CN110354698A - Sulfonated polyvinyl alcohol catalytic composite membrane and preparation method thereof - Google Patents
Sulfonated polyvinyl alcohol catalytic composite membrane and preparation method thereof Download PDFInfo
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- CN110354698A CN110354698A CN201910602375.8A CN201910602375A CN110354698A CN 110354698 A CN110354698 A CN 110354698A CN 201910602375 A CN201910602375 A CN 201910602375A CN 110354698 A CN110354698 A CN 110354698A
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- composite membrane
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- sodium alginate
- catalyst
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 34
- 239000012528 membrane Substances 0.000 title claims abstract description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940068984 polyvinyl alcohol Drugs 0.000 claims abstract description 33
- 239000000661 sodium alginate Substances 0.000 claims abstract description 33
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 33
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 235000019441 ethanol Nutrition 0.000 claims description 30
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 28
- 238000006555 catalytic reaction Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 7
- 238000001764 infiltration Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- YCOXCINCKKAZMJ-UHFFFAOYSA-N 4-hydroxy-3-methylbenzenesulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=CC=C1O YCOXCINCKKAZMJ-UHFFFAOYSA-N 0.000 claims description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 230000010148 water-pollination Effects 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract 3
- 238000007790 scraping Methods 0.000 abstract 2
- 238000005266 casting Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 230000000149 penetrating effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical group OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 5
- ZCLXQTGLKVQKFD-UHFFFAOYSA-N 3-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC(S(O)(=O)=O)=C1 ZCLXQTGLKVQKFD-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 102000010637 Aquaporins Human genes 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a sulfonated polyvinyl alcohol catalytic composite membrane and a preparation method thereof. The catalytic composite membrane is characterized by being of a sandwich structure, namely comprising a supporting layer, a separation layer and a catalytic layer. The support layer adopts a hydrophilic support body; the separating layer is formed by mixing MoS2Adding to Sodium Alginate (SA) to prepare a separation layer; the catalytic layer is prepared by crosslinking polyvinyl alcohol (PVA) by using an acid catalyst. The preparation method comprises the following steps: soaking the support body with deionized water for pretreatment; dissolving SA in MoS2Preparing a separation layer membrane casting solution in the dispersion, scraping the membrane and drying; and adding the PVA solution, the acid catalyst and the cross-linking agent together, stirring, coating on the dried separation layer, scraping the membrane, and drying in the air to prepare the catalyst layer. The invention adopts a chemical grafting method to graft an acid catalyst on a PVA chain, so that the polymer chain can have more acid sites; meanwhile, the loss of the catalyst can be reduced to the greatest extent by a chemical grafting method.
Description
Technical field
The invention belongs to Material Field and technical field of membrane separation, in particular to a kind of sulfonated polyethylene alcohol bilayer catalysis is multiple
Close film and preparation method.Polyvinyl alcohol catalysis composite membrane prepared by the present invention is mainly used for organic carboxyl acid and the esterification of Organic Alcohol is anti-
It answers.
Background technique
Ethyl acetate has a wide range of applications in human production life, for example as industrial solvent, can be applied to coating,
Adhesive, artificial leather etc.；As extractant, medicine, the production of the products such as organic acid can be applied to；As spice material, can answer
For whiskey, cream etc.；As extractant, many compounds can be extracted from aqueous solution, as organic solvent, separate carbohydrate
Shi Zuowei correct thermometer standard substance, so ethyl acetate using very extensive.And the synthesis of ethyl acetate is by second
What acid and ethyl alcohol obtained under acidic catalyst, this is a common reversible reaction.The by-product water generated in reaction can press down
The progress for making reaction, causes the yield of ethyl acetate to decline, and the production of ethyl acetate is to launch catalyst in traditional industry
In reaction solution, although the progress of reaction can be promoted, it will lead to the corrosion of reaction vessel and cause the pollution of environment, after
Continuous separation purifying technique also virtually increases production cost.So being necessary, pursuit for the reform of production of ethyl
The production of high-efficient energy-saving environment friendly meets current technique requirement.
