CN110872224A - Process for preparing adipic acid by catalytic oxidation of cyclohexane and preparation method of acid modified sepiolite catalyst - Google Patents
Process for preparing adipic acid by catalytic oxidation of cyclohexane and preparation method of acid modified sepiolite catalyst Download PDFInfo
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- CN110872224A CN110872224A CN201811022001.0A CN201811022001A CN110872224A CN 110872224 A CN110872224 A CN 110872224A CN 201811022001 A CN201811022001 A CN 201811022001A CN 110872224 A CN110872224 A CN 110872224A
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- acid
- catalyst
- cyclohexane
- adipic acid
- sepiolite
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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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
Abstract
The invention relates to an oxidation catalyst for preparing adipic acid by one-step oxidation of cyclohexane, which mainly solves the problems of low catalyst yield and poor selectivity in the prior art and avoids the pollution of nitric oxide generated by nitric acid to the environment in the oxidation process. The invention is prepared by adopting cheap sepiolite raw ore, modifying by different inorganic or organic acid, washing to neutrality, filtering and drying. The preparation method is simple and has good repeatability; the structure proportion of the active phase of the catalyst is adjustable by an acid treatment mode; the selectivity of adipic acid is higher when the conversion rate of cyclohexane is higher, and the highest selectivity of adipic acid is 62.3 percent; can be used in the industrial production of preparing adipic acid by one-step oxidation of cyclohexane.
Description
Technical Field
The present invention belongs to a process for preparing adipic acid by using cyclohexane as raw material in one step, and an acid modified sepiolite catalyst and a preparation method of the acid modified sepiolite catalyst used in the process.
Background
Adipic acid (also known as adipic acid) is white crystal at normal temperature, is one of the most important compounds in all aliphatic dicarboxylic acids produced industrially, is widely used for preparing polyamide nylon-66, polyurethane foam plastics, acidifiers in leavening agents, plastics and lubricant additives, and is used for producing intermediates of pharmacy and pesticides and bactericides; and also as a basic raw material for adiponitrile, hexamethylenediamine and polyester polyol in the organic synthesis industry. At present, with the rapid development of industries such as nylon, polyurethane and the like in China, the consumption of adipic acid is steadily increased, and the market competition is gradually intensified. The global annual production of adipic acid currently exceeds 350 million tons and is also on the increasing trend each year.
In the traditional industrial production process of adipic acid, a cyclohexane two-step synthesis oxidation process is mainly adopted, which accounts for 86% -93% of the total production capacity, the process comprises the steps of firstly carrying out air oxidation on cyclohexane under the catalysis of cobaltate homogeneous phase at high temperature (125 ℃ -165 ℃) and high pressure (8-15 atm) to obtain cyclohexanone and cyclohexanol (commonly called KA oil), and then oxidizing the KA oil into adipic acid under the catalysis of 40-50% nitric acid and vanadium base, although the process is adopted by nearly 95% of worldwide industrial production adipic acid, equipment is seriously corroded due to the use of concentrated nitric acid with strong oxidizing property, and a large amount of nitrogen oxides which seriously pollute the environment are generated; meanwhile, the process flow is complex and the reaction conditions are harsh, and HNO is added3High oxidation energy consumption and low yield, which always troubles the adipic acid production industryThe development of the process. At present, the synthesis of adipic acid is still a worldwide technical problem, so that research and development of a novel green and environment-friendly process with high yield of adipic acid is of great significance for industrial application. Aiming at the main defects of the two-step cyclohexane production process, domestic and foreign scholars conduct basic research on the one-step cyclohexane method, namely, the direct oxidation of cyclohexane to prepare adipic acid, and are dedicated to searching a new process which is more green, environment-friendly and concise. The green process for preparing adipic acid by the cyclohexane one-step oxidation method adopts green oxidants such as oxygen, air or hydrogen peroxide to replace HNO3The simple process of the one-step method replaces the complex process of the two-step method, and the green heterogeneous catalyst with high efficiency and low cost replaces the low-activity homogeneous catalyst, thereby conforming to the development direction of the green chemical industry. At present, scholars at home and abroad successively develop a plurality of new heterogeneous or homogeneous catalytic processes for the aerobic oxidation of cyclohexane, such as N-hydroxyphthalimide (NHPI), metalloaluminophosphates (MAPO, M: Mn, Co, Fe), zeolite Y and the like, and overcome the defects and make great progress. Loder first proposed acetate (Co (OAc) in 19402) The adipic acid is used as a catalyst, and air oxidation replaces nitric acid oxidation. Later, many scholars have studied and improved the homogeneous system, Tanaka has improved the loder method, add acetaldehyde as the auxiliary agent, at 90 ℃, 1.8MPa, react for 9h, cyclohexane conversion reaches 88%, adipic acid selectivity reaches 73%. Ishii et al developed a method for preparing adipic acid by directly oxidizing cyclohexane with molecular oxygen at 100 ℃ for 6 hours by using a mixture of N-hydroxyphthalimide (NHPI) and cobalt acetylacetonate as a catalyst and acetic acid as a solvent, wherein the cyclohexane conversion rate is 73% and the adipic acid selectivity is 53%, and the method is one of representatives in the field. However, the oxidation processes are homogeneous reactions, necessary reaction solvents and initiators are needed, the environment is still damaged, and the problems of complex reaction and separation processes, long process flow and the like are solved. Patents ZL 03118249.6 and CN 10137879B disclose the invention of metalloporphyrin catalytic oxidation of cyclohexane to prepare adipic acid, although the method has high catalytic efficiency, the metalloporphyrin type catalyst is expensive, the preparation method is complex, the reaction time is long, the reaction by-products are many, and the metalloporphyrin type catalyst cannot be recovered and reused.
