WO2015131852A1 - 一种复合型催化剂及其制备方法 - Google Patents

一种复合型催化剂及其制备方法 Download PDF

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WO2015131852A1
WO2015131852A1 PCT/CN2015/073783 CN2015073783W WO2015131852A1 WO 2015131852 A1 WO2015131852 A1 WO 2015131852A1 CN 2015073783 W CN2015073783 W CN 2015073783W WO 2015131852 A1 WO2015131852 A1 WO 2015131852A1
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catalyst
raney
composite catalyst
raney alloy
weight
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PCT/CN2015/073783
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English (en)
French (fr)
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戴伟
鲁树亮
蒋海斌
王国清
张晓红
彭晖
乔金樑
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Priority to EP15758855.9A priority Critical patent/EP3115106A4/en
Priority to JP2016572882A priority patent/JP6532487B2/ja
Priority to RU2016139298A priority patent/RU2677479C2/ru
Priority to KR1020167026231A priority patent/KR102045973B1/ko
Priority to CN201580006968.8A priority patent/CN106029225B/zh
Publication of WO2015131852A1 publication Critical patent/WO2015131852A1/zh
Priority to US15/257,603 priority patent/US10661254B2/en
Priority to SA516371803A priority patent/SA516371803B1/ar
Priority to US16/853,006 priority patent/US11241676B2/en

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    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/02—Impregnation, coating or precipitation
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    • B01J37/084—Decomposition of carbon-containing compounds into carbon
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    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
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    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07C2525/02—Raney nickel

Definitions

  • the present invention relates to a composite catalyst and a preparation method thereof; more particularly, to a catalyst in which a Raney alloy particle is dispersed as a dispersed phase in a continuous phase and a preparation method thereof.
  • the "Rani method” is a process for the preparation of an active metal catalyst comprising: i) first preparing an alloy of two or more components containing an active metal, and ii) then at least one metal The components are extracted, leaving a metal having a relatively high catalytic activity and having a porous structure. Step ii) is also referred to as "activation.”
  • M. Raney first invented the Raney nickel catalyst (Industrial and Engineering Chemistry, 1940, Vol. 32, 1199), which was prepared by first preparing a nickel-aluminum alloy and then dissolving the alloy in a strong alkali solution. Aluminum element, leaving nickel metal with a porous structure and high catalytic activity.
  • Raney catalysts include Raney nickel catalysts, Raney cobalt catalysts, Raney copper catalysts, and the like, with Raney nickel catalysts being the most common.
  • Raney nickel catalysts are usually present in the form of powders, which are flammable and inconvenient to operate, and are mostly used in small-scale catalytic hydrogenation reactions in the field of fine chemicals, and cannot be used in general fixed bed reactions.
  • Patent application CN1557918 discloses a shaped Raney nickel catalyst and a preparation method thereof, which is composed of aluminum and one or more of Ni, Co, Cu and Fe, and an inorganic powder such as pseudo-boehmite.
  • a natural or synthetic organic substance such as phthalocyanine powder or carboxymethyl cellulose is used as a channel templating agent, which is directly kneaded, molded, calcined, and activated by a caustic solution.
  • the resulting catalyst has a certain shape and strength and can be used as a fixed bed catalyst.
  • No. 5,536,694 discloses a shaped, activated Raney metal fixed bed catalyst which is formed by molding at least one catalyst alloy powder, pure Raney metal powder as a binder, a forming aid and a porogen, followed by calcination and Alkali activation is obtained.
  • Patent US 4,826,799 discloses a method for preparing a shaped Raney catalyst, which comprises uniformly mixing a Raney alloy with a polymer, mineral oil, etc. at a certain temperature, and then molding by extrusion or the like, and forming a polymer after molding. The polymer is burned off or the polymer is retained, and finally the activated metal is obtained by dissolving the aluminum metal with a strong alkali.
  • the method can easily obtain a shaped catalyst, but if the high molecular polymer is retained, the Raney alloy is encapsulated or covered by the high molecular polymer during the molding process, and the catalytic activity point is small, and the catalytic activity is low or even inactive; Roasting the high molecular weight polymer will cause a considerable amount of particles to sinter, resulting in reduced activity.
  • Raney catalyst which is highly active, has good selectivity, and has good particle strength and can be used in a fixed bed.
