CN102716769A - Preparation method of perfluorosulfonic acid nano composite fiber catalyst for esterification reaction - Google Patents
Preparation method of perfluorosulfonic acid nano composite fiber catalyst for esterification reaction Download PDFInfo
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Abstract
The invention relates to a preparation method of perfluorosulfonic acid nano composite fiber catalyst for esterification reaction. The preparation method is characterized in that the method comprises the following steps of: 1) preparing spinning suspension; 2) preparing perfluorosulfonic acid/polymer dispersing agent/nanoparticle composite fibers by adopting an electrostatic spinning technique under conditions of voltage being 8-25kV, jet filament receiving distance being 5-20cm, feeding speed being 0.2-2.0ml/h, temperature being 5-30DEG C and relative humidity being 20-80 percent; and 3) conducting physical and chemical treatment to the prepared nano fibers to obtain the perfluorosulfonic acid nano composite fibers with catalytic activity. The preparation method has the characteristics of the preparation technology is mature, the equipment is simple and easy to operate, the size of the perfluorosulfonic acid nano composite fiber catalyst is evenly and controllably distributed and reaches 100-2000nm, the specific surface area is high and reaches 20-100m<2>/g, the catalyst can be used for esterification reaction, the reaction conditions are moderate, the conversion rate is high and more than 95 percent, the equipment corrosiveness is small, the waste liquid is less, the catalyst is environmental-friendly and the recovery and regeneration performance of the catalyst is good.
Description
[technical field]
The present invention relates to the chemical catalyst preparing technical field, specifically, is a kind of perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification.
[background technology]
It is skeleton with the polytetrafluoroethylene (PTFE) structure that perfluorinated sulfonic resin (hereinafter to be referred as perfluorinated sulfonic acid) is one type, and the alkene ether structure is a side chain, and the terminal (per) fluoropolymer that has sulfonate group.Over nearly 40 years, it is widely used in fields such as barrier film that fuel cell barrier film, chlorine industry electrolyze table salt, solid polymer electrolyte with its good heat resistance, mechanical property, chemical property and chemical stability.Simultaneously, as a kind of solid super-strong acid, perfluorinated sulfonic acid also has catalytic action widely in reactions such as organic synthesis such as alkylation, acidylate, nitrated, sulfonation, phosphorylated, polymerization, condensation, etherificate, esterification, aquation and rearrangement.The perfluorinated sulfonic acid catalyst is compared with liquid acid catalyst, has non-corrosiveness, does not produce acid pickle, advantage such as product is easily separated, selectivity is high and can repeatedly use repeatedly; With general solid acid ratio, have advantages such as productive rate height, reaction condition is gentle, reaction speed is fast; Comparing with other acid cation exchange resin, have characteristics such as stronger acidity, serviceability temperature height, is the solid acid catalyst of comparatively ideal environmental sound.But, because in non-polar solven or gaseous environment, perfluorinated sulfonic acid is the graininess of dense non-porous usually, the not enough 0.02m of specific area
2/ g makes great deal of acidic sites (sulfonic acid group :-SO
3H) it is inner and can not effectively be utilized to be embedded in polymer, thereby the mass ratio that has reduced perfluorinated sulfonic acid is active, and therefore, the ratio that increases its specific surface and improve acid site capable of using is important measures that improve perfluorinated sulfonic acid catalysis potentiality.
In recent years, electrostatic spinning nano fiber had attracted many researchers' sight as a kind of functional material that has application prospect.Its maximum characteristics are exactly that specific area is big, thereby have increased surface-active, produce small-size effect, surface or interfacial effect, quantum size effect etc., all show specificity at chemistry, physics (heat, light, electromagnetism etc.) aspect of performance.And its preparation technology is simple; Can pass through its surface of regulation and control such as different polymer, spinning condition and post-processed method can, thereby utilize its huge specific area to tie up field such as material in separation and purification, pharmaceutical carrier, sensor and medical very good prospects for application is arranged all.
