CN115350726A - Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride - Google Patents
Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride Download PDFInfo
- Publication number
- CN115350726A CN115350726A CN202211144300.8A CN202211144300A CN115350726A CN 115350726 A CN115350726 A CN 115350726A CN 202211144300 A CN202211144300 A CN 202211144300A CN 115350726 A CN115350726 A CN 115350726A
- Authority
- CN
- China
- Prior art keywords
- acid
- fatty acid
- catalyst
- lignosulfonate
- acid triglyceride
- 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
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 80
- 239000000194 fatty acid Substances 0.000 title claims abstract description 80
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 80
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 17
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 76
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 38
- 239000005011 phenolic resin Substances 0.000 claims description 38
- 229920001568 phenolic resin Polymers 0.000 claims description 38
- 235000011187 glycerol Nutrition 0.000 claims description 27
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002028 Biomass Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 150000001299 aldehydes Chemical class 0.000 claims description 15
- 229920001896 polybutyrate Polymers 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 7
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 7
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005639 Lauric acid Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008035 bio-based plasticizer Substances 0.000 claims description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 4
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229960002446 octanoic acid Drugs 0.000 claims description 4
- FVIRGMIYFJWRGC-UHFFFAOYSA-N sulfurobromidic acid Chemical compound OS(Br)(=O)=O FVIRGMIYFJWRGC-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 229940005605 valeric acid Drugs 0.000 claims description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 4
- 235000012141 vanillin Nutrition 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 235000013824 polyphenols Nutrition 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 239000001087 glyceryl triacetate Substances 0.000 description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000005588 protonation Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229960002622 triacetin Drugs 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000004402 polyphenol group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
-
- 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
- C08G8/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of furfural
-
- 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
- C08G8/28—Chemically modified polycondensates
-
- 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
- C08G8/28—Chemically modified polycondensates
- C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesizing fatty acid triglyceride, a preparation method thereof, fatty acid triglyceride, a preparation method and application thereof. The preparation method of the catalyst for synthesizing the fatty acid triglyceride comprises the following steps: the catalyst is synthesized by taking lignosulfonate and biobased aldehyde monomers as raw materials through phenolic aldehyde condensation and two-step sulfonation reaction. The invention also discloses fatty acid triglyceride and a preparation method and application thereof. The catalyst for synthesizing the fatty acid triglyceride, the preparation method thereof, the fatty acid triglyceride, the preparation method and the application of the fatty acid triglyceride, disclosed by the invention, have the advantages that the solid acid catalyst with excellent water resistance and rich acid sites is synthesized by taking lignosulfonate as a raw material, and the catalyst has important practical significance for the efficient synthesis of the fatty acid triglyceride.
Description
Technical Field
The invention belongs to the technical field of fatty acid triglyceride bio-based plasticizers, and particularly relates to a catalyst for synthesizing fatty acid triglyceride, a preparation method of the catalyst, fatty acid triglyceride, a preparation method of the fatty acid triglyceride and application of the fatty acid triglyceride.
Background
The fatty acid triglyceride is an important chemical intermediate and is widely applied in the fields of surfactants, pharmaceutical intermediates, foods and the like. Industrially, often H 2 SO 4 HCl and HNO 3 The catalyst is used for catalyzing glycerin and fatty acid to be obtained through esterification reaction. Although the strong-acid homogeneous acid catalyst can show excellent catalytic activity under mild conditions, the strong-acid homogeneous acid catalyst has serious side reactions, equipment corrosion and the generation of a large amount of three-waste pollutants, and does not meet the development requirements of green chemical industry. Therefore, the development of highly active solid acids as catalysts instead of homogeneous strong acids for the above process is considered to be the most desirable option.
Around the development of the high-efficiency catalyst for synthesizing fatty acid triglyceride by fatty acid and glyceride, researchers do a great deal of research work and develop various types of solid acid catalysts such as supported type, heteropoly acid, oxide, metal salt and the like in succession. However, the catalyst generally has the defects of harsh conditions, poor selectivity and easy loss of active sites, and the industrial application of the solid acid catalyst is limited. The acidic ion exchange resin has the advantages of stable active sites and good reusability, and part of models are commercialized. However, the existing ion exchange resin has few acid sites and poor selectivity to fatty acid triglyceride, and esterification products mainly comprise fatty acid monoglyceride and fatty acid diglyceride.
In view of the above, the invention provides a novel catalyst for synthesizing fatty acid triglyceride, a preparation method thereof, fatty acid triglyceride, a preparation method thereof and application thereof.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a catalyst for synthesizing fatty acid triglyceride, which is a solid acid catalyst with excellent water resistance and rich acid sites synthesized by using lignosulfonate as a raw material, has simple process and has important practical significance for the high-efficiency synthesis of fatty acid triglyceride.
In order to realize the purpose, the adopted technical scheme is as follows:
the preparation method of the catalyst for synthesizing the fatty acid triglyceride comprises the following steps: the catalyst is synthesized by taking lignosulfonate and biobased aldehyde monomers as raw materials through phenolic aldehyde condensation and two-step sulfonation reaction.
Further, the preparation method comprises the following steps:
(1) Dissolving lignosulfonate and biomass aldehyde monomers in water, uniformly mixing, adding a hydrochloric acid solution, and performing phenolic aldehyde polycondensation reaction to obtain bio-based phenolic resin;
adding the bio-based phenolic resin into a sulfuric acid solution, carrying out ion exchange reaction, washing and drying to obtain acidified bio-based phenolic resin;
(2) Adding the acidified bio-based phenolic resin into an organic solvent, uniformly mixing, adding a sulfonating reagent for sulfonation reaction, washing to be neutral, and drying to obtain the catalyst for synthesizing the fatty acid triglyceride.
Still further, in the step (1), the ratio of the quantities of the lignosulfonate and the biomass aldehyde monomer is 1:1-4;
the temperature of the phenolic aldehyde polycondensation reaction is 60-120 ℃, and the time is 3-8h; the temperature of the ion exchange reaction is 25-60 ℃, and the time is 2-8h;
the concentration of the hydrochloric acid solution is 3mol/L, and the volume mass ratio of the hydrochloric acid solution to the lignosulfonate is 1mL:1-4g;
the concentration of the sulfuric acid solution is 2mol/L, and the volume mass ratio of the sulfuric acid solution to the bio-based phenolic resin is 100mL:1g of a compound;
in the step (2), the mass-to-volume ratio of the acidified bio-based phenolic resin to the organic solvent to the sulfonating reagent is 1g;
sulfonation reaction at N 2 Reacting for 2-24h at 0-30 ℃ in the atmosphere.
Still further, in the step (1), the lignosulfonate is one of sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate and ammonium lignosulfonate;
the biomass aldehyde monomer comprises one of furfural and vanillin which are derived from a biomass route;
in the step (2), the organic solvent is dichloromethane;
the sulfonating reagent is one of fluorosulfonic acid, chlorosulfonic acid, bromosulfonic acid, sulfamic acid, trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride.
Still further, the lignosulfonate is sodium lignosulfonate;
the sulfonating agent is chlorosulfonic acid.
The second purpose of the invention is to provide a catalyst for synthesizing fatty acid triglyceride, which is prepared by the preparation method and can solve the problems that homogeneous acid corrodes production equipment, is difficult to separate and generates a large amount of three wastes; the defects of easy loss of active components, poor reusability, low acid site concentration and poor selectivity to fatty acid triglyceride of the traditional solid acid catalyst are effectively overcome.
The third purpose of the invention is to provide a preparation method of fatty acid triglyceride, which adopts the catalyst and has the characteristics of good catalyst stability, high glycerol conversion rate, high fatty acid triglyceride selectivity and the like.
In order to realize the purpose, the adopted technical scheme is as follows:
a preparation method of fatty acid triglyceride comprises the following steps: mixing fatty acid and glycerin, adding the catalyst, and refluxing at 50-120 deg.C for 1-10 hr.
Further, the fatty acid is at least one of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid and lauric acid;
the molar ratio of the aliphatic acid to the glycerol is 1-12;
the dosage of the catalyst is 0.5-15wt% of that of the glycerol.
