CN110560161A - Preparation method of sulfonated phenolic resin type solid acid catalyst and application of sulfonated phenolic resin type solid acid catalyst in glycerol esterification reaction - Google Patents
Preparation method of sulfonated phenolic resin type solid acid catalyst and application of sulfonated phenolic resin type solid acid catalyst in glycerol esterification reaction Download PDFInfo
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- CN110560161A CN110560161A CN201910774049.5A CN201910774049A CN110560161A CN 110560161 A CN110560161 A CN 110560161A CN 201910774049 A CN201910774049 A CN 201910774049A CN 110560161 A CN110560161 A CN 110560161A
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- type solid
- resin type
- acid catalyst
- solid acid
- phenolic resin
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 239000011973 solid acid Substances 0.000 title claims abstract description 74
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229960003742 phenol Drugs 0.000 claims abstract description 29
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 28
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 14
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 14
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 21
- 239000005011 phenolic resin Substances 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 150000002989 phenols Chemical class 0.000 claims description 11
- 229940061610 sulfonated phenol Drugs 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 abstract description 42
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 45
- 239000000047 product Substances 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 16
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 16
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 15
- 230000032050 esterification Effects 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 11
- 239000004348 Glyceryl diacetate Substances 0.000 description 9
- 235000019443 glyceryl diacetate Nutrition 0.000 description 9
- 239000001087 glyceryl triacetate Substances 0.000 description 8
- 235000013773 glyceryl triacetate Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229960002622 triacetin Drugs 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 4
- 238000003965 capillary gas chromatography Methods 0.000 description 4
- 238000010812 external standard method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- APVVRLGIFCYZHJ-UHFFFAOYSA-N trioctyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCC)CC(=O)OCCCCCCCC APVVRLGIFCYZHJ-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WXGFMGXTPNKNEY-UHFFFAOYSA-N C=O.OC1=CC=C(C=C1)S(=O)(=O)O Chemical compound C=O.OC1=CC=C(C=C1)S(=O)(=O)O WXGFMGXTPNKNEY-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a sulfonated phenolic resin type solid acid catalyst and application of the sulfonated phenolic resin type solid acid catalyst in glycerol esterification reaction, and relates to the technical field of preparation of catalysts. The preparation method of the sulfonated phenolic resin type solid acid catalyst comprises the step of carrying out polycondensation reaction on p-hydroxybenzene sulfonic acid, phenol and paraformaldehyde by adopting a one-step polycondensation method to prepare the sulfonated phenolic resin type solid acid catalyst. The invention also provides a sulfonated phenolic resin type solid acid catalyst prepared by the preparation method, which can be applied to catalyzing the esterification reaction of glycerin. The preparation method of the sulfonated phenolic resin type solid acid catalyst provided by the invention has the advantages of simple process, safety and environmental protection, and the prepared sulfonated phenolic resin type solid acid catalyst has good stability and high catalytic activity, can catalyze glycerin to carry out esterification reaction at a lower temperature, and can be recycled.
Description
Technical Field
the invention relates to the technical field of catalyst preparation, in particular to a preparation method of a sulfonated phenolic resin type solid acid catalyst and application of the sulfonated phenolic resin type solid acid catalyst in glycerol esterification reaction.
Background
The traditional liquid acid (such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like) has high catalytic activity and low cost, but is easy to corrode equipment, unrecoverable, difficult in product separation, large in waste liquid generation and the like in the use process, and is not in accordance with the concept of green chemistry and sustainable development. Thus, environmentally friendly solid acid catalysts and their preparation and use as substitutes for liquid acids are receiving attention.
Among the various solid acid catalysts, the organic solid acid catalyst is an important species, and among them, the most common is a resin type solid acid catalyst, which has the advantages of water resistance, low active temperature, etc., has the characteristics of high efficiency and stability for acid catalytic reaction at a low temperature, is suitable for various condensation reactions and dehydration reactions, and many resin type solid acid catalysts are now commercially available.
