CN104968419B - Impurity removal method in macromolecular compound solution - Google Patents

Impurity removal method in macromolecular compound solution Download PDF

Info

Publication number
CN104968419B
CN104968419B CN201480006524.XA CN201480006524A CN104968419B CN 104968419 B CN104968419 B CN 104968419B CN 201480006524 A CN201480006524 A CN 201480006524A CN 104968419 B CN104968419 B CN 104968419B
Authority
CN
China
Prior art keywords
membrane
filtration
macromolecular compound
membrane module
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201480006524.XA
Other languages
Chinese (zh)
Other versions
CN104968419A (en
Inventor
松本秀树
永田美彰
永井洋
永井洋一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN104968419A publication Critical patent/CN104968419A/en
Application granted granted Critical
Publication of CN104968419B publication Critical patent/CN104968419B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/10—Cross-flow filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/025—Permeate series

Abstract

The present invention provides a kind of Impurity removal method in macromolecular compound solution, which is the membrane filtration by the cross flow configuration for configuring plural membrane module in series, and the method for removing low molecule impurity from the solution containing macromolecular compound, methods described meets following (A)～(C)：(A) macromolecular compound in solution has single-peaked molecular weight distribution；(B) the molecular cut off MWCO of filter membrane meets following (I) with number average molecular weight Mn of macromolecular compound and weight average molecular weight Mw：Mw×(Mw/Mn)‑3＜ MWCO ＜ Mw × (Mw/Mn)‑1(I)；(C) coefficient of alteration of the filtration pressure in membrane filtration between each membrane module is set to less than 10%.The method of the present invention can effectively suppress macromolecular compound to flow out in filtrate and can achieve the high rate of filtration.

