CN114702649B - Immobilized catalyst for continuous condensation in sorbic acid preparation and preparation method thereof - Google Patents
Immobilized catalyst for continuous condensation in sorbic acid preparation and preparation method thereof Download PDFInfo
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- CN114702649B CN114702649B CN202210406259.0A CN202210406259A CN114702649B CN 114702649 B CN114702649 B CN 114702649B CN 202210406259 A CN202210406259 A CN 202210406259A CN 114702649 B CN114702649 B CN 114702649B
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- sorbic acid
- polyester
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- crotonaldehyde
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- 235000010199 sorbic acid Nutrition 0.000 title claims abstract description 117
- 229940075582 sorbic acid Drugs 0.000 title claims abstract description 116
- 239000004334 sorbic acid Substances 0.000 title claims abstract description 116
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000009833 condensation Methods 0.000 title claims abstract description 91
- 230000005494 condensation Effects 0.000 title claims abstract description 91
- 239000003622 immobilized catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 116
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims abstract description 75
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000003112 inhibitor Substances 0.000 claims abstract description 36
- 238000006482 condensation reaction Methods 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 5
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 150000007524 organic acids Chemical group 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 107
- 230000007062 hydrolysis Effects 0.000 abstract description 38
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 38
- 239000007788 liquid Substances 0.000 description 56
- 239000000047 product Substances 0.000 description 56
- 230000008569 process Effects 0.000 description 37
- 238000002834 transmittance Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 230000005484 gravity Effects 0.000 description 25
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 description 20
- 238000007670 refining Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000935 solvent evaporation Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000011049 filling Methods 0.000 description 11
- 230000003301 hydrolyzing effect Effects 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WSWCOQWTEOXDQX-MQQKCMAXSA-N E-Sorbic acid Chemical compound C\C=C\C=C\C(O)=O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CHETUOSYZGKTOC-UHFFFAOYSA-L zinc;3-methylbutanoate Chemical compound [Zn+2].CC(C)CC([O-])=O.CC(C)CC([O-])=O CHETUOSYZGKTOC-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- -1 inorganic acid salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000014443 Pyrus communis Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- QAZYYQMPRQKMAC-FDGPNNRMSA-L calcium;(z)-4-oxopent-2-en-2-olate Chemical compound [Ca+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QAZYYQMPRQKMAC-FDGPNNRMSA-L 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical class O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Chemical class CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Chemical class CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000015092 herbal tea Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- YZSUHNYMDVSXAS-RJNTXXOISA-L zinc;(2e,4e)-hexa-2,4-dienoate Chemical compound [Zn+2].C\C=C\C=C\C([O-])=O.C\C=C\C=C\C([O-])=O YZSUHNYMDVSXAS-RJNTXXOISA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- WDHVIZKSFZNHJB-UHFFFAOYSA-L zinc;butanoate Chemical compound [Zn+2].CCCC([O-])=O.CCCC([O-])=O WDHVIZKSFZNHJB-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/005—Polyesters prepared from ketenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a solid-supported catalyst for continuous condensation in sorbic acid preparation and a preparation method thereof, belonging to the field of sorbic acid preparation. The method comprises the steps of dissolving a catalyst active component in a solvent A, soaking a carrier in a catalyst active component soaking solution, filtering, collecting solids, drying in vacuum, and roasting for the first time to obtain a solid-supported catalyst 1; dissolving a polymerization inhibitor in the solvent B; the immobilized catalyst 1 is immersed in polymerization inhibitor impregnating solution and then filtered, solid is collected, and the solid is dried in vacuum and then subjected to secondary roasting, so that the immobilized catalyst for continuous condensation in the preparation of sorbic acid is obtained; wherein the active component of the catalyst is zinc salt; the polymerization inhibitor is 1, 1-diphenyl-2-trinitrophenylhydrazine; the ratio of the catalyst active component to the polymerization inhibitor is controlled to be 100 (3-4). The immobilized catalyst is used for continuous condensation reaction in the preparation of sorbic acid, and the yield of the polyester is 97-98% based on crotonaldehyde; the sorbic acid yield after hydrolysis is 90-91% based on polyester.
Description
Technical Field
The invention relates to a solid-supported catalyst for continuous condensation in sorbic acid preparation and a preparation method thereof, belonging to the technical field of sorbic acid preparation.
Background
Basic information of sorbic acid:
alias name: b dienoic acid, aronic acid, hexadienoic acid, herbal tea acid, 2, 4-propenyl acrylic acid;
english name: a SORBIC ACID;
appearance properties: white needle-like or powdery crystals, slightly soluble in water, and soluble in various organic solvents;
CAS number 110-44-1;
the molecular formula is C6H8O2;
molecular weight 112.13;
melting point: 132-135 ℃;
density: 1.204a19 ℃;
structural formula:
action and use: sorbic acid is an unsaturated fatty acid; has good inhibition effect on saccharomycetes, mould and various fungi under acidic conditions; the sorbic acid molecular structure contains unsaturated carboxylic acid and has higher antibacterial activity than saturated carboxylic acid with the same carbon number; can be used as food additive to effectively prevent oxidation and dehydrogenation of fatty acid in food, and further inhibit bacterial microorganism breeding and reproduction; sorbic acid can be widely used as a preservative in the industries of foods, beverages, tobacco, medicines, cosmetics, agricultural products and the like.