The publication No. CN102614919A discloses a preparation method of a sulfonated crosslinked chitosan resin type solid acid catalyst, which takes chitosan as a raw material, firstly reacts with a crosslinking agent (glutaraldehyde or glyoxal) to prepare crosslinked chitosan, and then sulfonated crosslinked chitosan by concentrated sulfuric acid and chlorosulfonic acid to prepare sulfonated crosslinked chitosan solid acid.
The publication No. CN101786017A discloses a preparation method of a sulfonic group functionalized thiourea resin catalyst, which comprises the steps of firstly selecting a polythiourea resin with free sulfydryl by reacting a polythiol compound with a polyisocyanate compound, and then oxidizing the sulfydryl into a sulfonic group by using hydrogen peroxide to prepare the sulfonic group functionalized thiourea resin catalyst.
Phenolic resin is a traditional resin polymer, has simple preparation method, good acid resistance, thermal stability and mechanical strength, is widely applied to the manufacturing industries of flame-retardant materials, adhesives and grinding wheels, but has only few literature reports in the field of heterogeneous catalysis.
In 2013, Minakawa et al (Organic Letters 22 (2013): 5798-5801; Energy & Fuels 32 (2018): 12567-12576) use p-hydroxybenzene sulfonic acid and formaldehyde as raw materials to carry out polycondensation reaction at 120 ℃ for 6h to prepare a p-hydroxybenzene sulfonic acid-formaldehyde resin solid acid catalyst, and generate sulfonic acid functionalized phenolic resin by means of the polycondensation reaction of active hydrogen at the ortho-position of phenolic hydroxyl in the p-hydroxybenzene sulfonic acid and the formaldehyde. The method has simple preparation process and low raw material cost, and the prepared catalyst has excellent catalytic effect in esterification reaction of alcohol and carboxylic acid, but the catalyst is straight-chain phenolic resin, has poor thermal stability and is easy to dissolve in the reaction process, so that the stability is not high.
The publication No. CN101550223A discloses a sulfonated phenolic resin, a preparation method thereof and an application thereof as a catalyst, wherein the sulfonated phenolic resin is prepared by synthesizing phenolic resin by taking phenol and formaldehyde as raw materials, and then sulfonating the phenolic resin in the presence of concentrated sulfuric acid and fuming sulfuric acid, the sulfonated phenolic resin catalyst is used for catalytic synthesis reaction of trioctyl citrate and tributyl citrate, the esterification rate of the tributyl citrate is 99%, and the esterification rate of the trioctyl citrate is more than 96.0%. The preparation process adopts a two-step method, uses a large amount of solvent, concentrated sulfuric acid and fuming sulfuric acid in the sulfonation process, and has complex process, poor safety and environmental protection.
Disclosure of Invention
The invention provides a preparation method of the sulfonated phenolic resin type solid acid catalyst, which is simple in process, safe and environment-friendly, aiming at the problems in the resin type solid acid catalyst, and the sulfonated phenolic resin type solid acid catalyst prepared by the method has good stability and can be recycled.
The sulfonated phenolic resin type solid acid catalyst with a cross-linking structure is prepared by carrying out polycondensation reaction on p-hydroxybenzene sulfonic acid, phenol and paraformaldehyde through a one-step polycondensation method, and can effectively inhibit the defects of loss, difficult separation, easy decomposition and the like caused by dissolution of the catalyst, so that the stability and the reuse activity of the catalyst are improved.
The polycondensation reaction of hydroxybenzenesulfonic acid, phenol and paraformaldehyde is shown as a formula (I):
A preparation method of a sulfonated phenolic resin type solid acid catalyst comprises the following steps:
(1) Dissolving p-hydroxybenzene sulfonic acid, phenol, paraformaldehyde and p-methylbenzene sulfonic acid in a reaction solvent to carry out polycondensation;
(2) Carrying out desolventizing treatment on a product obtained by the polycondensation reaction in the step (1) to obtain a crude polycondensation product;
(3) And (3) washing the crude polycondensation product obtained in the step (2) by using absolute ethyl alcohol, separating, and drying insoluble substances to obtain the sulfonated phenolic resin type solid acid catalyst.
