, there is flexibility.And, when tube sheet is shaped or the running of gas separation membrane module time be exposed to high temperature, high pressure gas time, tube sheet does not produce crack, and the adaptation of air silk or the airtight performance between tube sheet and casing also no problem.
(embodiment in part B)
Form the curable epoxide thing of the tube sheet of the air silk element of this part invention, can obtain by heat-treating castable resin composition and make it solidify, this castable resin composition at least comprises: (a) novolak type epoxy compound and (b) end had and can react with the hycar of the functional group of epoxy reaction and the modified epoxy that obtains and (c) curing agent.Below, be described in detail.
< modified epoxy >
Modified epoxy can make novolak type epoxy compound { following, sometimes be also recited as epoxide (a) } and end have and can obtain with the hycar of the functional group of epoxy reaction { following, also sometimes be recited as compound (b) } reaction.
For the compound that the novolak type epoxy compound (a) of the invention of this part represents for following general formula (a).
[changing 16]
(in formula, R " represent alkyl or the hydrogen atom of carbon number 1 ~ 3, n represents the integer of 0 ~ 500, preferably 0 ~ 20.)
In formula (a), R " be preferably methyl or hydrogen atom.With regard to the epoxide (a) that above-mentioned general formula (a) represents, molecular weight is preferably 300 ~ 2000, and in addition, epoxide equivalent is preferably 150 ~ 250.As epoxide (a), can enumerate: jER152, jER154 that Mitsubishi Chemical's (strain) makes; EPICLON-N740, N-770, N-775 etc. that DIC (strain) makes; YDPN-638, YDCN-700 series etc. that Dongdu changes into (strain) makes; The D.E.N.438 etc. of Dow Chemical.
Having at the end of the invention for this part can with the hycar of the functional group of epoxy reaction { compound (b) }, as can with the functional group of epoxy reaction, such as carboxyl, amino, hydroxyl etc. can be enumerated, particularly preferably carboxyl.By 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) that such as preferred following general formula (b) represents.
[changing 17]
In formula (b), m represents the total of the repeat number of butadiene monomer unit, n represents the total of the repeat number of acrylonitrile monomer unit, when structure in [] exists more than 2, m, n represent the summation of the repeat number of respective unit, no matter exist as block, or with random existence, which can.
The molecular weight of the CTBN that above-mentioned general formula (b) represents preferably 2000 ~ 4000, such as, in CTBN, preferably containing 5 ~ 50 % by weight acrylonitrile monomer unit.As commercially available product, such as Emerald functional material Hypro can be enumerated tMcTBN1300 × 8, CTBN1300 × 13, CTBN1300 × 31 etc.
About modified epoxy, by relative epoxide (a) 100 weight portion, with preferred 5 ~ 50 weight portions, further preferably 5 ~ 20 weight portions mode mixing cpd (b) and make it react to obtain.When using the content of each compound to be the modified epoxy in above-mentioned scope, the tube sheet formed does not produce crack under high temperature, high pressure, in addition, does not also produce glass transition temperature and greatly reduces and the problem of being out of shape.In addition, only otherwise the goal of the invention of infringement this part, also other compound can be mixed.Reaction condition when preparing this modified epoxy is not particularly limited, but reaction temperature is preferably 100 ~ 200 DEG C, and the reaction time is preferably 2 ~ 5 hours.
< curing agent >
For the curing agent of the invention of this part, as long as the thermal curing agents of epoxy resin, be just not particularly limited, amine, phenols, acid anhydrides etc. can be enumerated, more preferably use acid anhydrides.As acid anhydrides, can enumerate such as: phthalic anhydride, pyromellitic acid anhydride, methyl-5-ENB-2,3-dicarboxylic anhydride (methylnadic anhydride), benzophenone tetracarboxylic dianhydride etc., particularly preferably methyl-5-ENB-2,3-dicarboxylic anhydride.
< curing accelerator >
For the castable resin composition of the invention of this part, curing accelerator can be contained as required, as curing accelerator, such as imidazolium compounds can be enumerated.As imidazolium compounds, can enumerate such as: glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole etc., particularly preferably 2-ethyl-4-methylimidazole.
< curable epoxide thing >
Form the curable epoxide thing of the tube sheet of the invention of this part, can by the castable resin composition (following, to be sometimes also recited as castable resin composition) being mixed with above-mentioned modified epoxy, curing agent and curing accelerator be as required heat-treated and is made it solidify to obtain.The mixed proportion of the modified epoxy in the preparation of castable resin composition and curing agent etc., can according to the functional group number of the epoxy-functional number of modified epoxy and curing agent, simultaneously according to suitably adjustment such as the viscosity of castable resin composition.It should be noted that, relative to modified epoxy 100 weight portion, curing accelerator is preferably 0 ~ 5 weight portion, is more preferably 0.1 ~ 3 weight portion.
With regard to heat treatment, such as preferably castable resin composition is carried out heat and the degree lost of one-step solidification to the mobility of castable resin composition, then, the resin of one-step solidification is at high temperature carried out Post RDBMS further.When carrying out Post RDBMS, the mode that physical property change preferably do not occur with tube sheet material in assembly running by the temperature more than final operating temperature of castable resin composition at assembly, such as preferably 100 DEG C ~ 250 DEG C, more preferably 120 DEG C more than heat treatment 2 ~ 10 hours.In addition, one-step solidification is not particularly limited, such as preferred lower than 100 DEG C, more preferably at 50 ~ 85 DEG C, carry out 2 ~ 24 hours.It should be noted that, when the resin of one-step solidification is heated to Post RDBMS temperature with the programming rate of 5 DEG C/below min, not due to the problem in the inner reaction heat generation thermal runaway produced sharp of castable resin composition, preferably.Carry out aftermentioned to the preparation method of tube sheet.
< gas separation membrane module >
Below, the structure of the gas separation membrane module of the invention of this part is described.
As the gas separation membrane module formed by hollow cortina, there will be a known so-called Bore Feed type and shell feed type.Such as, in the gas separation membrane module of Bore Feed type, as shown in Fig. 3 (A), many (such as hundreds of ~ hundreds thousand of) boundlings of hollow cortina B14 are made hollow tow, this hollow tow is accommodated at least there is mist entrance B11, through gas discharge outlet B12 and non-through in the casing B15 of gas discharge outlet B13, casing B15 is bonded in the mode that hollow cortina B14 is open state in two ends of this hollow tow, form tube sheet B16a and B16b, to lead to the non-space through gas discharge outlet B13 (non-through side) from mist entrance B11 supply gas and by the inner side of hollow cortina B14 and the mode of leading to through the space (through side) of gas discharge outlet B12 is isolated from the outside of hollow cortina B14 is formed.The casing B15 materials such as such as stainless steel and other metal materials, plastic material, fibre reinforced plastics material and pottery manufacture.In shell feed type gas separation membrane module, such as, as shown in Fig. 3 (B), tube sheet is formed in an end of hollow tow, lead to from mist entrance B11 supply gas the outside that the non-non-space through side through gas discharge outlet B13 is hollow cortina B14, the space through side led to through gas discharge outlet B12 forms in the inner side of hollow cortina B14.
In Fig. 3 (A) and (B), the hollow cortina B14 of mist in gas separation membrane module supplied from the mist entrance B11 of gas separation membrane module connects and between flow periods, high transmission gas preferentially through hollow cortina B14, be separated into a large amount of gas (through gas) containing high transmission gas and less containing high transmission gas, not through residual gas (non-through gas).Discharge from through gas discharge outlet B12 through gas, non-ly to discharge through gas discharge outlet B13 from non-through gas.From gas separation membrane module discharge non-through gas with through gas, according to purposes, only a side is recovered or both sides are recovered.
As the air silk for gas separation membrane, the thin and many air silks that diameter is little of thickness, even if midget plant is also formed as high membrane area, can improve separative efficiency, and also be preferred at economic aspect.Above-mentioned air silk can be enumerated such as thickness and be 10 ~ 500 μm and external diameter is the air silk of 50 ~ 2000 μm, is not particularly limited.In addition, gas separation membrane can be homogenieity, also can be the inhomogeneities such as composite membrane or anisotropic membrane, can also be micro-porous or imporosity.
Gas separation membrane can enumerate the gas separation membrane formed by ceramic materials such as polymeric material, zeolite etc. such as such as polyimides, PEI, polyamide, polyamidoimide, polysulfones, Merlon, silicone resin, cellulose-based polymer.As the gas separation membrane formed by polyimides, preference 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: arranged in parallel, cross arrangement, textile-like, helical form etc.In addition, hollow tow can have core pipe in substantially central portion, can to reel film at the peripheral part of hollow tow.And the form of hollow tow can be cylindric, tabular, corner post shape etc., can directly with above-mentioned form or bend to U-shaped or be wound into helical form and receive in casing.
Below, the manufacture method of the gas separation membrane module of the invention of this part is described.
First, the method that hollow cortina is carried out boundling as hollow tow is described.
As making hollow cortina hocket with the angle that relative direction of principal axis has 5 ~ 30 degree the method for mode boundling of cross arrangement, example method described as follows can be enumerated.1 ~ 100 hollow cortina utilizes the wire distribution guider come and gone with certain speed at the direction of principal axis of the tube (core pipe) becoming core to carry out wire distribution on core pipe, and meanwhile, core pipe rotates with certain speed.Therefore, hollow cortina does not carry out wire distribution abreast with axle, have relative direction of principal axis only rotary core pipe angle and carry out wire distribution.During wire distribution to end, be fixed at this hollow cortina, wire distribution guider turns back to reverse direction, carries out wire distribution further.Core pipe continues to equidirectional rotation, therefore, has relative direction of principal axis specifically identical with angle last time and be the angle in just in time contrary direction and carry out wire distribution.When being repeated, submitted for cross arrangement by the hollow cortina of wire distribution is carrying out wire distribution hollow cortina with contrary angle, boundling becomes hollow tow.
Below, the method for the tube sheet formed in the invention of this part is described.As forming the method for tube sheet, flospinning and standing forming process can be enumerated, but leave standstill forming process due to device easy and can boost productivity, therefore preferably.Below, an example of standing forming process is described.
Boundling there is the hollow tow of the hollow cortina B24 of specific length and radical to remove core pipe or after the state that has in the substantially central portion of bundle of being remained untouched by core pipe is accommodated in casing B22 with said method etc., be arranged at the assigned position in the mould B21 of end formed tube sheet, by above-mentioned hollow tow and columned casing B22 with end for lower and substantially keep vertical.Fig. 4 b represents the schematic diagram of this state.
The castable resin composition for the formation of tube sheet B23 of ormal weight is injected in mould B21.Fig. 4 c represents the schematic diagram of the state injecting castable resin composition.The method for implanting of castable resin composition is not particularly limited, but owing to easily evenly injecting castable resin composition in mould B21 and between hollow cortina B24, therefore the preferred syringe that uses from mould bottom injects.When the injection rate of castable resin composition is too fast, be difficult to, should the position of filling cast resin combination inject equably, therefore, preferably inject with the sufficient time.During castable resin composition is flow into mould B21, preferably suitably control the temperature of mould B21.Similarly, the temperature of castable resin composition is preferably controlled.
With regard to the castable resin composition before solidification, from the viewpoint of mouldability, be liquid at the temperature preferably when resin injection.
The viscosity of castable resin composition is not particularly limited, but the viscosity when resin injection during usual used temperature 70 ~ 90 DEG C is preferably lower than 120poise, particularly preferably lower than 20poise.At this, the viscosity of resin combination uses rotation viscometer suitably to measure.
There are the following problems: when viscosity during 70 ~ 90 DEG C of castable resin composition is more than 120poise, resin injection when tube sheet is shaping needs long-time, and the bubble produced when resin injection not easily disappears, and resin soaks in air silk intermembranous and produce space deficiently.
Inject castable resin composition in mould B21 after, by mould B21 and hollow tow are remained on uniform temperature and make castable resin composition carry out one-step solidification, form tube sheet B23.Temperature now lower than 100 DEG C, preferably 50 ~ 85 DEG C.During temperature height in this stage, the curing reaction of castable resin composition becomes fierce, has an impact to the intensity of the tube sheet finally obtained, therefore not preferred.
Make in the durability of tube sheet, mechanical property raising, preferably after the solidification of castable resin composition, castable resin composition is being heated further, carries out Post RDBMS thus.Temperature during Post RDBMS preferably 100 DEG C ~ 250 DEG C.When temperature during Post RDBMS is lower than 100 DEG C, the solidification of castable resin composition is insufficient, therefore not preferred.In addition, when temperature during Post RDBMS is too high, the curing reaction of castable resin composition becomes fierce, goes wrong in the intensity of tube sheet, therefore not preferred.When making castable resin composition carry out Post RDBMS, can be divided into repeatedly, heating in respective temperature respectively.
After making castable resin composition carry out Post RDBMS, by being cut off by tube sheet and making hollow cortina open-ended, keep open state at end air silk, make the air silk element with tube sheet set.
At this, when the both ends of hollow tow form tube sheet, after an end of hollow tow forms tube sheet, in another end, utilize same step to form tube sheet by utilizing above-mentioned steps and carry out.So-called after an end forms tube sheet, can be after tube sheet is cut off, making hollow cortina opening.In addition, also preferred an end being arranged in mould and injecting castable resin composition, before carrying out Post RDBMS, form tube sheet in another end, the step after Post RDBMS is carried out at both ends simultaneously after carrying out one-step solidification.
In the method that the gas separation membrane module of the invention by employing this part is separated mist, as long as the mist of separation admixture of gas of more than two kinds, be just not particularly limited.The gas separation membrane module of the invention of this part can suitably for the separation being separated, carrying out the hydrogen of the mist of self-contained hydrogen such as from nitrogen-rich gas and the oxygen rich gas of air, being separated (dehydration of organic vapor) etc. of steam from steam and the mixed vapour of organic vapor.
(technical scheme)
The invention that part B relates to is as described below.
1. a gas separation membrane module, it has:
The tow be made up of the many hollow cortina with gas separating property,
Have mist entrance, through gas discharge outlet and non-through gas discharge outlet and described hollow tow be configured in inner casing and
The tube sheet of at least one end of fixing described hollow tow,
Wherein, the curable epoxide thing that described tube sheet is solidified into by castable resin composition is formed, and this castable resin composition comprises: (a) novolak type epoxy compound and (b) end had and can react with the hycar of the functional group of epoxy reaction and the modified epoxy that obtains and (c) curing agent.
2. the gas separation membrane module as described in above-mentioned 1, wherein, described castable resin composition is also containing curing accelerator.
3. the gas separation membrane module as described in above-mentioned 1 or 2, wherein, described can be carboxyl with the functional group of epoxy reaction.
4., as the gas separation membrane module according to any one of above-mentioned 1 ~ 3, wherein, described curing agent is acid anhydrides.
