CN100376323C - A kind of metal foam hydrogenation catalyst and its preparation method and application - Google Patents
A kind of metal foam hydrogenation catalyst and its preparation method and application Download PDFInfo
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- CN100376323C CN100376323C CNB200410096609XA CN200410096609A CN100376323C CN 100376323 C CN100376323 C CN 100376323C CN B200410096609X A CNB200410096609X A CN B200410096609XA CN 200410096609 A CN200410096609 A CN 200410096609A CN 100376323 C CN100376323 C CN 100376323C
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- hydrogenation catalyst
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Abstract
The present invention discloses a foam metal hydrogenation catalyst, a preparing method thereof and application thereof. The hydrogenation catalyst of the present invention comprises foam metal carriers and effective quantities of noble metal active constituents loaded on the carriers, wherein the carriers can be prepared through a powder metallurgical method; the active constituents are loaded through a chemical plating method and are uniformly distributed on the outer surfaces of pore canals of the foam carriers. The catalyst of the present invention has the advantages of high catalytic activity, firm combination between the active constituents and the carriers, good stability, simple preparation processes, high porosity of the carriers, uniform pore diameter distribution, large specific surface area, small specific weight, high mechanical strength and good heat conduction performance. In addition, the catalyst also provides sufficient gas-liquid contacting area, benefits the mass transfer between a gas phase and a liquid phase, has the capability of application to catalytic distillation technology, and has excellent effects of reaction and separation.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and its production and application, concrete, relating to a kind of is the hydrogenation catalyst and its production and application of matrix carried noble metal active component with the foam metal.
Background technology
Foam metal is the new material that a kind of internal structure contains a large amount of holes, not only has the feature of porous materials such as density is low, porosity is high, specific surface is big, also has the fundamental characteristics of metals such as the strong and good heat conductivity of mechanical strength height, toughness.In chemical field, foam metal useful as catalysts carrier.Foam metal carrier can make catalyst activity component high degree of dispersion, can bring into play catalytic action more fully, and its heat conductivility is far superior to ceramic catalyst carrier.In addition, foam metal itself also can directly be used as catalyst.
The preparation method of foam metal is a lot, and as powder metallurgic method, foam melt method, seepage flow casting, galvanoplastic, bubble method, sputter deposited method, sintering process or the like, powder metallurgic method just is widely used at present.It is that aluminium powder or Al alloy powder are mixed with a kind of blowing agent powder that common powder metallurgic method prepares foamed aluminium, this mixture is pressed into closely knit metallic matrix, then to its heat temperature raising, rise to when temperature more than the fusing point of aluminium powder or Al alloy powder, blowing agent decomposes the gas that produces and forms countless pores in the aluminum or aluminum alloy inside of molten condition, after cooling off this aluminum substrate, can obtain the foamed aluminium product.
A kind of hydrogenation catalyst of function admirable not only requires to have big specific surface and high catalytic activity, also good heat-conducting will be arranged.For the hydrogenation reaction of strong heat release, the heat conductivility of catalyst is extremely important, in time removes reaction heat and can avoid the too high generation focus of temperature, avoids the generation of side reaction.Foam metal receives publicity in field of hydrogenation with himself characteristic.
CN1109922A discloses a kind of spongy foam nickel, and this nickel foam mainly as battery terminal, also can be used as hydrogenation catalyst.Preparation process comprises the substrate alligatoring, makes of magnetically controlled sputter method and electroplate with processes such as negative electrode, nickel plating, heat treatments.The advantage of this invention is that the nickel monoblock that makes is continuous, and purity is higher, and has reduced environmental pollution.But adopt this kind method to need high-temperature process, the preparation process complexity, cost is higher, and nickel is during as catalyst for hydrogenation, and activity is lower.
CN1152475A discloses the high-ferromagnetic non-crystalline alloy catalyst of a kind of nickeliferous, iron and phosphorus.This catalyst has the nickel of 45～91wt%, the iron of 2～40wt% and the phosphorus of surplus.This catalyst not only has higher activity, has higher ferromagnetism again, is suitable for magnetically stabilized bed reactor.But its specific area is only at 0.01-10m
2/ g, this has just limited its catalytic activity; And need externally-applied magnetic field to be fixed when placing in the magnetically stabilized bed reactor, limited its application.
CN1171749A discloses a kind of porous metals hydrogenation catalyst of the alloy based on aluminium and transition metal, it mediates alloy material and assistant, make mould again and carry out roasting, with the mechanograph after the alkali metal hydroxide processing roasting, the aluminium that dissolving is removed wherein obtains catalyst then.This preparation method has simplified original technology of preparing, has saved the adding of mineral oil, but adopting this method to prepare catalyst can produce a large amount of waste liquids, pollute.And transition metal is present in the metallic object in a large number, and can not bring into play catalytic action, causes catalyst activity lower.