In the step (1), the molar ratio of the p-hydroxybenzene sulfonic acid to the phenol is 1-9: 1, and the ratio of the sum of the molar numbers of the p-hydroxybenzene sulfonic acid and the phenol to the molar number of the paraformaldehyde calculated by formaldehyde is 1: 1.2-1.7.
The mol ratio of the p-hydroxybenzene sulfonic acid, the phenol and the paraformaldehyde is in the range, so that the sulfonated phenolic resin type solid acid catalyst with a cross-linked structure can be obtained, the cross-linked structure improves the specific surface area of the sulfonated phenolic resin type solid acid catalyst and the utilization efficiency of surface acid sites, increases the thermal stability of the sulfonated phenolic resin type solid acid catalyst, reduces the dissolution and inactivation, and the cross-linked structure ensures that the sulfonated phenolic resin type solid acid catalyst has good hydrophobicity and the acid sites are easy to contact.
The p-toluenesulfonic acid in the step (1) is an initiator of a polycondensation reaction, and the polycondensation reaction is induced, wherein the molar ratio of the p-toluenesulfonic acid to phenol is preferably 0.2-0.5: 1.
The reaction solvent in the step (1) is butanone.
The polycondensation reaction condition in the step (1) is that the condensation reflux is carried out for 4-8 h at the temperature of 100-150 ℃.
the temperature of the solvent removal treatment in the step (2) is preferably 40-60 ℃.
Further preferably, the solvent removal treatment in the step (2) further comprises vacuum drying, wherein the temperature of the vacuum drying is preferably 50-80 ℃, and the vacuum degree is preferably 0-0.8 MPa.
By vacuum drying, the reaction solvent can be further removed and the resin can be sufficiently cured.
The purpose of the washing with absolute ethanol described in step (3) is to remove unreacted monomers and initiator p-toluenesulfonic acid.
The invention also provides a sulfonated phenolic resin type solid acid catalyst prepared by the preparation method of the sulfonated phenolic resin type solid acid catalyst.
The application of the sulfonated phenolic resin type solid acid catalyst in catalyzing the esterification reaction of glycerin comprises the following steps: the glycerol and the acetic acid are uniformly mixed, and esterification reaction is carried out under the catalytic action of a sulfonated phenolic resin type solid acid catalyst.
The molar ratio of the glycerol to the acetic acid is 1: 1-9; the mass ratio of the glycerol to the sulfonated phenolic resin type solid acid catalyst is 60-600: 1.
the esterification reaction is carried out for 1-8 h at 50-80 ℃.
Compared with the prior art, the invention has the main advantages that:
(1) The invention overcomes the problems of complicated and unsafe preparation process of the resin type solid acid catalyst (concentrated sulfuric acid or hydrogen peroxide is used, etc.), easy dissolution of the catalyst, poor stability, etc., and the preparation method of the sulfonated phenolic resin type solid acid catalyst provided by the invention is simple, and the sulfonated phenolic resin type solid acid catalyst prepared by the preparation method has low price, good stability, high catalytic activity and can be recycled.
(2) by utilizing the preparation method of the sulfonated phenolic resin type solid acid catalyst, the prepared sulfonated phenolic resin type solid acid catalyst is used for catalyzing glycerol to perform esterification reaction, the reaction condition is mild, the conversion rate of the glycerol is high, and the selectivity of monoacetic glyceride and diacetic glyceride is good; the conversion rate of the glycerol can reach 84.3 percent, and the sum of the selectivity of the monoacetin and the diacetin reaches 99.9 percent.
(3) The activity of the sulfonated phenolic resin type solid acid catalyst provided by the invention is not obviously reduced after the sulfonated phenolic resin type solid acid catalyst is recycled for 5 times.
Drawings
FIG. 1 is an infrared spectrum of a sulfonated phenol resin type solid acid catalyst prepared in example 1.
