CN110961100B - 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
- Publication number
- CN110961100B CN110961100B CN201811157913.9A CN201811157913A CN110961100B CN 110961100 B CN110961100 B CN 110961100B CN 201811157913 A CN201811157913 A CN 201811157913A CN 110961100 B CN110961100 B CN 110961100B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cyclohexane
- cyclohexene
- dehydrogenation
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 230000002860 competitive effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 21
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 239000011701 zinc Substances 0.000 description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
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 a process for preparing cyclohexene by partial hydrogenation of benzene, so that the cyclohexane by-product in the process is dehydrogenated to be changed into cyclohexene, and the economic value of the by-product cyclohexane 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. preparing cyclohexane by benzene hydrogenation, preparing mixed K oil of cyclohexanone and cyclohexanol by cyclohexane oxidation, and preparing the cyclohexanone by dehydrogenating the residual cyclohexanol after separating the cyclohexanone from the K oil; 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 the energy consumption are huge. Therefore, the direct preparation of cyclohexene by partial dehydrogenation of the cyclohexane by-product 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, a carrier is alumina or titanium oxide, the reaction temperature is 400-600 ℃ and air is 0.05-1 s under 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 ZrO 2 -ZnO composition of ZrO in a support 2 The mass content is 80-95%, and the mass content of ZnO is 5-20%.
The passivating agent is MgO, caO, snO, znO or ZrO 2 One 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 filtering, the drying, the crushing, the forming and the roasting are carried out after the temperature programming is increased to 950 ℃, and the composite carrier is prepared.
The molding mode adopts a mechanical mode, so that the composite carrier has a thickness of 70m 2 /g-160m 2 The 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 90m 2 /g-140m 2 Specific 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 a reduction solution, drying, impregnating a passivant precursor in equal volume at 50-60 ℃, drying, and reducing by 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 zirconium nitrate solution of =91g/L, and [ Zn ] is taken 2+ ]0.174L of zinc nitrate solution (65 g/L) was mixed to prepare an acid solution. Taking 1mol/L of Na 2 CO 3 Taking 1.5L of deionized water as a base solution, heating the base solution to 80 ℃, carrying out parallel flow precipitation at a stirring speed of 300rpm, and controlling the pH value to be 9.5-10 after 40 minutes of precipitation. 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 [ Ru 3+ ]=33.3g/L and acetic acid =0.5ml, and the mixture was heated to 60 ℃, uniformly impregnated on 50g of the support 1, and dried. After drying, the mixture is added with NaBH in an excess of 0.2mol/L 4 The solution is reduced, washed, dried and then impregnated with [ Zn ] 2+ ]15ml of the solution (33.3 g/L), dried, and reduced at 400 ℃ under a hydrogen atmosphere by programming 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 ] =33.3g/L 2+ ]Catalyst 4 was prepared in 15ml of 3.33g/L solution.
Example 8
Preparing a catalyst: in example 5 [ Zn ] 2+ ]15ml of the solution was changed to [ Zn ] =33.3g/L 2+ ]=16.6g/L catalyst 5 was prepared from 15ml of solution.
TABLE 1 evaluation results of Activity of catalysts 1 to 5
| Catalyst and process for producing the same | Cyclohexane conversion rate% | 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 |
The 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 20ml/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 20ml/min.
Claims (8)
1. The application of the catalyst in preparing cyclohexene by cyclohexane dehydrogenation is characterized in that the catalyst comprises the following components in mass percent: 1-2% of ruthenium, 0.1-1% of passivating agent and the balance of composite carrier; the composite carrier is made of ZrO 2 -ZnO composition, zrO in a support 2 The mass content is 80-95%, and the mass content of ZnO is 5-20%; the passivating agent is ZnO.
2. Use of a catalyst according to claim 1 in the dehydrogenation of cyclohexane to cyclohexene, wherein the catalyst is prepared by a process comprising: preparing a composite carrier, impregnating the active component, and impregnating the active component and the passivating agent step by step to obtain the finished catalyst.
3. The use of the catalyst according to claim 2 in the preparation of cyclohexene from cyclohexane dehydrogenation, wherein the preparation of the composite carrier is carried out by coprecipitation, wherein a Zr-Zn precursor salt solution and a precipitant are precipitated under stirring to a pH value of 9.5-10, aging is carried out for 1h under the same conditions, and the composite carrier is prepared by filtering, drying, crushing, molding, programming to a temperature of 950 ℃ and roasting.
4. Use of a catalyst according to claim 3 in the dehydrogenation of cyclohexane to cyclohexene, wherein the shaping is performed mechanically, such that the composite support has a thickness of 70m 2 /g-160m 2 The specific surface area per gram and the strength are more than 100N/cm, and pore-forming agent is added for pore-forming and molding.
5. The use of a catalyst according to claim 4 in the dehydrogenation of cyclohexane to cyclohexene, wherein the shaping is by mechanical means such that the composite support has a size of 90m 2 /g -140 m 2 Specific surface area in g.
6. The use of the catalyst of claim 4 for the dehydrogenation of cyclohexane to cyclohexene wherein the pore former is at least one of an inorganic acid, an organic acid, sesbania powder, a cellulosic material, and a stearate.
7. The application of the catalyst in the preparation of cyclohexene through cyclohexane dehydrogenation according to claim 2, 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.