  • An object of the present invention is to provide a composite catalyst comprising carbon as a continuous phase and Raney alloy particles as a dispersed phase, wherein the Raney alloy particles are uniformly or unevenly dispersed in the continuous phase carbon And as described therein as continuous
  • the carbon of the phase is obtained by carbonization of at least one carbonizable organic material.
  • the catalyst has the following advantages: the preparation process is simple, the catalyst product has less impurities, the active metal loading is high, the catalyst particle strength is good, and the activity is high and the selectivity is good for the hydrogenation reaction.
  • Another object of the present invention is to provide a method of preparing the catalyst comprising the steps of:
  • a curable composition formulating a curable composition, the curable composition or a cured product thereof comprising a carbonizable organic substance, and the curable composition may be in the form of a liquid, a gel, a paste or a powder;
  • step b mixing the Raney alloy particles with the curable composition obtained in step a, then curing the resulting mixture, and optionally pulverizing the solidified mixture to obtain a catalyst precursor;
  • the catalyst precursor obtained in the step b is carbonized at a high temperature to obtain a composite catalyst.
  • the activated catalyst is obtained by the above activation method.
  • Yet another object of the present invention is to provide for the use of the activated catalyst in hydrogenation, dehydrogenation, amination, dehalogenation or desulfurization reactions.
  • Figure 1 shows a scanning electron micrograph of the carbonized catalyst particles prepared in Example 6.
  • the present invention is directed to a composite catalyst comprising a continuous phase of carbon and a Raney alloy particle as a dispersed phase, wherein the Raney alloy particles are uniformly or non-uniformly dispersed in the continuous phase carbon, and wherein the carbon as the continuous phase is composed of at least one Carbonized organic matter obtained after carbonization.
  • the Raney alloy comprises at least one Raney metal and at least one element that can be leached.
  • Ranier metal refers to a metal that is insoluble, catalytically active when activated by the Raney method. Examples of Raney metals include, but are not limited to, nickel, cobalt, copper, and iron.
  • elements that can be leached refers to an element that can be dissolved when activated by the Raney method. Examples of elements that can be leached include, but are not limited to, aluminum, zinc, and silicon.
  • the Raney alloy is selected from the group consisting of nickel aluminum alloys, cobalt aluminum alloys, and copper aluminum alloys.
  • the weight ratio of Raney metal to leached element in the Raney alloy is from 1:99 to 10:1, preferably from 1:10 to 4:1, more preferably 1:3. -2:1, most preferably about 1:1.
  • the particle size of the Raney alloy particles can be selected within a wide range.
  • the average particle diameter may be from 0.1 to 1000 ⁇ m, preferably from 1 to 500 ⁇ m, more preferably from 10 to 100 ⁇ m.
  • At least one promoter may also be introduced into the Raney alloy to form a multicomponent Raney alloy.
  • the at least one promoter may be selected from the group consisting of Mo, Cr, Ti, Pt, Pd, Rh, and Ru.
  • the amount of the accelerator may be from 0.01% by weight to 5% by weight based on the total weight of the Raney alloy.
  • carbonizable organic matter refers to those organic substances which can be treated at a certain temperature and an oxygen-poor or oxygen-free atmosphere to make all non-carbon elements such as hydrogen, oxygen, nitrogen, sulfur, etc.
  • the portion is volatilized and converted to a synthetic material having a higher carbon content (e.g., at least 80% by weight).
  • the obtained carbon-containing synthetic material has properties such as high temperature resistance, high strength, high modulus, and porosity.
  • the carbonizable organic substance is preferably an organic high molecular compound including a natural organic high molecular compound and a synthetic organic high molecular compound.
  • natural organic high molecular compounds include, but are not limited to, starch, modified starch, cellulose, carboxymethyl cellulose, and lignin.
  • synthetic organic high molecular compounds include, but are not limited to, plastics and rubbers, wherein the plastics include thermoset plastics and thermoplastics.
  • the carbonizable organic material is a thermoset plastic.
  • the carbonizable organic material is selected from the group consisting of epoxy resins, phenolic resins, furan resins, polystyrene, styrene-divinylbenzene copolymers, polyacrylonitrile, starch, modified starch, and viscose. At least one of fiber, lignin, cellulose, carboxymethyl cellulose, styrene butadiene rubber, and urethane rubber.
  • the carbonizable organics are selected from the group consisting of coal, natural asphalt, petroleum pitch, and coal tar pitch.
