CN114230458A - Method for separating alcohol ketonic acid complex oxidation product generated by air catalytic oxidation of cyclohexane - Google Patents
Method for separating alcohol ketonic acid complex oxidation product generated by air catalytic oxidation of cyclohexane Download PDFInfo
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- cyclohexanone
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 99
- 230000003647 oxidation Effects 0.000 title claims abstract description 84
- 239000002253 acid Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 216
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000047 product Substances 0.000 claims abstract description 58
- 238000005886 esterification reaction Methods 0.000 claims abstract description 45
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 10
- -1 ester compounds Chemical class 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000001361 adipic acid Substances 0.000 claims description 36
- 235000011037 adipic acid Nutrition 0.000 claims description 36
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 28
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 24
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 23
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 23
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 18
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 18
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 18
- 229940005605 valeric acid Drugs 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 claims description 11
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000001384 succinic acid Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- CVKFXBUVLBFHGO-UHFFFAOYSA-N cobalt 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Co].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 CVKFXBUVLBFHGO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000539 dimer Substances 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- ZWYCMWUUWAFXIA-UHFFFAOYSA-N iron(2+);5,10,15,20-tetraphenylporphyrin-22,23-diide Chemical compound [Fe+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C2=CC=C([N-]2)C(C=2C=CC=CC=2)=C2C=CC3=N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 ZWYCMWUUWAFXIA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- IPFASKMZBDWRNG-UHFFFAOYSA-N manganese 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Mn].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 IPFASKMZBDWRNG-UHFFFAOYSA-N 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 9
- 230000032050 esterification Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 150000004032 porphyrins Chemical class 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- RPYFZMPJOHSVLD-UHFFFAOYSA-N copper vanadium Chemical group [V][V][Cu] RPYFZMPJOHSVLD-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002576 ketones Chemical class 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
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- 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
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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- 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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- C07C2601/14—The ring being saturated
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Abstract
The invention discloses a method for separating alcohol ketonic acid complex oxidation products generated by air catalytic oxidation of cyclohexane, which is characterized in that after the cyclohexane is subjected to catalytic air oxidation, the oxidation reaction products are directly subjected to esterification reaction, mixed acid in the oxidation products is selectively converted into ester compounds, the esterification reaction products are separated by means of reduced pressure distillation, rectification and the like, and high-purity cyclohexanol, cyclohexanone and various ester compounds can be simultaneously obtained.
Description
Technical Field
The invention relates to a cyclohexane oxidation method, in particular to a method for efficiently separating alcohol ketonic acid complex oxidation products generated by catalytic oxidation of cyclohexane in air and oxidation, and belongs to the technical field of cyclohexane oxidation.
Background
Air oxidation of cyclohexane is an important process for the production of cyclohexanol, cyclohexanone, adipic acid, glutaric acid, succinic acid and valeric acid. Wherein, cyclohexanone and adipic acid are main raw materials for preparing nylon 6 and nylon 66 respectively, and cyclohexanol and glutaric acid, succinic acid and valeric acid are important basic chemical products. However, the physicochemical properties of cyclohexanol and cyclohexanone are very similar, and the physicochemical properties of adipic acid, glutaric acid, succinic acid and valeric acid are also very similar, and the traditional chemical separation process is difficult to be used for separating cyclohexanol and cyclohexanone or for separating a mixed carboxylic acid system of adipic acid, glutaric acid, succinic acid and valeric acid, while the traditional chemical separation process is more difficult to be applied to a complex product system of cyclohexanol, cyclohexanone, adipic acid, glutaric acid, succinic acid and valeric acid which are air oxidation products of cyclohexane for separating. In order to avoid the air oxidation of cyclohexane to present a complex product system which is difficult to separate, the patent technologies of US3530185A, US3957867A and the like disclose that the oxidation product is free of carboxylic acid products and only contains a mixture of cyclohexanol and cyclohexanone by controlling the lower conversion (less than 4%) of the air oxidation of cyclohexane, and cyclohexanol is converted into cyclohexanone by subjecting the mixture of cyclohexanol and cyclohexanone to catalytic dehydrogenation treatment. This process does not, however, lead to cyclohexanol products. Although the separation of single cyclohexanol and cyclohexanone from a mixture of cyclohexanol and cyclohexanone can be achieved by a high-precision rectification method, the energy consumption is particularly high and is not suitable for practical application in large-scale industry. The further oxidation of the mixture of cyclohexanol and cyclohexanone can be changed into a carboxylic acid mixed product with adipic acid as a main product, and the mixed carboxylic acid in an aqueous phase system can be separated from the mixed carboxylic acid by a multi-step recrystallization method, wherein the adipic acid with large difference in solubility and high content can be separated from the mixed carboxylic acid. The industry has taken advantage of this phenomenon