CN102553608A - Supported hydrogenation catalyst as well as preparation method and application thereof - Google Patents
Supported hydrogenation catalyst as well as preparation method and application thereof Download PDFInfo
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- CN102553608A CN102553608A CN201010605814XA CN201010605814A CN102553608A CN 102553608 A CN102553608 A CN 102553608A CN 201010605814X A CN201010605814X A CN 201010605814XA CN 201010605814 A CN201010605814 A CN 201010605814A CN 102553608 A CN102553608 A CN 102553608A
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Abstract
The invention discloses a supported hydrogenation catalyst as well as a preparation method and application thereof, belonging to the technical field of catalysis. The supported hydrogenation catalyst mainly comprises nickel, molybdenum and an aluminium oxide, wherein the nickel and the molybdenum are used as active components, the aluminum oxide is used as a supporter, one or more of carbonate and rare earth oxides are used as assistants, and the catalyst is prepared by using a dipping method. The catalyst is high in strength, low in stacking density, wide in operating temperature range and particularly suitable for a continuous reaction process for preparing decalin at one step through naphthalene hydrogenation at low pressure. The catalyst provided by the invention is used for naphthalene hydrogenation reaction under the reaction conditions that the pressure ranges from normal pressure to 5Mpa, the reaction temperature is 180-240 DEG C and the liquid control speed is 0.3-1.0h<-1>, the reaction is carried out in a fixed bed reactor, a decalin product is obtained through continuous reaction, and the conversion rate of naphtalin is up to over 99%.
Description
Technical field: the invention belongs to catalyst technical field, be specifically related to a kind of aromatic hydrocarbon hydrogenation catalyst.Be specially adapted to the tandem reaction sequence of low pressure naphthalene hydrogenation preparing decahydronaphthalene.
Background technology: decahydronaphthalene is claimed naphthalane again, is a kind of good high boiling organic solvent, can dissolve some macromolecular compound.The solvent that also can be used as coating is used to extract fat and wax, replaces turpentine oil to be used for the manufacturing of shoe polish, floor wax.Can be made into mixture with benzene and ethanol, can be used as the fuel of internal combustion engine, German useful decahydronaphthalene steam is made the report that torpedo drives.But decahydronaphthalene is catalytic hydrogenolysis under appropraite condition, emits pure hydrogen, is the good storage hydrogen medium of automobile fuel battery.
German Afflliated Company (Degussa AG) is abroad only arranged, European Chemos GmbH, du pont company, Dow Chemical Ltd, several companies such as Sigma-Aldrich produce the decahydronaphthalene product, and it costs an arm and a leg.Method through naphthalene hydrogenation preparing decahydronaphthalene all has research work both at home and abroad always; " two step of naphthalene hydrogenation reaction is made the method for decahydronaphthalene " its method of having reported among the Japan Patent JP160515A is: naphthalene first step hydrogenation generates naphthane; After the product rectifying separation, second step generated decahydronaphthalene by the naphthane hydrogenation.Chinese patent CN101658804A; A kind of preparation method and application thereof of high-performance supported metal silicide catalyst are disclosed; Carbonyls and organo-silicon compound are made the organic silicide presoma of metal that raw material obtains after low-temp reaction and distillation are purified; The organic silicide presoma of the metal that will distil loads on the carrier through the fluid bed metal organic chemical vapor deposition; Prepare high-performance supported metal silicide catalyst, can be used for the heterogeneous hydrogen catalysis reaction of relating to, like the selective hydrogenation of naphthalene hydrogenation, alkynes or diene etc.Wherein the product of naphthalene hydrogenation is a naphthane.
It is the loaded catalyst of active phase with low content, small size nano metal that a kind of employing is provided among the CN101602644A, the method for under lower pressure and temperature, synthesizing decahydronaphthalene by one step of naphthalene.Naphthalene and cyclohexane mixing are placed in the autoclave, add catalyst, reaction under 2MPa～5MPa, the conversion ratio of naphthalene reaches 100%, and the yield of decahydronaphthalene is up to 99%.Method for preparing catalyst: after the slaine of nickel dissolved, add γ-Al in water
2O
3, to going out clear liquid, drying gets catalyst precursor, with using after the catalyst reduction.In CN1546442A; Adopt naphthane as the solvent of solid raw naphthalene material, to adopt nickel catalyst technology of synthetic decahydronaphthalene of a step in the agitated reactor under lower pressure and temperature, its reaction pressure be that 6～12MPa, reaction temperature are 180 ℃～220 ℃, volume space velocity (LHSV) is 0.5h during liquid
-1～1.0h
-1, the conversion ratio of naphthalene reaches more than 98%, and the productive rate of decahydronaphthalene reaches 98%, and the side reaction thing is less than 1%.Above-mentioned patent is one-step method and makes decahydronaphthalene, though employed catalyst conversion ratio selectivity is all very high, the consersion unit that adopts is tank reactor, and reaction pressure is high, can not produce continuously.
Summary of the invention: the technical problem that the present invention will solve provides a kind of support type aromatic hydrocarbon hydrogenation catalyst.Be specially adapted to the reaction of low pressure naphthalene hydrogenation system decahydronaphthalene, in continuous fixed bed reaction or continuous.
Catalyst of the present invention is carrier with the aluminium oxide, is active constituent with metallic state and oxidation state nickel molybdenum, and adds auxiliary agent, compares with simple supporter nickel catalyst, can reduce reaction pressure significantly.Adopt catalyst of the present invention can one step of naphthalene hydrogenation be obtained decahydronaphthalene.And be reflected under the reaction condition that comparatively relaxes and carry out, therefore both reduced energy consumption, reduced the requirement of course of reaction again, the insecurity of having avoided operation with high pressure to bring equipment.This is reflected at fixed bed reactors and carries out successive reaction simultaneously, and the course of reaction air speed is higher, remarkable in economical benefits.
Technical scheme of the present invention realizes through following approach:
Catalyst of the present invention mainly is made up of the oxide of nickel, molybdenum and aluminium, is active constituent with nickel, molybdenum, and aluminium oxide is a carrier, is auxiliary agent with in carbonate, the rare earth oxide one or more; With the total catalyst weight is benchmark, and in weight content, alumina content is 60%～90%, and nickel oxide content is 5%～30%, and molybdenum oxide 1%～10%, auxiliary agent are 0.1%～1.0%; Specific area 150～the 400m of catalyst
2/ g, pore volume are 0.5～0.8ml/g.
This catalyst adopts the impregnation technology preparation, comprises preparing carriers and Preparation of Catalyst two parts.
Preparing carriers: the weight ratio of aluminium oxide and auxiliary agent in the carrier, aluminium oxide: auxiliary agent is 100: (0.1～2.0), and at room temperature aluminium oxide and auxiliary agent are mixed the adding ionized water by required weight, through steps such as overmulling stone roller, granulation, compressing tablet, calcinings, make carrier.The calcining heat of carrier is 400～800 ℃, and the time is 1～10 hour.
Described auxiliary agent is one or more in Na, K, La, Ce, Mg, the Ca oxide; Or a kind of in sodium carbonate or the potash.
Preparation of Catalyst:
1) get nickel nitrate crystal, ammonium molybdate crystal respectively, add low amounts of water, heating (50 ℃～90 ℃) is dissolved to nickel nitrate, ammonium molybdate fully;
2) with the carrier of above-mentioned preparation, immerse in the nickel nitrate solution of step 1), flooded 10～100 minutes, take out, drain, constant temperature slaking 1～10 hour, drying is 2～12 hours under 80 ℃～200 ℃, under 200 ℃～600 ℃, calcines 2～10 hours.
3) will be set by step 2) catalyst intermediate for preparing, immerse again in the solution of step 1) ammonium molybdate, flood taking-up 10～100 minutes; Drain, constant temperature slaking 1～10 hour, drying is 2～12 hours under 80 ℃～200 ℃; Under 200 ℃～600 ℃, calcined 2～10 hours, promptly get catalyst.
This catalyst is preferably calcined after drying.In calcination process, metallic compound mainly decomposes to generate stays metal and/or the metal oxide in the catalyst.Calcining heat usually in 200 ℃～600 ℃ scopes, preferred 300 ℃～500 ℃, common 2～10 hours of calcination time.Promptly get catalyst of the present invention.
Before catalyst of the present invention is used for hydrogenation reaction, carry out preparatory activating and reducing earlier, the oxygenate conversion that makes active component is a metallic state.Reducing atmosphere adopts hydrogen or hydrogen-containing gas.
The application process of naphthalene hydrogenation preparing decahydronaphthalene provided by the invention is: adopt decahydronaphthalene or naphthane as the solvent of solid raw naphthalene material, through after the preheating furnace preheating; Get into and carry out the liquid-phase hydrogenatin reaction in the fixed bed reactors; This reaction is successive reaction; Reaction condition is gentle, and pressure is that normal pressure～5MPa, reaction temperature are 180 ℃～240 ℃, volume space velocity (LHSV) is 0.3h during liquid
-1～1.0h
-1, the conversion ratio of naphthalene reaches more than 99%.
The specific embodiment: the present invention is done to describe in further detail through following examples:
Embodiment 1: preparation catalyst 1
Get commercially available high purity aluminium oxide 100g, get 1.2g sodium carbonate, soluble in waterly be made into certain density sodium carbonate liquor; Sodium carbonate liquor is added mixed the stone roller 50 minutes in the aluminium oxide; Granulation then, compressing tablet, calcining, calcining heat are 400 ℃～800 ℃, and the time is to make carrier A in 1 hour～10 hours.
