CN100496728C - Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use - Google Patents
Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use Download PDFInfo
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- CN100496728C CN100496728C CNB2005101260647A CN200510126064A CN100496728C CN 100496728 C CN100496728 C CN 100496728C CN B2005101260647 A CNB2005101260647 A CN B2005101260647A CN 200510126064 A CN200510126064 A CN 200510126064A CN 100496728 C CN100496728 C CN 100496728C
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Abstract
The present invention relates to a catalyst for benzene selective hydrogenation to prepare cyclohexence. Said catalyst includes carrier and the following active amponents: (by carrier content as reference) Ru 1-20 mass%, Fe 0.1-3.0 mass%, B 0.1-6.0 mass%, the described carrier is formed from 5-25 mass% of zeolite and 75-95 mass% of zirconium oxide. Said catalyst has higher cyclohexene selectivity.
Description
Technical field
The present invention is a kind of benzene selective hydrogenation to prepare cyclohexene catalyst and preparation method and application.Specifically, be a kind of benzene selective hydrogenation to prepare cyclohexene catalyst and preparation method of the boracic with chemical reducing agent preparation, and this catalyst is used for the method for benzene selective hydrogenation preparing cyclohexene.
Background technology
Cyclohexene is widely used in Organic Chemicals owing to having active two keys.In the production technology of caprolactam and adipic acid, can use cyclohexene as intermediate raw material in recent years.By benzene selective hydrogenation preparing cyclohexene, again by preparing cyclohexanol by cyclohexene hydration reaction, the cyclohexanol oxidation just obtains cyclohexanone and adipic acid.Above-mentioned technology has shortened the production procedure of caprolactam and adipic acid, has saved production cost, and very environmental protection.Therefore, the benzene selective hydrogenation to prepare cyclohexene catalyst of developing high activity, high selectivity has seemed very important.
After first is used for industrialization with benzene selective hydrogenation preparing cyclohexene from industrial group of Japanese Asahi Chemical Industry, the research of existing many this respects report.USP4,734,536 disclose a kind of preparation method of cyclohexene, and used catalyst is particle diameter≤200
Metal Ru, be co-catalyst with Zn salt, and the oxide, hydroxide or the hydrate that add Zr, Hf, Ti, Nb, Ta, Cr, Fe, Co, Al, Ga or Si are additive.Its method for preparing metal Ru adopts hydrogen reducing, and the selectivity that described catalyst system is used for preparing cyclohexene from benzene added with hydrogen is not high.
USP5,589,600 alloys that adopt the precipitation method and prepare Ru and Ni with the method for hydrogen reducing have good cyclohexene selectivity as the benzene selective hydrogenation catalyst.USP5,973,218 also disclose a kind of preparation method of cyclohexene, and wherein used catalyst is the Ru catalyst of non-loading type, regulates the selectivity that the sulfate concentration that is soluble in the aqueous phase improves cyclohexene in the benzene hydrogenation in the course of reaction.
USP6,060,423 to disclose a kind of gallium oxide/zinc oxide double oxide be carrier, supported V III family metal, the catalyst of preferred ruthenium.Adopt the active component precursor of load on the chemical reduction method reduction carrier in its preparation process, preferred chemical reducing agent is a sodium borohydride.This catalyst is used for preparing cyclohexene from benzene added with hydrogen, and higher selectivity and productive rate are arranged, but the benzene activity of conversion is not high.
CN1337386A discloses a kind of producing cyclohexene with benzene selective hydrogenation catalyst and manufacture method thereof, and this catalyst is made up 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 B, Na, K, the Li, and dispersant is a zirconia.Described Preparation of catalysts method be earlier 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 hydrogenation amorphous 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.
Summary of the invention
The catalyst and the preparation method that the purpose of this invention is to provide a kind of benzene selective hydrogenation to prepare cyclohexene.This catalyst adopts the chemical reducing agent preparation, has higher activity and selectivity.
Benzene selective hydrogenation to prepare cyclohexene catalyst provided by the invention, comprise carrier and be the following active component of content that benchmark calculates with the carrier: Ru1～20 quality %, Fe0.1～3.0 quality %, B0.1～6.0 quality %, described carrier is made up of the zeolite of 5～25 quality % and the zirconia of 75～95 quality %.
Catalyst of the present invention is a carrier with the zirconia that contains zeolite, and adopts chemical reducing agent to prepare catalyst, makes the cyclohexene selectivity of catalyst increase.
The specific embodiment
It is carrier that catalyst of the present invention adopts the zirconia that contains zeolite, with carrier and the aqueous solution that contains the compound of active component, uses sodium borohydride reduction again, makes after washing, drying.
Preferred 5～15 quality % of Ru content in the described catalyst, preferred 0.1～1.5 quality % of Fe content, preferred 0.1～3.0 quality % of B content.Preferred 5～20 quality % of the content of zeolite described in the carrier, the preferred modenite of described zeolite, ZSM-5 or β zeolite.
Preparation of catalysts method of the present invention, comprise zirconia and zeolite mixed and make the hybrid solid powder, again the water soluble compound solution of ruthenium and iron is made mixed liquor, to be uniformly dispersed after described pressed powder and the mixed liquor mixing, stir the alkaline aqueous solution that adds sodium borohydride down and fully react, isolate solid product, spend deionised water to solution and be neutral, use absolute ethanol washing again, dry then.The preferred modenite of described zeolite, ZSM-5 or β zeolite.
The water soluble compound of described ruthenium is selected from ruthenic chloride, ruthenium bromide or nitric acid ruthenium, preferred ruthenic chloride; The water soluble compound of iron is selected from iron chloride, ferric nitrate, frerrous chloride or ferrous nitrate, preferred iron chloride or frerrous chloride.
Catalyst of the present invention adopts chemical reducing agent preparation, the preferred NaBH of reducing agent
4Elder generation is mixed the zirconia and the zeolite of mixing during preparation with the water soluble compound solution of ruthenium and iron, stirs 1～5 hour, solid is evenly disperseed, again to wherein dropwise adding NaBH
4Be made into alkaline aqueous solution and fully react, active component is reduced into metallic state, stop to stir.20～30 ℃ static 4～20 hours, adopt solid and liquid in the centrifugal separation method separation product, it is 6～8 that solid is spent deionised water to pH value of solution value, use absolute ethanol washing again, drying under reduced pressure then, preferred 20～50 ℃ of baking temperature, be 10～20 hours suitable drying time.
In the said method, the alkaline aqueous solution of described sodium borohydride is the aqueous solution of sodium borohydride and NaOH, and wherein concentration sodium hydroxide is 0.5～5.0 quality %, and the concentration of sodium borohydride is 5～15 quality %.
The method of benzene selective hydrogenation to prepare cyclohexene provided by the invention is included under the existence of catalyst of the present invention, zinc additive and water, makes benzene selective hydrogenation under 120～180 ℃, 3.5～7.0MPa condition change into cyclohexene.
Described zinc additive is the compound that contains zinc, preferred zinc chloride, zinc sulfate, trbasic zinc phosphate or zinc hydroxide, more preferably zinc chloride or zinc sulfate.
In the described reaction, the concentration of zinc additive in the aqueous solution is 0.3～1.0 mol, and the volume ratio of water and benzene is 0.5～4.0:1.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare catalyst of the present invention.
Get 3 the gram β zeolite powders and 12 the gram zirconia powders mix, with 5.27 the gram RuCl
33H
2O (purity is 99.99%, and ruthenium content is 37+0.4%), 0.49 gram FeCl
24H
2O (analyzing pure) and 35 ml deionized water are made into mixed solution, add in the above-mentioned powder that mixes, and stir 1 hour, and solid is evenly disperseed.Stir and dropwise add down by 2.93 gram NaBH
4, the solution that is made into of 0.6 gram NaOH and 30 ml deionized water, dropwise, continue to stir 1 hour.Reduzate was left standstill 12 hours, and the clear liquid on solid upper strata is removed in centrifugation then.It is 6～8 that the gained solid spends deionised water to pH value of solution value, uses absolute ethanol washing again 3 times, 35 ℃ of drying under reduced pressure 12 hours, catalyst A, its composition sees Table 1, each constituent content all is that benchmark calculates with the carrier in the table 1.
Example 2
Method by example 1 prepares catalyst B, and different is with 0.75 gram β zeolite powder and 14.25 gram zirconia powders mixes and be used to prepare catalyst, and the composition of catalyst B sees Table 1.
Example 3
Method by example 1 prepares catalyst C, and different is with 2.25 gram β zeolite powders and 12.75 gram zirconia powders mixes and be used to prepare catalyst, and the composition of catalyst C sees Table 1.
Example 4
Method by example 1 prepares catalyst D, and different is in the preparation process, and 3 gram ZSM-5 zeolite powders and 12 gram zirconia powders are mixed used RuCl
33H
2The amount of O is 5.27 grams, FeCl
24H
2The amount of O is 0.49 gram, and the composition of catalyst D sees Table 1.
Example 5
Method by example 1 prepares catalyst E, and different is in the preparation process, and 3 gram modenite powder and 12 gram zirconia powders are mixed used NaBH during reduction
4Amount be 2.94 the gram, the composition of catalyst E sees Table 1.
Comparative Examples 1
Get 15 gram zirconia powders, prepare comparative catalyst M by the method for example 1, its composition sees Table 1.
Comparative Examples 2
Method by example 1 prepares catalyst n, and different is in the preparation process, and 4.5 gram β zeolite powders and 10.5 gram zirconia powders are mixed, and the composition of catalyst n sees Table 1.
Example 6
This case expedition catalyst of the present invention is used for the performance of producing cyclohexene with benzene selective hydrogenation reaction.
In batch reactor, add 10 gram catalyst, 40 gram zinc additive ZnSO
47H
2O, 280 ml deionized water feed hydrogen to Hydrogen Vapor Pressure and are 5.0MPa, are warming up to 140 ℃ that adjusting stir speed (S.S.) is 900 rev/mins, adds 140 milliliters of benzene and carries out the benzene selective hydrogenation reaction.Reaction result sees Table 2, table 3.
As shown in Table 2, catalyst of the present invention has suitable benzene conversion ratio than the comparative catalyst, illustrates that catalyst of the present invention has suitable benzene hydrogenation activity.Table 3 data show that then catalyst of the present invention has higher cyclohexene selectivity than the comparative catalyst.
Table 1
Table 2
Table 3
Claims (10)
1, a kind of benzene selective hydrogenation to prepare cyclohexene catalyst, comprise carrier and be the following active component of content that benchmark calculates with the carrier: Ru 1～20 quality %, Fe 0.1～3.0 quality %, B 0.1～6.0 quality %, described carrier is made up of the zeolite of 5～25 quality % and the zirconia of 75～95 quality %.
2, according to the described catalyst of claim 1, it is characterized in that in the described catalyst with the carrier being that the Ru content that benchmark calculates is 5～15 quality %, Fe content is 0.1～1.5 quality %, B content is 0.1～3.0 quality %.
3,, it is characterized in that described zeolite is modenite, ZSM-5 or β zeolite according to the described catalyst of claim 1.
4, the described Preparation of catalysts method of a kind of claim 1, comprise zirconia and zeolite mixed and make the hybrid solid powder, again the water soluble compound solution of ruthenium and iron is made mixed liquor, to be uniformly dispersed after described hybrid solid powder and the mixed liquor mixing, stir the alkaline aqueous solution that adds sodium borohydride down and fully react, isolate solid product, spend deionised water to solution and be neutral, use absolute ethanol washing again, dry then.
5, in accordance with the method for claim 4, it is characterized in that the water soluble compound of described ruthenium is selected from ruthenic chloride, ruthenium bromide or nitric acid ruthenium, the water soluble compound of iron is selected from iron chloride, ferric nitrate, frerrous chloride or ferrous nitrate.
6, in accordance with the method for claim 4, the alkaline aqueous solution that it is characterized in that described sodium borohydride is the aqueous solution of sodium borohydride and NaOH, and wherein concentration sodium hydroxide is 0.5～5.0 quality %, and the concentration of sodium borohydride is 5～15 quality %.
7, in accordance with the method for claim 4, it is characterized in that described zeolite is selected from modenite, ZSM-5 or β zeolite.
8, a kind of method of benzene selective hydrogenation to prepare cyclohexene is included under the existence of the described catalyst of claim 1, zinc additive and water, makes benzene selective hydrogenation under 120～180 ℃, 3.5～7.0MPa condition change into cyclohexene.
9, in accordance with the method for claim 8, it is characterized in that the concentration of described zinc additive in the aqueous solution is 0.3～1.0 mol, the volume ratio of water and benzene is 0.5～4.0:1.
10, in accordance with the method for claim 8, it is characterized in that described zinc additive is zinc chloride or zinc sulfate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101260647A CN100496728C (en) | 2005-11-30 | 2005-11-30 | Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use |
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| CNB2005101260647A CN100496728C (en) | 2005-11-30 | 2005-11-30 | Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102600888B (en) * | 2012-01-31 | 2015-02-18 | 湘潭大学 | Benzene hydrogenation catalyst as well as preparation method and application thereof |
| CN103785382B (en) * | 2012-11-01 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst and its preparation method and application |
| CN103785378B (en) * | 2012-11-01 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of Catalysts and its preparation method of partial hydrogenation of benzene cyclohexene and application |
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Non-Patent Citations (2)
| Title |
|---|
| 液相法苯选择加氢制环己烯反应条件的探讨. 吴敏等.合成纤维工业，第28卷第3期. 2005 |
| 液相法苯选择加氢制环己烯反应条件的探讨. 吴敏等.合成纤维工业，第28卷第3期. 2005 * |
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