The prior art comprises the following steps of:
the common method for continuously preparing sorbic acid comprises the steps of preparing crotonaldehyde, a solvent and a catalyst into a crotonaldehyde solution according to a certain proportion, pumping ketene and the crotonaldehyde solution into a condensation reactor for continuous condensation reaction, simultaneously pumping out a condensation liquid after the reaction, and then carrying out five working procedures of continuous solvent removal, continuous hydrolysis, continuous washing and continuous crystallization to prepare a sorbic acid tide product. Among them, the usual catalysts are zinc acetate, zinc butyrate, zinc isovalerate, zinc sorbate, zinc oleate, zinc stearate, zinc chloride, cobalt chloride, boron trifluoride, zinc acetylacetonate and calcium acetylacetonate. However, the uneven distribution of the catalyst in the reaction system in the process can lead to the reduction of the amount of the generated polyester, thereby affecting the yield of sorbic acid; and the catalyst in the condensation section can be brought into subsequent procedures to affect the quality of the product.
(1) Methods for preparing polyesters and sorbic acid from Daieqiao chemical industries, inc., china, CN1133679C,2004-01-07.
The invention adopts simple substances or compounds of manganese, cobalt, nickel, zinc, cadmium and other transition metals, pyridine, picoline and other nitrogen-containing alkaline compounds, salts of acetic acid, isobutyric acid, isovaleric acid and other organic acid, sulfates, nitrates and other inorganic acid salts, chlorides and other halides, acetylacetone complex salts and other complex salts and complexes as catalysts, and crotonaldehyde with the purity of more than 97 percent is used as a reactant, the yield (based on ketene) of the prepared polyester can reach 77 percent at most, and the color of the prepared high-purity sorbic acid after the decomposition of the polyester is better. The disadvantage of this process is that the catalyst of the condensation section is carried into the subsequent section, which may catalyze the polymerization of crotonaldehyde during the removal of excess crotonaldehyde by distillation under reduced pressure, resulting in an increased impurity content in the polyester.
(2) The preparation process of sorbic acid comprises the following steps: china, CN104262135A,2015-01-07.
The invention adopts a multielement catalyst consisting of anhydrous zinc acetylacetonate and calcium acetylacetonate to catalyze the condensation reaction, adopts a static mixing external circulation type tower condensation reactor to carry out the condensation reaction, and uses a film generator to continuously recycle crotonaldehyde, thereby reducing the tar yield and ensuring the quality of polyester. The process has the defects that the catalyst is separated out while the crotonaldehyde is recovered by a film generator, but a large amount of tar substances are attached to the separated catalyst, and the catalyst cannot be directly recycled.
Disclosure of Invention
In order to solve the problem that the existing condensation section catalyst is brought into a subsequent section to affect the product yield and quality, the invention provides the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde by immobilizing the catalyst on a carrier, solves the problem of uneven distribution of the traditional solid catalyst in a reaction system, realizes the continuity of the condensation section, improves the yield and quality of polyester, and has more controllable production process operation.
The first object of the present invention is to provide a method for preparing an immobilized catalyst for continuous condensation in the preparation of sorbic acid, comprising the steps of:
(1) Loading of the catalyst active components: dissolving the active component of the catalyst in the solvent A, wherein the mass ratio of the active component of the catalyst to the solvent A is 1 (7-9), so as to obtain the impregnation liquid of the active component of the catalyst; the carrier is put into the catalyst active component impregnating solution according to the mass ratio of the catalyst active component to the carrier spherical alumina carrier of (0.1-0.5): 1 for 45-50 h, then filtered, the solid is collected, and the first roasting is carried out after the vacuum drying, the roasting temperature is 300-500 ℃ and the roasting time is 2-5 h, thus obtaining the immobilized catalyst 1;
(2) Polymerization inhibitor loading: dissolving a polymerization inhibitor in the solvent B, wherein the mass ratio of the polymerization inhibitor to the solvent B is (1-2) 1000, so as to obtain a polymerization inhibitor impregnating solution; soaking the immobilized catalyst 1 in polymerization inhibitor soaking solution for 45-50 h, filtering, collecting solid, vacuum drying, and roasting for the second time at 600-700 ℃ for 2-5 h to obtain the immobilized catalyst for continuous condensation in sorbic acid preparation;
wherein the active component of the catalyst is zinc salt;
the polymerization inhibitor is 1, 1-diphenyl-2-trinitrophenylhydrazine;
the ratio of the catalyst active component to the polymerization inhibitor is controlled to be 100 (3-4).