  • the carbonizable organic substance is mixed with the Raney alloy particles, and then the obtained mixture is subjected to carbonization treatment to obtain a composite of carbon and Raney alloy particles, that is, the composite type catalyst of the present invention.
  • the Raney alloy promotes carbonization of the mixture, thereby allowing carbonization to proceed more completely.
  • the Raney alloy particles are dispersed in the continuous phase of the porous carbon and firmly bonded to the continuous phase of the carbon, so that the composite catalyst has high strength.
  • the Raney alloy particles are distributed in the porous carbon continuous phase, the solution can be easily contacted with the Raney alloy particles.
  • the Raney alloy particles can be easily activated to form a porous, highly active Raney metal. Moreover, it is believed that a small amount of amorphous carbon in the composite catalyst is also washed away during the activation process so that the continuous phase carbon material is reamed and more Raney alloy particles are exposed. Therefore, the composite catalyst of the present invention contains little or no Raney alloy particles which are not accessible by the alkali solution, so that the activated catalyst has high catalytic activity.
  • the content of the Raney alloy in the composite catalyst of the present invention may vary within a wide range, but is preferably from 10 to 90% by weight, preferably from 40 to 80% by weight, based on the total weight of the composite catalyst.
  • the shape of the composite catalyst of the present invention is not particularly limited as long as it is suitable for a fixed bed or fluidized bed process, and is particularly suitable for a fixed bed process.
  • the composite catalyst may be in the form of a sphere, a hemisphere, an annulus, a semi-annular body, a clover extrudate, a cylinder, a semi-cylindrical body, a hollow cylinder, a prism, a cube, a cuboid, a pellet, a pellet.
  • granules irregular granules, and the like.
  • the particle size of the composite catalyst of the present invention can vary over a wide range depending on the method of preparation and the intended use of the catalyst.
  • the average equivalent diameter of the composite catalyst particles is typically in the range of from 0.3 mm to 20 mm, preferably in the range of from 0.5 mm to 10 mm, more preferably in the range of from 1 mm to 8 mm.
  • the present invention further provides a method of preparing the above composite catalyst, comprising the steps of:
  • a curable composition formulating a curable composition, the curable composition or a cured product thereof comprising a carbonizable organic substance, and the curable composition may be in the form of a liquid, a gel, a paste or a powder;
  • step b mixing the Raney alloy particles with the curable composition obtained in step a, then curing the resulting mixture, and optionally pulverizing the solidified mixture to obtain a catalyst precursor;
  • the catalyst precursor obtained in the step b is carbonized at a high temperature to obtain a composite catalyst.
  • the Raney alloy particles and the carbonizable organic matter are as described in the first aspect.
  • the composition of the curable composition generally depends on the carbonizable organic material selected.
  • the selected carbonizable organic material is thermoplastic
  • the curable composition may consist essentially of the powder of the thermoplastic. Such a curable composition can be cured by heating-cooling.
  • the curable composition may comprise a carbonizable organic compound and a solvent and/or liquid dispersant.
  • Such curable compositions can be cured by at least partial removal of the solvent and/or liquid dispersant.
  • the solvent and liquid dispersant include, but are not limited to, water; C1-C8 alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethylhexanol; esters such as ethyl acetate, methyl acetate; Ketones such as acetone, methyl ethyl ketone, cyclohexanone; C5-C30 hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, heptane, octane, decane, dodecane, benzene, toluene, xylene a C1-C10 halogenated hydrocarbon.
  • the lower limit of the concentration of the carbonizable organic substance in such a curable composition may be 5, 10, 15, 20, 25, 30, 35 or 40% by weight, and the upper limit may be 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 wt%.
  • the curable composition may comprise a thermosetting resin and, if desired, a curing agent.
  • a curable composition can be cured by heating. Curing systems suitable for different thermosetting resins are well known to those skilled in the art.
  • one or more additives selected from the group consisting of binders, curing accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricating agents may be optionally added.
  • the amount of the additive used is a conventional amount, or can be adjusted according to actual conditions.
  • the formulated curable composition can be a liquid system, a liquid-solid system, a gel system or a powdered solid system.
  • the method of preparing a composite catalyst of the present invention comprises the steps of:
  • the curing system may be in the form of a liquid or a powder;
  • the catalyst precursor obtained in the step b is carbonized at a high temperature to obtain a composite catalyst.