Utilizing electrostatic spinning technique that perfluorinated sulfonic acid is processed nanofiber or as carrier perfluorinated sulfonic acid is distributed to the surface with electrostatic spinning nano fiber, thereby increase the specific area of perfluorinated sulfonic acid, is a kind of effective ways that improve perfluorinated sulfonic acid acid centre utilization rate.Yet perfluorinated sulfonic acid is the ion cluster form more in organic solvent, and viscosity is little; Be difficult for stretching, therefore simple perfluorinated sulfonic acid solution is difficult to directly be used for the electrostatic spinning process, all need in solution, add other polymer usually as dispersant (claiming to carry agent again) (H.Chen; J.Snyder, Y.Elabd, Macromolecules.2008; 41,128-135).At present, the research of spinning perfluorinated sulfonic acid about static mainly concentrates on fuel cell barrier film (J.Choi, P.N.Pintauro, P.T.Mather, Chemsuschem.2010,3,1245-1248; S.Molla, V.Compan, J.Power Sources.2011,196,2699-2708), high sensor (B.Dong, L.K.Winey, Y.Elabd, Nano Lett.2010,10, aspect such as 3785-3790).Domestic still haveing nothing to do in utilizing electrostatic spinning technique to prepare the patent documentation of perfluorinated sulfonic acid nanofiber,, only foreign literature has a small amount of report.Peter Pintauro etc. utilizes this method to prepare the nano fibrous membrane that contains perfluorinated sulfonic acid; And be used for the barrier film of direct fuel cell; Result (United States Patent (USP) " Nanocapillary Networks and Methods of Forming Same ", publication number: US 2010/0227247A1) have preferably been obtained.
The major advantage that adopts method of electrostatic spinning to prepare the perfluorinated sulfonic acid nano-fiber catalyst is that this method technology and equipment are all fairly simple, and the result is reliable and stable, and the specific area height, and controllable size, has good chemical stability, heat endurance.The perfluorinated sulfonic acid nano-composite fiber structure that obtains is continuous, has overcome traditional perfluorinated sulfonic acid catalysis material (like 13wt%Nafion/SiO
2Composite) is prone to shortcoming such as the difficult separation of brittle failure; And porosity is high, and the inner liquid holdup of catalyst is high in esterification, and reactant contacts with acidic-group easily, and catalytic activity is high.The present invention is when guaranteeing perfluorinated sulfonic acid nanofiber continuous structure; Can also in casting solution, add inorganic nanoparticles; Change the character of casting solution; Microscopic pattern to the perfluorinated sulfonic acid nano fibrous membrane is effectively regulated and control, and further increases its specific area and catalytic performance, has developed a kind of method for preparing the perfluorinated sulfonic acid nano-fiber catalyst based on electrostatic spinning technique.
[summary of the invention]
The objective of the invention is to overcome the deficiency of prior art, a kind of perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification is provided.
The objective of the invention is to realize through following technical scheme:
A kind of perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification, its concrete steps are:
(1) preparation spinning suspension
Perfluorinated sulfonic acid and polymeric dispersant are dissolved in the organic solvent, stir, in above-mentioned organic solution, slowly add inorganic nanoparticles, ultrasonic dispersion is stirred to evenly once more, and the organic and inorganic suspension that obtains is the electrostatic spinning casting solution;
In the described organic and inorganic suspension, the mass percent of its raw material is:
Described solution temperature is 20～95 ℃;
Said polymeric dispersant is one or more the mixture in polyether sulfone (PES), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), PEO (PEO), Kynoar (PVDF), the polyvinyl chloride (PVC);
Said organic solvent is N, dinethylformamide (DMF), N, the mixture of one or more among N-dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP), acetone, the isopropyl alcohol;
Said nano particle is silica (SiO
2), titanium dioxide (TiO
2), alundum (Al (Al
2O
3), calcium carbonate (CaCO
3) and nanocarbon particle in one or more mixtures, said inorganic nanoparticles diameter is 20～200nm;
(2) preparation contains the nano-composite fiber catalyst of perfluorinated sulfonic acid
Casting solution standing and defoaming 1～5h with in the step (1) changes in the electrostatic spinning apparatus.Open the high-voltage electrostatic power generator and the micro syringe propulsion plant carries out spinning, obtain the nano-composite fiber catalyst of diameter Distribution homogeneous and controllable;
Said electrostatic spinning process condition is: supply voltage is 8～25kV, and it is 0.2～2.0ml/h that micro syringe advances speed, spinning head internal diameter 0.4～0.8mm, and receiving system and distance between electrodes are 5～20cm;
Spinning atmosphere condition is: 5～30 ℃ of temperature, relative humidity are 20～80%;
Said nano-composite fiber catalyst diameter is 10～2000nm;
(3) post processing of nano-composite fiber catalyst
The nano-composite fiber that obtains in the step (2) is soaked more than the 24h with acid solution, take out washing, vacuum drying finally obtains having catalytic activity perfluorinated sulfonic acid nano-composite fiber catalyst to weight;
Above-mentioned acid solution is the HCl solution of 1M, mainly act as to promote the solvent that does not volatilize in the tunica fibrosa to exchange, and simultaneously perfluorinated sulfonic acid fully is converted into acid type, the nano-composite fiber catalyst that activation obtains.