As an embodiment of the present invention, the catalyst active component is at least one of zinc organic acid, zinc acetylacetonate and zinc oxide. Further preferred zinc organic acids are zinc iso-octoate and zinc iso-valerate.
As one embodiment of the present invention, the carrier is selected from activated carbon, siO 2 、Al 2 O 3 At least one of diatomaceous earth and MgO. Preferably SiO 2 And Al 2 O 3 。
As one embodiment of the present invention, the specific surface area of the carrier is 120-160 m 2 And/g, the total pore volume is more than or equal to 1.25mg/L.
As one embodiment of the present invention, the carrier is spherical and has a diameter of 1.3 to 2.3mm. Preferably 1.5 to 2mm in diameter.
As an embodiment of the present invention, the solvent a is an organic solvent. Ethanol and acetone are preferred.
The third object of the present invention is to provide a mass ratio of the pre-polymerization inhibitor to the supported catalyst 1 of (0.0025 to 0.02): 1.
It is a second object of the present invention to provide an immobilized catalyst prepared by the aforementioned method.
A third object of the present invention is to provide the use of the aforementioned supported catalyst for continuous condensation reactions in the preparation of sorbic acid.
As one embodiment of the invention, the mass of the active component of the catalyst in the immobilized catalyst is 1-5% of the mass of crotonaldehyde.
As one implementation mode of the invention, the multi-layer filling of the immobilized catalyst in the condensation reactor, wherein the mass of the catalyst active component in the immobilized catalyst is 1-5% of the mass of the crotonaldehyde, the immobilized catalyst is heated and activated every 20-30 days (under the protection of inert gas, the temperature is raised to 500-600 ℃ for 0.5-1 h), part of the immobilized catalyst is replaced, ketene and the crotonaldehyde continuously react under the action of the immobilized catalyst to generate condensation liquid, the refractive index of the condensation liquid is 1.468-1.470, and the specific gravity of the condensation liquid is 0.97-1.00 g/mL (12 ℃); calculated by crotonaldehyde, the yield of the polyester is 97-98%; the sorbic acid yield after hydrolysis is 90-91% based on polyester. The condensation liquid is subjected to solvent steaming, hydrolysis, decoloration and refining to obtain the finished product with sorbic acid content of more than 99% and light transmittance of more than 99%.
The invention has the advantages and effects that:
1) The immobilized catalyst of the invention simultaneously immobilizes the catalyst active component and the polymerization inhibitor on the carrier, can be heated up for activation (under the protection of inert gas, the temperature is raised to 500-600 ℃ for 0.5-1 h), is repeatedly used, and reduces the production cost; the diameter of the immobilized catalyst is 1.5-2 mm, and the specific surface area is 120-160 m 2 And/g, the total pore volume is more than or equal to 1.25mg/L, the catalyst has larger void ratio and specific surface area, the efficiency of the catalyst can be fully exerted, sufficient gas-liquid contact area is provided for the reaction, and the mass transfer between the gas phase and the liquid phase is facilitated.
2) According to the immobilized catalyst disclosed by the invention, the catalyst and the polymerization inhibitor are immobilized on a carrier at the same time, and by selecting the loading parameters of the active components (the mass ratio of the active components of the catalyst to the solvent, the mass ratio of the active components of the catalyst to the carrier, the impregnation time, the roasting temperature and the roasting time), the loading parameters of the polymerization inhibitor (the mass ratio of the polymerization inhibitor to the solvent, the mass ratio of the polymerization inhibitor to the immobilized catalyst 1, the impregnation time, the roasting temperature and the roasting time) and the addition mass ratio of the active components of the catalyst to the polymerization inhibitor are optimally selected, so that the occurrence of side reactions in the condensation reaction is effectively inhibited, the refractive index of the condensation liquid is 1.468-1.470 after 12 hours, and the specific gravity of the condensation liquid is 0.97-1.00 g/mL (12 ℃); the yield of the polyester is 97-98% based on crotonaldehyde, and the molecular weight distribution in the polyester is more reasonable: the polyester has a molecular weight of less than 2000 and less than 15%, a molecular weight of 2000-8000 and more than 60%, and a molecular weight of more than 8000 and less than 25%; the yield of sorbic acid after hydrolysis is 90-91% based on polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with the sorbic acid content of 99.0-99.9% and the transmittance of 99.2-99.5%.
3) The research of the invention shows that the following technical effects can be achieved only under the condition that the addition mass ratio of the specific catalyst active component (such as zinc isooctanoate) to the polymerization inhibitor (1, 1-diphenyl-2-trinitrophenylhydrazine) is as follows: after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.468-1.470, and the specific gravity of the condensed liquid is 0.97-1.00 g/mL (12 ℃); the yield of the polyester is 97-98% based on crotonaldehyde, and the molecular weight distribution in the polyester is more reasonable: the polyester has a molecular weight of less than 2000 and less than 15%, a molecular weight of 2000-8000 and more than 60%, and a molecular weight of more than 8000 and less than 25%; the yield of sorbic acid after hydrolysis is 90-91% based on polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with the sorbic acid content of 99.0-99.9% and the transmittance of 99.2-99.5%.
4) The research of the invention discovers that the loading sequence of the active components and the polymerization inhibitor has obvious influence on the yield of polyester, the yield of sorbic acid, the sorbic acid content of finished products and the transmittance. By adopting the specific loading method, the yield of the polyester is 97-98% based on crotonaldehyde, and the molecular weight distribution in the polyester is more reasonable: the polyester has a molecular weight of less than 2000 and less than 15%, a molecular weight of 2000-8000 and more than 60%, and a molecular weight of more than 8000 and less than 25%; the yield of sorbic acid after hydrolysis is 90-91% based on polyester; the condensation liquid is subjected to solvent steaming, hydrolysis, decoloration and refining to obtain the finished product with the sorbic acid content of 99.0-99.9% and the light transmittance of 99.2-99.5%; the above technical effects cannot be achieved after the load sequence is changed.
Drawings
FIG. 1 is a condensation reactor apparatus diagram;
FIG. 2 is a flow chart of the preparation of the supported catalyst.
Detailed Description
In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The continuous condensation reaction process of ketene and crotonaldehyde comprises the following steps: as shown in figure 1, ketene and secondary condensation reaction liquid are continuously fed at the flow rate of 1000mL/min and 6mL/min, and are continuously mixed by a micro-interface unit I to obtain a micron-sized bubble system, the micron-sized bubble system enters a primary circulation absorption tower to be continuously condensed, the reaction is carried out at 58 ℃ for 2 hours, the condensation liquid after the reaction is pumped to a solvent recovery process (solvent evaporation process) at the flow rate of 7.5mL/min, and the balance of kettle liquid is maintained; the first-stage unreacted ketene is discharged from the upper part of the tower and enters a second-stage reaction system, the part of ketene (unreacted ketene) and crotonaldehyde preparation solution are continuously fed according to the flow of 600mL/min and 5.5mL/min, and are continuously mixed in a micro-interface unit II to obtain a micron-sized bubble system, the micron-sized bubble system enters a second-stage circulating absorption tower to be continuously condensed, the reaction is carried out at 35 ℃, the residence time is 1h, the condensed solution after the reaction is injected into the first-stage reaction system according to the flow of 6mL/min, the balance of kettle liquid is maintained, and tail gas is discharged into a tail gas incineration system.
The testing method comprises the following steps:
refractive index of the condensate: the refractive index of the water was 1.3330 at 20℃and 1.3325 at 25℃and 1.3305 at 40℃before measurement using an Abstract refractometer, the refractive index of which was calibrated using a calibration prism or water. The temperature should be adjusted to 20.+ -. 0.5 ℃ unless otherwise specified. When in measurement, the reading should be repeated three times, and the average value of the three readings is the refractive index of the test sample.
Determination of molecular weight in polyester: liquid chromatography.
Crotonaldehyde residue in polyester: gas chromatography.
Sorbic acid content in crude product: liquid chromatography.
Content of pear acid in hydrolysate: liquid chromatography.
Content of pear acid in the alcohol washing liquid: liquid chromatography.
Example 1
The preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 100g of zinc isooctanoate was dissolved in 800g of ethanol, to which 1000g of a zinc isooctanoate having a diameter of 1.5mm and a specific surface area of 130m was added 2 Immersing/g spherical alumina carrier for 48h, filtering, collecting solid, vacuum drying, and roasting for the first time (roasting for 4h at 300 ℃) to obtain the immobilized catalyst 1; then 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine is dissolved in 2097g of water, the immobilized catalyst 1 is added into the solution, the solution is filtered after being immersed for 48 hours, the solid is collected, and the solution is dried in vacuum and then is roasted for the second time (roasting for 4 hours at 650 ℃) to obtain the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
With the condensation reactor apparatus of fig. 1, the supported catalyst was packed in multiple layers in a condensation reactor: the loading mode of the solid catalyst adopts dense phase loading, and the solid catalyst is arranged at the middle lower part of the condensation reaction kettle and the middle part of the circulating absorption tower. The continuous condensation reaction process of ketene and crotonaldehyde is as described above, wherein the mass of the active component of the catalyst in the supported catalyst is 3% of the mass of crotonaldehyde, and the condensation liquid is taken after continuous reaction for 12 hours. The mass calculation method of the catalyst active components in the immobilized catalyst comprises the following steps: the mass of the immobilized catalyst is 1 that of the spherical alumina carrier.
