CN100358615C - Method for preparing facilitated transport membrane of branched neopentyl ethylene diamine for CO2 separation - Google Patents
Method for preparing facilitated transport membrane of branched neopentyl ethylene diamine for CO2 separation Download PDFInfo
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- CN100358615C CN100358615C CNB2006100133333A CN200610013333A CN100358615C CN 100358615 C CN100358615 C CN 100358615C CN B2006100133333 A CNB2006100133333 A CN B2006100133333A CN 200610013333 A CN200610013333 A CN 200610013333A CN 100358615 C CN100358615 C CN 100358615C
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- film
- ethylene diamine
- separation
- branched
- ethylenediamine
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Abstract
The present invention discloses a method for preparing branched neopentyl ethylenediamine facilitated transfer film for separation CO2, which belongs to a preparation technique of a film. The process of the method comprises: a polysulfone flat-plate film or a polyethersulfone flat-plate film or a hollow-fiber film of the polysulfone flat-plate film and the polyethersulfone flat-plate film is used as a basal film; after the basal film is processed, casting film liquid is prepared by the cross blending of branched neopentyl ethylenediamine which are synthesized by using tetrabromide; neopentane and refined ethylenediamine as raw materials and polyvinyl alcohol and is coated on the basal film; after a coating layer is dried, silicon rubber water miscible liquid is coated on the surface layer of a composite film, and the branched neopentyl ethylenediamine facilitated transfer film for separating CO2 is obtained by drying. The present invention has the advantages that the CO2 /CH4 separation factor of the prepared facilitated transfer film is from 30 to 100, the CO2 infiltration rate is from 2 to 9*10<-5>cm<3>(STP)cm<-2>s<-1>cmHg<-1>; the process is simple, and the film formation properties and the pressure resistance of the facilitated transfer film are good.
Description
Technical field
The present invention relates to a kind of separation of C O that is used for
2Branched neopentyl ethylene diamine promote the transport membranes preparation method, belong to separation of C O
2The technology of preparing of promotion transport membranes.
Background technology
The developing history of dendritic polymer is shorter, and its application in gas separation membrane is also less, is applied to CO
2The film separation field both at home and abroad except that this scientific research group, only has external minority scholar to engage in this research at present, is mostly to utilize dendritic polymer to prepare supported liquid membrane, is used for separation of C O
2The dendritic polymer fixed carrier composite membrane rarely found.
A.Sarma Kovvali etc. are immersed in porous Kynoar (PVDF) flat sheet membrane in polyamide-based dendritic polymer of 0 generation (PAMAM dendrimer) liquid and have prepared PAMAM dendritic polymer supported liquid membrane.At low CO
2Divide and depress CO
2/ N
2Separation factor near 19000, CO
2Infiltration rate be 1.1 * 10
-5Cm
3(STP) cm
-2s
-1CmHg
-1, but the voltage endurance capability of film is very low, and pressure slightly raises, and separation factor just sharply descends, at 8cmHgCO
2It only is 50 that branch is depressed separation factor.
Tai-Shung Chung etc. respectively with 0 generation PAMAM dendritic polymer and 1～3 generation polypropylene imines dendritic polymer 6FDA-prehnitene polyimide film is carried out crosslinked modification, prepared the polyimide film of the crosslinked modification that dendritic polymer causes by cross-linking reaction in the methanol solution that polyimide film is immersed in dendritic polymer.The voltage endurance capability of this film is stronger, but CO
2Infiltration rate and CO
2/ CH
4Separation factor all lower, CO
2Infiltration coefficient depress at 35 ℃, 10atm charging and reach maximum, be 568 Barrer, CO
2/ CH
4Separation factor be 22.8.
Shuhong Duan etc. are support membrane with the polysulfone hollow fibre milipore filter, the hollow-fibre membrane inboard is injected in the aqueous acetic acid circulation of shitosan, afterwards the hollow-fibre membrane inboard is injected in the methanol aqueous solution circulation of PAMAM dendritic polymer, obtained PAMAM dendritic polymer hollow fiber composite membrane.The CO of film
2Infiltration rate and CO
2/ N
2Separation factor and the voltage endurance capability of film all reach higher index, at 2atm feeding gas (CO
2/ N
2=5/95) under the pressure, CO
2Infiltration rate be 1.8 * 10
-4Cm
3(STP) cm
-2s
-1CmHg
-1, CO
2/ N
2Separation factor be 256, yet the amino in this composite membrane shitosan is to CO
2The promotion transfer function is also arranged, therefore can not think the effect of PAMAM dendritic polymer merely.
Therefore, be very necessary at this area new masking technique of exploitation with the separating property of improving the dendritic polymer film.
