CN113651685A - Process for preparing dicarboxylic acid by two-step oxidation of cycloalkane - Google Patents
Process for preparing dicarboxylic acid by two-step oxidation of cycloalkane Download PDFInfo
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- CN113651685A CN113651685A CN202111125053.2A CN202111125053A CN113651685A CN 113651685 A CN113651685 A CN 113651685A CN 202111125053 A CN202111125053 A CN 202111125053A CN 113651685 A CN113651685 A CN 113651685A
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- oxidation
- dicarboxylic acid
- acid
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- cycloalkane
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 150000001924 cycloalkanes Chemical class 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 title claims description 105
- 230000003647 oxidation Effects 0.000 title claims description 83
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 230000008020 evaporation Effects 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 48
- 230000008569 process Effects 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- -1 imide compound Chemical class 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 230000008719 thickening Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011949 solid catalyst Substances 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 150000003949 imides Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000003930 superacid Substances 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 238000003912 environmental pollution Methods 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 34
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000001361 adipic acid Substances 0.000 description 17
- 235000011037 adipic acid Nutrition 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 12
- 150000001991 dicarboxylic acids Chemical class 0.000 description 10
- 239000002699 waste material Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012476 oxidizable substance Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000005675 cyclic monoalkenes Chemical class 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- C07C51/31—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
-
- 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/316—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with oxides of nitrogen or nitrogen-containing mineral acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
A process for preparing dicarboxylic acid from cyclic alkane includes such steps as catalytic oxidizing of cyclic alkane and catalyst in oxidizing reactor, separating out unreacted cyclic alkane and solvent by flash evaporation and distillation, dewatering cyclic alkane and solvent, cooling, crystallizing, filtering to obtain coarse dicarboxylic acid and filtrate, returning the filtrate to oxidizing reactor, oxidizing the coarse dicarboxylic acid by nitric acid under the action of catalyst, filtering, cooling, crystallizing, centrifugal separation, dissolving filter dregs, removing Co ions, decoloring and recrystallizing to obtain dicarboxylic acid product, concentrating, smelting, cooling and tabletting. The invention has the advantages of high single-pass conversion rate of the naphthenic hydrocarbon, small evaporation circulation amount, low nitric acid consumption, high carbon yield, small environmental pollution and low energy consumption, and has outstanding cost advantage and environmental protection advantage.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for preparing dicarboxylic acid by two-step oxidation of cycloalkane.
Background
The dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, and terephthalic acid, and adipic acid is the most important dicarboxylic acid. Part of the dicarboxylic acids may be oxidatively cleaved by the cycloalkane and thus mainly produce dicarboxylic acids having a carbon chain containing the same number of carbon atoms as the number of carbon atoms constituting the cycloalkane. Specifically, cyclohexane produces adipic acid and cyclododecane produces dodecanedioic acid. Dicarboxylic acids having carbon chains with the same number of carbon atoms are produced as by-products, which have one to several carbon chains with a reduced number of carbon atoms. For example, cyclohexane produces adipic acid and also produces succinic acid and glutaric acid as by-products.
