CN102974342A - Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof Download PDFInfo
- Publication number
- CN102974342A CN102974342A CN2012105133867A CN201210513386A CN102974342A CN 102974342 A CN102974342 A CN 102974342A CN 2012105133867 A CN2012105133867 A CN 2012105133867A CN 201210513386 A CN201210513386 A CN 201210513386A CN 102974342 A CN102974342 A CN 102974342A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cyclohexene
- benzene
- selective hydrogenation
- preparation
- 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.)
- Granted
Links
Classifications
-
- 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for preparing cyclohexene from benzene by selective hydrogenation and a preparation method thereof. The invention mainly solves the problems of low benzene conversion rate, poor cyclohexene selectivity and quick catalyst deactivation in the technique for synthesizing cyclohexene from benzene by selective hydrogenation. By using one substance or a mixture of two substances as a dispersion supporter, noble metal as an active component and transition metal oxide as a assistant, the transition metal oxide treated by the special preparation technique well solves the problems. The operating conditions of the catalyst in the cyclohexene synthesis reaction from benzene by selective hydrogenation are as follows: the temperature is 100-300 DEG C; the hydrogen pressure is 2.0-6.0 MPa; the benzene/distilled water medium ratio is 0.1-3.0 (wt/wt); and the sulfate additive/catalyst ratio is 5.0-15.0. The selective hydrogenation catalytic reaction from benzene has favorable cyclohexene yield.
Description
Technical field
The present invention relates to the Catalysts and its preparation method that a kind of benzene selective hydrogenation generates cyclohexene, can be applied in the standby industrial production of cyclohexene of benzene selective Hydrogenation, high selectivity with high activity and cyclohexene, can effectively avoid deep hydrogenation and other side reaction of benzene, and reaction stability is good.
Background technology
Cyclohexene is a kind of important organic synthesis intermediate, have active two keys, as Organic Chemicals, can be widely used in the production of medicine, agricultural chemicals, agricultural chemicals, feed addictive, polyester and other fine chemicals, especially the deep processing product cyclohexanone of cyclohexene and adipic acid are a large amount of intermediates that use in the synthetic polyamide fiber.Since the eighties in 20th century, the external proposition produced cyclohexene by the benzene selective hydrogenation, and successfully realized industrialization.After the nineties, the importance of benzene selective hydrogenation to prepare cyclohexene catalyst just causes the attention of the large R﹠D institution of China, key university and petro-chemical corporation, but progress is slow.The novel catalyst that exploitation has independent intellectual property right shortens the distance of China and developed country, and tool is of great significance.
The RuCl of E.I.Du Pont Company in 1972
3For catalyst has carried out benzene hydrogenation in autoclave, in reaction system, add entry simultaneously, the cyclohexene yield is 32%(DE2221139).US5589600 discloses a kind of Ru-Ni bimetallic catalyst that uses the coprecipitation preparation.The highest yield 40%.Japan's Asahi Kasei Corporation uses the Ru-Zn catalyst (US4734536) of precipitation method preparation, and the highest yield of cyclohexene can reach 50%, and has successfully realized industrialization, and its industrial index is: cyclohexene yield 30%, selective 80%.But because the unsupported catalyst preparation method is more loaded down with trivial details, the utilization rate of noble metal Ru is low, causes the expensive of catalyst, and relatively more responsive to sulfide, has had a strong impact on the life-span of catalyst.As unsupported nano-scale particle catalyst, there are the problem of product and catalyst separation and serious catalyst loss problem simultaneously, so become new focus for the loaded catalyst research of this problem.
Domestic aspect CN13373786A discloses a kind of benzene selective hydrogenation to prepare cyclohexene catalyst and manufacture method thereof, and this catalyst is comprised of active component, auxiliary agent, additive and four kinds of components of dispersant.Described active component is a kind of among Ru, Th, the Pa, and auxiliary agent is a kind of among W, Fe, Co, Ni, Zn, Mo or the Cd, and additive is a kind of among Na, B, K, the Li, and dispersant is zirconia.The preparation method of described catalyst be with active component and auxiliary agent precursor adsorption on dispersant, with the chemical reducing agent reduction, its reducing agent that uses is NaBH again
4, then gained solids wash, drying are made catalyst.
CN1446625A discloses a kind of benzene selective amorphous hydrogenating ruthenium boron catalyzer, this catalyst is the catalyst of supported amorphous Ru-B or RuB-M alloy, described M is one or more among Fe, Co, Ni, Zn or the Cr, and carrier is zirconia, silica or aluminium oxide.This catalyst can improve the activity of benzene selective hydrogenation.The mode of above several Kaolinite Preparation of Catalysts has used different prescriptions to form, and has obtained higher cyclohexene yield.But because the course of reaction of benzene cyclohexene mainly is mass transport limitation, mass-transfer efficiency directly determines ultimate yield.Therefore the physico-chemical property of carrier has important effect to the dispersion effect of active component and the mass transfer effect of raw material and product.
Summary of the invention
The purpose of this invention is to provide a kind of novel preparing cyclohexene from benzene added with hydrogen Catalysts and its preparation method with high activity, high selectivity and good stability.This catalyst compares in the past that catalyst has larger specific area, average pore size and porosity, therefore can guarantee that the benzene selective hydrogenation has higher mass-transfer efficiency, can under equal activity component load quantity, reach better reaction effect.
A kind of benzene selective hydrogenation that the present invention proposes generates the catalyst of cyclohexene, is comprised of active component, auxiliary agent and dispersible carrier, and active component accounts for 1 ~ 10wt%, and auxiliary agent accounts for 0.01 ~ 2wt%, and all the other are dispersible carrier, and its gross weight satisfies 100%; Wherein: dispersible carrier is ZrO
2, SiO
2Or TiO
2In more than one, active component be among Ru, Pt or the Pa any, auxiliary agent be among Fe, Co, Ni, Cu, Mn or the Zn any.
A kind of benzene selective hydrogenation that the present invention proposes generates the preparation method of the catalyst of cyclohexene, and concrete steps are as follows:
(1) under the normal temperature, the presoma salt of dispersible carrier and ammoniacal liquor produce precipitation according to the mixed in molar ratio afterreaction of 1:1 ~ 20, are precipitated oxide carrier, with sedimentation and filtration, obtain gel behind the ageing 12h; With the gel adding hydrogen peroxide that is dissolved in the water, regulator solution pH value is 9.0 ~ 12.0, and is behind the aging backflow 50h that sedimentation and filtration is dry and in 300 ~ 600 ℃ of lower roasting 2 ~ 5h under 70 ~ 99 ℃ of temperature, obtains dispersible carrier; Oxide carrier and hydrogen peroxide mol ratio are 1:0.1 ~ 5;
(2) active component presoma salt and auxiliary agent presoma salt are mixed with solution in proportion, impregnated on the dispersible carrier that step (1) obtains, adding ammoniacal liquor regulator solution pH value is 10 ~ 12, dry behind the ageing 1h, 400 ℃ of lower roastings, 180 ~ 300 ℃ of reduction 3h namely obtain required catalyst in hydrogen stream.
Among the present invention, the presoma salt of described dispersible carrier is ethyl orthosilicate, ZrO
2Or TiO
2Hydrochloride.
Among the present invention, active component presoma salt is Ru, Pt or Pd nitrate.
Among the present invention, auxiliary agent presoma salt is Fe, Co, Ni, Cu, Mn or Zn nitrate.
Catalyst of the present invention service condition in the reaction of benzene selective synthesizing cyclohexene by hydrogenation is: 100 ~ 300 ℃ of temperature; Hydrogen pressure 2.0MPa ~ 6.0MPa; Benzene/distilled water medium=0.1 ~ 3.0(wt/wt); Sulphate additives/catalyst=5.0 ~ 15.0; The reaction of benzene selective hydrogenation catalyst has good cyclohexene yield.
Compare with the catalyst of now having reported, advantage of the present invention is:
1, the catalyst of the present invention's preparation, the active selective integrated performance index that waits has reached the commercial Application standard.
2, compare with in the past with ZrO
2Be the catalyst of dispersible carrier, the catalyst of the present invention's preparation has the pore passage structure that more is fit to the benzene selective hydrogenation reaction.
3, precipitating reagent uses cheap ammoniacal liquor, need not expensive NaOH, and the catalyst preparation cost is low.
4, the method need not used expensive NaBH
4As reducing agent, further reduced the integrated cost of catalyst.
The specific embodiment
Further specify the present invention below by embodiment.
Embodiment 1
With commercially available ZrO
2For subsequent use behind 300 ℃ of lower roasting 2h.With a certain amount of RuCl
3XH
2O be dissolved in distilled water (with metal quality account for the dispersible carrier quality 8%), after the equal-volume vacuum impregnation, place 85 ℃ of dry 24h of moving air, and in the 5ml/min hydrogen stream 250 ℃ the reduction 3h.Obtain catalyst A.