5., as the gas separation membrane module according to any one of above-mentioned 2 ~ 4, wherein, described curing accelerator is imidazolium compounds.
[part C: even if the separating film module etc. that at high temperature also can work well]
(technical field)
Invention disclosed in this part relates to a kind of separating film module, and above-mentioned separating film module has the air silk element of the tube sheet integratedly set of hollow tow after specific epoxy resin component solidification be made up of the many hollow cortina with selective penetrated property.Even if in particular to the separating film module etc. that a kind of impact suppressing the thermal expansion of tube sheet to produce at high temperature also can work well.
(background technology)
The gas separation membrane module of hollow fiber type possesses the hollow container of air silk element and this element of collecting with the tow be made up of the many hollow cortina with selective penetrated property usually.The hollow tow of air silk element, its one or both ends utilize the cured plate of resin (tube sheet) to be fixed on the end of container.In addition, unstrpped gas introducing port is at least provided with in a reservoir, through gas discharge outlet and non-through gas discharge outlet.
With regard to gas separation membrane, generally speaking, the gas supplied is more HTHP, and the transmission rates of gas is larger.Therefore, when using gas separation membrane module, research compressor reducer etc. are supplied to assembly after unstrpped gas being compressed sometimes.Gas after this compression is according to circumstances supplied to sometimes at the very high temperature of 149 DEG C ~ 260 DEG C.
But, when using separating film module under hot conditions as above, such as likely create in tube sheet component because of tube sheet generation thermal expansion stress concentrate, or, produce because of result from this concentrate tube sheet crack and lose the problems such as the air-tightness of separating film module.Therefore, generally speaking, gas separation membrane module is supplied to by specially cooling with the gas of the high temperature after the compressions such as compressor reducer.About the use under high temperature, existing separating film module also remains room for improvement (such as, based on the parts efficient design etc. of the specific condition of high temperature).And then, be no matter whether the separating film module of high temperature, seeking to develop and a kind ofly the structure of separating film module is simplified further and miniaturized structure can be contributed to.
The invention of this part completes in view of above-mentioned problem, its object is to provide a kind of separating film module, the impact that above-mentioned separating film module suppresses the thermal expansion of tube sheet to produce, even if at high temperature also can work well.In addition, other object is, provides a kind of and seeks the simplification of the structure of separating film module, the structure favourable to miniaturization/lightweight.
Main inventive main points disclosed in this part are as described below.
1. a separating film module, possesses:
By the hollow tow that the many hollow cortina boundling with selective penetrated property becomes;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and have the end winding support of this bundle in the end of above-mentioned cylindrical container simultaneously by the tube sheet of the inside and outside isolated function of above-mentioned cylindrical container; With
By the annular seal component sealed between the outer peripheral face of above-mentioned tube sheet and the inner peripheral surface of above-mentioned cylindrical container;
Described separating film module uses under the high temperature conditions, wherein,
Being provided with the periphery of above-mentioned annular seal component, above-mentioned tube sheet does not arrange stage portion.
According to such formation, owing to not arranging stage portion at the periphery installing ring-type containment member (following in detail) on tube sheet, therefore, compared with the existing structure being configured with O ring with the stage portion at tube sheet, suppress stress when at high temperature using to concentrate the impact of generation.
" annular seal component " in this part refers to that, by the containment member of the ring-type sealed between tube sheet outer peripheral face and cylindrical container inner peripheral surface, its cross sectional shape is not particularly limited.As annular seal component, can for such as O ring (cross sectional shape is circular), can be maybe cross sectional shape be respectively roughly V-type, generally u-shaped V-seal part, U-shaped seal etc.And then, also comprise the situation of ellipse, rectangle, polygonal, X-type prismatic shapes.
" under hot conditions " refers in the scope of 80 DEG C ~ 300 DEG C.
" cylindrical container " is not limited to the container of both ends open, also comprises the container of only one end open.
Gas separation membrane module can be used for the purposes that such as oxygen separating, nitrogen separation, hydrogen separation, steam separation, carbon dioxide separation, organic vapor are separated.
(the 1st embodiment in part C)
Fig. 5 is the schematic diagram of the basic comprising representing gas separation membrane module.It should be noted that, in the following description, illustrate some embodiments, but each embodiment is not independently, the content of each embodiment can proper combination.
As shown in Figure 5, this gas separation membrane module 1 possesses the container 10 as the hollow tow 15 of the bundle of the many hollow cortina 14 with selective penetrated property and the roughly cartridge type of this hollow tow 15 of collecting.As an example, cylindrical container 10 is metal, 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 the following description, be described for the situation of circular cross-section (namely container 10 is cylindric).
Hollow cortina 14 can utilize current known hollow cortina, as long as having gas separating property can be just the hollow cortina of any materials.Be that the gas separating property of the hollow cortina that glass macromolecular material is formed is good under normal temperature (23 DEG C) by such as macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc., therefore preferably.
Hollow tow 15 is the tow become by the hollow cortina boundling of such as about 100 ~ 1000000.The shape of the hollow tow that boundling becomes is not particularly limited, but from the viewpoint of the easness of manufacture and the resistance to pressure of container, preferred boundling is columned hollow tow.In addition, illustrate the form having the substantial parallel arrangement of hollow cortina in Figure 5, but also can be the form of each hollow cortina cross arrangement.
Referring again to Fig. 5, in each end of container 10, be provided with tube sheet 30 in the end of hollow tow 15, be configured with annular seal component 17 at its peripheral part.As annular seal component 17, such as can for O ring (cross sectional shape is circular), or also can be cross sectional shape be respectively roughly V-type, generally u-shaped V-seal part, U-shaped seal etc.In the following description, be described for the situation of O ring.
As an example, tube sheet 30 is formed by the solidfied material (following in detail) of epoxy resin component, is formed as being embedded in such roughly discoid in the end of container 10.Multiple hollow cortina 14 runs 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 is collaborated by annular seal component and seals hollow cortina each other and between hollow cortina and container inner peripheral surface, has inner space and space outerpace, the bubble-tight function of maintenance of isolated hollow cortina.
As forming the cured resin of tube sheet 30, as long as possessing thermo-tolerance, the airtight material that can keep in air silk assembly, be just not particularly limited.When for the dehydration purposes of organic vapor or humidification purposes, preferably possesses the durability to steam simultaneously.Usually the thermosetting resin such as polyurethane, epoxy resin is preferably used.From the viewpoint of thermo-tolerance and intensity, particularly preferably use epoxy resin.For epoxy resin, such as, when nitrogen membrane module, epoxy resin described in Japanese Patent Publication 2-36287 etc. can be utilized, in addition, when organic vapor separation assembly, epoxy resin described in WO2009/044711 etc. can be utilized.
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.Cap 20 is formed mist introducing port 22A, cap 21 is formed non-through gas discharge outlet 22B.A part for the perisporium of container 10 is formed the outlet 12 through gas.It should be noted that, as described later, 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 is just without any restriction.
Below, be described with reference to the peripheral structure of Fig. 6 to tube sheet.Fig. 6 (a) represents an example of the structure of the assembly end that the invention of this part relates to, and Fig. 6 (b) represents other structure.
With regard to the gas separation membrane module shown in Fig. 6 (b), between the inner peripheral surface and the outer peripheral face of tube sheet 530 of cylindrical container 10, be provided with O ring 18, guarantee the air-tightness between two components thus.Specifically, a part for the peripheral part of tube sheet 530 forms stage portion 530s, chimeric on this stage portion 530s have O ring 18.When such structure, when at high temperature using gas separation membrane module 101, likely produce according to condition and stress occurs near this stage portion 530s of tube sheet 530 concentrate, tube sheet is damaged or damage bubble-tight unfavorable condition with this breakage.
In order to corresponding thereto, as shown in Fig. 6 (a), in the structure of present embodiment, be used in the tube sheet 30 that outer peripheral face does not arrange stage portion.For the diameter of tube sheet 30, in this embodiment, its total length certain (about alternate manner, carrying out aftermentioned with reference to Fig. 7).Be provided with rank portion 10s in the end of cylindrical container 10, thus, form the groove being used for chimeric O ring 18 at this step part.As an example, the cross sectional shape of groove is rectangle.O ring 18 is embedded in this groove, guarantees the air-tightness between the outer peripheral face of tube sheet and the inner peripheral surface of cylindrical container.
In addition, O ring 18 is also closely sealed with the inner face 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 cylindrical container with 1 O ring 18 and (ii) both sealing between cap and cylindrical container, therefore, do not need the O ring added.
It should be noted that, the device that cap 20 is fixed on cylindrical container 10 is not particularly limited, current known various mode (such as, utilizing bonding fixing, use to have fixing of fixture) can be adopted.
In the gas separation membrane module 1 of present embodiment as constructed as above, the periphery of O ring 18 is being installed, tube sheet 30 is not arranging stage portion.Therefore, compared with the existing structure that Fig. 6 (b) is such, the stress be not vulnerable to when at high temperature using concentrates the impact caused.Its result, can improve the thermo-tolerance as gas separation membrane module 1 entirety and reliability.
Such advantage is not limited to Fig. 6 (a), even if when the structure that Fig. 7 is such, also can similarly obtain.That is, in the form of Fig. 6 (a), in order to make explanation become simple, specified otherwise not being had to the device of the axial movement of restriction tube sheet 30, but be provided with this device in the formation of Fig. 7.
As shown in Figure 7, in this gas separation membrane module 1 ', entering inner side formation step 10t with predetermined distance from the end of container 10.In order to corresponding thereto, be also provided with step 30 ' t in the end of tube sheet 30 '.About other structure, identical with Fig. 6 (a).According to such formation, the end (diagram right side) of tube sheet 30 ' abuts with this step 10t and limits axial movement, and therefore, tube sheet can not enter its above inside.
It should be noted that, the gas separation membrane module more than enumerating Fig. 5 is that example is illustrated, and certainly, the invention of this part also can be applied to other formation.Such as, the assembly of the type that the assembly that also can be preferably applied to shell feed type (shell feed type) or the carrying out being provided with Purge gas introducing port further on cylindrical container purify.
(the 2nd embodiment in part C)
Fig. 8 represent the structure of assembly end of the second embodiment one example, Fig. 8 (a) represents state during normal temperature, Fig. 8 (b) represent use time and high temperature time state.
The gas separation membrane module of Fig. 8 is identical with above-mentioned embodiment, possesses harness and has the hollow tow 15 of the many hollow cortina with selective penetrated property and the cylindrical container 10 of this hollow tow of collecting.In addition, the cap 20 possessing the tube sheet 38 arranged in the end of hollow tow 15 and install in the end of cylindrical container 10.Add the symbol identical with above-mentioned accompanying drawing in the structural portion same with above-mentioned embodiment, omit repeat specification.
As shown in Fig. 8 (a), in this gas separation membrane module, the mode being slightly less than the internal diameter of the inner peripheral surface 10a of cylindrical container 10 with the diameter of the tube sheet 38 during normal temperature is formed, between the outer peripheral face and the inner peripheral surface 10a of cylindrical container of tube sheet 38, produce gap.It should be noted that, the material of tube sheet 38 is identical with above-mentioned embodiment, is the resin materials such as epoxy resin, the material that the thermal coefficient of expansion for the material (be metal as an example) than cylindrical container 10 is large.
This gas separation membrane module uses in the scope of such as 80 DEG C ~ 300 DEG C.As shown in Fig. 8 (b), be configured to tube sheet 38 in use and be heated to set point of temperature, undertaken expanding by thermal expansion, the inner peripheral surface 10a of its outer peripheral face and cylindrical container is closely sealed thus.Utilize this closely sealed, the air-tightness between two components can be guaranteed.
When using this gas separation membrane module, assembly fully being heated up, after guaranteeing the air-tightness of tube sheet 38 and cylindrical container 10, carries out the supply of mist.
In the above-described configuration, between tube sheet and cylindrical container, sealing effectiveness is played by making tube sheet 38 that thermal expansion occur.Therefore, in order to seal between two components, do not need arrange O ring in addition or the outer peripheral face of tube sheet is carried out bonding with the inner peripheral surface of cylindrical container.In addition, when making tube sheet 38 carry out thermal expansion, the stress putting on cylindrical container 10 also diminishes, and therefore, is also favourable in breakage that can prevent cylindrical container 10 etc.
It should be noted that, in the above description, suppose that tube sheet is epoxy resin and the situation that cylindrical container is metal is illustrated, but about the material of cylindrical container, as long as thermal coefficient of expansion is just not limited to metal than the little material of tube sheet.In addition, do not illustrate in fig. 8, but also can arrange for the sealing device by sealing between cap 20 and cylindrical container 10.Such as, the annular seal component that can utilize the annular seal component configured between the inner peripheral surface and the outer peripheral face of cylindrical container 10 of cap 20 or configure between the inner face and the end face of cylindrical container 10 of cap 20.
(the 3rd embodiment in part C)
Fig. 9 represents an example of the structure of assembly end of the third embodiment.It should be noted that, the assembly intention of the 1st and the 2nd embodiment at high temperature uses, and about the gas separation membrane module of Fig. 9, is not particularly limited serviceability temperature.
The gas separation membrane module of Fig. 9 is same with above-mentioned 2 embodiments, possesses: harness has the hollow tow 15 of the many hollow cortina with selective penetrated property; Accommodate the cylindrical container 10 of described air silk bundle; The cap 20 of the tube sheet 30 arranged in the end of hollow tow 15 and the end being installed on cylindrical container 10.In addition, the O ring 18 will sealed between tube sheet and cylindrical container is also provided with.Add the symbol identical with above-mentioned accompanying drawing in the structural portion same with above-mentioned embodiment, omit repeat specification.
In the formation of Fig. 9, in a part for the perisporium of cylindrical container 10, formed and be used for the opening portion 10h be discharged to through gas outside this cylindrical container through hollow cortina.In addition, in a part for the perisporium of cap 20, be also formed with opening portion 20h in position corresponding thereto.To be provided with hollow discharge pipe 41 by the mode of two opening portion 10h, 20h.In the gas separation membrane module of Fig. 9, this discharge pipe 41 plays the effect through gas discharge outlet 12 as Fig. 5, therefore, do not arrange Fig. 5 such through gas discharge outlet 12.
This discharge pipe 41 also has in addition as the function by cap 20 and cylindrical container 10 stationary device.That is, by making discharge pipe 41 lead to two opening portion 10h, 20h, the axial movement between restriction cap 20 and cylindrical container 10 and the movement of direction of rotation.
In order to fix two components 10,20 more firmly, the hold-down screw 42 added shown in Fig. 9 can be utilized.The screwed hole that this hold-down screw 42 is formed with the perisporium at cap 20 is communicated with, and its front end enters a part for the perisporium of cylindrical container 10.The negative thread be fixed by hold-down screw 42 can be formed on cap 20, also can be formed on cylindrical container.It should be noted that, steady pin also can be utilized to replace hold-down screw.
