CN104492492A - Preparation method for polymerization esterification catalytic membrane - Google Patents
Preparation method for polymerization esterification catalytic membrane Download PDFInfo
- Publication number
- CN104492492A CN104492492A CN201410617869.0A CN201410617869A CN104492492A CN 104492492 A CN104492492 A CN 104492492A CN 201410617869 A CN201410617869 A CN 201410617869A CN 104492492 A CN104492492 A CN 104492492A
- Authority
- CN
- China
- Prior art keywords
- solution
- membrane
- catalytic membrane
- polymer
- catalytic
- 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.)
- Pending
Links
Abstract
A disclosed preparation method for a polymerization esterification catalytic membrane is characterized by comprising: weighing a solid catalyst SO4<2->/ZnFe2O4 and dissolving in water to prepare a solution 1, weighing a polymer and dissolving in water to prepare a solution 2, mixing the solution 1 and the solution 2 to prepare a casting solution, then immersing a polyvinylidene fluoride penetration vaporization flat-sheet membrane in the casting solution, fully infiltrating a penetration vaporization compact layer with the casting solution for 10 min, then rapidly putting in a saturated sodium sulfate coagulation bath for film forming, so as to prepare a porous catalytic membrane, then immersing in a glutaraldehyde acidic solution with the concentration of 10 wt% to perform further crosslinking on the catalytic membrane, taking out the membrane, washing to be neutral, then putting in a vacuum dryer for heating drying, so as to prepare the polymerization esterification catalytic membrane. The polymer is a mixture of sulfonated polysulfones and sulfonated poly(ether-ether-ketone), the sulfonic acid group substitution degree of the polymer is 6%-9%, and the pore size of the catalytic membrane is 2-40 mu m. The membrane is simple to prepared and good in catalytic effect.
Description
Technical field
The present invention relates to a kind of polymerization esterification thermal stability method.
Background technology
Existing organic carboxylic ester is important fine chemical product, be commonly used for solvent and spices, can be used for the raw material and intermediate etc. in the plasticizer of synthetic perfume, cosmetics, food and feed additive, surfactant, Antisepticize and mildew preventive, rubber and plastics, pharmaceuticals industry, also will be used as the biodiesel of alternative petrifaction diesel.And esterification is the important channel of preparing Ester, esterification needs to complete under catalyst action usually.
The traditional handicraft of synthesis organic carboxylic ester adopts sulphuric acid catalysis alcoholic acid esterification, and this method exists the shortcomings such as equipment corrosion is serious, side reaction is many, waste reaction solution is difficult, comprehensive production cost is high.In recent years, researcher can replace doing a lot of work in the new catalyst for esterification of sulfuric acid in searching, develops a series of excellent alcoholic acid esterification anti-.Heteropoly acid (HPA) be a kind of have determine to form containing the multinuclear polymer complex of oxo bridge, there is the cagelike structure feature being similar to molecular sieve.Because heteropoly acid can generate " false liquid phase " system with non-aqueous media polar solvent, and have stronger acidity, thus it can meet the requirement of esterification.[Journalof Molecular Catalysis A, 2005,240 (1-2): 109-118. Chinese science B collects, chemistry, 2005,35 (4): 324-330].Heteropolyacid catalyst has the advantages such as highly acid, abundance, convenient post-treatment, but it is in acidity homogenising, and the research of load fastness (not easily solution-off) aspect needs deeply.Solid super-strong acid has the feature of highly acid and solid catalyst because of it, and extremely researcher payes attention to [Journal ofMolecular Catalysis A:Chemical 2005,240 (1-2): 186-190; Organic chemistry, 2005,25 (11): 1490-1493].Although get equipment corrosion and the pollution problem that can alleviate direct esterification for sulfuric acid with solid super acid catalyst, this kind of catalyst easily run off, activity decrease is fast, the more high defect of cost.Therefore improving catalyst life and reducing its cost is the problem will putting forth effort at present to solve.The moisture simultaneously produced in heteropoly acid and solid acid catalysis reaction is not easily got rid of, and can cause the loss by dissolution of heteropoly acid passivation and catalyst, nor is beneficial to esterification and carries out to positive direction.At present conventional entrainer (as benzene) or adsorbent remove minor amount of water, but there is entrainer environmental pollution, adsorbent runs off and the problem such as subsequent technique is loaded down with trivial details.
Q.L.Liu, H.F.Chen. article " Modeling of esterification of acetic acidwithn-butanol in the presence of Zr (SO 4) 24H 2O coupled pervaporation " (" Journal ofMembrane Science " 2002, PVA composite membrane 196:171-178) is adopted to study the impact on acetic acid and n-butanol esterification of esterification reaction-infiltration evaporation integrated technology, experiment shows that at initial n-butanol/quality of acetic acid ratio be 1.98, the ratio 0.23cm-1 of membrane area and reactant liquor volume, under the condition of 80 DEG C, the ester productive rate of integrated technology is adopted to rise to about 90% by original about 75%.
Wang Lefu, " esterification is coupled the impact of infiltration evaporation membrane process on balanced sequence " (" Chemical Reaction Engineering and technique " 1999 of Li Xuehui, 15 (4): 443 ~ 449) in, adopt PVA/PAN composite membrane, investigate the reaction of infiltration evaporation-esterization and be coupled the building-up process factor of n-butyl acetate in composite film reactor to the impact of esterification chemical balance shifting, result shows, in higher reaction temperatures (80 DEG C) and higher initial reaction liquid, alcohol/sour mass ratio (being greater than 1.24) and high membrane area are with under the condition of the ratio (0.5cm-1) of reactant liquor volume, react the high yield reaching ester after 9 hours.Cationic ion-exchange resin class catalyst reaction mild condition, accessory substance is few, can be recycled, and is convenient to continuous prodution, to equipment corrosion-free [CatalysisToday, 2005,100 (3-4): 431-435; Applied chemistry, 2006,23 (8): 897-901].Resin catalyst has easily and the advantage of product separation, also has good catalytic activity to esterification.But because serviceability temperature its application lower is limited to, still deposit micro-water problem in the esterification reaction simultaneously.
Benedict D.J, Parulekar S.J, Tsai Shih-Perng. is at article " Pervaporation-assisted esterification of lactic and succinic acids with downstreamester recovery " (" Journal of Membrane Science " 2006, 281:435-445) disclose the experimental study of esterification reaction-infiltration evaporation integrated technology in ethyl lactate synthetic reaction adopting GFT-1005 film, result shows, at the ratio 0.091cm-1 of membrane area and reactant liquor volume, initial ethanol/lactic acid mass ratio is 0.64, under the condition of 95 DEG C, after 8 hours, ethyl lactate productive rate is about 85%.
The esterification reaction-infiltration evaporation membrane integrating technique that above-mentioned document relates to, be all or in higher reaction temperature or under the condition of high membrane area with the ratio of reactant liquor volume, be respectively used to or the esterification of liquid material of n-butyl acetate or ethyl lactate or isopropyl acetate etc., not yet relate to the lactate synthesis reaction of solid feed in reactant
The research of Membrane catalysis esterification causes the interest of people from the eighties in last century, early stage diffusion barrier itself does not possess catalysis, the infiltration evaporation only relying on film carrys out separation of material, promote esterification, start the film reaction process study of " difunctional " film on this basis, as [JMemb.Sci.1992 such as David, 73:129] prepare polystyrolsulfon acid/polyvinyl alcohol, polystyrolsulfon acid/polyacrylonitrile two class blend catalytic membrane, in the synthesis of propyl propionate, react 15 hours conversion ratios and reach more than 80%, obviously this film is subject to the restriction of catalytic efficiency in commercial applications.[the Journal of Molecular Catalysis such as Shao Shijun, 1995,9 (2): 90-95] have studied the catalyzing esterification effect of zirconium sulfate polyvinyl alcohol hybridized film to acetic acid and n-butanol, reaction temperature 90 DEG C, reaction time 9, little productive rate constantly reached 98%, selective 100% of reaction.Achieve good effect, but the reaction time is longer, and in hybridized film, catalyst easily runs off, the catalytic efficiency of hybridized film can with the increase of access times decline rapidly.Recently, [the Bioresource Technology such as Dube, 2007,98 (3): 639-647] two-phase membrane reactor is adopted to prepare biodiesel, at 60,65,70 DEG C of temperature, adopt variable concentrations acid base catalysator, feeding liquid flow velocity carries out semi-batch operation, separated from reaction system by unreacted grease with membrane reactor, the biodiesel that output is pure and the direction that molecular balance is generated towards product are moved.But the catalyst used is the conventional catalyst such as sulfuric acid and potassium hydroxide, the intrinsic shortcoming of these catalyst can not well overcome, and however, membrane reactor represents an important directions of current Esterification catalytic reaction.
