CN114315499A - Method for preparing benzene by dehydrogenation of naphthenic hydrocarbon - Google Patents
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Abstract
The invention relates to a method for preparing benzene by naphthenic hydrocarbon dehydrogenation, which takes NiX composite metal oxide (NiX-MO) prepared by taking NiX hydrotalcite as a precursor as a catalyst, and the active components are NiO, Ni: the proportion of X is adjustable between 1 and 6. Wherein the NiX-LDH is prepared by a urea hydrothermal method or a precipitation method, the NiX-MO is obtained by roasting the hydrotalcite, and the roasting temperature is 200-700 ℃. The catalyst can convert cyclohexane into benzene with high selectivity and has no obvious deactivation. The nickel-based catalyst improved based on hydrotalcite of the invention has the advantages of cyclohexane conversion rate of more than 80%, selectivity of more than 90%, reduction of product separation cost and good industrial application prospect.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a method for preparing benzene by cyclohexane dehydrogenation.
Technical Field
Cyclohexene is an important organic chemical raw material and is widely applied to the production of medicines, pesticides, fuels, detergents, explosives, feed additives, nylon, polyamide, polyester and other fine chemicals. Among the cyclohexene preparation processes, the benzene selective hydrogenation process is a method for preparing cyclohexene by selective hydrogenation by taking cheap benzene as a raw material, has the characteristics of high atom utilization rate, hydrogen source saving, less side reactions, environmental friendliness and the like, and has obvious advantages compared with the traditional cyclohexane-to-cyclohexanone process. At present, the cyclohexene devices newly built in China are all partial hydrogenation processes of benzene. However, in the partial hydrogenation of benzene, cyclohexane is inevitably produced. Through continuous optimization of a partial benzene hydrogenation catalyst, the selectivity of cyclohexene in the domestic market is basically maintained at about 80 percent at present, namely 20 percent of benzene is converted into a byproduct cyclohexane. If cyclohexane is subjected to dehydrogenation reaction to regenerate benzene, the utilization rate of raw materials can be effectively improved.
Patent publication No. CN106140155A discloses a catalyst for olefin production by dehydrogenation of pentane or hexane, and a preparation method and application thereof. The catalyst takes alumina as a carrier, takes one or more of Rh, Ru, Pt or Pd as a main active component, is matched with other elements as auxiliary active components, and can catalyze n-hexane or n-pentane to prepare olefin by dehydrogenation. But the conversion of the alkane is not high and it can be seen from the data of the examples that the process is mainly applicable to the dehydrogenation of n-hexane or n-pentane. Patent publication No. CN105037066A discloses a method for realizing Pt/C catalyst preparation and methylcyclohexane dehydrogenation in one step. However, the preparation method of the catalyst is too complicated, and the methyl cyclohexane is favorable for the dehydrogenation reaction due to the existence of methyl, so the dehydrogenation temperature is low. The CN107537560A patent reports that the activity and the stability of a cycloparaffin dehydrogenation catalyst taking modified MCM-41 as a carrier are effectively improved. However, the MCM-41 molecular sieve is weak in acidity, carbon deposit is inhibited, and meanwhile, the dispersibility and activity of Pt metal have no obvious advantages, while the traditional Al is adopted2O3The carrier is too strong in acidity, and carbon deposition on the surface of the catalyst is serious. The CN104785256B patent reports a Mg-Al-O composite oxide carrier, which aims to improve the carbon deposition resistance of the carrier. However, the catalyst is advantageous for the reaction of dehydrogenation of cycloalkane to prepare cyclohexene, and if the dehydrogenation activity is further improved to prepare benzene, the properties of the active metal and the carrier of the catalyst are still required to be further improved, and the carbon deposit resistance of the catalyst is improved.