FIG. 2 is a photograph showing reaction solutions obtained after the esterification reaction of glycerin catalyzed by the solid acid catalyst of sulfonated phenol-novolac resin type prepared in example 1 and the solid acid catalyst of sulfonated phenol-novolac resin type without phenol prepared in comparative example 1;
In the figure, (a) is a reaction liquid obtained after the sulfonated phenolic resin type solid acid catalyst prepared in example 1 catalyzes the esterification reaction of glycerol; (b) the reaction solution obtained by catalyzing the esterification reaction of glycerin by the phenol-free sulfonated phenolic resin type solid acid catalyst prepared in comparative example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It is to be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of the present invention, and that the starting materials used in the following examples are commercially available.
Example 1
Weighing 2.8g of p-hydroxybenzene sulfonic acid, 0.5g of phenol, 0.8g of paraformaldehyde, 0.3g of p-methylbenzene sulfonic acid and 4.2g of butanone, placing the p-methylbenzene sulfonic acid, the p-methylbenzene sulfonic acid and the butanone into a three-neck flask, carrying out polycondensation reaction for 6 hours at 120 ℃, cooling the obtained polycondensation product, carrying out desolventizing treatment at 40 ℃, then carrying out vacuum drying for 24 hours at 40 ℃, and grinding to obtain reddish brown powder; washing the reddish brown powder with absolute ethyl alcohol until the supernatant is transparent, taking out the precipitate, and drying in vacuum to obtain the sulfonated phenolic resin type solid acid catalyst with the molar ratio of the p-hydroxybenzene sulfonic acid to the phenol being 3: 1.
FIG. 1 is an infrared spectrum of a sulfonated phenol resin type solid acid catalyst having a molar ratio of p-hydroxybenzenesulfonic acid to phenol of 3:1, wherein the wave numbers are 3430 and 1360cm-1Is a characteristic of the phenolic hydroxyl groupA peak; 2920cm-1Is a characteristic peak of C-H bond stretching vibration in aliphatic compounds; 1617 cm-1，1478cm-1Is a characteristic peak of a carbon-carbon double bond in a benzene ring; 1215, 1165, 1120 and 1010cm-1Is a vibrational peak of the O ═ S ═ O bond in the sulfonic acid group; 1032cm-1Is a characteristic peak of a C-S bond; 609cm-1Is a characteristic peak of a hydroxyl group in a sulfonic acid group. The above results clearly show that 1) sulfonic acid groups have been successfully introduced into newly synthesized resins, 2) the synthesized resins contain both phenol and p-hydroxybenzenesulfonic acid, and 3) this is a resin having a crosslinked structure.
Example 2
Weighing 3.3g of p-hydroxybenzene sulfonic acid, 0.2g of phenol, 0.8g of paraformaldehyde, 0.3g of p-methylbenzene sulfonic acid and 4.2g of butanone, placing the mixture in a three-neck flask, carrying out polycondensation reaction for 8 hours at 100 ℃, cooling the obtained polycondensation product, carrying out desolventizing treatment at 60 ℃, then carrying out vacuum drying for 18 hours at 60 ℃, and grinding to obtain reddish brown powder; washing the reddish brown powder with absolute ethyl alcohol until the supernatant is transparent, taking out the precipitate, and drying in vacuum to obtain the sulfonated phenolic resin type solid acid catalyst with the molar ratio of the p-hydroxybenzene sulfonic acid to the phenol being 9: 1.
Example 3
Weighing 1.7g of p-hydroxybenzene sulfonic acid, 0.9g of phenol, 1.0g of paraformaldehyde, 0.3g of p-methylbenzene sulfonic acid and 4.2g of butanone, placing the p-methylbenzene sulfonic acid, the p-methylbenzene sulfonic acid and the butanone into a three-neck flask, carrying out polycondensation reaction for 4 hours at the temperature of 150 ℃, cooling the obtained polycondensation product, carrying out desolventizing treatment at the temperature of 60 ℃, then carrying out vacuum drying for 12 hours at the temperature of 80 ℃, and grinding to obtain reddish brown powder; washing the reddish brown powder with absolute ethyl alcohol until the supernatant is transparent, taking out the precipitate, and drying in vacuum to obtain the sulfonated phenolic resin type solid acid catalyst with the molar ratio of the p-hydroxybenzene sulfonic acid to the phenol being 1:1.
