CN102924262A - Adipic acid preparation method - Google Patents
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Abstract
The invention discloses an adipic acid preparation method. The preparation method comprises the following steps: 1, oxidizing cyclohexane by a combined catalyst formed by an imide compound and a transition metal compound at 90-170DEG C under 0.8-3.0MPa, and carrying out flash evaporation and rectification to obtain a catalyzed product, wherein 1kg of cyclohexane needs 1-10000mg of the imide compound and 10-10000mg of the transmission metal compound; and 2, carrying out oxidation treatment of the catalyzed product obtained in step 1 in the presence of a Cu-V catalyst, carrying out cooling crystallization, centrifuging, re-crystallizing the obtained filter residues to obtain the adipic acid, and carrying out distillation, macro-porous resin adsorption and cooling of the obtained filtrate to obtain a diacid. The preparation method has the advantages of simplification of present technological processes for the production of the adipic acid through the oxidation of cyclohexane, omission of a water washing system, a cyclohexyl hydroperoxide saponification decomposition system, a cyclohexane rectification system, and a cyclohexanone and cyclohexanol rectification system, no consumption of caustic soda, and no generation of waste alkalis.
Description
Technical field
The present invention relates to chemosynthesis technical field, especially the preparation method of hexanodioic acid.
Background technology
Hexanodioic acid is important industrial chemicals, mainly for the production of nylon 66, urethane, softening agent etc.At present, the main method that prior art is produced hexanodioic acid is hexanaphthene two-step oxidation method, adopt French Long Baili technology, its technological process is: hexanaphthene is carried out liquid phase make cyclohexyl hydroperoxide without catalysis oxygen deprivation oxidation under certain temperature, pressure, the deep oxidation by product is removed in washing, then cyclohexyl hydroperoxide is carried out catalytic decomposition and obtain hexalin and pimelinketone, hexalin and pimelinketone after making with extra care are produced hexanodioic acid with nitric acid oxidation.Although this technique exists nitric acid oxidation technology maturation, advantage that products obtained therefrom purity is high, weak point is also arranged: the hexanaphthene per pass conversion is low, is generally about 3.8%; The hexanaphthene internal circulating load is large, and hexanaphthene Distallation systm load, energy consumption and manufacturing cost are high, has washes to discharge, and the nitric acid consumption is higher, complex technical process.
Another kind of technique is to adopt the hexanaphthene non-catalyst oxidation to obtain KA oil (mixture of pimelinketone and hexalin) equally, adopts nitric acid oxidation to obtain hexanodioic acid KA oil again, and subsequent step is identical with above-mentioned French Long Baili technology.This technical maturity is reliable, but the problem that has salkali waste to process.
Also have a kind of technique take benzene as raw material, after partial hydrogenation obtained tetrahydrobenzene, rehydrated generation hexalin was obtaining hexanodioic acid with the hexalin nitric acid oxidation, and subsequent technique is identical with French Long Baili technology.This technology has environmental protection and cost advantage.In general, the preparation technology that only limits at the raw material of nitric acid oxidation of the difference of all techniques is different.
Combine this, many scholars still are devoted to the research of air oxidation of cyclohexane novel method, novel process and hexanodioic acid new preparation process.Someone prepares hexanodioic acid take the acetate of Co, Mn, Cu as catalyzer with air or oxygen direct oxidation hexanaphthene, discloses the method that salt catalytic air oxidation hexanaphthene prepares hexanodioic acid of boring of using such as WO96.3365 and WO99.40058.These methods still exist cyclohexane conversion and adipic acid yield is low or production cost is high problem.
In recent years, the scholar is arranged to preparing hexalin take hexanaphthene as raw material NI catalysis catalytic oxidation and pimelinketone is studied, disclose a kind ofly in the presence of metal leaf beautiful jade catalyzer such as patent CN1435401A, prepared the technique of hexalin and pimelinketone by hexanaphthene; Patent CN 1269343A discloses a kind of in the presence of metal leaf beautiful jade catalyzer, the method for catalytic air oxidation alkane and naphthenic hydrocarbon.At present, in the presence of the catalysis of metalloporphyrin agent, the technique that is prepared hexalin and pimelinketone by hexanaphthene realizes industrialization in Ba Ling petrochemical industry branch office of China Petrochemical Industry, the method has solved that the hexanaphthene per pass conversion is low, the hexanaphthene internal circulating load is large, hexanaphthene Distallation systm load is high, saved the problem such as resolving cell operation, but technological process still comprises the unit operations such as washing, hexalin and pimelinketone rectifying, still has the acid waste water emission problem.
At present, R﹠D institution is also arranged to being studied as the raw material one-step oxidation process prepares hexanodioic acid take hexanaphthene, all the employing technique that to have inferior amide structure compound be the catalyst oxidizing ethyle alkyl is introduced such as patent CN01822566.7, CN01803724.0, CN00137320.X etc., invention company mainly is Japanese Daicel company, it is reported this technology successful Application on the small-scale pilot plant, but because it has that energy consumption is high, selectivity is low and engineering is amplified and had a big risk, cause this technology unanimously can't successful industrialization.Contain a large amount of carboxylic acid esters materials in its by-product diprotic acid in addition, cause this diprotic acid can't satisfy the market requirement of nylon acid.
Summary of the invention
The present invention is directed to deficiency, propose a kind of preparation method of hexanodioic acid, the hexanaphthene per pass conversion is high, the hexanaphthene internal circulating load is little, nitric acid consumes low.
In order to realize the foregoing invention purpose, the invention provides following technical scheme: a kind of preparation method of hexanodioic acid may further comprise the steps:
1., hexanaphthene oxidation under the combination catalyst that is consisted of by imide compound and transistion metal compound, the imide compound consumption is 1～10000mg/kg hexanaphthene, the transistion metal compound consumption is 10～10000mg/kg hexanaphthene; Temperature is 90 ℃～170 ℃, pressure 0.8～3.0MPa; Flash distillation, rectifying gets catalysate;
2., 1. catalysate oxide treatment under the copper vanadium catalyst of step, crystallisation by cooling, centrifugation, filter residue gets hexanodioic acid through recrystallization; Filtrate is cooled off to get diprotic acid through distillation, macroporous resin adsorption.
Preferably, step 1. in catalyzed oxidation be to be to carry out in the solvent at acetic acid, acetone or acetonitrile.
Preferably, the massfraction of described solvent is 10%～80%.
Preferably, step 1. in catalyzed oxidation be to be to carry out in 6%～50% oxygen-rich air or the oxygen-denuded air in oxygen concentration.
Preferably, 2. step contains the nitric acid of 40wt%～68wt% in the copper vanadium catalyst.
Preferably, step 1. in the imide compound catalyzer be structural formula as shown in the formula the compound of I:
Wherein: X is Sauerstoffatom or hydroxyl.
Preferably, described imide compound catalyzer is at least a in the adjacent naphthalimide of HP, N-hydroxyl, N-hydroxyl maleimide, N-hydroxy-succinamide and their derivative.
Preferably, described imide compound catalyzer is structural formula as shown in the formula the compound of II:
Wherein: R
1Or R
2Be hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, alkoxyl group, carboxyl, alkoxy carbonyl or acyl group.
Preferably, described R
1With R
2Be coupled together and form aromatic hydrocarbon or the two keys of non-aromatic hydrocarbon.
Preferably, step 2. in the copper vanadium catalyst mass percent of copper content be 0.1%～1.0%, content of vanadium is 10～10000mg/kg.
Preferably, step 2. nitric acid dosage and step 1. the weight ratio of catalyzed oxidation mixture be 1.5～3.0: 1.0.
Preferably, step 1. in transition metal be selected from titanium, vanadium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel and the copper a kind of; Described transistion metal compound comprises at least a of oxide compound, organic acid salt, inorganic acid salt, halogenide, alkoxide, mixture, oxygen acid and salt thereof, isopoly-acid and the salt thereof of transition metal and heteropolyacid and salt thereof; Be preferably and contain the cobalt compounds.
Compared with prior art, the present invention utilizes oxidizing ethyle alkyl under the existence of imide compound catalyzer; The above-mentioned oxidation mixture of oxidation under the effect of copper vanadium catalyst makes hexanodioic acid and diprotic acid again.Can solve well existing, the problems such as hexanaphthene internal circulating load large, nitric acid consumption height, complex technical process low by the hexanaphthene per pass conversion that exists in the cyclohexane oxidation adipic acid process processed.
Major advantage of the present invention and effect have: (1) hexanaphthene per pass conversion is increased to more than 10% by existing 3.8%, and the hexanaphthene internal circulating load reduces more than 50%, alleviates hexanaphthene Distallation systm load, reduces energy consumption and manufacturing cost; (2) eliminated washing cyclohexane oxidation product process, no acidic washes discharging; (3) under identical hexanodioic acid and diprotic acid output, the nitric acid consumption reduces nearly 30%; (4) can directly apply to existing hexanaphthene hexanodioic acid full scale plant processed, reach the purpose that reduces production costs and expand energy; (5) simplify the technological process that existing cyclohexane oxidation process is produced hexanodioic acid, save washing, decomposing cyclohexyl hydrogen peroxide and pimelinketone and hexalin distillation system.(4) the present invention does not need to consume caustic soda fully, does not have the processing problem of salkali waste yet.
The present invention is take hexanaphthene as raw material, is that oxygen source carries out imide compound (NI) catalyzed oxidation through air or oxygen-denuded air or oxygen-rich air, and mixture carries out a kind of method of nitric acid oxidation hexanodioic acid processed again.When adopting present method to produce hexanodioic acid, the diprotic acid such as the pentanedioic acid that this process can be generated, Succinic Acid reclaim.Present method not only have technical process short, do not need washing, do not need decomposing cyclohexyl hydrogen peroxide and pimelinketone and hexalin distillation system, avoid caustic soda consumption, the nitric acid consumption is low, hexanodioic acid and diprotic acid total recovery reach (having technique now is 78%) 95% or more, and in the production chemical product, avoided the salkali waste in the liquid phase air oxidation hexanaphthene process to process problem, the quantity discharged of the nitrogenous tail gas of decrease nitric acid oxidation part has reduced environmental pollution significantly simultaneously.
Embodiment
A kind of hexanaphthene that utilizes is raw material production hexanodioic acid and own, penta, the method of fourth mixture dicarboxylic acid product, hexanaphthene is at the imide compound of 1～10000mg/kg hexanaphthene, and under the existence of the combination catalyst of the transistion metal compound of 10～10000mg/kg hexanaphthene (being called for short the NI catalyzed oxidation), use acetic acid, acetone or acetonitrile are solvent, the solvent quality ratio is controlled at 10%～80%, temperature is at 90 ℃～170 ℃, pressure-controlling is under 0.8～3.0MPa pressure, with air or oxygen-rich air or oxygen-denuded air oxidizing ethyle alkyl, wherein oxygen concentration is controlled at 6%～50% in oxygen-rich air or the oxygen-denuded air, reclaim the unreacted hexanaphthene through flash separation again, get hexanaphthene NI catalyzed oxidation mixture behind the rectifying recovery of acetic acid, with 40%～68% nitric acid oxidation hexanaphthene NI catalyzed oxidation mixture hexanodioic acid processed and diprotic acid of cupric vanadium catalyst quality meter; The nitric acid oxidation product gets thick hexanodioic acid and crystalline mother solution through crystallisation by cooling, centrifugation; The thick hexanodioic acid of gained obtains smart hexanodioic acid through recrystallization; Thick crystallization of adipic acid mother liquor namely gets dicarboxylic acid product with smart crystallization of adipic acid mother liquor merging enrichment, melting, cooling junction plate behind enrichment recovery part nitric acid and copper vanadium catalyst.
Main component includes in the above-mentioned hexanaphthene mixture behind the NI catalyzed oxidation: hexalin, pimelinketone and hexanodioic acid comprise other oxidation productss C1～C6 monoprotic acid and 6 hydroxycaproic acid, hexanal acid, the diester class of C1～C6, cyclohexanediol, hexamethylene alcohol ketone, aldehydes.
Wherein the imide compound catalyzer is structural formula as shown in the formula the compound of I:
Wherein: X is Sauerstoffatom or hydroxyl, as at least a in HP, the adjacent naphthalimide of N-hydroxyl, N-hydroxyl maleimide, N-hydroxy-succinamide and their derivative.
Preferably, the imide compound catalyzer is structural formula as shown in the formula the compound of II:
Wherein: R
1Or R
2Be hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, alkoxyl group, carboxyl, alkoxy carbonyl or acyl group.Preferred, R
1With R
2Be coupled together and form aromatic hydrocarbon or the two keys of non-aromatic hydrocarbon.
In the nitric acid oxidation agent of above-mentioned cupric vanadium catalyst, the mass percent of copper content is 0.1%～1.0%, and content of vanadium is 10～10000mg/kg; The concentration of oxygenant nitric acid is 40%～68%.
The processing condition of the direct nitric acid oxidation of hexanaphthene NI catalyzed oxidation mixture hexanodioic acid processed and diprotic acid are: cyclohexane oxidation mixture and nitric acid are take the quality feed ratio of anhydride as 1.0: 1.5～3.0; The nitric acid oxidation reaction time is 0.5h～3.0h during periodical operation, and the nitric acid oxidation reaction mean residence time is 0.5h～4.0h during operate continuously; The nitric acid oxidation reaction temperature is 50 ℃～100 ℃; Periodical operation is gradient increased temperature, and many still series connection are adopted in operate continuously; The oxidizing reaction working pressure is 0.080～0.15MPa.
Hexanaphthene NI catalyzed oxidation adopts air or oxygen-rich air or oxygen-denuded air as oxygen source, and oxygen quality concentration is controlled at 6%～50%.
Every acquisition 100g hexanodioic acid and 19.6g diprotic acid, needing to drop into concentration is the nitric acid 380g～420g of 55% (weight) of cupric vanadium catalyst, and the ratio of resulting hexanodioic acid and diprotic acid quality and raw material hexanaphthene quality is followed successively by more than 1.24 and 0.25.Nitric acid oxidation product mixed solution carries out decrease temperature crystalline, and final temperature is 25 ℃～30 ℃, and crystallization time is 120～240min, can get adipic acid crystals and crystalline mother solution through centrifugation.The thick adipic acid crystals that obtains is added gac carries out recrystallization and gets final product to get smart hexanodioic acid.Crystalline mother solution is through enrichment recovery part nitric acid and carry out after twice resins exchange reclaim catalyzer copper vanadium, revaporization is concentrated into 140 ℃～180 ℃ of temperature of charge, namely greater than the melt temperature of mixed dibasic acid, again cooling junction plate can obtain glaucous, sheet oneself, penta, fourth mixed dibasic acid product.
Smart hexanodioic acid obtained above and dicarboxylic acid product, its product purity is successively: hexanodioic acid content＞99.5% (weight), diprotic acid content＞95% (weight), the relative content of hexanodioic acid, pentanedioic acid and Succinic Acid is followed successively by 15%～35%, 35%～60%, 15%～35% in the diprotic acid.
The techniques such as above-mentioned hexanaphthene NI catalyzed oxidation, flash separation, nitric acid oxidation can intermittently be carried out among the present invention, also can carry out continuously.
Describe the present invention below in conjunction with specific embodiment, the description of this part only is exemplary and explanatory, should any restriction not arranged to protection scope of the present invention.
Embodiment 1
In a 1L zirconium reactor, add following reactant: 0.5003g HP, 0.5010g cobalt naphthenate, 250.6g acetone, 250.2g hexanaphthene.At 100 ℃, react 1h under the 1.0MPa.Reaction distills out acetone and hexanaphthene after finishing under the normal pressure.After measured, hexanaphthene transforms 61.3g, and transformation efficiency is 24.5%, obtains oxidation products 107.6g.The reaction product that obtains is carried out nitric acid oxidation reaction.Nitric acid oxidation acid preparation: 400g concentration is the nitric acid of 63wt%, 10.0g cupric nitrate, 1.0g ammonium meta-vanadate.Under the normal pressure oxidizing acid is heated to 75 ℃, cyclohexane oxidation product is added dropwise to after heating for dissolving in the oxidizing acid, and time for adding is about 1.5h, and keeping temperature of reaction in the dropping process is 75 ℃, after reaction finishes, after the treating processess such as crystallization, recrystallization and mother liquor acid distillation, obtain the smart hexanodioic acid of 72.7g, obtain mixed dibasic acid 25.4g, by analysis, hexanodioic acid 3.1g in the mixed dibasic acid, pentanedioic acid 13.0g, Succinic Acid 8.8g.Count from hexanaphthene, the yield of hexanodioic acid is 71.2%, and the yield of pentanedioic acid is 13.5%, and the yield of Succinic Acid is 10.2%.The yield of diprotic acid adds up to 94.9%.
Embodiment 2
In a 1L zirconium reactor, add following reactant: 0.5004g N-maloyl imines, 1.5007g cobalt naphthenate, 350.5g acetone, 150.0g hexanaphthene.At 120 ℃, react 50min under the 1.0MPa.Reaction distills out acetone and hexanaphthene after finishing under the normal pressure.After measured, hexanaphthene transforms 42.1g, and transformation efficiency is 28.1%, obtains oxidation products 87.2g.The reaction product that obtains is carried out nitric acid oxidation reaction.Nitric acid oxidation acid preparation: 400g concentration is the nitric acid of 63wt%, 10.0g cupric nitrate, 0.9g Vanadium Pentoxide in FLAKES.Under the normal pressure oxidizing acid is heated to 75 ℃, cyclohexane oxidation product is added dropwise to after heating for dissolving in the oxidizing acid, and time for adding is about 1.5h, and keeping temperature of reaction in the dropping process is 75 ℃, after reaction finishes, after the treating processess such as crystallization, recrystallization and mother liquor acid distillation, obtain the smart hexanodioic acid of 48.1g, obtain mixed dibasic acid 16.2g, by analysis, hexanodioic acid 1.0g in the mixed dibasic acid, pentanedioic acid 8.4g, Succinic Acid 5.3g.Count from hexanaphthene, the yield of hexanodioic acid is 67.1%, and the yield of pentanedioic acid is 12.7%, and the yield of Succinic Acid is 8.9%.The yield of diprotic acid adds up to 88.7%.
Embodiment 3
In a 1L zirconium reactor, add following reactant: 0.5007g HP, 0.2510g Cobaltous diacetate, 250.1g acetic acid, 249.8g hexanaphthene.At 100 ℃, react 1h under the 1.0MPa.Reaction distills out hexanaphthene under the normal pressure after finishing, and vacuum fine distillates acetic acid.After measured, hexanaphthene transforms 64.7g, and transformation efficiency is 25.9%, obtains oxidation products 116.4g.The reaction product that obtains is carried out nitric acid oxidation reaction.Nitric acid oxidation acid preparation: 403g concentration is the nitric acid of 63wt%, 10.1g cupric nitrate, 0.9g Vanadium Pentoxide in FLAKES.Under the normal pressure oxidizing acid is heated to 75 ℃, cyclohexane oxidation product is added dropwise to after heating for dissolving in the oxidizing acid, and time for adding is about 1.5h, and keeping temperature of reaction in the dropping process is 75 ℃.After reaction finishes, after the treating processess such as crystallization, recrystallization and mother liquor acid distillation, obtain the smart hexanodioic acid of 76.4g, obtain mixed dibasic acid 28.4g, by analysis, hexanodioic acid 3.2g in the mixed dibasic acid, pentanedioic acid 14.5g, Succinic Acid 9.6g.Count from hexanaphthene, the yield of hexanodioic acid is 70.8%, and the yield of pentanedioic acid is 14.3%, and the yield of Succinic Acid is 9.6%, and the diprotic acid selectivity adds up to 95.7%.
Embodiment 4
In a 1L zirconium reactor, add following reactant: 0.4998g N-maloyl imines, 0.2009g Cobaltous diacetate, 251.0g acetic acid, 250.2g hexanaphthene.At 120 ℃, react 1h under the 1.0MPa.Reaction distills out hexanaphthene under the normal pressure after finishing, and vacuum fine distillates acetic acid.After measured, hexanaphthene transforms 60.1g, and transformation efficiency is 24.0%, obtains oxidation products 103.5g.The reaction product that obtains is carried out nitric acid oxidation reaction.Nitric acid oxidation acid preparation: 398g concentration is the nitric acid of 63wt%, 9.8g cupric nitrate, 0.8g Vanadium Pentoxide in FLAKES.Under the normal pressure oxidizing acid is heated to 75 ℃, cyclohexane oxidation product is added dropwise to after heating for dissolving in the oxidizing acid, and time for adding is about 1.5h, and keeping temperature of reaction in the dropping process is 75 ℃.After reaction finishes, after crystallization and recrystallization processing, obtain the smart hexanodioic acid of 69.3g, obtain mixed dibasic acid 26.3g, by analysis, hexanodioic acid 3.7g in the mixed dibasic acid, pentanedioic acid 12.6g, Succinic Acid 7.8g.Count from hexanaphthene, the yield of hexanodioic acid is 69.9%, and the yield of pentanedioic acid is 13.4%, and the yield of Succinic Acid is 9.3%.The yield of diprotic acid adds up to 92.6%.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (12)
1. the preparation method of a hexanodioic acid may further comprise the steps:
1., hexanaphthene oxidation under the combination catalyst that is consisted of by imide compound and transistion metal compound, the imide compound consumption is 1～10000mg/kg hexanaphthene, the transistion metal compound consumption is 10～10000mg/kg hexanaphthene; Temperature is 90 ℃～170 ℃, pressure 0.8～3.0MPa; Flash distillation, rectifying gets catalysate;
2., 1. catalysate oxide treatment under the copper vanadium catalyst of step, crystallisation by cooling, centrifugation, filter residue gets hexanodioic acid through recrystallization; Filtrate is cooled off to get diprotic acid through distillation, macroporous resin adsorption.
2. preparation method as claimed in claim 1 is characterized in that: step 1. in catalyzed oxidation be to be to carry out in the solvent at acetic acid, acetone or acetonitrile.
3. preparation method as claimed in claim 2, it is characterized in that: the massfraction of described solvent is 10%～80%.
4. preparation method as claimed in claim 1 is characterized in that: step 1. in catalyzed oxidation be to be to carry out in 6%～50% oxygen-rich air or the oxygen-denuded air in oxygen concentration.
5. preparation method as claimed in claim 1 is characterized in that: 2. step contains the nitric acid of 40wt%～68wt% in the copper vanadium catalyst.
6. preparation method as claimed in claim 1 is characterized in that: step 1. in the imide compound catalyzer be structural formula as shown in the formula the compound of I:
Wherein: X is Sauerstoffatom or hydroxyl.
7. preparation method as claimed in claim 6 is characterized in that: described imide compound catalyzer is at least a in the adjacent naphthalimide of HP, N-hydroxyl, N-hydroxyl maleimide, N-hydroxy-succinamide and their derivative.
8. preparation method as claimed in claim 6 is characterized in that: described imide compound catalyzer is structural formula as shown in the formula the compound of II:
Wherein: R
1Or R
2Be hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, alkoxyl group, carboxyl, alkoxy carbonyl or acyl group.
9. preparation method as claimed in claim 8 is characterized in that: described R
1With R
2Be coupled together and form aromatic hydrocarbon or the two keys of non-aromatic hydrocarbon.
10. preparation method as claimed in claim 1 is characterized in that: step 2. in the copper vanadium catalyst mass percent of copper content be 0.1%～1.0%, content of vanadium is 10～10000mg/kg.
11. preparation method as claimed in claim 5 is characterized in that: step 2. nitric acid dosage and step 1. the weight ratio of catalyzed oxidation mixture be 1.5～3.0: 1.0.
12. preparation method as claimed in claim 1 is characterized in that: step 1. middle transition metal is selected from titanium, vanadium, chromium, molybdenum, manganese, iron, ruthenium, cobalt, rhodium, nickel and the copper a kind of; Described transistion metal compound comprises at least a of oxide compound, organic acid salt, inorganic acid salt, halogenide, alkoxide, mixture, oxygen acid and salt thereof, isopoly-acid and the salt thereof of transition metal and heteropolyacid and salt thereof; Be preferably and contain the cobalt compounds.
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| CN104109083A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method of preparing adipic acid by directly oxidizing cyclohexane |
| CN104549520A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for preparing adipic acid by direct oxidation of cyclohexane |
| CN105665010A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Catalyst for preparation of adipic acid from cyclohexane by direct oxidation |
| CN108084012A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method that peroxyester prepares adipic acid |
| CN113651685A (en) * | 2021-09-25 | 2021-11-16 | 侯凤芹 | Process for preparing dicarboxylic acid by two-step oxidation of cycloalkane |
| CN113735703A (en) * | 2021-09-16 | 2021-12-03 | 宁夏瑞泰科技股份有限公司 | Method for effectively recovering dibasic acid and nitric acid from adipic acid wastewater |
| CN116273046A (en) * | 2023-04-11 | 2023-06-23 | 郑州中科新兴产业技术研究院 | Vanadium extraction tailings treatment method for catalyzing cyclohexane oxidation reaction |
| CN116375986A (en) * | 2023-02-24 | 2023-07-04 | 广西科学院 | All-wood cellulose-based polyester and preparation method thereof |
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