Embodiment 2
ZrOCl
28H
2O and NH
3H
2O makes precipitation according to the mol ratio of 1:3, make gel after, press Zr(OH)
4With the hydrogen peroxide ratio be that 1:0.2 adds, afterwards under 96 ℃, pH=11.5 behind the aging backflow 50h, filtration drying, and obtain at 520 ℃ of lower roasting 1h.With a certain amount of RuCl
3XH
2O be dissolved in distilled water (with metal quality account for the dispersible carrier quality 8%), after the equal-volume vacuum impregnation, place 85 ℃ of dry 24h of moving air, and in the 5ml/min hydrogen stream 250 ℃ the reduction 3h.Obtain catalyst B.
Embodiment 3
ZrOCl
28H
2O and NH
3H
2O makes precipitation according to 1:3, make gel after, press Zr (OH)
4With the hydrogen peroxide ratio be that 1:0.2 adds, afterwards under 96 ℃, pH=11.5 behind the aging backflow 50h, filtration drying, and obtain at 520 ℃ of lower roasting 1h.With a certain amount of RuCl
3XH
2O be dissolved in distilled water (with metal quality account for the dispersible carrier quality 8%), simultaneously add FeCl according to mol ratio Ru:Fe=1:0.2
3After, after the equal-volume vacuum impregnation, place 85 ℃ of dry 24h of moving air, and in the 5ml/min hydrogen stream 250 ℃ the reduction 3h.Obtain catalyst C.
Embodiment 4
ZrOCl
28H
2O and NH
3H
2O makes precipitation according to 1:3, make gel after, press Zr (OH)
4With the hydrogen peroxide ratio be that 1:0.2 adds, afterwards under 96 ℃, pH=11.5 behind the aging backflow 50h, filtration drying, and obtain at 520 ℃ of lower roasting 1h.With a certain amount of RuCl
3XH
2O be dissolved in distilled water (with metal quality account for the dispersible carrier quality 8%), simultaneously add Ni (NO according to mol ratio Ru:Ni=1:0.2
3)
2After, after the equal-volume vacuum impregnation, place 85 ℃ of dry 24h of moving air, and in the 5ml/min hydrogen stream 250 ℃ the reduction 3h.Obtain catalyst D.
Embodiment 5
ZrOCl
28H
2O and NH
3H
2O makes precipitation according to 1:3, make gel after, press Zr (OH)
4With the hydrogen peroxide ratio be that 1:0.2 adds, afterwards under 96 ℃, pH=11.5 behind the aging backflow 50h, filtration drying, and obtain at 520 ℃ of lower roasting 1h.With a certain amount of (NH
4)
6H
2W
12O
40.xH
2O be dissolved in distilled water (with the Ru mol ratio be 1:10), after the equal-volume vacuum impregnation, after 85 ℃ of dryings, and at 650 ℃ of lower roasting 2h.Again with a certain amount of RuCl
3XH
2O be dissolved in distilled water (with metal quality account for the dispersible carrier quality 8%), after the equal-volume vacuum impregnation, place 85 ℃ of dry 24h of moving air, and in the 20ml/min hydrogen stream 250 ℃ the reduction 3h.Obtain catalyst E.
Active selective determination:
The catalyst of choosing above embodiment carries out active selective determination, is determined in the miniature high pressure reaction still and carries out, the polytetrafluoro liner.Add 100ml water, 50ml benzene, 0.4g catalyst, 4.0gZnSO
47H
2O.With air in the hydrogen exchange still, stir speed (S.S.) 600rpm.80 ℃/h of heating rate.Regulate hydrogen pressure to 4.2Mpa, speed of agitator 1000rpm, and beginning timing.Relative percentage composition with benzene, cyclohexene and cyclohexane in the gas chromatographic analysis oil phase.Active selective calculation method:
Active: benzene conversion ratio (C
BZThe relative concentration * 100% of benzene in the)=product
Cyclohexene yield (Y
HECyclohexene relative concentration * 100% in the)=product
Selectively: the selective (S of cyclohexene
HE)=cyclohexene yield/benzene conversion ratio * 100%=Y
HE/ C
BZ* 100%
After table 1 had provided reaction 10,20,30min, the activity of different catalyst was selective:
When table 1 reaction 10,20,30min, the activity of different catalysts is selective
Claims (5)
1. the catalyst of a benzene selective hydrogenation generation cyclohexene is characterized in that being comprised of active component, auxiliary agent and dispersible carrier, and active component accounts for 1 ~ 10wt%, and auxiliary agent accounts for 0.01 ~ 2wt%, and all the other are dispersible carrier, and its gross weight satisfies 100%; Wherein: dispersible carrier is ZrO
2, SiO
2Or TiO
2In more than one, active component be among Ru, Pt or the Pd any, auxiliary agent be among Fe, Co, Ni, Cu, Mn or the Zn any.