It should be noted that, the annular seal component (not shown) for sealing between the inner peripheral surface of the perisporium by cap 20 and the outer peripheral face of cylindrical container 10 also can be set.Thus, the air-tightness between cap 20 and cylindrical container 10 can be guaranteed more fully.Fully carrying out with 1 O ring 18 between tube sheet-cylindrical container and between cap-cylindrical container during both sealing, sealing component can be omitted.
Illustrating in such formation above, for the formation of the component 41 for discharging through the stream of gas, also having both the effect of locking cap 20 and cylindrical container 10.Therefore, the structure of assembly simplifies, and then can seek lightweight, the miniaturization of assembly.
It should be noted that, in the example of figure 9, so that the discharge pipe 41 be discharged to outside cylindrical container through gas through hollow cortina is illustrated.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 discharge pipe 41 opening portion 10h, 20h by container and cap, only with fixed components such as hold-down screw 42 or steady pins, cap 20 is fixed on cylindrical container 10.When such formation, time compared with the formation of carrying out flange part described later to be fixed to one another with reference to Figure 10 (b), do not need to arrange flange part, therefore, favourable to the miniaturization of assembly.
This fixed component can be only 1, also can be more than 2, but more than 2, preferred fixed component is configured in circumferentially equably.
(other embodiment in part C)
Except above-mentioned embodiment, the invention of this part also can be mode such shown in Figure 10 (a), (b).These gas separation membrane module are same with above-mentioned embodiment, possess: harness has the hollow tow 15 of hollow cortina; Accommodate the cylindrical container 10 of this hollow tow; The tube sheet 30 arranged in the end of hollow tow 15; The cap 26,27 installed in the end of cylindrical container.In addition, the O ring 18 will sealed between the outer peripheral face of tube sheet and the inner peripheral surface of cylindrical container is also possessed.
In the formation of Figure 10 (a), cap 26 is fixed on cylindrical container 10 to be screwed into mode.That is, the female threaded portion formed in a part for the inner peripheral surface of cap 26 and the outer screw section engaging formed in a part for the outer peripheral face of cylindrical container 10 is configured to.Rotate to (with reference to Figure 10 (a)) under the state of the fixed position of regulation at cap 26, a part for O ring 18 abuts with the inner face of cap 26, thus, can guarantee the air-tightness of cylindrical container end and cap inner face.Same with above-mentioned embodiment, O ring 18 also guarantees the air-tightness between the outer peripheral face of tube sheet and the inner peripheral surface of cylindrical container.
In the formation of Figure 10 (b), cap 27 forms flange part 27f, meanwhile, cylindrical container 10 is also formed with flange part 10f corresponding thereto.Cap 27 and cylindrical container 10 fixing by fixing these flanges 27f, 10f to carry out by fixture 43.As fixture 43, such as, can use bolt and nut.In addition, screwed hole and the bolt of flange 10f formation can be also used in.Be not particularly limited with place each other, fixture 43 fastening rib portion, but fastening place preferably relates to the circumferencial direction of flange part, and equally spaced arrange.
(other embodiment another in part C)
The gas separation membrane module of the invention of this part also can be formation as shown in Figure 11.Figure 11 (a) is the sectional view of the example representing gas separation membrane module, and Figure 11 (b) is the figure after a part of Figure 11 (a) being amplified.
The gas separation membrane module of Figure 11 possesses: harness has the hollow tow 115 of hollow cortina; Accommodate the cylindrical container 110 of hollow tow; Tube sheet 130A, 130A of arranging at the both ends of hollow tow 115; The cap 120,121 installed in the end of cylindrical container 110.In addition, the O ring 118 arranged at the outer peripheral face of each tube sheet 130A is also possessed.
In this embodiment, cylindrical container 110 has the length direction tubing 111 extended and the end member 112,112 being installed on its two ends along assembly.The perisporium of the end member 112 of diagram left side (gas introduction side) is formed the outlet 112h through gas (example).
Each end member 112 is formed with flange part 112f.On the other hand, each cap 120,121 is also formed with flange part 120f, 121f.Docked by the flange part 120f of the flange part 112f and cap that make end member, same with the mode of Figure 10, use such as bolt and nut etc. (omitting diagram in fig. 11), cap 120 can be fixed on end member 112 (about cap 121, also identical).
As shown in Figure 11 (b), in this embodiment, tube sheet 130A is configured in the mode that a part for the inner peripheral surface of a part for the inner peripheral surface with cap 120 and cylindrical container 110 is closely sealed.The tube sheet 30 ' of each tube sheet 130A and Fig. 7 is same, and its outer peripheral face is formed as rank shape, and the rank portion of tube sheet outer peripheral face abuts with the rank portion of cylindrical container inner peripheral surface, limits the position of 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 is formed as ring-type.O ring 118 is configured with in the groove (cross sectional shape is rectangle) of the ring-type formed in a part of the flange part 112f by this stage portion 120s and end member 112.O ring 118 guarantees the air-tightness between tube sheet 130A and cap 120, guarantees the air-tightness between cap 120 and end member 112 simultaneously.
For the structure of cap 120, being illustrated the peripheral structure of O ring 118, about cap 121 side, is also same structure.As the device in holding flange portion, be not limited to the device utilizing screw bolt and nut, such as, can for relative to flange part 112f, 120f any one on the screwed hole that formed be screwed into the formation of bolt front end.
In the formation that above-mentioned Figure 11 is such, in a same manner as in the first embodiment, installing the periphery of O ring 118, tube sheet 130A does not arrange stage portion.Therefore, compared with the existing structure shown in Fig. 6 (b), the stress be not vulnerable to when at high temperature using concentrates the impact of generation.Its result, can improve the thermo-tolerance as gas separation membrane module entirety 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, can be suitable for selecting in the material of each component being favourable according to the proterties of each component.It should be noted that, the invention of this part does not limit therewith, can utilize tubing 111 and the such single cylindrical container of end member 112 integration yet.
The gas separation membrane module of the invention of this part can also be the assembly shown in Figure 12.This assembly is substantially same with the formation of Figure 10 (b), in the mode making the flange part 110f of the flange part 127f of cap 127 and cylindrical container 110 ' dock, cap 127 is fixed on cylindrical container 110 '.O number of rings and allocation position etc. are different from the assembly of Figure 10 (b).The assembly of tube sheet 130B and Figure 11 is same, closely sealed with a part for a part for the inner peripheral surface of cap 127 and the inner peripheral surface of cylindrical container 110 '.
One O ring 118 is configured in the groove 127g of the ring-type formed on the inner peripheral surface of cap 127, guarantees the air-tightness between tube sheet 130B and cap 127.The groove 127g of ring-type is not limited, but in the inner peripheral surface of cap 127, is formed in the position entering slightly inner side (diagram left side) from the end face of flange part 127f side.
2nd O ring 119 is configured between flange part 110f and flange part 127f.In this embodiment, the groove 110g of the ring-type flange part 110f of cylindrical container 110 formed is configured with O ring 119.So optional formation of O ring 119, utilizes this O ring 119, and gas can be prevented by leaking into outside between flange part 110f, 127f.
It should be noted that, certainly, the formation of such O ring 118,119 is not only the form described by Figure 12, but also can utilize with above-mentioned embodiment proper combination.In addition, the groove configuring the 2nd O ring 119 also can be formed at the flange part 127f of cap 127.
(summary of the invention)
The invention relating to part C is as described below.
1. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with selective penetrated property becomes;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and to have the end winding support of this bundle in the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously; With
Seal the annular seal component between the outer peripheral face of above-mentioned tube sheet and the inner peripheral surface of above-mentioned cylindrical container;
Described gas separation membrane module uses under the high temperature conditions, wherein,
Being provided with the periphery of above-mentioned annular seal component, above-mentioned tube sheet does not arrange stage portion.
2. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with selective penetrated property becomes;
Accommodate the cylindrical container of this hollow tow; With
Be arranged at the end of above-mentioned hollow tow and to have the end winding support of this bundle in the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously;
Described gas separation membrane module uses under the high temperature conditions, wherein,
Above-mentioned tube sheet is formed by the material that the thermal coefficient of expansion of the material than above-mentioned cylindrical container is large, and
At normal temperatures, between the outer peripheral face and the inner peripheral surface of above-mentioned cylindrical container of above-mentioned tube sheet, produce gap, when being warming up to set point of temperature, above-mentioned tube sheet expands, and the inner peripheral surface of its outer peripheral face and above-mentioned cylindrical container is closely sealed and play sealing effectiveness.
3. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with selective penetrated property becomes;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and to have the end winding support of this bundle in the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously; With
At the cap of the end that above-mentioned cylindrical container is installed; Wherein,
Form the tubular element of inside and outside stream being communicated with above-mentioned cylindrical container, (diametrically) runs through a part for above-mentioned cylindrical container and a part for above-mentioned cap and arranges.
4., as above-mentioned 3 above-mentioned gas separation membrane module, it also possesses:
Be communicated with a part for the perisporium of above-mentioned cap and play the fixed component of the effect fixing this cap and above-mentioned cylindrical container.
5. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with selective penetrated property becomes;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and to have the end winding support of this bundle in the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously; With
The cap installed in the end of above-mentioned cylindrical container; Wherein,
Possess and to be communicated with a part for the perisporium of above-mentioned cap and to play the fixed component of the effect fixing this cap and above-mentioned cylindrical container.
6. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with selective penetrated property becomes;
Accommodate the cylindrical container of this hollow tow;
Be arranged at the end of above-mentioned hollow tow and to have the end winding support of this bundle in the end of above-mentioned cylindrical container, the tube sheet of the inside and outside function of isolated above-mentioned cylindrical container simultaneously;
Be installed on the cap of the end of above-mentioned cylindrical container; With
Seal the annular seal component between the outer peripheral face of above-mentioned tube sheet and the inner peripheral surface of above-mentioned cylindrical container;
Wherein, the mode above-mentioned cap being fixed on above-mentioned cylindrical container is as follows:
I () utilizes in the threaded portion that a part for the inner peripheral surface of above-mentioned cap is formed and the mode that is fixed in the threaded portion that a part for the outer peripheral face of the above-mentioned cylindrical container opposed with it is formed; Or
(ii) the flange part fixture of the flange part of above-mentioned cap and the above-mentioned cylindrical container opposed with it is linked and the mode that is fixed.
7., as the gas separation membrane module according to any one of above-mentioned 3 ~ 6, wherein, above-mentioned annular seal component also seals between above-mentioned cap and above-mentioned cylindrical container.
[part D: cost, the gas separation membrane module also favourable to the simplification of structure when changing can be controlled]
(technical field)
Invention disclosed in this part relates to the gas separation membrane module that many hollow cortina that a kind of utilization has a selective penetrated property carries out gas separaion.In particular to a kind of can control change time cost and also the separating film module also favourable to the simplification of structure.
(background technology)
The gas separation membrane module of hollow fiber type possesses the cylindrical container of air silk element and this element of collecting with the tow be made up of the many hollow cortina with selective penetrated property usually.The hollow tow of air silk element, its one or both ends utilize the cured plate of resin (tube sheet) to be fixed on the end of container.In the end of cylindrical container, cap component is installed, thus by airtight in container.
In existing gas separation membrane module, as mentioned above, be provided with cap component in the end of cylindrical container, these cap components form 1 main body as a whole, therefore, when changing separating film module, need to change component integration.Therefore, there are the following problems: originally do not need the cap component etc. changed also to change together, and the cost changing parts raises.
On the other hand, also can consider only to change the air silk element in main body, but now, such as, need the built-in structure etc. that air silk element is loaded and unloaded in main body, cause the complicated of modular construction, also unfavorable to lightweight.
The invention of this part completes in view of above-mentioned problem, its object is to, and provides a kind of and can control cost when changing and to the simplification of structure is also favourable and miniaturization is easy to gas separation membrane module.
The main disclosed main inventive main points of this part are as described below.
1. a gas separation membrane module, possesses:
The hollow tow be made up of many hollow cortinas is contained in the box (cartridge) in cylindrical container;
The cap component installed at the both ends of this box;
By the containment member sealed between above-mentioned each cap component and above-mentioned box; With
By the fixture that above-mentioned cap component interfixes;
Wherein, above-mentioned box is configured to install in the mode that can change each other at above-mentioned cap component.
According to such formation, provide a kind of and can control cost when changing and to the simplification of structure is also favourable and miniaturization is easy to gas separation membrane module.
(embodiment in part D)
Below, with reference to accompanying drawing, an embodiment of the invention of this part is described.It should be noted that, the invention of this part is not limited to the formation shown in following form, can carry out the adding or omit of parts, the change etc. of shape as required.
As shown in figure 13, this gas separation membrane module 201 (following, also referred to as separating film module) possesses: the box 210 containing the tubular of hollow tow 215 in inside; The cap component 220,221 installed at its both ends; With the fixed bar 245 etc. that these cap components 220,221 are fixed.
The cylindrical container 211 that box 210 has both ends open, the hollow tow 215 received therein and tube sheet 230,231.Tube sheet 230,231 keeps the end of hollow tow 215, and isolated cylindrical container 211 is inside and outside simultaneously.
Hollow tow 215 can utilize current known hollow tow.The hollow tow that hollow cortina 214 boundling of about 100 ~ 1000000 such as can become by hollow tow 215.As long as hollow cortina 214 has gas separating property, it can be just the hollow tow of any materials.Such as, be the hollow cortina that glass macromolecular material is formed by macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. under normal temperature (23 DEG C), its gas separating property is good, therefore preferably.The shape of the hollow tow that boundling becomes is not particularly limited, from the viewpoint of the easness of manufacture and the resistance to pressure of container, columned hollow tow can be become for boundling.It should be noted that, illustrate the form having the substantial parallel arrangement of hollow cortina 214 in fig. 13, but also can be the form of each hollow cortina cross arrangement.
The cross sectional shape of cylindrical container 211 can be the arbitrary shapes such as circle, ellipse or polygonal.In the following description, the example of circle is described.As an example, cylindrical container 211 can by being undertaken processing making by 1 metal pipe.In the present embodiment, as an example, preferably as the device (that is, for not having the structure of locking cap component on the cylindrical container) cylindrical container 211 of box side not arranged for cap component 220,221 being fixed on cylindrical container 211.Thus, the making of processing, the such as flange to cylindrical container 211, the formation of screwed hole, the configuration etc. of steady pin is not needed.
As shown in figure 14, be formed with internal circle groove 217 near the end in the inside of cylindrical container 211, inner-diameter portion whose becomes large.As described later, internal circle groove 217 embeds a part for tube sheet 230,231.Vacate the interval of regulation from this internal circle groove 217, be formed with another internal circle groove 218 in inner side (direction away from end) further.About each internal circle groove 217,218, the cross sectional shape of the groove dug can be such as rectangle type, substantially rectangular type, trapezoidal type or roughly trapezoidal type.