The mature process known to date for oxidative cleavage of cyclic chain alkanes and the ultimate formation of dicarboxylic acids is air oxidation to form cycloalkanones and cycloalkanols, which are further oxidized by nitric acid to form dicarboxylic acids. The process has low conversion rate of the cycloalkane, the target products of air oxidation are the cycloalkanone and the cycloalkanol, deep oxidation products such as acid, ester, hydroxycarboxylic acid and the like generated in the process are taken as waste to be removed, the carbon yield of the cycloalkane is low, and a large amount of wastewater is generated to pollute the environment; in the process of oxidizing the cycloalkanone and the cycloalkanol by nitric acid, the consumption of the nitric acid is high, and a large amount of nitrogen oxide is released to pollute the atmosphere by isothermal gas. For example, the process for producing the mixture of adipic acid and C4-C6 dicarboxylic acid by using cyclohexane comprises the following steps: performing air liquid phase oxidation on cyclohexane at a certain temperature and under a certain pressure to prepare cyclohexane oxidation liquid containing cyclohexyl hydroperoxide, cyclohexanone, cyclohexanol, acid, ester, hydroxycaproic acid and the like, and removing deep oxides such as acids, lipids, hydroxycaproic acid and the like generated in the air oxidation process through the procedures of water washing or saponification, decomposition, rectification and the like to form pollutants such as saponified waste alkali liquor, acidic water and the like, thereby finally obtaining KA oil (a mixture of cyclohexanol and cyclohexanone); the KA oil (mixture of cyclohexanol and cyclohexanone) is oxidized by nitric acid to produce a mixture of adipic acid and C4-C6 dicarboxylic acid. The single-pass conversion rate of cyclohexane in the process is low, and is generally 3% -4%; the comprehensive carbon yield of useful main and side products is low, about 76 percent; the cyclohexane circulation amount is large, the energy consumption of a cyclohexane distillation system is high, washing waste acid water or saponification waste alkali liquor is discharged, the nitric acid consumption is high, the process is complex, the cost is high, and the environmental pollution is serious.
In order to improve the problem of low carbon yield of cyclic alkanes, processes have been developed in which a cyclic monoolefin-based hydration process produces a cycloalkanol, which is further oxidized to a dicarboxylic acid using nitric acid, such as the hydration of cyclohexene to produce cyclohexanol, which is oxidized to a dicarboxylic acid using nitric acid to produce a dicarboxylic acid (primarily adipic acid). Compared with the air oxidation process of the cycloparaffin, the process has the advantages of obviously improving the yield of effective main and side products, having obvious cost advantage and environmental protection advantage, but still consuming a large amount of nitric acid, producing a large amount of cycloparaffin as a byproduct and consuming a large amount of cycloparaffin as a byproduct by using the air oxidation process of the cycloparaffin.
In order to solve the problems of the above processes, research has focused on the direct air oxidation of cycloalkanes to produce the corresponding dicarboxylic acids, which has been a major problem for 20 years.
Many researchers have been working on new processes for the direct preparation of dicarboxylic acids by air oxidation of cycloalkanes. Such as patents WO96.3365, WO99.40058 disclosed by the world intellectual property organization international office; patents CN103285911A, CN103755544A, CN106391123A, CN107983397A, CN10325406A, CN104109083A, CN105254491B, CN1157605A, CN105665010A, CN110872224A, CN111233652A, CN112125795A, CN102816254A, CN104226317A, CN105384622A, CN1535947A, CN101239899A, CN01822566.7, CN01803724.0 and the like published by the chinese intellectual property office. The series of patents focus on the method for directly preparing dicarboxylic acid by catalytic oxidation of cycloalkane and the selection and preparation of the catalyst thereof, and particularly on the research of preparing adipic acid from cyclohexane. They differ in that different catalysts or combinations of catalysts are used. The catalysts used in these patents mainly include transition metal compounds, carbon nitride, phthalocyanine metals, activated carbon supported nanogold catalysts, alloy catalysts, imide compounds of imide skeleton, metalloporphyrin or its derivatives, titanium silicalite molecular sieves, modified sepiolite or their mixtures, etc. By using the catalysts, the reaction speed of air oxidation of the cycloalkane is changed to different degrees, but the methods disclosed in the patent have the problems of low yield of useful main and side products, serious environmental pollution, difficult recovery of the catalyst and solvent, poor quality of dicarboxylic acid products, higher cost compared with the existing process and the like to different degrees, so that an industrial process route and an industrial product for directly preparing the dicarboxylic acid by catalytic oxidation of the cycloalkane are not seen.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing dicarboxylic acid by oxidizing cycloalkane in two steps, so as to realize high single-pass conversion rate and high yield of oxidation of cycloalkane, reduce cyclic evaporation amount of cycloalkane and consumption of nitric acid, and reduce environmental pollution and energy consumption.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing dicarboxylic acid by two-step oxidation of cycloalkane comprises the following specific process steps:
(1) continuously feeding the raw material cycloalkane and catalyst into oxidation reaction still, using oxygen-containing gas to make catalytic oxidation, after the reaction is stable, continuously extracting oxidation liquor, separating unreacted portion of cycloalkane and solvent from oxidation liquor by means of flash evaporation and distillation process, dewatering the separated cycloalkane and solvent, returning them into oxidation reaction still, cooling and crystallizing residual oxidation liquor, filtering to obtain crude dicarboxylic acid and filtrate, returning the filtrate into oxidation reaction still,
(2) washing the obtained crude dicarboxylic acid with water, carrying out second-step oxidation on the washed crude dicarboxylic acid with nitric acid under the action of a catalyst, filtering an oxidation solution obtained in the second-step oxidation to remove a solid catalyst, cooling, crystallizing, centrifugally separating, dissolving obtained filter residues, removing cobalt ions, decoloring, recrystallizing to obtain a dicarboxylic acid product, thickening, melting and cooling the filtrate to form a dicarboxylic acid byproduct.
