CN112794795B - Production process of cobalt-based catalyst for preparing cyclohexanone by oxidation of cyclohexene and laughing gas - Google Patents
Production process of cobalt-based catalyst for preparing cyclohexanone by oxidation of cyclohexene and laughing gas Download PDFInfo
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- CN112794795B CN112794795B CN202110147710.7A CN202110147710A CN112794795B CN 112794795 B CN112794795 B CN 112794795B CN 202110147710 A CN202110147710 A CN 202110147710A CN 112794795 B CN112794795 B CN 112794795B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/316—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with oxides of nitrogen or nitrogen-containing mineral acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/30—Improvements relating to adipic acid or caprolactam production
Abstract
The invention discloses a production process for preparing cyclohexanone by oxidizing cyclohexene and laughing gas by using a cobalt-based catalyst, which is mainly applied to a synthesis section of adipic acid in a nylon industrial chain. The cobalt-based catalyst is a cobalt-containing salt, oxide, simple substance or cobalt-containing solid catalyst. The invention adopts nitrous oxide (laughing gas) and cyclohexene in the nitrogen oxide waste gas generated by the adipic acid working section to directly react under the action of the catalyst to produce cyclohexanone, and the process not only solves the problem of treating the waste gas laughing gas, but also reduces the consumption of oxygen in the adipic acid working section, and simultaneously reduces the energy consumption and three-waste treatment in the cyclohexanol oxidation process. Therefore, the catalyst and the process have good application prospect, have the advantages of optimizing reaction products, reducing separation cost and the like, and accord with the development trend of green chemical industry.
Description
Technical Field
The invention relates to a production process for preparing cyclohexanone by oxidizing cyclohexene and laughing gas by using a cobalt-based catalyst, which is applied to the nylon industry in the chemical production process. The technology belongs to the fields of catalyst synthesis, clean utilization of nylon chemical industry and air pollution control.
Background
The chemical industry is closely related to our life, is an indispensable important component in the economic development of China, and promotes the economic development of China. At present, the environmental pollution problem caused by chemical production is very serious, and along with the national advocated sustainable development strategy, the green chemical technology is gradually developed.
The cyclohexanone and the cyclohexanone (the mixture of the two is commonly called KA oil) are widely used organic chemical raw materials, most of industry is used for preparing caprolactam and adipic acid, and nylon-66 is prepared through a series of reactions. With the vigorous development of chemical fiber industry in China in recent years, the demand of adipic acid and caprolactam is increased increasingly, and the demand of cyclohexanol and cyclohexanone is increased accordingly, so that the development of cyclohexanone industry is promoted. Cyclohexanone has irreplaceable application in the fields of anti-aging agents, medicines and pesticides, and can also be used as an organic solvent and the like.
Laughing gas (N) 2 O) is one of six greenhouse gases, which has been listed under the "united nations climate change framework convention", and which, due to its extremely stable nature, can remain in the atmosphere for a long period of time up to about 150 years. The main hazard of laughing gas is to destroy the ozone layer, form ozone layer cavities, and finally cause greenhouse effect. Laughing gas is known to be the most damaging substance to the ozone layer at present, and its Global Warming Potential (GWP) is about CO 2 300 times of (2). The relevant literature indicates that N 2 O is growing at a rate of 0.2% per year, i.e. it is slowly eroding our ozone layer and causing damage. N in the atmosphere 2 O mostly comes from tail gas discharged from industrial production, and the largest discharge amount is generated in the industrial production process of adipic acid and nylon-66; other sources are automobile exhaust, biomass combustion, waste water, municipal solid waste and the like. N (N) 2 O is extremely stable in chemical nature, and how it is decomposed or treated to reduce N 2 The impact of O on atmospheric pollution is a research hotspot in the chemical field in recent years.
Adipic acid is a major intermediate in the production of nylon-66, and is typically produced by a nitric acid oxidation process, which is relatively mature and low cost. However, the disadvantage of this process is that large amounts of nitrogen oxides are produced during industrial production, which contain a high content of N 2 O。N 2 O has strong oxidizing property, and N is used 2 O is used as an oxidant to catalyze cyclohexene to synthesize cyclohexanone, and has a great research prospect in the chemical field.
In view of this, the present invention has been made. The invention provides a method for producing cyclohexanone by directly reacting laughing gas and cyclohexene in nitrogen oxide waste gas generated by an adipic acid working section under the action of a catalyst, which not only solves the problem of treatment of waste laughing gas, but also reduces the consumption of oxygen in the adipic acid working section, and simultaneously reduces the energy consumption and three wastes in the oxidation process of cyclohexanol.