Multiple opening portion 212 for being discharged to the outside by the gas in container is formed in the part being formed with internal circle groove 218.The number of opening portion 212 and position are not particularly limited.As an example, can to form multiple opening 212 at equal intervals around cylindrical container 211.As shown in figure 14, in the periphery of cylindrical member 211 and than internal circle groove 218 a little in the inner part (direction away from cylinder end) be formed with the circumferential groove 219 for chimeric elastic ring component R2 described later.
For the tube sheet 230 and 231 (with reference to Figure 13) of box 210, be epoxy resin as an example, be formed as such roughly discoid in the end of embedding container 211.Because tube sheet 230 and tube sheet 231 are essentially same structure, therefore, only a tube sheet 230 is described below.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, by the set integratedly of many hollow cortinas 214, in addition, completely cuts off the inside and outside of cylindrical container 211.As long as form the cured resin of tube sheet to possess sufficient durability and can to keep in air silk assembly airtight, be just not particularly limited.When for dewater purposes or humidification purposes, preferably possess the durability to steam simultaneously.Usually the thermosetting resin such as polyurethane, epoxy resin is preferably used.Consider from durability aspect and intensity aspect, particularly preferably use epoxy resin.Epoxy resin is such as when nitrogen membrane module, epoxy resin described such in Japanese Patent Publication 2-36287 etc. can be utilized, in addition, when organic vapor separation assembly, epoxy resin described such in WO2009/044711 etc. can be utilized.Tube sheet preferably utilizes centrifugal forming, leaves standstill the known method formation such as shaping.
It should be noted that, in above-mentioned, inside and outside the referring to that tube sheet " completely cuts off " cylindrical container utilizes tube sheet to carry out substantial completely cutting off, and the peripheral part of tube sheet is not necessarily adhered to the inner face of cylindrical container.
As shown in figure 13, a part for tube sheet 230 is outstanding a little from the end of cylindrical container 211, and the periphery along the end of tube sheet 230 forms fillet surface (taper surface).As the operation making tube sheet 230, as an example, first, in cylindrical container 211, configure hollow tow 215, not shown mould (example) is installed in the end of cylindrical container 211 in this condition.Then, resin by injection make it solidify in this mould and in cylindrical container 211.After resin solidification, take mould, cut off the end of the resin after solidification, form the end face of tube sheet 230 thus, make hollow cortina 214 open-ended simultaneously.The fillet surface of tube sheet 230 can utilize mould to be formed, and also can be formed by the secondary operations after resin solidification.
Owing to being formed with internal circle groove 217 in cylindrical container 211, therefore, the resin of tube sheet 230 is also filled in this groove 217.Its result, a part for tube sheet 230 engages with internal circle groove 217, carries out the axial location of tube sheet 230 relative to cylindrical container 211.Usually, when using separating film module 201, the pressure in the direction be squeezed in cylindrical container 211 relative to tube sheet 230 works.Formation according to the present embodiment, because a part for tube sheet 230 engages with internal circle groove 217, therefore, not because tube sheet 230 is squeezed in cylindrical container 211 by pressure when using.
Then, with reference to Figure 13, Figure 15, the structure of cap component 220,221 is described.In this embodiment, because cap component 220,221 is essentially same structure, therefore, only a cap component 220 is described below, only the different piece of cap component 221 is described.Being not particularly limited the material of cap component 220,221, such as, also can be metal.It should be noted that, certainly, each cap component 220,221 can have different shapes, and the shape of each cap component 220,221 can according to the purposes of separating film module or the suitable change of specification.
As shown in Figure 13, Figure 15, cap component 220 has the shape of bottomed cylindrical.Specifically, as shown in Figure 15 (A), the end face 220A with the opening portion covering the cylindrical container 211 and cylindrical portion 220B extended from its circumference.
End face 220A is formed the gas introduction port P1 for importing mist.Internal circle groove 227a, 227b is formed in the inner side of cylindrical portion 220B.As shown in figure 13, internal circle groove 227a embeds the elastic ring component R1 (detailed content is as described below) for sealing.When cap component 220 is embedded in cylindrical container 211, another internal circle groove 227b is for the formation of the gas flow path P3 of reciprocal a week in cylindrical container 211.It should be noted that, another cap component 221 is formed non-through gas discharge outlet P2.
Gas flow path P3 (Figure 13) is communicated with multiple opening portions 212 of cylindrical container 211, and the gas of internal tank is flow in gas flow path P3 by each opening portion 212.1 outlet 223 that this gas is formed from the cylindrical portion 220B of cap is discharged to the outside.It should be noted that, in the form of Figure 13, cap component 221 does not have form the structure (opening portion) being equivalent to outlet 223.But, according to the purposes etc. of assembly, cap component 221 arranges opening portion, meanwhile, corresponding thereto, can one or more opening portions 212 be set on cylindrical container 211.
When referring again to Figure 15, cylindrical portion 220B is formed with the multiple through hole 220h for making fixed bar 245 (Figure 13, following in detail) insert.In this embodiment, 6 through hole 220h are in a circumferential direction to configure at equal intervals.Like this, cylindrical portion 220B is formed through hole 220h and formation wherein by fixed bar 245, favourable in following.That is, according to such formation, the cylindrical portion 220B as a part for cap 220 keeps fixed bar 245, therefore, does not need the special structure arranged in addition on cap component 220 for keeping fixed bar.Therefore, the miniaturization of cap component 220 and then separating film module 201 can be sought, also contribute to the lightweight of assembly.
It should be noted that, the radical of fixed bar 245 is not limited to 6, also can be more than 1 ~ 5 or 7.As an example, as shown in figure 16, also can be 3,4 or 8 etc.The material of fixed bar 245 is not particularly limited, and as an example, can be metal.
As shown in Figure 15 (B), in cylindrical portion 220B, in the part of outlet 223 opening, a part of cylindrical portion 220B is cut, and forms par 220f.In addition, in the bottom of cylindrical portion 220B, as an example, be formed with the par 220g for preventing separating film module from rolling.
As shown in figure 13, the internal circle groove 227a of cap component is embedded with the flexible sealing component R1 between sealed pipe plate 230 and cap component 220.Elastic ring component R1 is configured to all residue in cap component 220 side when taking above-mentioned box 210 when changing from cap component 220.As elastic ring component R1, such as, it also can be O ring (cross sectional shape is circular).Or the V-seal part of roughly V-type that can be cross sectional shape be respectively, cross sectional shape are the U-shaped seal etc. of roughly U-shaped.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 component R2 is configured to be embedded in the circumferential groove 219 of cylindrical container 211, is sealed thus between two components.This elastic ring component R2 also as described above, can utilize the various seals such as O ring, V-seal part or U-shaped seal.
As shown in Figure 13, Figure 15, cap component 220,221 utilizes 6 (one example) fixed bars 245 and the nut 246 installed at its two ends to interfix each other.In the present embodiment, as mentioned above, be the structure utilizing the cap component 220,221 that to interfix as the fixture that other parts prepare relative to box 210.Therefore, not needing to arrange the flange etc. for fixing at box 210 side (particularly cylindrical member 211), the structure of box 210 can be simplified.
It should be noted that, the fixture for locking cap component 220,221 is not limited thereto, and can utilize various fixture.Such as, can be that one end of fixed bar is large diameter head, at other end mounting nuts.Or, can at the inner circumferential screw cutting of the through hole 220h of cap component 220, meanwhile, corresponding thereto, at boom end also screw cutting, boom end is screwed in through hole 220h.Or, mechanical link locking cap component other mechanical device each other can be utilized, such as, with the mechanical device using the mode at the two ends of holder assembly (cap component 220,221) to be fixed.
And then, be not limited to be fixed on cap component 220,221 mechanical device each other, also can be utilized as the mechanical device and the mechanical device that box 210 is set in the mode that can load and unload between cap component 220,221 that each cap component 220,221 are fixed on the fixed position of regulation.Such as, be equipped with the device of separating film module or a part for equipment works as base member (not shown), each cap component 220,221 its basic component relative can be utilized to be fixed such formation.
In the separating film module 201 of present embodiment, carry out such as following gas separaion: the air of pressurized state is directed to internal tank by gas introduction port P1, this air is fed to its inside from the open end of hollow cortina 214.At forced air in hollow cortina 214 between flow periods, oxygen-enriched air optionally penetrates into outside film, through oxygen-enriched air move to (through space, side) in the space of the hollow tow be accommodated with between tube sheet.Should be discharged to the outside from as through the opening portion 212 of gas discharge outlet and opening portion 223 through gas.On the other hand, not through nitrogen-rich air be discharged to the outside through gas discharge outlet P2 through the non-of gas discharge outlet from as non-via another opening of hollow cortina 214.
In gas separation membrane module 201 described above, the box 210 containing hollow tow 215 is configured to be installed between cap component 220,221 in removable mode.Therefore, only replacing box when changing, not needing to change component integration, therefore, the cost changing parts can be controlled.
On the other hand, also can consider only to change the structure that the element of the air silk element 215 being equivalent to inside is such, but now, need the built-in structure etc. that these replacing parts are loaded and unloaded in cylindrical container 211.Corresponding thereto, in assembly 201, the cylindrical container 211 as a part for box 210 directly works as the main body of assembly 201, therefore, does not need complicated structure.It is favourable to the lightweight of separating film module 201 entirety, particularly can expect particularly preferably to apply in the light-weighted field of assembly at such as aviation field etc.
And then above-mentioned formation is that the fixture (245,246) with the parts different from box 210 links cap component 220,221.Therefore, the structural portion (such as flange part etc.) formed on cylindrical container 211 for linking cap component is not needed.Therefore, the structure of box 210 can be simplified, in addition, also can control manufacturing cost.
In addition, to be above-mentionedly constructed as follows: elastic ring component R1 remains on the inner circumferential of cap component 220,221, when taking box 210 when changing, ring element R1 all residues in cap member side.Such formation with arrange compared with ring element R1 in box 210 side, favourable to the manufacturing cost of control box 210.
As shown in figure 13, in the formation of present embodiment, the periphery due to the end along tube sheet 230 is formed with fillet surface (taper surface), therefore, successfully can insert the end of tube sheet 230 in elastic ring component R1.
Above, be illustrated with reference to the working of an invention mode of accompanying drawing to this part, but the invention of this part is not limited to illustrated form, can carry out various change.Such as, about the containment member for sealing between each component, its shape and allocation position can suitably change.Except elastic ring component R1, R2, also additional containment member can be set.
As shown in figure 13, in the above-described embodiment, exemplified with the formation of flexible ring element R2 chimeric on the periphery of cylindrical container 211, but the invention of this part is not limited thereto, following formation can be adopted: in the inner circumferential of cap component 220,221, be provided with elastic ring component R2 and replacing at box time this elastic ring component R2 residue in cap component 220,221 side.Now, owing to not needing to form circumferential groove 219 on the cylindrical container 211 of box 210, therefore, can the manufacturing cost of control box 211 further.
In the above-described embodiment, exemplified with the example of the separating film module of the so-called boring feed type of formation (Bore Feed type), but the invention of this part also can be applied to the separating film module forming shell feed type (shell feedType).Now, corresponding with shell feed type (shell feed Type) box be configured to above-mentioned explanation such be installed on cap component each other in the mode that can change.
(technical scheme)
The invention relating to part D is as described below.
1. a gas separation membrane module, possesses:
The hollow tow be made up of many hollow cortinas is contained in the box in cylindrical container;
Be installed on the cap component at the both ends of this box;
Seal the containment member between above-mentioned each cap component and above-mentioned box; With
By the fixture that above-mentioned cap component interfixes;
Wherein, above-mentioned box is configured to be installed on above-mentioned cap component each other in the mode that can change.
2. the gas separation membrane module as described in above-mentioned 1, wherein, as above-mentioned fixture, has and links above-mentioned cap component at least 1 fixed bar each other,
Each cap component is formed the through hole that above-mentioned fixed bar is inserted.
3. the gas separation membrane module as described in above-mentioned 1 or 2, wherein, above-mentioned cap component is installed in the mode of the end being covered in above-mentioned cylindrical container,
Above-mentioned containment member is the elastic ring component configured between the periphery of above-mentioned box and the inner circumferential of above-mentioned cap component.
4. the gas separation membrane module as described in above-mentioned 3, wherein, above-mentioned elastic ring component remains on the inner circumferential of above-mentioned cap component, and the mode all residuing in above-mentioned cap member side during to take above-mentioned box when changing from above-mentioned cap component is formed.
5. as the gas separation membrane module according to any one of above-mentioned 1 ~ 4, wherein, above-mentioned box has the inside and outside tube sheet for keeping the end of above-mentioned hollow tow to completely cut off above-mentioned cylindrical container simultaneously,
Internal circle groove is formed in the inside of above-mentioned cylindrical container and towards the region of above-mentioned tube sheet,
A part for above-mentioned tube sheet engages with this internal circle groove.
[part E: the gas separation membrane module that gas separaion can be implemented efficiently]
(technical field)
The invention of this part relates to a kind of gas separation membrane module utilizing hollow cortina to carry out gas separaion, and particularly one can implement the gas separation membrane module of gas separaion efficiently in the assembly of so-called boring feed type (bore feed type).
(background technology)
The gas separation membrane module of hollow fiber type possesses usually: have the air silk element of the hollow tow be made up of the many hollow cortina with selective penetrated property and the hollow casing of this hollow tow of collecting.The hollow tow of air silk element, its one or both ends utilize the cured plate of resin (tube sheet) to be fixed.In addition, casing is provided with mist entrance, through gas vent and not through gas vent etc.
For the purpose of effective divided gas flow, such as in Japanese Unexamined Patent Publication 2000-262838, disclose a kind of gas separation membrane module, described gas separation membrane module is formed as follows: in assembly mist being supplied to the so-called boring feed type in hollow cortina (bore feed Type), be coated to a part for hollow tow with film structural component, clamp hollow cortina with the flowing of the flowing of carrier gas and mist and become convection current.
In the gas separation membrane module of above-mentioned patent document 1, by limiting the flow direction of carrier gas, the validation of gas separaion can be sought, but be boring feed type (bore feed Type) and do not utilize in the gas separation membrane module of carrier gas (Purge gas), the efficiency improving gas separaion is also important.The invention of this part completes in view of above-mentioned problem, and its object is to provides a kind of gas separation membrane module can implementing gas separaion in the assembly of boring feed type (bore feed Type) efficiently.
Main inventive main points disclosed in this part are as described below.
1. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with gas separating property becomes;
There is mist entrance, through gas vent and the casing being configured with above-mentioned hollow tow not through gas vent and in inside; With
2 tube sheets fixing by the both ends of above-mentioned hollow tow;
The mist imported from above-mentioned mist entrance is supplied in above-mentioned hollow cortina by described gas separation membrane module, by making a part for this mist through carrying out gas separaion, wherein,
I () is not arranged for supplying the structure through gas cleaning gas for discharging through above-mentioned hollow cortina,
(ii) a kind of film structural component is also possessed, it is the film structural component of the gas impermeability (also comprising the film structural component of gas impermeability in fact) of the outer peripheral face being wound in above-mentioned hollow tow, wherein, abut with the above-mentioned tube sheet in mist direction of the supply downstream in fact with one end, mode that the other end is left from the above-mentioned tube sheet of mist direction of the supply upstream side configures.
According to the invention of this part, utilization is wound in the flow direction of film structural component control through gas of hollow tow, flow inversely (detailed content as described later) with the direction of the supply of mist, therefore, in the assembly of boring feed type (bore feed Type), gas separaion can be implemented efficiently.
(embodiment in 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 the basic comprising of the gas separation membrane module schematically showing present embodiment.
Gas separation membrane module 601 shown in Figure 17 is the gas separation membrane module of boring feed type (bore feed Type), possesses: the hollow tow 615 become by many hollow cortina 614 boundlings; Accommodate the casing 610 of this hollow tow; With the tube sheet 621,622 arranged at the both ends of hollow tow 615.
Hollow cortina 614 can utilize current known hollow cortina, as long as have gas separating property, can be just the hollow cortina of any materials.As an example, be the hollow cortina that glass macromolecular material is formed by macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. under normal temperature (23 DEG C), its gas separating property is good, therefore preferably.
Hollow tow 615 is the hollow tow become by hollow cortina 614 boundling of such as about 100 ~ 1000000.The shape of the hollow tow 615 that boundling becomes is not particularly limited, but from the viewpoint of the easness of manufacture and the resistance to pressure of casing, as an example, preferably cylindric.Illustrate the form having the substantial parallel arrangement of hollow cortina 614 in fig. 17, but also can be the form of each hollow cortina cross arrangement.
The mist utilizing hollow cortina 614 to be separated is not particularly limited, and such as, can be also the large gas of permeability of more than 2 and the admixture of gas of the little gas of permeability for comprising relative to the ratio of the transmission rates of diffusion barrier.The gas separation membrane module 601 of present embodiment may be used for from mist, being separated specific gas composition in every way.Such as, the dehumidifying of various gas, the humidification of various gas, rich nitrogen or oxygen enrichment etc. can be carried out.
Tube sheet 621,622 is corresponding with casing cross sectional shape and be arranged to discoid, the end of the hollow tow 615 of set under the state of opening maintaining each hollow cortina 614.Tube sheet 621,622 can be the thermoplastic resin such as polyethylene or polypropylene or the thermosetting resin containing epoxy resin or polyurethane resin etc.Tube sheet 621,622 plays the effect of the many hollow cortinas 614 of set integratedly.In addition, the effect of the hollow cortina 614 of sealing each other and between the inner face of hollow tow 615 and casing 610 is played.As shown in figure 17, form 1 confined space 618 (as described later, having through gas discharge outlet 610c) by casing 610 and 2 tube sheets 621,622, in this confined space 618 import through hollow cortina 614 through gas.And then, form mist space 619a by casing 610 and tube sheet 621, formed not through gas compartment 619b by casing 610 and tube sheet 622.It should be noted that, in order between sealed pipe plate 621,622 and the inner face of casing 610, other sealing device can be set.
It should be noted that, as the epoxy resin for tube sheet 621,622, such as when nitrogen membrane module, epoxy resin described such in Japanese Patent Publication 2-36287 etc. can be utilized, in addition, when organic vapor separation assembly, epoxy resin described such in WO2009/044711 etc. can be utilized.
As shown in figure 17, casing 610 is arranged to roughly cylindric as a whole.Casing 610 has the mist entrance 610a for being imported to by mist in casing 610 at upstream side (left side of figure), have not through gas vent 610b on downstream (right side of figure), have through gas vent 610c in sidewall portion.Number through gas vent 610c can be 1, also can be multiple.Multiple can along the sidewall portion of casing 610 to configure at equal intervals through gas vent 610c.In this embodiment, the position (specifically, do not have the position of the exposed portion A1 of the hollow tow 615 of described later film structural component 631) close with the tube sheet 621 of upstream side is formed at through gas vent 610c.
From the mist that mist entrance 610a imports, enter in each hollow cortina 614 from the end face of tube sheet 621, flow towards downstream therein.Now, the part in mist penetrates into outside hollow cortina 614, should be admitted in confined space 618 through gas, and then, be discharged to outside casing via through gas vent 610c.On the other hand, directly not flowing towards downstream in hollow cortina 614 through gas not through hollow cortina, is sent to film from the end face in downstream, then, via not being discharged to outside casing through gas vent 610b.
It should be noted that, Figure 17 schematically shows casing 610, specifically, can be the formation of the such casing of Figure 19.In this embodiment, casing 610 has the cylindrical structural member 611 of both ends opening and is installed on the cap 612,613 at its both ends.Cylindrical member 611 and cap 612,613, as an example, can be metal, plastics system or pottery system.Each cap 612,613 is formed with mist entrance 610a respectively, not through gas vent 610b.As an example, mist entrance 610a and can not be formed at the central part (being seen as central part from cap frontal) of cap 612,613 through gas vent 610b.
As shown in Figure 17, Figure 18, in the gas separation membrane module 601 of present embodiment, be wound with film structural component 631 in the periphery of hollow tow 615.The mode that film structural component 631 abuts with tube sheet 622 in fact with one end 631a, the other end 631b leaves the distance of regulation from tube sheet 621 is configured.In fig. 17, do not represent with region symbol A1 (exposed portion) of the hollow tow 615 of film structural component 631 covering.Film structural component 631 can to cover 50% ~ 95% of the outer surface of hollow tow, the mode of preferably 75% ~ 92% formed.In addition, film structural component 631 also can be formed as follows: both ends and each tube sheet close to and admittedly cover the whole outer surface of hollow tow, near tube sheet 621, on film structural component 631, open one or more holes.
It should be noted that, the end of film structural component " abuts in fact " and refers to: the situation that (i) film end abuts with tube sheet completely; (ii) such as, according to the situation etc. manufactured, film end and the close situation of tube sheet under the state producing gap a little between film end and tube sheet.On the other hand, when tube sheet is epoxy resin etc., when film end enters in tube sheet, (such as, make film end be embedded in tube sheet and the situation etc. that tube sheet is solidified), likely with this part for starting point, tube sheet breaks or produces damage.Therefore, the preferred mode not entering tube sheet inside with film end is formed sometimes.
As long as the material of film structural component 631 gas impermeability in fact can be just any material.It should be noted that, " in fact gas impermeability " refers to: the gas permeation of film structural component 631 is enough little, can limit the stream of gas.Can be such as the plastic foils such as polyimides, polyethylene, polypropylene, polyamide, polyester.Wherein, in heat resistance, solvent resistance, processability, preferred polyimides.Except plastic foil, it also can be the metal forming such as aluminium or stainless steel.The thickness of film can in the scope of tens of μm ~ number mm.Film structural component 631 can be formed as tubular each other by the lateral margin of a set film, maybe can use and not have jointed cylindrical member.As set film device each other, such as bonding agent, adhesive tape etc. can be utilized.
Suppose when not configuring film structural component 631, as shown in the arrow f3 of Figure 18, the direction of advance through gas from hollow cortina 614 is cross flow direction (direction namely intersected with hollow cortina 614).On the other hand, when being wound with film structural component 631 as in the present embodiment on hollow tow 615, preventing scattering and disappearing through gas, as shown in arrow f2, is the direction flowing of adverse current at the direction of the supply f1 of relative mist through gas.
Below, an example of the using method of the separating film module of present embodiment as constructed as above is described.It should be noted that, the using method of the assembly of present embodiment is not limited to following method.
First, mist is imported to the mist space 619a in casing 610 from mist entrance 610a.This mist imported enters in each hollow cortina 614 from the end face of tube sheet 621 and also moves towards downstream therein.Now, the pressure in preferred hollow cortina 614 higher than the pressure of confined space 618, such as, preferably with the pressure feed mist of 0.01MPaG ~ 10MPaG; Confined space 618 is made to be decompression state.Now, a part for mist, optionally through hollow cortina 614, passes out to the confined space 618 outside hollow cortina 614.On the other hand, not through gas directly in hollow cortina 614 to downstream flowing, from the end face in downstream pass out to hollow cortina 614 not through gas compartment 619b.
Gas through hollow cortina 614 is directed in the confined space 618 in casing 610.As shown in figure 18, particularly in the region being wound with film structural component 631, utilize the effect of film structural component 631, scattering and disappearing through gas can be prevented, flow in the arrow f2 direction reverse with the direction of the supply f1 of mist through gas.Then, through gas via the outside being discharged to casing 610 through gas vent 610c (with reference to Figure 17).Not through gas send from the end of downstream side of hollow cortina 614 after, via not being discharged to the outside through gas vent 610b.
In separating film module 601 described above, utilizing film structural component 631 to prevent scattering and disappearing through gas, meanwhile, is the direction flowing of adverse current in the relative mist direction of the supply through gas.Therefore, the separative efficiency improving gas can be sought.
(summary of the invention)
The invention relating to part E is as described below.
1. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with gas separating property becomes;
There is mist entrance, through gas vent and the casing being configured with above-mentioned hollow tow not through gas vent and in inside; With
2 tube sheets at the both ends of fixing above-mentioned hollow tow;
The mist imported from above-mentioned mist entrance is supplied in above-mentioned hollow cortina, by making a part for this mist through carrying out gas separaion, wherein,
I () does not have to arrange structure for supplying Purge gas, described Purge gas for discharge through above-mentioned hollow cortina through gas,
(ii) a kind of film structural component is also possessed, it is the film structural component of the gas impermeability of the outer peripheral face being wound in above-mentioned hollow tow, wherein, abut with the above-mentioned tube sheet in mist direction of the supply downstream in fact with one end, the other end is configured away from the mode of the above-mentioned tube sheet of mist direction of the supply upstream side.
2. the gas separation membrane module as described in above-mentioned 1, wherein, is formed in the mode that an above-mentioned end of film structural component does not enter the inside of above-mentioned tube sheet.
3. the gas separation membrane module as described in above-mentioned 1 or 2, wherein, above-mentioned be arranged to surround through gas vent there is no the part of the above-mentioned casing of the exposed portion of the above-mentioned hollow tow of above-mentioned film structural component.
4., as the gas separation membrane module according to any one of above-mentioned 1 ~ 3, wherein, above-mentioned film structural component is configured to cover 50% ~ 95% of the outer surface of above-mentioned hollow tow in from an above-mentioned tube sheet to the region of another tube sheet.
5., as the gas separation membrane module according to any one of above-mentioned 1 ~ 4, wherein, the material of above-mentioned film structural component is polyimides.
[part F: prevent the gas separation membrane module that gas spills from the clearance portion between film end and tube sheet]
(technical field)
The invention of this part relates to a kind of gas separation membrane module utilizing hollow cortina to carry out gas separaion, in particular to one in the assembly of boring feed type (bore feed Type), prevent gas from spilling from the clearance portion between film end and tube sheet and the gas separation membrane module of gas separaion can be implemented efficiently.
(background technology)
The gas separation membrane module of hollow fiber type possesses usually: have the air silk element of the hollow tow be made up of the many hollow cortina with selective penetrated property and the hollow casing of this air silk element of collecting.The hollow tow of air silk element, its one or both ends utilize the cured plate of resin (tube sheet) to be fixed.In addition, casing is provided with mist entrance, through gas vent and not through gas vent etc.
For the purpose of divided gas flow effectively, such as in Japanese Unexamined Patent Publication 2000-262838, disclose a kind of gas separation membrane module, described gas separation membrane module, in assembly mist being supplied to boring feed type of the what is called in hollow cortina (bore feed Type), is coated to the part of hollow tow with film structural component and the mode clamping hollow cortina with the flowing of the flowing of carrier gas and mist and become convection current is formed.
In the gas separation membrane module of above-mentioned document, the validation of gas separaion can be sought by the flow direction limiting carrier gas, but in the gas separation membrane module not utilizing carrier gas (Purge gas), the efficiency improving gas separaion is also important.On the other hand, no matter with or without utilizing Purge gas, in order to seek the further validation of gas separaion, it is effective for preventing gas from spilling from the clearance portion (detailed content as described later) between film end and tube sheet.
The invention of this part completes in view of above-mentioned problem, its object is to provide a kind of gas separation membrane module, described gas separation membrane module is in the assembly of boring feed type (bore feed Type), prevent gas from spilling from the clearance portion between film end and tube sheet, gas separaion can be implemented efficiently.
Main inventive main points disclosed in this part are as described below.
1. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with gas separating property becomes;
There is mist entrance, through gas vent and the casing being configured with above-mentioned hollow tow not through gas vent and in inside;
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, described film structural component with the above-mentioned tube sheet in one end and mist direction of the supply downstream close to and the other end from the above-mentioned tube sheet of mist direction of the supply upstream side away from mode be configured; With
The hermetically-sealed construction of the clearance portion between an above-mentioned end of diaphragm seal component and above-mentioned tube sheet.
According to the invention of this part, a kind of gas separation membrane module can be provided, described gas separation membrane module, in the assembly of boring feed type (bore feed Type), prevents gas from spilling from the clearance portion between film end and tube sheet, can implement gas separaion efficiently.
(embodiment in part F)
Below, with reference to accompanying drawing, the invention of this part embodiment is described.It should be noted that, in figure 21, as an example, more specifically show the shape of casing (detailed content is as described below).
Gas separation membrane module (hreinafter referred to as assembly) 801 shown in Figure 20, Figure 21 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 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 to the inner side of hollow cortina 814.
Hollow cortina 814 can utilize current known hollow cortina, as long as have gas separating property, can be just any materials.As an example, be the hollow cortina that glass macromolecular material is formed by macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. under normal temperature (23 DEG C), its gas separating property is good, therefore preferably.
Hollow tow 815 is the hollow tow become by hollow cortina 814 boundling of such as about 100 ~ 1000000.The shape of the hollow tow that boundling becomes is not particularly limited, but from the viewpoint of the easness of manufacture and the resistance to pressure of container, as an example, preferably cylindric.In addition, illustrate the form having the substantial parallel arrangement of hollow cortina 814 in fig. 20, but can be the form of each hollow cortina cross arrangement.
The mist utilizing hollow cortina 814 to be separated is not particularly limited, and such as, can be the large gas of permeability of more than 2 and the admixture of gas of the little gas of permeability for comprising relative to the ratio of the transmission rates of diffusion barrier.The gas separation membrane module 801 of present embodiment may be used for being separated specific gas composition from mist in every way.Such as, the dehumidifying of various gas, the humidification of various gas, rich nitrogen or oxygen enrichment etc. can be carried out.