Infiltration evaporation (PV) is a more emerging technology.Infiltration evaporation utilizes feed liquid film upstream and downstream component chemical
Potential difference is that driving force realizes mass transfer, realizes selectivity to the difference of different component compatibility and resistance to mass tranfer in feed liquid using film.
And esterification is one typically by the reversible reaction of balance controlled, it can in time will be in reaction using Pervaporation Technology
The moisture of generation is discharged in time, and reaction is constantly mobile to side is generated in this way, and then acetic acid conversion is continuously improved.And utilize infiltration
Vaporisation techniques achieve the purpose that separation, it is important to make a kind of difunctional catalysis composite membrane of high-hydrophilic.Composite membrane is main
Comprising two layers, separating layer and Catalytic Layer.The effect of separating layer is that the moisture for generating reaction is separated, the main work of Catalytic Layer
With being that esterification is promoted to carry out.The selection of the membrane material of separating layer and Catalytic Layer is typically all hydrophilic material, such as poly- second
Enol (PVA), sodium alginate, hydroxyethyl cellulose etc..And Catalytic Layer is highly hydrophilic in addition to having, and also wants necessary and catalyst
It dissolves each other, wherein polyvinyl alcohol is exactly a kind of good material.
For hydrophilic filmogen, PVA is a kind of very common osmosis vaporizing compound membrane matrix membrane material, it has
There are high-hydrophilic, good heat resistance and chemical resistance, and cheap and easy to get.Sodium alginate has high-hydrophilic, high viscosity, resistance to height
The performance of temperature, and functional group is more in its molecular formula, is suitble to be modified, so wider in the application of infiltration evaporation field.In PVA base
Catalyst is introduced in film physical blending and chemical graft method.Chinese patent CN109092086A (2018) discloses a kind of poly-
Ethylene alcohol catalysis composite membrane and preparation method thereof, i.e., by the way that the method for physical blending is by polyvinyl alcohol and poly- (styrene sulfonic acid-is altogether
Poly- maleic acid), polystyrolsulfon acid or poly- (vinyl alcohol-block-styrene sulfonic acid) acidic catalyst are added in PVA solution,
Half interpenetrating network structure is formed, achievees the purpose that rugged catalyst.It applies in the catalysis reaction of ethyl acetate, esterification turns
Rate reaches 89-96%.Chinese patent CN104492492A (2014) discloses a kind of polymerization esterification catalysis membrane preparation method,
It is characterized in solid catalyst SO4 2-/ZnFe2O4It is configured to aqueous solution, prepares catalytic membrane with polymer solution blend.This method
Generally can combined coefficient with higher, but catalyst be easy be lost enter reaction solution in, this is also to need to be improved.
Summary of the invention
The purpose of the invention is to improve the deficiency of previous catalytic membrane and to prepare a kind of sulfonated polyethylene alcohol catalysis compound
Film；It is a further object of the present invention to provide the preparation methods of above-mentioned sulfonated polyethylene alcohol catalysis composite membrane.The present invention uses this side
The catalysis composite membrane of method preparation has the characteristics of high throughput, high separation factor, can promote the progress of esterification.
Technical solution of the present invention: in the preparation of bilayer catalysis composite membrane, the preparation of separating layer is also to the separation of film and flux
There is direct influence.Two-dimensional material molybdenum disulfide is added in we in general hydrophilic material.Molybdenum disulfide is typical dredge
Water-based material will form therebetween a kind of repulsion when hydrophilic and hydrophobic material mixes, and form a kind of virtual aquaporin,
The separation for accelerating moisture, can make the moisture quick separating generated in esterification go out in this way, and then improve the conversion ratio of acetic acid.
P-hydroxybenzenyl sulfonate, 3- hydroxy benzene sulfonic acid or o-cresol sulfonic acid these catalyst, as urging on document and patent
The acidic catalyst changed on composite membrane does not have been reported that also.And hydroxyl and sulfonic group, sulfonic group are had on these catalyst phenyl ring
Hydrogen ion, the effect as acidic catalyst are provided；And hydroxyl and PVA can be realized grafting, reach quick fixed catalyst
Purpose.To reduce the loss of catalyst, this is also the meaning for being catalyzed composite membrane.
