CN1160152C - Catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparing process - Google Patents
Catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparing process Download PDFInfo
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- CN1160152C CN1160152C CNB001332783A CN00133278A CN1160152C CN 1160152 C CN1160152 C CN 1160152C CN B001332783 A CNB001332783 A CN B001332783A CN 00133278 A CN00133278 A CN 00133278A CN 1160152 C CN1160152 C CN 1160152C
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- catalyst
- cyclohexanone
- cyclohexanol dehydrogenation
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Abstract
The present invention relates to a catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation and a preparation method thereof, which belongs to the technical field of catalysts. The catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation mainly comprises the following components (m/m): 20% to 70% of cupric oxide, 28% to 70% of zinc oxide, 1% to 10% of alumina, 0.1% to 5% of the mixture of rare metal compounds and 0 to 1.0% of alkali metal compound; the catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation is prepared by a coprecipitation method. The catalyst of the present invention is used for preparing cyclohexanone by cyclohexanol dehydrogenation, and has high low-temperature activity, high cyclohexanone selectivity and high catalytic stability.
Description
Technical field: a kind of cyclohexanone catalyst by cyclohexanol dehydrogenation and preparation method thereof, the metal catalyst technical field is specifically related to a kind of Catalysts and its preparation method that is used for preparing cyclohexanone by cyclohexanol dehydrogenation.
Background technology: cupric oxide-Zinc oxide catalytic is all reported in many documents and patent to some extent, as A Spntaet al, Czechoslovakia Patent 151,166Dec.15,1973; U.S Pat.3,652,460 Mar, 28,1972; Chiu ef al.U.S Pat.4,670,605 Jun, 2,1987.As described in document, the general Cu-series catalyst that adopts of cyclohexanol dehydrogenation part is compared with the ZnO/CaCO3 catalyzer in the domestic and international large-scale caprolactam production apparatus, its service temperature low (220 ℃-260 ℃), and the pimelinketone selectivity is higher.U.S.Pat.4,670,605 have set forth in Cu-series catalyst and to introduce base agent and help improving catalyst dehydrogenation activity and selectivity.From industrial practice, the cyclohexanone catalyst by cyclohexanol dehydrogenation that exploitation has higher catalyst activity (particularly low temperature active), selectivity and stability has realistic meaning.
Summary of the invention: the objective of the invention is to develop a kind of cyclohexanone catalyst by cyclohexanol dehydrogenation and preparation method thereof with higher hexalin low-temperature dehydrogenation activity, pimelinketone selectivity and catalytic stability.
The present invention is achieved like this: its catalyzer is formed and is comprised that mainly content (m/m) is respectively cupric oxide, zinc oxide, the aluminum oxide of 20%-70%, 28%-70%, 1%-10%, and the mixture of content (m/m) 0.1%-5% scarce metallic compound is made the alkali metal compound of structural promoter A and content 0-1.0% and made coagent B.
Structural promoter A is one or both the mixture in the compound of yttriums such as Pt, Pb, Ru, Rh, La, Ce, and coagent B is a kind of in the compound of alkali metals such as Li, Na, K, Rb, Cs.
Cupric oxide, zinc oxide, the suitable content (m/m) of aluminum oxide are respectively 25%-50%, 45%-70%, 3%-8%, and the suitable content (m/m) of structural promoter A is 0.1%-2%.
Catalyzer of the present invention adopts the method for co-precipitation to be prepared: mainly may further comprise the steps, the nitrate mixed solution and the precipitation agent of copper, zinc and the aluminium of content are as mentioned above carried out precipitin reaction, precipitation agent can be K
2CO
3, Na
2CO
3, NH
4HCO
3, (NH
4)
2CO
3, a kind of in NaOH, KOH or the ammoniacal liquor, the control precipitation temperature is 30 ℃-80 ℃, after precipitation was finished, ageing 20min-30min added that auxiliary agent filters, washs, dry, calcining and compression molding and make.
Embodiment:
Below in conjunction with embodiment the present invention is described in detail.
Embodiment 1
Getting 1M copper nitrate solution 1200mL, 1M zinc nitrate solution 2400mL mixes with 3M aluminum nitrate solution 100mL, under 30 ℃ of-80 ℃ of conditions, join in the sodium carbonate solution of 10%-15% (m/m) while stirring rapidly mixing solutions, then at 30 ℃ of-80 ℃ of ageing 20min-30min, after washing, add the 10g auxiliary agent, filter again, dry, granulation, drying particulate is at 280 ℃ of-400 ℃ of roasting 4-6h, and compression molding promptly gets the catalyzer finished product then.
Embodiment 2
In specification is in the tubular reactor of φ 32 * 2mm, and the catalyzer loading amount is 50ml (a former granularity), hexalin air speed 0.6h
-1Under the condition, the auxiliary agent B of different content is as shown in table 1 to the influence of the catalyst activity that example 1 method makes.
The activity and the selectivity of table 1 development sample and similar catalyst sample (introduction)
230 ℃ of auxiliary agent B
Catalyzer title content/transformation efficiency/selectivity/
(m/m)％ ％ ％
Catalyzer sample (introduction) 43.5 99.0
Development sample 006 1.0 46.7 99.0
Development sample 009 0.5 48.8 99.6
Embodiment 3
Under example 2 reaction conditionss, the auxiliary agent A of different content is as shown in table 2 to the influence of activity of such catalysts.