Tube sheet 821,822 is corresponding with the shape of casing 810 and be set to roughly discoid, the end of fixation hollow tow 815 under the state of opening maintaining each hollow cortina 814.Tube sheet 821,822 can be the thermoplastic resin such as polyethylene or polypropylene or the thermosetting resin containing epoxy resin or polyurethane resin etc.Tube sheet 821,822 plays the effect of the many hollow cortinas 814 of set integratedly.In addition, the effect of the hollow cortina 814 of sealing each other and between the inner face of hollow tow 815 and casing 810 is played.As shown in figure 20, form 1 confined space 818 (as described later, having through gas discharge outlet 810c) by casing 810 and 2 tube sheets 821,822, in this confined space 818 import through hollow cortina 814 through gas.And then, form mist space 819a by casing 810 and tube sheet 821, formed not through gas compartment 819b by casing 810 and tube sheet 822.It should be noted that, in order between sealed pipe plate 821,822 and the inner face of casing 810, also other sealing device can be set.
It should be noted that, as the epoxy resin for tube sheet 821,822, such as when nitrogen membrane module, epoxy resin described such in Japanese Patent Publication 2-36287 etc. can be utilized, in addition, when organic vapor separation assembly, epoxy resin described such in WO2009/044711 etc. can be utilized.
As shown in figure 20, casing 810 is set to roughly cylindric as a whole.Casing 810 has the mist entrance 810a for being imported by mist in casing 810 at upstream side (left side of figure), have not through gas vent 810b on downstream (right side of figure), have through gas vent 810c in sidewall portion.Number through gas vent 810c can be 1, also can be multiple.Multiple can along the sidewall portion of casing 810 to configure at equal intervals through gas vent 810c.In this embodiment, the position (specifically, do not have the position of the exposed portion A1 of the hollow tow 815 of described later film structural component 831) close with the tube sheet 821 of upstream side is formed at through gas vent 810c.
From the mist that mist entrance 810a imports, enter in each hollow cortina 814 from the end face of tube sheet 821 and also flow towards downstream therein.Now, the part in mist penetrates into outside hollow cortina 814, should be fed in confined space 818 through gas, and then, be discharged to outside casing via through gas vent 810c.On the other hand, directly not flowing towards downstream in hollow cortina 814 through gas not through hollow cortina, is sent to film from the end face in downstream, then, via not being discharged to outside casing through gas vent 810b.
It should be noted that mist entrance 810a and/or not through gas vent 810b can be configured to its central shaft consistent with the central shaft (i.e. the central shaft of hollow tow 815) of casing 810.In addition, as shown in the example of Figure 21 (A), casing 810 can have cylindrical structural member 811 and be installed on the tube sheet retaining member 813 (one is not shown) at 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 is certain line part 813a, diameter dimension is greater than this line part 813a large-diameter portion 813b and the tapered portion 813c that diameter dimension slowly diminishes.It should be noted that, as shown in Figure 21 (A), tube sheet 822 have the hollow cortina embedded portion 822a that there is hollow cortina 814 and its periphery do not have hollow cortina 814 without dirty portion 822b.
As shown in Figure 20, Figure 21, in the gas separation membrane module 801 of present embodiment, be wound with film structural component 831 at the outer peripheral face of hollow tow 815.The mode that film structural component 831 is close with tube sheet 822 with one end 831a (also referred to as film end 831a), the other end 831b leaves the distance of regulation from tube sheet 821 is configured.In fig. 20, do not represented by symbol A1 (exposed portion) with the region of the coating hollow tow 815 of film structural component 831.Film structural component 831 can be formed with 50% ~ 95% of outer surface of coating hollow tow, the mode of preferably 70% ~ 92%.In addition, film structural component 831 can be formed as follows: both ends and each tube sheet close to and cover the whole outer surface of hollow tow, near tube sheet 821, film structural component 831 is opened one or more holes.
As long as film structural component 831 is the material of gas impermeability in fact, it can be just any material.It should be noted that, " in fact gas impermeability " refers to that the gas permeation of film structural component is enough little, can limit the stream of gas.Can be such as the plastic foils such as polyimides, polyethylene, polypropylene, polyamide, polyester.Wherein, in heat resistance, solvent resistance, processability, preferred polyimides.Except plastic foil, it also can be the metal forming such as aluminium or stainless steel.The thickness of film can in the scope of tens of μm ~ number mm.
Film structural component 831 can be formed as tubular each other by the lateral margin of a set film, or also can use and do not have jointed cylindrical member.As the lateral margin device each other of set film, such as bonding agent, adhesive tape etc. can be utilized.
It should be noted that, such as, when tube sheet is epoxy resin, when film end enters in tube sheet, (such as, make film end be embedded in tube sheet material and the situation etc. be cured), likely with this part for starting point, tube sheet breaks or produces damage.Therefore, in the present embodiment, film end is formed in the mode be not embedded in tube sheet.On the other hand, when for such formation, as shown in figure 21, between film end 831a and tube sheet 822, likely produce clearance portion A31 (in order to illustrate, the size of clearance portion A31 exaggerated describes).
As shown in Figure 20, Figure 21, in the present embodiment, the hermetically-sealed construction 850 of the clearance portion A31 between diaphragm seal end 831a and tube sheet 822 is provided with.In this embodiment, hermetically-sealed construction 850 is configured in film two sides in the mode clamping film 831a, and the mode surround with hollow tow 815 is formed as 2 bands 851,853 (with reference to Figure 21) of tubular.
Band 851,853 is formed by the material of saturable liquid resin material (be epoxy as an example), in other words, is formed by the material of the capillary force with regulation.As long as band 851,853 has the material of such function, can be just any materials, such as, can for enrolling the mesh material (such as cloth-like or netted material) that fiber makes.Fiber can be such as chemical fibre or natural fiber, also can utilize glass fibre or carbon fiber etc.
As 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 configures in the mode extending to tube sheet 822 side from film end 831a.The part of extending of each band 851,853 be embedded in tube sheet 822 without dirty portion 822b.
As shown in Figure 21 (A), the 1st band 851 is pasted with the fixation adhesive tape 855 sealing band 851 being fixed on film structural component 831.As an example, fixation adhesive tape 855 can attach in the peripheral part mode of reciprocal a week at hollow tow 815.Fixation adhesive tape 855 can be reeled more than two circles, or only can attach fixation adhesive tape 855 in a part for peripheral part.
As shown in Figure 21 (B), the overlapping portion of 2 bands 851,853 can be fixed by fixture 857.As fixture 857, as an example, can be the mechanical device fixing two components, also can be the pin of such as stapler.In addition, such as also silk or wire etc. can be utilized.
As described later, band 851,853 has the function preventing from spilling from clearance portion A31 through gas.Spill to prevent efficiently, the region towards at least clearance portion A31 in band 851,853 is impregnated with resin material and the state of solidification.Thus, give gas impermeability to band 851,853, its result, can prevent spilling of gas further.It should be noted that, process as above can only to an enforcement in 2 bands 851,853.
Film structural component 831 and hermetically-sealed construction 850 such as can make as follows.It should be noted that, following operation is a simple example, and the invention of this part is not by any restrictions such as this process sequences.
First, hollow tow 815 and casing (material of such as Figure 21) is prepared.In addition, prepare 1 film structural component 831 of size being formed as specifying, meanwhile, to clamp mode near the 831a of its end at 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 be wound in hollow tow 815 and fixed with such as adhesive tape (not shown).Then, the assigned position in casing 810 configures hollow tow 815, form tube sheet 821,822 at the both ends of hollow tow 815.Tube sheet 821,822 can by being filled in the end of hollow tow 815 and making it solidify to be formed by epoxy material.
Be specifically described with the example of Figure 21.As one example, epoxy material be filled in following state under carry out: the casing 810 having hollow tow 815 to enter is remained on vertical direction and in casing bottom, mould (not shown) is installed.Now, as shown in Figure 21 (A), the front end that the liquid level of the epoxy material of filling is set in band 851,853 to be embedded in tube sheet 822 but not to 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 (at least comprising the region of the part towards clearance portion A31), soak into epoxy material.
Then, the tube sheet 822 after solidification tube sheet material being solidified by cut-out on assigned position, makes hollow cortina 814 opening.Then, as required, carry out the assembling procedure (operation etc. such as make casing 810 complete) same with existing operation, assembly is completed.
It should be noted that, can with following be arranged in order film structural component 831 and band 851,853: first, the 2nd band 853 is wound in hollow tow 815, then, winding film structural component 831, then, winding the 1st band 851.
Below, an example of the using method of the separating film module of present embodiment as constructed as above is described.It should be noted that, the using method of the assembly of present embodiment is not limited to following method.
First, mist is imported to the mist space 819a in casing 810 from mist entrance 810a.This mist imported enters in each hollow cortina 814 from the end face of tube sheet 821 and also moves towards downstream therein.Now, the pressure in preferred hollow cortina 814 higher than the pressure of confined space 818, such as, preferably with the pressure feed mist of 0.01MPaG ~ 10MPaG; Confined space 818 is made to be decompression state.Now, a part for mist, optionally through hollow cortina 814, is sent to the confined space 818 outside hollow cortina 814.On the other hand, not through gas directly in hollow cortina 814 towards downstream flowing, from the end face in downstream be released to hollow cortina 814 not through gas compartment 819b.
Suppose when not configuring film structural component 831, as shown in the arrow f3 of Figure 21 (B), the direction of advance through gas from hollow cortina 814 is cross flow direction (direction namely intersected with hollow cortina 814).Or, as shown in f4, the direction of advance through gas be the flowing contrary with f2 such and flow path direction, and, be the flowing that f3 is such.On the other hand, as in the present embodiment, when hollow tow 815 being wound with film structural component 831, scattering and disappearing through gas can be prevented, be the direction flowing of the arrow f2 of adverse current at the direction of the supply f1 of relative mist through gas, its result, can improve the efficiency of gas separaion.Particularly in the present embodiment, be provided with the hermetically-sealed construction 850 that clearance portion A31 is sealed, can prevent from escaping to outside through gas by this clearance portion A31.Therefore, scattering and disappearing through gas can be prevented more reliably, the validation of gas separaion can be carried out more well.
Preventing from spilling the structure that can native directly be embedded in tube sheet 822 by making film end 831a through gas to realize, now, likely producing as described above with breaking or damaging for the tube sheet 822 of starting point near the 831a of film end.Corresponding thereto, in the present embodiment, for burying the formation of the band 851,853 of the component different from film structural component 831 underground, therefore, by being suitable for the material selecting band, the generation of breaking or damaging of such tube sheet 822 can be prevented.
As mentioned above, even if band 851,85 is mesh material, compared with the situation of any band is not set, also spilling through gas can be suppressed.But in the present embodiment, and then impregnated with resin material band 851,853 also in this solidification, therefore, can prevent spilling through gas more reliably.
(other embodiment)
Above, a mode of the invention of this part is illustrated, but the invention of this part is not limited to foregoing, can various change be carried out.
Such as, can for only having the mode of any one in the 1st and the 2nd band 851,853.In addition, the fixation adhesive tape 855 the 1st band 851 being fixed on film structural component 831 also can omit.In addition, the fixture 857 (with reference to Figure 21 (B)) of fixing the overlapping portion of 2 bands 851,853 also can be omitted.
Figure 22 represents other seal ring structure, and the schematic sectional view that Figure 22 (A) is component integration, Figure 22 (B) is its magnified partial view.In this embodiment, for hermetically-sealed construction, illustrate and have the packing material 891 configured in the mode of the clearance portion A31 between landfill film structural component 831 and tube sheet 822.For packing material 891, as an example, it can be the resin material (as an example for heat-resistance silicone) injected in the mode of surrounding film structural component 831.Utilize such packing material 891, also can prevent from spilling from clearance portion A31 through gas, its result, the assembly can implementing effective gas separaion can be obtained.Packing material 891 such as can be formed by the following method: form tube sheet 822 in casing after, and wall box is formed one or more holes, injects packing material 891 and make it solidify from hole.
The place arranging such packing material 891 is not limited to the position shown in Figure 22.Such as shown in Figure 23, between film structural component 831 and casing 810, leave the position of predetermined distance from clearance portion A31, packing material 893 can be configured.As 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 with can block the flowing of gas mode and to configure in the periphery of film structural component 831 mode of reciprocal a week, for its width, as an example, can be more than about the 3mm ~ 5mm outer surface of the such as film (0.5%).
Or, at the periphery of film structural component 831 packing material of reciprocal a week, can fill in broader (length) scope in the mode in the gap between landfill film structural component 831 and casing 810, such as, the scope of more than 10% of the outer surface of cover layer component can be accounted for.
In addition, as shown in figure 24, the gas separation membrane module of the invention of this part can have the structure for making Purge gas flow.This gas separation membrane module possess hollow tow 915, casing 910, fixation hollow tow 915 both ends 2 tube sheets 921,922, be wound in the hermetically-sealed construction 950 of the film structural component 931 of the gas impermeability of the outer peripheral face of hollow tow and the clearance portion between the end of diaphragm seal component 931 and tube sheet 922.This gas separation membrane module also possesses the core pipe 971 for delivery of purge gas.
Same with the assembly of Figure 20, casing 910 has mist entrance 910a at upstream side (left side of figure), has through gas vent 910c in sidewall portion.Than tube sheet 922 farther downstream the structure of side and the assembly of Figure 20 slightly different, formed not through gas vent 910b in the sidewall portion of casing 910, at the central part of casing 910 by core pipe 971.
Core pipe 971 is the inaccessible and component of another one opening of one in two ends, and opening portion is becoming the direction configuration in downstream (tube sheet 922 side).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 has hole 971a becoming the region between 2 tube sheets 921,922.
For assembly as constructed as above, the principle of basic gas separaion is identical with the assembly of Figure 20.Supply Purge gas from the opening portion (Purge gas entrance 910d) of core pipe 971, this Purge gas passing hole 971a is released in the confined space 918 in casing 910.This Purge gas between hollow cortina 914 f2 direction (the relative mist direction of the supply is the direction of adverse current) flowing, by be released in isospace through gas extrusion to through gas vent 910c side, promote the discharge through gas thus.
In the assembly utilizing such Purge gas, the hermetically-sealed construction 950 of the clearance portion between diaphragm seal component 931 and tube sheet 922 is also preferably set.Hermetically-sealed construction 950 also can use any one in above-mentioned various structures.Thus, prevent from spilling from clearance portion through gas and Purge gas, make to flow well in f2 direction through gas and Purge gas, its result, can seek the further validation of gas separaion.
(summary of the invention)
The invention relating to part F is as described below.
