CN1337386A - Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn - Google Patents
Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn Download PDFInfo
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- CN1337386A CN1337386A CN01122208A CN01122208A CN1337386A CN 1337386 A CN1337386 A CN 1337386A CN 01122208 A CN01122208 A CN 01122208A CN 01122208 A CN01122208 A CN 01122208A CN 1337386 A CN1337386 A CN 1337386A
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- catalyzer
- benzene
- active ingredient
- selective hydrogenation
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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
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a catalyst for benzene selective hydrogenation to prepare cyclohexene and its preparation method. Said method is characterized by that firstly, it makes the active component and adjuvant precursor be adsorbed on the dispersing agent, then adopts chemical method to make reduction to obtain the catalyst whose active component is small in grain size and high dispersion. Said preparation process is implemented at room temp., said process is simple. When the conversion rate of benzene is 40%, the cyclohexene selectivity can be up to about 85%.
Description
The present invention relates to a kind of commercial catalysts and preparation method thereof.
Tetrahydrobenzene has active pair of key, and is quite extensive as the Organic Chemicals purposes.But tetrahydrobenzene direct hydration system hexalin particularly, direct oxidation preparing cyclohexanone and hexanodioic acid, thus shortened the operational path that hexanodioic acid and ε-Ji Neixianan are produced.Hexanodioic acid and ε-Ji Neixianan are respectively the raw materials of producing nylon 66 and nylon 6.Along with the development of synthon and rubber industry, the demand of nylon 66 and nylon 6 is increased day by day, so preparing cyclohexene from benzene added with hydrogen has very essential industry using value, can bring huge economic benefit.Yet be difficult to rest on the stage that generates tetrahydrobenzene because tetrahydrobenzene than the easier hydrogenation of benzene, reacts, so preparing cyclohexene from benzene added with hydrogen once was that peoples dream is thought.Seek appropriate catalyst, improve the yield of tetrahydrobenzene, become the key point of problem.
1934, Truffault found that tetrahydrobenzene is the intermediate product of benzene hydrogenation, has indicated the possibility of producing cyclohexene with benzene selective hydrogenation under catalyst action.Nineteen fifty-seven, the Anderson experiment confirm existence of tetrahydrobenzene in the benzene hydrogenation product, but under prevailing condition, the selectivity of tetrahydrobenzene is very low, growing amount is few.Hartog in 1963 etc. find that the selection hydrogenation of liquid phase benzene on Ru, the Rh catalyzer is more favourable to generating tetrahydrobenzene.Nineteen sixty-five Stanmicarbon, nineteen sixty-eight Hartog are reported in respectively and add an amount of Fatty Alcohol(C12-C14 and C12-C18) in the reaction system as properties-correcting agent, can improve the yield of tetrahydrobenzene.Up to the end of the sixties, the selectivity of producing cyclohexene with benzene selective hydrogenation is still not high.A patent (patent No.: Ger.Offen2221 of du pont company in 1972,139.7) claim, add additives such as water-soluble metal inorganic salt or metal carbonyl in aqueous phase system, carry out the reaction of ruthenium catalysis benzene selective hydrogenation, the tetrahydrobenzene yield reaches more than 32%.Have only Japan to realize suitability for industrialized production up to now in the world, this is that first is used for industrialized producing cyclohexene with benzene selective hydrogenation catalyzer in the world.China refreshing horse group is by technology introduction, makes China become in the world second by the industrialized country of producing cyclohexene with benzene selective hydrogenation.
From 1981 to 2000, have 100 multinomially about the patent of preparing cyclohexene from benzene added with hydrogen, wherein mainly concentrate on industrial of Japanese Asahi Chemical Industry.Mostly relevant Preparation of catalysts is pickling process, the precipitator method, chemical mixing method.Chemical reduction method has Japanese Patent JP 59186,932[84,186,932], but the benzene transformation efficiency has only 14.4%, and the tetrahydrobenzene selectivity has only 6.3%.Also have JP 63 243,038[88,243,038], reaction 120min benzene transformation efficiency is 42.0%, all the other all patents all greatly differ from each other with the present invention.