The activity and the selectivity of table 2 development sample and similar catalyst sample (introduction)
230 ℃ of auxiliary agent A
Catalyzer title content/transformation efficiency/selectivity/
(m/m)％ ％ ％
Catalyzer sample (introduction) 43.5 99.0
Development sample 011 0.1 45.8 99.7
Development sample 014 1.0 47.8 99.5
Development sample 014 4.0 44.7 99.0
Catalyzer of the present invention is used for preparing cyclohexanone by cyclohexanol dehydrogenation, has higher low temperature active, pimelinketone selectivity and catalytic stability.
Claims (6)
1, a kind of cyclohexanone catalyst by cyclohexanol dehydrogenation, it is characterized in that it comprises that mainly content (m/m) is respectively cupric oxide, zinc oxide, the aluminum oxide of 20%-70%, 28%-70%, 1%-10%, the mixture of the scarce metallic compound of content (m/m) 0.1-5% and the alkali metal compound of content＞0-1.0%.
2, a kind of cyclohexanone catalyst by cyclohexanol dehydrogenation as claimed in claim 1 is characterized in that alkali metal compound is a kind of in the compound of Li, Na, K, Rb, Cs alkali metal.
3, a kind of cyclohexanone catalyst by cyclohexanol dehydrogenation as claimed in claim 1 or 2, the mixture that it is characterized in that scarce metallic compound are one or both the mixture in the compound of Pd, Pt, Ru, Rh, La, Ce yttrium.
4, a kind of cyclohexanone catalyst by cyclohexanol dehydrogenation as claimed in claim 1 is characterized in that the content (m/m) of cupric oxide, zinc oxide, aluminum oxide is respectively 25%-50%, 45%-70%, 3%-8%.
5, a kind of cyclohexanone catalyst by cyclohexanol dehydrogenation as claimed in claim 1, the content (m/m) that it is characterized in that the mixture of scarce metallic compound is 0.1%-2%.
6, a kind of preparation method of cyclohexanone catalyst by cyclohexanol dehydrogenation according to claim 1 is characterized in that it is to adopt the nitrate mixed solution and the precipitation agent of copper, zinc and aluminium to carry out precipitin reaction, and precipitation agent can be K
2CO
3, Na
2CO
3, NH
4HCO
3, (NH
4)
2CO
3, a kind of in NaOH, KOH or the ammoniacal liquor, the control precipitation temperature is 30 ℃-80 ℃, after precipitation was finished, ageing 20min-30min added that auxiliary agent filters, washs, dry, calcining and compression molding and make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001332783A CN1160152C (en) | 2000-11-30 | 2000-11-30 | Catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001332783A CN1160152C (en) | 2000-11-30 | 2000-11-30 | Catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1356170A CN1356170A (en) | 2002-07-03 |
| CN1160152C true CN1160152C (en) | 2004-08-04 |
Family
ID=4595616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001332783A Expired - Fee Related CN1160152C (en) | 2000-11-30 | 2000-11-30 | Catalyst for preparing cyclohexanone by dehydrogenating cyclohexanol and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1160152C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344597C (en) * | 2005-12-28 | 2007-10-24 | 浙江工业大学 | Process for preparing cyclohexone by catalyzing oxidating cyclohexol |
| CN102247854B (en) * | 2011-07-26 | 2013-06-19 | 烟台大学 | Catalyst for preparing cyclohexanone by virtue of cyclohexanol dehydrogenation as well as preparation method thereof |
| CN102500420B (en) * | 2011-11-30 | 2014-03-05 | 大丰海嘉诺药业有限公司 | Alcohol gas phase dehydrogenation catalyst, preparation method thereof and application |
| CN104511277A (en) * | 2013-10-08 | 2015-04-15 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexanone from cyclohexanol through gas-phase dehydrogenization and preparation method thereof |
| CN103861626B (en) * | 2014-03-25 | 2015-08-05 | 山东科技大学 | Cyclohexanone catalyst by cyclohexanol dehydrogenation and application thereof |
| CN104399474A (en) * | 2014-11-20 | 2015-03-11 | 西安近代化学研究所 | Catalyst for synthesizing methoxy acetone through alcohol dehydrogenization, preparation method and application of catalyst |
| CN105709725B (en) * | 2014-12-04 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of catalyst for producing methyl ethyl ketone and its preparation method and application |
| CN105709752B (en) * | 2014-12-04 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of Catalysts of Dehydrogenation Secondary Butand and its preparation method and application |
| CN109331826B (en) * | 2018-09-13 | 2021-08-24 | 北京华和拓科技开发有限责任公司 | Catalyst for preparing cyclohexanone by cyclohexanol dehydrogenation, preparation method and application thereof |
| CN113181924A (en) * | 2020-01-14 | 2021-07-30 | 万华化学集团股份有限公司 | High-strength dehydrogenation catalyst and preparation method and application thereof |
-
2000
- 2000-11-30 CN CNB001332783A patent/CN1160152C/en not_active Expired - Fee Related
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|---|---|
| CN1356170A (en) | 2002-07-03 |
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Granted publication date: 20040804 Termination date: 20161130 |