1. a gas separation membrane module, possesses:
By the hollow tow that the many hollow cortina boundling with gas separating property becomes;
There is mist entrance, through gas vent and the casing being configured with above-mentioned hollow tow not through gas vent and in inside;
2 tube sheets at the both ends of fixing above-mentioned hollow tow;
Be wound in the film structural component of the gas impermeability of the outer peripheral face of above-mentioned hollow tow, described film structural component with the above-mentioned tube sheet in one end and mist direction of the supply downstream close to and the mode that the other end is left from the above-mentioned tube sheet of mist direction of the supply upstream side be configured; With
To the hermetically-sealed construction that the clearance portion between the above-mentioned end of film structural component and above-mentioned tube sheet seals.
2. the gas separation membrane module as described in above-mentioned 1, wherein, above-mentioned hermetically-sealed construction has band, described band is wound in radially inner side or the outside of above-mentioned film structural component in an above-mentioned end of film structural component, and extend from this end towards above-mentioned tube sheet side, a part of extending is embedded in above-mentioned tube sheet.
3. the gas separation membrane module as described in above-mentioned 2, wherein, as above-mentioned band, has the 1st band and the 2nd band,
Described 1st band is formed by the saturable material of aqueous resin material, is wound in the radial outside of above-mentioned film structural component;
Described 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. the gas separation membrane module as described in above-mentioned 2 or 3, wherein, above-mentioned band is mesh material.
5. the gas separation membrane module as described in above-mentioned 3 or 4, wherein, in above-mentioned band at least towards in the region of above-mentioned clearance portion, impregnated with resin material also solidifies, and seals above-mentioned clearance portion thus.
6. the gas separation membrane module as described in above-mentioned 3, wherein, above-mentioned hermetically-sealed construction also has the fixation adhesive tape above-mentioned 1st band being fixed on above-mentioned film structural component.
7. the gas separation membrane module as described in above-mentioned 3, wherein, above-mentioned hermetically-sealed construction also has fixture, the extension that described fixture is used for fixing above-mentioned 1st band extended from an above-mentioned end of film structural component and the extension of above-mentioned 2nd band extended from an above-mentioned end of film structural component.
8. the gas separation membrane module as described in above-mentioned 1, wherein, above-mentioned hermetically-sealed construction has the packing material configured in the mode of the above-mentioned clearance portion between an above-mentioned end of landfill film structural component and above-mentioned tube sheet.
9., as the gas separation membrane module according to any one of above-mentioned 1 ~ 8, its mode not entering the inside of above-mentioned tube sheet with an above-mentioned end of film structural component is formed.
10., as the gas separation membrane module according to any one of above-mentioned 1 ~ 9, wherein, the material of above-mentioned film structural component is polyimides.
[part G: the gas separation membrane module fully guaranteeing the sealing property of tube sheet periphery]
(technical field)
The present invention relates to a kind of gas separation membrane module utilizing hollow cortina to carry out gas separaion, in particular to a kind of gas separation membrane module etc., even if described gas separation membrane module is when using cure shrinkage to be relatively easy to 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 module of hollow fiber type possesses usually: have the air silk element of the hollow tow be made up of the many hollow cortina with selective penetrated property and the hollow casing of this air silk element of collecting.The one or both ends of hollow tow utilize the cured plate of resin (tube sheet) to be fixed.
Usual the supplied gas of gas separation membrane is more HTHP, and the transmission rates of gas is larger.Therefore, when using gas separation membrane module, sometimes studying and being supplied to assembly by after the compressions such as unstrpped gas compressor reducer.Gas after this compression is according to circumstances 149 DEG C ~ about 260 DEG C sometimes.
But, there are the following problems: when carrying out the assembly of separation of mist of high temperature as above, need to use the tube sheet material with heat resistance, but such tube sheet material is the easy cure shrinkage when being cured usually, its result, the sealing property of tube sheet periphery is likely insufficient.The invention of this part completes in view of this aspect, its object is to provide a kind of separating film module etc., even if described separating film module is when using cure shrinkage to be relatively easy to tube sheet material, also can guarantee the sealing property of tube sheet periphery fully, and then can at high temperature use well.
Main inventive main points disclosed in this part are as described below.
The gas separation membrane module of a mode of the invention of this part possesses:
By the hollow tow that the many hollow cortina boundling with gas separating property becomes;
The casing of above-mentioned hollow tow is configured with in inside; With
The tube sheet of at least one end of fixing above-mentioned hollow tow;
Described gas separation membrane module is formed in the mode that the outer peripheral face of above-mentioned tube sheet is not bonding with the inner peripheral surface of above-mentioned casing,
Wherein, described gas separation membrane module also possesses the containment member will sealed between the outer peripheral face of above-mentioned tube sheet and the inner peripheral surface of above-mentioned casing.
In addition, the manufacture method of the gas separation membrane module of a mode of the invention of this part, described gas separation membrane module possesses: the tube sheet of at least one end of the hollow tow become by the many hollow cortina boundling with gas separating property, the casing being configured with above-mentioned hollow tow in inside and fixing above-mentioned hollow tow, wherein, described manufacture method comprises following steps:
The step of the part release agent application that at least above-mentioned tube sheet in the inner peripheral surface of above-mentioned casing connects,
The step of a part of filled thermoset resin in above-mentioned casing,
By make above-mentioned thermosetting resin cured form above-mentioned tube sheet step and
Above-mentioned thermosetting resin cured after the step of containment member is set between the outer peripheral face and the inner peripheral surface of above-mentioned casing of above-mentioned tube sheet.
It should be noted that, described in the term in this description is defined as follows.
" hot conditions " or " high temperature " refers in the scope of such as 80 DEG C ~ 300 DEG C.
" cylindrical container " is not limited to the container of both ends open, also comprises the container of only one end open.
According to the invention of this part, a kind of gas separation membrane module etc. can be provided, even if described gas separation membrane module is when using cure shrinkage to be relatively easy to tube sheet material, also the sealing property of tube sheet periphery can fully be guaranteed, and, even if at high temperature, also can use well.
(embodiment in part G)
Below, with reference to accompanying drawing, the invention of this part embodiment is described.It should be noted that, in fig. 25, as an example, more specifically show the shape of casing (following in detail).In addition, the formation of following explanation is the formation of expression one example after all, and gas separation membrane module of the present invention is not limited to these and forms.
Gas separation membrane module (following, also referred to as assembly) 1001 shown in Figure 25, Figure 26 possesses: the hollow tow 1015 become by many hollow cortina 1014 boundlings, the casing 1010 of accommodating this hollow tow and the tube sheet 1021,1022 arranged 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 to the inner side of hollow cortina 1014.
Hollow cortina 1014 can utilize current known hollow cortina, as long as have gas separating property, can be just the hollow cortina of any materials.As an example, be the hollow cortina that glass macromolecular material is formed by macromolecular material, particularly polyimides, polysulfones, PEI, polyphenylene oxide, Merlon etc. under normal temperature (23 DEG C), gas separating property is good, therefore preferably.
Hollow tow 1015 is the hollow tow become by hollow cortina 1014 boundling of such as about 100 ~ 1000000.The shape of the hollow tow 1015 that boundling becomes is not particularly limited, but from the viewpoint of the easness of manufacture and the resistance to pressure of container, as an example, preferably cylindric.In addition, illustrate the form having the substantial parallel arrangement of hollow cortina 1014 in fig. 25, but can be the form of each hollow cortina cross arrangement.
The mist utilizing hollow cortina 1014 to be separated is not particularly limited, and such as, can be the large gas of permeability of more than 2 and the admixture of gas of the little gas of permeability for comprising relative to the ratio of the transmission rates of diffusion barrier.The gas separation membrane module 1001 of present embodiment may be used for being separated specific gas composition from mist in every way.Such as, the dehumidifying of various gas, the humidification of various gas, rich nitrogen or oxygen enrichment etc. can be carried out.
Tube sheet 1021,1022 is corresponding with the shape of casing 1010 and be formed as roughly discoid (detailed content is as described below), the end of fixation hollow tow 1015 under the state of opening maintaining each hollow cortina 1014.Tube sheet plays the effect each other of the hollow cortina of sealing in this embodiment.Tube sheet can also be the thermoplastic resin such as polyethylene or polypropylene or the thermosetting resin containing epoxy resin or polyurethane resin etc.Below, the example that tube sheet is thermosetting resin is described.
It should be noted that, as the epoxy resin for tube sheet 1021,1022, such as when nitrogen membrane module, epoxy resin described such in Japanese Patent Publication 2-36287 etc. can be utilized, in addition, when organic vapor separation assembly, epoxy resin described such in WO2009/044711 etc. can be utilized.
As shown in figure 25, in the present embodiment, form 1 confined space 1018 (as described later, having through gas discharge outlet 1010c) by casing 1010 and 2 tube sheets 1021,1022, in this confined space 1018 import through hollow cortina 1014 through gas.And then, form mist space 1019a by casing 1010 and tube sheet 1021, formed not through gas compartment 1019b by casing 1010 and tube sheet 1022.
As shown in figure 25, casing 1010 is set to roughly cylindric as a whole.Casing 1010 has the mist entrance 1010a for importing mist in casing 1010 at upstream side (left side of figure), have not through gas vent 1010b on downstream (right side of figure), have through gas vent 1010c in sidewall portion.Number through gas vent 1010c can be 1, also can be multiple.Multiple can along the sidewall of casing 1010 to configure at equal intervals through gas vent 1010c.
From the mist that mist entrance 1010a imports, enter in each hollow cortina 1014 from the end face of tube sheet 1021, flow towards downstream therein.Now, the part in mist be penetrated into outside hollow cortina 1014 through gas, should be admitted in confined space 1018 through gas, then, be discharged to outside casing via through gas vent 1010c.On the other hand, directly not flowing to downstream in hollow cortina 1014 through gas not through hollow cortina, is sent to film from the end face in downstream, then, via not being discharged to outside casing through gas vent 1010b.
It should be noted that, mist entrance 1010a and/or can not to be configured to its central shaft through gas vent 1010b consistent with the central shaft (i.e. the central shaft of hollow tow 1015) of casing 1010.In addition, as shown in the example of Figure 26, casing 1010 can have cylindrical structural member 1011 and be installed on the cap component 1012 (one is not shown) at its both ends.Cylindrical member 1011 and cap component 1012 can be metal as an example.
Specifically, cylindrical structural member 1011 is internal diameters is d 0hollow unit and form heavy section 1011a, 1011b in its end.1st heavy section 1011a is arranged near the end face of cylindrical structural member 1011, and the internal diameter of this part is formed as than internal diameter d 0little.2nd heavy section 1011b is arranged at than the 1st heavy section 1011a more by inside direction of principal axis, and the internal diameter of this part is also formed as than internal diameter d 0little.The internal diameter of the part between heavy section 1011a and heavy section 1011b is greater than the internal diameter of two heavy section 1011a, 1011b, can be d as an example 0.
Corresponding with such structure of cylindrical structural member 1011, tube sheet 1021 is formed as following shape.Namely, as 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 outside), wherein, is that maximum mode is arranged with the diameter of mid portion 1021b.In this embodiment, the boundary of part 1 1021a and part 2 1021b is taper surface.In addition, the boundary of part 2 1021b and the 3rd part 1021c is for facing directly in (face at the Directional Extension of the orthogonality of center shaft with cylindrical structural member).
When using separating film module 1001, utilize the pressure of mist, tube sheet 1021 applies the power this tube sheet being squeezed into the direction in cylindrical structural member 1011.But the formation such according to Figure 26, a part for tube sheet 1021 and heavy section 1011b abut, and can limit the movement of tube sheet 1021 thus, and therefore, tube sheet 1021 can not be squeezed into inside.
It should be noted that, do not limit, but the connecting portion 1021f of the part 2 1021b of tube sheet and the 3rd part 1021c can be provided with R shape.Thus, the stress that can relax in this part is concentrated and is prevented the breakage etc. of tube sheet.
The example of Figure 26 represents that tube sheet 1021 is thermosetting resin and the state making the diametric shrinkage of tube sheet 1021 some because of cure shrinkage.When such formation, likely fully can not guaranteeing the sealing between tube sheet 1021 and cylindrical structural member 1011, therefore, in the present embodiment, being provided with the containment member 1060 of the ring-type for sealing between two components.
As shown in figure 26, the rank portion 1021s of ring-type is formed at the peripheral part of the part 1 1021a of tube sheet.The inner peripheral surface of this rank portion 1021s and cylindrical structural member 1011 collaborates, and integrally forms the groove C1 of ring-type, is configured with the containment member 1060 of ring-type in this groove C1.
Containment member 1060 is the annular element formed by elastic component, also can for being embedded in the part (such as O ring etc.) in groove C1.Or, can for the resin material of sealing to be filled in groove C1 and the part being solidified by this resin material and work as containment member.The cross sectional shape of O ring can be circular, also can be oval.As " part of the ring-type be made up of elastic component ", except O ring, can be the V-seal part of roughly V-type, generally u-shaped U-shaped seal etc. for cross sectional shape.And then, can be such as the part of rectangle, polygonal or X-type prismatic shapes.It should be noted that, in the example of Figure 26, seal between containment member 1060 pairs of tube sheets 1021 and casing 1010, also seal between tube sheet 1021 and cap component 1012 simultaneously.
In addition, the structure shown in Figure 26 is an example after all, to the invention of this part without any restriction.Such as, the part 1 1021a of tube sheet can be identical with the diameter of the 3rd part 1021c.Or, can use and form such tube sheet by part 1 1021a and the 3rd part 1021c.In addition, the face between part 1 1021a and 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, containment member 1060 pairs of tube sheets 1021, to seal between casing 1010 and cap component 1012, but also can be different from the containment member between tube sheet 1021 and casing 1010, possess the containment member between casing 1010 and cap component 1012 in addition.
Figure 27 is the sectional view in the A-A line of Figure 26.As shown in the drawing, also recess 1011d, 1011d can be formed with at two places of the inner peripheral surface of cylindrical structural member 1011.Now, tube sheet component enters into this recess 1011d, 1011d and is cured (detailed content is as described below), and its result can prevent the rotation of tube sheet 1021.It should be noted that, the number of recess 1011d is not particularly limited, 1 can be only, also can be more than 3.
Manufacturing the method for the gas separation membrane module 1001 formed as mentioned above, can be method as described below as an example.That is, the manufacture method of present embodiment comprises following steps:
The step of a part release agent application that () at least connects at tube sheet in the inner peripheral surface of casing;
B () part in casing fills the step of the thermosetting resin before solidification;
C () is by making the thermosetting resin cured step forming tube sheet after being filled; With
D () arranges the step of the containment member of ring-type after thermosetting resin cured between the outer peripheral face and the inner peripheral surface of casing of tube sheet.