The specific technical solution of the present invention: a kind of sulfonated polyethylene alcohol catalysis composite membrane, it is characterised in that the composite membrane is
Three-decker, supporting layer are hydrophily supporter；Separating layer is by MoS2It is added in sodium alginate (SA), is handed over after coating film forming
Connection；Catalytic Layer is acidic catalyst cross-linking polyvinyl alcohol (PVA)；The ethanol water that disintegrate-quality score is 90%, infiltration
Flux is 100-600gm-2·h-1, separation factor 200-500；Applied to being catalyzed acetic acid in infiltration evaporation catalytic film reactor
With ethyl alcohol esterification, 12h, acetic acid conversion 88-98% are reacted.
It is preferred that above-mentioned acidic catalyst is p-hydroxybenzenyl sulfonate or o-cresol sulfonic acid.
The present invention also provides a kind of methods for preparing above-mentioned sulfonated polyethylene alcohol catalysis composite membrane, and specific steps are such as
Under:
(1) pretreatment of supporting layer: hydrophily supporter (preferably PAN supporter) is impregnated in deionized water, is removed
Glycerol on supporter；
(2) prepared by separating layer: weighing MoS2Powder is put in deionized water, and ultrasound can be obtained point to enough dissolving each other with water energy
Sodium alginate (SA) powder is added in dispersion liquid, and the mass concentration of control sodium alginate (SA) solution is 1-3%, is placed on 30-60 DEG C of water
Heating stirring after constant temperature stands row's bubble, is taken out stand-by to dissolving in bath；Then the SA solution after standing is coated in knifing machine
In step (1) on pretreated supporter, the height that scraper lifts is set as 0.2-0.6mm, after drying, in calcium chloride solution
After middle immersion, deionized water is rinsed, and is dried stand-by；
(3) preparation of Catalytic Layer: preparation mass concentration is 3-8% polyvinyl alcohol (PVA) solution, and acidic catalyst is added,
Crosslinking agent is added, stirs, is then coated in the separating layer dried in step (2), the height that knifing machine scraper lifts
It is set as 0.3-0.7mm, is placed in filter at room temperature, is dried stand-by.
MoS in preferred steps (2)2Additional amount be sodium alginate (SA) quality 0.5-3%.
The concentration of calcium chloride solution is 0.2-0.7M in preferred steps (2), and soaking time is 10-30 minutes.
The addition quality of crosslinking agent is the 0.05-1.7% of polyvinyl alcohol (PVA) solution quality in preferred steps (3).
Acidic catalyst additive amount is the 0.1-0.3 of polyvinyl alcohol (PVA) molar ratio in preferred steps (3).
Crosslinking agent described in preferred steps (3) is glutaraldehyde, maleic acid or citric acid.
Knifing rate described in preferred steps (2) and step (3) is 5-30mmin-1。
The utility model has the advantages that
1) the present invention relates to a kind of novel sulfonated polyethylene alcohol catalysis composite membranes: its catalyst be p-hydroxybenzenyl sulfonate,
3- hydroxy benzene sulfonic acid or o-cresol sulfonic acid.These catalyst itself have sulfonic acid group, can effective catalytic esterification, acetic acid
For quasi- rate in 88-98%, the alcohol-water separation factor is 200-500, permeation flux 100-600gm-2·h-1。
2) this catalysis composite membrane combination Pervaporation Technology can break the limitation of chemical reaction equilibrium, promote reaction forward
It carries out, also, is catalyzed composite membrane and can be realized catalysis and isolation integral, reduce corrosion of the catalyst to reaction vessel, reduce
The cost of subsequent treatment process.
3) the double-deck catalysis composite membrane prepared by the present invention, compared with general document, separation factor with higher and
The performance index of flux, film is preferable.
4) the preparation method of the product of the invention is simple, does not need some special instrument and equipments, and production is simple, answers in industry
With with certain application potential.