Get nickel nitrate crystal, ammonium molybdate crystal respectively, place 90 ℃ of temperature water-bath heating,, get solution B, C to dissolving fully.
With carrier A, immerse in 90 ℃ of solution B of constant temperature, flooded 10～100 minutes; Take out, drain and place another beaker to place 90 ℃ of temperature constant temperature water baths slaking 1～10 hour, again 80 ℃～200 ℃ dry 2～12 hours down; Calcined 2～10 hours down at 200 ℃～600 ℃ at last; Get catalyst intermediate, repeat said method dipping solution C again, promptly get catalyst 1.The setting of the concentration of metal compound solution should make catalyst finally contain 19% nickel oxide in the dipping solution, 1.2% molybdenum oxide, 0.15% auxiliary agent/aluminium oxide.(all being weight percentage)
Embodiment 2, preparation catalyst 2
Repeat embodiment 1, the concentration that changes metallic compound in the dipping solution is set, and makes catalyst finally contain 19.4% nickel oxide, 4.3% molybdenum oxide, 0.20% auxiliary agent/aluminium oxide.(all being weight percentage)
Embodiment 3, preparation catalyst 3
Repeat embodiment 1, the concentration that changes metallic compound in the dipping solution is set, and makes catalyst finally contain 25.5% nickel oxide, 1.1% molybdenum oxide, 0.20% auxiliary agent/aluminium oxide.(all being weight percentage)
Embodiment 4, preparation catalyst 4
Repeat embodiment 1, the concentration that changes metallic compound in the dipping solution is set, and makes catalyst finally contain 25% nickel oxide, 4.0% molybdenum oxide, 0.22% auxiliary agent/aluminium oxide.(all being weight percentage)
Above-mentioned catalyst carries out activity rating on original catalyst particle size pressurization evaluating apparatus.Appreciation condition is following:
1. catalyst reduces with following condition:
Catalyst loading amount: former granularity 90mL
Reducing gases: high-purity hydrogen
Reduction pressure: normal pressure
Reduction temperature: 380 ℃～400 ℃
Hydrogen air speed: 1000h
-1～1500h
-1
2. catalyst carries out activity rating with following condition:
Pressure: 1.0MPa～2.0MPa
Reaction temperature: 200 ℃～220 ℃
Liquid air speed: 0.5h
-1
3. under these conditions naphthalene conversion ratio % such as following table
| Numbering | Naphthalene conversion ratio % |
| Embodiment 1 | 99.0 |
| Embodiment 2 | 99.2 |
| Embodiment 3 | 99.0 |
| Embodiment 4 | 99.4 |
Claims (6)
1. load hydrogenation catalyst is characterized in that it mainly is made up of the oxide of nickel, molybdenum and aluminium, is active constituent with nickel, molybdenum, Al
2O
3Being carrier, is auxiliary agent with in carbonate, the rare earth oxide one or more, is benchmark with the total catalyst weight; In weight content; Alumina content is 60%～90%, and nickel oxide content is 5%～30%, molybdenum oxide 1%～10%; Auxiliary agent is 0.1%～1.0%, the specific area 150～400m of catalyst
2/ g, pore volume are 0.5～0.8ml/g.
2. Preparation of catalysts method according to claim 1; It is characterized in that catalyst adopts the impregnation technology preparation; Comprise preparing carriers and Preparation of Catalyst two parts, the method for making of said carrier comprises following process: aluminium oxide and auxiliary agent are mixed the adding ionized water by required weight, and the weight ratio of aluminium oxide and auxiliary agent is 100: (0.1～2.0); Through overmulling stone roller, granulation, compressing tablet, calcining, make carrier; The calcining heat of carrier is 400 ℃～800 ℃, and the time is 1～10 hour; Dipping process may further comprise the steps:
1) gets nickel nitrate crystal, ammonium molybdate crystal respectively, add low amounts of water, heat 50 ℃～90 ℃, dissolve fully to nickel nitrate, ammonium molybdate;
2) with the carrier of above-mentioned preparation, immerse in the nickel nitrate solution of step 1), flooded 10～100 minutes, take out, drain, constant temperature slaking 1～10 hour, drying is 2～12 hours under 80 ℃～200 ℃, under 200 ℃～600 ℃, calcines 2～10 hours;
3) will be set by step 2) catalyst intermediate for preparing, immerse again in the solution of step 1) ammonium molybdate, flood taking-up 10～100 minutes; Drain, constant temperature slaking 1～10 hour, drying is 2～12 hours under 80 ℃～200 ℃; Under 200 ℃～600 ℃, calcined 2～10 hours, promptly get catalyst.
3. catalyst according to claim 1 is characterized in that said auxiliary agent is one or more in Na, K, La, Ce, Mg, the Ca oxide.
4. Application of Catalyst according to claim 1 is characterized in that before being used for hydrogenation reaction carry out preparatory activating and reducing earlier, the oxygenate conversion that makes active component is a metallic state, and reducing atmosphere adopts hydrogen or hydrogen-containing gas.
5. Application of Catalyst according to claim 1, it is characterized in that being used for the naphthalene is catalytic material hydrogenation preparing decahydronaphthalene, to adopt decahydronaphthalene or naphthane be the solvent of solid raw naphthalene material, in fixed bed reactors in the technology of the synthetic decahydronaphthalene of successive reaction.
6. like the said Application of Catalyst of claim 5, it is characterized in that reaction pressure is normal pressure～5MPa, reaction temperature is 180 ℃～240 ℃, volume space velocity (LHSV) is 0.3h during liquid
-1～1.Oh
-1, the conversion ratio of naphthalene reaches more than 99%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941093A (en) * | 2012-09-26 | 2013-02-27 | 中国科学院山西煤炭化学研究所 | Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation |
| CN103285886A (en) * | 2013-03-07 | 2013-09-11 | 中国石油大学(华东) | Catalyst for synthesis of decalin by one-step hydrogenation of naphthalene and method thereof |
| CN104128185A (en) * | 2014-07-07 | 2014-11-05 | 中国科学院山西煤炭化学研究所 | Tetralin synthesis catalyst, and preparation method and application thereof |
| CN107597108A (en) * | 2017-09-21 | 2018-01-19 | 西南化工研究设计院有限公司 | A kind of naphthane Hydrogenation is for catalyst of decahydronaphthalene and its preparation method and application |
| CN107626344A (en) * | 2017-10-27 | 2018-01-26 | 西南化工研究设计院有限公司 | A kind of catalyst, preparation and the application of crude naphthalene Hydrogenation naphthane and decahydronaphthalene |
| CN108325517A (en) * | 2018-01-18 | 2018-07-27 | 中国石油大学(华东) | A kind of catalyst and preparation method thereof for naphthalene selective hydrogenation production naphthane |
| CN109647457A (en) * | 2018-12-06 | 2019-04-19 | 中国科学院山西煤炭化学研究所 | A kind of naphthalene adds the catalyst and preparation method and application of hydrogen naphthane and decahydronaphthalene |
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| CN1733663A (en) * | 2005-08-10 | 2006-02-15 | 中国石油化工集团公司 | Decahydronaphthalene continuous hydrogenation synthesis method |
| CN101147871A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel catalyst for selective hydrogenation |
| CN101230289A (en) * | 2007-01-23 | 2008-07-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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| CN1733663A (en) * | 2005-08-10 | 2006-02-15 | 中国石油化工集团公司 | Decahydronaphthalene continuous hydrogenation synthesis method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941093A (en) * | 2012-09-26 | 2013-02-27 | 中国科学院山西煤炭化学研究所 | Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation |
| CN103285886A (en) * | 2013-03-07 | 2013-09-11 | 中国石油大学(华东) | Catalyst for synthesis of decalin by one-step hydrogenation of naphthalene and method thereof |
| CN104128185A (en) * | 2014-07-07 | 2014-11-05 | 中国科学院山西煤炭化学研究所 | Tetralin synthesis catalyst, and preparation method and application thereof |
| CN107597108A (en) * | 2017-09-21 | 2018-01-19 | 西南化工研究设计院有限公司 | A kind of naphthane Hydrogenation is for catalyst of decahydronaphthalene and its preparation method and application |
| CN107597108B (en) * | 2017-09-21 | 2019-10-18 | 西南化工研究设计院有限公司 | A kind of naphthane adds hydrogen to prepare catalyst of decahydronaphthalene and its preparation method and application |
| CN107626344A (en) * | 2017-10-27 | 2018-01-26 | 西南化工研究设计院有限公司 | A kind of catalyst, preparation and the application of crude naphthalene Hydrogenation naphthane and decahydronaphthalene |
| CN108325517A (en) * | 2018-01-18 | 2018-07-27 | 中国石油大学(华东) | A kind of catalyst and preparation method thereof for naphthalene selective hydrogenation production naphthane |
| CN108325517B (en) * | 2018-01-18 | 2020-10-09 | 中国石油大学(华东) | Catalyst for producing tetrahydronaphthalene by naphthalene selective hydrogenation and preparation method thereof |
| CN109647457A (en) * | 2018-12-06 | 2019-04-19 | 中国科学院山西煤炭化学研究所 | A kind of naphthalene adds the catalyst and preparation method and application of hydrogen naphthane and decahydronaphthalene |
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Application publication date: 20120711 |