Said esterification is acid alcohol direct esterification reaction, and wherein said acid is the aliphatic acid of 2C～12C, and said alcohol is the fatty alcohol of 1C～6C.
Compared with prior art, good effect of the present invention is:
(1) the perfluorinated sulfonic acid content of receiving in the composite fibre catalyst according to the invention can regulated in the scope greatly, and polymeric dispersant can change according to different application requirements, has improved the potential application of nano fibrous membrane that is obtained greatly;
(2) acid centre is positioned at fiber surface in the nano-composite fiber catalyst according to the invention, in esterification, is easy to approachingly, has active high characteristics;
(3) nano-composite fiber catalyst of the present invention because the special physical arrangement of nano particle helps the absorption of reactant, improves the activity of acid centre;
(4) nano-composite fiber catalyst macrostructure of the present invention is continuous, is easy to reclaim and regeneration, and it is few, little to equipment corrosion, environmentally friendly to produce waste liquid.
[description of drawings]
Fig. 1 is the sem photograph of a kind of perfluorinated sulfonic acid/polyvinyl alcohol nano composite fibre;
Fig. 2 is the sem photograph of a kind of perfluorinated sulfonic acid/polyether sulfone/silica nanometer composite fibre;
Fig. 3 is the sem photograph of a kind of perfluorinated sulfonic acid/polyether sulfone/nano titania composite fibre.
[specific embodiment]
The present invention below is provided a kind of specific embodiment that is used for the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method of esterification.
Embodiment 1
Preparation perfluorinated sulfonic acid/polyvinyl alcohol nano composite fibre catalyst is used for acetate-ethyl esterification reaction
1, take by weighing methyl alcohol 2.0g, normal propyl alcohol 4.0g, deionized water 14.0g, stirring at room becomes even mixed solvent; Get 1.2g polyvinyl alcohol (PVA:1799) and 3.0g perfluorinated sulfonic acid (PFSA), 95 ℃ of heating for dissolving, magnetic agitation obtains organic solution to evenly;
2, above-mentioned solution is cooled to room temperature; Standing and defoaming 4h changes electrostatic spinning apparatus over to and carries out spinning, and condition is: supply voltage 18kV; Feeding rate 0.3ml/h; The distance of regulating between receiver and the spinning head (internal diameter 0.4mm) is 10cm, obtains perfluorinated sulfonic acid/polyvinyl alcohol nano composite fibre (Fig. 1), and its specific area is 32m
2/ g;
3, with above-mentioned nano-composite fiber with 1M HCl solution soaking 24h, take out with deionized water and clean, vacuum drying 12h;
4, get 1mol acetate, 2mol ethanol mixes, and adds the above-mentioned perfluorinated sulfonic acid of 0.5g/polyvinyl alcohol nano composite fibre, is heated to 75 ℃ after mixing, and keeps 8h.The acetate conversion ratio reaches 95.3%, and nanofiber in the filtering solution is cleaned with deionized water, calculates the nano-composite fiber rate of recovery after the vacuum drying and reaches 96.2%.
Embodiment 2
Preparation perfluorinated sulfonic acid/polyether sulfone/silica nanometer composite fibre catalyst is used for acetate-methanol esterification reaction
1, take by weighing 3.0g polyether sulfone (PES) and be dissolved in 15.0g N, in the N-dimethylacetylamide (DMAc), add 1.0g perfluorinated sulfonic acid (PFSA), 60 ℃ of water-bath magnetic agitation obtain organic solution to evenly.In above-mentioned organic solution, add 1.0g silica (SiO
2) nano particle, normal temperature magnetic agitation 12h behind the sonicated 2h obtains uniform organic and inorganic suspension;
2, with above-mentioned organic and inorganic suspension standing and defoaming 2h; Change electrostatic spinning apparatus over to and carry out spinning; Condition is: supply voltage 16kV, and feeding rate 1.0ml/h, the distance of regulating between receiver and the spinning head (internal diameter 0.7mm) is 12cm; Obtain perfluorinated sulfonic acid/polyether sulfone/silica nanometer composite fibre (Fig. 2), its specific area is 82m
2/ g;
3, with above-mentioned nano-composite fiber with 1M HCl solution soaking 24h, take out with deionized water and clean, vacuum drying 12h;
4, get 1mol acetate, the 2mol methanol mixed adds the above-mentioned perfluorinated sulfonic acid/polyether sulfone of 1g/silica nanometer composite fibre, is heated to 80 ℃ after mixing, and keeps 8h.The acetate conversion ratio reaches 95.7%, and nanofiber in the filtering solution is cleaned with deionized water, calculates its rate of recovery after the vacuum drying and reaches 97.3%.