By release agent application as the step of above-mentioned (a), in the curing process of step (c), tube sheet (be epoxy resin as an example) is from the demoulding well casing (be metal as an example).Suppose that, when not using releasing agent, when resin solidification, likely tube sheet does not leave from main body, according to circumstances on tube sheet, produces crack etc.
In the step of above-mentioned (b), not shown mould can be installed on the end of cylindrical structural member 1011, implement the injection of tube sheet resin in this condition.Now, mould has the protuberance of the ring-type corresponding with the rank portion 1021s of tube sheet (with reference to Figure 26), utilizes this protuberance, can form rank portion 1021s on tube sheet.
In the step of above-mentioned (d), as mentioned above, the annular resilient components such as such as O ring can be embedded in groove C1, or in groove C1 resin by injection make it solidify, containment member 1060 can be formed thus.
According to the above gas separation membrane module 1001 that such present embodiment is described, even if when the cure shrinkage because of tube sheet 1021 can not guarantee the sealing between tube sheet outer peripheral face and casing inner peripheral surface, also containment member 1060 is provided with separately, therefore, the sealing between two components can be guaranteed fully.
It is favourable to the situation of the gas separation membrane module particularly at high temperature used.That is, generally speaking, not easily the material of cure shrinkage has and has elasticity and glass transition temperature is low, lack the trend of heat resistance.On the other hand, the tube sheet material of excellent heat resistance has the trend of easy cure shrinkage.Suppose when use the material of such heat resistance and tube sheet formation like that bonding with casing, likely apply extension stress because of the cure shrinkage of tube sheet material, tube sheet produce crack.Corresponding thereto, according to the present embodiment, prevent the bonding of tube sheet material by release agent application in casing, meanwhile, utilize annular seal component to guarantee the sealing between tube sheet and casing.Therefore, can provide a kind of to prevent from producing crack on tube sheet and the gas separation membrane module also guaranteeing sealing property fully.
It should be noted that in the above description, 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.Or, only the such structure of Figure 26 can be set on a tube sheet.And then, the structure of tube sheet, annular seal component and casing is not limited to the assembly of boring feed type (borefeed Type) as the present embodiment, also can be applicable to the assembly of shell feed type (shell feed Type), the assembly of other type can also be applied to.
(summary of the invention)
The invention that part G relates to is as described below.
1. a gas separation membrane module, possesses:
The hollow tow that the many hollow cortina boundling with gas separating property is become,
Be configured with in inside above-mentioned hollow tow casing and
The tube sheet of at least one end of fixing above-mentioned hollow tow;
Described gas separation membrane module is formed in the mode that the outer peripheral face of above-mentioned tube sheet is not bonding with the inner peripheral surface of above-mentioned casing,
Wherein, described gas separation membrane module also possesses the containment member to sealing between the outer peripheral face of above-mentioned tube sheet and the inner peripheral surface of above-mentioned casing.
2. the gas separation membrane module as described in above-mentioned 1, wherein, above-mentioned tube sheet has and collaborates with the inner peripheral surface of above-mentioned casing and form the rank portion of the groove of ring-type.
3. the gas separation membrane module as described in above-mentioned 1 or 2, wherein, above-mentioned casing has the cylindrical member surrounding above-mentioned hollow tow and the cap component arranged in the end of this cylindrical member,
Above-mentioned cylindrical member is formed the heavy section that inner-diameter portion whose diminishes, and above-mentioned tube sheet abuts with this heavy section, prevents above-mentioned tube sheet to the movement inside the direction of principal axis of above-mentioned cylindrical member thus.
4., as the gas separation membrane module according to any one of above-mentioned 1 ~ 3, wherein, above-mentioned containment member is the annular resilient component of the groove being embedded in above-mentioned ring-type.
5. the manufacture method of a gas separation membrane module, described gas separation membrane module possesses: the tube sheet of at least one end of the hollow tow become by the many hollow cortina boundling with gas separating property, the casing being configured with above-mentioned hollow tow in inside and fixing above-mentioned hollow tow, wherein, described gas separation membrane module comprises following steps:
The step of the part release agent application that at least above-mentioned tube sheet in the inner peripheral surface of above-mentioned casing connects,
The step of a part of filled thermoset resin in above-mentioned casing,
By make above-mentioned thermosetting resin cured form above-mentioned tube sheet step and
Above-mentioned thermosetting resin cured after the step of containment member is set between the outer peripheral face and the inner peripheral surface of above-mentioned casing of above-mentioned tube sheet.
[embodiment]
[relating to the embodiment of part A]
Below, the invention of embodiment to part A is utilized to be further described.It should be noted that, the invention of part A is not limited to following embodiment.
The assay method > of the glass transition temperature (Tg) of the hollow cortina of <
According to the assay method of the extrapolation Glass Transition initial temperature of JIS K7121, use Shimadzu Seisakusho Ltd. DSC50 device, under sample size 2mg, blanket of nitrogen gas, implement the mensuration of glass transition temperature (Tg) with 10 DEG C/min from room temperature to 400 DEG C.
The assay method > of the form trait rate of the hollow cortina of <
In the mensuration of form trait rate, the length before and after the heat treatment air silk of 200mm length being maintained in the hot air type thermostat of 175 DEG C 2 hours is measured.Length after heat treatment is set to form trait rate relative to the ratio of the length of the script before heat treatment.
The assay method > of < solution viscosity
The solution viscosity of polyimide solution uses rotation viscometer (the shear rate 1.75sec of rotor -1) measure at temperature 100 DEG C.
< Production Example 1>
In the removable flask being provided with mixer and nitrogen ingress pipe, 4 are added together with solvent 4-chlorophenol 1882g, 4 '-(hexafluoroisopropylidenyl)-bis-(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, while pass into nitrogen limit under agitation carry out polymerization imidization reaction 20 hours at reaction temperature 190 DEG C in flask, prepare the aromatic polyimide solution that polyimides concentration is 17 % by weight.Solution viscosity during 100 DEG C of this aromatic polyimide solution is 1940 pools.
The above-mentioned aromatic polyimide solution be prepared into is filtered with the wire netting of 400 meshes, it can be used as doping liquid, use the device for spinning possessing air silk spinning nozzle, from air silk spinning nozzle (circular open portion external diameter 1000 μm, circular open portion slit width 200 μm, core opening portion external diameter 400 μm) circular open portion ejection doping liquid, simultaneously from core opening portion ejection nitrogen, form hollow filamentous, after it is passed through in blanket of nitrogen, impregnated in solidification liquid makes it solidify, carry-over pinch rolls are utilized to draw, obtain moistening hollow cortina.Then, this hollow cortina dry, heats 30 minutes further, obtains hollow cortina 1 at 250 DEG C.
The hollow cortina 1 of gained roughly external diameter is 410 μm, and internal diameter is 280 μm.Form tow element by hollow cortina, then, form gas separation membrane module by the tow element of these each hollow cortinas.
Below in embodiment 1,2, use the air separation membrane module 1 that have employed the hollow cortina 1 of above-mentioned manufacture, in comparative example 1,2, use and have employed the air separation membrane module 2 of following hollow cortina 2 or have employed the air separation membrane module 3 of hollow cortina 3.
Characteristic etc. about each hollow cortina is shown in table 1.Glass transition temperature, form trait rate utilize said method to measure.
[table 1]
*1: hollow cortina 1 is less than 300 degree at glass transition temperature not to be existed, and can not measure with said method.
*2:P ' o2oxygen transmission rates when representing 40 DEG C.
Various situations about each air separation membrane module are shown in table 2.
[table 2]
The embodiment 1> of < part A
With pressure 0.2MPaG, the air of 175 DEG C is supplied to air separation membrane module 1, is 12% through the oxygen concentration in gas and nitrogen-rich air mode adjusts air quantity delivered with non-, operates continuously under this condition.In each elapsed time after starting running, the flow of the nitrogen-rich air made by mensuration.Measurement result is shown in Fig. 1.In addition, according to measurement result, calculate air separation membrane after 0 hour, 140 hours, 2069 hours from running oxygen transmission rates (P ' o2), the ratio of the display Oxygen Transmission Rate of separating property and nitrogen transmission rates (P ' o2/ P ' n2).The results are shown in table 3.
In the moment started running (0 hour), P ' o2be 35.4 × 10 -5cm 3(STP)/cm 2seccmHg, the flow of the nitrogen-rich air obtained by air separation membrane module 1 is 0.748Nm 3/ h.Constantly little through 140 after running starts, P ' o2be 33.4 × 10 -5cm 3(STP)/cm 2seccmHg, reduced by only 5.6% when starting than running.P ' after running starts after 2069 hours o2be 31.4 × 10 -5cm 3(STP)/cm 2seccmHg, reduces 11% when starting than running.The flow of the nitrogen-rich air that the air separation membrane module 1 after by running after 2069 hours obtains is 0.65Nm 3/ h, the moment started than running only reduces 13%.From this result, even if 175 DEG C of runnings 2000 hours, air separation membrane module 1 also maintains gas separation membrane ability.
The comparative example 1> of < part A
Use air separation membrane module 2, attempt mensuration similarly to Example 1, but violent in the contraction of 175 DEG C of hollow cortinas, can not nitrogen-rich air be obtained.The deformation etc. of hollow fragmentation, broken string, tube sheet is observed in the air separation membrane module 2 being held in 175 DEG C.
The comparative example 2> of < part A
Except using air separation membrane module 3, operate under condition similarly to Example 1, measure the flow of the nitrogen-rich air in each elapsed time.Measurement result is shown in Fig. 1.The P ' in the moment started running o2be 19.3 × 10 -5cm 3(STP)/cm 2seccmHg, the flow of the nitrogen-rich air obtained by air separation membrane module is 0.625Nm 3/ h.After running starts after 140 hours, the P ' of diffusion barrier o2be 11.3 × 10 -5cm 3(STP)/cm 2seccmHg, decreases 41% than when bringing into use, and the flow of the nitrogen-rich air obtained by air separation membrane module is 0.419Nm 3/ h, decreases 35% than when bringing into use.
The embodiment 2> of < part A
Adjust air quantity delivered in the mode that the oxygen concentration in manufactured nitrogen-rich air is 5%, in addition, measure similarly to Example 1.Measurement result is shown in Fig. 2.The flow of the nitrogen-rich air in the moment started running is 0.18Nm 3/ h.The flow of the nitrogen-rich air after running starts after 2069 hours is 0.15Nm 3/ h, terminates in minimizing 16%.From this result, similarly to Example 1, even if at 175 DEG C through 2000 hours, air separation membrane module 1 also maintains gas separation membrane ability.
[relating to the embodiment of part B]
Below, utilize the invention of embodiment to part B to be described, but the present invention is not limited to embodiment.
< embodiment 1>
(manufacture of castable resin composition)
Polyglycidyl ether 100 weight portion of mixed phenol Novolac and carboxyl terminal hycar (molecular weight 3100) 10 weight portions, heat 3 ~ 4 hours, prepare modified epoxy at 150 DEG C.Modified epoxy 100 weight portion, methyl-5-ENB-2,3-dicarboxylic anhydride 80 weight portion and 2-ethyl-4-methylimidazole 0.3 weight portion prepared by mixing system, carry out stirring and having prepared castable resin composition.
(evaluation of the formability of tube sheet)
As shown in Figure 4 b such mould in be configured with by 12000 hollow cortinas of polyimides (length: 100cm, external diameter: 500 μm) boundling become tow.Make the front end of tow for lower and upright in fact, the castable resin composition prepared by above-mentioned gimmick being slowly injected into insulation is in the mould of 70 DEG C.It is about 90mm that the amount of castable resin composition is controlled so as to thickness.After injection, carry out 12 hours one-step solidifications at 70 DEG C after, be heated to 142 DEG C and carry out 4 hours Post RDBMS, carrying out the shaping of tube sheet thus.After solidification, from casing, take out air silk element and observed by visual, and then tube sheet to be cut as roughly two halves and to the state of central part also by carrying out visualization.
Its result, tube sheet after forming does not observe crack.
[relating to the embodiment of part E]
Below, represent the situation being wound with film structural component and the result not having the response of the gas separation membrane module of situation about reeling to simulate.Table 1 represents the response of assembly, and " pattern A (cross flow) " is the situation of film structural component of not reeling, and " pattern B (adverse current) " is for being wound with the situation of film structural component.Temperature is set to t=25 DEG C, the supply pressure of mist is set to PF=0.7MPaG and calculates.It should be noted that, at this, be that the separating film module that goods obtain is simulated to supplying as the air of mist, with nitrogen-rich air.This nitrogen-rich air is not as by being removed through gas of discharging from its end of downstream side in hollow cortina.Supply pressure in table and supply flow rate represent supply pressure and the flow of the air being respectively mist, goods concentration and flow of articles amount represent nitrogen concentration respectively as the nitrogen-rich air of the goods do not obtained through gas and flow, the rate of recovery represent as goods in the mist of supply not through the ratio ((goods flow/supply flow rate) * 100) that gas obtains.
[table 4]
As shown in table 4, with regard to identical supply flow rate FF (with reference to main body 1,2), the situation being 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 being wound with the main body 3 of film structural component can improve goods flow FR and the rate of recovery.That is, from these results, the efficient activity of winding film structural component to gas separaion is effective.

Claims (3)

1. use air separation membrane module to make a method for nitrogen-rich air by air-making, it is characterized in that,
The air of more than 150 DEG C is supplied to air separation membrane module,
The material that air separation membrane in described air separation membrane module is more than 300 DEG C by glass transition temperature is formed,
Described air separation membrane module when bringing into use, the Oxygen Transmission Rate of 175 DEG C (P ' o2) be 20 × 10 -5cm 3(STP)/cm 2more than seccmHg, and the Oxygen Transmission Rate of 175 DEG C and nitrogen transmission rates ratio (P ' o2/ p ' n2) be more than 1.8, and
140 little P ' are constantly employed at 175 DEG C o2and P ' o2/ P ' n2p ' before bringing into use described in maintenance o2and P ' o2/ p ' n2respective more than 90%.
2. the method for claim 1, is characterized in that,
Described air separation membrane placed 2 constantly little at 175 DEG C, the form trait rate of display more than 95%.
3. an explosion-proof method for airborne vehicle, is characterized in that,
Utilize the manufacture method described in claim 1 to manufacture nitrogen-rich air, be supplied to airborne vehicle fuel tank.
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JP2010247931A JP6067205B2 (en) 2010-11-04 2010-11-04 Method for producing nitrogen-enriched air from hot gas
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JP2010274619A JP5740952B2 (en) 2010-11-04 2010-12-09 Separation membrane module
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JP2011207647A JP5825008B2 (en) 2011-09-22 2011-09-22 Gas separation membrane module
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WO2015147103A1 (en) * 2014-03-27 2015-10-01 宇部興産株式会社 Asymmetric gas separation membrane, and methods for separating and recovering gases
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