CN113578383A - Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere - Google Patents
Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere Download PDFInfo
- Publication number
- CN113578383A CN113578383A CN202110909168.4A CN202110909168A CN113578383A CN 113578383 A CN113578383 A CN 113578383A CN 202110909168 A CN202110909168 A CN 202110909168A CN 113578383 A CN113578383 A CN 113578383A
- Authority
- CN
- China
- Prior art keywords
- sulfonic acid
- polystyrene microsphere
- emulsion
- furfuryl alcohol
- ethyl levulinate
- 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
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000004005 microsphere Substances 0.000 title claims abstract description 60
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 47
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 41
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 title claims abstract description 30
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 230000008961 swelling Effects 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000839 emulsion Substances 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011973 solid acid Substances 0.000 description 7
- 229910006069 SO3H Inorganic materials 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229940058352 levulinate Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 3
- -1 Levulinic acid ester Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N laevulinic acid Natural products CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- B01J31/063—Polymers comprising a characteristic microstructure
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- 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)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of sulfonic acid modified polystyrene microspheres and a method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using the sulfonic acid modified polystyrene microspheres, and belongs to the technical field of heterogeneous catalysis. The sulfonic acid functionalized polystyrene microsphere catalyst is prepared by a specific emulsion polymerization swelling mode, the synthesis steps are simple, the raw materials are cheap and easy to obtain, the specific surface area is large, and the recovery is easy; meanwhile, the catalyst can be used for catalytic reaction, furfuryl alcohol is reduced into ethyl levulinate in a high selectivity mode, the catalyst can be used repeatedly, the catalytic performance cannot be reduced, and the requirement for green sustainable development is met.
Description
Technical Field
The invention relates to preparation of sulfonic acid modified polystyrene microspheres and a method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using the sulfonic acid modified polystyrene microspheres, and belongs to the technical field of heterogeneous catalysis.
Background
The biomass energy is a renewable energy source, and has the characteristics of being recyclable, wide in distribution, clean and the like. Levulinic acid ester is used as a biomass energy source and has wide application in many fields. The catalyst traditionally used for synthesizing levulinate ester is strong
Inorganic acids of acidic nature (HCl, H)2SO4And HF), although inexpensive, have the disadvantages of polluting the environment, corroding equipment and not being easily separated from the product. At present, from the aspects of environmental protection and economy, a heterogeneous catalysis system is used for synthesizing the levulinate, so that the catalyst is easy to separate and recover, and the catalytic activity is higher than that of a homogeneous catalysis process. In recent years, solid acid catalysts including sulfated metal oxides, ion exchange resins, sulfonic acid functional functionalized SBA-15, and heteropolyacid functional silica have been widely used in the synthesis of levulinic acid esters. However, these solid acid catalysts have some disadvantages, such as: the appearance is not uniform, and the contact of the catalyst and the reaction furfuryl alcohol is easily influenced, so that the acid catalytic activity is low. At present, according to Hongli Tian et al, the sulfonated solid acid catalyst can achieve a better levulinate preparation effect only by catalytic reaction for 3 hours at 160 ℃. Peng et al byPreparation of sulfonated industrial lignosulfonate with-SO3H. The carbonaceous solid acid of-COOH and phenolic hydroxyl groups needs to react for 8 hours at 110 ℃ to obtain better levulinate preparation effect. In addition, the falling of active sites in the reaction process can cause poor stability, large mass transfer resistance and poor thermal stability of the catalyst. Therefore, the development and utilization of the environment-friendly solid acid catalyst with high efficiency and stability are an important direction for green chemical research.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a sulfonic acid functionalized polystyrene microsphere catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing sulfonic acid functionalized polystyrene microsphere catalyst comprises the following steps:
(1) mixing styrene, an initiator, ethanol, ethylene glycol monomethyl ether and polyvinylpyrrolidone, and carrying out polymerization reaction in an inert atmosphere to obtain polystyrene seed microspheres;
(2) dissolving a surfactant and butyl phthalate in water to obtain emulsion A; dispersing the polystyrene seed microspheres obtained in the step (1) in water to prepare a dispersion liquid; then adding the dispersion liquid into the emulsion A, and uniformly mixing to obtain a mixed liquid; adding styrene, divinyl benzene, toluene and an initiator into water, and uniformly mixing to obtain emulsion B; adding the emulsion B into the mixed solution for swelling reaction, and adding polyvinyl alcohol for reaction after the swelling reaction is finished to obtain monodisperse crosslinked polystyrene microspheres;
(3) and (3) mixing the monodisperse crosslinked polystyrene microsphere obtained in the step (2) with concentrated sulfuric acid for modification, and obtaining the sulfonic acid functionalized polystyrene microsphere after the modification.
In one embodiment of the present invention, the initiator comprises either or both of benzoyl peroxide and lauroyl peroxide.
In one embodiment of the present invention, the inert gas comprises one of nitrogen or argon.
In one embodiment of the invention, in the step (1), the temperature of the polymerization reaction is 30-100 ℃, and the reaction time is 20-30 h. Specifically, the reaction can be carried out for 24h at 80 ℃.
In one embodiment of the present invention, in the step (1), the particle size of the obtained polystyrene seed microsphere is 3 um.
In one embodiment of the invention, polyvinylpyrrolidone, PVP, has a weight average molecular weight of 130W.
In one embodiment of the invention, the mass ratio of styrene to polyvinylpyrrolidone is 25: (3-5).
In one embodiment of the invention, the amount ratio of styrene to ethanol is 0.4 to 0.6 g/mL; specifically, 0.43g/mL may be used.
In one embodiment of the present invention, the amount ratio of styrene to ethylene glycol methyl ether is 0.3 g/mL.
In one embodiment of the invention, the mass fraction of initiator relative to styrene is 4%.
In one embodiment of the present invention, in the step (2), the concentration of the polystyrene seed microspheres in the dispersion is 0.05-0.2 g/mL. Specifically, 0.067g/mL can be used.
In one embodiment of the present invention, in the step (2), the surfactant is one or more selected from sodium lauryl sulfate, sodium dodecylbenzene sulfonate and polyoxyethylene nonylphenol ether.
In one embodiment of the present invention, the concentration of the surfactant in the emulsion A in the step (2) is 0.5-5 mg/mL. Specifically, 3.125mg/mL can be selected.
In one embodiment of the present invention, the concentration of butyl phthalate in the emulsion A in the step (2) is 10-20 mg/mL. Specifically, 13.125mg/mL can be selected.
In one embodiment of the present invention, in the step (2), the mass ratio of the seed microspheres, the surfactant and the butyl phthalate is 2: 1: (4-5). Specifically, 2: 1: 4.2.
in one embodiment of the present invention, in the step (2), the blending is performed at room temperature; the time is 10-30 h.
In one embodiment of the present invention, the concentration of styrene in the emulsion B in the step (2) is 0.01-0.1 g/mL. Specifically, 0.0375g/mL can be used.
In one embodiment of the present invention, the concentration of divinylbenzene in the emulsion B in the step (2) is 0.03 to 0.10 g/mL. Specifically, 0.0625g/mL may be used.
In one embodiment of the present invention, the concentration of toluene in the emulsion B in the step (2) is 0.05-0.30 g/mL. Specifically, 0.1g/mL can be selected.
In one embodiment of the present invention, in the emulsion B in the step (2), the concentration of the initiator is 0.001-0.1 g/mL. Specifically, 0.00125g/mL can be selected.
In one embodiment of the present invention, in the step (2), the mass ratio of the styrene to the seed microspheres is 6: 1.
in one embodiment of the present invention, in the step (2), the mass ratio of the divinylbenzene to the seed microspheres is 10: 1.
in one embodiment of the present invention, in the step (2), the mass ratio of toluene to seed microspheres is 16: 1.
in one embodiment of the present invention, in the step (2), the mass ratio of the initiator to the styrene is 1: 30.
in one embodiment of the present invention, in step (2), the temperature of the swelling reaction is 70 ℃; the time is 24 h.
In one embodiment of the present invention, in step (2), the polyvinyl alcohol is used in a 10 wt% aqueous solution.
In one embodiment of the present invention, in the step (2), the mass ratio of the polyvinyl alcohol to the polystyrene seed microspheres is 2: 1.
in one embodiment of the invention, in the step (2), the temperature for adding the polyvinyl alcohol to react is 60-70 ℃; the time is 12-24 h.
In one embodiment of the present invention, in the step (2), the obtained monodisperse crosslinked polystyrene microsphere has a particle size of 10 um.
In one embodiment of the present invention, in the step (3), the temperature of the modification is 30-120 ℃ and the time is 2-20 h. Specifically, the reaction can be carried out for 12 hours at 60 ℃.