  • the Raney alloy particles and the carbonizable organic matter are as described in the first aspect.
  • the weight ratio of the Raney alloy particles to the curable composition is from 1:99 to 99:1, preferably from 10:90 to 90:10, more preferably from 25:75 to 75:25. Still more preferably 40:60-60:40.
  • a catalyst precursor is obtained by solidifying a mixture of Raney alloy particles and a curable composition and optionally pulverizing the solidified mixture.
  • the curing mode and process conditions depend on the composition of the curable composition and can be readily determined by one skilled in the art. For example, if a thermoplastic resin is used as the carbonizable organic substance in the curable composition, it can be achieved by heating the mixture of the Raney alloy particles and the curable composition to above the softening temperature of the thermoplastic resin and then cooling.
  • Curing of the curable composition if a thermosetting resin is used as the carbonizable organic in the curable composition, the curable combination can be achieved by heating the mixture of the Raney alloy particles and the curable composition to initiate a curing reaction Curing; if natural organic polymer compounds such as starch, modified starch, cellulose, carboxymethyl cellulose and lignin are used as carbonizable organics in the curable composition, the Raney can be removed by The liquid medium and/or heat in the mixture of alloy particles and the curable composition achieves curing of the curable composition. If desired, the cured mixture obtained by the curing operation can be processed into particles having the desired shape and size by any method known in the art such as cutting, cutting, stamping or crushing.
  • the particle size and shape of the catalyst precursor are substantially the same as those described for the composite catalyst in the first aspect.
  • the carbonization is generally carried out in a tubular furnace.
  • the carbonization operating temperature is generally 400 to 1900 ° C, preferably 600 to 950 ° C
  • the shielding gas is an inert gas such as nitrogen or argon, and carbonized for 1 to 12 hours.
  • the phenolic resin is carbonized at 850 ° C for 3 hours, it can be completely carbonized to form porous carbon. Higher carbonization temperatures can make the carbon obtained after carbonization more regular.
  • the composite catalyst of the present invention can be easily activated. This constitutes the third aspect of the invention.
  • the composite catalyst may be treated by dissolving a mine by treating with a caustic aqueous solution having a concentration of 0.5 to 50% by weight, preferably 1 to 40% by weight, more preferably 5 to 30% by weight, at 25 to 95 ° C for about 5 minutes to 72 hours.
  • a caustic aqueous solution having a concentration of 0.5 to 50% by weight, preferably 1 to 40% by weight, more preferably 5 to 30% by weight, at 25 to 95 ° C for about 5 minutes to 72 hours.
  • At least a portion of the niobium alloy may be activated by leaching elements such as at least one of aluminum, zinc, and silicon.
  • the caustic aqueous solution is an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. .
  • the invention relates to an activated Raney catalyst prepared by the above activation process.
  • the activated Raney comprises a carbonized organic material and activated Raney alloy particles as a carrier.
  • the present invention can easily control the loading of Raney metal in the activated catalyst by controlling the amount of Raney alloy particles added during the preparation of the catalyst and/or controlling the degree of activation of the catalyst.
  • the activated catalyst of the present invention has a Raney metal loading of from 1 to 90% by weight, preferably from 10 to 90% by weight, more preferably from 40 to 80% by weight, based on the total weight of the activated catalyst.
  • the activated catalyst of the present invention has good strength and can be used in a fixed bed or fluidized bed catalytic reaction.
  • the activated catalyst of the present invention can be used for hydrogenation, dehydrogenation, amination, Chemical reactions such as dehalogenation and desulfurization are preferably used in hydrogenation reactions such as hydrogenation of olefins, hydrogenation of alkynes, hydrogenation of aromatic hydrocarbons, hydrogenation of carbonyls, hydrogenation of nitro groups, hydrogenation of nitriles, and more preferably for use in aldehydes. Hydrogenation to produce alcohol, CO hydrogenation, benzene hydrogenation or hydrogenation of nitrobenzene to aniline.
  • the invention provides the use of an activated catalyst of the invention in a hydrogenation, dehydrogenation, amination, dehalogenation or desulfurization reaction.
  • the present invention is directed to a process for the conversion of an organic compound comprising contacting an organic compound starting material with an activated catalyst of the present invention under suitable conversion conditions, and recovering the converted organic compound.