The catalyst in the step (1) is one or a mixture of more of a transition metal compound, carbon nitride, phthalocyanine metal, an activated carbon supported nanogold catalyst, an alloy catalyst, an imide compound with an imide skeleton, metalloporphyrin or a derivative thereof, a titanium silicalite molecular sieve and modified sepiolite, and the catalyst system can have a solvent or does not have a solvent according to the respective requirements.
In the step (1), if the catalyst is a solid substance, the oxidation liquid is firstly removed with the solid catalyst by a filtration method, and then the oxidation liquid is subjected to flash evaporation and distillation process treatment.
The catalytic oxidation in the step (1) is carried out in oxygen-deficient air or oxygen-enriched air having an oxygen concentration of more than 8%.
In the step (2), the catalyst is copper, vanadium, ZSM-5, HZSM-5 and solid super-strong acid substances, the ZSM-5, the HZSM-5 and the solid super-strong acid substances are added into the reaction system together with the copper and vanadium catalyst, and the adding amount of the ZSM-5, the HZSM-5 and the solid super-strong acid substances is 0 to 30 g/100 g of nitric acid solution.
The reaction temperature in the step (1) is controlled to be 80-145 ℃, and the reaction pressure is controlled to be 0.01-10 Mpa.
In the step (2), the molar ratio of the crude dicarboxylic acid to the nitric acid is 1: 1-10 percent of nitric acid is added, and the mass concentration of the nitric acid is controlled to be 35-68 percent.
And (3) removing cobalt ions by using a resin adsorption method in the step (2).
The method has the outstanding characteristics that the advantages of high conversion rate of advanced air catalytic oxidation of the cycloalkane and high quality of the dicarboxylic acid prepared by nitric acid oxidation are comprehensively utilized, and various components obtained by air oxidation of the cycloalkane are converted into dicarboxylic acid products by the simplest, economical and reliable process to the maximum extent.
Compared with the prior art, in the first-step reaction, the invention utilizes the advantage of the catalytic activity of the existing cycloparaffin catalytic oxidation system, greatly improves the conversion rate of the cycloparaffin, and combines the technology that the filtrate is directly returned to the first-step oxidation reaction, so that the circulation amount of the cycloparaffin in the reaction system is greatly reduced, and the energy consumed by the repeated circulation of the cycloparaffin and the solvent in the reaction system is greatly reduced; the catalyst has lowered temperature for oxidation of cycloalkane, less condensation and other harmful side reactions, low power consumption and high reaction yield. Meanwhile, the first-step reaction abandons the method of removing the generated dicarboxylic acid in the processes of water washing, saponification and the like to pursue high-purity cycloalkanone and cycloalkanol in the traditional technology, and instead, the substances which can be further oxidized by air to generate the dicarboxylic acid, such as the cycloalkanone and the cycloalkanol, are returned to the first-step oxidation reaction again to be converted into the dicarboxylic acid, and the mixture which comprises the dicarboxylic acid, the hydroxycarboxylic acid, ester substances and the like and can not be oxidized by air is used as the raw material for the second-step nitric acid oxidation. By the method, a large amount of organic acid or organic acid salt in the original abandoned pickling water and saponified waste alkali liquor is changed into valuable, and the valuable is changed into dicarboxylic acid products after the second step of oxidation, so that the carbon yield is greatly improved, and the environmental pollution is reduced.
Compared with the prior art, the second-step oxidation reaction uses nitric acid as an oxidant, but the nitric acid plays a role in the second-step oxidation to convert substances which are not converted into dicarboxylic acid in the first-step oxidation, such as esters, hydroxycarboxylic acid and the like, into dicarboxylic acid; meanwhile, substances with poor thermal stability generated in the first-step oxidation reaction are converted into substances with good thermal stability, so that the product quality is ensured; the nitric acid oxidation of the conventional technology is mainly used for oxidizing the cycloalkanone and the cycloalkanol to convert the cycloalkanone and the cycloalkanol into the dicarboxylic acid. This is a substantial difference between the present technique and conventional nitric acid oxidation.
Compared with the prior patents, most of the prior patents do not use nitric acid for the second step oxidation, and do not see further treatment on the crystallized dicarboxylic acid by other methods, so that the obtained product has more oxidizable substances, high ester content, poor operability in the crystallization and filtration process, poor thermal stability of the product and incapability of meeting the quality index requirements, and industrial production is impossible. This patent overcomes this problem.
Taken together, over 75% of the oxygen atoms in the prior art product dicarboxylic acids are provided by nitric acid; whereas more than 90% of the oxygen atoms of the dicarboxylic acid product of the present technology are provided by gaseous oxygen and less than 10% of the oxygen atoms are provided by nitric acid. Thereby greatly reducing the consumption of nitric acid and lightening the environmental pollution.
The invention has the main advantages and effects that: (1) the single-pass conversion rate of the cycloalkane is improved to more than 10 percent from the prior 3-4 percent, and the recycle amount of the cycloalkane and the solvent is greatly reduced compared with a cycloalkane two-step oxidation method by combining the technology that the filtrate is directly returned to the first step of oxidation reaction, and meanwhile, the rectification process of intermediate products such as cycloalkanone and cycloalkanol is eliminated, so that the load of a distillation system is greatly reduced, and the energy consumption is greatly reduced; (2) the process of washing the oxidation product of the cycloalkane with water is eliminated, and no acidic washing wastewater is discharged; (3) the process of saponifying and decomposing the oxidation product of the cycloalkane is eliminated, and no saponifiable waste alkali liquor is discharged; (4) under the same dicarboxylic acid yield, the consumption of nitric acid is reduced by more than 85%; (5) compared with the air oxidation method of the naphthenic hydrocarbon, the carbon yield of the useful main and side products is improved from 76 percent to more than 94 percent. (6) The invention does not need to consume caustic soda at all, and does not have the problem of processing saponified waste lye; the amount of nitric acid tail gas treatment is also greatly reduced.
Detailed Description
The process of the present invention will be specifically described below with reference to specific examples using cyclohexane as an example.
Example 1
The 60 mol/h cyclohexane, acetic acid and catalyst (cobalt acetate in the example) continuously enter an oxidation reaction kettle according to the weight ratio (60:40:0.09) for catalytic oxidation by air, and the feeding space velocity is 0.6h-1(space velocity is in terms of reactor charge volume, the same applies below); the reaction temperature is 123 ℃, and the reaction pressure is 2.2 Mpa. After the reaction is stable, continuously extracting the oxidation liquid, sequentially feeding the oxidation liquid into a flash tower and a concentration tower, distilling cyclohexane, acetic acid and water out of the tower top, separating the water and the cyclohexane in a water separator, and returning the separated cyclohexane to the air oxidation kettle. The vacuum degree of the concentration tower is-0.015 MPa. And (3) discharging from the concentration tower kettle, feeding into a crystallizer, cooling the material in the crystallizer to crystallize and separate out dicarboxylic acid generated by the reaction, filtering crystallized magma by a filter, and returning part of the filtered mother liquor to the air oxidation kettle after treatment. Feeding the filtered crude dicarboxylic acid filter residue into a nitric acid oxidation reaction kettle, adding the crude dicarboxylic acid and the nitric acid according to a molar ratio of about (1: 4), and simultaneously adding catalysts such as copper, vanadium, ZSM-5 and the like; the concentration of nitric acid is 50%; cu+2The amount of (A) added is 0.5% (wt%) of the nitric acid reaction solution, V+5The addition amount of (A) is 0.1 percent (wt percent) of the nitric acid reaction solution, and a little ZSM-5 is added; the reaction temperature was 80 ℃ in the early stage and 90 ℃ in the late stage, and the residence time was 3 hours. 6.14kg/h of adipic acid is obtained after cooling crystallization, thickening filtration, centrifugal separation, resin cobalt ion removal, activated carbon decoloration, recrystallization, washing and drying of the nitric acid reaction liquid, and the yield of the adipic acid is 70.1 percent; the filtered nitric acid mother liquor and the recrystallized filtrate are treated to obtain 2.11kg/h of a C4-C6 dicarboxylic acid mixture, and the yield of the mixed dicarboxylic acid is 25.86%. The overall yield of dicarboxylic acid was 95.86%.
Example 2
60 mol/h cyclohexane, acetic acid and a catalyst (in this case, cobalt acetate) continuously enter an oxidation reaction kettle according to the weight ratio (60:45:0.07) for catalytic oxidation by air, and the feeding space velocity is 0.5h-1(space velocity is in terms of reactor charge volume, the same applies below); the reaction temperature is 118 ℃ and the reaction pressure is 2.5 Mpa. After the reaction is stable, continuously extracting the oxidation liquid, sequentially feeding the oxidation liquid into a flash tower and a concentration tower, distilling cyclohexane, acetic acid and water out of the tower top, separating the water and the cyclohexane in a water separator, and returning the separated cyclohexane to the air oxidation kettle. The vacuum degree of the concentration tower is-0.013 MPa. And (3) discharging from the concentration tower kettle, feeding into a crystallizer, cooling the material in the crystallizer to crystallize and separate out dicarboxylic acid generated by the reaction, filtering crystallized magma by a filter, and returning part of the filtered mother liquor to the air oxidation kettle after treatment. Feeding the filtered crude dicarboxylic acid filter residue into a nitric acid oxidation reaction kettle, adding the crude dicarboxylic acid and the nitric acid according to a molar ratio of about (1: 4.2), and simultaneously adding catalysts such as copper, vanadium, ZSM-5 and the like; the concentration of nitric acid is 53%; cu+2The amount of (A) added is 0.5% (wt%) of the nitric acid reaction solution, V+5The addition amount of (A) is 0.1 percent (wt percent) of the nitric acid reaction solution, and a little ZSM-5 is added; the reaction temperature was 82 ℃ at the early stage and 91 ℃ at the late stage, and the residence time was 3 hours. 6.03kg/h of adipic acid is obtained after cooling crystallization, thickening filtration, centrifugal separation, resin cobalt ion removal, activated carbon decoloration, recrystallization, washing and drying of the nitric acid reaction solution, and the yield of the adipic acid is 69.2 percent; the filtered nitric acid mother liquor and the recrystallized filtrate are treated to obtain 2.02kg/h of a C4-C6 dicarboxylic acid mixture, and the yield of the mixed dicarboxylic acid is 24.56%. The total yield of dicarboxylic acids was 94.96%.
Example 3
The 60 mol/h cyclohexane, acetic acid and catalyst (cobalt acetate in the example) continuously enter an oxidation reaction kettle according to the weight ratio (60:40:0.09) for catalytic oxidation by air, and the feeding space velocity is 0.7h-1(space velocity is in terms of reactor charge volume, the same applies below); the reaction temperature is 130 ℃, and the reaction pressure is 2.0 Mpa. After the reaction is stable, continuously extracting the oxidation liquid, sequentially feeding the oxidation liquid into a flash tower and a concentration tower, distilling cyclohexane, acetic acid and water out of the tower top, separating the water and the cyclohexane in a water separator, and returning the separated cyclohexane to the air oxidation kettle.The vacuum degree of the concentration tower is-0.014 Mpa. And (3) discharging from the concentration tower kettle, feeding into a crystallizer, cooling the material in the crystallizer to crystallize and separate out dicarboxylic acid generated by the reaction, filtering crystallized magma by a filter, and returning part of the filtered mother liquor to the air oxidation kettle after treatment. Feeding the filtered crude dicarboxylic acid filter residue into a nitric acid oxidation reaction kettle, adding the crude dicarboxylic acid and the nitric acid according to a molar ratio of about (1: 4.5), and simultaneously adding catalysts such as copper, vanadium, ZSM-5 and the like; the concentration of nitric acid is 40%; cu+2The amount of (A) added is 0.5% (wt%) of the nitric acid reaction solution, V+5The addition amount of (A) is 0.1 percent (wt percent) of the nitric acid reaction solution, and a little ZSM-5 is added; the reaction temperature was 83 ℃ in the early stage and 92 ℃ in the late stage, and the residence time was 3 hours. 6.14kg/h of adipic acid is obtained after cooling crystallization, thickening filtration, centrifugal separation, resin cobalt ion removal, activated carbon decoloration, recrystallization, washing and drying of the nitric acid reaction solution, and the yield of the adipic acid is 69.8%; the filtered nitric acid mother liquor and the recrystallized filtrate are treated to obtain 2.09kg/h of a C4-C6 dicarboxylic acid mixture, and the yield of the mixed dicarboxylic acid is 25.42%. The overall yield of dicarboxylic acid was 95.37%.
From the specific embodiment, the invention utilizes the advantage of catalytic activity of the existing cyclohexane catalytic oxidation system, greatly improves the conversion rate of cyclohexane, and greatly reduces the circulating amount of cyclohexane in the reaction system by combining the technology of directly returning filtrate to the first-step oxidation reaction, thereby greatly reducing the energy consumed by the repeated circulation of cyclohexane and solvent in the reaction system. The catalyst also reduces the temperature of the cyclohexane oxidation reaction, reduces the harmful side reactions such as condensation and the like, reduces the energy consumption and improves the reaction yield. Meanwhile, the first-step reaction abandons the traditional method that the generated dicarboxylic acid is removed by the processes of water washing, saponification and the like to pursue high-purity cyclohexanone and cyclohexanol, and instead, substances such as cyclohexanol, cyclohexanone and the like which can be further oxidized by air to generate dicarboxylic acid return to the first-step oxidation reaction again, and the mixture which comprises dicarboxylic acid, hydroxycarboxylic acid, ester substances and the like and can not be oxidized by air is used as the raw material of the second-step nitric acid oxidation. By the method, a large amount of organic acids or organic acid salts in the waste pickling water and saponification waste lye are changed into valuable substances, which are converted into adipic acid and C4-C6 dicarboxylic acid products by the second oxidation step, thereby greatly increasing the carbon yield and reducing the environmental pollution.
Although nitric acid, an oxidizing agent, is also used in the second-step oxidation reaction, the nitric acid plays a role in the second-step oxidation to convert substances which are not converted into dicarboxylic acid in the first-step oxidation, such as esters, hydroxycarboxylic acids, and the like, into dicarboxylic acid; meanwhile, substances with poor thermal stability generated in the first-step oxidation reaction are converted into substances with good thermal stability, so that the product quality is ensured; the nitric acid oxidation of the conventional technology is mainly used for oxidizing cyclohexanone and cyclohexanol into dicarboxylic acid. This is a substantial difference between the present technique and conventional nitric acid oxidation.