Relevant list of references is as follows:
[1]A.Sarma?Kovvali，Hua?Chen，Kamalesh?K.Sirkar，Dendrimer?Membranes：ACO
2-Selective?Molecular?Gate，J.Am.Chem.Soc.2000，122：7594～7595
[2]A.Sarma?Kovvali，K.K.Sirkar，Dendrimer?Liquid?Membranes：CO
2Separation?from?Gas?Mixtures，Ind.Eng.Chem.Res.2001，40：2502～2511
[3]Tai-Shung?Chung，Mei?Lin?Chng，K.P.Pramoda，Youchang?Xiao，PAMAMDendrimer-Induced?Cross-Linking?Modification?of?Polyimide?Membranes，Langmuir，2004，20：2966～2969
[4]Lu?Shao，Tai-Shung?Chung，Suat?Hong?Goh，Kumari?Pallathadka?Pramoda，Transport?Properties?of?Cross-Linked?Polyimide?Membranes?Induced?byDifferent?Generations?of?Diaminobutane(DAB)Dendrimers，Journal?ofMembrane?Science，2004，238：153～163
[5]Youchang?Xiao，Tai-Shung?Chung，Mei?Lin?Chng，Surface?Characterization，Modification?Chemistry，and?Separation?Performance?of?Polyimide?andPolyamidoamine?Dendrimer?Composite?Films，Langmuir，2004，20：8230～8238
[6]Shuhong?Duan，Takayuki?Kouketsu，Shingo?Kazama，Koichi?Yamada，Kazukiyo?Nagai，Benny?D.Freeman，Formation?and?Characterization?ofPAMAM?Dendrimer?Composite?Membrane?for?CO
2?Separation，InternationalCongress?on?Membranes?and?Membrane?Processes，2005，Korea
Summary of the invention
The object of the present invention is to provide a kind of separation of C O that is used for
2Branched neopentyl ethylene diamine promote the transport membranes preparation method.This inventive method operating process is simple, and the promotion transport membranes filming performance and the withstand voltage properties that make are good, has higher separation factor and excellent CO simultaneously
2Infiltration rate.
The present invention is realized by following technical proposals.A kind of separation of C O that is used for
2Branched neopentyl ethylene diamine promote the transport membranes preparation method, it is characterized in that comprising following process: with molecular cut off is that 30000～50000 polysulfones or polyether sulfone flat sheet membrane or their hollow-fibre membrane are basement membrane, after the preliminary treatment of dodecyl sodium sulfate dilute aqueous solution, standby; Is raw material with tetrabromo for neopentane and refining ethylenediamine, feeds intake in 35: 65～5: 95 by mass ratio, carries out the alkyl halide aminolysis reaction in 100～150 ℃, reacts 40～80 hours, synthesizes branched neopentyl ethylene diamine, adds 8～12molL again
-1Sodium hydrate aqueous solution, wherein the NaOH quality is that the raw material tetrabromo is for 80～95% of neopentane quality, again with pyridine extraction, to remove impurity B r
-, season penta entprol that obtains making with extra care; By mass ratio 85: 15～30: 70 with refining season penta entprol and molecular weight be that to obtain mass concentration be 1～10% casting solution for 50000～500000 polyvinyl alcohol blending; This casting solution is coated on through pretreated basement membrane top layer, coating layer thickness is 3～5 μ m, air dry under normal temperature is then prepared mass concentration again and is 1～20% silicon rubber aqueous emulsion and is coated on the composite membrane top layer, and air dry obtains being used for separation of C O under normal temperature
2Branched neopentyl ethylene diamine promote transport membranes.
Above-mentioned raw material tetrabromo is 15: 85～7: 93 for the quality proportioning of neopentane and ethylenediamine.
Above-mentioned alkyl halide aminolysis reaction temperature is 125～145 ℃, and the reaction time is 50～80 hours.
Above-mentioned be coated with membrane polymer season penta entprol and the polyvinyl alcohol mass ratio be preparation in 80: 20～50: 50, the mass concentration of casting solution is 3～5%.
The invention has the advantages that, employing be coated with membrane polymer for containing to CO
2Work the branched neopentyl ethylene diamine of the amino end group of carrier that promotes transfer function, surface active groups that they are a large amount of and highly branched molecular structure help improving prepared promotion transport membranes to CO
2The selection through performance.Manufacturing process of the present invention is simple, and the promotion transport membranes filming performance and the withstand voltage properties that make are good, and film is to CO
2/ CH
4The selection through performance be: CO
2/ CH
4Separation factor 30～100, CO
2Infiltration rate 2～9 * 10
-5Cm
3(STP) cm
-2s
-1CmHg
-1
Description of drawings
Fig. 1 is the electromicroscopic photograph of the embodiment of the invention 1 prepared promotion transport membranes surface texture.
Fig. 2 is the electromicroscopic photograph of film section structure among Fig. 1.