Description

Impurity removal method in macromolecular compound solution
Technical field
The present invention relates to a kind of remove low molecule impurity from the solution containing macromolecular compound by membrane filtration Method.Systems a kind of membrane filtration of the cross flow configuration by being arranged multiple membrane filtration modules in series, And the method for removing the low molecule impurity in the solution containing macromolecular compound.
Background technology
When making monomer polymerization to obtain macromolecular compound, exist in reaction solution after polymerization unreacted The low molecular impurity such as monomer or oligomer, polymerization solvent, initiator.In addition, work as that macromolecular compound is invested chemistry During reaction, the low molecule impurity such as unreacted reagent or reaction dissolvent in reaction solution after chemical reaction, is there is also.As The method for removing those low molecule impurity, it is known to which the membrane filtration of cross flow configuration is processed.Remember for example in patent document 1 It is loaded with：Diafiltration by using ceramic membrane is efficiently removing the residual monomers in polymer solution.
When the membrane filtration that the solution containing macromolecular compound is invested cross flow configuration is processed, along with the time Through at leisure in the gel layer of film Surface Creation hardly possible filterability, causing the rate of filtration to reduce.In order to suppress the drop of the rate of filtration Low, it is known that multiple membrane modules to be arranged in series, so as to increase membrane area.However, pressure can be increased because the series connection of membrane module is arranged Power is lost, and therefore produces in terms of the filtration pressure of each membrane module uneven.
In order to the problem is solved, record in patent document 2 and counterbalance valve has been arranged to each membrane module, and by each membrane filtration group The filtration pressure of part is adjusted to specified level.Thus, the load for putting on each membrane module can be set to fix, makes filtration yield steady for a long time Fixed.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open 3-66705 publication
Patent document 2：Japanese Patent Laid-Open No. Sho 59-179110 publication
Content of the invention
The macromolecular compound solution containing low molecule impurity membrane filtration process in, be intended to as much as possible suppression be set to pure The macromolecular compound that changes or concentrate object is flowed out in filtrate.If reducing the molecular cut off of filter membrane, can press down further Macromolecular compound processed is flowed out in filtrate, but sacrifices the rate of filtration.That is, in membrane filtration process, generally suppress macromolecule Compound is flowed out to and is in the relation that accepts or rejects in filtrate with the reduction of the suppression rate of filtration each other, it is difficult to can fully meet both Level under and deposit.In invention for example described in patent document 1, by membrane filtration process, condensate have lost 3 mass % ～9 mass %, are not that fully suppression macromolecular compound is flowed out in filtrate.
The problem of the present invention is to provide a kind of cross flow configuration by being arranged multiple membrane filtration modules in series Membrane filtration, and the method for removing low molecule impurity from the solution containing macromolecular compound, methods described effectively can suppress Macromolecular compound flows out in filtrate and can achieve the high rate of filtration.
The present inventor et al. has found, in the membrane filtration of cross flow configuration is processed, when the molecular weight of macromolecular compound Or the molecular cut off of molecular weight distribution and filter membrane in particular kind of relationship when, can effectively suppress macromolecular compound to flow out to In filtrate, and the rate of filtration is difficult to reduce.And, studied based on the opinion repeatedly, find by using by multiple membrane modules The membrane filtration of the cross flow configuration of arranged in series, and then the filtration pressure of each membrane module is adjusted to fix, in high filtration speed In, can effectively suppress macromolecular compound to flow out in filtrate.
The present invention is studied so as to complete repeatedly based on those opinions.
The problem is realized by the following means.
<1>A kind of method, is the membrane filtration by the cross flow configuration for configuring plural membrane module in series, And the method for low molecule impurity being removed from the solution containing macromolecular compound, and meet following (A)～(C)：
(A) macromolecular compound in solution has single-peaked molecular weight distribution；
(B) molecular cut off (Molecular Weight Cut Off, MWCO) of filter membrane and macromolecular compound Number average molecular weight Mn and weight average molecular weight Mw meet following (I),
Mw×(Mw/Mn)-3＜ MWCO ＜ Mw × (Mw/Mn)-1(I)；
(C) coefficient of alteration of the filtration pressure between each membrane module in membrane filtration is set to less than 10%.
<2>According to<1>The Mw/Mn of the macromolecular compound in described method, wherein solution is 2～6.
<3>According to<1>Or<2>Described method, wherein MWCO are less than 15000.
<4>According to<1>Extremely<3>Any one of method, wherein filter membrane be ceramic membrane.
<5>According to<1>Extremely<4>Any one of method, wherein the membrane filtration of cross flow configuration for diafiltration (diafiltration).
Method according to the invention it is possible to the fully high rate of filtration, and effectively suppression macromolecular compound is flowed out to In filtrate, while removing in the solution containing macromolecular compound for processing and carrying out using the membrane filtration of cross flow configuration Low molecule impurity.
Described and other features of the present invention can be suitably with reference to annexed drawings and brighter according to following record with advantage Really.
Description of the drawings
Fig. 1 is an embodiment of the membrane filtration system for representing the cross flow configuration used in the method for the present invention Figure.
[explanation of symbol]
1：Accumulator tank
2：Macromolecular compound solution (material solution)
3：Liquid-feeding pump
4：Filtrate takes out pipe
5：Percolate collection tubes
6：Pipe arrangement
Specific embodiment
Hereinafter, the method for the present invention is described in detail.
The method of the present invention is the membrane filtration by the cross flow configuration for configuring plural membrane module in series Process, and the method for removing the low molecule impurity in the solution containing macromolecular compound.By implementing the method for the present invention, low Molecular impurity through filter membrane (below, also referred to as " film ") and from filtrate remove, on the other hand, macromolecular compound not by Filter and residue in solution.
So-called in this specification " low molecule impurity ", is the solution containing macromolecular compound in processing for membrane filtration In the presence of compound, and be have to purify or concentrate the molecular weight of macromolecular compound of object than being set to (molecular weight divides Cloth) little compound.As low molecule impurity, for example, can enumerate：May be present in not anti-in the reaction solution after polymerisation Macromolecular compound is invested the chemical reactions such as modification reaction by monomer, oligomer, polymerization solvent and the initiator answered When, may be present in unreacted reagent or the reaction dissolvent in reaction solution.The usual molecular weight of low molecule impurity is less than 1000.