It is the Preparation of catalysts method of carrier with porous metals that W02000067903 discloses a kind of.Adopt earlier hot smelting legal system to be equipped with the alloy of metal such as al and ni, wash with aqueous slkalis such as NaOH or potassium hydroxide again,, generate Lacunaris metal carrier to remove the aluminium in the alloy, again carrier is contacted absorption with the aqueous slkali of noble metal, with water-soluble solvent carrier is washed at last.Adopting the method to prepare catalyst can the multiple auxiliary agent of load, and range of application is wider.But preparation process can produce a large amount of waste liquids, easily pollutes, and active constituent loading intensity is not high, easily runs off.
When the preparation metal carrier catalyst, can adopt the method for chemical plating that active layer is loaded on the carrier.Electroless plating technology has that thickness of coating is even, porosity is low, can be on nonmetal deposition, and characteristics such as plating, covering power deeply preferably, the application in industry is increasingly extensive in recent years.
Summary of the invention
The object of the present invention is to provide the novel hydrogenation catalyst that a kind of preparation process is simple, catalytic performance is good.
Catalyst of the present invention is carrier with the foam metal, is active component with the noble metal; And have low-density, Large ratio surface, high porosity and good heat-conducting, active constituent loading is firm, the catalytic activity height.This Preparation of catalysts process is simple, is easy to realize industrialization.
Hydrogenation catalyst of the present invention specifically comprises foam metal carrier, is carried on the noble metal active component of the effective dose on the carrier.
Described carrier is selected from a kind of in foamed aluminium and the aluminium alloy; Preferred described carrier is for adopting the foamed aluminium of powder metallurgic method preparation.Preferred described carrier satisfies: porosity is 60-85%, and the aperture is 5-15 μ m.Satisfy the foamed aluminium and the equal useful as catalysts carrier of aluminium alloy of above-mentioned requirements.
Foamed aluminium that the present invention is used and aluminium alloy can use method commonly known in the art to prepare.
Preferred described noble metal active component comprises and is selected from silver, gold, rhenium, ruthenium, rhodium, palladium and the platinum one or more.
Preferred described noble metal active component mainly is distributed on the inner/outer hole surface of foam carrier, is evenly distributed, and its decentralization is 40-50%.Decentralization is the parameter that is used for characterizing catalyst surface active component degree of scatter, is the coverage rate of active component at catalyst surface.
Preferred described noble metal active components contents is 0.01-0.1wt%, with the total restatement of catalyst.
Preferred described noble metal active component adopts electroless plating method to be carried on the carrier, and the catalyst that obtains is active high, and active component combines firmly with foam metal carrier.
Hydrogenization catalyst preparation method of the present invention may further comprise the steps:
1) preparation foam metal carrier
For 200-250 purpose spraying metal powder is a raw material, adopting diameter in ball mill is the steel ball of 5mm, and metal powder and pore forming agent are made mixed powder through mixing and ball milling, carries out moulding compacting, sintering, pore-creating then, obtains foam metal carrier with the particle diameter;
The pore forming agent that the present invention uses can be selected from and can be preferably NaCl by the water-soluble slaine of removing of separating.
2) preparation hydrogenation catalyst
Earlier foam metal carrier is immersed the solution that contains active component, impregnated carrier is immersed again carry out the chemical plating active component in the chemical plating fluid then.
The used electroless plating method of the present invention can use any method commonly known in the art.In prior art, chemical plating fluid that electroless plating method is used and process conditions are applicable to preparation catalyst of the present invention.
The described solution that contains active component can be the salting liquid of noble metal, as PdCl
2Deng.
Hydrogenation catalyst of the present invention can be used in hydrogenation reaction and the catalytic distillation reaction.As hydrogenation of unsaturated hydrocarbons, processes such as c 3 fraction catalytic distillation.
Hydrogenation catalyst of the present invention has following advantage:
1) hydrogenation catalyst of the present invention is made up of foam metal carrier and active component, and carrier has the high and big advantage of specific area of porosity, and active component is evenly distributed.
2) hydrogenation catalyst of the present invention is carrier with the foam metal, has high specific surface, excellent mechanical intensity heat conductivility, can be applicable in the hydrogenation reaction of strong heat release.