In one embodiment of the present invention, in the step (3), the concentration of the concentrated sulfuric acid is 98%.
In one embodiment of the present invention, in the step (3), the amount of the monodisperse crosslinked polystyrene microspheres and the concentrated sulfuric acid is 10g/80 mL.
In one embodiment of the present invention, in step (3), the modification is performed at a rotation speed of 100-800 rpm/min.
The invention provides a sulfonic acid functionalized polystyrene microsphere catalyst prepared by the preparation method.
The invention also provides the sulfonic acid functionalized polystyrene microsphere catalyst (PS-SO)3H) The application of the catalyst in preparing ethyl levulinate by catalyzing furfuryl alcohol and ethanol.
A method for preparing ethyl levulinate by catalyzing furfuryl alcohol and ethanol is characterized in that furfuryl alcohol and ethanol are used as substrates, and react under the action of the sulfonic acid functionalized polystyrene microsphere catalyst to obtain ethyl levulinate through catalytic preparation.
In one embodiment of the present invention, the amount of the sulfonic acid functionalized polystyrene microsphere catalyst is 0.05-0.075g/mmol furfuryl alcohol.
In one embodiment of the invention, the amount of ethanol is 4mL/mmol furfuryl alcohol.
In one embodiment of the present invention, the temperature of the reaction is 120-130 ℃.
In one embodiment of the invention, the reaction time is 1-2 h; preferably 1.5-2 h.
The invention has the beneficial effects that:
the sulfonic acid functionalized polystyrene microsphere catalyst is prepared by a specific emulsion polymerization swelling mode, the synthesis steps are simple, the raw materials are cheap and easy to obtain, the specific surface area is large, and the recovery is easy; meanwhile, the catalyst can be used for catalytic reaction, furfuryl alcohol is reduced into ethyl levulinate in a high selectivity mode, the catalyst can be used repeatedly, the catalytic performance cannot be reduced, and the requirement for green sustainable development is met.
The microsphere solid acid catalyst prepared by the invention has the characteristics of uniform size, strong acidity and stable structure, can be used for efficiently catalyzing and preparing the ethyl levulinate within 2 hours without higher temperature requirement, and has the yield of more than 94%.
Drawings
FIG. 1 is a scanning electron micrograph of microspheres obtained in example 1.
FIG. 2 is a Scanning Electron Micrograph (SEM) of the microspheres obtained in example 1.
FIG. 3 is an X-ray diffraction pattern of the microspheres obtained in example 1.
FIG. 4 is a nitrogen adsorption-desorption isotherm of the microspheres obtained in example 1.
FIG. 5 is a graph showing the pore size distribution (BET) of the microspheres obtained in example 1.
FIG. 6 is an X-ray photoelectron spectrum of the microsphere obtained in example 1.
FIG. 7 is a graph showing the effect of catalyst loading on microsphere catalyzed conversion of furfuryl alcohol to ethyl levulinate in example 3;
FIG. 8 is a graph showing the effect of reaction temperature and reaction time on microsphere-catalyzed conversion of furfuryl alcohol to ethyl levulinate in example 4;
FIG. 9 shows the results of repeated experiments in example 5 in which microspheres catalyze the conversion of furfuryl alcohol to ethyl levulinate.
Detailed Description
The sulfonic polystyrene microsphere solid acid material prepared by the invention is powdery, the microstructure of the material is represented by a Scanning Electron Microscope (SEM), the crystal structure of the material is represented by X-ray diffraction, the specific surface area of the material is tested by a full-automatic specific surface adsorption instrument, and the valence state of surface atoms of the material is represented by an X-ray photoelectron spectrum (XPS).
Method for determining ethyl levulinate by Gas Chromatography (GC):
quantitative analysis of the reactants and products was carried out by gas chromatography using model GC 9790 from Agilent technologies, Inc. The parameters of the gas chromatograph were set as follows, column: SE-54(60 m); a detector: a flame ionization detector; mobile phase: 0.1mL/min hydrogen, 0.1mL/min nitrogen, 0.2mL/min air; sample introduction amount: 0.30 mu L; column temperature: 200 ℃; a detector: 300 ℃; a sample inlet: at 300 ℃. Naphthalene is selected as an internal standard substance, and the product is quantitatively analyzed by adopting an internal standard method.