So-called in this specification " removing the low molecule impurity in the solution containing macromolecular compound ", as follows for including The connotation of situation：Low molecule impurity etc. is removed, while the solvent of the solution containing macromolecular compound is replaced into new solvent (may be the same or different with the solvent of material solution).
In the method for the present invention, the macromolecular compound that is set in the solution containing macromolecular compound of membrane filtration object With single-peaked molecular weight distribution.In addition, the number average molecular weight (Mn) of the macromolecular compound or weight averaged molecular Amount (Mw) meets aftermentioned specific relation with the molecular cut off (MWCO) of filter membrane.
Further, in the method for the present invention, by the variation of the filtration pressure between each membrane module for arranging in series in membrane filtration Coefficient adjustment becomes below particular value, so as to suppress the inequality of the filtration pressure between each membrane module.Thus, can make to put on each membrane module Load homogenization and effectively suppress macromolecular compound to flow out in filtrate, and then can achieve more stable for a long time filtration.
[membrane filtration of cross flow configuration]
Would indicate that the schematic diagram of membrane filtration of the cross flow configuration for being suitable to apply the method for the present invention in Fig. 1.Below More specific description is carried out to the method for the present invention with reference to Fig. 1.
As shown in figure 1, in the membrane filtration system of the cross flow configuration for being used in the present invention, q (q is more than 2 Integer, preferably 2～15 integer, more preferably 3～12 integer, and then preferably 4～10 integer) membrane module (M1～Mq) series connection Ground is arranged.Membrane module M1～MqIt is preferred that the membrane module of same performance.That is, as membrane module M1～Mq, preferably use with membrane area, Substantially the same mode of membrane material, strainability and manufacture.
It is stored in accumulator tank 1 and invests the macromolecular compound solution 2 (hereinafter also referred to as " material solution ") of filtration treatment Membrane module M is delivered to successively using pump 31、M2、M3、…Mq.During by each membrane module, contained in material solution At least a portion of some low molecule impurity is removed from filtrate through film.Through film during each membrane module is passed through Filtrate flows out to filtrate and takes out pipe 4, and is collected and removed by percolate collection tubes 5.
Used as pump 3, as long as the flow needed for can producing to material solution or pressure, then there is no particular restriction, can adopt Commonly used pump in the membrane filtration process of cross flow configuration.
By being located at the membrane module M of most downstreamqMaterial solution, be back to accumulator tank 1, and be optionally delivered to film again Component M1～MqAnd invest membrane filtration.Repeat the concentration needed for the operation is reduced to up to the low molecule impurity in material solution, Macromolecular compound can be purified in material solution or concentrate.
Membrane filtration in the method for the present invention is alternatively one adds solvent one side towards accumulator tank 1 circulates material solution Diafiltration.So-called diafiltration, is that the constant volume filtered in the state of the volume of material solution or quality to be remained fixation is filtered Operation.Solvent is added with the rate of outflow same speed with filtrate in diafiltration.For example, using the pump that can carry out constant speed liquor charging (omit diagram) and solvent is continuously added in the accumulator tank 1 described in Fig. 1.
Membrane module M is arranged in Fig. 1qDownstream VoPressure-regulating valve (valve) for material solution.Pressed by adjusting Force regulating valve VoAnd the pressure needed for filtration treatment can be given to each component.Through pressure-regulating valve VoAnd the material solution for adjusting Pressure for example using pressure gauge PoTo determine.
In Fig. 1, P1、P2、P3、…PqMembrane module M is respectively arranged at1、M2、M3、…MqPorch (accumulator tank side) pressure Power meter.Using pressure gauge P1、P2、P3、…PqTo determine the pressure of the material solution of each membrane module porch.
In Fig. 1, P1-1、P2-1、P3-1、…Pq-1Respectively to membrane module M1、M2、M3、…MqThe pressure of the filtrate of middle transmission film The pressure gauge being measured.Pressure gauge P1-1、P2-1、P3-1、…Pq-1It is respectively arranged at membrane module M1、M2、M3、…MqBe connected to Each filtrate of each membrane module takes out the coupling part of pipe 4.
In Fig. 1, V1、V2、V3、…VqRespectively to membrane module M1、M2、M3、…MqThe pressure of the filtrate of middle transmission film is adjusted The pressure-regulating valve (valve) of section.Can be by adjusting pressure-regulating valve V1、V2、V3、…VqTo adjust the filtration pressure of each membrane module.
During the membrane filtration of cross flow configuration is processed, for the material solution of conveying, when by pipe arrangement 6 or membrane module M1～MqWhen be subject to resistance and produce pressure loss.By the pressure loss, with pressure gauge P1、P2、P3、…Pq、PoOrder and Pressure measurements diminish.That is, in each membrane module, filter condition is different.
In the method for the present invention, by adjusting pressure-regulating valve V1、V2、V3、…VqBy the filtration pressure between each membrane module Coefficient of alteration is suppressed to fixing following.Herein, membrane module M1Filtration pressure be from pressure gauge P1Value deduct pressure gauge P1-1Value The value of gained, similarly, membrane module M2Filtration pressure be from pressure gauge P2Value deduct pressure gauge P2-1Value gained value, film group Part M3Filtration pressure be from pressure gauge P3Value deduct pressure gauge P3-1Value gained value, membrane module MqFiltration pressure be from pressure Meter PqValue deduct pressure gauge Pq-1Value gained value.Will be with each pressure gauge P1、P2、P3、…PqShown each pressure and pressure gauge PoThe pressure that the difference of shown pressure is suitable puts on the filtrate that corresponding filtrate is taken out in pipe 4, thus can suppress each membrane module Filtration pressure inequality.The pressure of filtrate is adjusted using pressure-regulating valve V1、V2、V3、…VqCome carry out.
In the present invention, by the coefficient of alteration (CV (%)=100 × [filtration of q membrane module of the filtration pressure between each membrane module The standard deviation of pressure]/[mean value of the filtration pressure of q membrane module]) it is set to less than 10%.The CV value preferably less than 7%, more excellent Select less than 5%, and then preferably less than 4%, and then more preferably less than 3%.In addition, the coefficient of alteration of the filtration pressure between each membrane module Usually more than 1%.
<Solution containing macromolecular compound (material solution)>
