CN110961100A - Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof - Google Patents
Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof Download PDFInfo
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- CN110961100A CN110961100A CN201811157913.9A CN201811157913A CN110961100A CN 110961100 A CN110961100 A CN 110961100A CN 201811157913 A CN201811157913 A CN 201811157913A CN 110961100 A CN110961100 A CN 110961100A
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- catalyst
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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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
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing cyclohexene through cyclohexane dehydrogenation and a preparation method thereof. The method is characterized by comprising two key steps of preparing a composite carrier, impregnating an active component and a passivating agent to obtain the dehydrogenation catalyst for preparing cyclohexene by partial dehydrogenation of cyclohexane. The catalyst can be used in the process of preparing cyclohexene by partial hydrogenation of benzene, so that the cyclohexane byproduct in the process is dehydrogenated into cyclohexene, and the economic value of the cyclohexane byproduct is improved.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for preparing cyclohexene through cyclohexane dehydrogenation, and a preparation method and application thereof
Background
There are two routes for producing cyclohexanone from benzene: 1. benzene is hydrogenated to prepare cyclohexane, the cyclohexane is oxidized to prepare mixed K oil of cyclohexanone and cyclohexanol, and after the K oil is separated out of the cyclohexanone, the remaining cyclohexanol is dehydrogenated to prepare the cyclohexanone; 2. partial hydrogenation of benzene is carried out to prepare a mixture of cyclohexene and cyclohexane, cyclohexane is separated out, the rest cyclohexene is hydrated to prepare cyclohexanol, and the cyclohexanol is dehydrogenated to prepare cyclohexanone. At present, due to various factors such as energy source, environmental protection and capacity, the production scale of the route 2 is gradually enlarged, and the byproduct cyclohexane obtained by partially hydrogenating the benzene in the route 2 is generally directly sold due to the limitation of yield and plant equipment. If the cyclohexane is dehydrogenated to produce benzene, the equipment investment and energy consumption are huge. Therefore, the method for directly preparing cyclohexene by partially dehydrogenating the cyclohexane byproduct in the route 2 has important practical significance and economic significance.
CN 103214336A discloses a method for preparing cyclohexene by oxidative dehydrogenation of cyclohexane, which takes K, Mg and Mo as active components, V as an auxiliary agent, and a carrier of alumina or titanium oxide, wherein the reaction temperature of the carrier and air is 400-600 ℃ at 0-5 KPa, the reaction time is 0.05-1 s, the cyclohexane conversion rate is close to 20%, and the cyclohexene selectivity can reach 46.98% at most. The method has high temperature, short reaction time and difficult control.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a catalyst for preparing cyclohexene from cyclohexane under mild reaction conditions, so that a byproduct cyclohexane in a benzene partial hydrogenation line is effectively utilized.
The purpose of the invention is realized by the following technical scheme: the catalyst for preparing cyclohexene by cyclohexane dehydrogenation comprises the following components in percentage by mass: 1 to 2 percent of ruthenium, 0.1 to 1 percent of passivating agent and the balance of composite carrier.
Typically, the composite support consists of ZrO2-ZnO composition, ZrO in a support2The mass content is 80-95%, and the mass content of ZnO is 5-20%.
The passivating agent is MgO, CaO, SnO, ZnO or ZrO2One kind of (1).
The preparation method of the cyclohexene catalyst by cyclohexane dehydrogenation comprises the steps of preparing a composite carrier, and dipping an active component and a passivating agent into the composite carrier step by step to obtain a finished product catalyst.
The preparation method of the composite carrier adopts a coprecipitation method, the Zr-Zn precursor salt solution and a precipitator are precipitated under the stirring condition until the pH value is 9.5-10, the aging is carried out for 1h under the same condition, the filtration, the drying, the crushing, the forming and the roasting at the programmed temperature of 950 ℃ are carried out, and the composite carrier is prepared.
The molding mode adopts a mechanical mode, so that the composite carrier has a thickness of 70m2/g-160m2The specific surface area per gram and the strength are more than 100N/cm, and pore-forming agent is added for pore-forming and molding.
The molding mode adopts a mechanical mode to ensure that the composite carrier has a length of 90m2/g-140m2Specific surface area per gram.
The pore-forming agent is at least one of inorganic acid, organic acid, sesbania powder, cellulose substances and stearate.
The impregnation method comprises the steps of impregnating a ruthenium precursor and a competitive adsorbent on a carrier in equal volume at 60 ℃, drying, reducing by using a reducing solution, drying, impregnating a passivator precursor in equal volume at 50-60 ℃, drying, and reducing by using hydrogen to obtain the catalyst.
The competitive adsorbent is one of volatile inorganic acid or organic acid.
The catalyst provided by the invention can inhibit the hydrogenation activity of ruthenium, improve the selectivity of cyclohexene, and reduce the reaction activation energy, so that the reaction can be carried out at 250-350 ℃. The traditional kettle type reaction is separated, and the catalyst can continuously react in a fixed bed reactor. The reaction time is easy to control, and the stability of the product quality is ensured.
Detailed Description
The present invention will be described in detail with reference to examples.
The preparation method of the cyclohexene catalyst by cyclohexane dehydrogenation comprises the following steps of preparing a composite carrier, and impregnating an active component and a passivating agent by the composite carrier step by step to obtain a finished product catalyst.