And continuously feeding for 12 hours, taking 600g of condensed liquid (the condensed liquid is extracted from a primary circulation absorption tower, and testing the refractive index of the condensed liquid), carrying out negative pressure recovery on crotonaldehyde, maintaining the vacuum at-0.095 to-0.1 MPa, heating to the kettle temperature of 120-130 ℃, and maintaining the kettle temperature of 120-130 ℃ for 10-30 minutes to obtain a polyester crude product. And analyzing the residual mass of crotonaldehyde in the crude polyester product.
The polyester yield calculation method comprises the following steps: 70/112% by mass of polyester/(total mass of crotonaldehyde-residual mass of crotonaldehyde in crude polyester-mass of recovered crotonaldehyde) ×100%
The hydrolysis process of polyester is to take 100g of crude polyester, add 300g of 25% concentrated hydrochloric acid, raise the temperature to 80-90 ℃ for reaction for 1-2 h, lower the temperature to 25 ℃ for filtration, wash the crude polyester obtained by filtration with 70% (V/V) alcohol solution, and measure the sorbic acid content in alcohol washing liquid, the sorbic acid content in the crude polyester and the sorbic acid content in hydrolysate.
The sorbic acid yield is calculated by the following steps: (sorbic acid mass in crude product, sorbic acid mass in alcohol washing liquid, sorbic acid mass in hydrolysate)/polyester mass is 100%
The purification process of crude sorbic acid comprises the following steps: 200g of crude sorbic acid is heated by 800g of 70% (V/V) alcohol solution until the sorbic acid is completely dissolved, 15g of active carbon is added for decoloration for 30min, the mixture is filtered while the mixture is hot, the filtrate is cooled to 40 ℃ at a constant speed of 5-8 ℃/h, then cooled to 15-20 ℃ at a constant speed of 10-12 ℃/h, the mixture is filtered by suction, and the wet product is washed by 200g of water, and is dried to obtain a sorbic acid finished product.
Tested, after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.469, and the specific gravity is 0.980g/mL (12 ℃); the yield of the polyester calculated by crotonaldehyde is 98.0%; the sorbic acid yield after hydrolysis was 90.2% based on polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product of sorbic acid with 99.20 percent and 99.5 percent of transmittance.
Example 2
The preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 100g of zinc isovalerate was dissolved in 800g of ethanol, to which 1000g of a zinc isovalerate having a diameter of 1.5mm and a specific surface area of 130m were added 2 Spherical alumina support per gramThe solid is filtered after being immersed for 48 hours, the solid is collected, and is dried in vacuum and then is roasted for the first time (roasting for 4 hours at 300 ℃) to obtain the immobilized catalyst 1; then 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine is dissolved in 2097g of water, the immobilized catalyst 1 is added into the solution, the solution is filtered after being immersed for 48 hours, the solid is collected, and the solution is dried in vacuum and then is roasted for the second time (roasting for 4 hours at 650 ℃) to obtain the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
The solid supported catalyst is filled in a condensation reactor in a multi-layer manner, the mass of the active component of the catalyst in the solid supported catalyst is 3% of the mass of crotonaldehyde, and the condensation liquid is obtained after continuous reaction for 12 hours.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Tested, after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.469, and the specific gravity is 0.981g/mL (12 ℃); the yield of the polyester calculated by crotonaldehyde is 97.6%; the sorbic acid yield after hydrolysis was 90.8% based on polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with 99.15 percent of sorbic acid and 99.2 percent of transmittance.
Example 3
The preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 100g of zinc isooctanoate was dissolved in 800g of ethanol, to which 1000g of a zinc isooctanoate having a diameter of 1.5mm and a specific surface area of 130m was added 2 The spherical silica carrier per gram is immersed for 48 hours, filtered, the solid is collected, the first roasting (roasting for 4 hours at 300 ℃) is carried out after vacuum drying, the immobilized catalyst 1 is obtained, then 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine is dissolved in 2097g of water, the immobilized catalyst 1 is added into the water, the filtration is carried out after 48 hours of immersion, the solid is collected, and the vacuum drying is carried outAnd (3) performing a second roasting (roasting for 4 hours at 650 ℃) to obtain the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Tested, after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.469, and the specific gravity is 0.99g/mL (12 ℃); the yield of the polyester calculated by crotonaldehyde is 97.1%, and the yield of sorbic acid after hydrolysis is 90.0% based on the polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with the sorbic acid content of 99.35 percent and the transmittance of 99.2 percent.
Example 4
Referring to example 1, the only difference is in adjusting the loading parameters of the active ingredient: the mass ratio of the active component (zinc isooctanoate) to the solvent (ethanol) of the catalyst is 1:7 to 9, the mass ratio of the active component of the catalyst (zinc iso-octoate) to the spherical alumina carrier of the carrier is 0.1 to 0.5: 1. the dipping time is 45-50 h, the roasting temperature is 300-500 ℃ and the roasting time is 2-5 h; the ratio of the added mass of the catalyst active component (zinc isooctanoate) to the added mass of the polymerization inhibitor (1, 1-diphenyl-2-trinitrophenylhydrazine) is controlled to be 100:3 to 4; polymerization inhibitor loading parameters: the mass ratio of the polymerization inhibitor (1, 1-diphenyl-2-trinitrophenylhydrazine) to the solvent is 1-2: 1000. the mass ratio of the polymerization inhibitor to the immobilized catalyst 1 is 0.0025-0.02: 1. the dipping time is 45-50 h, the roasting temperature is 600-700 ℃ and the roasting time is 2-5 h.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Through testing, after the continuous feeding is carried out for 12 hours, the refractive index of the condensed liquid is 1.468-1.470, and the specific gravity of the condensed liquid is 0.97-1.00 g/mL (12 ℃). The yield of the polyester is 97-98% based on crotonaldehyde, and the molecular weight distribution in the polyester is more reasonable: the polyester has a molecular weight of less than 2000 and less than 15%, a molecular weight of 2000-8000 and more than 60%, and a molecular weight of more than 8000 and less than 25%; the yield of sorbic acid after hydrolysis is 90-91% based on polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with the sorbic acid content of 99.0-99.9% and the transmittance of 99.2-99.5%.
Comparative example 5
With reference to example 1, the only difference is that the addition amount of the catalyst active component (zinc iso-octoate) was adjusted, and the addition amounts of the support spherical alumina support and the polymerization inhibitor (1, 1-diphenyl-2-trinitrophenylhydrazine) and other parameters were controlled to be unchanged; so that the mass ratio of the catalyst active component (zinc isooctanoate) to the polymerization inhibitor (1, 1-diphenyl-2-trinitrophenylhydrazine) is 100:2 or 100:6.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
According to tests, when the ratio of the catalyst active component (zinc isooctanoate) to the polymerization inhibitor (1, 1-diphenyl-2-trinitrophenylhydrazine) is 100:2 by mass, the refractive index of the condensation liquid is 1.466 after 12 hours of continuous feeding, and the specific gravity of the condensation liquid is 0.98g/mL (12 ℃); the yield of polyester is 72.5% based on crotonaldehyde; the sorbic acid yield after hydrolysis was 80.9% based on polyester; the finished product sorbic acid content of the condensed liquid is 98.3 percent and the transmittance is 96.8 percent after the condensed liquid is subjected to solvent steaming, hydrolysis, decoloration and refining. When the ratio of the adding mass of the catalyst active component (zinc isooctanoate) to the adding mass of the polymerization inhibitor (1, 1-diphenyl-2-trinitrophenylhydrazine) is 100:6, the refractive index of the condensation liquid is 1.467 after continuous feeding for 12 hours, and the specific weight of the condensation liquid is 0.97g/mL (12 ℃); the yield of polyester, calculated as crotonaldehyde, was 77.3%; the sorbic acid yield after hydrolysis was 75.4% based on polyester; the finished product sorbic acid content of the condensed liquid is 98.8 percent after solvent evaporation, hydrolysis, decoloration and refining, and the transmittance is 92.4 percent.
Comparative example 6 (1, 1-diphenyl-2-trinitrophenylhydrazine impregnation and post-treatment procedure was omitted)
Referring to example 1, the only difference is that 1, 1-diphenyl-2-trinitrophenylhydrazine impregnation and post-treatment steps are omitted, specifically: the preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 100g of zinc isooctanoate was dissolved in 800g of ethanol, to which 1000g of a zinc isooctanoate having a diameter of 1.5mm and a specific surface area of 130m was added 2 And (3) immersing the spherical alumina carrier per gram for 48 hours, filtering, collecting solids, drying in vacuum, and roasting for the first time (roasting for 4 hours at 300 ℃) to obtain the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
The test shows that after the continuous feeding is carried out for 12 hours, the refractive index of the condensation liquid is 1.467, and the specific gravity of the condensation liquid is 0.99g/mL (12 ℃); the yield of the polyester is 77.1 percent based on crotonaldehyde; the sorbic acid yield after hydrolysis was 79.4% based on polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with the sorbic acid content of 98.4 percent and the transmittance of 95.4 percent.
Comparative example 7
With reference to example 1, the only difference is that zinc iso-octoate is simultaneously impregnated with 1, 1-diphenyl-2-trinitrophenylhydrazine and calcined, in particular:
the preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 100g of zinc isooctanoate and 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine are dissolved in 800g of ethanol, to which 1000g of a catalyst having a diameter of 1.5mm and a specific surface area of 130m are added 2 And (3) immersing the spherical alumina carrier per gram for 48 hours, filtering, collecting solids, drying in vacuum, and roasting (roasting for 4 hours at 300 ℃) to obtain the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Tested, after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.466, and the specific gravity is 1.13g/mL (12 ℃); the yield of the polyester calculated by crotonaldehyde is 88.1 percent; the sorbic acid yield after hydrolysis was 73.5% based on polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with 99% of sorbic acid and 97.4% of transmittance.