Specific embodiment
Further the present invention is illustrated below by specific embodiment, but the present invention is not limited only to this.
Embodiment 1
(1) pretreatment of supporting layer: PAN supporter being cut out appropriately sized, is put into deionized water and is impregnated 6 hours, with
It is fixed on a glass with width adhesive tape afterwards, for use.
(2) it the preparation of separating layer: prepares sodium alginate (SA) solution of 3wt%: weighing molybdenum disulfide powder (molybdenum disulfide
For lamellar structure) 0.09g, 40g deionized water is added, with cell disruptor ultrasound 3h, so prepares dispersion with 100mL volumetric flask
Liquid then uses ultrasonic cleaner ultrasound 6h, for use；Above-mentioned 97ml dispersion liquid is poured into beaker, 3g sodium alginate powder is added
End covers preservative film, is placed on 60 DEG C of stirred in water bath and is heated to dissolving, and is then shut off stirring switch, and constant temperature stands 3 hours, takes
It is stand-by out；Knifing: the knifing machine of the sodium alginate soln after standing is coated on PAN supporter, the height that scraper lifts is set
For 0.5mm, knifing rate is 5mmin-1.After drying, it is immersed in the calcium chloride solution of 0.5M 10 minutes, a large amount of deionized water
It rinses, dries stand-by.
(2) preparation of Catalytic Layer: preparing the PVA solution 20g of the 8wt% of 20g, be added p-hydroxybenzenyl sulfonate (Aladdin,
65% aqueous solution) 0.97g (catalyst account for PVA molar ratio 0.1) stands 3h, adds citric acid 0.34g after mixing evenly,
80 DEG C of stirring 6h, stirring, are then coated in the separating layer done, the height that knifing machine scraper lifts is set as 0.5mm, knifing
Rate is 5mmin-1, dry at room temperature, for use.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 250Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.
Reflection 12h is obtained to calculate the quasi- rate of acetic acid with content of material in gas Chromatographic Determination reaction solution and penetrating fluid
Conversion ratio is 91.35%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g is true in reaction process
Reciprocal of duty cycle maintains 250Pa or so, and bath temperature controls at 75 DEG C, took a sample at interval of 1 hour, continuously take 3 times, with gas phase color
The content of water and ethyl alcohol in spectrum measurement reaction solution and penetrating fluid, so that calculating separation factor is 396, flux 102gm-2·h-1。
Embodiment 2
(1) pretreatment of supporting layer: PAN supporter being cut out appropriately sized, is put into deionized water and is impregnated 8 hours, with
It is fixed on a glass with width adhesive tape afterwards, for use.
(2) it the preparation of separating layer: prepares sodium alginate (SA) solution of 1.5wt%: weighing molybdenum disulfide powder (two first
Molybdenum sulfide is lamellar structure) 0.03g, 40g deionized water is added, with cell disruptor ultrasound 2h, is so prepared with 100mL volumetric flask
Dispersion liquid then uses ultrasonic cleaner ultrasound 8h, for use；Above-mentioned 98.5ml dispersion liquid is poured into beaker, 1.5g seaweed is added
Sour sodium powder end, covers preservative film, is placed on 30 DEG C of stirred in water bath and is heated to dissolving, and then constant temperature stands 2 hours, takes out stand-by；
Knifing: the knifing machine of the sodium alginate soln after standing is coated on PAN supporter, the height that scraper lifts is set as
0.45mm, knifing rate are 20mmin-1, after drying, it is immersed in the calcium chloride solution of 0.4M 20 minutes, deionized water is rinsed
It 1 minute, dries stand-by.
(2) preparation of Catalytic Layer: preparing the PVA solution 20g of 5wt%, and catalyst p-hydroxybenzenyl sulfonate 1.82g is added and (urges
Agent accounts for the 0.3 of PVA molar ratio), after mixing evenly, 1h is stood, crosslinking agent glutaraldehyde 0.01g is added, stirred, be then coated with
In the separating layer done, the height that knifing machine scraper lifts is set as 0.7mm, and knifing rate is 20mmin-1, dry in the air at room temperature
It is dry, for use.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 250Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.
Reflection 12h is obtained to calculate the quasi- rate of acetic acid with content of material in gas Chromatographic Determination reaction solution and penetrating fluid
Conversion ratio is 95.68%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g is true in reaction process
Reciprocal of duty cycle maintains 250Pa or so, and bath temperature controls at 75 DEG C, took a sample at interval of 1 hour, continuously take 3 times, with gas phase color
The content of water and ethyl alcohol in spectrum measurement reaction solution and penetrating fluid, so that calculating separation factor is 290, flux 554gm-2·h-1。
Embodiment 3
(1) pretreatment of supporting layer: PAN supporter being cut out appropriately sized, is put into deionized water and is impregnated 12 hours, with
It is fixed on a glass with width adhesive tape afterwards, for use.
(2) it the preparation of separating layer: prepares sodium alginate (SA) solution of 1wt%: weighing molybdenum disulfide powder (two sulphur first
Change molybdenum is lamellar structure) 0.005g, 40g deionized water is added, with cell disruptor ultrasound 0.5h, is so prepared with 99mL volumetric flask
Dispersion liquid then uses ultrasonic cleaner ultrasound 10h, for use；Above-mentioned dispersion liquid is poured into beaker, 1g sodium alginate powder is added
End covers preservative film, is placed on 35 DEG C of stirred in water bath and is heated to dissolving, and is then shut off stirring switch, and constant temperature stands 4 hours, takes
It is stand-by out；Knifing: the knifing machine of the sodium alginate soln after standing is coated on supporter, the height that scraper lifts is set as
0.2mm, knifing rate are 30mmin-1, after drying, it is immersed in the calcium chloride solution of 0.2M 30 minutes, deionized water is rinsed,
It dries stand-by.
(2) preparation of Catalytic Layer: preparing the PVA solution 20g of 3wt%, and o-cresol sulfonic acid (purity 65%) 0.98g is added
(catalyst account for PVA molar ratio 0.25) stands 3h, adds glutaraldehyde 0.02g, be then coated with after mixing evenly
In dry separating layer, the height that knifing machine scraper lifts is set as 0.5mm, and knifing rate is 30mmin-1, it dries at room temperature, to
With.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 250Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.
Reflection 12h is obtained to calculate the quasi- rate of acetic acid with content of material in gas Chromatographic Determination reaction solution and penetrating fluid
Conversion ratio is 98%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g, vacuum degree in reaction process
250Pa or so is maintained, bath temperature controls at 75 DEG C, took a sample at interval of 1 hour, continuously take 3 times, surveyed with gas-chromatography
Determine the content of water and ethyl alcohol in reaction solution and penetrating fluid, so that calculating separation factor is 268, flux 158gm-2·h-1。
Embodiment 4
(1) pretreatment of supporting layer: PAN supporter being cut out appropriately sized, is put into deionized water and is impregnated 24 hours, with
It is fixed on a glass with width adhesive tape afterwards, for use.
(2) it the preparation of separating layer: prepares sodium alginate (SA) solution of 1.5wt%: weighing molybdenum disulfide powder (two first
Molybdenum sulfide is lamellar structure) 0.03g, 40g deionized water is added and is so matched with 98.5mL volumetric flask with cell disruptor ultrasound 3h
Dispersion liquid processed then uses ultrasonic cleaner ultrasound 6h, for use；Above-mentioned dispersion liquid is poured into beaker, 1.5g sodium alginate is added
Powder covers preservative film, is placed on 30 DEG C of stirred in water bath and is heated to dissolving, and is then shut off stirring switch, and constant temperature stands 2 hours,
It takes out stand-by；Knifing: the knifing machine of the sodium alginate soln after standing is coated on supporter, the height that scraper lifts is set as
0.6mm, knifing rate are 15mmin-1After drying, it is immersed in the calcium chloride solution of 0.7M 10 minutes, deionized water is rinsed,
It dries stand-by.
