CN117466860A - Method for preparing benzoic acid and co-producing epsilon-caprolactone through biomimetic catalysis and serialization - Google Patents
Method for preparing benzoic acid and co-producing epsilon-caprolactone through biomimetic catalysis and serialization Download PDFInfo
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- CN117466860A CN117466860A CN202311449911.8A CN202311449911A CN117466860A CN 117466860 A CN117466860 A CN 117466860A CN 202311449911 A CN202311449911 A CN 202311449911A CN 117466860 A CN117466860 A CN 117466860A
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- Prior art keywords
- caprolactone
- benzoic acid
- epsilon
- bimetallic
- quaternary
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 119
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 59
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 59
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 28
- 230000003592 biomimetic effect Effects 0.000 title claims abstract description 23
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 78
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000004032 porphyrins Chemical group 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000001802 infusion Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 12
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229940095102 methyl benzoate Drugs 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 48
- 238000007254 oxidation reaction Methods 0.000 abstract description 23
- 230000003647 oxidation Effects 0.000 abstract description 22
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 238000010813 internal standard method Methods 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000005086 pumping Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229920001610 polycaprolactone Polymers 0.000 description 6
- 239000004632 polycaprolactone Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000004966 inorganic peroxy acids Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000004967 organic peroxy acids Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- LSRPARCOXAUYNP-UHFFFAOYSA-N cyclohexylidene(oxido)oxidanium Chemical compound [O-][O+]=C1CCCCC1 LSRPARCOXAUYNP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
-
- 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
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization, which comprises the steps of carrying out catalytic oxidation on benzaldehyde and cyclohexanone by taking bimetallic quaternary porphyrin as a catalyst, dispersing the bimetallic quaternary porphyrin into a solvent, wherein the mass of the bimetallic quaternary porphyrin is 1-100 ppm; adding benzaldehyde and cyclohexanone into a reaction system, heating to 55-75 ℃, continuously introducing air, adjusting the air flow speed to 35-105mL/min, maintaining the set temperature, and obtaining the products benzoic acid and epsilon-caprolactone at the flow speed of 3-11mL/min of an infusion pump. The catalyst of the method has the advantages of high product selectivity, low cost, few byproducts, low reaction temperature, high productivity and the like. The invention provides a method for continuously preparing benzoic acid and co-producing epsilon-caprolactone, which has the advantages of high efficiency, good safety and environmental protection.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization.
Background
Benzoic acid is also called benzoic acid, is a scale-like or needle-like crystal with stable chemical structure, is not easy to oxidize, is aromatic acid with the simplest structure, belongs to unitary weak acid, and is an important organic chemical raw material and chemical reaction intermediate. Meta substitution, neutralization, salification, ester formation, etc. reactions can occur, and many derivatives can be derived. The application of the composition widely comprises food preservative, emulsion, toothpaste, jam or other food bacteriostat, alkyd resin modifier, dye intermediate, dye mordant, medicinal products, plasticizer, raw materials of the perfume, fiber intermediate and the like, and is also an important raw material for producing caprolactam and benzoic acid. The production method of benzoic acid mainly includes benzylidene trichlorohydrolysis method, phthalic anhydride decarboxylation method, toluene liquid phase air oxidation method, toluene potassium permanganate oxidation method, benzamide normal pressure microwave heating method and H 2 O 2 Catalytic oxidation process. In the synthesis method, a toluene liquid phase air oxidation method is mainly adopted; the benzyl trichloro hydrolysis method contains chlorine which is not suitable for the food industry; the phthalic anhydride decarboxylation method is not easy to refine, has high cost, and is only used in the drug products with small manufacturing dosage; the oxidation method of toluene potassium permanganate is widely used for synthesizing benzoic acid in a laboratory, has high cost and is not suitable for industrial production; the normal pressure microwave heating method of benzamide has not been reported at present; h 2 O 2 The catalytic oxidation method is gradually paid attention to by the green technology, but H 2 O 2 Limited oxidizing power and susceptibility to thermal decomposition, often requires the addition of excess H 2 O 2 So as to realize more conversion of benzaldehyde, thereby causing resource waste and potential safety hazard. Currently, O is utilized 2 Air is used as an oxygen source, the oxygen source is cheap, green and pollution-free, the reaction process has mild conditions and the reaction is efficient, and the method is feasible.