Example 4
70mg of the sulfonated phenol-formaldehyde resin type solid acid catalyst prepared in example 1, 4.6g of glycerol and 9.0g of acetic acid are weighed into a 100ml round bottom flask, the round bottom flask is placed into an oil bath kettle, stirring is started after the temperature is raised to 70 ℃, and the time is counted, wherein the esterification reaction time is 1-8 h. After the reaction is finished, cooling the reaction system to room temperature, centrifuging the reaction solution, taking supernatant, measuring by using capillary gas chromatography, and carrying out quantitative analysis by using an external standard method. The conversion of glycerol and the selectivity of the esterification products (monoacetin, diacetin and triacetin) at different reaction times are shown in table 1.
Table 1 shows the conversion of glycerol and the selectivity of the esterification products at different reaction times
| reaction time (h) | 1 | 5 | 7 | 8 |
| Glycerol conversion (%) | 38.2 | 73.9 | 81.6 | 81.7 |
| Glycerol monoacetate selectivity (%) | 89.1 | 74.9 | 68.0 | 67.1 |
| Diacetin selectivity (%) | 10.8 | 24.5 | 30.9 | 31.7 |
| Triacetin selectivity (%) | 0.1 | 0.6 | 1.1 | 1.2 |
Example 5
The method is the same as the process of the embodiment 4, except that the reaction time is 7 hours, and the reaction temperature is controlled to be 50-80 ℃. The conversion of glycerol and the selectivity of the esterification products at different temperatures are shown in table 2.
Table 2 shows the conversion of glycerol and the selectivity of the esterification products at different temperatures
| Reaction temperature (. degree.C.) | 50 | 60 | 70 | 80 |
| Glycerol conversion (%) | 33.9 | 55.0 | 81.6 | 83.8 |
| Glycerol monoacetate separationSelectivity (%) | 91.1 | 83.5 | 68.0 | 57.6 |
| Diacetin selectivity (%) | 8.8 | 16.2 | 30.9 | 40.2 |
| Triacetin selectivity (%) | 0.1 | 0.3 | 1.1 | 2.2 |
Example 6
The method is the same as the process of the embodiment 4, except that the reaction time is set to be 7 hours, and the molar ratio of the glycerol to the acetic acid is controlled to be 1: 1-9. The conversion of glycerol and the selectivity of the esterification product at different molar ratios of acetic acid to glycerol are shown in Table 3.
Table 3 shows the conversion of glycerol and the selectivity of the esterification products for different molar ratios of acetic acid to glycerol
| Molar ratio of glycerol to acetic acid | 1:1 | 1:3 | 1:6 | 1:9 |
| Glycerol conversion (%) | 52.0 | 81.6 | 82.7 | 84.3 |
| Glycerol monoacetate selectivity (%) | 83.4 | 68.0 | 65.3 | 62.1 |
| Diacetin selectivity (%) | 16.4 | 30.9 | 33.3 | 35.9 |
| Triacetin selectivity (%) | 0.2 | 1.1 | 1.4 | 2 |
Example 7
70mg of the sulfonated phenol resin type solid acid catalyst prepared in example 1 to 3, 4.6g of glycerol and 9.0g of acetic acid were weighed in a 100ml round bottom flask, the round bottom flask was placed in an oil bath, stirring was started after the temperature was raised to 70 ℃, and the reaction time was started to be 7 hours. After the reaction is finished, cooling the reaction system to room temperature, centrifuging the reaction solution, taking supernatant, measuring by using capillary gas chromatography, and carrying out quantitative analysis by using an external standard method. The conversion of glycerol and the selectivity of the esterification products (monoacetin, diacetin and triacetin) at different reaction times are shown in table 4.
