CN101045682A - Method for retrieving organic acid, ester from cyclic ethane oxidation liquid - Google Patents
Method for retrieving organic acid, ester from cyclic ethane oxidation liquid Download PDFInfo
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Abstract
This invention supplies a method of reclaiming organic acid and ester from cyclohexane oxidation liquid. in the process of Cyclohexanone production, using water to extract the oxidation liquid after cyclohexane oxidation to obtain acidic water solution, then carry out catalytic oxidationm to obtain water solution containing acid and ester; next by two-stage evaporation, fusion acid and ester that water content less than 10 percent will be obtained. Adding in spririts, catalyzer and water slug agent for esterification, then mixed acid and ester product will obtained. This invention relates to synthetic method of 1 - hydroxy -2-methyl-4 -acetoxy - 2-butylene that is importance intermediate of vitamin A acetas. Existing method all are hard to reach content selectivity and yield, used catalyzer is incapable of applying and has lost. It takes basicity anion exchange resin as catalyzer, in the spirits solvent, makes 1 -hydroxy-2-methyl-4-acetoxy-2-butyene carry out ester exchange reaction, and without intermission distil outgrowth off reaction system in the reaction, recovering solvent after reaction by distilling. Then through filtration to catalyst separate crude product and catalyzer.
Description
Technical field
The present invention relates to a kind of method that from cyclohexane oxide solution, reclaims organic acid, ester
Background technology
The cyclohexanone production process route mainly contains phenol hydrogenation, hexanaphthene liquid phase air oxidation, cyclohexene hydration etc.The hexanaphthene liquid-phase air oxidation is main in the world pimelinketone, cyclohexanol production operational path, and its technology is simply ripe, and it is less to one-time fix investment, and present 90% Cyclohexanone Production adopts cyclohexane oxidation process.
Cyclohexane oxidation process can be divided into again catalysis and non-catalyst oxidation method, no catalysis method be under high temperature, high pressure directly with air with cyclohexane oxidation, domestic main Cyclohexanone Production producer all adopts this method.The transformation efficiency that this method is produced pimelinketone is generally 3.5-4%, and the product yield of hexanaphthene is about 82% relatively, and Dutch DSM N. V. adopts non-catalyst oxidation.Germany BASF AG adopts traditional cobalt salt catalytic air oxidation technology, and its device transformation efficiency is about 4%, relatively the product yield about 80% of hexanaphthene.The CyclopoL technology of Poland Polimerx group exploitation is the cobalt salt catalytic air oxidation method of a still multicellular reactor, and its process characteristic is the last handling process that has improved oxide compound, the product yield about 80% of the relative hexanaphthene of this technology.And in recent years, it is representative that domestic cyclohexane bionic catalyzed oxidation with Hunan University's exploitation prepares the research of pimelinketone novel process, the catalyzed oxidation novel process of exploitation does not have Catalytic processes with tradition and compares, though transformation efficiency has improved, temperature of reaction, system pressure have reduced, but product yield is still not high, and its technology produces more relatively by product under the constant situation of principal product.In a word, no matter catalysis is arranged or no catalysis air oxidation of cyclohexane prepares pimelinketone technology, its product yield is suitable, and by-products content is all higher.The by product main ingredient is various organic acids and ester, comprising various caproic acid hydrogen peroxide, monoprotic acid, diprotic acid (mainly being Succinic Acid, pentanedioic acid, hexanodioic acid), alcohol acid and Ester.
At present, the cyclohexane oxidation that Cyclohexanone Production producer is adopted prepares the pimelinketone technological process: hexanaphthene is through obtaining containing the oxidation liquid of principal product (cyclohexyl hydroperoxide, hexalin, pimelinketone) and all kinds of by products after the atmospheric oxidation, oxidation liquid then decomposes neutralization reaction; In water, alkali environment, the principal product cyclohexyl peroxide resolves into pimelinketone and hexalin in the oxidation liquid, has mainly generated organic acid sodium salt after the byproduct reaction; After decomposing neutralization reaction, system is carried out separating of organic phase and inorganic phase, organic phase is the refining step that pimelinketone and hexalin mixture enter postorder, and the inorganic basic organic acid sodium-salt aqueous solution (abbreviation saponification waste lye) that produces after the by-product destruction neutralization reaction that is mutually enters aftertreatment.There are two kinds of processing modes in Cyclohexanone Production producer to this by product waste lye at present, a kind of neutralisation, and a kind of is burning method.The shortcoming that neutralisation is handled saponification waste lye is to discharge, COD (chemical oxygen demand) up to ten thousand sewage suitable with waste lye quantity; And the shortcoming of burning method is that useful organism a large amount of in the by product is all burnt, generate carbonic acid gas, water and the very low inorganic carbonate sodium salt of attached value, incomplete combustion causes topsoil on the one hand, and some irretrievable yellow soda ash products are dissolved in the water and discharge with waste water formation on the other hand.
Therefore, organic acid, ester by product in the cyclohexane oxide solution are reclaimed, no matter still be that the catalyzed oxidation novel process all is of great importance to hexanaphthene non-catalyst oxidation technology.
CN1069631 discloses a kind of method of obtaining hexanodioic acid and diprotic acid.Its technological process is to contain in the cyclohexane oxide solution by product organic acid acid waste water after heating evaporation concentrates under normal pressure or the decompression, be to carry out thermolysis between 90 ℃～105 ℃ or be that catalyzer carries out cartalytic decomposition effect in normal pressure, temperature with the variable valency metal ions, mixed solution after the decomposition carries out oxidizing reaction with nitric acid, generates hexanodioic acid and diprotic acid mixed solution.Obtain the solid diprotic acid through enrichment, crystallization, filtration, drying and activated carbon treatment again.There is the shortcoming of following two aspects in this method: 1, with the by product after the further oxidizing ethyle alkyl oxidation of nitric acid, and complex process, raw material is difficult for producing and stores, and environmental pollution is big in the production process; 2, the product postprocessing process after the oxidation (crystallization, filtration, drying etc.) technical process is long, and investment is big, should not be used for output little by-product recovery.
CN1651390 discloses a kind of method for preparing hexanodioic acid with the cyclohexane oxidation liquid pickling water hydrogen peroxide catalytic oxidation.CN83308 discloses a kind of method with the cyclohexane oxidation liquid pickling water preparing hexane diacid by nitric acid catalyzed oxidation.These two kinds of methods are primarily aimed in being the production equipment of purpose product with the hexanodioic acid, the oxidising process of the acid washing water behind the cyclohexane oxidation the former to have adopted hydrogen peroxide be oxygenant, it is oxygenant that the latter has adopted the not too disagreeableness salpeter solution of environment, the last handling process of acid has all adopted crystallization, filtration, exsiccant process, suitable with the CN1069631 patented technology, there is the raw materials cost height, facility investment is big, the recovery product is single, and the by product in the cyclohexane oxide solution does not all obtain the shortcoming of efficient recovery except that hexanodioic acid.
Summary of the invention
The objective of the invention is the defective that exists at prior art, provide that a kind of technology is simple, facility investment is little, operation easier is little, consumptions is low, good economy performance, method that the by-product recovery rate is high, organic acid, ester in the recovery cyclohexane oxide solution.
The invention provides a kind of method that reclaims organic acid, ester from cyclohexane oxide solution, this method may further comprise the steps:
1, in the Cyclohexanone Production process, the oxidation liquid water behind the cyclohexane oxidation extracts, and control water oil phase extracted the water-soluble substances in the oxidation liquid than 10: 1～70: 1 in the extraction process, obtained containing the acidic aqueous solution of a small amount of hexalin, pimelinketone; With hexanaphthene the tart aqueous solution is stripped again, control profit in the extraction process and compare 1: 1～2: 1, reclaim a small amount of hexalin, the pimelinketone carried secretly in the acidic aqueous solution, obtain containing the acidic aqueous solution of caproic acid hydrogen peroxide, alcohol acid, monocarboxylic acid, di-carboxylic acid, non-hexalin ester class.
2, acidic aqueous solution enters oxidation reactor, adds catalyzer, 90 ℃～110 ℃ of temperature, under pressure 0.1Mpa～0.3Mpa, carries out catalyzed oxidation with the gas of molecule-containing keto, obtains containing the aqueous solution of acid, ester; Catalyzer is a kind of metal-salt or their metallo-organic complex or their mixture of cobalt, manganese, iron, zinc, copper, chromium, nickel, molybdenum, ruthenium, the add-on of catalyzer is as the criterion at 0.1mg/kg～50mg/kg with the content of control metal ion, the gas of molecule-containing keto comprises pure oxygen, ozone, air, and vapour-liquid ratio was controlled at 20: 1～80: 1.
3, the aqueous solution that contains acid, ester enters the single vaporization device, carries out air distillation, steam the moisture of aqueous solution cumulative volume 40%～50% after, enter second evaporator, under absolute pressure 30kPa～70kPa, remove moisture content, obtain the water yield less than 10% fusion acid, ester mixture;
The mixture of 4, fusion acid, ester enters esterifier, add alcohols material, catalyzer, band aqua, wherein alcohols material is selected from a kind of in ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, isohexyl alcohol, n-Octanol, isooctyl alcohol, the hexalin; The add-on of alcohols material is as the criterion at 2: 1～4: 1 with the control acid-alcohol ratio; Catalyzer is selected from a kind of in sulfuric acid, solid super-strong acid, modified cation-exchange resin, tosic acid, the sodium pyrosulfate; The weight ratio of catalyst consumption and fusion acid total amount is 1: 100～1: 200; The band aqua is to be selected from toluene, dimethylbenzene, hexanaphthene, benzene, 1, a kind of in 2-ethylene dichloride, the methyl alcohol; The add-on of band aqua accounts for system cumulative volume 10%～20%; Carry out esterification, temperature of reaction control is as the criterion with normal backflow of guarantee system, finish esterification after, obtain the mixed acid ester product.
The present invention has following positive effect:
1, the organic acid more than 70%, ester obtain reclaiming in the cyclohexane oxide solution, and simultaneously, the sodium hydroxide consumption that can make cyclohexane oxidation prepare pimelinketone technology reduces by 50%;
2,, utilize by-product production to go out to have the nitration mixture ester byproduct of economic worth, be used for high boiling solvent and softening agent industry, turn waste into wealth;
3, reduced in the existing cyclohexanone production process process by 50% saponification waste lye by product, environment protection has been had positive meaning;
4, by the separation of by-products in the simple washing process realization cyclohexane oxide solution; Under the effect of metal catalyst, carry out catalyzed oxidation; By product after the oxidation under unseparated situation, direct esterification after the vacuum hydro-extraction.Its technology is simple, facility investment is little, operation easier is little;
5, in esterification reaction process, add the band aqua, reduced system temperature, utilize band aqua and water to form the principle of azeotropic mixture, the water that generates is constantly removed, thereby disequilibrated, esterification is tending towards fully, make reaction thoroughly.
Embodiment
Below in conjunction with embodiment the present invention is described in detail.
Embodiment 1:
About 170 ℃ of temperature, pressure is under the condition of 1..05Mpa, hexanaphthene overflow successively carries out liquid phase through 6 placed in-line stills for air blowing and does not have catalytic air oxidation, by-products content is respectively from the cyclohexane oxide solution that the 6# stills for air blowing come out: total acid 0.3%, total ester 0.32%, water-soluble peroxide 0.35%, this oxidation liquid temperature after the interchanger heat exchange is reduced to 90 ℃ and is laggardly gone into water wash column, by 10: 1 profit compare carry out water washing after, content of by-products is respectively total acid 0.1% in the oxidation liquid, total ester 0.2%, water-soluble peroxide 0.07%, obtain content and be respectively total acid 6%, total ester 5%, the total mistake is 4.5% and hexalin, cyclohexanone content is respectively 0.4%, 0.2% sour water, sour water is squeezed into the back extraction tower by pressure reduction, by 1～2: 1 profit is compared the adding fresh cyclohexane, make hexalin in the sour water, pimelinketone reclaims, sour water enters stills for air blowing then, drop into the Manganese Porphyrin catalyzer, making system catalyst content is 10ppm, open ozonizer, vapour-liquid ratio was controlled at 20: 1, organic constituent in the sour water and oxygen molecule generation oxidizing reaction, reaction time was controlled at 2 hours.Enter distillation tower after the sour water oxidizing reaction, elder generation's air distillation, limit monitoring water-content changes, treat that water-content is at 30% o'clock, the system vacuum distillation, vacuum control is at 50kpa, with sour water carry dense to moisture be 8%, total acid content 57%, total ester content 20%, the concentrated acid liquid of other organism 15%, concentrated acid liquid is squeezed into esterifier at last, carry out esterification, add methyl alcohol, sulfuric acid, toluene, the weight ratio of sulfuric acid consumption and sour total amount are 1/200, and the control acid-alcohol ratio is 3: 1, the toluene amount accounts for system cumulative volume 20%, temperature of reaction is controlled at 75 ℃, reacts 3 hours, carries out rectification under vacuum after esterification is finished and obtains nitration mixture dimethyl ester product.
Embodiment 2:
About 170 ℃ of temperature, pressure is under the condition of 1.10Mpa, hexanaphthene overflow successively carries out liquid phase through 5 placed in-line stills for air blowing and does not have catalytic air oxidation, by-products content is respectively from the cyclohexane oxide solution that the 5# stills for air blowing come out: total acid 0.28%, total ester 0.30%, water-soluble peroxide 0.30%, this oxidation liquid boils off 40% hexanaphthene by a flashing tower, temperature is reduced to 89 ℃ and is laggardly gone into water wash column after the interchanger heat exchange then, by 20: 1 profit compare carry out water washing after, content of by-products is respectively total acid 0.11% in the oxidation liquid, total ester 0.25%, water-soluble peroxide 0.10%, obtain content and be respectively total acid 8%, total ester 7.5%, the total mistake is 7% and hexalin, cyclohexanone content is respectively 0.5%, 0.3% sour water, sour water is squeezed into the back extraction tower by pressure reduction, compare the adding fresh cyclohexane by 1: 1 profit, make hexalin in the sour water, pimelinketone reclaims, sour water enters stills for air blowing then, drop into manganese acetate catalyst, making system catalyst content is 5ppm, bubbling air, vapour-liquid ratio was controlled at 60: 1, organic constituent in the sour water and airborne oxygen molecule generation oxidizing reaction, and reaction time was controlled at 3 hours.Enter distillation tower after the sour water oxidizing reaction; elder generation's air distillation; limit monitoring water-content changes; treat that water-content is at 40% o'clock; the system vacuum distillation; vacuum control is at 60kpa; sour water is carried dense to moisture 9%; total acid content 61%; total ester content 21%; the concentrated acid water of other organism 9%; concentrated acid water is after pump is squeezed into esterifier; carry out esterification; add isooctyl alcohol; solid super acid catalyst; and benzene; the weight ratio of catalyst consumption and sour total amount is 1/100, and the control acid-alcohol ratio is 3: 1, adds the band aqua that accounts for system cumulative volume 15%; temperature of reaction control is as the criterion with normal backflow of guarantee system, carries out rectification under vacuum after esterification is finished and obtains nitration mixture dioctyl ester product.
Embodiment 3:
About 150 ℃ of temperature, pressure is under the condition of 0.9Mpa, hexanaphthene overflow successively carries out liquid phase through 4 placed in-line stills for air blowing catalytic air oxidation is arranged, by-products content is respectively from the cyclohexane oxide solution that the 4# stills for air blowing come out: total acid 0.9%, total ester 0.40%, water-soluble peroxide 0.30%, this oxidation liquid boils off 40% hexanaphthene by a flashing tower, temperature is reduced to 89 ℃ and is laggardly gone into water wash column after the interchanger heat exchange then, by 20: 1 profit compare carry out water washing after, content of by-products is respectively total acid 0.15% in the oxidation liquid, total ester 0.28%, water-soluble peroxide 0.12%, obtain content and be respectively total acid 13%, total ester 8%, the total mistake is 8% and hexalin, cyclohexanone content is respectively 0.45%, 0.29% sour water, sour water is squeezed into the back extraction tower by pressure reduction, compare the adding fresh cyclohexane by 1: 1 profit, make hexalin in the sour water, pimelinketone reclaims, sour water enters stills for air blowing then, drop into the ferrous porphyrin catalyzer, making system catalyst content is 1ppm, feed pure oxygen, organic constituent in the sour water and oxygen molecule generation oxidizing reaction, vapour-liquid ratio was controlled at 40: 1, and reaction time was controlled at 2.5 hours.Enter distillation tower after the sour water oxidizing reaction; elder generation's air distillation; limit monitoring water-content changes; treat that water-content is at 40% o'clock; the system vacuum distillation; vacuum control is at 62kpa; sour water is carried dense to moisture 6%; total acid content 65%; total ester content 20%; the concentrated acid water of other organism 9%; concentrated acid water is after pump is squeezed into esterifier; carry out esterification; add hexalin; modified cation-exchange resin and dimethylbenzene; the weight ratio of catalyst consumption and sour total amount is 1/100, and the control acid-alcohol ratio is 2: 1, adds the band aqua that accounts for system cumulative volume 10%; temperature of reaction control is as the criterion with normal backflow of guarantee system, carries out rectification under vacuum after esterification is finished and obtains nitration mixture hexamethylene alcohol ester product.
Embodiment 4:
About 145 ℃ of temperature, pressure is under the condition of 0.85Mpa, hexanaphthene overflow successively carries out liquid phase through 4 placed in-line stills for air blowing catalytic air oxidation is arranged, by-products content is respectively from the cyclohexane oxide solution that the 4# stills for air blowing come out: total acid 1.0%, total ester 0.48%, water-soluble peroxide 0.33%, this oxidation liquid temperature after the interchanger heat exchange is reduced to 90 ℃ and is laggardly gone into water wash column, by 30: 1 profit compare carry out water washing after, content of by-products is respectively total acid 0.15% in the oxidation liquid, total ester 0.26%, water-soluble peroxide 0.09%, obtain content and be respectively total acid 14.5%, total ester 8.2%, the total mistake is 6% and hexalin, cyclohexanone content is respectively 0.4%, 0.25% sour water, sour water is squeezed into the back extraction tower by pressure reduction, compare the adding fresh cyclohexane by 1: 1 profit, make hexalin in the sour water, pimelinketone reclaims, sour water enters stills for air blowing then, drop into the copper phthalocyanine catalyzer, making system catalyst content is 0.1ppm, feed pure oxygen, vapour-liquid ratio was controlled at 50: 1, organic constituent in the sour water and oxygen molecule generation oxidizing reaction, reaction time was controlled at 2 hours.Enter distillation tower after the sour water oxidizing reaction; elder generation's air distillation; limit monitoring water-content changes; treat that water-content is at 40% o'clock; the system vacuum distillation; vacuum control is at 50kpa; sour water is carried dense to moisture 7%; total acid content 64%; total ester content 22%; the concentrated acid water of other organism 7%; concentrated acid water is after pump is squeezed into esterifier; carry out esterification; add propyl carbinol; modified cation-exchange resin and dimethylbenzene; the weight ratio of catalyst consumption and sour total amount is 1/100, and the control acid-alcohol ratio is 2.5: 1, adds the band aqua that accounts for system cumulative volume 10%; temperature of reaction control is as the criterion with normal backflow of guarantee system, carries out rectification under vacuum after esterification is finished and obtains nitration mixture dibutylester product.
Embodiment 5:
About 167 ℃ of temperature, pressure is under the condition of 1.08Mpa, hexanaphthene overflow successively carries out liquid phase through 6 placed in-line stills for air blowing and does not have catalytic air oxidation, by-products content is respectively from the cyclohexane oxide solution that the 6# stills for air blowing come out: total acid 0.32%, total ester 0.3%, water-soluble peroxide 0.23%, this oxidation liquid temperature after the interchanger heat exchange is reduced to 88 ℃ and is laggardly gone into water wash column, by 40: 1 profit compare carry out water washing after, content of by-products is respectively total acid 0.11% in the oxidation liquid, total ester 0.22%, water-soluble peroxide 0.05%, obtain content and be respectively total acid 6.5%, total ester 3.4%, the total mistake is 5% and hexalin, cyclohexanone content is respectively 0.36%, 0.27% sour water, sour water is squeezed into the back extraction tower by pressure reduction, compare the adding fresh cyclohexane by 1.5: 1 profit, make hexalin in the sour water, pimelinketone reclaims, sour water enters stills for air blowing then, drop into the Cobaltous diacetate catalyzer, making system catalyst content is 20ppm, feed pure oxygen, vapour-liquid ratio was controlled at 45: 1, organic constituent in the sour water and oxygen molecule generation oxidizing reaction, reaction time was controlled at 2.5 hours.Enter distillation tower after the sour water oxidizing reaction; elder generation's air distillation; limit monitoring water-content changes; treat that water-content is at 40% o'clock; the system vacuum distillation; vacuum control is at 55kpa; sour water is carried dense to moisture 9%; total acid content 62%; total ester content 21%; the concentrated acid water of other organism 8%, concentrated acid water carry out esterification after pump is squeezed into esterifier; add methyl alcohol; tosic acid and toluene; the weight ratio of catalyst consumption and sour total amount is 1/100, and the control acid-alcohol ratio is 3: 1, adds the band aqua that accounts for system cumulative volume 20%; temperature of reaction control is as the criterion with normal backflow of guarantee system, carries out rectification under vacuum after esterification is finished and obtains nitration mixture dimethyl ester product.
Embodiment 6:
About 150 ℃ of temperature, pressure is under the condition of 1.0Mpa, hexanaphthene overflow successively carries out liquid phase through 5 placed in-line stills for air blowing catalytic air oxidation is arranged, by-products content is respectively from the cyclohexane oxide solution that the 5# stills for air blowing come out: total acid 0.74%, total ester 0.40%, water-soluble peroxide 0.38%, this oxidation liquid temperature after the interchanger heat exchange is reduced to 85 ℃ and is laggardly gone into water wash column, by 50: 1 profit compare carry out water washing after, content of by-products is respectively total acid 0.15% in the oxidation liquid, total ester 0.23%, water-soluble peroxide 0.05%, obtain content and be respectively total acid 9.5%, total ester 4.5%, the total mistake is 8.6% and hexalin, cyclohexanone content is respectively 0.34%, 0.28% sour water, sour water is squeezed into the back extraction tower by pressure reduction, compare the adding fresh cyclohexane by 1: 1 profit, make hexalin in the sour water, pimelinketone reclaims, sour water enters stills for air blowing then, drop into the cobalt naphthenate catalyzer, making system catalyst content is 5ppm, bubbling air, vapour-liquid ratio was controlled at 80: 1, organic constituent in the sour water and oxygen molecule generation oxidizing reaction, reaction time was controlled at 3 hours.Enter distillation tower after the sour water oxidizing reaction; elder generation's air distillation; limit monitoring water-content changes; treat that water-content is at 40% o'clock; the system vacuum distillation; vacuum control is at 45kpa; sour water is carried dense to moisture 7%; total acid content 70%; total ester content 18%; the concentrated acid water of other organism 5%, concentrated acid water carry out esterification after pump is squeezed into esterifier; add methyl alcohol; solid acid w and toluene; the weight ratio of catalyst consumption and sour total amount is 1/100, and the control acid-alcohol ratio is 2: 1, adds the band aqua that accounts for system cumulative volume 15%; temperature of reaction control is as the criterion with normal backflow of guarantee system, carries out rectification under vacuum after esterification is finished and obtains nitration mixture dimethyl ester product.
Claims (1)
1, a kind of method that from cyclohexane oxide solution, reclaims organic acid, ester, it is characterized in that: this method may further comprise the steps:
A, in the Cyclohexanone Production process, the oxidation liquid water behind the cyclohexane oxidation extracts, control water oil phase extracted the water-soluble substances in the oxidation liquid than 10: 1～70: 1 in the extraction process, obtained containing the acidic aqueous solution of a small amount of hexalin, pimelinketone; With hexanaphthene the tart aqueous solution is stripped again, control profit in the reextraction process and compare 1: 1～2: 1, reclaim a small amount of hexalin, the pimelinketone carried secretly in the acidic aqueous solution, obtain containing the acidic aqueous solution of caproic acid hydrogen peroxide, alcohol acid, monocarboxylic acid, di-carboxylic acid, non-hexalin ester class;
B, acidic aqueous solution enter oxidation reactor, add catalyzer, 90 ℃～110 ℃ of temperature, under pressure 0.1Mpa～0.3Mpa, carry out catalyzed oxidation with the gas of molecule-containing keto, obtain containing the aqueous solution of acid, ester; Catalyzer is a kind of metal-salt or their metallo-organic complex or their mixture of cobalt, manganese, iron, zinc, copper, chromium, nickel, molybdenum, ruthenium, the add-on of catalyzer is as the criterion at 0.1mg/kg～50mg/kg with the content of control metal ion, the gas of molecule-containing keto comprises pure oxygen, ozone, air, and vapour-liquid ratio was controlled at 20: 1～80: 1;
C, the aqueous solution that contains acid, ester enter the single vaporization device, carry out air distillation, steam the moisture of aqueous solution cumulative volume 40%～50% after, enter second evaporator, under absolute pressure 30kPa～70kPa, remove moisture content, obtain water-content less than 10% fusion acid, ester mixture;
The mixture of D, fusion acid, ester enters esterifier, add alcohols material, catalyzer, band aqua, wherein alcohols material is selected from a kind of in ethanol, propyl alcohol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, n-hexyl alcohol, isohexyl alcohol, n-Octanol, isooctyl alcohol, the hexalin; The add-on of alcohols material is as the criterion at 2: 1～4: 1 with the control acid-alcohol ratio; Catalyzer is selected from a kind of in sulfuric acid, solid super-strong acid, modified cation-exchange resin, tosic acid, the sodium pyrosulfate; The weight ratio of catalyst consumption and fusion acid total amount is 1: 100～1: 200; The band aqua is to be selected from toluene, dimethylbenzene, hexanaphthene, benzene, 1, a kind of in 2-ethylene dichloride, the methyl alcohol; The add-on of band aqua accounts for system cumulative volume 10%～20%; Carry out esterification, temperature of reaction control is as the criterion with normal backflow of guarantee system, finish esterification after, obtain the mixed acid ester product.
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| CN102276007B (en) * | 2010-06-12 | 2013-04-03 | 中国石油化工集团公司 | Method for treating sewage produced during cyclohexanone production by adopting extraction method |
| CN102012188A (en) * | 2010-10-28 | 2011-04-13 | 中国石油化工股份有限公司 | Anti-corrosion method for tail gas heat exchange tower in cyclohexane oxidation technology |
| CN102012188B (en) * | 2010-10-28 | 2012-11-28 | 中国石油化工股份有限公司 | Anti-corrosion method for tail gas heat exchange tower in cyclohexane oxidation technology |
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| CN104030912A (en) * | 2014-05-23 | 2014-09-10 | 重庆华峰化工有限公司 | Environment-friendly method for preparing binary acid by recycling cyclohexane oxidation byproducts |
| CN105315128A (en) * | 2015-10-28 | 2016-02-10 | 衢州群颖化学科技有限公司 | Method for preparing KA oil through cyclohexane oxidation |
| CN105315128B (en) * | 2015-10-28 | 2017-04-12 | 江西科苑生物药业有限公司 | Method for preparing KA oil through cyclohexane oxidation |
| CN112441914A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Separation and purification method of oxidation liquid in process of preparing dibasic acid by one-step oxidation of cycloalkane |
| CN112441914B (en) * | 2019-09-04 | 2022-11-04 | 中国石油化工股份有限公司 | Separation and purification method of oxidation liquid in process of preparing dibasic acid by one-step oxidation of cycloalkane |
| CN114230458A (en) * | 2020-09-09 | 2022-03-25 | 长沙资材科技有限公司 | Method for separating alcohol ketonic acid complex oxidation product generated by air catalytic oxidation of cyclohexane |
| CN113548770A (en) * | 2021-07-14 | 2021-10-26 | 刘炳鑫 | Cyclohexanone-containing sewage treatment process and device |
| CN113548770B (en) * | 2021-07-14 | 2023-11-21 | 刘炳鑫 | Process and device for treating sewage containing cyclohexanone |
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