Comparative example 8
With reference to example 1, the only difference is that the loading order of zinc isooctanoate and 1, 1-diphenyl-2-trinitrophenylhydrazine is changed:
the preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine are dissolved in 2097g of water, to which 1000g of a catalyst having a diameter of 1.5mm and a specific surface area of 130m are added 2 Per g of spherical alumina carrier, impregnating for 48h and filteringCollecting solid, drying in vacuum, and roasting for the first time (roasting for 4 hours at 650 ℃) to obtain the immobilized catalyst 1; then 100g zinc iso-octoate is dissolved in 800g ethanol, the immobilized catalyst 1 is added, the mixture is immersed for 48 hours, then filtered, the solid is collected, dried in vacuum and roasted for the second time (roasting for 4 hours at 300 ℃) to obtain the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Tested, after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.467, and the specific gravity is 0.99g/mL (12 ℃); the yield of the polyester calculated by crotonaldehyde is 84.2%, the yield of sorbic acid after hydrolysis is 79.4% based on the polyester, and the finished product sorbic acid prepared by the condensation liquid after solvent evaporation, hydrolysis, decoloration and refining has the content of 98.5% and the transmittance of 95.7%.
Comparative example 9
With reference to example 1, the only difference is that the mass ratio of the catalyst active component zinc iso-octoate to the carrier is adjusted to be 0.05:1, specifically:
the preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 50g of zinc isooctanoate was dissolved in 400g of ethanol, to which 1000g of a zinc isooctanoate having a diameter of 1.5mm and a specific surface area of 130m were added 2 Immersing/g spherical alumina carrier for 48h, filtering, collecting solid, vacuum drying, and roasting for the first time (roasting for 4h at 300 ℃) to obtain the immobilized catalyst 1; then 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine is dissolved in 2097g of water, the immobilized catalyst 1 is added into the solution, the solution is filtered after being immersed for 48 hours, the solid is collected, and the solution is dried in vacuum and then is roasted for the second time (roasting for 4 hours at 650 ℃) to obtain the catalyst for continuous condensation of ketene and crotonaldehydeThe catalyst is immobilized in the reaction.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Tested, after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.466, and the specific gravity is 1.11g/mL (12 ℃); the yield of the polyester calculated by crotonaldehyde is 72.9%, the yield of sorbic acid after hydrolysis is 63.6% based on the polyester, and the finished product prepared by the condensation liquid through solvent evaporation, hydrolysis, decoloration and refining has 96.5% of sorbic acid content and 90% of transmittance.
Comparative example 10
Referring to example 1, the only difference is that the carrier impregnation time was changed:
the preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 100g of zinc isooctanoate was dissolved in 400g of ethanol, to which 1000g of a zinc isooctanoate having a diameter of 1.5mm and a specific surface area of 130m was added 2 Immersing/g spherical alumina carrier for 10h, filtering, collecting solid, vacuum drying, and roasting for the first time (roasting for 4h at 300 ℃) to obtain the immobilized catalyst 1; then 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine is dissolved in 2097g of water, the immobilized catalyst 1 is added into the solution, the solution is filtered after being immersed for 48 hours, the solid is collected, and the solution is dried in vacuum and then is roasted for the second time (roasting for 4 hours at 650 ℃) to obtain the immobilized catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Tested, the refractive index of the condensation liquid is 1.460, and the specific gravity is 0.91g/mL (12 ℃) after continuous feeding for 12 hours; the yield of the polyester calculated by crotonaldehyde is 79.2%, the yield of sorbic acid after hydrolysis is 67.1% based on the polyester, and the finished product prepared by the condensation liquid through solvent evaporation, hydrolysis, decoloration and refining has 97.9% of sorbic acid content and 97.4% of transmittance.
Comparative example 11
The preparation method of the immobilized catalyst for the continuous condensation reaction of ketene and crotonaldehyde comprises the following specific steps: 100g of zinc isooctanoate was dissolved in 800g of ethanol, to which 1000g of a zinc isooctanoate having a diameter of 1.5mm and a specific surface area of 130m was added 2 The solid was collected by immersing the spherical alumina carrier per gram for 48 hours, then conducting the first calcination (calcination at 600 ℃ C. For 4 hours) after vacuum drying to obtain the supported catalyst 1, then dissolving 3.15g of 1, 1-diphenyl-2-trinitrophenylhydrazine in 2097g of water, adding the supported catalyst 1 thereto, immersing for 48 hours, then conducting the filtration, collecting the solid, conducting the second calcination (calcination at 650 ℃ C. For 4 hours) after vacuum drying to obtain the supported catalyst used in the continuous condensation reaction of ketene and crotonaldehyde.