Definition and calculation of conversion and yield:
conversion refers to the percentage of conversion of a certain reactant. Yield is the percentage of the total amount of reactants produced by the desired product. The specific calculation method is as follows:
the present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
EXAMPLE 1 preparation of sulfonic acid group polystyrene microsphere catalyst
(1) Weighing 0.6g of benzoyl peroxide, dissolving in 15g of styrene, mixing with 35mL of ethanol, 50mL of ethylene glycol monomethyl ether and 1.8g of PVP (130W) solution, introducing nitrogen, and reacting at 80 ℃ for 24h to obtain 3um polystyrene seed microspheres (3-PS);
(2) dissolving 0.25g of sodium dodecyl benzene sulfonate (SDS) in 80mL of water, adding 1.05g of butyl phthalate (DBP), and uniformly mixing by ultrasonic to form emulsion A; dispersing 0.5g of the seed microspheres prepared in the step (1) in 7.5mL of water to prepare a dispersion liquid; adding the dispersion liquid into the emulsion, and stirring at room temperature (200rpm) for 20 hours to obtain a mixed liquid A;
adding 3g of styrene (St), 5g of Divinylbenzene (DVB), 8g of toluene and 0.1g of Benzoyl Peroxide (BPO) into 80mL of aqueous solution, and ultrasonically mixing the mixture to form emulsion B; adding the emulsion B into the mixed solution A, carrying out heat preservation at 70 ℃ for carrying out swelling reaction for 24h, adding 10mL of 10% polyvinyl alcohol (PVA, molecular weight 25 ten thousand) aqueous solution after the swelling reaction is finished, reacting at 70 ℃ for 24h, separating and collecting solids, and washing with ethanol to obtain 10um monodisperse crosslinked polystyrene microspheres (10-PS);
(3) reacting 10g of the microspheres prepared in the step (2) with 80mL of concentrated sulfuric acid (commercially available concentrated sulfuric acid with the concentration of 98%) at 60 ℃ for 12h to obtain 10um sulfonic polystyrene microspheres (PS-SO)3H)。
As can be seen from the infrared diagram shown in fig. 1: 3420cm-1The peak of hydroxyl group at (1) is obviously enhanced, 2916cm-1And 1725cm-1The vibration absorption peaks at (A) correspond to the stretching vibration of C-H and C ═ O, and PS-SO is proved3Benzene rings and carbonyl groups are present in H. The infrared absorption peak of PS is compared with that of PS, and PS-SO is found3The vibration absorption peak of the benzene ring skeleton of H is 1637cm-1To enhance and widen. In addition, at 1600-1700cm-1The absorption peaks in between indicate the presence of a characteristic peak in the material in C ═ C stretch mode. 1226cm-1，1172cm-1And 1585cm-1The absorption peak at (a) corresponds to stretching vibration of the C ═ C group, demonstrating the presence of a benzene ring in PS-SO 3H. At 1057 and 1014cm-1Has obvious absorption peaks which are respectively sulfonic acid groups (-SO)3H) Symmetric stretching vibration of middle O-S-O and-SO3 2-590cm of asymmetric stretching vibration-1The weak absorption peak is the absorption peak of C-S. It is shown that the sulfonic acid group is successfully fixed on the surface of PS in a covalent bond manner instead of the hydrogen atom on the benzene ring. The peak intensities of C-H and C ═ O are significantly reduced. The above results show that-SO3H was successfully attached to the surface of the PS microspheres.
As can be seen from the SEM image of FIG. 2, PS-SO3The number of micropores in H is very high; although the specific surface area and pore volume are limited, the larger pore size can promote FA to PS-SO3The H active sites diffuse, facilitating the reaction. As can be seen from FIG. 2, the obtained microspheres have uniform size and particle size of about 10 μm.
As can be seen from fig. 3, all samples showed broad diffraction peaks and weak diffraction peaks of 15 to 30 ° and 35 to 50 °, respectively, which correspond to graphite lattices of the (002) and (100) crystal planes, indicating that both are amorphous carbon structures.
As can be seen from the nitrogen adsorption and desorption isotherms in FIG. 4, PS-SO3H is a typical type IV isotherm; when N is present2The relative adsorption pressure (P/P0) is lowTo 0.01 in PS-SO3H isothermal on-line to N2Has higher adsorption capacity.
From the BET diagram of fig. 5, the material is a mesoporous material; the results show that PS-SO3The H catalyst has a uniform mesoporous structure; the specific surface area of the catalyst was 128.04m2Per g, pore volume of 0.19cm3(g), the particle diameter is 5.2 nm. The catalyst has better catalytic activity because of large specific surface aperture. Because of the spherical holes, the inner diameter is about 2nm larger than that of the traditional aperture analysis method (BJH).