Epsilon-caprolactone is a nontoxic novel polyester monomer, and the polymerization product of epsilon-caprolactone is biodegradable Polycaprolactone (PCL). PCL and its copolymer obtained by copolymerizing epsilon-caprolactone or other monomers are high molecular materials with good biocompatibility, innocuity, biodegradability and good drug permeability, and can be better applied to biomedical engineering. Epsilon-caprolactone is an excellent organic solvent and an important organic synthesis intermediate, has good solubility for some insoluble resins, can be prepared by reacting with various compounds, has fine chemicals with unique properties, is mainly used as a monomer to prepare high-performance polycaprolactone, polycaprolactone polyol and polycaprolactone polyurethane, and is widely applied to biodegradable plastics, medical high polymer materials, synthetic leather, adhesives and the like. The current method is to synthesize epsilon-caprolactone by using cyclohexanone oxidation method, which can be divided into peroxy acid and H according to different oxidants 2 O 2 、O 2 Aldehydes, biological enzymes, and the like. The peroxy acid can be divided into inorganic peroxy acid and organic peroxy acid, the inorganic peroxy acid oxidizes the cyclohexanone B-V and rearranges and has the advantage of mild reaction and low cost, but the inorganic peroxy acid oxidizes the cyclohexanone and has the problems of low reaction rate, low product selectivity and the like; the cyclohexanone oxide by organic peroxy acid has the advantages of strong oxidizing capability, high reaction yield, low price, high product selectivity and the like, but the storage and transportation of the organic peroxy acid have great risks, and the concentration of byproduct acid in the rectification and purification process of the reaction liquid can catalyze the epsilon-caprolactone polymerization reaction. H 2 O 2 When cyclohexanone is oxidized, relatively clean and low cost, but H 2 O 2 The oxidation capability is limited, more oxidant is often needed to realize more cyclohexanone conversion, and water generated in the reaction can lead to epsilon-caprolactone hydrolysis, and meanwhile, the epsilon-caprolactone hydrolysis is severely decomposed by heating, so that potential safety hazards exist in the storage and transportation processes. The enzyme in the biological oxidation method has the characteristics of high efficiency and specificity, and the subsequent waste is easy to degrade, but the culture of the biological enzyme or other microorganisms has instability, high input cost and lower yield. O (O) 2 O in aldehyde co-oxidation system 2 Low cost, wide source, environment friendship, mild reaction condition,Safe raw materials, high reaction efficiency and the like. The Chinese patent No. 113461652B uses an intermittent reaction kettle as a reaction instrument, uses activated alumina loaded copper oxide as a catalyst, and introduces oxygen for 1-5 hours, thus being environment-friendly and almost free from byproducts. However, the intermittent reaction time is long, oxygen is introduced for a long time, unreacted oxygen is removed, and resource waste is caused.
The method can be divided into the following steps according to different reactors: batch reactors and continuous reactors, but batch reactors may be charged with air/O 2 The direct use of batch reactors has limited selectivity and conversion to oxidize cyclohexanone are low. Compared with the traditional process, the continuous process has the advantages of high product yield, high reaction rate, good process safety and the like. Aiming at the advantages and disadvantages of the existing production methods of the two substances, a method for preparing benzoic acid and co-producing epsilon-caprolactone by catalyzing the selective oxidation of benzaldehyde and cyclohexanone is urgently needed, and the method is mild in reaction condition, high in selectivity of benzoic acid and epsilon-caprolactone, few in byproducts and environment-friendly.
Disclosure of Invention
Aiming at the defects of the benzoic acid and epsilon-caprolactone generation method in the background technology, the invention mainly solves the technical problem of providing a method for preparing benzoic acid and epsilon-caprolactone in a biomimetic catalysis continuous mode, wherein air is used as an oxidant, bimetallic porphyrin is used as a catalyst, and the unique macrocyclic structure and the capability of activating molecular oxygen are utilized. The reaction system has the characteristics of easy operation, mild reaction conditions, high catalytic efficiency and the like, and the selectivity of benzoic acid and epsilon-caprolactone is high, few byproducts are produced, and the reaction can be carried out at a lower reaction temperature.
