CN104276937A - Method for preparing adipic acid and C4-6-dibasic acid from cyclohexane oxidation reaction byproduct - Google Patents
Method for preparing adipic acid and C4-6-dibasic acid from cyclohexane oxidation reaction byproduct Download PDFInfo
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- CN104276937A CN104276937A CN201410301645.9A CN201410301645A CN104276937A CN 104276937 A CN104276937 A CN 104276937A CN 201410301645 A CN201410301645 A CN 201410301645A CN 104276937 A CN104276937 A CN 104276937A
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- cyclohexane
- diprotic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Abstract
The invention belongs to the technical field of organic synthesis and particularly relates to a method for preparing adipic acid and C4-6-dibasic acid from a cyclohexane oxidation reaction byproduct, aiming at solving the technical problem that the method for preparing adipic acid and C4-6-dibasic acid from the cyclohexane oxidation reaction byproduct can be used for preparing adipic acid and C4-6-dibasic acid by taking the cyclohexane oxidation reaction byproduct as a raw material. The technical scheme is as follows: the method for preparing adipic acid and C4-6-dibasic acid from the cyclohexane oxidation reaction byproduct comprises the following steps of a, separating the byproduct contained in cyclohexane oxidation reaction liquid; b, transforming the byproduct into adipic acid and C4-6-dibasic acid; c, separating and recovering adipic acid and C4-6-dibasic acid. The method disclosed by the invention can be used for separating the byproduct generated in the process of a cyclohexane air oxidation-alkaline saponification decomposition process and successfully transforming into important chemical products, namely adipic acid and C4-6-dibasic acid and achieves the effects of reducing consumption, reducing emission, sufficiently utilizing resources and changing wastes into valuables.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to prepare hexanodioic acid and C by cyclohexane oxidation by product
4 ~ 6the method of-diprotic acid.
Background technology
Hexanodioic acid is important aliphatic dibasic acid, is important industrial chemicals and intermediate, mainly for the manufacture of nylon-66, urethane, softening agent, lubricant, sterilant and tackiness agent etc.
C
4 ~ 6-diprotic acid refers to the mixed dibasic acid be made up of succinic acid, pentanedioic acid, hexanodioic acid, also known as nylon acid, is also important industrial chemicals, can be used as the raw material producing multiple urethane foam; If utilize C
9~ C
10primary alconol can obtain high-quality tenderizer to mixed dibasic acid esterification, for polyvinyl chloride, makes it have excellent cold conditions shock resistance; Mixed dibasic acid dimethyl ester (DBE) can be obtained as paint solvent with methanol esterification, there is the performance such as use safety, preventing pollution environment; If mixed dibasic acid is carried out separation obtain hexanodioic acid, pentanedioic acid, succinic acid, then purposes is wider.
In existing industrial production technology, the production technique of hexanodioic acid is divided into hexanaphthene technique, tetrahydrobenzene technique and Butadiene Extraction Process by raw materials used, its cyclohexane technique is the main technique of producing hexanodioic acid, 70% of hexanodioic acid production all adopts hexanaphthene technique with upper in the world.Hexanaphthene technique is also known as two-step penetration method: first obtain the cyclohexane oxide solution containing cyclohexyl hydroperoxide and a small amount of by product by air oxidation of cyclohexane, then carry out catalytic decomposition in the basic conditions, rectifying separation obtains hexalin and cyclohexanone mixture (KA oil); Then with the obtained hexanodioic acid of nitric acid oxidation KA oil, and C is obtained by crystallization of adipic acid mother liquor
4 ~ 6-diprotic acid.Wherein, the first step atmospheric oxidation process of hexanaphthene is non-catalyst oxidation, and the transformation efficiency of hexanaphthene is in 3.5 ~ 5.0%, KA oil selectivity 80 ~ 88%, and KA oil consumption hexanaphthene amount per ton is at 970 ~ 1040kg; KA oil nitric acid oxidation produces the selectivity of hexanodioic acid 89 ~ 93%, and hexanodioic acid consumption KA oil mass per ton is at 730 ~ 760kg; Produce in hexanodioic acid process at hexanaphthene two-step penetration method, obtain C simultaneously
4 ~ 6the output of-diprotic acid is 3.5 ~ 5% of hexanodioic acid output.Comprehensively, hexanaphthene two-step penetration method produces the overall selectivity of hexanodioic acid 71 ~ 81%, by the C obtained
4 ~ 6the output of-diprotic acid is added up, then hexanaphthene two-step penetration method produces hexanodioic acid and C
4 ~ 6the overall selectivity of-diprotic acid is 76 ~ 84.5%.This shows to produce hexanodioic acid, coproduction C at hexanaphthene two-step penetration method
4 ~ 6in-diprotic acid process, the hexanaphthene of 15.5 ~ 24% is about had to generate by product or carbonic acid gas or have a small amount of loss.Analyze the operating process of hexanaphthene two-step penetration method, the process that its hexanaphthene generates by product is mainly the first step atmospheric oxidation process, as produced a large amount of waste lye (organism accounts for 10 ~ 20% of hexanodioic acid output) containing organic acid salt in the alkali saponified catalytic decomposition process of cyclohexyl hydroperoxide, the lightweight oil (accounting for 1.2 ~ 1.8% of hexanodioic acid output) obtained in Distillation recovery hexanaphthene and rectifying separation hexalin and pimelinketone process and X oil (accounting for 2.5 ~ 3.8% of hexanodioic acid output), the waste lye wherein containing organic acid salt is the maximum place to go of the by product that air oxidation of cyclohexane process generates.According to hexanaphthene non-catalytic oxidation reaction mechanism, the reaction that oxidation generation cyclohexyl hydroperoxide occurs hexanaphthene belongs to the free radical type reaction mechanism having branch, therefore inevitably there is the deep oxidation reaction of a small amount of hexanaphthene, thus generate some organic acids, ester and other oxidized byproduct, as C
1~ C
6monoprotic acid (comprising 6 hydroxycaproic acid, hexanal acid), C
2~ C
6the derivative (as cyclohexanediol, hexamethylene alcohol ketone, cyclohexenol or cyclonene etc.) etc. of diprotic acid, ester class, cyclohexanol/cyclohexanone.These by products in the heterogeneous catalysis decomposition reaction process of further cyclohexyl hydroperoxide, with the NaOH aqueous solution carry out neutralizing, major part proceeds in alkali lye after saponification reaction, especially organic acid and ester deter-mation class, thus generates the waste lye containing organic acid sodium.This type of waste lye can not discharge, need to carry out burning disposal, therefore this technological process will consume a large amount of alkali lye, produce a large amount of reluctant industrial caustic simultaneously, more it's a pity and wasted the inevitable by product (as above-mentioned organism) being converted into useful Chemicals generated in cyclohexane oxidation process.
In sum, since hexanaphthene liquid phase air oxidation process application, the treatment process of domestic and international many investigators to the waste lye produced in air oxidation of cyclohexane-alkali saponified decomposition course has carried out large quantity research, except the industrial burning method treatment process generally adopted, also have and adopt acid neutralization and then reclaim organic chemical method.Though burning method is the industrial treatment process generally adopted, it not a kind of good method.Though acid neutralization and then to reclaim organic chemical method be a kind of conventional treatment process, but the treating processes three wastes are more, adopt in sulfuric acid as patent US3859335, US3993691, US4052441 and after waste lye separates black acid liquid, black acid liquid is first dewatered, esterification is carried out after fractionation by distillation goes out monoprotic acid under low temperature and high vacuum condition again, Methyl glutarate, dimethyl adipate, hydroxycaproic acid methyl esters product can be obtained through being separated, complex technical process, have more waste water to generate, and the organic by-products rate of recovery is low; The technical characterstic of patent CN1177576A is need not in fresh mineral acid and waste lye, use instead in by-product hydrochloric acid and Waste Sulfuric Acid and waste lye, and then be that extraction agent extracts saponated sewage with isooctyl alcohol and isomer thereof, but still it is low to there is organic by-product recovery rate.The general thought of these patented technologies is: with acid (various mineral acid) neutralization, then with proper method recovery organism wherein.In circulation like this, first employ a large amount of alkali lye when processing the by product in cyclohexane oxidation cyclohexanol/cyclohexanone process, after consume again a large amount of mineral acids when reclaiming organism from waste lye, therefore this treating processes is both uneconomical, and not environmentally, the three wastes are more, and the organic by-products rate of recovery is low.
Patent CN101045682A (2007) is according to the ultimate principle of liquid-liquid extraction, water extraction oxidation solution is adopted to obtain acidic aqueous solution, then catalyzed oxidation is carried out, again through evaporation concentration, carry out esterification with alcohols material in the presence of a catalyst, obtain mixed organic acid ester after process further.The treating processes of this patent, not only cost is high, three waste discharge is many, and by-product recovery rate low (other the nonacid organic by-products as generated in cyclohexane oxidation process is not reclaimed), reclaim product (mixed organic acid ester) value added low simultaneously.
Patent CN1184802A (1998) introduces a kind of method preparing diacid from similar cyclohexane oxidation product washing sour water, the method process washing sour water adopting catalytic hydrogenation, evaporation concentration, nitric acid oxidation is proposed, treating processes exists obviously not enough: (1) catalytic hydrogenation uses precious metal as catalyzer such as Pd, and working pressure is high, add production cost; (2) being reduced into alcohol compound after making the shortenings such as the existing carbonyl compound in former acid waste water, thus when adopting nitric acid oxidation, increasing nitric acid dosage.Patent CN1193009A (1998) adopts this type of washing sour water of method process of evaporation concentration, ω-HPOCaP decomposition, nitric acid oxidation, obtains hexanodioic acid and succinic acid, pentanedioic acid, hexanodioic acid mixed dibasic acid.Compared with patent CN1184802A (1998), this patent have technical process short, do not need the advantages such as high-tension apparatus, easy and simple to handle, nitric acid consumption is low, but the purity of the succinic acid obtained, pentanedioic acid, hexanodioic acid mixed dibasic acid is lower, and after acquisition hexanodioic acid and diprotic acid, still there is a certain amount of raffinate to need process further, namely the organism in washing sour water be not all converted into useful products and reclaim.
Patent CN1927804A (2007) is on the basis of CN1193009A (1998), there is provided a kind of produce from cyclohexane oxidation hexalin and pimelinketone process containing produce in the washing sour water of HPOCaP non-metallic ion 4,5, the method for 6-carbon dicarboxylic acid, this patented method does not have the deficiency of above-mentioned patent (CN1193009A, CN1184802A), not only during nitric acid oxidation nitric acid unit consumption low, there is no residual liquid discharge, and obtain purity higher 4,5,6-carbon dicarboxylic acid.But patent CN1193009A (1998), CN1927804A (2007) and patent CN1184802A (1998) etc. are all produce C for the acid waste water produced in hexanaphthene oxygen deprivation oxidation process
4 ~ 6-diprotic acid, for the by product produced in air oxidation of cyclohexane-alkali saponified decomposition technique process separation, reclaim, be converted into hexanodioic acid and mixed dibasic acid (C
4 ~ 6-diprotic acid) technique all do not relate to.Because hexanaphthene oxygen deprivation oxidising process is different with the processing parameter of air oxidation of cyclohexane process, oxygenant oxygen level different, the by product kind produced is different with amount, therefore for the recycling of the by product of air oxidation of cyclohexane process generation, hexanodioic acid and C is especially translated into
4 ~ 6-diprotic acid, improves hexanaphthene two-step penetration method and produces hexanodioic acid and C
4 ~ 6the method of-diprotic acid yield does not also have patent and bibliographical information.
Summary of the invention
Technical problem to be solved by this invention is to provide one and prepares hexanodioic acid and C by cyclohexane oxidation by product
4 ~ 6the method of-diprotic acid, with the by product of cyclohexane oxidation for raw material prepares hexanodioic acid and C
4 ~ 6-diprotic acid.Technical scheme of the present invention is:
Hexanodioic acid and C is prepared by cyclohexane oxidation by product
4 ~ 6the method of-diprotic acid, comprises the steps:
A, cyclohexane oxidation;
Separation of by-products in b, step a in oxidation liquid: the oxidation liquid oil phase that cyclohexane oxidation process is obtained, the 1st extraction tower is sent into continuously from bottom, make it in the 1st extraction tower, carry out reverse extracting and washing, by the 1st extraction tower bottom collection wash water solution with the de-salted water aqueous phase from tower top; The aqueous phase wash water solution of the 1st extraction tower bottom collection is sent into the 2nd extraction tower continuously from top, makes it in the 2nd extraction tower and carry out reverse reextraction from the oil phase fresh cyclohexane at the bottom of tower to wash, by the 2nd extraction tower bottom collection wash water solution;
C, by product are converted into hexanodioic acid and C
4 ~ 6-diprotic acid: the wash water solution obtained by step b carries out evaporation concentration under decompression or condition of normal pressure, and steam output is 40 ~ 75wt%; Be that oxygenant carries out oxidizing reaction by the concentrated solution nitric acid obtained, adopt gradient nitric acid oxidation reaction process, temperature of reaction is 50 ~ 95 DEG C, the periodical operation reaction times is 3 ~ 5h, the operate continuously residence time is 10 ~ 15h, the concentration range of oxygenant nitric acid is 55 ~ 95%, and in concentrated solution, the quality feed ratio of organism and nitric acid is 1.0 ﹕ 1.5 ~ 2.5;
D, hexanodioic acid and C
4 ~ 6the separation of-diprotic acid: the nitric acid oxidation reaction liquid obtained by step c carries out crystallisation by cooling, suction filtration, obtains crystal and filtrate; Crystallization final temperature controls at 15 ~ 25 DEG C, and crystallization time is at 2 ~ 8h; Gained crystal is thick crystallization of adipic acid, and gained filtrate is C
4 ~ 6-diprotic acid solution;
Refining of e, thick hexanodioic acid: thick adipic acid crystals steps d obtained is carried out recrystallization and produced smart hexanodioic acid; Recrystallization condition is: add 0.1 ~ 1.5% gac and be made into 30% solution, and bleaching temperature is 70 ~ 90 DEG C, bleaching time 0.5 ~ 1.5h, and crystallization final temperature is at 20 ~ 30 DEG C, and crystallization time is at 4 ~ 6h; Or reclaim in the thick crystallization of adipic acid feeding hexanodioic acid recrystallization full scale plant obtained in steps d, to increase smart hexanodioic acid output;
F, C
4 ~ 6the recovery of-diprotic acid: filtrate steps d obtained carries out concentrating under decompression or condition of normal pressure, C is produced in melting, section
4 ~ 6-diprotic acid; Concentrated, melting final temperature controls at 130 ~ 160 DEG C; Or the filtrate obtained in steps d is sent in diprotic acid recovery full scale plant to increase diprotic acid output.
Concrete, the non-catalyst oxidation being oxidized to air, oxygen-denuded air, oxygen-rich air or pure oxygen described in step a.
Concrete, in step b, extraction tower is packing tower or tray column.
Concrete, in step b, during reverse extraction, pressure is 0.1 ~ 0.6MPa, the volume ratio of extraction temperature 660 ~ 90 DEG C, oil phase cyclohexane oxidation Ye ︰ aqueous phase is 80 ~ 110 ︰ 1.
Preferably, in step b, during reverse extraction, the volume ratio of pressure 0.3 ~ 0.5MPa, extraction temperature 65 ~ 75 DEG C, oil phase cyclohexane oxidation Ye ︰ aqueous phase is 90 ~ 100 ︰ 1.
Concrete, in step b reverse when stripping pressure be 0.1 ~ 0.5MPa, 60 ~ 90 DEG C, the volume ratio of oil phase fresh Huan Ji Wan ︰ aqueous phase is 2 ~ 6 ︰ 1.
Preferably, in step b, during reverse reextraction, pressure is 0.3 ~ 0.5MPa, the volume ratio of extraction temperature 65 ~ 75 DEG C, oil phase fresh Huan Ji Wan ︰ aqueous phase is 3 ~ 4 ︰ 1.
Concrete, the nitric acid oxidation reaction in step c is operate continuously, and temperature of reaction is 60 ~ 90 DEG C, the residence time 12 ~ 15h, and the concentration range of nitric acid is 60 ~ 65%.
Wherein, the nitric acid oxidation reaction periodical operation in step c is that gradient increased temperature or operate continuously adopt multi-floating bodies.
Preferably, in steps d, crystallization final temperature is 20 DEG C, crystallization time 4 ~ 8h.
Preferably, concentrated in steps d, melting final temperature controls at 140 ~ 150 DEG C.
In the present invention, oxygen-denuded air refer to adopt nitrogen by Dilution air to oxygen level lower than the oxygen level in air.No matter but adopt oxygen-denuded air, air or oxygen-rich air and even pure oxygen, it is identical to the oxidation reaction process of hexanaphthene and mechanism, all the reactions carried out between oxygen molecule and hexanaphthene molecule, therefore generated principal product and by product kind are identical, just the amount of various by product is incomplete same, so all can adopt the technology of the present invention to process.
Under a small amount of production or laboratory situation, nitric acid oxidation process can adopt periodical operation; The inventive method industrially can be adopted to carry out operate continuously, be applicable to scale operation.But be also unrestricted to continuous process, and be more suitable for continuous prodution.
In step c of the present invention, the wash water solution obtained by step b carries out evaporation concentration under decompression or condition of normal pressure, and when steam output is 40 ~ 75wt%, in the concentrated solution obtained, organic content is at 40 ~ 50wt%, is applicable to carry out subsequent operations.
Owing to being 80 DEG C under the boiling point normal pressure of hexanaphthene, the temperature of therefore washing cyclohexane oxide solution should control below 80 DEG C, as hexanaphthene volatilization loss can be caused more than 80 DEG C or causes danger, and therefore should lower than 80 DEG C under extracting operation temperature normal pressure.If but when operating under elevated pressure, suitably service temperature can be improved.As at laboratory treatment cyclohexane oxide solution, when not using supercharging equipment, atmospheric extraction can be adopted.In the industrial production, after cyclohexane oxide solution washes out by product, also to carry out the decomposition reaction of next step cyclohexyl hydroperoxide, this reaction needed is carried out under certain pressure and temperature, therefore for ensureing continuity and the operability of technological operation, preferably extract under a certain pressure, therefore in the industrial production, preferred extracting pressure is 0.3 ~ 0.5MPa.
Beneficial effect of the present invention:
Effectively can solve the industrial air oxidation of cyclohexane-alkali saponified decomposition technique technology generally adopted at present by the present invention and produce Problems existing in hexalin and pimelinketone method.The separation of by-products that the present invention will produce in air oxidation of cyclohexane-alkali saponified decomposition technique process, and successful conversion is important Chemicals hexanodioic acid and C
4 ~ 6-diprotic acid, turns waste into wealth.Because the by product will produced in air oxidation of cyclohexane process has carried out effective separation, therefore at the principal product of air oxidation of cyclohexane reaction---in the alkali saponified decomposition technique of cyclohexyl hydroperoxide, decrease the consumption of raw material alkali 30 ~ 50%; Meanwhile, reduce by 20 ~ 40% waste lye discharges, in the process of burning disposal waste lye, save the energy consumption of about 20 ~ 40%.
The inventive method is by the by product obtaining adipic acid existed in air oxidation of cyclohexane liquid and C
4 ~ 6-diprotic acid, have technical process short, do not need the advantages such as high-tension apparatus, easy and simple to handle, nitric acid consumption is low, and the separation efficiency of the by product existed in air oxidation of cyclohexane liquid reaches 40 ~ 70%, in the by product separated, total organic content is 15 ~ 25wt%.Wherein, ω in organism-HPOCaP content is 40 ~ 60wt%, C
2~ C
6diacid content is 20 ~ 50wt%, C
1~ C
6monoprotic acid content is 10 ~ 20wt%, neutrals (comprising ester class, cyclohexanediol, hexamethylene alcohol ketone, cyclohexenol or cyclonene, aldehydes etc.) content is 20 ~ 50wt%), the conversion rate of recovery > 90% of the by product separated.
Adopt method of the present invention, under the prerequisite not increasing the consumption of raw material hexanaphthene, the production equipment of a set of annual output 70000 tons of hexanodioic acids, can produce smart hexanodioic acid 1400 ~ 2000 tons, C by the by product separated in hexanaphthene the first step oxidation reaction process
4 ~ 6-diprotic acid 2500 ~ 3500 tons, thus make hexanaphthene two-step penetration method produce hexanodioic acid, coproduction C
4 ~ 6the adipic acid yield of the prior art of-diprotic acid and C
4 ~ 6-diprotic acid yield improves 2 ~ 3% and 80 ~ 110% respectively, improves resource utilization.
Embodiment
Oxygen-denuded air refer to adopt nitrogen by Dilution air to oxygen level lower than the oxygen level in air.No matter but adopt oxygen-denuded air, air or oxygen-rich air and even pure oxygen, it is identical to the oxidation reaction process of hexanaphthene and mechanism, all the reactions carried out between oxygen molecule and hexanaphthene molecule, therefore generated principal product and by product kind are identical, just the amount of various by product is incomplete same, so all can adopt the technology of the present invention to process.
Under a small amount of production or laboratory situation, nitric acid oxidation process can adopt periodical operation; The inventive method industrially can be adopted to carry out operate continuously, be applicable to scale operation.But be also unrestricted to continuous process, and be more suitable for continuous prodution.
In step c of the present invention, the wash water solution obtained by step b carries out evaporation concentration under decompression or condition of normal pressure, and when steam output is 40 ~ 75wt%, in the concentrated solution obtained, organic content is at 40 ~ 50wt%, is applicable to carry out subsequent operations.
Owing to being 80 DEG C under the boiling point normal pressure of hexanaphthene, the temperature of therefore washing cyclohexane oxide solution should control below 80 DEG C, as hexanaphthene volatilization loss can be caused more than 80 DEG C or causes danger, and therefore should lower than 80 DEG C under extracting operation temperature normal pressure.If but when operating under elevated pressure, suitably service temperature can be improved.As at laboratory treatment cyclohexane oxide solution, when not using supercharging equipment, atmospheric extraction can be adopted.In the industrial production, after cyclohexane oxide solution washes out by product, also to carry out the decomposition reaction of next step cyclohexyl hydroperoxide, this reaction needed is carried out under certain pressure and temperature, therefore for ensureing continuity and the operability of technological operation, preferably extract under a certain pressure, therefore in the industrial production, preferred extracting pressure is 0.3 ~ 0.5MPa.
Below by way of specific embodiment, the present invention is described in further detail, but the present invention is not restricted to embodiment.
Embodiment 1 adopts the inventive method to produce hexanodioic acid and C
4 ~ 6-diprotic acid
80kg air oxidation of cyclohexane liquid is got from air oxidation of cyclohexane device, in extraction tower, be in a ratio of 100 with deionized water by oil/water wash, the wash water solution fresh cyclohexane obtained is 3 carry out backwash and wash by oil/water, obtain wash water solution 1.26kg altogether, wherein organic content is 20.6% (weight), wash temperature is 70 DEG C, working pressure normal pressure.The washing water obtained are carried out atmospheric evaporation concentrate, the light constituent amount distilled out is 60%, obtains concentrated solution and is divided into 2 parts:
(1) 1 part is the nitric acid oxidation of 60% with content, and temperature of reaction adopts gradient increased temperature: 55 ± 5 DEG C, 65 ± 5 DEG C, 75 ± 5 DEG C, 85 ± 5 DEG C, total reaction time is 3h, and nitric acid dosage is 270g, the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 1% gac and be made into 30% solution, recrystallization after 80 DEG C of conditions decolouring 1h, crystallization and recrystallization final temperature control at 20 DEG C, and crystallization time is 4h.The adipic acid crystals that recrystallization obtains carries out the smart adipic acid product of dry 38.2g white; Twice crystallization filtrate merged, evaporation concentration is to final temperature 155 DEG C, and cooling section obtains 78.5g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.48%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 28.52%, pentanedioic acid 50.5%, succinic acid 21.43%, and diprotic acid total content is 94.6%.
(2) 1 parts is the nitric acid oxidation of 55% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 5 DEG C, 70 ± 5 DEG C, 80 ± 5 DEG C, 90 ± 5 DEG C, total reaction time is 4h, and nitric acid dosage is 285g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 1.5% gac and be made into 30% solution, recrystallization after 70 DEG C of conditions decolouring 0.5h, crystallization and recrystallization final temperature control at 15 DEG C, and crystallization time is 3h.The adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 37.6g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 160 DEG C, and cooling section obtains 79.9g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.57%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 27.02%, pentanedioic acid 50.25%, succinic acid 22.73%, and diprotic acid total content is 93.9%.
Embodiment 2 adopts the inventive method to produce hexanodioic acid and C
4 ~ 6-diprotic acid
85kg air oxidation of cyclohexane liquid is got from air oxidation of cyclohexane device, in extraction tower, be in a ratio of 110 with deionized water by oil/water wash, the wash water solution fresh cyclohexane obtained is 4 carry out backwash and wash by oil/water, obtain wash water solution 1.28kg altogether, wherein organic content is 21.8% (weight), wash temperature is 65 DEG C, and working pressure is normal pressure.The washing water obtained are carried out atmospheric evaporation concentrate, the light constituent amount distilled out is 58%, obtains concentrated solution and is divided into 2 parts:
(1) 1 part is the nitric acid oxidation of 60% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 5 DEG C, 70 ± 5 DEG C, 80 ± 5 DEG C, 90 ± 5 DEG C, total reaction time is 4h, and nitric acid dosage is 275g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 0.5% gac and be made into 30% solution, recrystallization after 90 DEG C of conditions decolouring 1h.Crystallization and recrystallization final temperature control at 20 DEG C, and crystallization time is 3.5h.The adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 41.2g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 155 DEG C, and cooling section obtains 79.6g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.58%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 28.17%, pentanedioic acid 51.5%, succinic acid 20.33%, and diprotic acid total content is 95.1%.
(2) 1 parts is the nitric acid oxidation of 65% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 5 DEG C, 70 ± 5 DEG C, 80 ± 5 DEG C, 90 ± 5 DEG C, total reaction time is 3h, and nitric acid dosage is 260g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 0.6% gac and be made into 30% solution, recrystallization after 80 DEG C of conditions decolouring 1.5h.Crystallization and recrystallization final temperature control at 15 DEG C, and crystallization time is 4h.The adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 42.1g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 160 DEG C, and cooling section obtains 80.1g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.52%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 27.52%, pentanedioic acid 50.22%, succinic acid 22.26%, and diprotic acid total content is 94.9%.
Embodiment 3 adopts the inventive method to produce hexanodioic acid and C
4 ~ 6-diprotic acid
75kg air oxidation of cyclohexane liquid is got from air oxidation of cyclohexane device, in extraction tower, be in a ratio of 95 with deionized water by oil/water wash, the wash water solution fresh cyclohexane obtained is 4 carry out backwash and wash by oil/water, obtain wash water solution 1.209kg altogether, wherein organic content is 18.5wt%, wash temperature is 65 DEG C, working pressure normal pressure.The washing water obtained are carried out atmospheric evaporation concentrate, the light constituent amount distilled out is 62%, obtains concentrated solution and is divided into 2 parts:
(1) 1 part is the nitric acid oxidation of 65% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 5 DEG C, 70 ± 5 DEG C, 80 ± 5 DEG C, 90 ± 5 DEG C, total reaction time is 4h, and nitric acid dosage is 275g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 1% gac and be made into 30% solution, recrystallization after 75 DEG C of conditions decolouring 1h.Crystallization and recrystallization final temperature control at 20 DEG C, and crystallization time is 3.5h, and the adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 37.8g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 160 DEG C, and cooling section obtains 68.2g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.48%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 28.67%, pentanedioic acid 51.2%, succinic acid 20.13%, and diprotic acid total content is 94.7%.
(2) 1 parts is the nitric acid oxidation of 60% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 5 DEG C, 70 ± 5 DEG C, 80 ± 5 DEG C, 90 ± 5 DEG C, total reaction time is 3h, and nitric acid dosage is 280g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 0.5% gac and be made into 30% solution, recrystallization after 85 DEG C of conditions decolouring 1.5h.Crystallization and recrystallization final temperature control at 15 DEG C, and crystallization time is 4h, and the adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 36.5g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 160 DEG C, and cooling section obtains 69.8g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.52%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 27.52%, pentanedioic acid 50.22%, succinic acid 22.26%, and diprotic acid total content is 94.6%.
Embodiment 4 adopts the inventive method to produce hexanodioic acid and C
4 ~ 6-diprotic acid
70kg air oxidation of cyclohexane liquid is got from air oxidation of cyclohexane device, in extraction tower, be in a ratio of 90 with deionized water by oil/water wash, the wash water solution fresh cyclohexane obtained is 4 carry out backwash and wash by oil/water volume ratio, obtain wash water solution 1.225kg altogether, wherein organic content is 18.4wt%, wash temperature is 65 DEG C, working pressure normal pressure.The washing water obtained are carried out atmospheric evaporation concentrate, the light constituent amount distilled out is 63%, obtains concentrated solution and is divided into 2 parts:
(1) 1 part is the nitric acid oxidation of 65% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 5 DEG C, 70 ± 5 DEG C, 80 ± 5 DEG C, 90 ± 5 DEG C, total reaction time is 3.5h, and nitric acid dosage is 270g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 1.5% gac and be made into 30% solution, recrystallization after 80 DEG C of conditions decolouring 1h.Crystallization and recrystallization final temperature control at 15 DEG C, and crystallization time is 4h, and the adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 36.2g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 155 DEG C, and cooling section obtains 68.2g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.38%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 28.27%, pentanedioic acid 50.5%, succinic acid 21.23%, and diprotic acid total content is 94.1%.
(2) 1 parts is the nitric acid oxidation of 60% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 5 DEG C, 70 ± 5 DEG C, 80 ± 5 DEG C, 90 ± 5 DEG C, total reaction time is 4h, and nitric acid dosage is 280g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 1% gac and be made into 30% solution, recrystallization after 85 DEG C of conditions decolouring 1h.Crystallization and recrystallization final temperature control at 20 DEG C, and crystallization time is 3h.The adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 36.4g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 160 DEG C, and cooling section obtains 68.5g oyster white, laminar diprotic acid.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.42%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 27.22%, pentanedioic acid 51.12%, succinic acid 21.66%, and diprotic acid total content is 94.1%.
Embodiment 5 adopts the inventive method to produce hexanodioic acid and C
4 ~ 6-diprotic acid
70kg air oxidation of cyclohexane liquid is got from air oxidation of cyclohexane device, in extraction tower, be in a ratio of 80 with deionized water by oil/water wash, the wash water solution fresh cyclohexane obtained is 4 carry out backwash and wash by oil/water, obtain wash water solution 1.348kg altogether, wherein organic content is 16.9wt%, wash temperature is 70 DEG C, working pressure normal pressure.The washing water obtained are carried out atmospheric evaporation concentrate, the light constituent amount distilled out is 55%, obtains concentrated solution and is divided into 2 parts:
(1) 1 part is the nitric acid oxidation of 95% with content, and temperature of reaction adopts gradient increased temperature: 55 ± 5 DEG C, 65 ± 5 DEG C, 75 ± 5 DEG C, 85 ± 5 DEG C, 95 ± 5 DEG C, total reaction time is 4h, and nitric acid dosage is 190g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 1% gac and be made into 30% solution, recrystallization after 80 DEG C of conditions decolouring 1.5h.Crystallization and recrystallization final temperature control at 20 DEG C, and crystallization time is 4h, and the adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 36.4g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 155 DEG C, and cooling section obtains 70.2g oyster white, laminar dicarboxylic acid product.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.28%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 28.17%, pentanedioic acid 51.52%, succinic acid 20.31%, and diprotic acid total content is 92.1%.
(2) 1 parts is the nitric acid oxidation of 80% with content, and temperature of reaction adopts gradient increased temperature: 60 ± 3 DEG C, 66 ± 3 DEG C, 72 ± 3 DEG C, 78 ± 3 DEG C, 84 ± 3 DEG C, 90 ± 3 DEG C, total reaction time is 3h, and nitric acid dosage is 210g.By the nitric acid oxidation reaction liquid crystallisation by cooling, the suction filtration that obtain.Wherein, obtain thick adipic acid crystals and add 1.5% gac and be made into 30% solution, recrystallization after 85 DEG C of conditions decolouring 1h.Crystallization and recrystallization final temperature control at 20 DEG C, and crystallization time is 3h.The adipic acid crystals that recrystallization obtains obtains the smart adipic acid product of 36.5g white after carrying out drying; Twice crystallization filtrate merged, evaporation concentration is to final temperature 160 DEG C, and cooling section obtains 69.7g oyster white, laminar diprotic acid.Through liquid-phase chromatographic analysis: in smart adipic acid product, hexanodioic acid content is 99.42%; In dicarboxylic acid product, the relative content of three kinds of diprotic acid is followed successively by hexanodioic acid 27.28%, pentanedioic acid 51.36%, succinic acid 21.36%, and diprotic acid total content is 93.1%.
According to the result of embodiment 1 ~ 5, in a set of annual output 70000 tons of adipic acid plants, enforcement the inventive method consumption the year before last NaOH30% alkali lye amount is 2.8 ten thousand tons (wherein in air oxidation of cyclohexane liquid, the alkali number of acid and ester consumption accounts for 65% ~ 75%, is calculated as 1.96 ten thousand tons by 70%), the salkali waste liquid measure of discharge is about 50,000 tons.As cyclohexane conversion be 3.5%, hexalin and pimelinketone selectivity be 82%, hexanodioic acid selectivity is 92%, C
4 ~ 6-diprotic acid output is 4% of hexanodioic acid output, then air oxidation of cyclohexane liquid measure is 147.1458 ten thousand tons, after producing by the inventive method, the NaOH30% alkali lye consumption of reduction with reduce waste lye emission result in table 1, the hexanodioic acid of increase and C
4 ~ 6-diprotic acid output and yield the results are shown in Table 2.
Table 1 reduces soda ash consumption and reduces waste lye emission result table (year)
In table 1, each index illustrates:
(1) index such as " H+/% ", " ester/% ", " mistake/% " is the analysis indexes that current hexanodioic acid manufacturer normally produces.Wherein: " H+/% " is the percentage volumetric molar concentration of the carboxyl of organic acid by-product all in cyclohexane oxide solution; " ester/% " for organic acid acetic by product in cyclohexane oxide solution press hexanodioic acid dicyclohexano ester calculate mass percentage; " mistake/% " refers to the mass percentage that in cyclohexane oxide solution, superoxide calculates by cyclohexyl hydroperoxide;
(2) " quality/t " refers to the quality of the NaOH30% alkali lye reduced or the quality of few waste discharge alkali lye, and unit is ton (symbol t), wherein:
The calculation formula of the quality of the NaOH30% alkali lye reduced=[(enter out H+ in cyclohexane oxide solution poor × difference × cyclohexane oxide solution total amount × 2/310 of cyclohexane oxide solution total amount+enter out ester content in cyclohexane oxide solution)/100] × 40/30%;
The NaOH30% alkali lye quality of the reduction of the calculation formula of the quality of few waste discharge alkali lye=obtain+enter out H+ differential conversion in cyclohexane oxide solution becomes organic acid quality (w1)+enter out the differential conversion of ester content in cyclohexane oxide solution to become the quality of organic acid acetic (w2)+enter out the quality (w3) that the differential conversion of peroxide level in cyclohexane oxide solution becomes ω-HPOCaP.Example: in embodiment 1 w1=147.1458 × (0.0056-0.0023) × 70 (organic acid molecular-weight average)/100, w2=147.1458 × (0.10-0.08)/100, w3=147.1458 × (3.03-2.97)/100.
(3) " than/% " for reducing the per-cent of alkali lye consumption or few waste discharge alkali lye, wherein:
Reduce quality × 100%/(28000 × 70%) of the NaOH30% alkali lye of calculation formula=reduction that alkali lye consumes;
Few waste discharge alkali lye quality × 100%/50000 of calculation formula=few waste discharge alkali lye.
Table 2 improves hexanodioic acid and C
4 ~ 6-diprotic acid yield result table (year)
Claims (10)
1. prepare hexanodioic acid and C by cyclohexane oxidation by product
4 ~ 6the method of-diprotic acid, is characterized in that: comprise the steps:
A, cyclohexane oxidation;
Separation of by-products in b, step a in oxidation liquid: the oxidation liquid oil phase that cyclohexane oxidation process is obtained, the 1st extraction tower is sent into continuously from bottom, make it in the 1st extraction tower, carry out reverse extracting and washing, by the 1st extraction tower bottom collection wash water solution with the de-salted water aqueous phase from tower top; The aqueous phase wash water solution of the 1st extraction tower bottom collection is sent into the 2nd extraction tower continuously from top, makes it in the 2nd extraction tower and carry out reverse reextraction from the oil phase fresh cyclohexane at the bottom of tower to wash, by the 2nd extraction tower bottom collection wash water solution;
C, by product are converted into hexanodioic acid and C
4 ~ 6-diprotic acid: the wash water solution obtained by step b carries out evaporation concentration under decompression or condition of normal pressure, and steam output is 40 ~ 75wt%; Be that oxygenant carries out oxidizing reaction by the concentrated solution nitric acid obtained, adopt gradient nitric acid oxidation reaction process, temperature of reaction is 50 ~ 95 DEG C, the periodical operation reaction times is 3 ~ 5h, the operate continuously residence time is 10 ~ 15h, the concentration range of oxygenant nitric acid is 55 ~ 95%, and in concentrated solution, the quality feed ratio of organism and nitric acid is 1.0 ﹕ 1.5 ~ 2.5;
D, hexanodioic acid and C
4 ~ 6the separation of-diprotic acid: the nitric acid oxidation reaction liquid obtained by step c carries out crystallisation by cooling, suction filtration, obtains crystal and filtrate; Crystallization final temperature controls at 15 ~ 25 DEG C, and crystallization time is at 2 ~ 8h; Gained crystal is thick crystallization of adipic acid, and gained filtrate is C
4 ~ 6-diprotic acid solution;
Refining of e, thick hexanodioic acid: thick adipic acid crystals steps d obtained is carried out recrystallization and produced smart hexanodioic acid; Recrystallization condition is: add 0.1 ~ 1.5% gac and be made into 30% solution, and bleaching temperature is 70 ~ 90 DEG C, bleaching time 0.5 ~ 1.5h, and crystallization final temperature is at 20 ~ 30 DEG C, and crystallization time is at 4 ~ 6h; Or reclaim in the thick crystallization of adipic acid feeding hexanodioic acid recrystallization full scale plant obtained in steps d, to increase smart hexanodioic acid output;
F, C
4 ~ 6the recovery of-diprotic acid: filtrate steps d obtained carries out concentrating under decompression or condition of normal pressure, C is produced in melting, section
4 ~ 6-diprotic acid; Concentrated, melting final temperature controls at 130 ~ 160 DEG C; Or the filtrate obtained in steps d is sent in diprotic acid recovery full scale plant to increase diprotic acid output.
2. the method for claim 1, is characterized in that: the non-catalyst oxidation being oxidized to air, oxygen-denuded air, oxygen-rich air or pure oxygen described in step a.
3. as the method for claim 1 or 2, it is characterized in that: in step b, extraction tower is packing tower or tray column.
4. the method as described in any one of claims 1 to 3, is characterized in that: in step b, during reverse extraction, pressure is 0.1 ~ 0.6MPa, the volume ratio of extraction temperature 660 ~ 90 DEG C, oil phase cyclohexane oxidation Ye ︰ aqueous phase is 80 ~ 110 ︰ 1.
5. method as claimed in claim 4, is characterized in that: in step b, during reverse extraction, the volume ratio of pressure 0.3 ~ 0.5MPa, extraction temperature 65 ~ 75 DEG C, oil phase cyclohexane oxidation Ye ︰ aqueous phase is 90 ~ 100 ︰ 1.
6. the method according to any one of Claims 1 to 5, is characterized in that: in step b reverse when stripping pressure be 0.1 ~ 0.5MPa, 60 ~ 90 DEG C, the volume ratio of oil phase fresh Huan Ji Wan ︰ aqueous phase is 2 ~ 6 ︰ 1.
7. method as claimed in claim 6, is characterized in that: in step b, during reverse reextraction, pressure is 0.3 ~ 0.5MPa, the volume ratio of extraction temperature 65 ~ 75 DEG C, oil phase fresh Huan Ji Wan ︰ aqueous phase is 3 ~ 4 ︰ 1.
8. the method as described in any one of claim 1 ~ 7, is characterized in that: the nitric acid oxidation reaction in step c is operate continuously, and temperature of reaction is 60 ~ 90 DEG C, the residence time 12 ~ 15h, and the concentration range of nitric acid is 60 ~ 65%.
9. the method as described in any one of claim 1 ~ 8, is characterized in that: in steps d, crystallization final temperature is 20 DEG C, crystallization time 4 ~ 8h.
10. the method as described in any one of claim 1 ~ 9, is characterized in that: concentrated in steps d, melting final temperature controls at 140 ~ 150 DEG C.
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| CN109456166A (en) * | 2018-11-30 | 2019-03-12 | 重庆华峰化工有限公司 | A method of binary acid is prepared using cyclohexane oxidation byproduct X oil |
| 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 |
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| CN113651685A (en) * | 2021-09-25 | 2021-11-16 | 侯凤芹 | Process for preparing dicarboxylic acid by two-step oxidation of cycloalkane |
| CN113651685B (en) * | 2021-09-25 | 2024-02-09 | 侯凤芹 | Process for preparing dicarboxylic acids by two-stage oxidation of cyclic alkanes |
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