3) adopt powder metallurgic method to prepare foamed aluminium, technology is simple, and cost is lower, and equipment investment is few, and the material connectedness is good, and shape is controlled, is suitable for making catalyst carrier.
4) with foamed aluminium as catalyst carrier for hydrgenating, in high-temperature calcination process, can generate one deck oxide on the foamed aluminium top layer, catalyst activity components such as palladium are easier to combine with carrier, give full play to the catalytic action to hydrogenation reaction.
5) adopt electroless plating method supported catalyst active component, component mainly is distributed in the inside and outside surface of foamed material, is evenly distributed, and method is simple and easy to control.
6) new catalyst of the present invention can provide the place of sufficient gas-liquid contact mass transfer, not only has higher hydrogenation catalyst performance, also has stronger centrifugation, can be used for preparing catalytic distillation structure, is applied in the catalytic distillation reaction.
The specific embodiment
Embodiment 1
With the noble metal active component is palladium, and the preparation process of hydrogenation catalyst of the present invention is described in detail in detail:
1) preparation foamed aluminium carrier
1, adopting particle diameter is raw material for 200-250 purpose spraying aluminium powder (industrial products);
2, powder process: with particle diameter is the NaCl powder of 0.125mm, dry 2h in baking oven;
3, mix: is that 2: 1: 10 ratio is weighed with aluminium powder, pore forming agent NaCl powder, steel ball with mass ratio, joins in the Universal ball grinding machine and sealing, charges into N
2Protection, the mixing rotating speed is 120r/m, incorporation time 1h makes mixed powder;
4, moulding compacting: the powder that mixes is put into hydraulic press suppress, pressure 300～500MPa, pressing speed 0.05m/s～0.02m/s, dwell time 3～5min;
5, sintering: the sample after the compression moulding is put into the Muffle furnace sintering, and 600 ℃ are incubated 90～150min down;
6, pore-creating: the sample behind the sintering is put into water, remove pore forming agent NaCl with dissolving, make the foamed aluminium carrier, porosity is 75%, and average pore size is 10 μ m.
2) preparation hydrogenation catalyst
1, soaking palladium: with 1) the foamed aluminium carrier 250g that obtains immerses in the 200ml palladium solution solution composition and process conditions: hydrofluoric acid (HF) 170ml/L, boric acid (H
3BO
3) 65g/L, palladium (PdAC
2) 70g/L, 40 ℃ of temperature, 30 seconds time;
2, chemical palladium-plating: the sample that will flood palladium immerses in the 500ml chemical plating fluid and carries out chemical palladium-plating, and chemical plating fluid is formed and process conditions: PdCl
22g/L, NH
4Cl 27g/l, NH
3H
2O (28%) 150ml/l, HCl (38%) 4ml/l, NaH
2PO
2H
2O 12g/l, pH 9.8 ± 0.1,42～58 ℃ of temperature, time 2min;
3, behind the sample plating palladium, place baking oven inner drying 3h, promptly getting palladium content is the foamed aluminium catalyst of 0.07wt%, and the decentralization of palladium is 46.5%.
Embodiment 2
With the catalyst that embodiment 1 obtains, be applied in the reaction of butynediols hydrogenation generation butanediol.The porosity of foam carrier is 80%, and specific surface is about 50m
2/ g, catalytic active component is a palladium, catalyst is made the cylindrical shape of Ф 5 * 5mm.Normal pressure activity rating device adopts the blistering reaction pipe of a vertical Ф 20mm, and reaction tube places water bath with thermostatic control, and the front portion is provided with flowmeter.Earlier with H
2For source of the gas activates catalyst under 120 ℃, reduce to 80 ℃ again, add reactant liquor then, and feed H
2, keep under the condition of Hydrogen Vapor Pressure 3.5MPa and react.Behind certain hour, take a sample, adopt the gas chromatograph analysis.The result shows that the conversion per pass of butynediols reaches 80%, and selectivity reaches 85%.
Embodiment 3
Adopt the method for embodiment 1, prepare foamed aluminium catalyst of the present invention.The porosity of foam carrier is 72%, average pore size 10 μ m, the about 80m of specific surface
2/ g, its main active constituent is Pt, and content is 0.085%, and the decentralization on carrier is 48.7%, catalyst is made the cylinder of Ф 3 * 3mm;
Above-mentioned catalyst is applied in the hydrogenation reaction of reforming raffinate oil, raw material mainly consists of C
5～C
8, 60～120 ℃ of boiling ranges, density 0.67～0.69g/cm
3, alkene mass fraction 1.5%～5.0%, aromatic hydrocarbons mass fraction 1.0%～3.0%, (every 100g oil generates the mg number of Br to bromine index 3500～5000, down together.); Hydrogen: general hydrogen level steel cylinder hydrogen.Get the 20ml catalyst, at operating pressure 0.2MPa, LHSV2.9h
-1, hydrogen to oil volume ratio is 340, under 180 ℃ of the reaction temperatures, can make the bromine index of hydrogenation products reduce to 10, the conversion of olefines rate is greater than 95%.
Embodiment 4
Adopt the method for embodiment 1 to make hydrogenation catalyst of the present invention, carrying the palladium amount is 0.05wt%, and the decentralization on carrier is 40%, carrier porosity 75%, average pore size 10 μ m, the about 80m of specific surface
2/ g makes catalyst the cylindrical shape of Ф 3 * 5mm.
Above-mentioned catalyst is used for the drippolene selective hydrogenation.With analogies styrene and cyclohexane mixture is raw material, wherein contains styrene 85% (molar content); Adopt the small-sized trickle bed of 10mL that catalyst is screened.Employing is accelerated method at 70 ℃ of reaction temperatures, pressure 1.8MPa, reaction time 4h, air speed 40h
-1, hydrogen to oil volume ratio 720 (excessive) condition under catalyst of the present invention is estimated, cinnamic conversion ratio can reach 70%.
Embodiment 5
Hydrogenation catalyst of the present invention can be prepared into the catalytic distillation filler that is of a size of Ф 100 * 50mm, is applied to the c 3 fraction catalytic distillation and selects in hydrogenation and removing propine and allene (MAPD) technology.
The method of employing embodiment 1 obtains carrying the foam metal of palladium, and the carrier porosity is 75%, the about 70m of specific surface
2/ g, palladium content are 0.08wt%, and the palladium decentralization is 78%, are made into the cylinder that is of a size of Ф 100 * 50mm, promptly get the catalytic distillation filler.The filler member that makes is packed in the Ф 100mm catalytic distillation tower conversion zone.Catalytic distillation tower height 6m divides rectifying section, conversion zone and stripping section, the high 5m of rectifying section and stripping section, the random packing of filling φ 6 * 6mm stainless steel cannon ring; The high 1m of conversion zone, the metal catalytic that makes of packing into altogether distills 20 of fillers.Raw material feeds from the conversion zone bottom, and cat head obtains product.Feed composition is as shown in the table.
| Component | C 2 0 | C 3 0 | C 3 ＝ | C 3 ＝＝ | C 3 ≡ | C 4 | C 5 |
| Mole fraction (%) | 0.02 | 2.50 | 72.14 | 1.08 | 2.09 | 19.43 | 2.72 |
At reaction temperature 40-50 ℃, reaction pressure 1.6-1.8MPa, liquid phase feeding volume space velocity 2h
-1, hydrogen alkynes is than testing under 1.1 the condition.The result shows that this catalytic distillation structure has good reaction and separating property, and by catalytic distillation, propine and allene content are reduced to below the 3ppm in the cat head discharging, and propene yield is up to 103%.
Claims (8)
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| CNB200410096609XA CN100376323C (en) | 2004-12-03 | 2004-12-03 | A kind of metal foam hydrogenation catalyst and its preparation method and application |
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|---|---|---|---|
| CNB200410096609XA CN100376323C (en) | 2004-12-03 | 2004-12-03 | A kind of metal foam hydrogenation catalyst and its preparation method and application |
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| CN1781595A CN1781595A (en) | 2006-06-07 |
| CN100376323C true CN100376323C (en) | 2008-03-26 |
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| CN103977840B (en) * | 2014-05-13 | 2016-06-15 | 中国科学院山西煤炭化学研究所 | A kind of high-termal conductivity catalyst carrier and preparation method and application |
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| CN114377685B (en) * | 2020-10-22 | 2024-02-27 | 上海迅凯新材料科技有限公司 | Nickel-based catalyst, preparation method and application thereof in hydrogenation synthesis of 1,3-butanediol |
| CN112908570A (en) * | 2021-01-22 | 2021-06-04 | 和骋新材料科技(上海)有限公司 | Special catalysis piece of enameling machine |
| CN114411179B (en) * | 2021-12-31 | 2024-09-06 | 西北工业大学 | Method for preparing 1, 4-butanediol by electrocatalytic hydrogenation of 1, 4-butynediol |
| CN115845854A (en) * | 2022-11-28 | 2023-03-28 | 高潞空气化工产品(上海)能源科技有限公司 | High-thermal-conductivity high-temperature-resistant catalyst and preparation method and application thereof |
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