Summary of the invention
The object of the invention is to propose a kind of polymerization esterification thermal stability method.
For reaching this object, the present invention by the following technical solutions:
A kind of polymerization esterification thermal stability method, it is characterized in that: take solid catalyst SO42-/ZnFe2O4 wiring solution-forming 1 soluble in water, taking polymer wiring solution-forming 2 soluble in water, mixed solution 1 and solution 2 obtain casting solution, then polyvinylidene fluoride permeable vaporizing Flat Membrane is immersed in casting solution, after making infiltration evaporation compacted zone and casting solution fully infiltrate 10 minutes, put into rapidly saturated sodium sulphate coagulating bath and make it film forming, make the catalytic membrane of loose structure, then soak in 10wt% glutaraldehyde acid solution, catalytic membrane is cross-linked further, take out the washing of this film to neutral, then heat drying in vacuum drying chamber, obtained polymerization esterification catalytic membrane, polymer is the mixture of SPSF and sulfonated polyether-ether-ketone, described polymer sulfonic acid group substitution value is 6%-9%, catalytic membrane aperture 2-40 μm.
Detailed description of the invention
Embodiment 1
A kind of polymerization esterification thermal stability method, it is characterized in that: take solid catalyst SO42-/ZnFe2O4 wiring solution-forming 1 soluble in water, taking polymer wiring solution-forming 2 soluble in water, mixed solution 1 and solution 2 obtain casting solution, solution 1 and solution 2 mass ratio are 1: 1, then polyvinylidene fluoride permeable vaporizing Flat Membrane is immersed in casting solution, after making infiltration evaporation compacted zone and casting solution fully infiltrate 10 minutes, put into rapidly saturated sodium sulphate coagulating bath and make it film forming, make the catalytic membrane of loose structure, then soak in 10wt% glutaraldehyde acid solution, catalytic membrane is cross-linked further, take out the washing of this film to neutral, then heat drying in vacuum drying chamber, this film is heat drying 24 hours obtained polymerization esterification catalytic membrane in the vacuum drying chamber of 80 DEG C, polymer is the mixture of SPSF and sulfonated polyether-ether-ketone, described polymer sulfonic acid group substitution value is 6%, catalytic membrane aperture 2-40 μm.
Embodiment 2
A kind of polymerization esterification thermal stability method, it is characterized in that: take solid catalyst SO42-/ZnFe2O4 wiring solution-forming 1 soluble in water, taking polymer wiring solution-forming 2 soluble in water, mixed solution 1 and solution 2 obtain casting solution, solution 1 and solution 2 mass ratio are then polyvinylidene fluoride permeable vaporizing Flat Membrane to be immersed in casting solution at 2: 1, after making infiltration evaporation compacted zone and casting solution fully infiltrate 10 minutes, put into rapidly saturated sodium sulphate coagulating bath and make it film forming, make the catalytic membrane of loose structure, then soak in 10wt% glutaraldehyde acid solution, catalytic membrane is cross-linked further, take out the washing of this film to neutral, then heat drying in vacuum drying chamber, this film is heat drying 24 hours obtained polymerization esterification catalytic membrane in the vacuum drying chamber of 80 DEG C, polymer is the mixture of SPSF and sulfonated polyether-ether-ketone, described polymer sulfonic acid group substitution value is 6%, catalytic membrane aperture 2-40 μm.