2. a benzene selective hydrogenation as claimed in claim 1 generates the preparation method of the catalyst of cyclohexene, it is characterized in that concrete steps are as follows:
(1) under the normal temperature, the presoma salt of dispersible carrier and ammoniacal liquor produce precipitation according to the mixed in molar ratio afterreaction of 1:1 ~ 20, are precipitated oxide carrier, with sedimentation and filtration, obtain gel behind the ageing 12h; With the gel adding hydrogen peroxide that is dissolved in the water, regulator solution pH value is 9.0 ~ 12.0, and is behind the aging backflow 50h that sedimentation and filtration is dry and in 300 ~ 600 ℃ of lower roasting 2 ~ 5h under 70 ~ 99 ℃ of temperature, obtains dispersible carrier; Oxide carrier and hydrogen peroxide mol ratio are 1:0.1 ~ 5;
(2) active component presoma salt and auxiliary agent presoma salt are mixed with solution in proportion, impregnated on the dispersible carrier that step (1) obtains, adding ammoniacal liquor regulator solution pH value is 10 ~ 12, dry behind the ageing 1h, 400 ℃ of lower roastings, 180 ~ 300 ℃ of reduction 3h namely obtain required catalyst in hydrogen stream.
3. a kind of benzene selective hydrogenation according to claim 2 generates the preparation method of the catalyst of cyclohexene, and the presoma salt that it is characterized in that described dispersible carrier is ethyl orthosilicate, ZrO
2Or TiO
2Hydrochloride.
4. a kind of benzene selective hydrogenation according to claim 2 generates the preparation method of the catalyst of cyclohexene, it is characterized in that active component presoma salt is Ru, Pt or Pd nitrate.
5. a kind of benzene selective hydrogenation according to claim 2 generates the preparation method of the catalyst of cyclohexene, it is characterized in that auxiliary agent presoma salt is Fe, Co, Ni, Cu, Mn or Zn nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210513386.7A CN102974342B (en) | 2012-12-05 | 2012-12-05 | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210513386.7A CN102974342B (en) | 2012-12-05 | 2012-12-05 | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102974342A true CN102974342A (en) | 2013-03-20 |
| CN102974342B CN102974342B (en) | 2014-12-10 |
Family
ID=47848859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210513386.7A Expired - Fee Related CN102974342B (en) | 2012-12-05 | 2012-12-05 | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102974342B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785379A (en) * | 2014-03-04 | 2014-05-14 | 河北石焦化工有限公司 | Preparation method and production device of catalyst for cyclohexene preparation through benzene selective hydrogenation |
| CN105727944A (en) * | 2016-03-25 | 2016-07-06 | 福州大学 | Preparation method of ZrO2 nanosheet supported ruthenium catalyst |
| CN114904519A (en) * | 2022-05-25 | 2022-08-16 | 上海昊澜机电设备有限公司 | Preparation method of novel hydrogenation catalyst |
| CN115945202A (en) * | 2022-12-30 | 2023-04-11 | 河南省生物基材料产业研究院有限公司 | Catalyst for co-production of tetrahydrofuran and 2-methylfuran by gas-phase continuous decarbonylation of furfural and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5589600A (en) * | 1992-02-05 | 1996-12-31 | Basf Aktiengesellschaft | Preparation of cyclohexene by partial hydrogenation of benzene |
| CN1424293A (en) * | 2002-12-12 | 2003-06-18 | 复旦大学 | Benzene selective hydrogenation carried ruthenium based catalyst and its preparation |
| CN101733083A (en) * | 2008-11-14 | 2010-06-16 | 中国石油化工股份有限公司 | Method for preparing titanium-containing catalyst carrier |
| CN102600888A (en) * | 2012-01-31 | 2012-07-25 | 湘潭大学 | Benzene hydrogenation catalyst as well as preparation method and application thereof |
-
2012
- 2012-12-05 CN CN201210513386.7A patent/CN102974342B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5589600A (en) * | 1992-02-05 | 1996-12-31 | Basf Aktiengesellschaft | Preparation of cyclohexene by partial hydrogenation of benzene |
| CN1424293A (en) * | 2002-12-12 | 2003-06-18 | 复旦大学 | Benzene selective hydrogenation carried ruthenium based catalyst and its preparation |
| CN101733083A (en) * | 2008-11-14 | 2010-06-16 | 中国石油化工股份有限公司 | Method for preparing titanium-containing catalyst carrier |
