CN101781217B - Method for high-selectivity co-production of nitrocyclohexane and adipic acid - Google Patents
Method for high-selectivity co-production of nitrocyclohexane and adipic acid Download PDFInfo
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- CN101781217B CN101781217B CN 201010125321 CN201010125321A CN101781217B CN 101781217 B CN101781217 B CN 101781217B CN 201010125321 CN201010125321 CN 201010125321 CN 201010125321 A CN201010125321 A CN 201010125321A CN 101781217 B CN101781217 B CN 101781217B
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- nitrocyclohexane
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Abstract
The invention relates to a method for the high-selectivity co-production of nitrocyclohexane and adipic acid, which adopts nitrogen oxide NOx as the nitrating and oxidizing agent, carrys out continuous gas-phase catalysis or non-catalytic nitration and oxidation reaction on cyclohexane. By effectively setting the conditions of the concentration ratio, the reaction temperature and the reaction time of the reactants and optimizing the reaction pressure as well as catalysts and assistants, the invention realizes the simultaneous high-selectivity co-production of the nitrocyclohexane and the adipic acid of different ratios, and the reduction product NO generated by the nitration and oxidation reaction can be recycled for cyclic utilization. The method of the invention has high resource efficiency, less waste generation, simple process flow and device and low production cost, and is an environment-friendly synthetic method.
Description
Technical field
The present invention relates to the method for a kind of high-selectivity co-production of nitrocyclohexane and hexanodioic acid.
Background technology
Nitrocyclohexane is colourless oil liquid, and molecular formula is C
6H
11NO
2, molecular weight is 129.1571, boiling point is 205.5 ℃, and is water insoluble, is soluble in the organic solvents such as ethanol, ether, chloroform, benzene, is a kind of important organic solvent and chemical intermediate, but partial hydrogenation is reduced to cyclohexanone-oxime or complete hydro-reduction is hexahydroaniline.The synthetic traditional method of nitrocyclohexane is as nitrating agent hexanaphthene to be carried out nitration reaction with nitre-sulphur nitration mixture or nitric acid and acetic anhydride etc.There are the multiple side reactions such as oxidation, hydrolysis, hydroxylation in the poor selectivity of the method, so last handling process is complicated, and generation contains spent acid and the waste water of organic compound in a large number, control expense is high, and problem of environmental pollution is serious, with clean production require far apart.
Adopt oxynitride (NO
x) directly carry out the synthetic method of vaporphase nitration alkane as nitrating agent, can avoid using a large amount of sulfuric acid, free acid in the reaction product is few, separate easily, discharging is few, but can follow living oxidation side reaction, Main By product has corresponding alcohol, aldehyde, ketone, acid or nitric ether and nitrous acid ester, and deep oxidation by product CO
2And H
2O etc.Canadian Patent CA710356 (A) and US Patent No. 3255262 (A) have been reported a kind of method of hexanaphthene vaporphase nitration synthesizing nitryl hexanaphthene: this method is mainly take the productive rate that improves nitrocyclohexane as purpose, temperature of reaction can change between 220～375 ℃, and the residence time can change between 20～150 seconds; Particularly when temperature of reaction was 260 ℃, the transformation efficiency of hexanaphthene was 24%, and gained nitrocyclohexane productive rate is 81% (based on nitrating agent).Related side reaction all is to generate a large amount of deep oxidation by product CO in these patent reports
2And H
2O.
Hexanodioic acid (ADA) is commonly called as adipic acid, is white solid under the normal temperature, molecular formula (CH
2)
4(COOH)
2, molecular weight 146.1430,152 ℃ of normal fusing points; Be widely used in the fields such as plastics, resin, food, for the manufacture of nylon 66, softening agent, lubricating grease, sterilant and tackiness agent etc.The present industrial manufacture process more complicated of hexanodioic acid: obtain KA oil (mixture that mainly contains pimelinketone and hexalin) by cyclohexane oxidation first, and then carry out nitric acid oxidation take KA oil as raw material and obtain hexanodioic acid.Wherein, the per pass conversion of cyclohexane oxidation process and KA oil yield are all very low, generally are respectively 3%～5% and 82%～83%; The per pass conversion of nitric acid oxidation KA oil process and adipic acid yield are generally respectively 5%～12% and 90%～94%, and nitric acid dosage is large, 1.3 tons in the nitric acid of 1 ton of product consumption 68% of every production, and produce a large amount of CO, NO
x, N
2The toxic gases such as O.Along with the enhancing of people's environmental consciousness, the green chemistry process of research synthesizing adipic acid is significant, mainly carries out research and development at aspects such as synthetic route, oxygenant, catalyzer at present, but makes progress unhappy.
Summary of the invention
Purpose of the present invention aims to provide the processing method of a kind of high-selectivity co-production of nitrocyclohexane and two kinds of products of hexanodioic acid, can realize simultaneously the production of these two products, and by-product is low, have high resource utilization, few generation of waste materials, lower production cost, environment amenable production method.
X is greater than 1 oxynitride NO
xIt is the material that a class has strong nitrated and oxygenizement, under certain condition, can make hexanaphthene that nitrated and oxidizing reaction occurs, except generating corresponding nitration product, also can generate simultaneously many by products, such as alcohol, aldehyde, ketone, acid or ester etc., particularly generate easily deep oxidation by product CO
2And H
2O.But, the contriver finds, if regulate and control suitable reaction conditions, can only produce few by product, and generation purpose nitration product and oxidation products, be nitrocyclohexane and hexanodioic acid, and after the reduzate NO that produces of reaction process can reclaim, allocate the molecular oxygen recycling of suitable proportion into.Like this, oxynitride NO
xThe principal reaction formula of using with cyclohexane give can be written as:
The present invention proposes a kind of employing oxynitride NO
xAs the nitration oxidation agent, hexanaphthene is carried out continuous gas phase catalysis or the reaction of non-catalytic nitration oxidation, the method of high-selectivity co-production of nitrocyclohexane and hexanodioic acid, it is characterized in that by the condition in reactant concn proportioning, temperature of reaction and reaction times effectively is set, and in addition preferred reaction pressure and catalyzer and auxiliary agent reach simultaneously nitrocyclohexane and two kinds of products of hexanodioic acid of high-selectivity co-production different ratios, and the reduzate NO that the nitration oxidation reaction produces can recycle and reuse.
The objective of the invention is to realize by following manner:
By hexanaphthene and oxynitride NO
xDirectly carry out the vaporphase nitration oxidizing reaction, reactant oxynitride NO
xWith the mol ratio of hexanaphthene be 0.1～10.0, temperature of reaction is at 200 ℃～300 ℃, the residence time is 30 seconds～200 seconds, thereby high-selectivity co-production obtains nitrocyclohexane and hexanodioic acid; The reduzate NO recycle and reuse that the nitration oxidation reaction produces; Its described oxynitride NO
xMiddle x is not less than 1.0.
Specific implementation process of the present invention is:
With hexanaphthene and the oxynitride NO after the vaporization
xGas is sent into a tubular reactor and is carried out the vaporphase nitration oxidizing reaction; Reactant oxynitride NO
xMiddle x is preferably greater than 1.0 less than 3.0, and particularly preferably x=1.5～2.5 are (such as NO
2, N
2O
3Or N
2O
4, N
2O
5Deng); Oxynitride NO
xWith the mol ratio of hexanaphthene be 0.1～10.0, particularly preferably be 0.5～5.0; Temperature of reaction is at 200 ℃～300 ℃, and preferred temperature of reaction is 240 ℃～280 ℃; Reaction pressure is normal pressure～10 normal atmosphere (absolute pressure); The residence time is 30 seconds～200 seconds, and the preferred residence time is 45 seconds～100 seconds; The reduzate NO that nitration oxidation reaction produces is recyclable, and N utilization ratio wherein is greater than 90%, and can reach more than 95%; Thereby high-selectivity co-production obtains nitrocyclohexane and hexanodioic acid.