Compared with the prior patents, most of the prior patents do not use nitric acid for the second step oxidation, and do not see further treatment on the crystallized dicarboxylic acid by other methods, so that the obtained product has more oxidizable substances, high ester content, poor operability in the crystallization and filtration process, poor thermal stability of the product and incapability of meeting the quality index requirements, and industrial production is impossible. This patent overcomes this problem.
In summary, 75% of oxygen atoms in the mixture of adipic acid and C4-C6 dicarboxylic acid in the prior art are provided by nitric acid; more than 90% of oxygen atoms in the mixture of adipic acid and C4-C6 dicarboxylic acid are provided by gas oxygen, and less than 10% of oxygen atoms are provided by nitric acid. Thereby greatly reducing the consumption of nitric acid and lightening the environmental pollution.
Claims (8)
1. A method for preparing dicarboxylic acid by two-step oxidation of cycloalkane is characterized by comprising the following specific process steps:
(1) continuously feeding the raw material cycloalkane and catalyst into oxidation reaction still, using oxygen-containing gas to make catalytic oxidation, after the reaction is stable, continuously extracting oxidation liquor, separating unreacted portion of cycloalkane and solvent from oxidation liquor by means of flash evaporation and distillation process, dewatering the separated cycloalkane and solvent, returning them into oxidation reaction still, cooling and crystallizing residual oxidation liquor, filtering to obtain crude dicarboxylic acid and filtrate, returning the filtrate into oxidation reaction still,
(2) washing the obtained crude dicarboxylic acid with water, carrying out second-step oxidation on the washed crude dicarboxylic acid with nitric acid under the action of a catalyst, filtering an oxidation solution obtained in the second-step oxidation to remove a solid catalyst, cooling, crystallizing, centrifugally separating, dissolving obtained filter residues, removing cobalt ions, decoloring, recrystallizing to obtain a dicarboxylic acid product, thickening, melting and cooling the filtrate to form a dicarboxylic acid byproduct.
2. The method for preparing dicarboxylic acid by two-step oxidation of cycloalkane according to claim 1, wherein the catalyst in step (1) is one or more selected from transition metal compounds, carbon nitride, phthalocyanine metal, activated carbon supported nanogold catalyst, alloy catalyst, imide compound of imide skeleton, metalloporphyrin or its derivative, titanium silicalite molecular sieve and modified sepiolite, and the catalyst system may be present or absent of solvent according to its respective requirements.
3. The process for preparing dicarboxylic acid from cycloalkane by two-step oxidation according to claim 1, wherein in step (1), if the catalyst is solid, the oxidation liquid is first filtered to remove the solid catalyst, and then subjected to flash evaporation and distillation.
4. The process for preparing dicarboxylic acid by two-step oxidation of cycloalkane according to claim 1, wherein the catalytic oxidation in step (1) is carried out in oxygen-poor air or oxygen-rich air having an oxygen concentration of more than 8%.
5. The method for preparing dicarboxylic acid from cycloalkane by two-step oxidation according to claim 1, wherein in step (2), the catalyst is copper, vanadium, ZSM-5, HZSM-5, solid super acid and copper and vanadium catalyst are added into the reaction system, and the amounts of ZSM-5, HZSM-5, solid super acid added are 0-30 g/100 g nitric acid solution.
6. The method is characterized in that the reaction temperature in the step (1) is controlled to be 80-145 ℃, and the reaction pressure is controlled to be 0.01-10 Mpa.
7. The process for producing a dicarboxylic acid by two-step oxidation of a cycloalkane according to claim 1, wherein in the step (2), the crude dicarboxylic acid and nitric acid are mixed in a molar ratio of 1: 1-10 percent of nitric acid is added, and the mass concentration of the nitric acid is controlled to be 35-68 percent.
8. The two-step oxidation process for preparing dicarboxylic acid from cycloalkane according to claim 1, wherein in step (2), cobalt ion is removed by resin adsorption.
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