In the method for the present invention, macromolecular compound is dissolved in material solution.In the method for the present invention, in material solution Macromolecular compound show single-peaked molecular weight distribution.The weight average molecular weight (Mw) of the macromolecular compound is preferably 10000～200000, more preferably 10000～100000, and then preferably 10000～50000.In addition, used in the present invention The Mw/Mn of macromolecular compound preferably 2～6, more preferably 2～5, and then preferably 2～4.When the macromolecule chemical combination in material solution When the Mw/Mn of thing is in the scope, can more effectively reduce the loss of macromolecular compound when membrane filtration is processed.
In material solution, there is no particular restriction for the species of the contained macromolecular compound for being set to purify or concentrate object. If being illustrated, can enumerate：Polyvinyl alcohol compound, pvpylated compound, petchem, polypropylene acidifying Compound, polymethyl acid compound, polyvinyl acetate compounds, polyvinyl, polyethylene glycol compound, polyphenyl second Ene compound, cellulosic cpd, gelatin compound, polyacrylic acid ester compounds, polymethacrylate compounds and contain The constituent of the macromolecular compound of the illustration is used as the copolymer of Component units.Furthermore, by " chemical combination in this specification When this word of thing " invests end and calls, or when representing compound with specific title or chemical formula, as long as no especially saying Bright, then in addition to compound itself, it is additionally operable to include the connotation of following form：Its salt, its complex compound, its ion, to described Compound imports specific substituent.
As the polyvinyl alcohol compound, for example, can enumerate：PVA-203 (Kuraray company manufacture, Mw be 21000) and Its derivative or PVA-205 (Kuraray company manufactures, and Mw is 35000) and its derivative.
As the pvpylated compound, for example, can enumerate：(Tokyo is melted into work to polyvinylpyrrolidone K15 Industry company manufactures, and Mw is 10000) and its derivative or PVP K30 (Tokyo chemical conversion industry company manufactures, and Mw is 40000) and its derivative.
In the present invention, as long as the solvent dissolving of material solution is set to purify or concentrate the macromolecular compound of object, then simultaneously It is not particularly limited, if the hydrophily of macromolecular compound is high, can be using water or the mixed solvent of water and water-soluble organic solvent (below, water and water being collectively referred to as " water system solvent " with the mixed solvent of water-soluble organic solvent), if hydrophobicity is high, can make With the low organic solvent of polarity.In the present invention, macromolecular compound is preferably water-soluble high-molecular compound.In addition, the situation Under preferably use water system solvent as solvent.So-called in this specification " water-soluble high-molecular compound ", refers to 25 for water Solubility at DEG C is the macromolecular compound of more than 0.1 mass %.Water-soluble high-molecular compound is preferably for 25 DEG C of water Under solubility be 0.5 mass % more than.In addition, so-called " water-soluble organic solvent ", refers to for the dissolving at 25 DEG C of water The organic solvent that spends more than for 10 mass %.Water-soluble organic solvent preferably can be with having that water equably mixes with arbitrary ratio Machine solvent.
In addition, the solvent that added suitably is selected also dependent on physical property and the purposes of macromolecular compound during diafiltration.
As the example of the solvent added when the solvent in material solution or diafiltration, can enumerate：Water, n-hexane, positive heptan The hydrocarbon compounds such as alkane, the ester compounds such as methyl acetate, ethyl acetate, butyl acetate, methyl alcohol, ethanol, normal propyl alcohol, isopropanol, just The lower alcohols such as butanol, isobutanol, the 3rd butanol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), DAA, cyclopentanone, ring The aliphatic ketones such as hexanone, ethylene glycol, diethylene glycol, triethylene glycol, glycerine, propane diols, glycol monoethyl ether or ethylene glycol list second Ether, propylene glycol monomethyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol phenyl ether, propane diols phenyl ether, diethylene glycol list Methyl ether or diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether or Triethylene glycol ethyl ether, dibutyl fourth The ether compounds such as ether, tetrahydrofuran, methyl ring amyl ether, dioxane, propionitrile, 1-METHYLPYRROLIDONE, 2-Pyrrolidone, dimethyl Formamide, dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), dimethylacetylamide, are alternatively those mixed solvent.
<Membrane module>
For the viewpoint of resistance to pressure, membrane module preferably entirety column type or the screw type of the present invention.In addition, the material of film is simultaneously It is not particularly limited, ceramic membrane can be alternatively for organic film, but for heat resistance, the viewpoint of chemical-resistant, preferably use pottery Porcelain film.As the material of ceramic membrane, can enumerate：Aluminum oxide, titanium oxide, silica, zirconium oxide etc..In addition, it is possible to use bag Silicon carbide-containing or the ceramic membrane of silicon nitride.In addition, the film comprising multiple material can be used.
Can be broad range using the membrane area of membrane module.If by taking ceramic membrane as an example, usual 1 is 0.2m2~ 0.5m2Left and right, till which is arranged 100 or so on 1 component.
<Molecular cut off>
So-called molecular cut off (MWCO), is defined as the minimum that rejection (rejection rate) is more than 90% Molecular weight.MWCO is typically on the basis of polyethylene glycol material being evaluated.Determination method is for example recorded in Japanese Patent Laid-Open In 2009-226268.The molecular cut off of the seperation film used in the present invention is to adopt material on the basis of polyethylene glycol to enter Row is evaluated and manufacturer's nominal value of gained.Furthermore, rejection is obtained with following formula.
Rejection (%)=100 × { 1- [through solution concentration (quality %)/material solution concentration (quality %)] }
In the method for the present invention, molecular cut off (MWCO) and the Mn of macromolecular compound and Mw of filter membrane meet following Formula (I).
Mw×(Mw/Mn)-3＜ MWCO ＜ Mw × (Mw/Mn)-1(I)
By the reduction of the rate of filtration using the MWCO for meeting formula (I), can be suppressed, and macromolecule can be suppressed further Compound is flowed out in filtrate.That is, can make to be generally in two characteristics of the relation of choice and deposit with higher level.
MWCO preferably less than 15000, more preferably 3000～10000, and then preferably 3000～5000.
There is no particular restriction for the temperature of the enforcement method of the present invention, can be according to the physical property of macromolecular compound or solvent etc. Appropriate selection, but generally carry out at a temperature of 10 DEG C～90 DEG C.
As long as implementing below maximum working (operation) pressure (MWP) of the filtration pressure of the method for the present invention by the membrane module for using, then have no Especially limit, but be preferably set in the range of 0.1MPa～1.0MPa and implement, and then be preferably set to 0.3MPa～0.7MPa.
In addition, implement the method for the present invention when flow velocity there is no particular restriction, preferably by the film surface line in each membrane module Speed is set in the range of 0.5m/s～4m/s and implements.
Below based on embodiment, the present invention will be described in more detail, but the present invention is not limited to those.
[embodiment]
[assay method]
<The rate of filtration>
([gross mass of filtrate]/[material solution quality] becomes 3.0 till rinsing ratio is 3.0 times to carry out diafiltration Till times), the gross area of the film that the gross mass of the filtrate of gained is had divided by required time (h) and all of membrane module (m2) amount of filtrate of time per unit elementary membrane of gained is set to the rate of filtration (unit：L/m2·h).
<Macromolecular compound is to the discharge rate in filtrate>
Macromolecular compound is to be asked by following formula to the discharge rate (below, also referred to as " discharge rate ") in filtrate Go out.
Discharge rate (%)=100 × [flowing out to the gross mass of the macromolecular compound in filtrate]/[contained in material solution The gross mass of some macromolecular compounds]
(flowing out to the gross mass of the macromolecular compound in filtrate)
To be percolated be 3.0 times to rinsing ratio when whole filtrates for flowing out accumulate (pool).Extract therein In the small-sized aluminium cup of 1.0g to 5mL volume, dry 1 hour at 100 DEG C with fan drying machine.Then, using vacuum drier And be dried under conditions of 60 DEG C, 1 hour, below 400Pa.The quality of the solid constituent of remaining is set to macromolecule chemical combination The quality of thing, so as to calculate the quality of the macromolecular compound in total filtrate.
(gross mass of contained macromolecular compound in material solution)
As described later, the gross mass of contained macromolecular compound in material solution is material solution 40kg × 10%= 4kg.
<Mn、Mw、Mw/Mn>
The Mn of macromolecular compound and Mw are measured as follows.Used in following embodiments and comparative example In the mean molecule quantity of PVA-203, Mw is 2.39 for the Mw/Mn that 21000, Mn are 8800, PVA-203.Following embodiments and compare Methacrylic acid 2- acetoacetoxyethyl (AAEM)-methyl methacrylate (MMA) copolymer used in example flat In average molecular weight Mw be 145000, Mn be 31000, Mw/Mn be 4.68.PVA-203 the and AAEM-MMA copolymer is respectively provided with Single-peaked molecular weight distribution.
(assay method of Mn, Mw)
PVA-203 be using gel permeation chromatography (manufacture of HLC-8220GPC, Dong Cao company), and by following conditions To determine Mn, Mw.Measurement result is set to the molecular weight of polyethylene glycol conversion.
Tubing string：TSK α-M (manufacture of Dong Cao company)
Eluent：The solution of methanol/water=7/3, containing 0.1mol/L sodium chloride
Tubing string temperature：40℃
Flow velocity：1.0mL/min
AAEM-MMA copolymer is using gel permeation chromatography (manufacture of HLC-8220GPC, Dong Cao company), and under passing through State condition to determine Mn, Mw.Measurement result is set to the molecular weight of polystyrene conversion.
Tubing string：TSK gel GMHXL+TSK gel G4000HXL+TSK gel G2000HXL (manufacture of Dong Cao company)
Eluent：THF (containing stabilizer)
Tubing string temperature：40℃
Flow velocity：1.0mL/min
The membrane filtration for carrying out the cross flow configuration shown in Fig. 1 is processed.Membrane filtration is processed be set to diafiltration (comparative example 1～ 4th, embodiment 1～5).Details is below described.
[comparative example 1]
As shown in figure 1,5 are reached the ceramic membrane tubular ceramic essence milipore filters that beautiful (TAMI) company manufactures using France (INSIDE CeRAM FineUF) (molecular cut off is 1000, and membrane area is 0.35m2) membrane module (M1～M5) join in series Put (in Fig. 1, q=5).Prepare comprising polyvinyl alcohol (PVA-203, Kuraray company manufacture) 10 mass %, 45 mass % of pure water, The material solution 40kg of 45 mass % of dimethyl sulfoxide (DMSO) (DMSO), is added in accumulator tank 1, with film surface linear speed at 80 DEG C Its circulation is spent for 1.05m/s and make using liquid-feeding pump 3, implements diafiltration till rinsing ratio is 3.0 times.Made using pure water By the solvent added in diafiltration.
Diafiltration start when and diafiltration start after every 60 minutes, with pressure gauge PoThe mode for becoming 0.5 ± 0.02MPa is adjusted Seamless force regulating valve Vo, while adjusting pressure-regulating valve V1～V5, thus make the filtration of each membrane module in diafiltration press to 0.5 ±0.02MPa.Filtration pressure when each pressure is adjusted is calculated to each each membrane module (every 60 points in addition to when diafiltration starts Clock will carry out the filtration pressure before pressure adjustment) mean value.The filtration of each membrane module during the mean value is set to be percolated Pressure, calculates the coefficient of alteration (CV) of the filtration pressure between each membrane module according to the filtration pressure of each membrane module.
Show the result in table 1.
[embodiment 1]
The ceramic membrane match manufactured using insulator Fitow section (NGK filtec) company flies spy's (Cefilt) NF (molecular cut off For 3000, membrane area is 0.35m2) replace France to reach the ceramic membrane tubular ceramic essence milipore filter of beautiful (TAMI) company manufacture (INSIDE CeRAM FineUF) (molecular cut off is 1000, and membrane area is 0.35m2), in addition, with 1 phase of comparative example Same mode is percolated.
Show the result in table 1.
[embodiment 2]
Ceramic membrane tubular ceramic essence milipore filter (the INSIDE CeRAM of beautiful (TAMI) company manufacture is reached using France FineUF) (molecular cut off is 5000, and membrane area is 0.35m2) replace France to reach the ceramic-film tube of beautiful (TAMI) company manufacture (molecular cut off is 1000 to formula pottery essence milipore filter (INSIDE CeRAM FineUF), and membrane area is 0.35m2), except this with Outward, to be percolated with 1 identical method of comparative example.
Show the result in table 1.
[embodiment 3]
Ceramic membrane tubular ceramic essence milipore filter (the INSIDE CeRAM of beautiful (TAMI) company manufacture is reached using France FineUF) (molecular cut off is 8000, and membrane area is 0.35m2) replace France to reach the ceramic-film tube of beautiful (TAMI) company manufacture (molecular cut off is 1000 to formula pottery essence milipore filter (INSIDE CeRAM FineUF), and membrane area is 0.35m2), except this with Outward, to be percolated with 1 identical mode of comparative example.
Show the result in table 1.
[comparative example 2]
The ceramic membrane match manufactured using insulator Fitow section (NGK filtec) company flies spy's (Cefilt) NF (molecular cut off For 10000, membrane area is 0.35m2) replace France to reach the ceramic membrane tubular ceramic essence milipore filter of beautiful (TAMI) company manufacture (INSIDE CeRAM FineUF) (molecular cut off is 1000, and membrane area is 0.35m2), in addition, with 1 phase of comparative example Same method is percolated.
Show the result in table 1.
[embodiment 4]
In embodiment 1, by the arranged in series 5 of membrane module instead of 10, in addition, with same as Example 1 Mode is percolated.
Show the result in table 1.
[comparative example 3]
In embodiment 1, pressure-regulating valve V is not carried out1～V5The adjustment pressure of filtrate (adjustment), in addition, with reality Apply 1 identical mode of example to be percolated.Filter the filtration pressure (M in the first stage when starting1) it is 0.62MPa, phase III (M3) For 0.50MPa, the 5th stage (M5) it is 0.42MPa.
Show the result in table 1.
[embodiment 5]
As shown in figure 1,2 are reached the ceramic membrane tubular type ceramic super-filtering films that beautiful (TAMI) company manufactures using France (INSIDE CeRAM UF) (molecular cut off is 15000, and membrane area is 0.5m2) membrane module (M1～M2) configure in series (in Fig. 1, q=2).Prepare comprising 0 mass % of AAEM-MMA copolymer 1,75 mass % of toluene, 15 mass % of tetrahydrofuran original Material solution 40kg, is added in accumulator tank, makes with membrane surface linear velocity as 1.05m/s and using liquid-feeding pump 3 at 25 DEG C Its circulation, implements diafiltration till rinsing ratio is 3.0 times.Toluene is used as the solvent added in diafiltration.
Diafiltration start when and diafiltration start after every 60 minutes, with pressure gauge PoThe mode for becoming 0.3 ± 0.02MPa is adjusted Seamless force regulating valve Vo, while adjusting pressure-regulating valve V1～V2, thus make the filtration of each membrane module in diafiltration press to 0.3 ±0.02MPa.Filtration pressure when each pressure is adjusted is calculated to each each membrane module (every 60 points in addition to when diafiltration starts Clock will carry out the filtration pressure before pressure adjustment) mean value.The filtration of each membrane module during the mean value is set to be percolated Pressure, calculates the coefficient of alteration (CV) of the filtration pressure between each membrane module according to the filtration pressure of each membrane module.
[comparative example 4]
The ceramic membrane tubular type ceramic super-filtering film (INSIDE CeRAM UF) for reaching beautiful (TAMI) company manufacture using France (cuts It is 50000 to stay molecular weight, and membrane area is 0.5m2) replace France to reach the ceramic membrane tubular type Ceramic excessive filtration of beautiful (TAMI) company manufacture (molecular cut off is 15000 to film (INSIDE CeRAM UF), and membrane area is 0.5m2), in addition, with same as Example 5 Mode be percolated.
Show the result in table 1.
[table 1]
Comparative example 1 is the less example of the MWCO than defined in the present invention of filter membrane.The result of comparative example 1 is to filter Speed is not good enough, until filtering the required time length for terminating to 16 hours (comparative example 1).Herein, real in the embodiment, comparative example Diafiltration is applied till rinsing ratio is 3.0 times, but in practical stage, in order in a higher degree that macromolecular compound is pure Change, it is assumed that improve rinsing ratio further.When rinsing ratio is improved, until membrane filtration between embodiment 1～3 and comparative example 1 The difference of required time till process terminates becomes apparent from.
Comparative example 2 is the bigger example of the MWCO than defined in the present invention of filter membrane.In comparative example 2, the rate of filtration adds Hurry up, macromolecular compound is improved to the discharge rate in filtrate.
Comparative example 3 is the example of the filtration pressure for not adjusting each membrane module.In this case macromolecular compound is in filtrate Discharge rate is improved.And, different from comparative example 2, the rate of filtration is not lifted yet.
On the other hand, in embodiment 1～4, discharge rate is suppressed below as little as 2.8 mass %, and the rate of filtration also becomes 4.5L/m2This good result of more than h.
Hereinafter the result is described in detail.
Although embodiment 1 increased the MWCO of 3 times of filter membranes compared with comparative example 1, but with regard to discharge rate, with comparative example 1 compares and suppresses low, and unexpected result is that the rate of filtration is lifted.Though the reason is indefinite, one of them is speculated Factor is to be jammed in affecting in the pore of film by molecule.I.e., it is believed that in the case of the comparative example 1 that MWCO is 1000, film Pore little, the molecule for therefore not only transmitting pore in filtration is few, and it is also few to be adsorbed in the molecule of pore, as a result, difficult The obturation of the film caused in the pore of film is jammed in produce because of molecule.On the other hand, it is believed that in the enforcement that MWCO is 3000 In example 1, compared with the comparative example 1 that MWCO is 1000, molecule is easily adsorbed in the pore of film, and the phenomenon causes of pore Divide inaccessible and cause the discharge rate of macromolecular compound to reduce.And then speculate that the obturation of the pore is coarse, it is difficult to low molecular The transmission of solvent plays impact.According to the embodiment 1 and the result of comparative example 1：By MWCO is set in the present invention More than the lower limit of defined, low discharge rate can be made with the high rate of filtration with higher level and deposit.
Although embodiment 2 is till the molecular cut off of filter membrane increases to 5 times compared with comparative example 1, but discharge rate is 1.8 mass % and somewhat rise from comparative example 1, the rate of filtration is substantially improved on the contrary, until filter terminate till required time Foreshorten to 14.6 hours.
Embodiment 3 is the upper limit example that somewhat reduce of the MWCO than defined in the present invention of film.Embodiment 3 and comparative example 1 compares, and MWCO also increases by 8 times.However, discharge rate is also suppressed to this low-level of 2.8 mass % in the embodiment 3, on the contrary The rate of filtration is especially lifted than comparative example 1, foreshortens to 13.1 hours until the required time till terminating is filtered.
In addition, compared with the embodiment 2 of the MWCO of filter membrane less than embodiment 3 3000, the discharge rate of the embodiment 3 is only But rise 1.5 times or so, but in the comparative example 2 of the MWCO bigger than embodiment 3 2000 of film, the discharge rate steeply rises, with Embodiment 3 is compared and increases to 2.8 times or so.Though the reason is indefinite, if thinking the MWCO of filter membrane than being advised in the present invention Fixed is big, then macromolecular compound readily penetrates through the pore of film, and macromolecule is difficult to block in pore, so as to practical effect MWCO is difficult to reduce.
According to the result, by the MWCO of film is set in the present invention below the higher limit of defined, can be with higher Level make low discharge rate with the high rate of filtration and deposit.
In addition, being also shown for according to the result of embodiment 4：If the series connection for increasing membrane module arranges number, can keep low Discharge rate, and can significantly shorten the required time of membrane filtration process.
Embodiment 5 and comparative example 4 are the examples for using AAEM-MMA copolymer as macromolecular compound.According to embodiment 5 result understands：The MWCO of film is set in the present invention in the range of defined, and the variation system by the filtration pressure of each inter-module Number is set in the regulation of the present invention, thus can be maintained the sufficient rate of filtration and effectively be suppressed discharge rate.
The present invention and its embodiment are illustrated, as long as but inventors believe that no specify, then do not exist The arbitrary detail section for illustrating is limited the invention, and should not violate the invention shown in the scope of appended claims Widely explained in the case of spirit and scope.
The present invention advocates Japan Patent Patent 2013-63046 based on March 25th, 2013 in Japan's proposition patent application And on March 13rd, 2014 proposes the priority of Japan Patent Patent 2014-050229 of patent application in Japan, herein with reference to this A part for records a little and that its content is incorporated to this specification.