Table 4 shows the conversion of glycerol and the selectivity of the esterification products at different molar ratios of p-hydroxybenzenesulfonic acid to phenol
| Molar ratio of p-hydroxybenzene sulfonic acid to phenol | 9:1 | 3:1 | 1:1 |
| Glycerol conversion (%) | 82.8 | 81.6 | 42.0 |
| Glycerol monoacetate selectivity (%) | 63.7 | 68.0 | 85.0 |
| Diacetin selectivity (%) | 34.9 | 30.9 | 14.4 |
| Triacetin selectivity (%) | 1.4 | 1.1 | 0.5 |
example 8
70mg of the solid acid catalyst of the sulfonated phenol resin type prepared in example 1, 4.6g of glycerin and 9.0g of acetic acid were weighed into a 100ml round bottom flask, the round bottom flask was placed in an oil bath, and stirring and timing were started after the temperature was raised to 70 ℃ for 7 hours. After the reaction is finished, cooling the reaction system to room temperature, centrifuging the reaction liquid, recovering the catalyst, washing for 3 times by using absolute ethyl alcohol, drying by using a vacuum oven, recycling, taking supernatant, measuring by using capillary gas chromatography, and quantitatively analyzing by using an external standard method, wherein the conversion rate of the glycerol and the selectivity of the esterification product after different recycling times are shown in table 5.
TABLE 5 conversion of glycerol and selectivity of esterification products after different recycling times
| Number of times of recycling | 1 | 2 | 3 | 4 | 5 |
| Glycerol conversion (%) | 81.6 | 76.5 | 74.8 | 74.4 | 72.2 |
| Glycerol monoacetate selectivity (%) | 68.0 | 70.5 | 71.8 | 72.2 | 74.1 |
| Diacetin selectivity (%) | 30.9 | 28.5 | 27.3 | 27.0 | 25.3 |
| Triacetin selectivity (%) | 1.1 | 1.0 | 0.9 | 0.8 | 0.6 |
Example 9
70mg of the solid acid catalyst of the sulfonated phenol resin type prepared in example 1, 4.6g of glycerin and 9.0g of acetic acid were weighed into a 100ml round bottom flask, the round bottom flask was placed in an oil bath, and stirring and timing were started after the temperature was raised to 70 ℃. After 1h of reaction, the catalyst was filtered off and the filtrate was allowed to continue the reaction. After the reaction, the reaction system was cooled to room temperature, a small amount of liquid was taken and measured by capillary gas chromatography, and quantitative analysis was performed by external standard method, and the conversion of glycerin and the selectivity of esterification product at different times are shown in table 6.
TABLE 6 conversion of glycerol and selectivity of esterification products for different reaction times of the filtrate
| Reaction time (h) | 1 | 2 | 5 | 7 |
| Glycerol conversion (%) | 38.2 | 40.3 | 45.8 | 49.1 |
| Glycerol monoacetate selectivity (%) | 89.1 | 88.2 | 86.6 | 84.2 |
| Diacetin selectivity (%) | 10.8 | 11.7 | 13.2 | 15.5 |
| Triacetin selectivity (%) | 0.1 | 0.1 | 0.2 | 0.3 |
Comparative example 1
Weighing 2.8g of p-hydroxybenzene sulfonic acid, 0.8g of paraformaldehyde, 0.3g of p-methylbenzene sulfonic acid and 4.2g of butanone, placing the p-hydroxybenzene sulfonic acid, the paraformaldehyde, the p-methylbenzene sulfonic acid and the butanone into a three-neck flask, carrying out polycondensation reaction for 6 hours at 120 ℃, cooling an obtained polycondensation product, carrying out desolventizing treatment at 40 ℃, then carrying out vacuum drying for 24 hours at 40 ℃, and grinding to obtain reddish brown powder; washing the reddish brown powder with absolute ethyl alcohol until the supernatant is transparent, taking out the precipitate, and drying in vacuum to obtain the sulfonated phenolic resin type solid acid catalyst containing no phenol.
70mg of the solid acid catalyst of sulfonated phenol resin type prepared in example 1 and the above solid acid catalyst of sulfonated phenol resin type containing no phenol, 4.6g of glycerin and 9.0g of acetic acid were weighed out in a 100ml round bottom flask, the round bottom flask was placed in an oil bath, and when the temperature was raised to 70 ℃, stirring was started and timing was started, and the reaction time was 7 hours. After the reaction, the reaction solution was allowed to stand and cooled.
As can be seen from FIG. 2, the copolymer resin of phenol and p-hydroxyphenylsulfonic acid with a cross-linked structure is very stable, and p-hydroxyphenylsulfonic acid is not dissolved out or lost in the reaction process, so that the reaction solution is colorless and transparent after the reaction; in the reaction process of the sulfonated phenolic resin without phenol, the p-hydroxybenzene sulfonic acid swells and runs off, so that the reaction liquid is reddish-brown turbid liquid after the reaction.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a sulfonated phenolic resin type solid acid catalyst is characterized in that p-hydroxybenzene sulfonic acid, phenol and paraformaldehyde are subjected to polycondensation reaction by a one-step polycondensation method to prepare the sulfonated phenolic resin type solid acid catalyst.
2. The method for producing a sulfonated phenol resin type solid acid catalyst according to claim 1, comprising:
(1) Dissolving p-hydroxybenzene sulfonic acid, phenol, paraformaldehyde and p-methylbenzene sulfonic acid in a reaction solvent to carry out polycondensation;
(2) Carrying out desolventizing treatment on the product obtained by the polycondensation reaction in the step (1) to obtain a crude polycondensation product;
(3) And (3) washing the crude polycondensation product obtained in the step (2) by using absolute ethyl alcohol, separating, and drying insoluble substances to obtain the sulfonated phenolic resin type solid acid catalyst.
3. The method for preparing a sulfonated phenol resin type solid acid catalyst according to claim 2, wherein the molar ratio of the p-hydroxyphenylsulfonic acid to the phenol in the step (1) is 1 to 9:1, and the ratio of the sum of the molar numbers of the p-hydroxyphenylsulfonic acid to the phenol to the molar number of paraformaldehyde in terms of formaldehyde is 1:1.2 to 1.7.
4. the method for preparing the sulfonated phenol-formaldehyde resin type solid acid catalyst according to claim 2, wherein the molar ratio of the p-toluenesulfonic acid to the phenol in the step (1) is 0.2 to 0.5: 1.
5. The method for preparing the sulfonated phenolic resin type solid acid catalyst according to claim 2, wherein the condensation reaction in the step (1) is performed under the condition of condensing reflux for 4-8 h at 100-150 ℃.
6. The method for preparing a sulfonated phenol resin type solid acid catalyst according to claim 2, wherein the temperature of the solvent removal treatment in the step (2) is 40 to 60 ℃.
7. The method for preparing the sulfonated phenol resin type solid acid catalyst according to claim 2 or 6, wherein the solvent removal treatment in the step (2) further comprises vacuum drying, wherein the temperature of the vacuum drying is 50 to 80 ℃, and the vacuum degree is 0 to 0.8 MPa.
8. The sulfonated phenolic resin type solid acid catalyst is prepared by the method for preparing the sulfonated phenolic resin type solid acid catalyst according to any one of claims 1 to 7.
9. The application of the sulfonated phenolic resin type solid acid catalyst in catalyzing the esterification reaction of glycerol according to claim 8, wherein glycerol and acetic acid are uniformly mixed, and the esterification reaction is carried out under the catalysis of the sulfonated phenolic resin type solid acid catalyst; the molar ratio of the glycerol to the acetic acid is 1: 1-9; the mass ratio of the glycerol to the sulfonated phenolic resin type solid acid catalyst is 60-600: 1.
10. The application of the sulfonated phenolic resin type solid acid catalyst in catalyzing glycerol esterification reaction according to claim 8, wherein the esterification reaction is carried out for 1-8 hours at 50-80 ℃.
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