Embodiment 3
Preparation perfluorinated sulfonic acid/polyether sulfone/nano titania composite fibre catalyst is used for laurate-methanol esterification reaction
1, take by weighing 3.0g polyether sulfone (PES) and be dissolved in 14.8g N, in the dinethylformamide (DMF), add 1.0g perfluorinated sulfonic acid (PFSA), 60 ℃ of water-bath magnetic agitation obtain organic solution to evenly.In above-mentioned organic solution, add 1.2g titanium dioxide (TiO
2) nano particle, normal temperature magnetic agitation 12h behind the sonicated 2h obtains uniform organic and inorganic suspension;
2, with above-mentioned organic and inorganic suspension standing and defoaming 2h; Change electrostatic spinning apparatus over to and carry out spinning; Condition is: supply voltage 10kV, and feeding rate 0.5ml/h, the distance of regulating between receiver and the spinning head (internal diameter 0.7mm) is 10cm; Obtain perfluorinated sulfonic acid/polyether sulfone/nano titania composite fibre (Fig. 3), its specific area is 80.7m
2/ g;
3, with above-mentioned nano-composite fiber with 1M HCl solution soaking 24h, take out with deionized water and clean, vacuum drying 12h;
4, get the 200g laurate, the 160g methanol mixed adds the above-mentioned perfluorinated sulfonic acid/polyether sulfone of 1.5g/nano titania composite fibre catalyst, and stirring is heated to 70 ℃ after mixing up evenly, keeps 10h.Reaction steams unreacted methanol after finishing, and standing separation goes out nano-composite fiber catalyst and water, obtains thick product laurate methyl alcohol ester; The laurate conversion ratio reaches 98.2%; Nanofiber in the filtering solution is cleaned with deionized water, calculates its rate of recovery after the vacuum drying and reaches 98.3%.
Characteristics of the present invention are that mature preparation process is simple, the perfluorinated sulfonic acid nano-composite fiber diameter Distribution homogeneous and controllable that obtains, and specific area is high; It is gentle to be used for the direct esterification reaction condition; Catalytic efficiency is high, and is little to equipment corrosion, and it is few to produce waste liquid; Environmentally friendly, catalyst recovery and regenerability are good.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (10)
1. perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification is characterized in that concrete steps are:
(1) preparation spinning suspension
Perfluorinated sulfonic acid and polymeric dispersant are dissolved in the organic solvent, stir, in above-mentioned organic solution, slowly add inorganic nanoparticles, ultrasonic dispersion is stirred to evenly once more, and the organic and inorganic suspension that obtains is the electrostatic spinning casting solution;
(2) preparation contains the nano-composite fiber catalyst of perfluorinated sulfonic acid
Casting solution standing and defoaming 1～5h with in the step (1) changes in the electrostatic spinning apparatus; Open the high-voltage electrostatic power generator and the micro syringe propulsion plant carries out spinning, obtain the nano-composite fiber catalyst of diameter Distribution homogeneous and controllable;
(3) post processing of nano-composite fiber catalyst
The nano-composite fiber that obtains in the step (2) is soaked more than the 24h with acid solution, take out washing, vacuum drying finally obtains having catalytic activity perfluorinated sulfonic acid nano-composite fiber catalyst to weight.
2. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1 is characterized in that in said step (1), in the described organic and inorganic suspension, the mass percent of its raw material is:
3. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1 is characterized in that in said step (1), described solution temperature is 20～95 ℃.
4. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1; It is characterized in that; In said step (1), described polymeric dispersant is one or more the mixture in polyether sulfone (PES), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), PEO (PEO), Kynoar (PVDF), the polyvinyl chloride (PVC).
5. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1; It is characterized in that; In said step (1), described organic solvent is N, dinethylformamide (DMF); N, the mixture of one or more among N-methylacetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP), acetone, the isopropyl alcohol.
6. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1 is characterized in that in said step (1), described nano particle is silica (SiO
2), titanium dioxide (TiO
2), alundum (Al (Al
2O
3), calcium carbonate (CaCO
3) and nanocarbon particle in one or more mixtures, said inorganic nanoparticles diameter is 20～200nm.
7. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1; It is characterized in that; In said step (2), described electrostatic spinning process condition is: supply voltage is 8～25kV, and it is 0.2～2.0ml/h that micro syringe advances speed; Spinning head internal diameter 0.4～0.8mm, receiving system and distance between electrodes are 5～20cm.
8. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1 is characterized in that in said step (2), spinning atmosphere condition is: 5～30 ℃ of temperature, relative humidity are 20～80%.
9. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1 is characterized in that in said step (2), said nano-composite fiber catalyst diameter is 10～2000nm.
10. the perfluorinated sulfonic acid nano-composite fiber Preparation of catalysts method that is used for esterification as claimed in claim 1; It is characterized in that; In said step (3), described acid solution is the HCl solution of 1M, mainly act as to promote the solvent that does not volatilize in the tunica fibrosa to exchange; Simultaneously perfluorinated sulfonic acid fully is converted into acid type, the nano-composite fiber catalyst that activation obtains.
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| CN104638283A (en) * | 2015-02-09 | 2015-05-20 | 大连交通大学 | Electrostatic spinning method for preparing sponge-shaped Nafion membrane |
| CN105002658A (en) * | 2015-08-19 | 2015-10-28 | 哈尔滨工业大学 | Preparation method and driving method of remotely controllable multiple shape memory polymer composite fibrous membrane |
| CN105038996A (en) * | 2015-07-24 | 2015-11-11 | 河南工程学院 | Nanofiber composite membrane reactor |
| CN105040278A (en) * | 2015-07-24 | 2015-11-11 | 河南工程学院 | Preparation method for composite nanofiber membrane for producing biodiesel |
| WO2016095207A1 (en) * | 2014-12-19 | 2016-06-23 | Rhodia Operations | Carbon/fluoropolymer composite and manufacturing methods thereof |
| CN107282140A (en) * | 2016-03-31 | 2017-10-24 | 华东理工大学 | A kind of perfluorinated sulfonic resin/PES/TiO2-ZrO2The preparation method of solid acid doughnut catalyst filling |
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| WO2016095207A1 (en) * | 2014-12-19 | 2016-06-23 | Rhodia Operations | Carbon/fluoropolymer composite and manufacturing methods thereof |
| CN104638283A (en) * | 2015-02-09 | 2015-05-20 | 大连交通大学 | Electrostatic spinning method for preparing sponge-shaped Nafion membrane |
| CN105038996A (en) * | 2015-07-24 | 2015-11-11 | 河南工程学院 | Nanofiber composite membrane reactor |
| CN105040278A (en) * | 2015-07-24 | 2015-11-11 | 河南工程学院 | Preparation method for composite nanofiber membrane for producing biodiesel |
| CN105040278B (en) * | 2015-07-24 | 2017-08-25 | 河南工程学院 | For the preparation method for the composite nano-fiber membrane for producing biodiesel |
| CN105038996B (en) * | 2015-07-24 | 2019-01-11 | 河南工程学院 | Nano-fiber composite film reactor |
| CN105002658A (en) * | 2015-08-19 | 2015-10-28 | 哈尔滨工业大学 | Preparation method and driving method of remotely controllable multiple shape memory polymer composite fibrous membrane |
| CN105002658B (en) * | 2015-08-19 | 2017-11-03 | 哈尔滨工业大学 | The preparation method and driving method of remote-controllable Multiple Shape memory polymer composite cellulosic membrane |
| CN107282140A (en) * | 2016-03-31 | 2017-10-24 | 华东理工大学 | A kind of perfluorinated sulfonic resin/PES/TiO2-ZrO2The preparation method of solid acid doughnut catalyst filling |
| CN107282140B (en) * | 2016-03-31 | 2019-11-19 | 华东理工大学 | A kind of perfluorinated sulfonic resin/PES/TiO2-ZrO2The preparation method of solid acid doughnut catalyst filling |
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