Claims (5)

1. a kind of method, is the membrane filtration by the cross flow configuration for configuring plural membrane module in series, and from The method that solution containing macromolecular compound removes low molecule impurity, and meet following (A)～(C)：
(A) macromolecular compound in solution has single-peaked molecular weight distribution；
(B) number average molecular weight Mn and the weight averaged molecular of the molecular cut off MWCO of filter membrane and macromolecular compound Amount Mw meets following (I),
Mw×(Mw/Mn)-3＜ MWCO ＜ Mw × (Mw/Mn)-1(I)；
(C) coefficient of alteration of the filtration pressure in membrane filtration between each membrane module is set to less than 10%,
Wherein, coefficient of alteration=100% of the filtration pressure between each membrane module × [standard deviation of the filtration pressure of q membrane module]/ [mean value of the filtration pressure of q membrane module].
2. method according to claim 1, the wherein Mw/Mn of the macromolecular compound in solution are 2～6.
3. method according to claim 1 and 2, wherein molecular cut off are less than 15000.
4. method according to claim 1 and 2, wherein filter membrane are ceramic membrane.
5. method according to claim 1 and 2, the wherein membrane filtration of cross flow configuration are diafiltration.
CN201480006524.XA 2013-03-25 2014-03-25 Impurity removal method in macromolecular compound solution Active CN104968419B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2013-063046 2013-03-25
JP2013063046 2013-03-25
JP2014-050229 2014-03-13
JP2014050229A JP5960183B2 (en) 2013-03-25 2014-03-13 Method for removing impurities in polymer compound solution
PCT/JP2014/058372 WO2014157256A1 (en) 2013-03-25 2014-03-25 Method for removing impurities in high-molecular-weight compound solution

Publications (2)

Publication Number Publication Date
CN104968419A CN104968419A (en) 2015-10-07
CN104968419B true CN104968419B (en) 2017-03-08

Family

ID=51624222

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480006524.XA Active CN104968419B (en) 2013-03-25 2014-03-25 Impurity removal method in macromolecular compound solution

Country Status (3)

Country Link
JP (1) JP5960183B2 (en)
CN (1) CN104968419B (en)
WO (1) WO2014157256A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7228651B1 (en) 2021-09-14 2023-02-24 木村化工機株式会社 Solvent recovery system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS543893A (en) * 1977-06-11 1979-01-12 Ebara Infilco Co Ltd Purification of polymeric material-containing liquid
JPS59179110A (en) * 1983-03-30 1984-10-11 Nitto Electric Ind Co Ltd Operating method of filter module
JPH0366705A (en) * 1989-08-04 1991-03-22 Kao Corp Method for purifying polymer
CN1100337A (en) * 1993-06-30 1995-03-22 普拉塞尔技术有限公司 Modified poly(phenylene oxide) based membranes for enhanced fluid separation
US5490939A (en) * 1994-03-03 1996-02-13 Bayer Aktiengesellschaft Process for reconcentrating overspray from one-component coating compositions
JP2002201266A (en) * 1999-12-21 2002-07-19 Sumitomo Chem Co Ltd Water-soluble thermosetting resin and paper-strength- at-wet enhancer having this resin as effective component

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS543893A (en) * 1977-06-11 1979-01-12 Ebara Infilco Co Ltd Purification of polymeric material-containing liquid
JPS59179110A (en) * 1983-03-30 1984-10-11 Nitto Electric Ind Co Ltd Operating method of filter module
JPH0366705A (en) * 1989-08-04 1991-03-22 Kao Corp Method for purifying polymer
CN1100337A (en) * 1993-06-30 1995-03-22 普拉塞尔技术有限公司 Modified poly(phenylene oxide) based membranes for enhanced fluid separation
US5490939A (en) * 1994-03-03 1996-02-13 Bayer Aktiengesellschaft Process for reconcentrating overspray from one-component coating compositions
JP2002201266A (en) * 1999-12-21 2002-07-19 Sumitomo Chem Co Ltd Water-soluble thermosetting resin and paper-strength- at-wet enhancer having this resin as effective component

Also Published As

Publication number Publication date
JP2014208775A (en) 2014-11-06
CN104968419A (en) 2015-10-07
WO2014157256A1 (en) 2014-10-02
JP5960183B2 (en) 2016-08-02

Similar Documents

Publication Publication Date Title
WO2014142311A1 (en) Resin composition, membrane-forming stock solution, porous membrane, and hollow fiber membrane, water treatment device, electrolyte support, and separator using porous membrane
CN102806022A (en) Method for preparing polyacrylonitrile (PAN)-base microporous membrane
CN104968419B (en) Impurity removal method in macromolecular compound solution
WO2018181365A1 (en) Porous membrane, membrane module, water treatment device, and method for manufacturing porous membrane
US20050206049A1 (en) Water-soluble acrylic binder, method for producing the same, ceramic slurry composition, method for producing the same, monolithic ceramic electronic part and method for manufacturing the same
WO2013022660A1 (en) Polymer blend membranes
JP5612899B2 (en) Non-aqueous pigment dispersion composition
WO2022209594A1 (en) Method for producing polyvinyl alcohol resin
JP5584585B2 (en) Graft polymer
CN105611993A (en) Process for manufacturing fluoropolymer membranes
JP5820714B2 (en) Pigment dispersion for color filters
JP2011042751A (en) N-vinyl carbazole polymer and method for producing n-vinyl carbazole
CN112480296B (en) Hydrophilic modified ethylene-chlorotrifluoroethylene copolymer, preparation method and application thereof
KR101712000B1 (en) Membrane consiting of block copolymer and method manufacturing the same
JP4081083B2 (en) Method for producing acrylic cross-linked resin porous body
EP3786193A1 (en) Particles
JP5820715B2 (en) Pigment dispersion for color filters
JP2019130522A (en) Hollow fiber membrane, manufacturing method of hollow fiber membrane, and production method of beer, wine or japanese sake using hollow fiber membrane
JP3880558B2 (en) Dispersant for suspension polymerization of vinyl compound and suspension polymerization method
CN102190756B (en) Polyacrylonitrile-based carbon fibers, and precursor material thereof
JP2011256263A (en) Manufacturing method of (meth)acrylic copolymer, and (meth)acrylic copolymer
JP3650520B2 (en) Polymerization method of vinyl chloride monomer
JP2023072496A (en) Method for producing vinyl chloride-based polymer, composition and chain transfer agent
JP5848123B2 (en) Method for producing polymer compound
CN113562710A (en) Method for reducing solvent residue in lithium bis (fluorosulfonyl) imide

Legal Events

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