According to the process of example 1, using the condensation reactor apparatus of fig. 1, filling a plurality of layers of supported catalysts in a condensation reactor, wherein the mass of the active components of the catalysts in the supported catalysts is 3% of the mass of crotonaldehyde, continuously reacting for 12 hours, taking a condensation solution, and testing the refractive index and specific gravity of the condensation solution; and preparing a crude polyester product according to the process of the example 1, and calculating the yield of the polyester; and according to the process of example 1, hydrolyzing the polyester, purifying the crude sorbic acid to obtain a sorbic acid finished product, and calculating the yield of the polyester, the yield of the sorbic acid, the content of the sorbic acid finished product and the transmittance.
Tested, after 12 hours of continuous feeding, the refractive index of the condensed liquid is 1.469, and the specific gravity is 0.98g/mL (12 ℃); the crotonaldehyde is used for calculating the yield of the polyester to be 80.2%, the sorbic acid yield after hydrolysis is 77.3% based on the polyester, and the finished product sorbic acid content and the transmittance of the finished product prepared by evaporating solvent, hydrolyzing, decolorizing and refining the condensed liquid are 98.6%.
Example 12 optimization of the Mass ratio of the catalyst active Components to crotonaldehyde in the Supported catalyst
Referring to example 1, the difference was only that the mass ratio of the catalyst active component (zinc iso-octoate) to crotonaldehyde in the supported catalyst was adjusted to 0.05% to 7%. The polyester yield based on crotonaldehyde and sorbic acid yield after hydrolysis are shown in table 1 based on the variation of the mass ratio of the polyester with the catalyst active component in the supported catalyst to crotonaldehyde.
TABLE 1 polyester yield in terms of crotonaldehyde and sorbic acid yield after hydrolysis based on the variation of the mass ratio of the polyester to the catalyst active component in the supported catalyst to crotonaldehyde
Example 13
The supported catalyst in example 1 was continuously used for 27 days, then, the temperature was raised again for activation (under the protection of inert gas, the temperature was raised to 500 to 600 ℃ and the temperature was maintained for 0.5 to 1 hour), and then, the catalyst was continuously used for 12 hours, and then, the condensate was obtained.
The test shows that the refractive index of the condensed liquid is 1.469, and the specific gravity is 0.99g/mL (12 ℃); the yield of the polyester calculated by crotonaldehyde is 97.4%, and the yield of sorbic acid after hydrolysis is 90.2% based on the polyester; the condensation liquid is subjected to solvent evaporation, hydrolysis, decoloration and refining to obtain the finished product with 99.31 percent of sorbic acid and 99.3 percent of transmittance.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and 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 (8)
1. A method for preparing an immobilized catalyst for continuous condensation in sorbic acid preparation, which is characterized by comprising the following steps:
(1) Loading of the catalyst active components: dissolving a catalyst active component in a solvent A, wherein the mass ratio of the catalyst active component to the solvent A is 1 (7-9), so as to obtain a catalyst active component impregnating solution; placing the carrier in a catalyst active component impregnating solution according to the mass ratio of the catalyst active component to the carrier of (0.1-0.5): 1 for 45-50 hours, filtering, collecting solid, drying in vacuum, and roasting for the first time at the temperature of 300-500 ℃ for 2-5 hours to obtain the immobilized catalyst 1;
(2) Polymerization inhibitor loading: dissolving a polymerization inhibitor in a solvent B, wherein the mass ratio of the polymerization inhibitor to the solvent B is (1-2) 1000, so as to obtain a polymerization inhibitor impregnating solution; soaking the immobilized catalyst 1 in polymerization inhibitor impregnating solution for 45-50 h, filtering, collecting solids, drying in vacuum, and roasting for the second time at 600-700 ℃ for 2-5 h to obtain an immobilized catalyst for continuous condensation in sorbic acid preparation;
wherein the active component of the catalyst is organic acid zinc;
the polymerization inhibitor is 1, 1-diphenyl-2-trinitrophenylhydrazine;
the carrier is spherical alumina or spherical silica;
the ratio of the catalyst active component to the polymerization inhibitor is controlled to be 100 (3-4).
2. The method of claim 1, wherein the specific surface area of the carrier is 120-160 m 2 And/g, the total pore volume is more than or equal to 1.25mg/L.
3. The method of claim 1, wherein the carrier is spherical and has a diameter of 1.3-2.3 mm.
4. The method according to claim 1, wherein the solvent a is an organic solvent.
5. The method according to claim 1, wherein the mass ratio of the polymerization inhibitor to the supported catalyst 1 is (0.0025 to 0.02): 1.
6. The supported catalyst produced by the method of any one of claims 1 to 5.
7. Use of the supported catalyst of claim 6 in a continuous condensation reaction of ketene and crotonaldehyde in the preparation of sorbic acid.
8. The use according to claim 7, wherein the mass of the active component of the catalyst in the supported catalyst is 1-5% of the mass of crotonaldehyde.
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