CN101961661B - Organo-metallic catalyst for preparing cyclohexane by hydrogenation of benzene and preparation method and application thereof - Google Patents
Organo-metallic catalyst for preparing cyclohexane by hydrogenation of benzene and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an organo-metallic catalyst for preparing cyclohexane by hydrogenation of benzene and a preparation method and application thereof. The preparation method comprises the steps of: reacting RuCl3 with a ligand S1, wherein the mol ratio of the RuCl3 to the ligand S1 is 1:1.1-2.0; reacting Ru-S1 with a ligand S2 according to the mol ratio of 1:10-20, and then reacting with anhydrous sodium carbonate and 1,3-cyclohexadien according to the mol ratio of 1:2:2-1:3:3 to obtain Ru-S1-S2; reacting N-methylimidazole with 1-chlorobutan according to the mol ratio of 1:1-2 with ethylbenzene as a solvent under normal pressure at a temperature of 30-120 DEG C to obtain [BMIM]Cl; and placing the Ru-S1-S2 and the [BMIM]Cl in a fixed bed reactor for reacting to obtain an ionic liquid catalyst, wherein the mol content of the Ru-S1-S2 is 2-5 percent. The invention is used for preparing the cyclohexane by the hydrogenation of the benzene, wherein the conversion rate of the benzene reaches 20-35 percent and the selectivity of the cyclohexane reaches above 65-87 percent.
Description
Technical field
The invention belongs to preparing cyclohexene from benzene added with hydrogen catalyst development field, be specifically related to a kind of preparing cyclohexene from benzene added with hydrogen organo-metallic catalyst.
Background technology
Cyclohexene is widely used in as Organic Chemicals in the production of raw material and other chemical products of medicine and pesticide intermediate, feed addictive, polyester and nylon etc.; Particularly prepare cyclohexene by the benzene partial hydrogenation; Produce cyclohexanol by cyclohexene; Reoxidizing the process route of producing adipic acid compares with the process route that the complete hydrogenation route of benzene is produced adipic acid; Have the advantages that to save resource, flow process weak point, efficient energy-saving, no discarded object and environmental pollution, the security that has also improved production process simultaneously.Benzene partial hydrogenation cyclohexene is unmanageable reaction on unfavorable on the thermodynamics, the dynamics, carry out catalyst research, improve the cyclohexene yield, have better economic and social benefit.First has published the patent that the benzene selective hydrogenation is produced cyclohexene to the Drinkard of E.I.Du Pont Company in 1972 in the world.Companies of Asahi Chemical Industry in 1988 have taken the lead in realizing the industrialization of benzene selective hydrogenation to prepare cyclohexene in the world, and the core of this technology is a catalyst.This catalyst mainly comprises major catalyst, dispersant, co-catalyst.The particle that major catalyst is formed by metal Ru and zinc salt, average crystallite directly are 5 nanometers, and this value increases along with running; Dispersant is a zirconia; Co-catalyst is zinc hydroxide, zinc sulfate.In process of production, add the selectivity that water improves cyclohexene, increase the separation process and the complexity of product.U.S. Pat 4,734,536 have reported a kind of typical ruthenium black catalyst, and this catalyst adopts precipitation method preparation, and ruthenium content is high in the catalyst, and cost is higher.Introduced support type non-crystaline amorphous metal benzene partial hydrogenation cyclohexene Preparation of catalysts method among Chinese patent CN1714932A, the CN1446625A.The non-crystaline amorphous metal that the catalyst of in CN1714932A, introducing adopts metal Ru, light rare earth and metalloid boron to form loads on the zirconia; Catalyst at first is configured to catalyst slurry with catalyst, water, zinc sulfate and zirconia in use; Under hydrogen pressure 1～5Mpa, 100～200 ℃ of temperature, 300～500 rev/mins of mixing speeds, the condition of 5～30 hours time, carry out passivation then, import benzene at last and carry out hydrogenation reaction.This method needs repeatedly washing to produce the contaminated wastewater thing in catalyst preparation process, and complicated steps in the catalyst use is owing to make water increase the separation process and the complexity of reaction purpose product as additive.The catalyst of in CN1446625A, introducing is made up of the carrier material of metal Ru, metalloid boron, metal or modified metal oxide agent and oxide or metal hydroxides, and ruthenium mainly exists with the form of the amorphous alloy of ruthenium-boron or ruthenium boron-metal in the catalyst.Used metal or metal oxide can be one or more in the metallic element; Carrier material is one or more in inorganic oxide, the precipitation of hydroxide.At first will add water, zinc sulfate additive when using this catalyst to carry out the benzene partial hydrogenation, reaction condition is that temperature is 120～160 ℃, and pressure is 3.0～6.0MPa.Catalyst preparation process is complicated, brings pollutant, complicated operating process.
Summary of the invention
The objective of the invention is to simplify catalyst preparation process, solve the problem of bringing pollutant in the prior art.Catalyst in use need not add other additive, simplifies the separation problem of product, and a kind of preparing cyclohexene from benzene added with hydrogen organo-metallic catalyst is provided simultaneously.
Preparing cyclohexene from benzene added with hydrogen organo-metallic catalyst provided by the present invention is the catalyst activity component with the precious metal element ruthenium, with C
6(CH
3)
6(hexamethylbenzene), C
6H
6(benzene), C
5H
5(cyclopentadiene), C
7H
8(toluene) or cyclohexadiene compounds are first part S1 and the C
6(CH
3)
6(hexamethylbenzene), C
6H
6(benzene), C
5H
5(cyclopentadiene), C
7H
8(toluene) or cyclohexadiene compounds are that the second part S2 forms metal complex, and general formula is Ru-S1-S2.
The present invention adopts chemical synthesis process to prepare organo-metallic catalyst, and concrete steps are following:
1) with RuCl
3With the first part S1 mol ratio be 1: 1.1～2.0 ratio, in organic alcohol solvent, under 60～90 ℃, condition of normal pressure, react preparation Ru-S1 product.
2) with Ru-S1 product and the second part S2 be 1: 10～20 ratio in molar ratio, under 165～190 ℃, condition of normal pressure, react preparation Ru-S2 product.
3) with Ru-S2 product and natrium carbonicum calcinatum, 1; It is 1: 2: 2～1: 3: 3 ratio in molar ratio that 3-encircles two hexenes; In organic alcoholic solution, under normal pressure, stirring, 70-90 ℃, the nitrogen protection condition, reacted 2～10 hours, stop reaction, cool off catalyst product Ru-S1-S2.
4) be that raw material, ethylbenzene are solvent with N-methylimidazole and chloro-normal butane; The mol ratio of N-methylimidazole and chloro-normal butane is 1: 1～2; Solvent load is 0.5～2.5mL/g raw material; At normal pressure, 30～120 ℃ of following reaction 5～60h, reaction naturally cools to room temperature after finishing, and product gets product [BMIM] Cl (chloro n-formyl sarcolysine base nitrogen normal-butyl imidazoles) through washing, decompression distillation, vacuum drying.
5) [BMIM] Cl for preparing in Ru-S1-S2 for preparing in the step 3) and the step 4) is placed fixed bed reactors; In organic alcohol solvent, inert gas shielding, normal pressure, 20～50 ℃; Behind reaction 0.5～2.0h; Naturally cool to room temperature, decompression distillation promptly gets ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2] to constant weight, and the molar content of Ru-S1-S2 is 2～5% in the catalyst.
Catalyst and 10mL benzene that step 5) is made drop in the autoclave; 3 times, hydrogen exchange 3 times of using nitrogen replacement successively; Under 50 ℃, 1Mpa, mixing speed 300rpm condition, reacted 1～15 minute, the conversion ratio of benzene is 30%, and the selectivity of cyclohexene is 70%.
Wherein, the reaction in the step 1) is preferably at normal pressure, and 70-85 ℃ is reacted 2～6h down.
Step 2) cleaning solvent described in is n-hexane or ether; The Ru-S1 and the second part S2 mol ratio preferred 1: 8～15, preferred 170～190 ℃ of reaction temperature, preferred 2～4h of time.
Organic alcohol described in the step 3) is methyl alcohol, ethanol or n-butanol; Described inert gas is nitrogen, argon gas, helium or neon; Reaction in the step 3) is preferably at normal pressure, 70～90 ℃ of following reaction 3～8h.
Cleaning solvent described in the step 4) is toluene or ethylbenzene; The mol ratio of N-methylimidazole and chloro-normal butane preferred 1: 1.1～1.5, the preferred 1.0～1.5mL/g raw material of solvent load, preferred 70～90 ℃ of reaction temperature, preferred 12～30h of time.
Organic alcohol described in the step 5) is methyl alcohol, ethanol or n-butanol; Described inert gas is nitrogen, helium, neon or argon gas; Reaction condition be normal pressure, 25～35 ℃ the reaction 0.1～0.5 hour.
Catalyst provided by the present invention is applicable to that benzene hydrogenation prepares the cyclohexene reaction.
The invention effect
Compare with existing preparing cyclohexene from benzene added with hydrogen catalyst and preparation thereof, the present invention has following beneficial effect:
1) catalyst of the present invention belongs to green catalyst, does not have waste gas, waste liquid and waste residue to produce in the preparation process, and the non-environmental-pollution problem belongs to environmental type Catalyst Production technology.
2) catalyst applications of the present invention is in the preparing cyclohexene from benzene added with hydrogen reaction, and reaction condition is gentle, under the condition of normal temperature, low pressure, carries out, and the conversion ratio of benzene reaches 20-35%, and the selectivity of cyclohexene reaches 65-87%.
3) catalyst of the present invention can be used for producing the process of cyclohexene, and reaction temperature is low, cuts down the consumption of energy, and reduce production cost, and the product cyclohexene is easy to and catalyst separation.
The specific embodiment
Below in conjunction with embodiment the present invention is described further, but the present invention is not limited to following embodiment.
Embodiment 1
With 2.0 gram ruthenium trichlorides, 10.0 milliliters of 2-methyl-5-isopropyls-1, the 3-cyclohexadiene is dissolved in 100 milliliters of absolute ethyl alcohols, places 150 milliliters there-necked flask; Under 70 ℃, condition of normal pressure, react, stop reaction after 2.5 hours, cool to room temperature; Get red precipitate; After filtering, with absolute ethanol washing filter cake 3 times, through filter, after the drying [RuCl
2(C
10H
16)]
2Be Ru-S1, product yield is 61%.
With 1.0 gram Ru-S1 that make and 10 gram C
6(CH
3)
6Place reaction tube at 170 ℃, react under the condition of normal pressure, stop reaction after 5 hours, cool to room temperature, behind n-hexane washing reaction product 5 times, vacuum drying obtains product [RuCl
2(C
6(CH
3)
6)]
2, being Ru-S2, product yield is 70%.
With the 0.5 gram RuS2 that makes, 0.5 gram natrium carbonicum calcinatum, 2 grams 1; The absolute ethyl alcohol that 3-encircles two hexenes and 40 milliliters places 100 milliliters there-necked flask; Reaction is 4 hours under normal pressure, stirring, 75 ℃, nitrogen protection condition, stops reaction, and crystallisation by cooling gets product [Ru (C
6(CH
3)
6) (C
6H
8)], being Ru-S1-S2, product yield is 60%.
Get 41gN-methylimidazole, 50g chloro-normal butane, 50mL ethylbenzene places 150 milliliters there-necked flask, under 106 ℃, condition of normal pressure; Stop reaction behind the reaction 24h; Get product, product adopts toluene wash to remove the N-methylimidazole, and washing agent is removed in decompression distillation; Get ionic liquid [BMIM] Cl, product yield is 97%.
Get 0.2 restrain Ru-S1-S2,20g [BMIM] Cl places there-necked flask, at normal pressure, N
2React after 1.0 hours under protection, 70 ℃ of conditions, stop reaction, cool to room temperature naturally; Decompression distillation then; Absolute ethyl alcohol is removed in vacuum drying, obtains ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2], and the molar content of [Ru-S1-S2] is 2% in the catalyst.
To make ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2] 0.13 gram catalyst and 15mL benzene and 100mL water and place autoclave; Earlier with the interior air of nitrogen replacement still 3 times; Use the interior nitrogen of hydrogen exchange still 3 times again; Reaction is 0.1 hour under 50 ℃, 1Mpa, mixing speed 300rpm, and the conversion ratio of benzene is 21%, and the selectivity of cyclohexene is 87%.
Embodiment 2
With 2.0 gram ruthenium trichlorides, 10.0 milliliters of 2-methyl-5-isopropyls-1, the 4-cyclohexadiene is dissolved in the there-necked flask that 100 milliliters of absolute ethyl alcohols place 150 milliliters, under 75 ℃, condition of normal pressure, reacts; 2.0 stop reaction after hour; Cool to room temperature gets red precipitate, after filtering; With absolute ethanol washing filter cake 5 times, through filter, dry product [RuCl
2(C
10H
16)]
2Be Ru-S1, product yield is 63%.
With 1.0 gram Ru-S1 that make and 10 gram C
6(CH
3)
6Place reaction tube at 180 ℃, react under the condition of normal pressure, stop reaction after 3 hours, cool to room temperature, behind n-hexane washing reaction product 5 times, vacuum drying obtains product [RuCl
2(C
6(CH
3)
6)]
2, being Ru-S2, product yield is 78%.
With the 0.5 gram [RuCl that makes
2(C
6(CH
3)
6)]
2, 0.5 gram natrium carbonicum calcinatum, 5 gram benzene and 40 milliliters absolute ethyl alcohol place 100 milliliters there-necked flask, reaction is 6 hours under normal pressure, stirring, 70 ℃, nitrogen protection condition, stops reaction, crystallisation by cooling gets product [Ru (C
6(CH
3)
6) (C
6H
6)], being Ru-S1-S2, product yield is 63%.
Get 41gN-methylimidazole, 50g chloro-normal butane, 50mL ethylbenzene places 150 milliliters there-necked flask, under 106 ℃, condition of normal pressure; Stop reaction behind the reaction 24h; Get product, product adopts toluene wash to remove the N-methylimidazole, and washing agent is removed in decompression distillation; Get ionic liquid [BMIM] Cl, product yield is 97%.
Get 0.5 restrain Ru-S1-S2 and 10g [BMIM] Cl, 25 milliliters absolute ethyl alcohol place 100 milliliters there-necked flask, at normal pressure, N
2React after 1.5 hours under protection, 78 ℃ of conditions, stop reaction, cool to room temperature naturally; Decompression distillation then; Absolute ethyl alcohol is removed in vacuum drying, obtains ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2], and the molar content of [Ru-S1-S2] is 5% in the catalyst.
To make ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2] 0.1 gram catalyst and 10mL benzene and 100mL water and place autoclave; Air in elder generation's nitrogen replacement still 3 times; Use the interior nitrogen of hydrogen exchange still 3 times again; Reaction is 0.1 hour under 50 ℃, 0.5Mpa, mixing speed 300rpm, and the conversion ratio of benzene is 35%, and the selectivity of cyclohexene is 83%.
Embodiment 3
With 2.0 gram ruthenium trichlorides, 10.0 milliliters of 2-methyl-5-isopropyls-1, the 3-cyclohexadiene is dissolved in 100 milliliters of anhydrous propyl alcohol, places 150 milliliters there-necked flask; Under 85 ℃, condition of normal pressure, react, stop reaction after 3.0 hours, cool to room temperature; Get red precipitate; After filtering, with absolute ethanol washing filter cake 4 times, through filter, dry product [RuCl
2(C
10H
16)]
2Be Ru-S1, product yield is 81%.
With 1.0 gram Ru-S1 that make and 10 gram C
6(CH
3)
6As in the reaction tube at 182 ℃, react under the condition of normal pressure, stop after 3 hours the reaction, cool to room temperature, behind n-hexane washing reaction product 5 times, vacuum drying obtains product [Ru (C
6Me
6) Cl
2]
2Be Ru-S2, product yield is 76%.
The absolute ethyl alcohol of the 0.5 gram Ru-S2 that makes, 0.5 gram natrium carbonicum calcinatum, 5 gram cyclopentadiene and 40 milliliters is placed 100 milliliters there-necked flask; Reaction is 6 hours under normal pressure, stirring, backflow, nitrogen protection condition; Stop reaction, crystallisation by cooling gets product [Ru (C
6(CH
3)
6) (C
5H
5)], being Ru-S1-S2, product yield is 76%.
Get 41gN-methylimidazole, 50g chloro-normal butane, 50mL ethylbenzene and place 150 milliliters there-necked flask; Under 106 ℃, condition of normal pressure, stop reaction behind the reaction 24h, product; Product adopts toluene wash to remove the N-methylimidazole; Washing agent is removed in decompression distillation, gets ionic liquid [BMIM] Cl, and product yield is 97%.
Get 0.3 gram Ru-S1-S2 and 10g [BMIM] Cl, 25 milliliters absolute ethyl alcohol places 100 milliliters there-necked flask, at normal pressure, N
2React after 1.5 hours under protection, 78 ℃ of conditions, stop reaction, cool to room temperature naturally, decompression distillation, absolute ethyl alcohol is removed in vacuum drying, obtains ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2], and the molar content of [Ru-S1-S2] is 3% in the catalyst.
To make ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2] 0.2 gram catalyst and 10mL benzene and 100mL water and place autoclave; Air in elder generation's nitrogen replacement still 3 times; Use the interior nitrogen of hydrogen exchange still 3 times again; Reaction is 0.15 hour under 30 ℃, 1.5Mpa, mixing speed 300rpm, and the conversion ratio of benzene is 30%, and the selectivity of cyclohexene is 65%.
Claims (2)
1. preparing cyclohexene from benzene added with hydrogen organo-metallic catalyst preparation method is characterized in that:
1) with 2.0 gram ruthenium trichlorides, 10.0 milliliters of 2-methyl-5-isopropyls-1, the 4-cyclohexadiene is dissolved in the there-necked flask that 100 milliliters of absolute ethyl alcohols place 150 milliliters, under 75 ℃, condition of normal pressure, reacts; 2.0 stop reaction after hour; Cool to room temperature gets red precipitate, after filtering; With absolute ethanol washing filter cake 5 times, through filter, dry product [RuCl
2(C
10H
16)]
2Be Ru-S1, product yield is 63%;
1.0 gram Ru-S1 that 2) will make and 10 gram C
6(CH
3)
6Place reaction tube at 180 ℃, react under the condition of normal pressure, stop reaction after 3 hours, cool to room temperature, behind n-hexane washing reaction product 5 times, vacuum drying obtains product [RuCl
2(C
6(CH
3)
6)]
2, being Ru-S2, product yield is 78%;
0.5 gram [the RuCl that 3) will make
2(C
6(CH
3)
6)]
2, 0.5 gram natrium carbonicum calcinatum, 5 gram benzene and 40 milliliters absolute ethyl alcohol place 100 milliliters there-necked flask, reaction is 6 hours under normal pressure, stirring, 70 ℃, nitrogen protection condition, stops reaction, crystallisation by cooling gets product [Ru (C
6(CH
3)
6) (C
6H
6)], being Ru-S1-S2, product yield is 63%;
4) get 41gN-methylimidazole, 50g chloro-normal butane, 50mL ethylbenzene places 150 milliliters there-necked flask, under 106 ℃, condition of normal pressure; Stop reaction behind the reaction 24h; Get product, product adopts toluene wash to remove the N-methylimidazole, and washing agent is removed in decompression distillation; Get ionic liquid [BMIM] Cl, product yield is 97%;
5) get 0.5 restrain Ru-S1-S2 and 10g [BMIM] Cl, 25 milliliters absolute ethyl alcohol place 100 milliliters there-necked flask, at normal pressure, N
2React after 1.5 hours under protection, 78 ℃ of conditions, stop reaction, cool to room temperature naturally; Decompression distillation then; Absolute ethyl alcohol is removed in vacuum drying, obtains ionic-liquid catalyst [BMIM] Cl/ [Ru-Sl-S2], and the molar content of [Ru-S1-S2] is 5% in the catalyst.
2. preparing cyclohexene from benzene added with hydrogen organo-metallic catalyst preparation method is characterized in that:
1) with 2.0 gram ruthenium trichlorides, 10.0 milliliters of 2-methyl-5-isopropyls-1, the 3-cyclohexadiene is dissolved in 100 milliliters of anhydrous propyl alcohol, places 150 milliliters there-necked flask; Under 85 ℃, condition of normal pressure, react, stop reaction after 3.0 hours, cool to room temperature; Get red precipitate; After filtering, with absolute ethanol washing filter cake 4 times, through filter, dry product [RuCl
2(C
10H
16)]
2Be Ru-S1, product yield is 81%;
1.0 gram Ru-S1 that 2) will make and 10 gram C
6(CH
3)
6Place reaction tube at 182 ℃, react under the condition of normal pressure, stop reaction after 3 hours, cool to room temperature, behind n-hexane washing reaction product 5 times, vacuum drying obtains product [Ru (C
6Me
6) Cl
2]
2Be Ru-S2, product yield is 76%;
The absolute ethyl alcohol of the 0.5 gram Ru-S2 that 3) will make, 0.5 gram natrium carbonicum calcinatum, 5 gram cyclopentadiene and 40 milliliters places 100 milliliters there-necked flask; Reaction is 6 hours under normal pressure, stirring, backflow, nitrogen protection condition; Stop reaction, crystallisation by cooling gets product [Ru (C
6(CH
3)
6) (C
5H
5)], being Ru-S1-S2, product yield is 76%;
4) get 41gN-methylimidazole, 50g chloro-normal butane, 50mL ethylbenzene and place 150 milliliters there-necked flask; Under 106 ℃, condition of normal pressure, stop reaction behind the reaction 24h, product; Product adopts toluene wash to remove the N-methylimidazole; Washing agent is removed in decompression distillation, gets ionic liquid [BMIM] Cl, and product yield is 97%;
5) get 0.3 gram Ru-S1-S2 and 10g [BMIM] Cl, 25 milliliters absolute ethyl alcohol places 100 milliliters there-necked flask, at normal pressure, N
2React after 1.5 hours under protection, 78 ℃ of conditions, stop reaction, cool to room temperature naturally, decompression distillation, absolute ethyl alcohol is removed in vacuum drying, obtains ionic-liquid catalyst [BMIM] Cl/ [Ru-S1-S2], and the molar content of [Ru-S1-S2] is 3% in the catalyst.
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| US9045381B2 (en) | 2010-10-19 | 2015-06-02 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN102909076A (en) * | 2012-11-08 | 2013-02-06 | 江南大学 | Ion liquid catalyst for synthesizing diethyl carbonate by urea alcoholysis and preparation method thereof |
| US9512157B2 (en) * | 2012-11-30 | 2016-12-06 | Elevance Renewable Sciences, Inc. | Methods for preparing ruthenium carbene complexes and precursors thereto |
| IL234479A0 (en) | 2014-09-04 | 2014-12-02 | Yeda Res & Dev | Liquid-organic hydrogen carrier system based on catalytic peptide formation and hydrogenation using 2-aminoethanol and 2-(methylamino)ethanol |
| IL234478A0 (en) | 2014-09-04 | 2014-12-02 | Yeda Res & Dev | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN109529820B (en) * | 2018-12-19 | 2021-11-30 | 利安隆科润(浙江)新材料有限公司 | Preparation method of catalyst for preparing benzotriazole ultraviolet absorber by catalytic hydrogenation |
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| US5852130A (en) * | 1995-06-16 | 1998-12-22 | Institut Francais Du Petrole | Catalytic composition based on transition metal complexes, and a process for the hydrogenation of unsaturated compounds |
| CN101138741A (en) * | 2007-10-12 | 2008-03-12 | 华东师范大学 | Ionic liquid loaded ruthenium catalyst containing pyridine ligand and producing method thereof |
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