CN102974342B - 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
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- CN102974342B CN102974342B CN201210513386.7A CN201210513386A CN102974342B CN 102974342 B CN102974342 B CN 102974342B CN 201210513386 A CN201210513386 A CN 201210513386A CN 102974342 B CN102974342 B CN 102974342B
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- cyclohexene
- benzene
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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 industrial production of benzene selective Hydrogenation for cyclohexene, the 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, there are 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 synthetic polyamide fiber.Since the eighties in 20th century, external proposition produced cyclohexene by 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.Exploitation has the novel catalyst of 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 water, cyclohexene yield is 32%(DE2221139 simultaneously).US5589600 discloses a kind of Ru-Ni bimetallic catalyst that uses coprecipitation to prepare.The highest yield 40%.The Ru-Zn catalyst (US4734536) that Japan Asahi Kasei Corporation is used the precipitation method to prepare, 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 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 more responsive to sulfide, had a strong impact on the life-span of catalyst.As unsupported nano-scale particle catalyst, there is the problem of product and catalyst separation and serious catalyst loss problem, so become new focus for the loaded catalyst research of this problem simultaneously.
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 in Ru, Th, Pa, and auxiliary agent is a kind of in W, Fe, Co, Ni, Zn, Mo or Cd, and additive is a kind of in Na, B, K, Li, and dispersant is zirconia.The preparation method of described catalyst be by active component and auxiliary agent precursor adsorption on dispersant, then with chemical reducing agent reduction, the reducing agent of its use is NaBH
4, then by gained solids wash, the dry catalyst that makes.
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 in Fe, Co, Ni, Zn or 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 been used different formulas to form, and has obtained higher cyclohexene yield.But because the course of reaction of benzene cyclohexene is mainly mass transport limitation, mass-transfer efficiency directly determines ultimate yield.Therefore the physico-chemical property of carrier has important effect to the mass transfer effect of the dispersion effect of active component and raw material and product.
Summary of the invention
The object 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 is compared catalyst in the past and is had larger specific area, average pore size and porosity, therefore can guarantee that 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, active component, auxiliary agent and dispersible carrier, consists of, 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 meets 100%; Wherein: dispersible carrier is ZrO
2, SiO
2or TiO
2in more than one, active component be in Ru, Pt or Pa any, auxiliary agent be in Fe, Co, Ni, Cu, Mn or 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 normal temperature, the presoma salt of dispersible carrier and ammoniacal liquor according to the mixed in molar ratio of 1:1 ~ 20 after reaction produce precipitation, be precipitated oxide carrier, by sedimentation and filtration, after ageing 12h, obtain gel; Gel is dissolved in the water and adds hydrogen peroxide, and regulator solution pH value is 9.0 ~ 12.0, at 70 ~ 99 ℃ of temperature, after aging backflow 50h, by sedimentation and filtration dry and at 300 ~ 600 ℃ roasting 2 ~ 5h, obtain 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 to solution in proportion, impregnated on the dispersible carrier that step (1) obtains, adding ammoniacal liquor regulator solution pH value is 10 ~ 12, dry after ageing 1h, roasting at 400 ℃, in hydrogen stream, 180 ~ 300 ℃ of reduction 3h, obtain required catalyst.
In the present invention, the presoma salt of described dispersible carrier is ethyl orthosilicate, ZrO
2or TiO
2hydrochloride.
In the present invention, active component presoma salt is Ru, Pt or Pd nitrate.
In 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 that prepared by the present invention, the active selective integrated performance index that waits has reached commercial Application standard.
2, compare with in the past with ZrO
2for the catalyst of dispersible carrier, catalyst prepared by the present invention has the pore passage structure that is more applicable to benzene selective hydrogenation reaction.
3, precipitating reagent is used cheap ammoniacal liquor, need not expensive NaOH, and catalyst preparation cost is low.
4, the method does not need to use expensive NaBH
4as reducing agent, further reduced the integrated cost of catalyst.
The specific embodiment
Below by embodiment, further illustrate the present invention.
Embodiment 1
By commercially available ZrO
2standby after roasting 2h at 300 ℃.By a certain amount of RuCl
3xH
2o be dissolved in distilled water (with metal quality account for dispersible carrier quality 8%), after equal-volume vacuum impregnation, be placed in the dry 24h of 85 ℃ of moving airs, and in 5ml/min hydrogen stream at 250 ℃ of reduction 3h.Obtain catalyst A.
Embodiment 2
ZrOCl
28H
2o and NH
3h
2o makes precipitation according to the mol ratio of 1:3, makes after gel, by Zr(OH)
4with hydrogen peroxide ratio be that 1:0.2 adds, after under 96 ℃, pH=11.5 after aging backflow 50h, filtration drying, and roasting 1h obtains at 520 ℃.By a certain amount of RuCl
3xH
2o be dissolved in distilled water (with metal quality account for dispersible carrier quality 8%), after equal-volume vacuum impregnation, be placed in the dry 24h of 85 ℃ of moving airs, and in 5ml/min hydrogen stream at 250 ℃ of reduction 3h.Obtain catalyst B.