Among the figure, finger-like pore partly is the polyether sulfone base membrane layer of film; Finger-like top tight section is the branched neopentyl ethylene diamine coating of film; The part of turning white of compacted zone very thin surface is silastic-layer.
The specific embodiment
Embodiment 1
Weighing 2.342g (6.04mmol) tetrabromo places the 100mL there-necked flask for neopentane, adds the refining ethylenediamine of 30.56g (509.3mmol) again, installs condenser pipe and agitator, and reaction is 72 hours in 140 ℃ of oil baths, synthetic branched neopentyl ethylene diamine.The ethylenediamine that decompression distillation is excessive adds 5mL 10molL
-1Sodium hydrate aqueous solution is used the extraction of 3 * 10mL pyridine, again to remove impurity B r
-, decompression distillation pyridine, season penta entprol that obtains the making with extra care reaction equation formula as follows of entprol (synthetic season penta).Weighing 1g molecular weight be 70000 polyvinyl alcohol and 3.67g season penta entprol, adding 128.8g distilled water, to be mixed with mass concentration be 3.5% casting solution, it is coated on the pretreated polyether sulfone flat plate ultrafiltration membrane of dodecyl sodium sulfate dilute aqueous solution (molecular cut off is 30000), air dry under normal temperature, be that 5% silicon rubber aqueous emulsion is coated on the composite membrane top layer, air dry under normal temperature again with mass concentration.Use pure CO
2And CH
4Gas carries out performance test to prepared promotion transport membranes.Test result: when feed gas pressure is 143.5～991.2cmHg, CO
2/ CH
4Separation factor be 52～19, CO
2Infiltration rate 8.14～3.56 * 10
-5Cm
3(STP) cm
-2s
-1CmHg
-1Use mist 10vol%CO again
2/ 90vol%CH
4Prepared promotion transport membranes is carried out performance test.Test result: when feed gas pressure is 188.5～1163.8cmHg, CO
2/ CH
4Separation factor be 33～8, CO
2Infiltration rate 6.94～3.29 * 10
-5Cm
3(STP) cm
-2s
-1CmHg
-1
Embodiment 2
Weighing 2.143g (5.53mmol) tetrabromo places the 100mL there-necked flask for neopentane, adds the refining ethylenediamine of 12.874g (214.6mmol) again, installs condenser pipe and agitator, and reaction is 55 hours in 125 ℃ of oil baths, synthetic branched neopentyl ethylene diamine.The ethylenediamine that decompression distillation is excessive adds 4.5mL 10molL
-1Sodium hydrate aqueous solution is used the extraction of 3 * 10mL pyridine, again to remove impurity B r
-, decompression distillation pyridine, season penta entprol that obtains making with extra care.Weighing 1g molecular weight be 400000 polyvinyl alcohol and 1.5g season penta entprol, adding 68.9g distilled water, to be mixed with mass concentration be 5% casting solution, it is coated on the pretreated polysulfones flat plate ultrafiltration membrane of dodecyl sodium sulfate dilute aqueous solution (molecular cut off is 50000), air dry under normal temperature, be that 15% silicon rubber aqueous emulsion is coated on the composite membrane top layer, air dry under normal temperature again with mass concentration.Use mist 10vol%CO
2/ 90vol%CH
4Prepared promotion transport membranes is carried out performance test.Test result: when feed gas pressure is 166～1171.3cmHg, CO
2/ CH
4Separation factor be 24～6, CO
2Infiltration rate 6.13～3.02 * 10
-5Cm
3(STP) cm
-2s
-1CmHg
-1
Embodiment 3
Weighing 1g molecular weight be 300000 polyvinyl alcohol and 1g season penta entprol, adding 55.1g distilled water, to be mixed with mass concentration be 3.5% casting solution, it is coated on the pretreated polyether sulfone flat plate ultrafiltration membrane of dodecyl sodium sulfate dilute aqueous solution (molecular cut off is 30000), air dry under normal temperature, be that 5% silicon rubber aqueous emulsion is coated on the composite membrane top layer, air dry under normal temperature again with mass concentration.Use mist 10vol%CO
2/ 90vol%CH
4Carry out performance test to promoting transport membranes.Test result: when feed gas pressure is 196～1291.3cmHg, CO
2/ CH
4Separation factor be 18～4, CO
2Infiltration rate 5.32～2.11 * 10
-5Cm
3(STP) cm
-2s
-1CmHg
-1
Claims (4)
1. one kind is used for separation of C O
2Branched neopentyl ethylene diamine promote the transport membranes preparation method, it is characterized in that comprising following process: with molecular cut off is that 30000～50000 polysulfones or polyether sulfone flat sheet membrane or their hollow-fibre membrane are basement membrane, after the preliminary treatment of dodecyl sodium sulfate dilute aqueous solution, standby; Is raw material with tetrabromo for neopentane and refining ethylenediamine, feeds intake in 35: 65～5: 95 by mass ratio, carries out the alkyl halide aminolysis reaction in 100～150 ℃, reacts 40～80 hours, synthesizes branched neopentyl ethylene diamine, adds 8～12molL again
-1Sodium hydrate aqueous solution, wherein the NaOH quality is that the raw material tetrabromo is for 80～95% of neopentane quality, again with pyridine extraction, to remove impurity B r
-, season penta entprol that obtains making with extra care; By mass ratio 85: 15～30: 70 with refining season penta entprol and molecular weight be that to obtain mass concentration be 1～10% casting solution for 50000～500000 polyvinyl alcohol blending; This casting solution is coated on through pretreated basement membrane top layer, coating layer thickness is 3～5 μ m, air dry under normal temperature is then prepared mass concentration again and is 1～20% silicon rubber aqueous emulsion and is coated on the composite membrane top layer, and air dry obtains being used for separation of C O under normal temperature
2Branched neopentyl ethylene diamine promote transport membranes.
2. by the described separation of C O that is used for of claim 1
2Branched neopentyl ethylene diamine promote the transport membranes preparation method, it is characterized in that: the raw material tetrabromo is 15: 85～7: 93 for the quality proportioning of neopentane and ethylenediamine.
3. by the described separation of C O that is used for of claim 1
2Branched neopentyl ethylene diamine promote the transport membranes preparation method, it is characterized in that: alkyl halide aminolysis reaction temperature is 125～145 ℃, the reaction time is 50～80 hours.
4. by the described separation of C O that is used for of claim 1
2Branched neopentyl ethylene diamine promote the transport membranes preparation method, it is characterized in that: casting solution penta entprol and polyvinyl alcohol mass ratio quarterly is to prepare in 80: 20～50: 50, and the mass concentration of casting solution is 3～5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100133333A CN100358615C (en) | 2006-03-20 | 2006-03-20 | Method for preparing facilitated transport membrane of branched neopentyl ethylene diamine for CO2 separation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100133333A CN100358615C (en) | 2006-03-20 | 2006-03-20 | Method for preparing facilitated transport membrane of branched neopentyl ethylene diamine for CO2 separation |
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|---|---|
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| CN100358615C true CN100358615C (en) | 2008-01-02 |
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|---|---|---|---|
| CNB2006100133333A Expired - Fee Related CN100358615C (en) | 2006-03-20 | 2006-03-20 | Method for preparing facilitated transport membrane of branched neopentyl ethylene diamine for CO2 separation |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101574629B (en) * | 2008-05-09 | 2011-04-20 | 中国石油天然气股份有限公司 | Preparation method of polyvinyl alcohol/polyether sulfone pervaporation composite membrane |
| CN104418303B (en) * | 2013-09-04 | 2016-11-23 | 中国石油化工股份有限公司 | The process of carbon dioxide in a kind of membrance separation removing conversion gas |
| CN105561811B (en) * | 2014-11-05 | 2018-05-01 | 上海交通大学 | Environment-friendly liquid supports carbon dioxide separation film |
| CN105727764B (en) * | 2014-12-08 | 2018-05-04 | 中国石油天然气股份有限公司 | Photopolymerization modified polyallylamine solid support film and preparation method thereof |
| CN114105778A (en) * | 2021-12-21 | 2022-03-01 | 重庆三峡学院 | Preparation method of pentaerythrityl tetradiamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286279A (en) * | 1992-12-14 | 1994-02-15 | W. L. Gore & Associates, Inc. | Gas permeable coated porous membranes |
| US5356461A (en) * | 1990-11-28 | 1994-10-18 | Akzo N.V. | Gas separation membrane |
| CN1363414A (en) * | 2001-12-26 | 2002-08-14 | 天津大学 | Process for preparing composite membrane to separate CO2 gas |
-
2006
- 2006-03-20 CN CNB2006100133333A patent/CN100358615C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5356461A (en) * | 1990-11-28 | 1994-10-18 | Akzo N.V. | Gas separation membrane |
| US5286279A (en) * | 1992-12-14 | 1994-02-15 | W. L. Gore & Associates, Inc. | Gas permeable coated porous membranes |
| CN1363414A (en) * | 2001-12-26 | 2002-08-14 | 天津大学 | Process for preparing composite membrane to separate CO2 gas |
Non-Patent Citations (2)
| Title |
|---|
| Facilitated transport of CO2 throughpolyethylenimine/poly(vinyl alcohol) blend membrane. Hideto Matsuyama et al.J.of membrane science,Vol.163 . 1999 * |
| Selective permeation of carbon dioxide through plasmapolymerized membrane from diisopropylamine. Hideto Matsuyama et al.J.of membrane science,Vol.92 . 1994 * |
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