The Ru-Zn catalyzer of Japanese industry use, the most approaching with the present invention on performance, but belong to precipitator method preparation.Japanese Patent JP 10,330,294[98,330,294] reported that the precipitator method prepare the method for preparing cyclohexene from benzene added with hydrogen catalyzer.This method steps is many, and the cycle is long, and alkali-washing waste liquid easily causes environmental pollution.The present invention has then avoided these shortcomings.
Composition of this catalyzer and preparation method and existing patented technology are all inequality.The characteristics of this catalyzer are:
The object of the present invention is to provide a kind of high-activity high-selectivity preparing cyclohexene from benzene added with hydrogen Catalysts and its preparation method.This method is neither the traditional pickling process and the precipitator method, be not again chemical mixing method and chemical reduction method in general sense, it has overcome the deficiencies in the prior art, has reduced the middle-chain of catalyst preparation process, make Preparation of Catalyst have good repeatability, non-environmental-pollution.
Technical scheme provided by the present invention is:
The producing cyclohexene with benzene selective hydrogenation catalyzer, mainly become to be grouped into for four kinds by active ingredient, auxiliary agent, additive and dispersion agent, the weight percent of these four kinds of compositions is: active ingredient: auxiliary agent: additive: dispersion agent=1: 0.001～0.1: 0.1～1: 5～10.Wherein: active ingredient is a kind of among Ru, Th, the Pa, and auxiliary agent is a kind of among W, Ni, Fe, Co, Zn, Mo, the Cd, and additive is a kind of among B, Na, K, the Li, and dispersion agent is SiO
2, ZrO
2, Al
2O
3, one or both the mixture among the MgO.
Above-mentioned producing cyclohexene with benzene selective hydrogenation Preparation of catalysts method is:
A, with 1 part of active ingredient precursor at room temperature with after the pure water dissolving, add 0.001～0.1 part auxiliary agent, stirring and dissolving becomes solution 1;
B, in solution 1, add 5～10 parts of dispersion agents, stirred 0.5～2 hour, become solution 2;
C, under whipped state, add 1 part reductive agent in the solution 2, the active ingredient in the solution 2 is become metallic state with aids reduction, filter then, wash, drying, promptly make the catalyzer of producing cyclohexene with benzene selective hydrogenation.
Wherein, employed chemical reducing agent is NaBH
4Or AlLiH
4Or HCOH.
Compared with prior art, the invention has the advantages that:
1, the pickling process that the present invention need not be traditional activity component impregnation on carrier, also the precipitator method that need not be traditional, the active ingredient post precipitation is restored, but utilize the thought of chemisorption, at first be adsorbed on the dispersion agent active ingredient and auxiliary agent precursor, and then with chemical process reduction, obtain that the active ingredient particle diameter is little, the catalyzer of high dispersive.High dispersive makes catalyzer have good active, and auxiliary agent makes catalyzer have good selectivity.This activity of such catalysts component concentration is 1/6～1/7 of a Ru-Zn catalyzer, and the activity index height is used it for producing cyclohexene with benzene selective hydrogenation, is 40% o'clock at the benzene transformation efficiency, and the tetrahydrobenzene selectivity reaches about 85%, thereby has good industrial application value.
2, Preparation of catalysts process of the present invention all is at room temperature to carry out from start to finish, thereby facility investment is few, and the preparation method is simple, and condition is controlled easily, the catalyzer good reproducibility; Production process does not have waste, non-environmental-pollution.
Embodiment:
The method for preparing the producing cyclohexene with benzene selective hydrogenation catalyzer is as follows:
1, gets a certain amount of RuCl
3.xH
2O (containing Ru37%) at room temperature with the pure water dissolving, makes RuCl
3Solution; Accurately take by weighing a certain amount of (accounting for the 0.1-10% of Ru in metal) FeCl then
2Or FeSO
47H
2O adds RuCl
3In the solution, stirring and dissolving becomes solution 1.
2, in solution 1, add ZrO
2Make dispersion agent, amount is a benchmark with metal Ru, and Ru accounts for ZrO
2Weight percent is 5-20%.Stir about 1 hour.
3, use NaBH
4Make reductive agent, dropwise add under whipped state in the solution 2, the active ingredient in the solution 2 is become metallic state with aids reduction, filter then, washing solids to pH value is 7.
4,, promptly make the catalyzer of selective hydrogenation of benzene to produce cyclic ethylene with vacuum-drying under the solids room temperature that obtains.
Above-mentioned catalyzer is used for the preparing cyclohexene from benzene added with hydrogen reaction under the following conditions: 140 ℃, the 5.0MPa hydrogen pressure adds 100ml water in the reaction system, 0.8 gram catalyzer, 14.4gZnSO
47H
2O, pre-treatment 22h under the stir speed (S.S.) 1000rpm adds 58ml benzene, reaction 10min, the benzene transformation efficiency reaches 40%, and the tetrahydrobenzene selectivity reaches 85%.
Claims (7)
1, producing cyclohexene with benzene selective hydrogenation catalyzer, mainly become to be grouped into for four kinds by active ingredient, auxiliary agent, additive and dispersion agent, it is characterized in that: the weight percent of these four kinds of compositions is: active ingredient: auxiliary agent: additive: dispersion agent=1: 0.001～0.1: 0.1～1: 5～10.
2, according to the said catalyzer of claim 1, it is characterized in that: active ingredient is a kind of among Ru, Th, the Pa.
3, according to the said catalyzer of claim 1, it is characterized in that: auxiliary agent is a kind of among W, Ni, Fe, Co, Zn, Mo, the Cd.
4, according to the said catalyzer of claim 1, it is characterized in that: additive is a kind of among B, Na, K, the Li.
5, according to the said catalyzer of claim 1, it is characterized in that: dispersion agent is SiO
2, ZrO
2, Al
2O
3, one or both the mixture among the MgO.
6, a kind of method for preparing producing cyclohexene with benzene selective hydrogenation catalyzer as claimed in claim 1 is characterized in that:
A, with 1 part of active ingredient precursor at room temperature with after the pure water dissolving, add 0.001～0.1 part auxiliary agent, stirring and dissolving becomes solution 1;
B, in solution 1, add 5～10 parts of dispersion agents, stirred 0.5～2 hour, become solution 2;
C, under whipped state, add 1 part reductive agent in the solution 2, the active ingredient in the solution 2 is become metallic state with aids reduction, filter then, wash, drying, promptly make the said catalyzer of claim 1.
7, according to the manufacture method of the said producing cyclohexene with benzene selective hydrogenation catalyzer of claim 6, it is characterized in that: employed chemical reducing agent is NaBH
4Or AlLiH
4Or HCOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011222085A CN1176886C (en) | 2001-06-15 | 2001-06-15 | Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011222085A CN1176886C (en) | 2001-06-15 | 2001-06-15 | Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1337386A true CN1337386A (en) | 2002-02-27 |
| CN1176886C CN1176886C (en) | 2004-11-24 |
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|---|---|---|---|
| CNB011222085A Expired - Fee Related CN1176886C (en) | 2001-06-15 | 2001-06-15 | Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304109C (en) * | 2004-08-12 | 2007-03-14 | 郑州大学 | Preparing of cyclobexene catalyst for benzene selective hydrogenation its preparation method and regulating method and regeneration method |
| CN1978053B (en) * | 2005-11-30 | 2010-06-23 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by benzene selective hydrogenation, its preparing method and use |
| CN102600841A (en) * | 2012-03-09 | 2012-07-25 | 郑州大学 | Monolayer dispersible catalyst for selective hydrogenation of benzene to cyclohexene and preparation method thereof |
| CN102690162A (en) * | 2012-05-31 | 2012-09-26 | 中国天辰工程有限公司 | Method for producing cyclohexene by using high-purity benzene as raw materials |
| CN103288574A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Method for preparing cyclohexene by benzene selective hydrogenation |
| CN103288577A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Method for preparing cyclohexene |
| CN103665282A (en) * | 2012-08-31 | 2014-03-26 | 台橡股份有限公司 | Method for hydrogenating polymer and hydrogenated polymer thereof |
| CN108997266A (en) * | 2018-08-06 | 2018-12-14 | 江苏清泉化学股份有限公司 | A kind of 2,2- bis- (2- furyl) propane adds the method for hydrogen 2,2- bis- (2- tetrahydrofuran base) propane |
| CN112844378A (en) * | 2020-12-29 | 2021-05-28 | 厦门大学 | Method for regulating and controlling interaction between nano metal particles and gel type oxide carrier |
-
2001
- 2001-06-15 CN CNB011222085A patent/CN1176886C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304109C (en) * | 2004-08-12 | 2007-03-14 | 郑州大学 | Preparing of cyclobexene catalyst for benzene selective hydrogenation its preparation method and regulating method and regeneration method |
| CN1978053B (en) * | 2005-11-30 | 2010-06-23 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by benzene selective hydrogenation, its preparing method and use |
| CN103288577B (en) * | 2012-02-29 | 2015-08-19 | 北京安耐吉能源工程技术有限公司 | A kind of method preparing tetrahydrobenzene |
| CN103288574A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Method for preparing cyclohexene by benzene selective hydrogenation |
| CN103288577A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Method for preparing cyclohexene |
| CN103288574B (en) * | 2012-02-29 | 2016-01-20 | 北京安耐吉能源工程技术有限公司 | A kind of benzene selective hydrogenation prepares the method for tetrahydrobenzene |
| CN102600841B (en) * | 2012-03-09 | 2013-07-10 | 郑州大学 | Monolayer dispersible catalyst for selective hydrogenation of benzene to prepare cyclohexene and preparation method thereof |
| CN102600841A (en) * | 2012-03-09 | 2012-07-25 | 郑州大学 | Monolayer dispersible catalyst for selective hydrogenation of benzene to cyclohexene and preparation method thereof |
| CN102690162A (en) * | 2012-05-31 | 2012-09-26 | 中国天辰工程有限公司 | Method for producing cyclohexene by using high-purity benzene as raw materials |
| CN102690162B (en) * | 2012-05-31 | 2015-01-28 | 中国天辰工程有限公司 | Method for producing cyclohexene by using high-purity benzene as raw materials |
| CN103665282A (en) * | 2012-08-31 | 2014-03-26 | 台橡股份有限公司 | Method for hydrogenating polymer and hydrogenated polymer thereof |
| CN103665282B (en) * | 2012-08-31 | 2016-12-07 | 台橡股份有限公司 | Method for hydrogenating polymer and hydrogenated polymer thereof |
| CN108997266A (en) * | 2018-08-06 | 2018-12-14 | 江苏清泉化学股份有限公司 | A kind of 2,2- bis- (2- furyl) propane adds the method for hydrogen 2,2- bis- (2- tetrahydrofuran base) propane |
| CN108997266B (en) * | 2018-08-06 | 2020-06-09 | 浙江清和新材料科技有限公司 | Method for preparing 2, 2-di (2-tetrahydrofuryl) propane by hydrogenating 2, 2-di (2-furyl) propane |
| CN112844378A (en) * | 2020-12-29 | 2021-05-28 | 厦门大学 | Method for regulating and controlling interaction between nano metal particles and gel type oxide carrier |
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| Publication number | Publication date |
|---|---|
| CN1176886C (en) | 2004-11-24 |
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Granted publication date: 20041124 Termination date: 20100615 |