The invention aims at realizing the following scheme:
a method for preparing benzoic acid and co-producing epsilon-caprolactone through biomimetic catalysis and serialization comprises the following steps:
(1) Preparing a raw material, wherein the raw material comprises cyclohexanone, bimetallic tetraporphyrin (wherein metals are single bimetallic or different bimetallic combinations of iron, manganese, nickel, copper, zinc, cobalt and the like), and a solvent (the solvent is one or mixed solvents of acetonitrile, benzonitrile, dichloromethane, 1, 2-dichloroethane, N, N-dimethylformamide, ethyl acetate, sec-butyl acetate and methyl benzoate);
(2) Reacting in a screw bottle, dispersing bimetallic quaternary porphyrin into methyl benzoate solvent, adding benzaldehyde and cyclohexanone, and sealing the system;
(3) Oxygen or air is introduced to react in a continuous method to prepare the benzoic acid and epsilon-caprolactone.
According to the invention, the simple metalloporphyrin structure is shown in the following figure (I):
in the step (1), the weight of the bimetallic porphyrin metal is 1-100 ppm, preferably 30-70 ppm;
in step (3), the reaction temperature is 40-80 ℃, preferably 55-75 ℃; the gas flow rate is 20-120mL/min, preferably 35-105mL/min; the flow rate of the infusion pump is 1-12mL/min, and the flow rate of the infusion pump is 3-11mL/min.
The oxidant is oxygen, and the oxygen is oxygen in air.
The analysis method of the reaction result comprises the following steps: after the reaction, a proper amount of reaction solution was taken and analyzed. And (3) taking naphthalene as an internal standard, performing gas chromatographic analysis, and calculating the conversion rate of benzaldehyde and cyclohexanone and the selectivity of benzoic acid and epsilon-caprolactone.
The invention takes bimetallic quaternary porphyrin as a catalyst to prepare benzoic acid and coproduce epsilon-caprolactone by synergistic catalytic oxidation, and the catalyst bimetallic quaternary porphyrin has better activity and selectivity, the highest benzaldehyde conversion rate can reach 20-50%, the highest benzoic acid selectivity can reach 80-99%, the highest cyclohexanone conversion rate can reach 20-50%, and the highest epsilon-caprolactone selectivity can reach 80-99%.
The beneficial effects of the invention are as follows: the invention relates to a method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention has high conversion rate of reaction substrates, high selectivity of products, mild reaction conditions and lower energy consumption.
2. The invention adopts bimetallic quaternary porphyrin as a catalyst and oxygen as an oxidant to directly oxidize benzaldehyde and cyclohexanone by a one-step method, and has the advantages of simple process and mild reaction conditions.
3. The bimetallic quaternary porphyrin used in the invention has high catalytic activity and excellent suitability for reaction, and the reaction efficiency can be greatly improved only by the ppm level.
4. The catalyst used in the invention has the advantages of small dosage, simple process, green and safe, and good industrial application prospect.
Drawings
FIG. 1 is a chromatogram of a line sample for analysis of a product by gas chromatography in example 1.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to enable those skilled in the art to more readily understand the advantages and features of the invention and to make a clear and concise definition of the scope of the invention.
Example 1
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding 12.4ppm of bimetallic quaternary porphyrin catalyst into a 500mL screw bottle, adding 296.7mL of acetonitrile as a solvent, adding 1mol of benzaldehyde and 1mol of cyclohexanone, taking air with a gas flow rate of 35mL/min as an oxygen source, and pumping the reaction liquid with an infusion pump flow rate of 3 mL/min. Naphthalene is used as an internal standard substance, the naphthalene is placed in a low-temperature reactor after continuous reaction at 35 ℃ so as to reduce the temperature of a reaction liquid, a low-boiling-point vaporized organic matter is liquefied into a liquid phase, a gas chromatographic analysis product is used for online sampling, and the product is quantified by adopting an internal standard method, wherein a specific chromatogram is shown in figure 1.
The results show that the conversion rate of benzaldehyde is 21%, the selectivity of the product benzoic acid is 83%, the conversion rate of cyclohexanone is 20%, and the selectivity of the product epsilon-caprolactone is 82%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 2
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding 12.4ppm of a bimetallic quaternary porphyrin catalyst into a 500mL screw bottle, adding 186.3mL of benzonitrile as a solvent, adding 2mol of benzaldehyde, 1mol of cyclohexanone, taking air with a gas flow rate of 45mL/min as an oxygen source, and pumping the reaction liquid with a transfusion pump flow rate of 4 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 40 ℃, the gas chromatograph is used for analyzing the product by on-line sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 22%, the selectivity of the product benzoic acid is 84%, the conversion rate of cyclohexanone is 21%, and the selectivity of the product epsilon-caprolactone is 85%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 3
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding 12.4ppm of the required bimetallic quaternary porphyrin catalyst into a 500-mL screw bottle, adding 75.9mL of dichloromethane as a solvent, adding 3mol of benzaldehyde, 1mol of cyclohexanone, taking air with a gas flow rate of 55mL/min as an oxygen source, and pumping the reaction liquid with an infusion pump flow rate of 5 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 50 ℃, the gas chromatograph is used for analyzing the product by on-line sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 24%, the selectivity of the product benzoic acid is 85%, the conversion rate of cyclohexanone is 24%, and the selectivity of the product epsilon-caprolactone is 87%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 4
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding 12.4ppm of the needed bimetallic quaternary porphyrin catalyst into a 500mL screw bottle, adding 232.8mL of 1, 2-dichloroethane as a solvent, adding 2mol of benzaldehyde and 0.5mol of cyclohexanone, taking air with the gas flow rate of 65mL/min as an oxygen source, and pumping the reaction liquid with the flow rate of an infusion pump of 6 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 55 ℃, on-line sampling is carried out, gas chromatography is used for analyzing products, and an internal standard method is adopted for quantifying the products.
The results show that the conversion rate of benzaldehyde is 26%, the selectivity of the product benzoic acid is 86%, the conversion rate of cyclohexanone is 27%, and the selectivity of the product epsilon-caprolactone is 88%, which shows that the oxidation catalytic method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 5
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding 12.4ppm of the required bimetallic quaternary porphyrin catalyst into a 500mL screw bottle, adding 177.6mLN, N-dimethylformamide as a solvent, adding 2.5mol of benzaldehyde and 0.5mol of cyclohexanone, taking air with a gas flow rate of 75mL/min as an oxygen source, and pumping the reaction liquid with a transfer pump flow rate of 7 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 65 ℃, the gas chromatography is used for analyzing the product by online sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 28%, the selectivity of the product benzoic acid is 88%, the conversion rate of cyclohexanone is 27%, and the selectivity of the product epsilon-caprolactone is 90%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 6
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding a bimetallic quaternary porphyrin catalyst required by 12.4ppm into a 500mL screw bottle, adding ethyl acetate as a solvent, adding 2mol of benzaldehyde and 1mol of cyclohexanone, wherein the total volume is 500mL after the ratio of reactants to the solvent is 1:1, taking air with the gas flow rate of 85mL/min as an oxygen source, and pumping the reaction liquid with the flow rate of an infusion pump of 8 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 70 ℃, the gas chromatograph is used for analyzing the product by on-line sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 28%, the selectivity of the product benzoic acid is 89%, the conversion rate of cyclohexanone is 29%, and the selectivity of the product epsilon-caprolactone is 91%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 7
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding a bimetallic quaternary porphyrin catalyst required by 12.4ppm into a 500mL screw bottle, adding methyl benzoate as a solvent, adding 2mol of benzaldehyde and 1mol of cyclohexanone, wherein the total volume is 500mL after the ratio of reactants to the solvent is 1.5:1, taking air with the gas flow rate of 85mL/min as an oxygen source, and pumping the reaction liquid with the flow rate of an infusion pump of 7 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 60 ℃, the gas chromatograph is used for analyzing the product by on-line sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 30%, the selectivity of the product benzoic acid is 90%, the conversion rate of cyclohexanone is 30%, and the selectivity of the product epsilon-caprolactone is 91%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 8
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding a bimetallic quaternary porphyrin catalyst required by 12.4ppm into a 500mL screw bottle, adding sec-butyl acetate as a solvent, adding 2mol of benzaldehyde and 1mol of cyclohexanone, wherein the total volume is 500mL after the ratio of reactants to the solvent is 1.75:1, taking air with the gas flow rate of 95mL/min as an oxygen source, and pumping the reaction liquid with the flow rate of an infusion pump of 8 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 80 ℃, the gas chromatography is used for analyzing the product by online sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 29%, the selectivity of the product benzoic acid is 94%, the conversion rate of cyclohexanone is 28%, and the selectivity of the product epsilon-caprolactone is 93%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 9
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding a bimetallic quaternary porphyrin catalyst required by 12.4ppm into a 500mL screw bottle, adding methyl benzoate as a solvent, adding 2mol of benzaldehyde and 1mol of cyclohexanone, wherein the total volume is 500mL after the ratio of reactants to the solvent is 2:1, taking air with the gas flow rate of 105mL/min as an oxygen source, and pumping the reaction liquid with the flow rate of an infusion pump of 9 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 90 ℃, the gas chromatography is used for analyzing the product by online sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 26%, the selectivity of the product benzoic acid is 95%, the conversion rate of cyclohexanone is 27%, and the selectivity of the product epsilon-caprolactone is 96%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Example 10
A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization comprises the following steps:
adding 12.4ppm of a needed bimetallic quaternary porphyrin catalyst into a 500mL screw bottle, adding acetonitrile, benzonitrile, dichloromethane, 1, 2-dichloroethane, N, N-dimethylformamide, ethyl acetate, sec-butyl acetate and methyl benzoate as solvents, adding 2mol of benzaldehyde and 1mol of cyclohexanone, wherein the ratio of reactants to the solvents is 2.5:1, the total volume is 500mL, the air with the gas flow rate of 85mL/min is taken as an oxygen source, and the reaction liquid is pumped into the bottle by an infusion pump with the flow rate of 7 mL/min. Naphthalene is used as an internal standard, the naphthalene is placed in a low-temperature reactor after continuous reaction at 95 ℃, the gas chromatography is used for analyzing the product by online sampling, and the internal standard method is adopted for quantifying the product.
The results show that the conversion rate of benzaldehyde is 23%, the selectivity of the product benzoic acid is 99%, the conversion rate of cyclohexanone is 25%, and the selectivity of the product epsilon-caprolactone is 99%, which shows that the oxidation catalysis method used in the invention can be used for efficiently preparing benzoic acid from benzaldehyde and co-producing epsilon-caprolactone.
Claims (6)
1. A method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalysis and serialization is characterized in that bimetallic quaternary porphyrin is dispersed into a solvent, wherein the mass of the bimetallic quaternary porphyrin is 1-100 ppm; after reactants benzaldehyde and cyclohexanone are added according to the mol ratio of 1:1-5:1, air with the flow rate of 35-105mL/min is continuously introduced, and the reaction is carried out at the set temperature of 35-95 ℃ and the flow rate of an infusion pump of 3-11mL/min, so that the products benzoic acid and epsilon-caprolactone are obtained.
2. The method for preparing benzoic acid and co-producing epsilon-caprolactone by biomimetic catalytic serialization according to claim 1, wherein the structure of the bimetallic quaternary porphyrin is shown in formula 1:
wherein M is 1 Is one of iron, manganese, nickel, copper, zinc and cobalt;
M 2 is one of iron, manganese, nickel, copper, zinc and cobalt.
3. The method for preparing the benzoic acid co-production epsilon-caprolactone by biomimetic catalytic serialization according to claim 1, wherein the solvent is one or a mixed solvent of acetonitrile, benzonitrile, dichloromethane, 1, 2-dichloroethane, N, N-dimethylformamide, ethyl acetate, sec-butyl acetate and methyl benzoate.
4. The method for preparing benzoic acid and epsilon-caprolactone by biomimetic catalytic serialization according to claim 1, wherein the reaction temperature is 35-75 ℃.
5. The method for preparing benzoic acid and epsilon-caprolactone by biomimetic catalytic serialization according to claim 1, wherein the adding amount of the catalyst bimetallic quaternary porphyrin is 10-80 ppm.
6. The method for preparing benzoic acid and epsilon-caprolactone by biomimetic catalysis and serialization according to claim 1, wherein the bimetallic quaternary porphyrin is purchased from Changsha material technology Co.
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