Disclosure of Invention
The invention aims at solving the problems of using corrosive concentrated nitric acid raw materials and generating three wastes which seriously pollute the environment, namely nitric oxide, nitric acid vapor, waste acid liquid and the like in the traditional adipic acid production process, provides a green process for preparing adipic acid by catalyzing the oxidation of cyclohexane by molecular oxygen by using acid modified sepiolite in one step, solves the problems of environmental pollution, high atomic rate, high production cost and the like in the current production process, and simultaneously has the advantages of easily obtained catalyst raw materials and low price; the acid modification process of the catalyst is simple.
The technical scheme of the invention is as follows: a preparation method of a series of acid modified sepiolite comprises the following steps in sequence: taking sepiolite, carrying out acid modification treatment on the sepiolite by using different inorganic acids (hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid) and organic acids (acetic acid, monochloroacetic acid, trichloroacetic acid and benzenesulfonic acid) under the conditions of different temperatures, acid concentrations, stirring time and the like, washing the sepiolite to be neutral by using deionized water after treatment, and then filtering, drying and grinding the sepiolite.
The sepiolite modified by acid is adopted in the invention, so that the structure of the sepiolite is changed. Because structural units of the sepiolite are internal channel structures with average pore sizes formed by silicon-oxygen tetrahedrons and magnesium-oxygen octahedrons in an alternating mode, the sepiolite Si-O-Mg-O-Si bonds are changed into two Si-OH bonds by adopting acid treatment, namely, the sepiolite has an open structure, and the internal channel communicated surface structure is obviously changed, so that the specific surface area and the integral catalytic performance of the catalyst are improved.
The modified catalyst can regulate and control the catalytic activity of the catalyst due to different acidification treatment time (0.5-15 h), temperature (20-120 ℃) and acid concentration (0.1-10 mol/L), namely the sepiolite acid treatment temperature is preferably 40-100 ℃, the acidification treatment time is preferably 3-12 h, and the acid concentration is preferably 3-9 mol/L.
The sepiolite series catalyst modified by acid in the method can be used for selective oxidation of cyclohexane, and is particularly suitable for catalyzing molecular oxygen to oxidize cyclohexane to prepare adipic acid in one step. The oxidation reaction conditions comprise that the reaction temperature is 120-170 ℃, the reaction pressure is 0.4-2.0 MPa, the oxidant is air or oxygen, the reaction time is 1-15 h, and the dosage of the catalyst is 0.01-20% of the mass fraction of the reactants.
Detailed description of the preferred embodimentsthe following examples are intended to illustrate, but not limit the invention. Examples are as follows:
example 1: at the temperature of 130 ℃ and the pressure of 1MPa, 9.4g of cyclohexane and 0.075g of nitric acid modified sepiolite are added into a high-pressure reaction kettle to react by taking oxygen as an oxidant. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 12.76% and the adipic acid selectivity was 43.91%.
Example 2: at the temperature of 140 ℃ and the pressure of 1MPa, 9.4g of cyclohexane and 0.075g of sulfuric acid modified sepiolite are added into a high-pressure reaction kettle by taking air as an oxidant to react. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 11.05% and the adipic acid selectivity was 41.85%.
Example 3: at the temperature of 140 ℃ and the pressure of 1MPa, 9.4g of cyclohexane and 0.075g of acetic acid modified sepiolite are added into a high-pressure reaction kettle by taking air as an oxidant to react. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 10.45% and the adipic acid selectivity was 48.69%.
Example 4: at the temperature of 140 ℃ and the pressure of 1MPa, 9.4g of cyclohexane and 0.075g of phosphoric acid modified sepiolite are added into a high-pressure reaction kettle by taking air as an oxidant to react. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 9.91% and the adipic acid selectivity was 42.95%.
Example 5: at the temperature of 140 ℃ and the pressure of 1MPa, 9.4g of cyclohexane and 0.075g of hydrochloric acid modified sepiolite are added into a high-pressure reaction kettle to react by taking air as an oxidant. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 9.14% and the adipic acid selectivity was 24.19%.
Example 6: at the temperature of 140 ℃ and the pressure of 1MPa, 9.4g of cyclohexane and 0.075g of trifluoroacetic acid modified sepiolite are added into a high-pressure reaction kettle to react by taking air as an oxidant. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 8.21% and the adipic acid selectivity was 47.53%.
Example 7: at the temperature of 140 ℃ and the pressure of 1MPa, 9.4g of cyclohexane and 0.075g of trichloroacetic acid modified sepiolite are added into a high-pressure reaction kettle to react by taking air as an oxidant. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 9.40% and the adipic acid selectivity was 43.40%.
Example 8: 9.4g of cyclohexane and 0.075g of nitric acid modified sepiolite which is treated at 60 ℃ for 7 hours are added into a high-pressure reaction kettle for reaction at the temperature of 140 ℃ and the pressure of 1MPa by taking air as an oxidant. The results of the reaction for 4 hours were as follows: the cyclohexane conversion was 11.49% and the adipic acid selectivity was 62.31%.
Claims (2)
1. A green process for preparing adipic acid by cyclohexane conversion is characterized in that an acid modified sepiolite catalyst is prepared and used for catalyzing the oxidation reaction, and comprises the following steps: cyclohexane is used as a raw material, acid modified sepiolite is used as a catalyst, air or oxygen is used as an oxidant, and the catalyst is catalytically converted into a product mainly containing adipic acid under the conditions that the operating pressure is 0.4-2.0 MPa, the operating temperature is 120-170 ℃, the dosage of the catalyst is 0.01-20% of the mass of the cyclohexane, and the reaction time is 1-15 hours.
2. A green process for preparing adipic acid by cyclohexane conversion is characterized in that a catalyst and a preparation method of the catalyst comprise the following steps: the catalyst as claimed in claim 1, wherein the catalyst is acid-modified sepiolite: the inorganic acid mainly comprises hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and the organic acid mainly comprises acetic acid, monochloroacetic acid, trichloroacetic acid and benzenesulfonic acid; the catalytic activity of the catalyst can be regulated, namely the acid treatment temperature of the sepiolite is preferably 40-60 ℃, the acid treatment time is preferably 3-12 h, and the acid concentration is preferably 3-9 mol/L.
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| CN201811022001.0A CN110872224A (en) | 2018-09-04 | 2018-09-04 | Process for preparing adipic acid by catalytic oxidation of cyclohexane and preparation method of acid modified sepiolite catalyst |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535947A (en) * | 2003-04-08 | 2004-10-13 | 湖南大学 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
| CN101239899A (en) * | 2008-03-10 | 2008-08-13 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
| EP2006323A1 (en) * | 2007-06-22 | 2008-12-24 | E.I. Du Pont De Nemours And Company | Process for the production of polyester nanocomposites |
| CN105622385A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Process for preparing adipic acid through cleaning catalytic oxidation of cyclohexanone, catalyst, and catalyst preparation method |
-
2018
- 2018-09-04 CN CN201811022001.0A patent/CN110872224A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535947A (en) * | 2003-04-08 | 2004-10-13 | 湖南大学 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
| EP2006323A1 (en) * | 2007-06-22 | 2008-12-24 | E.I. Du Pont De Nemours And Company | Process for the production of polyester nanocomposites |
| CN101239899A (en) * | 2008-03-10 | 2008-08-13 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
| CN105622385A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Process for preparing adipic acid through cleaning catalytic oxidation of cyclohexanone, catalyst, and catalyst preparation method |
Non-Patent Citations (3)
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| 唐永翔等: "用于环己烷氧化的Co_3O_4/海泡石催化剂的制备和第一性原理研究", 《常州大学学报(自然科学版)》 * |
| 唐雷等: "酸改性海泡石负载钌-硼合金催化苯选择加氢制环己烯", 《石油化工》 * |
| 李翔: "环己烷氧化催化剂的制备及其催化性能研究", 《中国优秀硕士学位论文库工程科技Ⅰ辑》 * |
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Effective date of registration: 20211202 Address after: Hunan Normal University, 36 Lushan Road, Yuelu District, Changsha City, Hunan Province, 410081 Applicant after: HUNAN NORMAL University Applicant after: XIANGTAN SEPIOLITE TECHNOLOGY CO.,LTD. Address before: Hunan Normal University, 36 Lushan Road, Yuelu District, Changsha City, Hunan Province, 410081 Applicant before: HUNAN NORMAL University Applicant before: XIANGTAN YUAN YUAN SEPIOLITE NEW MATERIAL CO.,LTD. |
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