8. Use of a catalyst according to claim 7 in the dehydrogenation of cyclohexane to cyclohexene wherein the competing adsorbent is one of a volatile inorganic or organic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157913.9A CN110961100B (en) | 2018-09-30 | 2018-09-30 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157913.9A CN110961100B (en) | 2018-09-30 | 2018-09-30 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110961100A CN110961100A (en) | 2020-04-07 |
| CN110961100B true CN110961100B (en) | 2022-12-20 |
Family
ID=70028770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811157913.9A Active CN110961100B (en) | 2018-09-30 | 2018-09-30 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110961100B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535941A (en) * | 2003-04-09 | 2004-10-13 | 中国石油化工股份有限公司 | Selected hydrogenation catalyst support, its preparation method and catalyst containing the support |
| CN1617766A (en) * | 2002-01-29 | 2005-05-18 | 埃克森美孚研究工程公司 | Treatment of supported catalysts |
| CN102600888A (en) * | 2012-01-31 | 2012-07-25 | 湘潭大学 | Benzene hydrogenation catalyst as well as preparation method and application thereof |
| CN102921410A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method of cyclohexane noble metal Ru catalyst by benzene hydrogenation |
| CN104148062A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method of catalyst |
| CN104785256A (en) * | 2015-03-30 | 2015-07-22 | 湘潭大学 | Preparation method and application of catalyst for preparing cyclohexene through cyclohexane dehydrogenation |
| CN105363473A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Low-carbon olefin platinum catalyst made through dehydrogenation of low-carbon alkane |
| CN105727944A (en) * | 2016-03-25 | 2016-07-06 | 福州大学 | A kind of preparation method of ZrO2 nano sheet supported ruthenium catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6753351B2 (en) * | 2002-01-29 | 2004-06-22 | Exxonmobil Research And Engineering Company | Supported catalyst activation |
-
2018
- 2018-09-30 CN CN201811157913.9A patent/CN110961100B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617766A (en) * | 2002-01-29 | 2005-05-18 | 埃克森美孚研究工程公司 | Treatment of supported catalysts |
| CN1535941A (en) * | 2003-04-09 | 2004-10-13 | 中国石油化工股份有限公司 | Selected hydrogenation catalyst support, its preparation method and catalyst containing the support |
| CN102600888A (en) * | 2012-01-31 | 2012-07-25 | 湘潭大学 | Benzene hydrogenation catalyst as well as preparation method and application thereof |
| CN102921410A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method of cyclohexane noble metal Ru catalyst by benzene hydrogenation |
| CN104148062A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method of catalyst |
| CN105363473A (en) * | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Low-carbon olefin platinum catalyst made through dehydrogenation of low-carbon alkane |
| CN104785256A (en) * | 2015-03-30 | 2015-07-22 | 湘潭大学 | Preparation method and application of catalyst for preparing cyclohexene through cyclohexane dehydrogenation |
| CN105727944A (en) * | 2016-03-25 | 2016-07-06 | 福州大学 | A kind of preparation method of ZrO2 nano sheet supported ruthenium catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Yan Xuhua et al.Selective hydrogenation of benzene to cyclohexene over Ru-Zn/ZrO2 catalysts prepared by a two-step impregnation method.《JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL》.2015,第413卷第85-93页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110961100A (en) | 2020-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101306368B (en) | Preparation method of butynediol two-step hydrogenation to butanediol two-stage hydrogenation catalyst | |
| CN104148065A (en) | Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof | |
| EP3590595A1 (en) | Ni-coated al203@si02 catalyst, preparation method thereof and application thereof | |
| CN106824204B (en) | A kind of attapulgite loaded Raney nickel and preparation method and application | |
| CN106582668B (en) | Alloy-loaded hydrogenation saturation catalyst and preparation method thereof | |
| CN103769090A (en) | Ruthenium-palladium/carbon catalyst and preparation method thereof | |
| CN107899583A (en) | It is a kind of to prepare catalyst of ethanol and preparation method thereof for methyl methanol syngas | |
| CN110961100B (en) | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof | |
| CN114433100B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| CN111298791B (en) | Preparation method of composite carrier catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation | |
| CN107930635B (en) | Catalyst for co-production of methyl isobutyl ketone and diisobutyl ketone | |
| CN109647394B (en) | Catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof | |
| CN115121270A (en) | A kind of catalyst for selective hydrogenation synthesis of 2-ethylhexanal and application method thereof | |
| CN107185548B (en) | Method for preparing cyclohexylbenzene by selective hydrogenation of biphenyl | |
| CN108114729A (en) | A kind of anthraquinone hydrogenation catalyst and its preparation method and application | |
| CN108067225B (en) | Preparation method of catalytic wet oxidation catalyst and organic wastewater treatment method | |
| CN108069827B (en) | Method for preparing 1, 4-butynediol and co-producing propiolic alcohol | |
| CN117899870A (en) | Synthesis of MN/MgO supported catalyst and method for catalyzing furfural to prepare furfuryl alcohol | |
| CN111111655B (en) | Preparation method of heterogeneous catalyst for selective hydrogenation of 1, 4-butynediol | |
| CN116020437A (en) | Hydrogenation catalyst system and preparation method and application thereof | |
| CN116020532A (en) | Catalyst, preparation method and application thereof, and preparation method of cyclohexanone | |
| CN107824191A (en) | A kind of zirconia-supported catalyst based on the copper-based microballoon of ternary and preparation method thereof | |
| CN111744540A (en) | Solid acid catalyst and application thereof in esterification reaction | |
| CN114471608B (en) | Method for refining and purifying diethylene glycol through hydrofining | |
| CN112717941A (en) | Ester hydrogenation catalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |