CN1176886C - 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 prepnInfo
- Publication number
- CN1176886C CN1176886C CNB011222085A CN01122208A CN1176886C CN 1176886 C CN1176886 C CN 1176886C CN B011222085 A CNB011222085 A CN B011222085A CN 01122208 A CN01122208 A CN 01122208A CN 1176886 C CN1176886 C CN 1176886C
- Authority
- CN
- China
- Prior art keywords
- benzene
- catalyst
- selective hydrogenation
- solution
- cyclohexene
- 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.)
- Expired - Fee Related
Links
Classifications
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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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a catalyst for preparing cyclohexene from benzene by selective hydrogenation and a preparation method thereof. In the method, active constituents and the precursors of auxiliary agents are absorbed on a dispersing agent firstly, and the active constituents and the precursors of the auxiliary agents are reduced by a chemical method to obtain the catalyst with the small grain diameter of the active constituent and high dispersity. The preparation of the catalyst is carried out at room temperature and has the advantages of simple method, easy control of conditions, good repeatability of the catalyst and no environmental pollution; the catalyst is used for preparing the cyclohexene from the benzene by the selective hydrogenation, the selectivity of the cyclohexene achieves about 85% when the conversion rate of the benzene is 40%, so the catalyst has high industrial application value.
Description
Affiliated technical field:
The present invention relates to a kind of commercial catalysts and preparation method thereof.
Background technology:
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 material 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 crucial industrial application value, can bring huge economic benefit.Yet generate the tetrahydrobenzene stage because tetrahydrobenzene than the easier hydrogenation of benzene, reacts to be difficult to rest on, so preparing cyclohexene from benzene added with hydrogen once was that peoples dream is thought.Seek appropriate catalyst, improve the tetrahydrobenzene yield, 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 liquid phase method benzene selective hydrogenation is more favourable to generating tetrahydrobenzene on Ru, the Rh catalyzer.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 chemical industrial company of Japanese Asahi Chemical Industry.Mostly relevant Preparation of catalysts is pickling process, the precipitator method, chemical mixing method etc.Chemical reduction method has Japanese Patent JP59186,932[84,186,932], but the benzene transformation efficiency has only 14.4%, and the tetrahydrobenzene selectivity has only 6.3%.Also have JP63243,038[88,243,038], reaction 120min, benzene transformation efficiency 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 JP10,330,294[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.
Summary of the invention:
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:
A kind of producing cyclohexene with benzene selective hydrogenation catalyzer mainly is made up of active constituent, auxiliary agent, additive and dispersion agent, and wherein Ru is an active ingredient, and M is an auxiliary agent, and B is an additive, ZrO
2Be dispersion agent, the weight percent of these four kinds of compositions is: with ZrO
2Be benchmark, Ru is ZrO
210～20%; M is Zn and Fe, and M is 0.1～10% of Ru; B is 10～100% of Ru.
The method for preparing the producing cyclohexene with benzene selective hydrogenation catalyzer is:
A., with a active ingredient precursor at room temperature with after the pure water dissolving, add auxiliary agent by given weight percent, stir into solution 1;
B, to add weight in solution 1 be 5～10 times the dispersion agent ZrO of Ru
2, stirred 0.5～2 hour, become solution 2;
Under c, the whipped state, in solution 2, add reductive agent NaBH by given weight percent
4, be metallic state with active ingredient and aids reduction in the solution 2, filter then, washing, drying promptly gets product.
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 reduced, 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 the 1/6-1/7 of 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 is at room temperature carried 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.
Specific embodiments:
Embodiment:
1, gets a RuCl
3.xH
2O (containing Ru37%) at room temperature with the pure water dissolving, makes RuCl
3Solution; Accurately take by weighing then a certain amount of (in metal account for Ru 0.1～10%) FeCl
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%, and stir about 1 hour becomes solution 2;
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 producing cyclohexene with benzene selective hydrogenation 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 Ru-M-B/ZrO
2Catalyzer, 14.4gZnSO
47H
2O, pre-treatment 22h under the stir speed (S.S.) 1000r/min adds 58ml benzene, reaction 10min, the benzene transformation efficiency reaches 40%, and the tetrahydrobenzene selectivity reaches 85%.
Claims (2)
1, a kind of producing cyclohexene with benzene selective hydrogenation catalyzer is made up of active constituent, auxiliary agent, additive and dispersion agent, and wherein Ru is an active ingredient, and M is an auxiliary agent, and B is an additive, ZrO
2Be dispersion agent, it is characterized in that: the weight percent of these four kinds of compositions, with ZrO
2Be benchmark, Ru is ZrO
210-20%, M is Zn or Fe, is the 0.1-10% of Ru, B is the 10-100% of Ru.
2, prepare the method for the described producing cyclohexene with benzene selective hydrogenation catalyzer of claim 1, it is characterized in that:
A, with a active ingredient precursor at room temperature with after the pure water dissolving, add auxiliary agent by weight percent given in the claim 1, stir into solution 1;
B, in solution 1, add the 5-10 dispersion agent ZrO doubly that weight is Ru
2, stirred 0.5-2 hour, become solution 2;
C, under whipped state, in solution 2, add reductive agent NaBH by given weight percent in the claim 1
4, be metallic state with active ingredient and aids reduction in the solution 2, filter then, washing, drying promptly gets product.
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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1337386A CN1337386A (en) | 2002-02-27 |
| CN1176886C true CN1176886C (en) | 2004-11-24 |
Family
ID=4664636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011222085A Expired - Fee Related CN1176886C (en) | 2001-06-15 | 2001-06-15 | Catalyst for selective hydrogenation of benzene to produce cyclohexane and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1176886C (en) |
Families Citing this family (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 |
| 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 |
| 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 |
| 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 |
| TWI494335B (en) * | 2012-08-31 | 2015-08-01 | Tsrc Corp | Method for hydrogenating polymer and hydrogenated polymer thereof |
| 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 |
-
2001
- 2001-06-15 CN CNB011222085A patent/CN1176886C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1337386A (en) | 2002-02-27 |
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Granted publication date: 20041124 Termination date: 20100615 |