Embodiment 3
A kind of polymerization esterification thermal stability method, it is characterized in that: take solid catalyst SO42-/ZnFe2O4 wiring solution-forming 1 soluble in water, taking polymer wiring solution-forming 2 soluble in water, mixed solution 1 and solution 2 obtain casting solution, solution 1 and solution 2 mass ratio are 3: 1, then polyvinylidene fluoride permeable vaporizing Flat Membrane is immersed in casting solution, after making infiltration evaporation compacted zone and casting solution fully infiltrate 10 minutes, put into rapidly saturated sodium sulphate coagulating bath and make it film forming, make the catalytic membrane of loose structure, then soak in 10wt% glutaraldehyde acid solution, catalytic membrane is cross-linked further, take out the washing of this film to neutral, then heat drying in vacuum drying chamber, this film is heat drying 24 hours obtained polymerization esterification catalytic membrane in the vacuum drying chamber of 80 DEG C, polymer is the mixture of SPSF and sulfonated polyether-ether-ketone, described polymer sulfonic acid group substitution value is 6%, catalytic membrane aperture 2-40 μm.
Embodiment 4
A kind of polymerization esterification thermal stability method, it is characterized in that: take solid catalyst SO42-/ZnFe2O4 wiring solution-forming 1 soluble in water, taking polymer wiring solution-forming 2 soluble in water, mixed solution 1 and solution 2 obtain casting solution, solution 1 and solution 2 mass ratio are 3: 2, then polyvinylidene fluoride permeable vaporizing Flat Membrane is immersed in casting solution, after making infiltration evaporation compacted zone and casting solution fully infiltrate 10 minutes, put into rapidly saturated sodium sulphate coagulating bath and make it film forming, make the catalytic membrane of loose structure, then soak in 10wt% glutaraldehyde acid solution, catalytic membrane is cross-linked further, take out the washing of this film to neutral, then heat drying in vacuum drying chamber, this film is heat drying 24 hours obtained polymerization esterification catalytic membrane in the vacuum drying chamber of 80 DEG C, polymer is the mixture of SPSF and sulfonated polyether-ether-ketone, described polymer sulfonic acid group substitution value is 6%, catalytic membrane aperture 2-40 μm.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And these belong to spirit institute's apparent change of extending out of the present invention or change and are still among protection scope of the present invention.
Claims (1)
1. a polymerization esterification thermal stability method, it is characterized in that: take solid catalyst SO42-/ZnFe2O4 wiring solution-forming 1 soluble in water, taking polymer wiring solution-forming 2 soluble in water, mixed solution 1 and solution 2 obtain casting solution, then polyvinylidene fluoride permeable vaporizing Flat Membrane is immersed in casting solution, after making infiltration evaporation compacted zone and casting solution fully infiltrate 10 minutes, put into rapidly saturated sodium sulphate coagulating bath and make it film forming, make the catalytic membrane of loose structure, then soak in 10wt% glutaraldehyde acid solution, catalytic membrane is cross-linked further, take out the washing of this film to neutral, then heat drying in vacuum drying chamber, obtained polymerization esterification catalytic membrane, polymer is the mixture of SPSF and sulfonated polyether-ether-ketone, described polymer sulfonic acid group substitution value is 6%-9%, catalytic membrane aperture 2-40 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410617869.0A CN104492492A (en) | 2014-11-05 | 2014-11-05 | Preparation method for polymerization esterification catalytic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410617869.0A CN104492492A (en) | 2014-11-05 | 2014-11-05 | Preparation method for polymerization esterification catalytic membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104492492A true CN104492492A (en) | 2015-04-08 |
Family
ID=52933994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410617869.0A Pending CN104492492A (en) | 2014-11-05 | 2014-11-05 | Preparation method for polymerization esterification catalytic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104492492A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088959A (en) * | 2006-06-14 | 2007-12-19 | 山东理工大学 | Prepn process of multifunctional honeycomb ceramic filter element |
| CN101301628A (en) * | 2008-07-01 | 2008-11-12 | 天津工业大学 | Film for catalyzing esterification and preparation thereof |
| US20130168228A1 (en) * | 2011-04-12 | 2013-07-04 | Geoffrey A. Ozin | Photoactive Material Comprising Nanoparticles of at Least Two Photoactive Constituents |
-
2014
- 2014-11-05 CN CN201410617869.0A patent/CN104492492A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088959A (en) * | 2006-06-14 | 2007-12-19 | 山东理工大学 | Prepn process of multifunctional honeycomb ceramic filter element |
| CN101301628A (en) * | 2008-07-01 | 2008-11-12 | 天津工业大学 | Film for catalyzing esterification and preparation thereof |
| US20130168228A1 (en) * | 2011-04-12 | 2013-07-04 | Geoffrey A. Ozin | Photoactive Material Comprising Nanoparticles of at Least Two Photoactive Constituents |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20130244861A1 (en) | Composite catalytic membrane applied to catalytic esterification and preparation method thereof | |
| CN101301628B (en) | Film for catalyzing esterification and preparation thereof | |
| EP3587431B1 (en) | Method for preparing levoglucosenone by catalytic pyrolysis of biomass | |
| CN104117297A (en) | Preparation method of pervaporation composite membrane filled with hydrophobically modified nano calcium carbonate | |
| CN101773860A (en) | Carbon-based solid acid catalyst synthesized by one-step hydrothermal carbonization process | |
| CN110935335B (en) | High-hydrophilicity polymer hybrid membrane and preparation method thereof | |
| CN1907550A (en) | Preparation method for hollow fiber osmosis vaporation permeable complex film | |
| CN103331108A (en) | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane | |
| CN105478020A (en) | MOFs/NaA molecular sieve composite membrane for acetic acid dehydration and preparation method for MOFs/NaA molecular sieve composite membrane | |
| CN102553457B (en) | Preparation method of microporous membrane with hydrophilicity and hydrophobicity | |
| CN104492492A (en) | Preparation method for polymerization esterification catalytic membrane | |
| CN101545213A (en) | Method for preparing PDMS/PVDF composite membrane | |
| CN102671712A (en) | Preparation method of novel solid superacid catalyst and application thereof in catalysis of microcrystalline cellulose for synthesis of levulinic acid | |
| CN100551505C (en) | A kind of diffusion barrier that is used for separation of methanol/dimethyl carbonate azeotrope and preparation method thereof | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN103933868A (en) | Preparation method of methanol-water ceramic-based hollow-fiber-penetrated vaporized composite membrane | |
| CN109485629A (en) | A kind of production technology of anhydrous propanone contracting glycerol | |
| CN101412917A (en) | Method for preparing biodiesel | |
| CN103254158B (en) | Method and device for producing furfural by using biomass hydrolysis coupling pervaporation separation technology | |
| CN110327971A (en) | A kind of preparation method and application of acidic ionic liquid catalysts | |
| CN104492485A (en) | Acidic ionic liquid-coated polymeric core solid acid material catalyst and preparation method thereof | |
| CN107497307A (en) | A kind of preparation method of the special infiltrating and vaporizing membrane of perfume industry | |
| JP2013006142A (en) | Catalyst for hydrolysis of plant-base material, and method of manufacturing saccharide | |
| CN106977388A (en) | A kind of method that oxygen catalytic oxidation biomass prepares formic acid | |
| CN101722003B (en) | Catalyst loaded on titanium dioxide for epoxidation of esters and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150408 |
|
| RJ01 | Rejection of invention patent application after publication |