The present invention also can introduce ratio or the raising reaction efficiency that catalyzer and auxiliary agent generate to change nitrocyclohexane and hexanodioic acid, the optional HP of doing for oneself of its catalyzer, N, N '-dihydroxyl pyromellitic diimide, N-hydroxyl-1,8-naphthalimide or 3,4, the imide analog compounds such as 5,6-tetrachloro-HP; Auxiliary agent is 9,10-anthraquinone, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-amino-4-chloroanthraquinone, 2-chloroanthraquinone or Isosorbide-5-Nitrae-diamino-2, the anthraquinone analog compounds such as 3-dichloroanthraquinone.
By aforesaid method of the present invention, the overall selectivity of nitrocyclohexane and hexanodioic acid can be up to more than 95% even 99% (based on hexanaphthene), and wherein the selectivity of hexanodioic acid namely can be controlled at more than 5%, even can control and reach more than 20%.
A kind of like this employing oxynitride NO
xAs the nitration oxidation agent, directly hexanaphthene is carried out the nitration oxidation reaction, obtain simultaneously technique thinking and the method for nitrocyclohexane and two kinds of products of hexanodioic acid of highly selective, be that prior art is not all studied and related to.And the overall selectivity of nitrocyclohexane and hexanodioic acid very high (based on hexanaphthene) in the technique of the present invention, so no matter be to nitrocyclohexane or hexanodioic acid, all be that a resource efficiency height, generation of waste materials are few, technical process and equipment is simple, production cost is low environmentally benign synthesis.Relatively existing Production Processes of Adipic Acid particularly, the present invention is especially directly from hexanaphthene, the method that single step reaction obtains, significantly process simplification and equipment, minimizing refuse produce, reduce product cost.
The production technique of relatively existing nitrocyclohexane and hexanodioic acid, by this method of the present invention, obtain nitrocyclohexane and two kinds of products of hexanodioic acid by the hexanaphthene single step reaction that sets out, and both overall selectivitys are very high, with respect to existing technique thinking of the present invention and scheme new change arranged.
The contriver is by control suitable reaction conditions and oxynitride NO
xCarry out the vaporphase nitration oxidizing reaction, the nitrocyclohexane of high-selectivity co-production different ratios and hexanodioic acid, and by-product is low, is a synthetic route that meets Sustainable development.It not only can significantly be simplified technique, reduce cost, and can increase substantially resource utilization.Adopt oxynitride NO
xAs the nitration oxidation agent, very pure stable, in nitration oxidation process of the present invention, produce hardly spent acid, seldom produce other by products, reaction product is separated easily, reaction conditions is not harsh, technical process is simple, and nitration oxidation agent reduzate NO can be recycled, and is expected to realize the production that cleans of nitrocyclohexane and hexanodioic acid.
Specific embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention.
Embodiment 1:
Liquid cyclohexane is inputted by constant-flux pump, after the preheating section gasification, presses hexanaphthene: NO
2=2: 1 mole proportioning and NO
2Be mixed into tubular reactor, react under 300 ℃, about 50 seconds of the mean residence time of gas phase mixture enters the receiving flask through condenser condenses from reactor reaction product out.Mixture in the receiving flask is divided into two layers.The upper strata is with after mark is analyzed in the gas-chromatography, and the transformation efficiency that adopts material balance to calculate hexanaphthene is 15.5%, and the selectivity of nitrocyclohexane is 67.2%; Lower floor filters to isolate hexanodioic acid through crystallization, and oven dry is weighed, and the selectivity that gets its hexanodioic acid is 5.2%; Both overall selectivitys 72.4%, the selectivity of other by products are 27.6%
Embodiment 2:
Reactions steps is with embodiment 1, and difference is that temperature of reaction is 250 ℃.The transformation efficiency of hexanaphthene is 12.6%, and the selectivity of nitrocyclohexane is 78.1%, and the selectivity of hexanodioic acid is 21.8%, and both overall selectivitys 99.9% almost do not have other by products to produce.
Embodiment 3:
Reactions steps is with embodiment 1, and difference is that temperature of reaction is 200 ℃.The transformation efficiency of hexanaphthene is 6.5%, and the selectivity of nitrocyclohexane is 73.9%, and the selectivity of hexanodioic acid is 5.3%, and both overall selectivitys 79.2%, the selectivity of other by products are 20.8%.
Embodiment 4:
Reactions steps is with embodiment 1, and difference is, NO
2: hexanaphthene=0.1: 1, temperature of reaction are 250 ℃.The transformation efficiency of hexanaphthene is 2.1%, and the selectivity of nitrocyclohexane is 92.6%, and the selectivity of hexanodioic acid is 7.4%, and overall selectivity 99.9% does not almost have other by products to produce.
Embodiment 5:
Reactions steps is with embodiment 1, and difference is, hexanaphthene: N
2O
5=1: 1 mole proportioning, temperature of reaction are 280 ℃.The transformation efficiency of hexanaphthene is 14.7%, and the selectivity of nitrocyclohexane is 88.3%, and the selectivity of hexanodioic acid is 10.2%, and both overall selectivitys 98.5%, the selectivity of other by products only are 1.5%.
Embodiment 6:
Reactions steps is with embodiment 1, difference is, temperature of reaction is 250 ℃, and catalyzer is HP, and auxiliary agent is 9, the 10-anthraquinone, the transformation efficiency of hexanaphthene is 18.2%, and the selectivity of nitrocyclohexane is 89.0%, and the selectivity of hexanodioic acid is 9.1%, both overall selectivitys 98.1%, the selectivity of other by products are 1.9%.
Claims (5)
1. the method for a high-selectivity co-production of nitrocyclohexane and hexanodioic acid is characterized in that: by hexanaphthene and oxynitride NO
xDirectly carry out the vaporphase nitration oxidizing reaction, reactant oxynitride NO
xWith the mol ratio of hexanaphthene be 0.1～10.0, temperature of reaction is at 240 ℃～280 ℃, the residence time is 45 seconds～100 seconds, thereby high-selectivity co-production obtains nitrocyclohexane and hexanodioic acid; The reduzate NO recycle and reuse that the nitration oxidation reaction produces; Its described oxynitride NO
xMiddle x is not less than 1.0.
2. method according to claim 1 is characterized in that: NO
xMiddle x is 1≤x≤3.
3. method according to claim 1 is characterized in that: NO
xMiddle x is 1.5≤x≤2.5.
4. method according to claim 1, it is characterized in that: its reaction pressure is normal pressure～10 normal atmosphere (absolute pressure).
5. method according to claim 1 is characterized in that: reactant oxynitride NO
xWith the mol ratio of hexanaphthene be 0.5～5.0.
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|---|---|---|---|---|
| WO2022174628A1 (en) | 2021-02-22 | 2022-08-25 | 湘潭大学 | Method for co-producing adipic acid and cyclohexanone oxime from cyclohexane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172534B (en) * | 2011-03-17 | 2013-03-13 | 湘潭大学 | Nitration catalyst and preparation method and application thereof |
| CN103288626B (en) | 2013-06-21 | 2014-12-10 | 湘潭大学 | Method for co-producing adipic acid and nitrocyclohexane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101074198A (en) * | 2007-06-22 | 2007-11-21 | 湘潭大学 | Synthesis of nitrocyclohexane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101074198A (en) * | 2007-06-22 | 2007-11-21 | 湘潭大学 | Synthesis of nitrocyclohexane |
Non-Patent Citations (1)
| Title |
|---|
| 李光洪 等.气相硝化制备硝基环己烷的工艺研究.《湖南师范大学自然科学学报》.2007,第30卷(第2期),81-82. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022174628A1 (en) | 2021-02-22 | 2022-08-25 | 湘潭大学 | Method for co-producing adipic acid and cyclohexanone oxime from cyclohexane |
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