Example 1
Preparing a composite carrier: taking [ Zr ]4+]1L of 91g/L zirconium nitrate solution, [ Zn ] is taken2+]0.174L of 65g/L zinc nitrate solution was mixed to prepare an acid solution. Taking 1mol/L of Na2CO3Taking 1.5L of deionized water as base solution, heating the base solution to 80 deg.C, stirring at 300rpm for precipitation,the pH value is controlled between 9.5 and 10 after precipitation is finished for 40 minutes. Aging at 80 deg.C for 1 hr, filtering, washing, drying, crushing, grinding, granulating, oven drying, and tabletting. And (3) programming the temperature to 950 ℃, and roasting the tablets for 3 hours to obtain the carrier 1.
Example 2
Preparing a composite carrier: the amount of the zinc nitrate solution used in example 1 was changed to 0.247L, and the remainder was unchanged to obtain carrier 2.
Example 3
Preparing a composite carrier: the amount of the zinc nitrate solution used in example 1 was changed to 0.052L, and the remainder was unchanged to obtain carrier 3.
Example 4
Preparing a catalyst: taking 15ml of ruthenium solution in which [ Ru3+]The mixture was heated to 60 ℃ and uniformly impregnated on 50g of the carrier 1, followed by drying, and acetic acid (0.5 ml) was mixed thereto (33.3 g/L). After drying, the NaBH is used in excess of 0.2mol/L4The solution is reduced, washed, dried and then impregnated with [ Zn ]2+]15ml of the solution (33.3 g/L) was dried and reduced at 400 ℃ under a hydrogen atmosphere for 3 hours to obtain catalyst 1.
Example 5
Preparing a catalyst: catalyst 2 was prepared by changing the carrier 1 from example 4 to carrier 2.
Example 6
Preparing a catalyst: catalyst 3 was prepared by changing the carrier 1 to carrier 3 in example 4.
Example 7
Preparing a catalyst: in example 4, [ Zn ]2+]15ml of the solution was changed to [ Zn ] at 33.3g/L2+]Catalyst 4 was prepared as 3.33g/L solution 15 ml.
Example 8
Preparing a catalyst: in example 5 [ Zn ]2+]15ml of the solution was changed to [ Zn ] at 33.3g/L2+]15ml of the solution (16.6 g/L) gave catalyst 5.
TABLE 1 evaluation results of Activity of catalysts 1 to 5
Catalyst and process for preparing same | Cyclohexane conversion rate% | And (4) cyclohexene selectivity. Is based on |
1 | 19.4 | 81.8 |
2 | 19.6 | 80.9 |
3 | 20.2 | 81.8 |
4 | 25.5 | 65.0 |
5 | 22.3 | 71.7 |
Reaction conditions are as follows: the diameter of the reactor is 1.8cm, the reaction pressure is 0.2MPa, the temperature is 310 ℃, and the nitrogen flow is 20 ml/min.
TABLE 2 evaluation results of catalyst 1 Activity under different reaction conditions
Reaction conditions are as follows: the reactor diameter was 1.8cm and the nitrogen flow was 20 ml/min.
Claims (10)
1. A catalyst for preparing cyclohexene by cyclohexane dehydrogenation is characterized by comprising the following components in parts by mass: 1 to 2 percent of ruthenium, 0.1 to 1 percent of passivating agent and the balance of composite carrier.
2. The catalyst according to claim 1, wherein the composite support is made of ZrO2-ZnO composition, ZrO in a support2The mass content is 80-95%, and the mass content of ZnO is 5-20%.
3. The catalyst of claim 1, wherein the passivating agent is MgO, CaO, SnO, ZnO, ZrO2One kind of (1).
4. A method for preparing a catalyst used in the preparation of cyclohexene by cyclohexane dehydrogenation as claimed in claim 1, wherein the composite carrier is prepared by impregnating the active component, and the finished catalyst is obtained by impregnating the active component and the passivating agent step by step.
5. The preparation method of the catalyst according to claim 4, wherein the preparation of the composite carrier is carried out by coprecipitation, wherein the Zr-Zn precursor salt solution and the precipitant are precipitated under stirring to pH 9.5-10, and are aged for 1h under the same condition, and the composite carrier is prepared by filtering, drying, crushing, forming, and roasting at the programmed temperature of 950 ℃.
6. The method for preparing the catalyst according to claim 5, wherein the forming is performed mechanically so that the composite carrier has a thickness of 70m2/g-160m2The specific surface area per gram and the strength are more than 100N/cm, and pore-forming agent is added for pore-forming and molding.
7. The method for preparing the catalyst according to claim 6, wherein the forming is performed mechanically so that the composite carrier has a thickness of 90m2/g -140 m2Specific surface area per gram.
8. The method according to claim 6, wherein the pore-forming agent is at least one of an inorganic acid, an organic acid, sesbania powder, a cellulose-based substance, and a stearate.
9. The preparation method of the catalyst according to claim 4, wherein the impregnation method comprises the steps of impregnating a ruthenium precursor and a competitive adsorbent on a carrier at 60 ℃ in equal volume, drying, reducing with a reducing solution, drying, impregnating a passivating agent precursor at 50-60 ℃ in equal volume, drying, and reducing with hydrogen to obtain the catalyst.
10. The method of claim 9, wherein the competitive adsorbent is one of a volatile inorganic acid or an organic acid.
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Cited By (1)
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CN112892613A (en) * | 2021-01-29 | 2021-06-04 | 福建永荣科技有限公司 | Catalyst regeneration process of cyclohexane dehydrogenation benzene preparation device |
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Cited By (1)
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