to develop a more mature process for the production of adipic acid: 50% -60% of excessive nitric acid is used for oxidizing KA oil at 60-80 ℃ and 0.1-0.4 MPa in a two-stage reactor connected in series, a catalyst is a copper-vanadium system (0.1% -0.5% of copper and 0.1% -0.2% of vanadium), the yield is 92% -96% of a theoretical value, after a reactant is steamed out of the nitric acid, high-purity adipic acid can be obtained through twice crystallization and refining, although the yield of adipic acid obtained through oxidation of a mixture of cyclohexanol and cyclohexanone is high, the yield and the selectivity of cyclohexanol and cyclohexanone obtained through oxidation of cyclohexane are low, and therefore, the utilization rate of the cyclohexane raw material and an intermediate product is low in the process of performing two-step oxidation reaction on the cyclohexane raw material to the adipic acid. In recent years, there are reports related to the preparation of KA oil and adipic acid by directly subjecting cyclohexane to air catalytic oxidation, for example, chinese patent (CN1850756A) discloses that 1 to 100PPM metalloporphyrin is added to cyclohexane raw material as a catalyst, and 1 to 20atm of air or oxygen-enriched air or oxygen-depleted air is introduced, and the mixture of cyclohexanol, cyclohexanone and adipic acid with a content of more than 90% can be obtained by reacting for 45 to 120 minutes at 120 to 160 ℃. In fact, when adipic acid is produced by these techniques, in addition to adipic acid, a small amount of succinic acid, valeric acid, glutaric acid, etc. is present, and the oxidation product is a complex mixed carboxylic acid system. The complex mixed product system is a non-aqueous system, and the physical and chemical properties of the substances such as solubility, acidity and the like are relatively small, so that the separation is difficult. This patent does not disclose a process and method for separating cyclohexanol, cyclohexanone and adipic acid from a complex product system of air oxidation of cyclohexane. Chinese patent (CN121892C) discloses a technology for producing adipic acid by catalyzing cyclohexane, cyclohexanol, cyclohexanone and cyclohexene single raw materials or a mixture of cyclohexanol and cyclohexanone by using 1-100 PPM monometallic porphyrin or mu-oxygen bimetallic porphyrin or a mixed catalyst formed by the monometallic porphyrin or the mu-oxygen bimetallic porphyrin and transition metal salt or oxide at the temperature of 1-20atm and 50-200 ℃, and the technology provides a scheme for producing adipic acid by oxidizing cyclohexane or cyclohexane oxidation products, namely cyclohexanol and cyclohexanone. Chinese patent (CN101337879A) discloses that cyclohexane is oxidized for 45-120 minutes by introducing 5-12 atm of air or oxygen-enriched and oxygen-deficient air under the action of 1-50 PPM monometallic porphyrin or mu-oxygen bimetallic porphyrin or mixed catalyst formed by the monometallic porphyrin or the mu-oxygen bimetallic porphyrin and transition metal salt or oxide, controlling the reaction temperature to be 140-160 ℃; enabling the oxidation reaction mixture to enter a flash separator, and flashing at the temperature of 78-155 ℃ and under the pressure of 0.1-1.0 atm to enable low-boiling-point products of cyclohexane, cyclohexanol and cyclohexanone to become gas, so that the gas is separated from adipic acid with the content of more than 80%; and continuously and circularly oxidizing the low-boiling-point product, and separating and purifying the high-boiling-point oxidation product to obtain a refined adipic acid product. The method has the advantages that the conversion rate of the cyclohexane can reach 95 percent through the recycling of the cyclohexane and the secondary oxidation of the cyclohexanol and the cyclohexanone, but because of the deep oxidation phenomenon in the secondary oxidation of the cyclohexanol and the cyclohexanone, the yield of the adipic acid is only 70 percent, other cyclohexane oxidation products of succinic acid, glutaric acid, valeric acid and the like are close to 25 percent, and a method for purifying and separating mixed acid is not provided in the patent technology, wherein only high-content adipic acid products are separated.
Technical content
Aiming at the defects of the existing cyclohexane oxidation product separation technology, the invention aims to provide a method for realizing efficient air catalytic oxidation of cyclohexane and completely separating complex oxidation products such as alcohol, ketone, acid and the like to obtain cyclohexanol, cyclohexanone and various ester compounds with higher additional values.
In order to achieve the technical purpose, the invention provides a method for separating a complex oxidation product of ketonic acid of alcohol generated by air catalytic oxidation of cyclohexane, which comprises the following steps:
1) performing air oxidation reaction on cyclohexane under the catalytic action to obtain a cyclohexane solution containing cyclohexanol, cyclohexanone and mixed acid; the mixed acid comprises valeric acid, adipic acid, succinic acid and glutaric acid;
2) the cyclohexane solution containing cyclohexanol, cyclohexanone and mixed acid is subjected to flash evaporation to recover cyclohexane, and the cyclohexane returns to the air oxidation reaction process, so that a mixture containing cyclohexanol, cyclohexanone and mixed acid is obtained;
3) carrying out esterification reaction on a mixture containing cyclohexanol, cyclohexanone and mixed acid and methanol, carrying out reduced pressure distillation separation on an esterification reaction product, distilling and recovering the methanol, returning to the esterification reaction process, and carrying out sectional distillation separation to obtain methyl valerate, a mixture of cyclohexanol and cyclohexanone and mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate;
4) oxidizing the cyclohexanol and cyclohexanone mixture with a hydrogen peroxide solution to generate cyclohexanone precipitate, carrying out solid-liquid separation to obtain cyclohexanone peroxide crystals and cyclohexanol, hydrolyzing the cyclohexanone peroxide to obtain a mixed solution of cyclohexanone and water, standing for layering, and collecting upper-layer cyclohexanone; or, carrying out catalytic dehydrogenation on the cyclohexanol and cyclohexanone mixture to obtain cyclohexanone; or, carrying out catalytic oxidation on the cyclohexanol and cyclohexanone mixture to obtain mixed acid, and returning to the esterification reaction process;
5) and (3) carrying out vacuum rectification on the mixed ester to respectively obtain dimethyl adipate, dimethyl succinate and dimethyl glutarate products.
As a preferred scheme, the air oxidation reaction of cyclohexane under the catalysis is carried out under the following conditions: the temperature is 150-170 ℃, the time is 1.5-2.5 hours, the air pressure is 14-16 atm, metalloporphyrin is used as a catalyst, or metalloporphyrin and transition metal oxide are combined to be used as a catalyst, and the concentration of the catalyst in cyclohexane is 1-50 PPM. Under the preferable reaction conditions, higher cyclohexane conversion rate can be obtained, and the cyclohexane conversion rate can be controlled to be 20-40%.
As a further preferable mode, the metalloporphyrin compound is at least one of iron tetraphenylporphyrin, iron tetra-p-chlorophenylporphyrin, cobalt tetraphenylporphyrin, copper tetraphenylporphyrin, manganese tetraphenylporphyrin, iron mu-dimer tetraphenylporphyrin, cobalt tetra-p-chlorophenylporphyrin, copper tetra-p-chlorophenylporphyrin, manganese tetra-p-chlorophenylporphyrin, and iron mu-dimer tetra-p-chlorophenylporphyrin; the transition metal salt is at least one of acetate or naphthenate of cobalt and/or manganese. The catalysts are common catalysts which can be used for air catalytic oxidation of cyclohexane in the prior art, most preferably metalloporphyrin compounds, while the single use effect of common transition metal salts is poor, and the catalysts need to be matched with a proper proportion of metalloporphyrin compounds, for example, the proportion of the metalloporphyrin catalysts is not less than 10%, preferably not less than 30%.
As a preferred scheme, the conditions for recovering cyclohexane from a cyclohexane solution containing cyclohexanol, cyclohexanone and mixed acid by flash evaporation are as follows: the temperature is 70-90 ℃, and the pressure is 0.5-1 atm. The selective recovery of cyclohexane can be controlled under preferred conditions.
As a preferred scheme, the esterification reaction condition of the mixture containing cyclohexanol, cyclohexanone and mixed acid and methanol is as follows: the molar ratio of the methanol to the mixed acid is 1-2: 1, and the mixed acid reacts for 6-7 hours at the temperature of 70-90 ℃ in the presence of a concentrated sulfuric acid catalyst, wherein the mixed acid is measured by the molar amount of carboxyl groups contained in the mixed acid. Under the preferable reaction condition, higher esterification reaction efficiency can be obtained, and the esterification conversion rate of the mixed acid can reach 95-98%.
As a preferred scheme, the conditions of separating the esterification reaction product by reduced pressure distillation are as follows: distilling and recovering methanol under the conditions of the pressure of 80-90 kPa and the temperature of 45-55 ℃, distilling and recovering methyl valerate under the conditions of the pressure of 30-40 kPa and the temperature of 60-70 ℃, distilling and recovering a mixture of cyclohexanol and cyclohexanone under the conditions of the pressure of 10-20 kPa and the temperature of 70-90 ℃, and finally distilling and recovering mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate under the conditions of the pressure of 1.7-5 kPa and the temperature of 90-115 ℃. The primary separation of esterification reaction products can be realized by strictly controlling the reduced pressure distillation conditions, high-purity methanol and methyl valerate products can be obtained, dimethyl adipate, dimethyl succinate, dimethyl glutarate and the like are recovered in a mixed ester form, and cyclohexanol and cyclohexanone are also recovered in a mixture form.
Preferably, the hydrogen peroxide solution is dropwise added into the mixture of cyclohexanol and cyclohexanone, the mixture is stirred and reacted at the temperature of 15-40 ℃, cyclohexanone peroxide precipitate is separated out, and the reaction is stopped until no precipitate is separated out. The selective oxidation of cyclohexanone can be realized by the hydrogen peroxide oxidation method to quantitatively generate cyclohexanone peroxide, and the solubility of cyclohexanone peroxide in cyclohexanol is low, so that the cyclohexanone peroxide and cyclohexanol can be separated by simple filtering separation.
As a preferred scheme, the hydrolysis reaction process is as follows: and (3) putting cyclohexanone peroxide into water, heating to 60-80 ℃ and carrying out hydrolysis reaction. The cyclohexanone peroxide can be regenerated into cyclohexanone by heating in a large amount of water, and the cyclohexanone has low water solubility and density less than that of water, so that oil-water separation can be realized.