(2) preparation of Catalytic Layer: preparing the PVA solution 20g of 5wt%, and p-hydroxybenzenyl sulfonate 0.608g is added, and (catalyst accounts for
The 0.1 of PVA molar ratio), after mixing evenly, glutaraldehyde 0.03g is added, stirring is then coated in the separating layer done, scrapes
The height that film machine scraper lifts is set as 0.3mm, and knifing rate is 15mmin-1, dry at room temperature, for use.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 250Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.
Reflection 12h is obtained to calculate the quasi- rate of acetic acid with content of material in gas Chromatographic Determination reaction solution and penetrating fluid
Conversion ratio is 89.214%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g is true in reaction process
Reciprocal of duty cycle maintains 250Pa or so, and bath temperature controls at 65 DEG C, took a sample at interval of 1 hour, continuously take 3 times, with gas phase color
The content of water and ethyl alcohol in spectrum measurement reaction solution and penetrating fluid, so that calculating separation factor is 410, flux 366gm-2·h-1。
Claims (9)
1. a kind of sulfonated polyethylene alcohol catalysis composite membrane, it is characterised in that the composite membrane is three-decker, and supporting layer is hydrophily
Supporter；Separating layer is by MoS2It is added in sodium alginate, coating film forming post-crosslinking；Catalytic Layer is that acidic catalyst crosslinking is poly-
Vinyl alcohol；The ethanol water that disintegrate-quality score is 90%, permeation flux 100-600gm-2·h-1, separation factor
For 200-500；Applied to acetic acid and ethyl alcohol esterification is catalyzed in infiltration evaporation catalytic film reactor, 12h, acetic acid conversion are reacted
Rate is 88-98%.
2. sulfonated polyethylene alcohol catalysis composite membrane according to claim 1, it is characterised in that the acidic catalyst is pair
Hydroxy benzene sulfonic acid or o-cresol sulfonic acid.
3. a kind of method for preparing sulfonated polyethylene alcohol catalysis composite membrane as described in claim 1, the specific steps of which are as follows:
(1) pretreatment of supporting layer: hydrophily supporter is impregnated in deionized water, the glycerol on supporter is removed；
(2) prepared by separating layer: weighing MoS2Powder is put in deionized water, and dispersion liquid can be obtained to enough dissolving each other with water energy in ultrasound,
Sodium alginate powder is added, the mass concentration for controlling sodium alginate soln is 1-3%, is placed on heating stirring in 30-60 DEG C of water-bath
To dissolution, after constant temperature stands row's bubble, take out stand-by；Then the knifing machine of the SA solution after standing is coated in step (1)
On pretreated supporter, the height that scraper lifts is set as 0.2-0.6mm, after drying, after impregnating in calcium chloride solution, goes
Ionized water rinses, and dries stand-by；
(3) preparation of Catalytic Layer: preparation mass concentration is 3-8% poly-vinyl alcohol solution, and acidic catalyst is added, adds crosslinking
Agent, stirring, is then coated in the separating layer dried in step (2), the height that knifing machine scraper lifts is set as 0.3-
0.7mm is placed in filter at room temperature, is dried stand-by.
4. according to the method described in claim 3, it is characterized in that MoS in step (2)2Additional amount be sodium alginate quality
0.5-3%.
5. according to the method described in claim 3, it is characterized in that in step (2) calcium chloride solution concentration be 0.2-0.7M,
Soaking time is 10-30 minutes.
6. according to the method described in claim 3, it is characterized in that the addition quality of crosslinking agent is that polyvinyl alcohol is molten in step (3)
The 0.05-1.7% of liquid quality.
7. according to the method described in claim 3, it is characterized in that acidic catalyst additive amount is that polyvinyl alcohol rubs in step (3)
The 0.1-0.3 of your ratio.
8. according to the method described in claim 3, it is characterized in that crosslinking agent described in step (3) is glutaraldehyde, maleic acid
Or citric acid.
9. according to the method described in claim 3, it is characterized in that knifing rate described in step (2) and step (3) is 5-
30m·min-1。
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