Disclosure of Invention
Aiming at the problems of adipic acid working section in the current nylon industry: (1) The conversion rate of the cyclohexanol and cyclohexanone prepared by cyclohexene oxidation is low, and the subsequent cyclohexanol oxidation process is needed after the poor selectivity; (2) The subsequent nitric acid oxidation process produces a portion of laughing gas that is difficult to handle. The invention provides a production process for preparing cyclohexanone by oxidizing cyclohexene and laughing gas by using a cobalt-based catalyst, which realizes the technological process of synthesizing the cyclohexanone by the cyclohexene and the laughing gas under the cobalt-based catalyst and solves the problems of low conversion rate, poor selectivity, complicated subsequent cyclohexanol oxidation process and difficult treatment of laughing gas.
In order to solve the technical problems, the invention adopts the following technical scheme:
a cobalt-based catalyst is used for the production process of preparing cyclohexanone by oxidation of cyclohexene and laughing gas, and comprises the following steps: adding cyclohexene into a kettle type reactor, adding a solvent and a cobalt-based catalyst, closing and sealing the kettle type reactor after filling, replacing air in the kettle with nitrogen for 2-3 times after sealing, replacing nitrogen with laughing gas for 2-3 times, ensuring that the reaction system is in a laughing gas atmosphere, and reacting for 10 hours under the conditions that the reaction temperature is 200-450 ℃ and the reaction absolute pressure is 1.0-5.0 MPa.
The reaction solvent is an organic solvent with a boiling point of 200 ℃ or higher, such as N-methylpyrrolidone, N N dimethylacetamide, benzyl alcohol, tridecane, diformate or ethyl benzoate.
Further, nitrous oxide in the nitrogen oxide waste gas generated by the adipic acid working section is adopted by the laughing gas.
Further, the cobalt-based catalyst adopts one or more of cobalt salts, oxides, simple substances or solid catalysts containing cobalt.
Further, the cobalt salt is one or more of cobalt nitrate, cobalt chloride, cobalt acetate, cobalt sulfate, cobalt sulfite, cobalt carbonate or cobalt phosphate.
Further, the cobalt oxide is one or more of cobalt monoxide, cobaltosic oxide and cobaltosic oxide.
Further, the simple substance of cobalt refers to a simple substance of metallic cobalt or a mixture containing simple substances of metallic cobalt.
Further, the cobalt-containing solid catalyst is one or more of a cobalt-containing heteropolyacid, a molecular sieve, a MOF or a COF.
The invention relates to a process for preparing cyclohexanone by oxidizing cyclohexene and laughing gas, which is characterized in that the process of generating cyclohexanone by oxidizing the laughing gas and cyclohexene as by-products is adopted in an adipic acid working section in the nylon production process.
The invention adopts nitrous oxide (laughing gas) and cyclohexene in the nitrogen oxide waste gas generated by the adipic acid working section to directly react under the action of the catalyst to produce cyclohexanone, and the process not only solves the problem of treating the waste gas laughing gas, but also reduces the consumption of oxygen in the adipic acid working section, and simultaneously reduces the energy consumption and three-waste treatment in the cyclohexanol oxidation process.
The invention has the beneficial effects that: 1. the cobalt-based catalyst has good catalytic performance, can promote the rapid reaction of cyclohexene and laughing gas, and the product in the reaction mainly takes cyclohexanone as the main component, so that the cost of subsequent separation of the product is greatly reduced. 2. The process for synthesizing cyclohexanone from laughing gas and cyclohexene has the advantages of reducing the emission of laughing gas which pollutes waste gas, solving the problem of waste gas treatment, realizing the recycling of waste gas in the section and conforming to the development concept of green chemical industry. Therefore, the invention has good application prospect, has the advantages of optimizing reaction products, reducing separation cost and the like, and accords with the development trend of green chemical industry.
Drawings
FIG. 1 shows a process for preparing adipic acid from cyclohexane in nylon industry.
FIG. 2 shows the comprehensive utilization process of cyclohexane (ene) adipic acid laughing gas in nylon industry chain.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are to be considered in an illustrative sense only and are not intended to limit the invention.
Example 1
The production process of the cobalt-based catalyst for preparing cyclohexanone by oxidizing cyclohexene and laughing gas in the embodiment comprises the following steps:
the catalyst is directly purchased or self-made.
Catalyst evaluation was performed in a 100mL stainless steel batch kettle reactor, the reactor was leak-tested with nitrogen before starting the reaction, and experiments were performed after the test tightness was acceptable.
1.0g of cyclohexene serving as a reaction raw material is weighed and added into a kettle-type reactor, 20.0g of N, N-dimethylacetamide serving as a solvent and 0.1g of cobalt nitrate serving as a catalyst are added; after filling, closing and sealing the reaction kettle, after sealing, replacing air in the kettle with nitrogen for 2-3 times, and then replacing nitrogen with laughing gas for 2-3 times; ensuring that the reaction system is under laughing gas atmosphere, and introducing laughing gas to 1.0Mpa; heating, namely, heating the reaction system to 220 ℃ by a temperature control and heating furnace, and simultaneously increasing the reaction pressure; after each parameter is stable, starting timing reaction, after the reaction time is 10 hours, cooling, and analyzing the composition of gas phase and liquid phase products. The cyclohexene conversion, the selectivity for cyclohexanol, cyclohexanone and benzene were calculated.
Example 2
The same procedure is as in example 1, without solvent, without catalyst, and otherwise with example 1.
Example 3
The same as in example 1, benzyl alcohol as solvent, cobalt acetate as catalyst and the other same as in example 1.
Example 4
The procedure of example 1 is followed, with benzyl alcohol as solvent and FeZSM-5 as catalyst.
Example 5
The procedure of example 1 is followed, with benzyl alcohol as solvent and CoZSM-5 as catalyst.
Example 6
The solvent benzyl alcohol and catalyst were not used in the same manner as in example 1, and the other steps were performed in example 1.
The evaluation results of the examples are shown in Table 1.
Table 1 results of catalyst evaluation
As is clear from Table 1, in example 1, the introduction of the cobalt nitrate catalyst and the addition of the N, N dimethylacetamide solvent promoted the conversion of cyclohexene and cyclohexanone was the main product, as compared with example 2.
Also example 3 compared to example 2, it was confirmed that cobalt acetate catalyst and benzyl alcohol solvent promote the reaction of cyclohexene and laughing gas, and cyclohexanone is the main product.
Example 5 in comparison with example 4, the Fe-based catalyst is able to oversatalyst the reaction of cyclohexene and laughing gas, but the main product is benzene; while the main products become cyclohexanone and cyclohexanol with Co-based catalysts. However, the supported solid catalyst of comparative example 5 was less active than the cobalt-based salt catalyst of example 1.
Example 6 compared to example 3, the reaction can occur in benzyl alcohol solvent without catalyst, but with lower cyclohexene conversion and the principal product still being benzene.
The above examples demonstrate that the cobalt-based catalyst has the property of catalyzing the reaction of cyclohexene and laughing gas, and that the primary product is cyclohexanone. Provides a new process and thought for the synthesis section of adipic acid in nylon industry chains. Not only solves the problem of treating waste gas laughing gas, but also reduces the consumption of oxygen in the adipic acid working section, and simultaneously reduces the energy consumption and three wastes treatment in the cyclohexanol oxidation process. Has the advantages of optimizing reaction products, reducing separation cost and the like, and accords with the development trend of green chemical industry.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (2)
1. A production process for preparing cyclohexanone by oxidizing cyclohexene and laughing gas by using a cobalt-based catalyst is characterized by comprising the following steps: adding cyclohexene into a kettle type reactor, adding a solvent and a cobalt-based catalyst, closing and sealing the kettle type reactor after filling, replacing air in the kettle with nitrogen for 2-3 times after sealing, replacing nitrogen with laughing gas for 2-3 times, ensuring that a reaction system is in a laughing gas atmosphere, and reacting for 10 hours under the conditions that the reaction temperature is 200-450 ℃ and the reaction absolute pressure is 1.0-5.0 MPa;
the reaction solvent is N-methyl pyrrolidone, N-dimethylacetamide, benzyl alcohol, tridecane, diformate or ethyl benzoate;
the laughing gas adopts nitrous oxide in nitrogen oxide waste gas generated by an adipic acid working section;
the mass ratio of cyclohexene to cobalt-based catalyst is 1:0.1;
the cobalt-based catalyst is one or more of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate.
2. The production process according to claim 1 is applied to a synthesis section of adipic acid in nylon industrial chains.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015013350A1 (en) * | 2013-07-25 | 2015-01-29 | Shell Oil Company | PROCESS FOR PREPARING C10 to C30 ALCOHOLS |
| WO2018128959A1 (en) * | 2017-01-04 | 2018-07-12 | Shell Oil Company | A process for the preparation of adipic acid |
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| RU2227135C2 (en) * | 2002-03-20 | 2004-04-20 | Институт катализа им. Г.К. Борескова СО РАН | Method for preparing cyclopentanone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015013350A1 (en) * | 2013-07-25 | 2015-01-29 | Shell Oil Company | PROCESS FOR PREPARING C10 to C30 ALCOHOLS |
| WO2018128959A1 (en) * | 2017-01-04 | 2018-07-12 | Shell Oil Company | A process for the preparation of adipic acid |
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