As a preferred scheme, the conditions of the mixed ester by vacuum rectification are as follows: the number of tower plates is more than 20, and the rectification process is as follows: the pressure is 1.5-2 kPa, the temperature of the bottom of the rectifying still is higher than 115 ℃, and dimethyl succinate, dimethyl glutarate and dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still. The number of the trays is preferably 25 to 35. The preferable temperature of the bottom of the kettle is 120-135 ℃. The physical and chemical properties of the dimethyl succinate, the dimethyl glutarate and the dimethyl adipate are relatively similar, and products of the dimethyl succinate, the dimethyl glutarate and the dimethyl adipate with the average purity of more than 99 percent can be respectively obtained by performing pressure rectification under the optimal condition.
As a preferred scheme, a mixture of cyclohexanol and cyclohexanone is subjected to catalytic dehydrogenation at 200-210 ℃ and 0.01-0.1 MPa under the action of a palladium-carbon catalyst to obtain a cyclohexanone product; the dehydrogenation reaction of cyclohexanol is conventional in the prior art, and under the optimized reaction condition, the high-efficiency selective dehydrogenation and oxidation of cyclohexanol can be controlled, and the conversion rate reaches more than 98%. The palladium on carbon catalyst is used in catalytic amounts, as is well known in the art.
As a preferable scheme, the mixture of cyclohexanol and cyclohexanone is reacted for 60-120 minutes under the catalysis of metalloporphyrin under the conditions that the air pressure is 8-15 atm and the temperature is 140-160 ℃, so as to obtain the mixed acid. Under the optimized reaction condition, the cyclohexanol and cyclohexanone can be simultaneously and efficiently oxidized to obtain a mixed acid product taking adipic acid as a main component, wherein the adipic acid proportion is up to more than 70%, and the mixed acid product also comprises products such as valeric acid, succinic acid, glutaric acid and the like.
The metalloporphyrin catalyst is at least one of iron tetraphenylporphyrin, iron tetra-p-chlorophenylporphyrin, cobalt tetraphenylporphyrin, copper tetraphenylporphyrin, manganese tetraphenylporphyrin, iron mu-dimer tetraphenylporphyrin, cobalt tetra-p-chlorophenylporphyrin, copper tetra-p-chlorophenylporphyrin, manganese tetra-p-chlorophenylporphyrin and iron mu-dimer tetra-p-chlorophenylporphyrin.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) the technical scheme of the invention realizes the high-efficiency catalytic oxidation of cyclohexane, and the highest conversion rate of the cyclohexane can reach 40%.
2) The technical scheme of the invention realizes the internal circulation of the raw materials such as cyclohexane and methanol and the intermediate products such as cyclohexanol, cyclohexanone and mixed acid, improves the utilization rate of the raw materials or the intermediate products, and reduces the waste discharge.
3) The technical scheme of the invention realizes the high-efficiency and thorough separation of the cyclohexane complex oxidation product, can simultaneously obtain high-purity cyclohexanol, cyclohexanone and various ester compounds, and overcomes the technical problems that the prior art is difficult to separate the cyclohexane oxidation product and obtains fewer products.
4) The technical scheme of the invention greatly simplifies the separation process of the cyclohexane oxidation product by adopting the technical means of esterification, distillation, rectification and the like on the oxidation product, particularly for the separation of mixed carboxylic acid, the separation is generally carried out by a recrystallization method by utilizing the solubility difference of the carboxylic acid in the prior art, or the separation is carried out by a method of adjusting acidity by utilizing the acidity difference of the carboxylic acid, the processes are difficult to adapt to the separation process of the mixed carboxylic acid with the annual yield of more than 10 ten thousand tons in industry, the solubility difference of the mixed acid is small, the acidity difference is small, and the separation is easy to carry out by the technical means of distillation, rectification and the like after the esterification.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane comprises the following steps:
1) adding a cyclohexane raw material into a reaction kettle, adding 20PPM cobalt tetraphenylporphyrin, carrying out catalytic oxidation reaction at the temperature of 155 ℃, the time of 2.5 hours and the air pressure of 14atm to obtain a mixed solution of cyclohexanol, cyclohexanone, valeric acid, adipic acid, succinic acid, glutaric acid and cyclohexane, wherein the discharged gas mainly comprises nitrogen, and the discharged gas is cooled and recycled, so that the cyclohexane conversion rate is 30%;
2) flashing the mixed solution at 75 ℃ and under the pressure of 0.5atm, cooling and recovering the obtained cyclohexane, returning the cyclohexane to the oxidation process for recycling, and obtaining the rest of the mixture containing cyclohexanol, cyclohexanone and mixed acid;
3) carrying out esterification reaction on the mixture and methanol, wherein the molar ratio of the methanol to the mixed acid in the mixture is 1.2:1 (measured by the molar amount of carboxyl in the mixed acid), the esterification conversion rate of the mixed acid is 98 percent under the condition that concentrated sulfuric acid catalyst (the addition amount is catalytic amount) exists and at the temperature of 75 ℃ for 7 hours, the esterification reaction product is firstly distilled and recovered with the pressure of 82kPa and the temperature of 45 ℃, the methanol returns to the esterification reaction process, then methyl valerate is distilled and recovered with the pressure of 32kPa and the temperature of 60 ℃, then a mixture of cyclohexanol and cyclohexanone is distilled and recovered with the pressure of 12kPa and the temperature of 75 ℃, and finally the mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate is distilled and recovered with the pressure of 2kPa and the temperature of 95 ℃;
4) dropwise adding a hydrogen peroxide solution (with the concentration of 45%) into a mixture of cyclohexanol and cyclohexanone, stirring and reacting at the temperature of 25 ℃, separating out cyclohexanone peroxide precipitate, stopping dropwise adding the hydrogen peroxide solution until no precipitate is separated out during the reaction, performing solid-liquid separation to obtain cyclohexanone peroxide crystals and cyclohexanol, performing simple rectification on the cyclohexanol to obtain 99% cyclohexanol, placing the cyclohexanone peroxide crystals in water, heating to 65 ℃ for hydrolysis reaction to obtain a mixed solution of cyclohexanone and water, standing and layering, and collecting the upper-layer cyclohexanone; the cyclohexanone is further simply rectified to obtain the 99 percent cyclohexanone.
5) Carrying out reduced pressure rectification on the mixed ester, wherein the number of tower plates is 25, and the rectification process is as follows: the pressure is 1.5kPa, the temperature at the bottom of the rectifying still is 125 ℃, and 99 percent of dimethyl succinate, 99 percent of dimethyl glutarate and 99 percent of dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still.
Example 2
The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane comprises the following steps:
1) adding a cyclohexane raw material into a reaction kettle, adding 15PPM cobalt tetraphenylporphyrin and 15PPM cobalt acetate, carrying out catalytic oxidation reaction at 165 ℃ for 2.0 hours and under 15atm of air pressure to obtain a mixed solution of cyclohexanol, cyclohexanone, valeric acid, adipic acid, succinic acid, glutaric acid and cyclohexane, wherein the discharged gas component is mainly nitrogen, and the discharged gas component is cooled and recycled, so that the cyclohexane conversion rate is 25%;
2) flashing the mixed solution at 85 ℃ and under the pressure of 0.8atm, cooling and recovering the obtained cyclohexane, returning the cyclohexane to the oxidation process for recycling, and obtaining the rest of the mixture containing cyclohexanol, cyclohexanone and mixed acid;
3) carrying out esterification reaction on the mixture and methanol, wherein the molar ratio of the methanol to the mixed acid in the mixture is 1.8:1 (measured by the molar amount of carboxyl in the mixed acid), the esterification conversion rate of the mixed acid is 97 percent under the condition that concentrated sulfuric acid catalyst (the addition amount is catalytic amount) exists and at the temperature of 85 ℃ for 6.5 hours, the esterification reaction product is firstly distilled and recovered with excessive methanol under the conditions that the pressure is 90kPa and the temperature is 50 ℃, the methanol returns to the esterification reaction process, then methyl valerate is distilled and recovered under the pressure of 38kPa and the temperature of 65 ℃, then a mixture of cyclohexanol and cyclohexanone is distilled and recovered under the pressure of 18kPa and the temperature of 85 ℃, and finally the mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate is distilled and recovered under the pressure of 4kPa and the temperature of 110 ℃;
4) dropwise adding a hydrogen peroxide solution (industrial grade) into a mixture of cyclohexanol and cyclohexanone, stirring and reacting at the temperature of 30 ℃, separating out cyclohexanone peroxide precipitate, stopping dropwise adding the hydrogen peroxide solution until no precipitate is separated out during the reaction, performing solid-liquid separation to obtain cyclohexanone peroxide crystals and cyclohexanol, performing simple rectification on the cyclohexanol to obtain 99% of cyclohexanol, placing the cyclohexanone peroxide crystals in water, heating to 75 ℃ for hydrolysis reaction to obtain a mixed solution of cyclohexanone and water, standing and layering, and collecting the upper-layer cyclohexanone; the cyclohexanone is further simply rectified to obtain the 99 percent cyclohexanone.
5) Carrying out vacuum rectification on the mixed ester, wherein the number of tower plates is 30, and the rectification process is as follows: the pressure is 1.5kPa, the temperature at the bottom of the rectifying still is 130 ℃, and 99 percent of dimethyl succinate, 99 percent of dimethyl glutarate and 99 percent of dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still.
Example 3
The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane comprises the following steps:
1) adding a cyclohexane raw material into a reaction kettle, adding 40PPM of tetra-p-chlorophenylporphyrin manganese, carrying out catalytic oxidation reaction at 160 ℃, for 1.8 hours and under the air pressure of 14atm to obtain a mixed solution of cyclohexanol, cyclohexanone, valeric acid, adipic acid, succinic acid, glutaric acid and cyclohexane, wherein the discharged gas mainly comprises nitrogen, and the discharged gas is cooled, recovered and recycled, and the cyclohexane conversion rate is 35%;
2) flashing the mixed solution at 80 ℃ and 0.6atm, cooling and recovering the obtained cyclohexane, returning the cyclohexane to the oxidation process for recycling, and obtaining the rest mixture containing cyclohexanol, cyclohexanone and mixed acid;
3) carrying out esterification reaction on the mixture and methanol, wherein the molar ratio of the methanol to the mixed acid in the mixture is 2:1 (measured by the molar amount of carboxyl in the mixed acid), the esterification conversion rate of the mixed acid is 96% under the condition of concentrated sulfuric acid catalyst (the addition amount is catalytic amount) and at the temperature of 80 ℃ for 6.0 hours, the esterification reaction product is firstly distilled and recovered with excessive methanol under the conditions of the pressure of 90kPa and the temperature of 48 ℃, the methanol returns to the esterification reaction process, then methyl valerate is distilled and recovered under the pressure of 30kPa and the temperature of 70 ℃, then a mixture of cyclohexanol and cyclohexanone is distilled and recovered under the pressure of 15kPa and the temperature of 82 ℃, and finally the mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate is distilled and recovered under the pressure of 3.5kPa and the temperature of 105 ℃;
4) the cyclohexanol and cyclohexanone mixture is catalytically dehydrogenated at 205 deg.c and 0.05MPa in the presence of Pd-C catalyst to obtain cyclohexanone product with cyclohexanol converting rate of 98%, and the obtained cyclohexanone is simply distilled to obtain 99% cyclohexanone.
5) Carrying out reduced pressure rectification on the mixed ester, wherein the number of tower plates is 25, and the rectification process is as follows: the pressure is 1.8kPa, the temperature at the bottom of the rectifying still is 135 ℃, and 99 percent of dimethyl succinate, 99 percent of dimethyl glutarate and 99 percent of dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still.
Example 4
The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane comprises the following steps:
1) adding a cyclohexane raw material into a reaction kettle, adding 20PPM of tetra-p-chlorophenylporphyrin manganese and 20PPM of tetraphenylporphyrin copper, carrying out catalytic oxidation reaction at 165 ℃ for 2 hours under the condition that the air pressure is 14atm to obtain a mixed solution of cyclohexanol, cyclohexanone, valeric acid, adipic acid, succinic acid, glutaric acid and cyclohexane, wherein the discharged gas mainly comprises nitrogen, and the nitrogen is cooled, recovered and recycled, and the cyclohexane conversion rate is 40%;
2) flashing the mixed solution at 80 ℃ and 0.8atm, cooling and recovering the obtained cyclohexane, returning the cyclohexane to the oxidation process for recycling, and obtaining the rest mixture containing cyclohexanol, cyclohexanone and mixed acid;
3) carrying out esterification reaction on the mixture and methanol, wherein the molar ratio of the methanol to the mixed acid in the mixture is 1.8:1 (measured by the molar amount of carboxyl in the mixed acid), the esterification conversion rate of the mixed acid is 98 percent when the mixture reacts for 7.0 hours at the temperature of 80 ℃ in the presence of a concentrated sulfuric acid catalyst (the addition amount is a catalytic amount), the esterification reaction product is firstly distilled and recovered with the pressure of 80kPa and the temperature of 45 ℃, the methanol returns to the esterification reaction process, then methyl valerate is distilled and recovered at the pressure of 40kPa and the temperature of 65 ℃, then a mixture of cyclohexanol and cyclohexanone is distilled and recovered at the pressure of 15kPa and the temperature of 80 ℃, and finally the mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate is distilled and recovered at the pressure of 4kPa and the temperature of 105 ℃;
4) the cyclohexanol and cyclohexanone mixture is subjected to catalytic dehydrogenation at 210 ℃ and 0.08MPa under the action of a palladium-carbon catalyst (catalytic amount) to obtain a cyclohexanone product, wherein the conversion rate of the cyclohexanol is 99%, and the obtained cyclohexanone is subjected to simple distillation to obtain 99% cyclohexanone.
5) Carrying out reduced pressure rectification on the mixed ester, wherein the number of tower plates is 25, and the rectification process is as follows: the pressure is 1.8kPa, the temperature at the bottom of the rectifying still is 135 ℃, and 99 percent of dimethyl succinate, 99 percent of dimethyl glutarate and 99 percent of dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still.
Example 5
The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane comprises the following steps:
1) adding a cyclohexane raw material into a reaction kettle, adding 30PPM iron tetraphenylporphyrin, carrying out catalytic oxidation reaction at 165 ℃ for 2 hours and under the air pressure of 15atm to obtain a mixed solution of cyclohexanol, cyclohexanone, valeric acid, adipic acid, succinic acid, glutaric acid and cyclohexane, wherein the discharged gas mainly comprises nitrogen, and the nitrogen is cooled and recycled, and the cyclohexane conversion rate is 25%;
2) flashing the mixed solution at 80 ℃ and 0.9atm, cooling and recovering the obtained cyclohexane, returning the cyclohexane to the oxidation process for recycling, and obtaining the rest mixture containing cyclohexanol, cyclohexanone and mixed acid;
3) carrying out esterification reaction on the mixture and methanol, wherein the molar ratio of the methanol to the mixed acid in the mixture is 1.5:1 (calculated by the molar amount of carboxyl in the mixed acid), the esterification conversion rate of the mixed acid is 98 percent when the mixture reacts for 7.0 hours at the temperature of 85 ℃ in the presence of a concentrated sulfuric acid catalyst (the addition amount is a catalytic amount), the esterification reaction product is firstly distilled and recovered with excessive methanol under the conditions of the pressure of 85kPa and the temperature of 50 ℃, the methanol returns to the esterification reaction process, then the methyl valerate is distilled and recovered under the pressure of 35kPa and the temperature of 65 ℃, then the mixture of cyclohexanol and cyclohexanone is distilled and recovered under the pressure of 15kPa and the temperature of 80 ℃, and finally the mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate is distilled and recovered under the pressure of 4kPa and the temperature of 105 ℃;
4) under the catalysis of cobalt tetraphenylporphyrin (40PPM), the mixture of cyclohexanol and cyclohexanone reacts for 80 minutes under the conditions that the air pressure is 15atm and the temperature is 155 ℃, mixed acid of valeric acid, adipic acid, succinic acid and glutaric acid is obtained, the conversion rate of cyclohexanol and cyclohexanone is 98 percent, wherein the proportion of adipic acid is 75 percent, and the mixed acid returns to the esterification reaction process.
5) Carrying out reduced pressure rectification on the mixed ester, wherein the number of tower plates is 25, and the rectification process is as follows: the pressure is 1.8kPa, the temperature at the bottom of the rectifying still is 135 ℃, and 99 percent of dimethyl succinate, 99 percent of dimethyl glutarate and 99 percent of dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still.
Example 6
The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane comprises the following steps:
1) adding a cyclohexane raw material into a reaction kettle, adding 5PPM cobalt tetraphenylporphyrin and 10PPM iron [ mu ] -tetraphenylporphyrin, and carrying out catalytic oxidation reaction at 165 ℃ for 2.5 hours under the condition of 15atm of air pressure to obtain a mixed solution of cyclohexanol, cyclohexanone, valeric acid, adipic acid, succinic acid, glutaric acid and cyclohexane, wherein the discharged gas component is mainly nitrogen, and the mixed solution is cooled, recycled and has the cyclohexane conversion rate of 40%;
2) flashing the mixed solution at 80 ℃ and 1atm, cooling and recovering the obtained cyclohexane, returning the cyclohexane to the oxidation process for recycling, and obtaining the rest mixture containing cyclohexanol, cyclohexanone and mixed acid;
3) carrying out esterification reaction on the mixture and methanol, wherein the molar ratio of the methanol to the mixed acid in the mixture is 1.4:1 (calculated by the molar amount of carboxyl in the mixed acid), the esterification conversion rate of the mixed acid can reach 97 percent under the condition that concentrated sulfuric acid catalyst (the addition amount is catalytic amount) exists and at the temperature of 80 ℃ for 6.5 hours, the esterification reaction product is firstly distilled and recovered with excessive methanol under the conditions that the pressure is 85kPa and the temperature is 50 ℃, the methanol returns to the esterification reaction process, then the methyl valerate is distilled and recovered under the pressure of 35kPa and the temperature of 65 ℃, then the mixture of cyclohexanol and cyclohexanone is distilled and recovered under the pressure of 15kPa and the temperature of 80 ℃, and finally the mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate is distilled and recovered under the pressure of 4kPa and the temperature of 105 ℃;
4) reacting the mixture of cyclohexanol and cyclohexanone under the catalysis of 10PPM cobalt tetraphenylporphyrin and 20PPM cobalt tetra-p-chlorophenylporphyrin for 70 minutes at the temperature of 160 ℃ and under the air pressure of 18atm to obtain mixed acid of valeric acid, adipic acid, succinic acid and glutaric acid, wherein the conversion rate of the cyclohexanol and the cyclohexanone is 99 percent, the proportion of the adipic acid is 79 percent, and the mixed acid returns to the esterification reaction process.
5) Carrying out reduced pressure rectification on the mixed ester, wherein the number of tower plates is 25, and the rectification process is as follows: the pressure is 1.8kPa, the temperature at the bottom of the rectifying still is 135 ℃, and 99 percent of dimethyl succinate, 99 percent of dimethyl glutarate and 99 percent of dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still.
Claims (10)
1. A method for separating alcohol ketonic acid complex oxidation products generated by air catalytic oxidation of cyclohexane is characterized by comprising the following steps: the method comprises the following steps:
1) performing air oxidation reaction on cyclohexane under the catalytic action to obtain a cyclohexane solution containing cyclohexanol, cyclohexanone and mixed acid; the mixed acid comprises valeric acid, adipic acid, succinic acid and glutaric acid;
2) the cyclohexane solution containing cyclohexanol, cyclohexanone and mixed acid is subjected to flash evaporation to recover cyclohexane, and the cyclohexane returns to the air oxidation reaction process, so that a mixture containing cyclohexanol, cyclohexanone and mixed acid is obtained;
3) carrying out esterification reaction on a mixture containing cyclohexanol, cyclohexanone and mixed acid and methanol, carrying out reduced pressure distillation separation on an esterification reaction product, distilling and recovering the methanol, returning to the esterification reaction process, and carrying out sectional distillation separation to obtain methyl valerate, a mixture of cyclohexanol and cyclohexanone and mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate;
4) oxidizing the cyclohexanol and cyclohexanone mixture with a hydrogen peroxide solution to generate cyclohexanone precipitate, carrying out solid-liquid separation to obtain cyclohexanone peroxide solid and cyclohexanol, hydrolyzing the cyclohexanone peroxide solid to obtain cyclohexanone and water mixed solution, standing for layering, and collecting upper-layer cyclohexanone; or, carrying out catalytic dehydrogenation on the cyclohexanol and cyclohexanone mixture to obtain cyclohexanone; or, carrying out catalytic oxidation on the cyclohexanol and cyclohexanone mixture to obtain mixed acid, and returning to the esterification reaction process;
5) and (3) carrying out vacuum rectification on the mixed ester to respectively obtain dimethyl adipate, dimethyl succinate and dimethyl glutarate products.
2. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein: the air oxidation reaction of cyclohexane under the catalysis is carried out under the following conditions: the temperature is 150-170 ℃, the time is 1.5-2.5 hours, the air pressure is 14-16 atm, metalloporphyrin is used as a catalyst, or metalloporphyrin and transition metal oxide are combined to be used as a catalyst, and the concentration of the catalyst in cyclohexane is 1-50 PPM.
3. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane as claimed in claim 2, wherein: the metalloporphyrin compound is at least one of iron tetraphenylporphyrin, iron tetra-p-chlorophenylporphyrin, cobalt tetraphenylporphyrin, copper tetraphenylporphyrin, manganese tetraphenylporphyrin, iron mu-dimer tetraphenylporphyrin, cobalt tetra-p-chlorophenylporphyrin, copper tetra-p-chlorophenylporphyrin, manganese tetra-p-chlorophenylporphyrin and iron mu-dimer tetra-p-chlorophenylporphyrin; the transition metal salt is at least one of acetate or naphthenate of cobalt and/or manganese.
4. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein: the conditions for recovering cyclohexane from cyclohexane solution containing cyclohexanol, cyclohexanone and mixed acid by flash evaporation are as follows: the temperature is 70-90 ℃, and the pressure is 0.5-1 atm.
5. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein: the esterification reaction conditions of the mixture containing cyclohexanol, cyclohexanone and mixed acid and methanol are as follows: the molar ratio of the methanol to the mixed acid is 1-2: 1, and the mixed acid reacts for 6-7 hours at the temperature of 70-90 ℃ in the presence of a concentrated sulfuric acid catalyst, wherein the mixed acid is measured by the molar amount of carboxyl groups contained in the mixed acid.
6. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein: the conditions of the esterification reaction product after reduced pressure distillation separation are as follows: distilling and recovering methanol under the conditions of the pressure of 80-90 kPa and the temperature of 45-55 ℃, distilling and recovering methyl valerate under the conditions of the pressure of 30-40 kPa and the temperature of 60-70 ℃, distilling and recovering a mixture of cyclohexanol and cyclohexanone under the conditions of the pressure of 10-20 kPa and the temperature of 70-90 ℃, and finally distilling and recovering mixed ester of dimethyl adipate, dimethyl succinate and dimethyl glutarate under the conditions of the pressure of 1.7-5 kPa and the temperature of 90-115 ℃.
7. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein: dropwise adding a hydrogen peroxide solution into a mixture of cyclohexanol and cyclohexanone, stirring and reacting at the temperature of 15-40 ℃, separating out cyclohexanone peroxide precipitate, and stopping the reaction until no precipitate is separated out.
8. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein: the hydrolysis reaction process comprises the following steps: and (3) putting cyclohexanone peroxide into water, heating to 60-80 ℃ and carrying out hydrolysis reaction.
9. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein: the conditions of the mixed ester by vacuum rectification are as follows: the number of tower plates is more than 20, and the rectification process is as follows: the pressure is 1.5-2 kPa, the temperature of the bottom of the rectifying still is higher than 115 ℃, and dimethyl succinate, dimethyl glutarate and dimethyl adipate are respectively collected from the top, the middle and the bottom of the rectifying still.
10. The method for separating the alcohol ketonic acid complex oxidation product generated by the air catalytic oxidation of cyclohexane according to claim 1, wherein:
under the action of a palladium-carbon catalyst, carrying out catalytic dehydrogenation on the mixture of cyclohexanol and cyclohexanone at 200-210 ℃ and 0.01-0.1 MPa to obtain a cyclohexanone product;
alternatively, the first and second electrodes may be,
and reacting the mixture of the cyclohexanol and the cyclohexanone for 60-120 minutes under the catalysis of metalloporphyrin under the conditions that the air pressure is 8-15 atm and the temperature is 140-160 ℃ to obtain the mixed acid.
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| CN202010941347.1A Pending CN114230458A (en) | 2020-09-09 | 2020-09-09 | Method for separating alcohol ketonic acid complex oxidation product generated by air catalytic oxidation of cyclohexane |
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