Embodiment 3
ZrOCl
28H
2o and NH
3h
2o makes precipitation according to 1:3, makes after gel, by Zr (OH)
4with hydrogen peroxide ratio be that 1:0.2 adds, after under 96 ℃, pH=11.5 after aging backflow 50h, filtration drying, and roasting 1h obtains at 520 ℃.By a certain amount of RuCl
3xH
2o be dissolved in distilled water (with metal quality account for dispersible carrier quality 8%), simultaneously according to mol ratio Ru:Fe=1:0.2, add FeCl
3after, after equal-volume vacuum impregnation, be placed in the dry 24h of 85 ℃ of moving airs, and in 5ml/min hydrogen stream at 250 ℃ of reduction 3h.Obtain catalyst C.
Embodiment 4
ZrOCl
28H
2o and NH
3h
2o makes precipitation according to 1:3, makes after gel, by Zr (OH)
4with hydrogen peroxide ratio be that 1:0.2 adds, after under 96 ℃, pH=11.5 after aging backflow 50h, filtration drying, and roasting 1h obtains at 520 ℃.By a certain amount of RuCl
3xH
2o be dissolved in distilled water (with metal quality account for dispersible carrier quality 8%), simultaneously according to mol ratio Ru:Ni=1:0.2, add Ni (NO
3)
2after, after equal-volume vacuum impregnation, be placed in the dry 24h of 85 ℃ of moving airs, and in 5ml/min hydrogen stream at 250 ℃ of reduction 3h.Obtain catalyst D.
Embodiment 5
ZrOCl
28H
2o and NH
3h
2o makes precipitation according to 1:3, makes after gel, by Zr (OH)
4with hydrogen peroxide ratio be that 1:0.2 adds, after under 96 ℃, pH=11.5 after aging backflow 50h, filtration drying, and roasting 1h obtains at 520 ℃.By a certain amount of (NH
4)
6h
2w
12o
40.xH
2o be dissolved in distilled water (with Ru mol ratio be 1:10), after equal-volume vacuum impregnation, 85 ℃ dry after, and at 650 ℃ roasting 2h.Again by a certain amount of RuCl
3xH
2o be dissolved in distilled water (with metal quality account for dispersible carrier quality 8%), after equal-volume vacuum impregnation, be placed in the dry 24h of 85 ℃ of moving airs, and in 20ml/min hydrogen stream at 250 ℃ of reduction 3h.Obtain catalyst E.
Active selective determination:
The catalyst of choosing above embodiment carries out active selective determination, is determined in miniature high pressure reaction still and carries out, polytetrafluoro liner.Add 100ml water, 50ml benzene, 0.4g catalyst, 4.0gZnSO
47H
2o.With air in hydrogen exchange still, stir speed (S.S.) 600rpm.80 ℃/h of heating rate.Regulate hydrogen pressure to 4.2Mpa, speed of agitator 1000rpm, and start timing.Relative percentage composition with benzene, cyclohexene and cyclohexane in gas chromatographic analysis oil phase.Active selective calculation method:
Active: benzene conversion ratio (C
bZthe relative concentration * 100% of benzene in)=product
Cyclohexene yield (Y
hEcyclohexene relative concentration * 100% in)=product
Selective: the selective (S of cyclohexene
hE)=cyclohexene yield/benzene conversion ratio * 100%=Y
hE/ C
bZ* 100%
Table 1 has provided after reaction 10,20,30min, and the activity of different catalyst is selective:
When table 1 reaction 10,20,30min, the activity of different catalysts is selective
Claims (4)
1. benzene selective hydrogenation generates a preparation method for the catalyst of cyclohexene, and described catalyst 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 meets 100%; Wherein: dispersible carrier is ZrO
2, SiO
2or TiO
2in more than one, active component be in Ru, Pt or Pd any, auxiliary agent be in Fe, Co, Ni, Cu, Mn or Zn any; It is characterized in that concrete steps are as follows:
(1) under normal temperature, the presoma salt of dispersible carrier and ammoniacal liquor according to the mixed in molar ratio of 1:1 ~ 20 after reaction produce precipitation, be precipitated oxide carrier, by sedimentation and filtration, after ageing 12h, obtain gel; Gel is dissolved in the water and adds hydrogen peroxide, and regulator solution pH value is 9.0 ~ 12.0, at 70 ~ 99 ℃ of temperature, after aging backflow 50h, by sedimentation and filtration dry and at 300 ~ 600 ℃ roasting 2 ~ 5h, obtain 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 to solution in proportion, impregnated on the dispersible carrier that step (1) obtains, adding ammoniacal liquor regulator solution pH value is 10 ~ 12, dry after ageing 1h, roasting at 400 ℃, in hydrogen stream, 180 ~ 300 ℃ of reduction 3h, obtain required catalyst.
2. a kind of benzene selective hydrogenation according to claim 1 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 or basic zirconium chloride.
3. a kind of benzene selective hydrogenation according to claim 1 generates the preparation method of the catalyst of cyclohexene, it is characterized in that active component presoma salt is Ru, Pt or Pd nitrate.
4. a kind of benzene selective hydrogenation according to claim 1 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.
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| CN201210513386.7A CN102974342B (en) | 2012-12-05 | 2012-12-05 | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof |
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| CN201210513386.7A CN102974342B (en) | 2012-12-05 | 2012-12-05 | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
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 (2)
| Title |
|---|
| 负载型钌基催化剂催化苯选择加氢合成环己烯;路芳等;《化学进展》;20030731;第15卷(第4期);338-343 * |
| 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》.2003,第15卷(第4期),338-343. * |
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