The fourth purpose of the invention is to provide a new application of the fatty acid triglyceride prepared by the preparation method, and the fatty acid triglyceride is applied as a bio-based plasticizer for plasticizing PBC/PBAT and PEC/PBAT blending systems.
In order to realize the purpose, the adopted technical scheme is as follows:
the fatty acid triglyceride prepared by the preparation method is applied to the bio-based plasticizer.
Further, the applications are for plasticized polybutylene carbonate (PBC)/PBAT and poly (butylene succinate-co-butylene carbonate) (PEC)/PBAT blending systems.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes lignosulfonate and a bio-based aldehyde compound which also has active sites of sulfonation reaction as monomers, improves the water-resistant stability of bio-based phenolic resin through phenolic condensation reaction, and then improves the concentration of sulfonate through secondary sulfonation reaction to obtain bio-based solid acid with high water stability and high acid site concentration, which is used for catalyzing fatty acid and glycerol to synthesize fatty acid triglyceride through esterification reaction, and mainly solves the problems that homogeneous acid corrodes production equipment, is difficult to separate and generates a large amount of three wastes and the tradition; the defects of easy loss of active components, poor reusability, low acid site concentration and poor selectivity to fatty acid triglyceride of the traditional solid acid catalyst are effectively overcome. Thereby having the following advantages:
(1) The raw materials adopted by the invention belong to industrial and agricultural and forestry resource wastes, have reproducible attributes and accord with the sustainable development concept.
(2) The two-step process of phenolic aldehyde condensation and secondary sulfonic acid is adopted, so that the defect of complex direct protonation process of lignosulfonate is effectively overcome, and the method has the advantages of simple process and convenience for large-scale production.
(3) The obtained bio-based solid acid catalyst has the advantages of water-resistant stability and high acid site concentration, and shows excellent reusability and product selectivity in the reaction of synthesizing fatty acid triglyceride by an esterification method.
(4) The fatty acid triglyceride synthesized by the technology disclosed by the technical scheme has excellent plasticizing performance on a blending system consisting of PBC and the copolymers PEC and PBAT thereof.
Drawings
FIG. 1 is a photograph of the dispersion of the catalyst in the product after the reactions of comparative example 1 (a), example 2 (b) and example 2 (c);
FIG. 2 shows the elongation at break of the PBC/PBAT composite material by tributyrin.
Detailed Description
In order to further illustrate the catalyst for synthesizing fatty acid triglyceride and the preparation method thereof, fatty acid triglyceride and the preparation method and application thereof, and achieve the intended purpose of the invention, the following detailed description will be given to the catalyst for synthesizing fatty acid triglyceride and the preparation method thereof, fatty acid triglyceride and the preparation method and application thereof, and the specific implementation manner, structure, characteristics and efficacy thereof, which are provided by the present invention, in combination with the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The catalyst for synthesizing fatty acid triglyceride and the preparation method thereof, fatty acid triglyceride and the preparation method and application thereof according to the present invention will be described in further detail with reference to the following specific examples:
the lignosulfonate obtained from industrial papermaking wastewater contains abundant sulfonate in a molecular structure, and can be protonated to obtain a lignosulfonate catalyst with a renewable characteristic (CN201710383342. X and CN 201910450617.6). Lignosulfonic acid is readily soluble in water and cannot be used as an esterification catalyst. Therefore, the solid acid catalyst which is synthesized by taking the lignosulfonate as the raw material and has excellent water resistance and rich acid sites has important practical significance for the high-efficiency synthesis of the fatty acid triglyceride.
The catalyst for esterification synthesis of fatty acid and glycerin is obtained by phenolic condensation and sulfonation of lignosulfonate and biomass aldehyde monomers, and the preparation method comprises the following steps: carrying out polycondensation and protonation on a certain amount of lignosulfonate and biomass aldehyde monomers under an acidic condition to obtain biological amino acid resin; and then the prepared bio-based phenolic resin is subjected to sulfonation again, so that the number of acid sites is further increased. The invention also discloses a synthetic method for the fatty acid triglyceride and application of the fatty acid triglyceride. In the technical scheme of the invention, the catalyst has the advantages of high activity and high stability, and provides a new application of the aliphatic glyceride for plasticizing the PBC and the PBC copolymer of the fully biodegradable polymer.
The glycerol conversion and fatty acid triglyceride yields in the following examples were quantified using gas chromatography (GC-2014). And then separating, washing and drying the catalyst and the reaction product, and then carrying out a reusability test. The sulfonate concentration in the catalyst was determined by titration according to the literature (ACS Sustain. Chem. Eng.3 (2015) 1366).
Example 1:
(1) Preparing a catalyst:
a: dissolving lignosulfonate and biomass aldehyde monomer in water to form a uniform mixed solution, adding 3mol/L HCl into the solution, and performing phenolic aldehyde polycondensation at 60-120 DEG CReacting for 3-8h to obtain the bio-based phenolic resin. Then adding the bio-based phenolic resin into 2mol/L H 2 SO 4 Reacting in the solution at 25-60 ℃ for 2-8h to complete the ion exchange reaction, and washing and drying to obtain the acidified bio-based phenolic resin.
The lignosulfonate is one of sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate and ammonium lignosulfonate, preferably sodium lignosulfonate.
The biomass aldehyde monomer comprises one of furfural and vanillin which are derived from a biomass route.
The mass ratio of lignosulfonate to biomass aldehyde monomer was 1:1-4.
The volume mass ratio of the hydrochloric acid solution to the lignosulfonate is 1mL:1-4g;
the volume mass ratio of the sulfuric acid solution to the bio-based phenolic resin is 100mL:1g.
B: adding the acidified bio-based phenolic resin into an organic solvent (dichloromethane), quickly stirring and uniformly dispersing, adding a sulfonating reagent for further sulfonation reaction, and adding N 2 Reacting for 2-24h at 0-30 ℃ in the atmosphere, washing to be neutral, and drying to obtain the bio-based solid acid catalyst.
The sulfonating agent is one of fluorosulfonic acid, chlorosulfonic acid, bromosulfonic acid, sulfamic acid, trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride, and chlorosulfonic acid is preferred.
The mass-volume ratio of the acidified bio-based phenolic resin to the organic solvent to the sulfonating reagent is 1g.
(2) Synthesis of fatty acid triglyceride
Mixing fatty acid and glycerol, adding the catalyst, and reflux-reacting at 50-120 deg.C for 1-10 hr to obtain fatty glyceride.
Wherein the fatty acid is at least one of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid and lauric acid.
The molar ratio of fatty acid to glycerol is 1-12; the amount of the catalyst is 0.5-15wt% of the amount of the glycerol.
(3) Applications of the invention
The fatty acid triglyceride is applied as a bio-based plasticizer for plasticizing polybutylene carbonate (PBC)/PBAT and poly (butylene succinate-co-butylene carbonate) (PEC)/PBAT blending systems.
Example 2: reacting sodium lignin sulfonate with furfural
(1) Preparing a catalyst:
adding 6.0g of sodium lignosulfonate and 2.9g of furfural into water to form a uniform mixed solution, then adding 2mL of 3mol/L HCl, and carrying out phenolic aldehyde polycondensation reaction for 6 hours at 90 ℃ to obtain the bio-based phenolic resin. Then adding the bio-based phenolic resin into 2mol/L H 2 SO 4 Reacting in the solution (the volume mass ratio of the sulfuric acid solution to the bio-based phenolic resin is 100mL at 1g) at 25 ℃ for 2h to complete the ion exchange reaction, and washing and drying with deionized water to obtain the acidified bio-based phenolic resin.
Adding 1g of acidified bio-based phenolic resin into 20mL of dichloromethane, quickly stirring and uniformly dispersing, adding 2mL of chlorosulfonic acid reagent for sulfonation reaction, and adding N 2 Reacting for 24 hours at 0 ℃ in the atmosphere, washing with deionized water and absolute ethyl alcohol to neutrality, and drying to obtain the bio-based solid acid catalyst.
(2) Synthesis of fatty acid triglyceride
Adding acetic acid and glycerol in a molar ratio of 10.
(3) Applications of the invention
And (2) uniformly mixing 1-20 parts of fatty acid triglyceride and 100 parts of PBC/PBAT composite material on a high-speed mixer, wherein the mixing temperature is 100-250 ℃, the mixing time is 10-20min, putting the mixed material into an extruder, and carrying out extrusion granulation to obtain the fatty acid triglyceride plasticized PBC/PBAT composite material. According to the same method, a fatty acid triglyceride plasticized PEC/PBAT composite can be obtained.
Example 3: reaction of sodium lignosulfonate with aromatic aldehyde
The catalyst preparation procedure was the same as in example 2, except that: 4.5g of vanillin replaces furfural, and the bio-based solid acid catalyst is prepared.
Adding acetic acid and glycerol into a reactor at a molar ratio of 10.
Example 4: reaction of calcium lignosulphonate and furfural
The procedure for the preparation of the catalyst was the same as in example 2, except that 6.0g of calcium lignosulfonate was used in place of sodium lignosulfonate to prepare a bio-based solid acid catalyst.
Butyric acid and glycerol in a molar ratio of 10:1 were added to a reactor, stirred uniformly and heated to 100 ℃, and then the bio-based solid acid catalyst prepared in example 4 was added in an amount of 5wt% of glycerol, and the conversion rate of glycerol and the selectivity of tributyrin were analyzed in a reflux reaction for 4 hours.
Example 5: reaction of sodium lignosulfonate with furfural
The catalyst preparation procedure was the same as in example 2, except that a bio-based solid acid catalyst was prepared using sulfamic acid as the sulfonating agent.
Propionic acid and glycerol in a molar ratio of 10.
Example 6: esterification reaction of glycerin and lauric acid catalyzed by calcium lignosulphonate and furfural
The procedure for the preparation of the catalyst was the same as in example 2, except that the bio-based phenolic resin was reacted with H 2 SO 4 The ion exchange reaction temperature of (2) is 60 ℃ and the time is 6h.
Adding lauric acid and glycerol into a reactor at a molar ratio of 10.
Example 7.
Adding 6.0g of sodium lignosulfonate and 4.5g of aromatic aldehyde into water to form a uniformly mixed solution, then adding 3mol/L of HCl into the solution, and carrying out phenolic polycondensation reaction for 8 hours at 120 ℃ to obtain the bio-based phenolic resin. Then adding the bio-based phenolic resin into 2mol/L H 2 SO 4 Reacting for 4 hours in the solution at 30 ℃ to finish the ion exchange reaction, washing with deionized water and absolute ethyl alcohol, and drying to obtain the acidic bio-based phenolic resin.
Adding the acidic bio-based phenolic resin into 20mL of dichloromethane, quickly stirring and uniformly dispersing, adding 3.5mL of fluorosulfonic acid for further sulfonation reaction, and adding N 2 Reacting for 24 hours at 0 ℃ in the atmosphere, washing with deionized water and absolute ethyl alcohol to neutrality, and drying to obtain the bio-based solid acid catalyst.
Example 8.
Adding 5.2g of calcium lignosulphonate and 4.5g of aromatic aldehyde into water to form a uniformly mixed solution, then adding 3mol/L of HCl into the solution, and carrying out phenolic polycondensation reaction for 4 hours at 100 ℃ to obtain the bio-based phenolic resin. Then adding the bio-based phenolic resin into 2mol/L H 2 SO 4 And (3) reacting in the solution for 8 hours at the temperature of 30 ℃ to finish the ion exchange reaction, washing by deionized water and absolute ethyl alcohol, and drying to obtain the acidic bio-based phenolic resin.
Adding the acidic bio-based phenolic resin into 20mL of dichloromethane, quickly stirring and uniformly dispersing, adding 3.5mL of sulfamic acid for further sulfonation reaction, and adding N 2 Reacting for 12 hours at 0 ℃ in the atmosphere, washing with deionized water and absolute ethyl alcohol to neutrality, and drying to obtain the bio-based solid acid catalyst.
Example 9: reaction of ammonium lignosulfonate with furfural
The catalyst preparation procedure was the same as in example 2, except that:
(1) 0.01mol of ammonium lignosulfonate is adopted, the mass ratio of the ammonium lignosulfonate to furfural is 1:1, and the volume mass ratio of a hydrochloric acid solution to the ammonium lignosulfonate is 1mL:4g, and carrying out phenolic aldehyde polycondensation reaction at 120 ℃ for 3 hours.
Adopting bromosulfonic acid as a sulfonating reagent, wherein the mass-volume ratio of the acidified bio-based phenolic resin to the organic solvent to the sulfonating reagent is 1g.
Sulfonation reaction is carried out for 2h at 30 ℃.
(2) Propionic acid, butyric acid, valeric acid, caproic acid (molar ratio 1.
Example 10: reaction of potassium lignosulfonate with furfural
The catalyst preparation procedure was the same as in example 2, except that:
(1) 0.01mol of potassium lignosulfonate is adopted, the amount ratio of the potassium lignosulfonate to furfural is 1:4, and the volume-mass ratio of a hydrochloric acid solution to ammonium lignosulfonate is 1mL:1g, and carrying out phenolic aldehyde polycondensation reaction at 60 ℃ for 8 hours.
The mass-volume ratio of the acidified bio-based phenolic resin to the organic solvent and the sulfonating reagent is 1g.
Trifluoromethane sulfonic acid is adopted as a sulfonating reagent, and sulfonation reaction is carried out for 10 hours at 10 ℃.
Caprylic acid and lauric acid (in a molar ratio of 1:1) were used as fatty acids, in a molar ratio of 1:1 to glycerol.
Comparative example 1: preparation of lignosulfonic acid and catalytic properties thereof
Reference (ACS sustatin. Chem. Eng.3 (2015) 1366-1373.) lignin sulfonic acid was prepared by dissolving 3.0g sodium lignin sulfonate in 50ml deionized water and then slowly flowing it through an activated acidic resin column. The collected eluate was freeze-dried to obtain lignosulfonic acid. The catalytic performance of lignosulfonic acid in the esterification reaction of acetic acid and glycerol was evaluated according to the examples, and the product glycerol conversion was analyzed as well as the selectivity to triacetin.
Comparative example 2: condensation reaction of sodium lignosulfonate and formaldehyde and catalytic performance thereof
Reference (Green chem.17 (2015) 3644-3652.) the preparation of sodium lignosulfonate and formaldehyde condensation biobased acid resin. 3.0g of sodium lignosulfonate was dissolved in 5.2g of deionized water, 15mmol of formaldehyde was added and stirred, and finally 2.7mL of concentrated hydrochloric acid was slowly added and stirred for reaction at 90 ℃ for 6h. Filtering, washing and vacuum drying to obtain the phenolic resin. And then adding the dried solid into a 2mol/L sulfuric acid solution, stirring at room temperature for ion exchange for 2 hours, separating the solid, washing to be neutral by deionization, and drying at 120 ℃ overnight to obtain the bio-based phenolic resin solid acid. The catalytic performance of lignosulfonic acid in the esterification reaction of acetic acid and glycerol was evaluated according to the examples, and the product glycerol conversion and selectivity to triacetin were analyzed.
TABLE 1 sulfonate concentration and catalytic Properties of Bio-based solid acids of the different examples
And (4) conclusion: by comparing the comparative example 1 with the example, it can be found from fig. 1 that the water resistance of the biomass solid acid can be remarkably improved and the reusability of the catalyst can be remarkably improved by the macromolecule with the polyphenol structure obtained by the phenolic condensation reaction of the biomass aldehyde monomer and the lignosulfonate. Compared with the example, the comparison of the comparative example 2 shows that the aldehyde monomer containing the benzene ring and the furan ring has the active site of the sulfonation reaction, the sulfonic acid group can be introduced in the sulfonation reaction, the concentration of the acid site is increased, and the yield of the fatty acid triglyceride is obviously improved.
From fig. 2, it can be found that the fatty acid triglyceride with the branched structure contains rich ester groups and hydroxyl groups, and the compatibility of PBC and PBAT can be significantly improved by adding the fatty acid triglyceride into a PBC/PBAT blending system, so that the elongation at break of the composite material is significantly improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the catalyst for synthesizing fatty acid triglyceride is characterized by comprising the following steps: the catalyst is synthesized by taking lignosulfonate and biobased aldehyde monomers as raw materials through phenolic condensation and two-step sulfonation reaction.
2. The method of claim 1, comprising the steps of:
(1) Dissolving lignosulfonate and biomass aldehyde monomers in water, uniformly mixing, adding a hydrochloric acid solution, and performing phenolic aldehyde polycondensation reaction to obtain bio-based phenolic resin;
adding the bio-based phenolic resin into a sulfuric acid solution, carrying out ion exchange reaction, washing and drying to obtain acidified bio-based phenolic resin;
(2) And adding the acidified bio-based phenolic resin into an organic solvent, uniformly mixing, adding a sulfonation reagent for sulfonation reaction, washing to be neutral, and drying to obtain the catalyst for synthesizing the fatty acid triglyceride.
3. The production method according to claim 2,
in the step (1), the mass ratio of the lignosulfonate to the biomass aldehyde monomer is 1:1-4;
the temperature of the phenolic aldehyde polycondensation reaction is 60-120 ℃, and the time is 3-8h; the temperature of the ion exchange reaction is 25-60 ℃, and the time is 2-8h;
the concentration of the hydrochloric acid solution is 3mol/L, and the volume mass ratio of the hydrochloric acid solution to the lignosulfonate is 1mL:1-4g;
the concentration of the sulfuric acid solution is 2mol/L, and the volume mass ratio of the sulfuric acid solution to the bio-based phenolic resin is 100mL:1g of a compound;
in the step (2), the mass-to-volume ratio of the acidified bio-based phenolic resin to the organic solvent to the sulfonating reagent is 1g;
sulfonation reaction at N 2 Reacting for 2-24h at 0-30 ℃ in the atmosphere.
4. The production method according to claim 2,
in the step (1), the lignosulfonate is one of sodium lignosulfonate, potassium lignosulfonate, calcium lignosulfonate and ammonium lignosulfonate;
the biomass aldehyde monomer comprises one of furfural and vanillin which are derived from a biomass route;
in the step (2), the organic solvent is dichloromethane;
the sulfonating reagent is one of fluorosulfonic acid, chlorosulfonic acid, bromosulfonic acid, sulfamic acid, trifluoromethanesulfonic acid and trifluoromethanesulfonic anhydride.
5. The production method according to claim 4,
the lignosulfonate is sodium lignosulfonate;
the sulfonating agent is chlorosulfonic acid.
6. A catalyst for synthesizing fatty acid triglyceride, characterized in that the catalyst is prepared by the preparation method according to any one of claims 1 to 5.
7. The preparation method of the fatty acid triglyceride is characterized by comprising the following steps: mixing fatty acid and glycerin, adding the catalyst of claim 6, and refluxing at 50-120 deg.C for 1-10h.
8. The production method according to claim 7,
the fatty acid is at least one of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid and lauric acid;
the molar ratio of the aliphatic acid to the glycerol is 1-12;
the dosage of the catalyst is 0.5-15wt% of that of the glycerol.
9. Use of fatty acid triglycerides prepared by the process according to any of claims 7-8 in bio-based plasticizers.
10. Use according to claim 9,
the application is for plasticizing PBC/PBAT and PEC/PBAT blending systems.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211144300.8A CN115350726A (en) | 2022-09-20 | 2022-09-20 | Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211144300.8A CN115350726A (en) | 2022-09-20 | 2022-09-20 | Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115350726A true CN115350726A (en) | 2022-11-18 |
Family
ID=84007005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211144300.8A Pending CN115350726A (en) | 2022-09-20 | 2022-09-20 | Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115350726A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550223A (en) * | 2009-04-27 | 2009-10-07 | 西北师范大学 | Sulfonated phenolic resin and preparation and application as catalyst thereof |
| CN103570901A (en) * | 2013-10-08 | 2014-02-12 | 上海应用技术学院 | Preparation method of environment-friendly phenol aldehyde resin |
| CN109836403A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | The method for converting 5 hydroxymethyl furfural for biomass saccharide compound as catalyst using sulfomethylated lignin acidic group-aldehyde type resin |
| CN110560161A (en) * | 2019-08-21 | 2019-12-13 | 浙江大学 | Preparation method of sulfonated phenolic resin type solid acid catalyst and application of sulfonated phenolic resin type solid acid catalyst in glycerol esterification reaction |
-
2022
- 2022-09-20 CN CN202211144300.8A patent/CN115350726A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550223A (en) * | 2009-04-27 | 2009-10-07 | 西北师范大学 | Sulfonated phenolic resin and preparation and application as catalyst thereof |
| CN103570901A (en) * | 2013-10-08 | 2014-02-12 | 上海应用技术学院 | Preparation method of environment-friendly phenol aldehyde resin |
| CN109836403A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | The method for converting 5 hydroxymethyl furfural for biomass saccharide compound as catalyst using sulfomethylated lignin acidic group-aldehyde type resin |
| CN110560161A (en) * | 2019-08-21 | 2019-12-13 | 浙江大学 | Preparation method of sulfonated phenolic resin type solid acid catalyst and application of sulfonated phenolic resin type solid acid catalyst in glycerol esterification reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111957346B (en) | Etherification catalyst for preparing methyl tertiary butyl ether from methanol-tertiary butyl alcohol and preparation method thereof | |
| CN111604055B (en) | Catalyst for preparing acetophenone by oxidizing ethylbenzene and preparation method thereof | |
| CN107029784B (en) | A kind of Polymer-supported dual-core acidic ionic liquid catalyst and its preparation and application | |
| CN108558598A (en) | A kind of method that acid swelling poly ion liquid catalysis hexamethylene esters compound hydrolysis reaction prepares cyclohexanol | |
| CN115350726A (en) | Catalyst for synthesizing fatty acid triglyceride, preparation method of catalyst, fatty acid triglyceride, preparation method of fatty acid triglyceride and application of fatty acid triglyceride | |
| CN1332924C (en) | Method for esterifying organic acid | |
| CN111097516B (en) | Catalyst for synthesizing methyl methoxyacetate and preparation method thereof | |
| CN110227547A (en) | A kind of preparation method and applications of sulfomethylated lignin acid catalyst | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| CN1134399C (en) | Method for making bis-xylenols containing acid moieties | |
| CN111389462B (en) | Method for preparing biphenyl by using carboxylic acid functionalized super-crosslinked porous organic polymer loaded with nanogold | |
| CN101544562B (en) | Zeolite molecular sieve catalysis method for synthesizing sec-butyl acetate from acetic acid and butylenes. | |
| CN112574229B (en) | Method for preparing isosorbide by dehydrating sorbitol and preparation method of copolymer-based catalyst thereof | |
| CN111039863B (en) | Preparation method of rubber antioxidant TMQ | |
| CN113559930A (en) | Preparation method and application of solid catalyst taking sodium lignosulfonate as carrier | |
| CN108993537B (en) | Multi-stage gradient pore carbon-based sulfonic acid microsphere with uniform particle size, and preparation method and application thereof | |
| CN107033002B (en) | Method for synthesizing aromatic acid ester | |
| CN104926671A (en) | Method for preparing D-phenylalanine through asymmetric transformation of L-phenylalanine | |
| CN114011465B (en) | Granular porous perfluorinated sulfonic acid resin catalyst and preparation method and application thereof | |
| EP1286946A1 (en) | Method for producing carboxylic acid benzyl esters | |
| CN109575345A (en) | Sulfonated divinylbenzene polymer microballoon, preparation method and applications | |
| CN113061123B (en) | Method for preparing 2 (5H) -furanone and maleic acid by selective oxidation of furfural | |
| CN1687166A (en) | Perfluoro olefin sulfonate grafted ion exchange resin of polystyrens and preparation method thereof | |
| CN116832865A (en) | Modified resin catalyst, preparation method thereof and application thereof in methyl methacrylate synthesis reaction | |
| CN115850103B (en) | Preparation method of 3-amino-2-fluorobenzoic acid methyl ester |
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 |