| CN102600888A (en) * | 2012-01-31 | 2012-07-25 | 湘潭大学 | Benzene hydrogenation catalyst as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 路芳等: "负载型钌基催化剂催化苯选择加氢合成环己烯", 《化学进展》, vol. 15, no. 4, 31 July 2003 (2003-07-31), pages 338 - 343 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785379A (en) * | 2014-03-04 | 2014-05-14 | 河北石焦化工有限公司 | Preparation method and production device of catalyst for cyclohexene preparation through benzene selective hydrogenation |
| CN103785379B (en) * | 2014-03-04 | 2015-06-24 | 河北石焦化工有限公司 | Preparation method and production device of catalyst for cyclohexene preparation through benzene selective hydrogenation |
| CN105727944A (en) * | 2016-03-25 | 2016-07-06 | 福州大学 | Preparation method of ZrO2 nanosheet supported ruthenium catalyst |
| CN105727944B (en) * | 2016-03-25 | 2018-06-15 | 福州大学 | A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst |
| CN114904519A (en) * | 2022-05-25 | 2022-08-16 | 上海昊澜机电设备有限公司 | Preparation method of novel hydrogenation catalyst |
| CN115945202A (en) * | 2022-12-30 | 2023-04-11 | 河南省生物基材料产业研究院有限公司 | Catalyst for co-production of tetrahydrofuran and 2-methylfuran by gas-phase continuous decarbonylation of furfural and preparation method thereof |
| CN115945202B (en) * | 2022-12-30 | 2024-08-16 | 河南省生物基材料产业研究院有限公司 | Catalyst for preparing tetrahydrofuran and co-producing 2-methylfuran by continuous decarbonylation of furfural gas phase and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102974342B (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN102600888A (en) | Benzene hydrogenation catalyst as well as preparation method and application thereof | |
| CN109999896B (en) | High-efficiency catalyst applied to preparation of cyclohexanone by selective hydrogenation of phenol and preparation method thereof | |
| CN102974342B (en) | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof | |
| CN112755996A (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation, preparation method and application | |
| CN102744085B (en) | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation | |
| CN110947382A (en) | Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
| CN107118076A (en) | A kind of method that dimethyl adipate gas phase hydrogenation prepares 1,6 hexylene glycols | |
| CN102372604B (en) | Method for preparing 1, 6-hexanediol by hydrogenating 1, 6-dimethyl adipate | |
| CN113976131B (en) | Heterogeneous catalyst and method for preparing 2, 5-furandimethylamine from 5-hydroxymethylfurfural | |
| CN104028267B (en) | A kind of method for making of benzene selective Hydrogenation cyclohexene noble metal Ru catalyst | |
| CN101961661B (en) | Organic metal catalyst for preparing cyclohexene by benzene hydrogenation and preparation method and application thereof | |
| CN104230641B (en) | Produce the method for isopropyl benzene | |
| CN104230635B (en) | The method of hydrogenation of acetophenone ethylbenzene processed | |
| CN102319562A (en) | The Preparation of catalysts method of producing cyclohexene with benzene selective hydrogenation and the catalyst for preparing through this method | |
| CN103769092B (en) | Hydrogenation catalyst of a kind of hydrogen dioxide solution production by anthraquinone process and preparation method thereof | |
| CN103769186B (en) | Anthraquinone hydrogenation catalyst and preparation method thereof | |
| CN103331160B (en) | Preparation method of high-dispersion copper-based catalyst based on non-precious metal | |
| CN1176886C (en) | Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn | |
| CN103191732B (en) | A kind of method of partial hydrogenation of benzene cyclohexene catalyst and production cyclohexene | |
| CN103769091B (en) | A kind of anthraquinone hydrogenation catalyst preparing hydrogen peroxide and preparation method thereof | |
| CN105582926B (en) | Terephthalic acid (TPA) hydrogenation catalyst | |
| CN103769093B (en) | A kind of anthraquinone hydrogenation catalyst and preparation method thereof | |
| CN102211035A (en) | Method for preparing V-ZSM-5 molecular sieve and catalytic property of molecular sieve on preparation of cyclohexanol and cyclohexanone by oxidizing cyclohexane | |
| CN100496728C (en) | Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20171205 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |