CN101185904B - Selectivity liquid phase hydrogenation catalyst and preparation method and use thereof - Google Patents
Selectivity liquid phase hydrogenation catalyst and preparation method and use thereof Download PDFInfo
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- CN101185904B CN101185904B CN200710019363XA CN200710019363A CN101185904B CN 101185904 B CN101185904 B CN 101185904B CN 200710019363X A CN200710019363X A CN 200710019363XA CN 200710019363 A CN200710019363 A CN 200710019363A CN 101185904 B CN101185904 B CN 101185904B
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Abstract
The invention relates to a catalyst, which is applicable to the selective liquid phase catalytic hydrogenation of Alpha, Beta-unsaturated carbonyl compounds to make corresponding unsaturated carbonyl compounds or unsaturated alcohol, being especially suitable for the selective hydrogenation of citral to make citronellal and/or citronellol. The catalyst of the invention is a metal component loadedon a structured composite nano carbon fiber, wherein, the metal component is selected from one of or a plurality of nickel, ruthenium, rhodium, palladium and platinum. The components of the catalyst are: 1) structured substrate, such as metal foam, honeycomb ceramic, carbon felt and ceramic fiber; 2) nano material coating, such as nano carbon fiber; 3) metal active component, such as nickel, ruthenium, rhodium, palladium and/or platinum. The invention effectively avoids deep reaction, thus enhancing the target product selectivity. The catalyst is prefabricated into a variety of shapes and installed in a reactor, so that the catalyst, the liquid phase reactants and the solution are easy to be separated, thus meanwhile reducing the loss of the catalyst.
Description
Technical field
The present invention relates to a kind of catalyst.This catalyst is applicable to α, and the selectivity liquid phase catalytic hydrogenation of β one beta-unsaturated carbonyl compounds is produced corresponding saturated carbonyls or unsaturated alcohol.Be particularly useful for the citral selective hydrogenation and produce citronellal and/or citronellol.
Background technology
Heterogeneous catalytic reaction, particularly gas-solid liquid three phase catalytic reaction, its speed can be subjected to the restriction of mass transfer usually.Consequently cause the overall budget reaction rate to descend.Mass transfer limit also can influence target product selectivity in the complex reaction.Be the complex reaction of target product particularly for those intermediate products with a series of successive reactions, as, citronellal and/or citronellol are produced in the citral selective hydrogenation, and mass transfer limit causes target product selectivity obviously to descend.Therefore, eliminating mass transfer limit is the important subject in catalysis engineering and reactor engineering field.Known technology is to adopt the superfine catalyst particle to eliminate or reduce the influence of mass transfer.Yet, produced new engineering problem thus.As, in paste state bed reactor, superfine catalyst particle and product separation difficulty; In fixed bed reactors, ultra-fine grain catalyst can cause bed pressure drop to increase.
Mass transfer limit is mainly from solid catalyst micropore inside diffusional resistance.And solid catalyst is introduced micropore reaches the raising activity with the method that increases specific surface purpose usually.Therefore, how preparing the catalysis material that has high-ratio surface and do not contain micropore is the key of eliminating inside diffusional resistance.
Carbon nano-fiber or CNT are the just novel carbon structures of a found class in 1991, because its special physicochemical performance becomes hot research in recent years, are the new materials that a class has application prospect very much.Carbon nano-fiber or nano-carbon tube load type catalyst and conventional oxide carrier are compared as aluminium oxide, silica, active carbon even load catalyst and to be shown unusual activity and selectivity.Carbon nano-fiber has sufficiently high outer specific surface, and the hole that forms between the fiber is used for heterogeneous catalytic reaction and can eliminates interior diffusion based on macropore.
α, the process for selective hydrogenation of beta-unsaturated carbonyl compound is disclosed, for example, in DE-A21 14 211 and DE-A28 39474.These two kinds of methods all are intermittently to carry out in the presence of palladium catalyst and alkali.The method of DE-A2839474 has been used the tertiary amine based on 15～50 weight % of initiation material, and the selectivity and the space-time yield of hydrogenation reaction all increase.CN99105566.7 provides a kind of more economical method that makes citral hydrogenation system citronellal.This method adopts in the filling bubble-column reactor that has product circulation and hydrogen circulation carries out hydrogenation, and reaction rate is significantly improved.Its reason is to use the filling bubble-column reactor that has product circulation and hydrogen circulation can reduce the catalyst surface thickness of liquid film, increases the catalyst surface density of hydrogen, that is improves external diffusion speed.Yet for α, the selective hydrogenation of beta-unsaturated carbonyl compound prepares saturated carbonyls or unsaturated alcohol reaction, and interior diffusion is having a strong impact on overall reaction rate and target product selectivity.In order to reduce interior diffusion, DE-A2839474 and CN99105566.7 use paste state bed reactor, and ultra-fine grain catalyst (particle diameter is the 0.5-100 micron) is suspended in the liquid phase.The weak point of these methods is: catalyst and product separation difficulty, catalyst attrition is big.If adopt to adopt fixed bed reactors, interior diffusion then becomes influences catalytic activity and bottleneck optionally, and bed pressure drop is excessive.
Summary of the invention
The purpose of this invention is to provide a kind of α that makes molecular formula (I), it is the Catalysts and its preparation method and the purposes of the unsaturated alcohol of (III) that β one beta-unsaturated carbonyl compounds prepares saturated carbonyls and/or the molecular formula that corresponding molecular formula is (II) through selective liquid-phase hydrogenation.This catalyst is specially adapted to citral hydrogenation preparing citronellal and citronellol.
Catalyst of the present invention is the metal component that loads on the structuring made from compound Nano carbon fiber.Wherein metal component is selected from one or more in nickel, ruthenium, rhodium, palladium and the platinum.This catalyst consists of: 1) structurized base material, as metal foam, ceramic honeycomb, carbon felt, ceramic fibre; 2) nano-material coating is as carbon nano-fiber; 3) metal active constituent is as nickel, ruthenium, rhodium, palladium and/or platinum.
Preparation of catalysts method of the present invention comprises: (1) with inorganic substrate, is processed into different shape as metal foam, ceramic honeycomb, carbon felt, ceramic fibre etc. according to the reactor size size; (2) with above-mentioned moulding material through lotion, drying (if required, also further roasting also can be at moulding material surface dip-coating last layer aluminium oxide), promptly obtain the structuring base material; (3) with one or more metal impregnations in chosen from Fe, cobalt, the nickel on the structuring base material, make activation structuring base material; (4) growing nano carbon fiber on activation structuring base material makes structuring made from compound Nano carbon fiber material by pyrolytic low-carbon alkanes or alkene; (5) be carrier with above-mentioned structuring made from compound Nano carbon fiber, one or more metal active constituents that are selected from nickel, nail, rhodium, palladium and the platinum are dispersed on the carrier.
Wherein structurized base material can be processed into various geometries, as cellular, cylindric, sheet, with adaptive response device size.Described metal active constituent can load on the nano-material coating with infusion process by the respective metal compound solution.Carbon nano-fiber can adopt dip coating with the dip-coating of carbon containing Polymer Solution on the structuring base material, high-temperature roasting makes in inert atmosphere again, also available low-carbon alkanes, alkene make through catalytic decomposition.
In the above-mentioned preparation process (5), be nickel as metal active constituent, load capacity is 1～20wt%, preferred 2～15wt%, more preferably 5～10wt%; As metal active constituent is nail, rhodium, palladium and/or platinum, and load capacity is 0.01～15wt%, preferred 0.2～5wt%, more preferably 0.5～1wt%.Above-mentioned catalyst is used for α, and the process conditions of the selective hydrogenation of beta-unsaturated carbonyl compound are: hydrogen partial pressure is that 1～200 Palestine and China carry out, preferred 1～100 crust, preferred especially 10～40 crust; Reaction temperature is 25～150 ℃, preferred 50～100 ℃.Hydrogenation reaction adopts continuous process, or adopts batch process.
Catalyst of the present invention is to α, and the beta-unsaturated carbonyl compound selective liquid-phase hydrogenation prepares corresponding saturated carbonyls and/or the unsaturated alcohol reaction table reveals unusual high activity and selectivity.Main cause is that catalyst of the present invention is made of the large aperture porous material, has thoroughly eliminated interior diffusion.Thereby reactant molecule is easy near the activated centre.The target product that what is more important is got off by desorption on the activated centre is easy to diffuse into the body phase, has avoided deep reaction effectively, thereby has improved target product selectivity.Catalyst of the present invention is used for hydrogenation reaction, can adopt the fixed bed reactors continued operation, also can adopt batch reactor.Catalyst is processed into various difformities in advance, is installed in the reactor, and catalyst is separated easily with liquid phase reactor thing and solvent, has reduced catalyst attrition simultaneously.
The specific embodiment
Embodiment 1: the 10.0g cordierite ((MgO) of the washing of learning from else's experience, drying
2-(Al
2O
3)
2-(SiO
2)
5) the type ceramic honeycomb, immerse 0.1M nickel nitrate solution 0.5h, take out through 120 ℃ of dry 4h, roasting 4h in 600 ℃ of air is cooled to 570 ℃, feeds 50% methane-nitrogen mixture 3h, makes structuring made from compound Nano carbon fiber material.As carrier, with 0.1M palladium nitrate solution dipping 0.5h, take out through 120 ℃ of dry 4h, roasting 4h in 500 ℃ of nitrogen makes the structuring made from compound Nano carbon fiber load type palladium catalyst that contains palladium 0.5wt%.
Embodiment 2: 0.1M citral-cyclohexane solution 200ml is added in the 500ml autoclave, add the catalyst 0.3g of embodiment 1 preparation, at 60 ℃, 10-40 Ba Qing depresses, and stirs 30min, the liquid phase mixture gas chromatographic analysis, citral conversion ratio＞90%, citronellal selectivity 90%.
Embodiment 3 (comparing embodiment): with commercially available 0.5%Pd/C catalyst (specific surface 850m
2/ g) replace the catalyst of embodiment 1 preparation, and carry out catalytic hydrogenation under embodiment 3 same reaction conditions, citral conversion ratio 90%, citronellal selectivity＜60%.
Embodiment 4: the 2.0g carbon felt of the washing of learning from else's experience, drying, immerse 0.1M nickel nitrate solution 0.5h, and take out through 120 ℃ of dry 4h, roasting 2h in 300 ℃ of air, 400 ℃ of hydrogen reducing 4h are warming up to 500 ℃, feed 25% ethene-nitrogen mixture 3h, make structuring made from compound Nano carbon fiber material.As carrier, with 1M nickel nitrate solution dipping 2h, take out through 120 ℃ of dry 4h, roasting 4h in 500 ℃ of nitrogen makes the structuring made from compound Nano carbon fiber load type palladium catalyst of nickeliferous 15wt%.
Embodiment 5: adopt fixed bed reactors, the Raney nickel of 0.5g embodiment 4 preparations of packing into is used 100ml/min hydrogen, 340 ℃ of reductase 12 h.After treating that temperature is reduced to 60 ℃, add 0.1M citral-cyclohexane solution, depress catalytic hydrogenation at 40 Ba Qing with 10ml/min.Citral conversion ratio 80%, citronellal selectivity＞90%.
Embodiment 6 (comparing embodiment): get 0.5g sheet 15%Ni/Al
2O
3The catalyst that replaces embodiment 4 preparations and carries out catalytic hydrogenation under the embodiment 5 same operation conditions, citral conversion ratio 80%, citronellal selectivity 46%.
Embodiment 7: replace cordierite type ceramic honeycomb among the embodiment 1 with ceramic fibre, and replace palladium nitrate with rhodium nitrate solution, other step makes the structuring made from compound Nano carbon fiber load type rhodium catalyst of rhodium-containing 0.5wt% with embodiment 1.
Embodiment 8: 200ml is contained citral 50wt%, and ethanol 45wt%, the mixed solution of trimethylamine 5wt% join in the 500ml autoclave, add the catalyst 0.5g of embodiment 7 preparations, at 80 ℃, 25 Ba Qing depress, stir 30min, liquid phase mixture gas chromatographic analysis, citral conversion ratio 93%, citronellal selectivity 3.4%, citronellol selectivity 76.3%, 3,4-dimethyl octanal selectivity 9.3%, 3,4-dimethyl octanol selectivity 11.0%.
Embodiment 9 (comparing embodiment): with 0.5%Rh/C catalyst (specific surface 850m
2/ g) replace the catalyst of embodiment 7 preparations, and carry out catalytic hydrogenation under embodiment 8 same reaction conditions.Citral conversion ratio 94%, citronellal selectivity 2.4%, citronellol selectivity 36.1%, 3,4-dimethyl octanal selectivity 7.5%, 3,4-dimethyl octanol selectivity 54.0%.
Embodiment 10: the 10.0g nickel foam of the washing of learning from else's experience, drying, immersion contains 2h in the phenolic resin aqueous solution of a little commercially available carbon nano-fiber suspension, taking-up is through 120 ℃ of dry 4h, carbonization 4h in 700 ℃ of nitrogen, be cooled to 600 ℃, feed 5% steam-nitrogen mixture activation 3h, make structuring made from compound Nano carbon fiber material.As carrier, with 0.2M ruthenium trichloride solution impregnation 0.5h, take out through 120 ℃ of dry 4h, reduce 4h in 340 ℃ of hydrogen, make the structuring made from compound Nano carbon fiber load ruthenium catalyst that contains ruthenium 2wt%.
Embodiment 11: add the ruthenium catalyst of 0.4g embodiment 10 preparations in the 500ml autoclave, use 200ml/min hydrogen, 340 ℃ of reductase 12 h.After treating that temperature is reduced to 100 ℃, add 0.5M Chinese cassia tree-aqueous isopropanol 150ml.Depress at 20-30 Ba Qing, stir 60min.Cinnamic acid conversion ratio 65%, cinnamyl alcohol selectivity 87%.
Embodiment 12 (comparing embodiment): with 2%Ru/C catalyst (specific surface 850m
2/ g) replace the catalyst of embodiment 10 preparations, and carry out catalytic hydrogenation under embodiment 11 same reaction conditions.Cinnamic acid conversion ratio 35%, cinnamyl alcohol selectivity 54%.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on those skilled in the art according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (5)
1. the catalyst of a selective liquid-phase hydrogenation is characterized in that composition comprises: structurized base material, nano-material coating and metal active constituent; Wherein structurized base material is an inorganic substrate: metal foam, ceramic honeycomb, carbon felt or ceramic fibre; Nano-material coating refers to carbon nano-fiber; Metal active constituent is one or more metals in nickel, ruthenium, rhodium, palladium and the platinum.
2. prepare the method for the catalyst of the described a kind of selective liquid-phase hydrogenation of claim 1, it is characterized in that: (1) is processed into different shape according to the reactor size size with described inorganic substrate; (2) with above-mentioned moulding material through washing, drying, obtain the structuring base material; (3) with one or more metal impregnations in chosen from Fe, cobalt, the nickel on the structuring base material, make activation structuring base material; (4) growing nano carbon fiber on activation structuring base material makes structuring made from compound Nano carbon fiber material by pyrolytic low-carbon alkanes or alkene; (5) be carrier with above-mentioned structuring made from compound Nano carbon fiber material, one or more metal active constituents that are selected from nickel, ruthenium, rhodium, palladium and the platinum are dispersed on the carrier.
3. method as claimed in claim 2 is characterized in that described structurized base material is processed into cellular, cylindric or sheet.
4. method as claimed in claim 2 is characterized in that: metal active constituent is a nickel in the step (5), nickeliferous 1～20wt% in the catalyst of wherein said selective liquid-phase hydrogenation.
5. method as claimed in claim 2 is characterized in that: metal active constituent is ruthenium, rhodium, palladium and/or platinum in the step (5), and the amount that contains ruthenium, rhodium, palladium and/or platinum in the catalyst of wherein said selective liquid-phase hydrogenation is 0.01～15wt%.
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| CN101185904B true CN101185904B (en) | 2011-01-19 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295531B (en) * | 2011-09-05 | 2013-09-18 | 浙江新和成股份有限公司 | Method for preparing citronellol by using hydrogenating citral |
| RU2547258C1 (en) * | 2014-01-09 | 2015-04-10 | Александр Адольфович Ламберов | Catalyst for selective hydrogenation of acetylene and diene hydrocarbons in c2-c5+-hydrocarbon fractions |
| CN104785295B (en) * | 2015-03-18 | 2018-03-06 | 杭州创培信息科技有限公司 | A kind of preparation method of high selectivity dopamine platinum carbon catalyst |
| CN105214655B (en) * | 2015-09-25 | 2017-07-28 | 北京化工大学 | A kind of preparation and application of non-loaded metallic catalyst |
| CN107442149A (en) * | 2016-05-31 | 2017-12-08 | 中国科学院金属研究所 | The foaming structure catalyst reacted for benzaldehyde Hydrogenation for phenmethylol and preparation |
| CN108794314A (en) * | 2017-04-28 | 2018-11-13 | 山东新和成药业有限公司 | A kind of method of citral hydrogenation synthesis citronellal |
| CN108610236B (en) * | 2018-04-20 | 2021-12-07 | 南京工业大学 | Method for improving selectivity of citronellal synthesized by hydrogenation |
| CN113546645B (en) * | 2021-09-23 | 2021-12-14 | 苏州欣诺科生物科技有限公司 | Ruthenium-iron bimetallic catalyst and preparation method and application thereof |
| CN115337936A (en) * | 2022-10-18 | 2022-11-15 | 无锡威孚环保催化剂有限公司 | Preparation of PtCo/C catalyst and method for catalyzing selective hydrogenation of alpha, beta-unsaturated aldehyde by using PtCo/C catalyst |
Citations (2)
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|---|---|---|---|---|
| CN1397490A (en) * | 2001-12-28 | 2003-02-19 | 南京师范大学 | Carbon atom wire and process for preparing carbon nanotube and carbon atom wire by pyrolyzing solid-state carbon source |
| CN1883807A (en) * | 2004-06-22 | 2006-12-27 | 三星Sdi株式会社 | Method of preparing catalyst for manufacturing carbon nanotubes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397490A (en) * | 2001-12-28 | 2003-02-19 | 南京师范大学 | Carbon atom wire and process for preparing carbon nanotube and carbon atom wire by pyrolyzing solid-state carbon source |
| CN1883807A (en) * | 2004-06-22 | 2006-12-27 | 三星Sdi株式会社 | Method of preparing catalyst for manufacturing carbon nanotubes |
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Address after: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee after: Jiangsu Polytechnic University Address before: 213016 Department of science and technology, Jiangsu Polytechnic University, Baiyun Road, Jiangsu, Changzhou Patentee before: Jiangsu Polytechnic University |
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