In summary, unlike the propane dehydrogenation catalyst, the main problems of the existing cycloalkane dehydrogenation catalyst are that the cycloalkane has a large molecular weight, is liquid at normal temperature, and has poor activity at low temperature, while carbon is easily deposited on the surface of the catalyst at high temperature, so that the catalyst is quickly deactivated, and has poor activity and stability.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a cyclohexane dehydrogenation catalyst and a preparation method thereof, which are used for preparing benzene by cyclohexane dehydrogenation so as to improve the utilization rate of raw material benzene in a process of preparing cyclohexene by selective hydrogenation of benzene and reduce the generation cost.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing benzene by dehydrogenation of naphthenic hydrocarbon comprises the following steps: taking cyclane as a raw material, and obtaining benzene through dehydrogenation reaction under the action of a catalyst; the catalyst is a composite oxide consisting of an active component NiO and an auxiliary agent X, and is expressed as NiX-MO; wherein MO represents an oxide, and the auxiliary agent X is one or more than one oxide of Al, Mg and Fe; the molar ratio of Ni to X is 1-6; the catalyst NiX-MO is obtained by roasting hydrotalcite NiX-LDH at 200-700 ℃ for 1-6 h.
Based on the above scheme, preferably, the baking atmosphere is air.
Based on the scheme, preferably, the hydrotalcite NiX-LDH is prepared by a urea hydrothermal method, and the method comprises the following steps:
1) dissolving Ni soluble metal salt and X soluble metal salt in water according to the required molar ratio to obtain metal salt solution;
2) dissolving urea in the metal salt solution, and uniformly stirring to obtain a mixed solution;
3) crystallizing the mixed solution at 70-180 ℃ for 6-72h, filtering, washing and drying to obtain hydrotalcite NiX-LDH.
Based on the scheme, preferably, the hydrotalcite NiX-LDH is prepared by a coprecipitation method, and comprises the following steps:
1) dissolving Ni soluble metal salt and X soluble metal salt in water according to the required molar ratio to obtain metal salt solution;
2) mixing NaOH and Na2CO3Dissolving the solution in water to obtain an alkali solution;
3) and (2) simultaneously dripping the metal salt solution and the alkali solution into a container, controlling the titration speed to keep the pH value of the solution at 7-10.5, stirring for 1-5h after the dripping is finished, then crystallizing for 6-72h at the temperature of 70-180 ℃, filtering, washing and drying to obtain a hydrotalcite precursor NiX-LDH.
Based on the above scheme, preferably, in step 1), the soluble metal salt of Ni is nickel nitrate or nickel acetate, and the soluble metal salt of X is nitrate or acetate of X.
Based on the above scheme, the molar ratio of urea to nickel is preferably 1-100.
Based on the above scheme, preferably, the cycloalkane is cyclohexane.
Based on the scheme, preferably, the reaction is a continuous fixed bed reaction, the molar ratio of cyclohexane to hydrogen is 1-50, wherein the hydrogen is used for relieving carbon deposition of the catalyst and is used as a carrier gas to carry cyclohexane into the reactor; the total pressure of the gas introduced into the fixed bed reactor is micro-positive pressure, and the total gas airspeed is 6000-plus-material 36000h-1Through a fixed bed reactor containing a catalyst.
Based on the above scheme, the reaction temperature is preferably 300-600 ℃.
Advantageous effects
The composite metal oxide prepared by taking the nickel-based hydrotalcite as the precursor has high specific surface area, high dispersibility and good thermal stability, and meanwhile, the prepared NiO is a P-type semiconductor and has more Ni vacancies which can cause the generation of electrophilic oxygen species which are beneficial to the activation of C-H bonds. The NiO-based catalyst prepared by using the hydrotalcite as the precursor is not only beneficial to the dispersion of NiO, but also beneficial to the improvement of the product selectivity.
The naphthenic dehydrogenation catalyst provided by the invention has proper acidity, can inhibit a large amount of carbon deposit on the surface of the catalyst, can improve the dispersibility of active components on the surface of a carrier, promotes the generation of more active phases on the surface of the catalyst, and improves the high-temperature activity and stability of the catalyst.
The catalyst has simple and repeatable preparation process, and has higher cyclohexane dehydrogenation activity (more than 80 percent) and higher benzene selectivity (more than 90 percent). Meanwhile, the catalyst has good stability, can be continuously used for more than 200h, and the activity is not obviously reduced.
Detailed Description
The present invention will be described in detail with reference to specific examples, which are not intended to limit the scope of the present invention.
Example 1
2, preparing a NiAl-MO catalyst: 11.64g of Ni (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, and 30g of urea was dissolved together in the above 500mL of ultrapure water. And continuously stirring the solution for a period of time, transferring the salt solution into a hydrothermal kettle with a polytetrafluoroethylene lining, crystallizing at 90 ℃ for 12 hours, cooling to room temperature, filtering, washing and drying to obtain a 2NiAl-LDH hydrotalcite precursor, and roasting at 500 ℃ for 4 hours to obtain the 2NiAl-MO catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 2NiAl-MO with a loading of 0.5ml and a cyclohexane to hydrogen molar ratio of 20, GHSV of 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
Example 2
3, preparing a NiAl-MO catalyst: 17.46g of Ni (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, and 30g of urea was dissolved together in the above 500mL of ultrapure water. Continuously stirring the solution for a period of time, transferring the salt solution into a hydrothermal kettle with polytetrafluoroethylene lining, crystallizing at 90 ℃ for 12 hours, cooling to room temperature, filtering, washing and drying to obtain the 2NiAl-LDH hydrotalcite precursorAnd roasting the mixture at 500 ℃ for 4 hours to obtain the 3NiAl-MO catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 3NiAl-MO with a loading of 0.5ml and a cyclohexane to hydrogen molar ratio of 20, GHSV of 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
Example 3
Preparation of 4NiAl-MO catalyst: 23.28g of Ni (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, and 36g of urea was dissolved together in the above 500mL of ultrapure water. And continuously stirring the solution for a period of time, transferring the salt solution into a hydrothermal kettle with a polytetrafluoroethylene lining, crystallizing at 90 ℃ for 12 hours, cooling to room temperature, filtering, washing and drying to obtain a 2NiAl-LDH hydrotalcite precursor, and roasting at 500 ℃ for 4 hours to obtain the 4NiAl-MO catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 4NiAl-MO with a loading of 0.5ml and a cyclohexane to hydrogen molar ratio of 20, GHSV of 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
Example 4
Preparation of 4NiAl-MO catalyst: 23.28g of Ni (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, and 36g of urea was dissolved together in the above 500mL of ultrapure water. And continuously stirring the solution for a period of time, transferring the salt solution into a hydrothermal kettle with a polytetrafluoroethylene lining, crystallizing at 130 ℃ for 48 hours, cooling to room temperature, filtering, washing and drying to obtain a 3NiAl-LDH hydrotalcite precursor, and roasting at 500 ℃ for 4 hours to obtain the 4NiAl-MO catalyst.
Cyclohexane dehydrogenation experiment at an internal diameter of 6mmIn a quartz tube reactor, the catalyst was 4NiAl-MO, the loading was 0.5ml, the molar ratio of cyclohexane to hydrogen was 20, the GHSV was 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
Example 5
3 preparing a NiMgAl-MO catalyst: 17.46g of Ni (NO)3)2·6H2O, 2.56g of Mg (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, and 36g of urea was dissolved together in the above 500mL of ultrapure water. And continuously stirring the solution for a period of time, transferring the salt solution into a hydrothermal kettle with a polytetrafluoroethylene lining, crystallizing at 90 ℃ for 12 hours, cooling to room temperature, filtering, washing and drying to obtain a 2NiAl-LDH hydrotalcite precursor, and roasting at 500 ℃ for 4 hours to obtain the 3NiMgAl-MO catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 3NiMgAl-MO with a loading of 0.5ml and a cyclohexane to hydrogen molar ratio of 20, GHSV of 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
Example 6
3, preparing a NiFe-MO catalyst: 17.46g of Ni (NO)3)2·6H2O and 8.08g Fe (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, and 36g of urea was dissolved together in the above 500mL of ultrapure water. And continuously stirring the solution for a period of time, transferring the salt solution into a hydrothermal kettle with a polytetrafluoroethylene lining, crystallizing at 90 ℃ for 12 hours, cooling to room temperature, filtering, washing and drying to obtain a 3NiFe-LDH hydrotalcite precursor, and roasting at 500 ℃ for 4 hours to obtain the 3NiFe-MO catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 3NiFe-MO, which was chargedThe filling amount is 0.5ml, the molar ratio of cyclohexane to hydrogen is 20, and the GHSV is 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
Example 7
3, coprecipitation preparation of a NiAl-MO catalyst: 17.46g of Ni (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, denoted as solution A, and 12.0g NaOH and 2.0g Na were added2CO3Dissolved in 200ml of pure water and marked as solution B. Adopting a coprecipitation method, simultaneously dripping A, B two solutions, controlling the dripping speed of A to be 1.0ml/min, controlling the dripping speed of B to be 0.5ml/min, controlling the pH value to be 9-10, and continuing stirring for 2h after the dripping is finished. And aging at 90 ℃ for 12h, cooling to room temperature, filtering, washing and drying to obtain a 3NiAl-LDH hydrotalcite precursor, and then roasting at 500 ℃ for 4h to obtain the 3NiAl-MO catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 3NiAl-MO with a loading of 0.5ml and a cyclohexane to hydrogen molar ratio of 20, GHSV of 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
Example 8
3, coprecipitation preparation of a NiAl-MO catalyst: 17.46g of Ni (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2O was dissolved together in 500mL of ultrapure water, denoted as solution A, and 12.0g NaOH and 2.0g Na were added2CO3Dissolved in 200ml of pure water and marked as solution B. And (3) simultaneously dripping the AB solution and the B solution by adopting a coprecipitation method, controlling the dripping speed of A to be 1.0ml/min, controlling the dripping speed of B to be 0.5ml/min, controlling the pH to be 9-10, and continuing stirring for 2 hours after the dripping is finished. Aging at 90 deg.C for 12h, cooling to room temperature, filtering, washing, drying to obtain 3NiAl-LDH hydrotalcite precursor, and calcining at 500 deg.C for 4h to obtain 3NiAl-MO catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 3NiAl-MO with a loading of 0.5ml and a cyclohexane to hydrogen molar ratio of 20, GHSV of 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After reacting for 300h, qualitative and quantitative analysis of the product is carried out by gas chromatography.
Comparative example 1
3, mechanically mixing and grinding the NiAlOx catalyst: 17.46g of Ni (NO)3)2·6H2O and 7.50g of Al (NO)3)3·9H2And directly mixing O, grinding and drying to obtain a precursor of the 3NiAlOx composite oxide, and then roasting at 500 ℃ for 4h to obtain the 3NiAlOx catalyst.
The cyclohexane dehydrogenation experiment was carried out in a quartz tube reactor having an internal diameter of 6mm and a catalyst of 3NiAlOx with a loading of 0.5ml and a cyclohexane to hydrogen molar ratio of 20 at GHSV of 15000h-1The reaction pressure is 0.1MPa, and the reaction temperature is 450 ℃. Cyclohexane is preheated in a preheating furnace at 180 ℃ before reaction and then passes through a reactor. After the reaction, the product was qualitatively and quantitatively analyzed by gas chromatography.
TABLE 1 reactivity of different catalysts
| Numbering | Catalyst and process for preparing same | Conversion of cyclohexane% | Benzene selectivity% |
| Example 1 | 2NiAl-MO | 81.6 | 92.9 |
| Example 2 | 3NiAl-MO | 84.8 | 93.2 |
| Example 3 | 4NiAl-MO | 83.3 | 93.5 |
| Example 4 | 4NiAl-MO | 82.2 | 94.8 |
| Example 5 | 3NiMgAl-MO | 81.4 | 92.6 |
| Example 6 | 3NiFe-MO | 84.5 | 93.9 |
| Example 7 | 3NiAl-MO | 83.4 | 93.5 |
| Example 8 | 3NiAl-MO | 84.8 | 92.4 |
| Comparative example 1 | 3NiAlOx | 53.7 | 88.3 |
Reaction conditions are as follows: 0.1MPa, 450 deg.C, GHSV 15000h-1。
Claims (9)
1. A method for preparing benzene by dehydrogenation of naphthenic hydrocarbon is characterized in that: taking cyclane as a raw material, and obtaining benzene through dehydrogenation reaction under the action of a catalyst; the catalyst is a composite oxide consisting of an active component NiO and an auxiliary agent X, and is expressed as NiX-MO; wherein MO represents an oxide, and the auxiliary agent X is one or more than one oxide of Al, Mg and Fe; the molar ratio of Ni to X is 1-6; the catalyst NiX-MO is obtained by roasting hydrotalcite NiX-LDH at 200-700 ℃ for 1-6 h.
2. The method of claim 1, wherein the firing atmosphere is air.
3. The process according to claim 1, characterized in that the hydrotalcite NiX-LDH is prepared by a urea hydrothermal method comprising the following steps:
1) dissolving Ni soluble metal salt and X soluble metal salt in water according to the required molar ratio to obtain metal salt solution;
2) dissolving urea in the metal salt solution, and uniformly stirring to obtain a mixed solution;
3) crystallizing the mixed solution at 70-180 ℃ for 6-72h, filtering, washing and drying to obtain hydrotalcite NiX-LDH.
4. The process according to claim 1, characterized in that the hydrotalcite NiX-LDH is prepared using a co-precipitation method comprising the steps of:
1) dissolving Ni soluble metal salt and X soluble metal salt in water according to the required molar ratio to obtain metal salt solution;
2) mixing NaOH and Na2CO3Dissolving the solution in water to obtain an alkali solution;
3) and (2) simultaneously dripping the metal salt solution and the alkali solution into a container, controlling the titration speed to keep the pH value of the solution at 7-10.5, stirring for 1-5h after the dripping is finished, then crystallizing for 6-72h at the temperature of 70-180 ℃, filtering, washing and drying to obtain a hydrotalcite precursor NiX-LDH.
5. The method according to claim 3 or 4, wherein in step 1), the soluble metal salt of Ni is nickel nitrate or nickel acetate, and the soluble metal salt of X is nitrate or acetate of X.
6. The method of claim 3, wherein: the molar ratio of the urea to the nickel is 1-100.
7. The method of claim 1, wherein: the cycloalkane is cyclohexane.
8. The method of claim 7, wherein: the reaction is a continuous fixed bed reaction, the molar ratio of cyclohexane to hydrogen is 1-50, the total pressure of gas introduced into the fixed bed reactor is micro-positive pressure, and the total airspeed of the gas is 6000-36000h-1。
9. The method of claim 1, wherein: the reaction temperature is 300-600 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848709A (en) * | 2012-11-30 | 2014-06-11 | 埃克森美孚化学专利公司 | Dehydrogenation process |
| CN104785256A (en) * | 2015-03-30 | 2015-07-22 | 湘潭大学 | Preparation method and application of catalyst for preparing cyclohexene through cyclohexane dehydrogenation |
| CN106622228A (en) * | 2017-01-05 | 2017-05-10 | 湘潭大学 | Cycloalkane dehydrogenation catalyst, preparation method thereof and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848709A (en) * | 2012-11-30 | 2014-06-11 | 埃克森美孚化学专利公司 | Dehydrogenation process |
| CN104785256A (en) * | 2015-03-30 | 2015-07-22 | 湘潭大学 | Preparation method and application of catalyst for preparing cyclohexene through cyclohexane dehydrogenation |
| CN106622228A (en) * | 2017-01-05 | 2017-05-10 | 湘潭大学 | Cycloalkane dehydrogenation catalyst, preparation method thereof and application |
Non-Patent Citations (4)
| Title |
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| ANAAM H. AL-SHAIKHALI ET AL.: "Non-precious bimetallic catalysts for selective dehydrogenation of an organic chemical hydride system", 《CHEMICAL COMMUNICATIONS》 * |
| SANTIAGO ARIAS ET AL.: "Preparation of NiAlZr-terephthalate LDHs with high Al and Zr content and their mixed oxides for cyclohexane dehydrogenation", 《APPLIED CLAY SCIENCE》 * |
| ZHIJUN XIA ET AL.: "Cyclohexane dehydrogenation over Ni-Cu/SiO2 catalyst: Effect of copper addition", 《CATALYSIS COMMUNICATIONS》 * |
| 陈佑宁: "《物理化学实验》", 31 January 2020 * |
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