As can be seen from FIG. 6, the XPS surface analysis result is consistent with the FT analysis result, and the functional group and polycyclic aromatic group contained in PS-SO3H can be further explained. In the figure, PS-SO3H is at S2PAnd O1SXPS spectra of binding energy regions. The S2p binding energy region can be fitted to two pairs of peaks generated by sulfonic acid functional groups, at 168.2eV and 169.2eV, respectively. The Ols binding energy region can be fitted with two peaks, the two peaks appearing at 532.1eV and 533.3eV, respectively, generated from the S-OH and S ═ O groups.
EXAMPLE 2 catalytic preparation of Ethyl levulinate
(1) 1mmol of furfuryl alcohol, 0.075g of PS-SO are weighed out3Adding H catalyst and 4mL of ethanol into a 25mL reactor with magnetons;
(2) and (3) placing the reactor in an oil bath kettle at 120 ℃ for stirring for 2h, and cooling to room temperature after the reaction is finished.
The conversion of furfuryl alcohol and the yield of ethyl levulinate were determined in the gas phase (GC) using 1mL of the reacted solution. The conversion of furfuryl alcohol was 99.7% and the yield of ethyl levulinate was 94.1%.
EXAMPLE 3 catalytic preparation of Ethyl levulinate
(1) 1mmol of furfuryl alcohol, 0.075g of PS-SO are weighed out3H and 4mL of ethanol are added into a 25mL reactor with magnetons;
(2) and (3) placing the reactor in an oil bath kettle at 120 ℃ for stirring for 1.5h, cooling to room temperature after the reaction is finished, and taking 1mL of solution after the reaction to measure the conversion rate of furfuryl alcohol and the yield of ethyl levulinate by GC.
Respectively replacing the 0.075g dosage of the microspheres in the step (1) with 0.025, 0.05 and 0.10,other conditions were unchanged; 1mL of the reacted solution was taken to determine the conversion of furfuryl alcohol and the yield of ethyl levulinate by GC. The results are shown in FIG. 7, PS-SO3The yields of ethyl levulinate obtained with H catalysts used at 0.025, 0.05, 0.075 and 0.10g were 87.32%, 92.55%, 94.7% and 86%, respectively.
EXAMPLE 4 catalytic preparation of Ethyl levulinate
(1) 1mmol of furfuryl alcohol, 0.075g of PS-SO are weighed out3Adding H catalyst and 4mL of ethanol into a 25mL reactor with magnetons;
(2) respectively placing the reactors in oil bath pots at 100 ℃, 110 ℃, 120 and 130 ℃ and respectively stirring for 1.5 h; after completion of the reaction, the reaction mixture was cooled to room temperature, and 1mL of the reacted solution was taken to determine the conversion of furfuryl alcohol and the yield of ethyl levulinate by GC. As a result, as shown in FIG. 8, the yields of ethyl levulinate obtained at 100, 110, 120 and 130 ℃ were 53.7%, 85.9%, 94.7% and 94.4%, respectively.
EXAMPLE 5 catalytic preparation of Ethyl levulinate
Example 2 after the reaction was completed, the used solid catalyst was separated by centrifugation, washed three times with ethanol, dried and put into the experimental case for recycling. The experimental result is shown in fig. 9, which shows that the yield of the ethyl levulinate is still as high as 90.4% after the prepared microspherical catalyst is recycled for 4 times.
Comparative example 1
Referring to example 2, the PS-SO in step (1)3The replacement of H with 3-PS, otherwise unchanged, gave a conversion of furfuryl alcohol and a yield of ethyl levulinate of 20.1% and 12.7%, respectively.
Comparative example 2
Referring to example 2, the PS-SO in step (1)3The H was replaced with 10-PS, otherwise unchanged, yielding a furfuryl alcohol conversion and an ethyl levulinate yield of 18.7% and 9.4%, respectively.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing sulfonic acid functionalized polystyrene microsphere catalyst is characterized by comprising the following steps:
(1) mixing styrene, an initiator, ethanol, ethylene glycol monomethyl ether and polyvinylpyrrolidone, and carrying out polymerization reaction in an inert atmosphere to obtain polystyrene seed microspheres;
(2) dissolving a surfactant and butyl phthalate in water to obtain emulsion A; dispersing the polystyrene seed microspheres obtained in the step (1) in water to prepare a dispersion liquid; then adding the dispersion liquid into the emulsion A, and uniformly mixing to obtain a mixed liquid; adding styrene, divinyl benzene, toluene and an initiator into water, and uniformly mixing to obtain emulsion B; adding the emulsion B into the mixed solution for swelling reaction, and adding polyvinyl alcohol for reaction after the swelling reaction is finished to obtain monodisperse crosslinked polystyrene microspheres;
(3) and (3) mixing the monodisperse crosslinked polystyrene microsphere obtained in the step (2) with concentrated sulfuric acid for modification, and obtaining the sulfonic acid functionalized polystyrene microsphere after the modification.
2. The method according to claim 1, wherein the mass ratio of styrene to polyvinylpyrrolidone is 25: (3-5).
3. The method of claim 1, wherein in step (2), the concentration of the polystyrene seed microspheres in the dispersion is 0.05-0.2 g/mL.
4. The method according to claim 1, wherein the concentration of the surfactant in the emulsion A in the step (2) is 0.5-5 mg/mL.
5. The method according to claim 1, wherein the concentration of butyl phthalate in the emulsion A in the step (2) is 10-20 mg/mL.
6. The method according to claim 1, wherein in the step (2), the mass ratio of the seed microspheres to the surfactant to the butyl phthalate is 2: 1: (4-5).
7. The method according to any one of claims 1 to 6, wherein in the emulsion B in the step (2), the concentration of styrene is 0.01 to 0.1 g/mL; the concentration of the divinylbenzene is 0.03-0.10 g/mL; the concentration of toluene is 0.05-0.30 g/mL.
8. A sulfonic acid functionalized polystyrene microsphere catalyst prepared by the method of any one of claims 1 to 7.
9. A method for preparing ethyl levulinate by catalyzing furfuryl alcohol and ethanol, which is characterized in that furfuryl alcohol and ethanol are used as substrates and react under the action of the sulfonic acid functionalized polystyrene microsphere catalyst of claim 8 to obtain the ethyl levulinate through catalysis.
10. The method of claim 9, wherein the sulfonic acid functionalized polystyrene microsphere catalyst is used in an amount of 0.05 to 0.075g/mmol of furfuryl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110909168.4A CN113578383A (en) | 2021-08-09 | 2021-08-09 | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110909168.4A CN113578383A (en) | 2021-08-09 | 2021-08-09 | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113578383A true CN113578383A (en) | 2021-11-02 |
Family
ID=78256487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110909168.4A Pending CN113578383A (en) | 2021-08-09 | 2021-08-09 | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113578383A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114210370A (en) * | 2021-12-20 | 2022-03-22 | 南京亘闪生物科技有限公司 | Preparation method of catalyst microspheres for preparing ethyl acetate |
| CN117983298A (en) * | 2024-03-29 | 2024-05-07 | 岳阳兴长石化股份有限公司 | Crosslinked polystyrene hollow microsphere catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448935A (en) * | 1976-06-10 | 1984-05-15 | National Starch And Chemical Corporation | Process for the preparation of crosslinked, sulfonated styrene polymers |
| CN102146148A (en) * | 2011-01-24 | 2011-08-10 | 吉林大学 | Sulfonated crosslinked polystyrene spheres and application thereof in ring-opening reaction |
| CN104861102A (en) * | 2015-05-27 | 2015-08-26 | 青岛大学 | Porous crosslinked polystyrene microsphere and preparation method thereof |
| CN107501448A (en) * | 2017-08-03 | 2017-12-22 | 华南理工大学 | A kind of preparation method and application of nanoscale sulfonated polystyrene microballoon |
| CN108250336A (en) * | 2018-01-23 | 2018-07-06 | 湖北新纵科病毒疾病工程技术有限公司 | A kind of preparation method of polystyrene microsphere |
| CN110894183A (en) * | 2018-09-12 | 2020-03-20 | 中国科学院宁波材料技术与工程研究所 | Alkyl levulinate and preparation method thereof |
-
2021
- 2021-08-09 CN CN202110909168.4A patent/CN113578383A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448935A (en) * | 1976-06-10 | 1984-05-15 | National Starch And Chemical Corporation | Process for the preparation of crosslinked, sulfonated styrene polymers |
| CN102146148A (en) * | 2011-01-24 | 2011-08-10 | 吉林大学 | Sulfonated crosslinked polystyrene spheres and application thereof in ring-opening reaction |
| CN104861102A (en) * | 2015-05-27 | 2015-08-26 | 青岛大学 | Porous crosslinked polystyrene microsphere and preparation method thereof |
| CN107501448A (en) * | 2017-08-03 | 2017-12-22 | 华南理工大学 | A kind of preparation method and application of nanoscale sulfonated polystyrene microballoon |
| CN108250336A (en) * | 2018-01-23 | 2018-07-06 | 湖北新纵科病毒疾病工程技术有限公司 | A kind of preparation method of polystyrene microsphere |
| CN110894183A (en) * | 2018-09-12 | 2020-03-20 | 中国科学院宁波材料技术与工程研究所 | Alkyl levulinate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAILIN CONG ET AL.: "Preparation of porous sulfonated poly(styrene-divinylbenzene) microspheres and its application in hydrophilic and chiral separation", 《TALANTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114210370A (en) * | 2021-12-20 | 2022-03-22 | 南京亘闪生物科技有限公司 | Preparation method of catalyst microspheres for preparing ethyl acetate |
| CN117983298A (en) * | 2024-03-29 | 2024-05-07 | 岳阳兴长石化股份有限公司 | Crosslinked polystyrene hollow microsphere catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Preparation of sulfonated ordered mesoporous carbon and its use for the esterification of fatty acids | |
| Gao et al. | Efficient mesoporous carbon-based solid catalyst for the esterification of oleic acid | |
| Wang et al. | Acid and base coexisted heterogeneous catalysts supported on hypercrosslinked polymers for one-pot cascade reactions | |
| CN113578383A (en) | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere | |
| Jiang et al. | Esterification of glycerol with acetic acid over SO3H-functionalized phenolic resin | |
| CN103182324B (en) | Preparation method of hydrophobic organic framework solid base catalyst | |
| Wang et al. | Immobilized phosphotungstic acid based ionic liquid: Application for heterogeneous esterification of palmitic acid | |
| CN101961660B (en) | Porous hybrid-resin solid acid catalyst and preparation method thereof | |
| Mou et al. | Synthesis of fuel bioadditive by esterification of glycerol with acetic acid over hydrophobic polymer-based solid acid | |
| CN101274269A (en) | Adsorption resin with centralized pore diameter and large Micropore specific surface area and method for producing the same | |
| CN112121853B (en) | Mesoporous hollow silica nanosphere loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silica nanosphere | |
| Xie et al. | Preparation of amphiphilic mesoporous carbon-based solid acid from kraft lignin activated by phosphoric acid and its catalytic performance for hydration of α-pinene | |
| Roslan et al. | Esterification reaction of free fatty acid in used cooking oil using sulfonated hypercrosslinked exchange resin as catalyst | |
| Li et al. | Selective esterification of glycerol with acetic acid to green fuel bio-additive over a lignosulfonate-based renewable solid acid | |
| CN101927185A (en) | Preparation of macroporous strong-acid cation-exchange resin catalyst and use thereof in catalytic synthesis of methyl 2-keto-L-gulonate | |
| CN102093499A (en) | Method for preparing adsorbent resin with ultra-high specific surface area | |
| Ling et al. | Porous polymer microsphere functionalized with benzimidazolium based ionic liquids as effective solid catalysts for esterification | |
| CN109046382A (en) | A kind of novel biomass carbon-based solid super acids preparation method | |
| Zhang et al. | Chemo-catalytic esterification and transesterification over organic Polymer-Based catalysts for biodiesel synthesis | |
| CN110483678B (en) | Catalyst for preparing isosorbide by dehydrating sorbitol and preparation method and application thereof | |
| CN104258906A (en) | Nano porous fixed acid catalyst with organic frame and synthesis method thereof | |
| Li et al. | Synthesis of hypercrosslinked polymers with a spherical shell structure for highly effective cycloaddition of CO 2 under ambient conditions | |
| CN114349890B (en) | Ultrahigh crosslinked resin and preparation method and application thereof | |
| CN114436809B (en) | Method for preparing diethyl maleate by carrying out depolymerization on lignin under catalysis of iron oxide loaded by USY molecular sieve | |
| CN113651780A (en) | Preparation method of 2, 5-tetrahydrofuran dimethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211102 |
|
| RJ01 | Rejection of invention patent application after publication |