  • the invention relates to a process for the hydrogenation of organic compounds which comprises contacting an organic compound starting material with an activated catalyst of the invention in the presence of hydrogen under suitable hydrogenation conditions, and recovering the hydrogenated organic compound.
  • the conversion process or the hydrogenation process is a fixed bed or fluidized bed process.
  • the catalyst of the invention is a shaped catalyst, has good particle strength and high activity, and can be used for fixed bed, moving bed or fluidized bed reaction.
  • the preparation method of the catalyst of the invention is simple and the cost is low.
  • a 100 ml catalyst precursor was weighed and placed in a tubular high temperature electric furnace. The temperature was raised to 600 ° C at a rate of 10 ° C/min under a nitrogen flow rate of 200 ml/min, maintained at this temperature for 3 hours, and then cooled to obtain a composite catalyst.
  • a 100 ml catalyst precursor was weighed and placed in a tubular high temperature electric furnace. The temperature was raised to 700 ° C at a rate of 10 ° C/min under a nitrogen flow rate of 200 ml/min, maintained at this temperature for 3 hours, and then cooled to obtain a composite catalyst.
  • a 100 ml catalyst precursor was weighed and placed in a tubular high temperature electric furnace. In The temperature was raised to 800 ° C at a rate of 10 ° C/min under a nitrogen flow rate of 200 ml/min, maintained at this temperature for 3 hours, and then cooled to obtain a composite catalyst.
  • step (2) Weigh 50g of the curable epoxy resin system prepared in step (1), and mix it with 110g 100 mesh-200 mesh nickel-aluminum alloy powder.
  • the Ni content in nickel-aluminum alloy is 48% ( Weight), aluminum content 52% by weight.
  • An appropriate amount of the above mixture was added to a mold having a cylindrical hole of ⁇ 5 mm, and the mold was placed in a flat vulcanizer, molded at a temperature of 120 ° C and a pressure of 7 MPa for 30 mins, and then at a temperature of 150 ° C and a pressure of 7 MPa. The lower molding is 90 mins. After cooling, the solidified product was taken out to obtain a particulate catalyst precursor.
  • a 100 ml catalyst precursor was weighed and placed in a tubular high temperature electric furnace. The temperature was raised to 600 ° C at a rate of 10 ° C/min under a nitrogen flow rate of 200 ml/min, maintained at this temperature for 3 hours, and then cooled to obtain a composite catalyst.
  • step (2) The material obtained in the step (1) was placed in a mold, and then molded on a tableting machine heated to 90 ° C to form a sheet having a thickness of 2 mm.
  • the sheet was further cured in a tablet press at 150 ° C and a pressure of 5 MPa for 10 min.
  • the cured 2 mm thick sheet was mechanically cut into pellets having a particle size of about 3-5 mm.
  • step (2) The material obtained in the step (1) was placed in a mold, and then molded on a tableting machine which had been heated to 90 ° C to form a sheet having a thickness of 2 mm.
  • the sheet was further cured in a tablet press at 150 ° C and a pressure of 5 MPa for 10 min.
  • the cured 2 mm thick sheet is mechanically cut into particles having a particle size of about 3-5 mm;
  • an alumina supported nickel metal catalyst was prepared by an impregnation method.
  • the catalyst contains 40% by weight of nickel metal and can be used for the reaction of low temperature methanation to remove trace CO from hydrogen.
  • Ni(NO 3 ) 2 ⁇ 6H 2 O was dissolved in 150 g of deionized water, and then 103 g of pseudoboehmite was added, and a 5% NaOH solution was added dropwise under stirring until the nickel precipitated completely.
  • the mixture of pseudoboehmite and nickel hydroxide is filtered and washed to near neutrality, dried at 120 ° C, calcined at 500 ° C, and tableted to obtain an alumina supported nickel metal catalyst. After reduction by hydrogen at 450 ° C, the catalyst contains 45% by weight of nickel metal, which can be used for the hydrogenation of aldehyde to produce alcohol.
  • the preparation method refers to the patent CN1557918, uses pseudo-boehmite as binder, adds Tianjing powder, dilute nitric acid, etc., kneads, extrudes and cuts into cylindrical small particles of diameter ⁇ 3mm ⁇ 3mm, and is baked at 900°C. After that, the alkali wash is activated, washed with deionized water until near neutral, and stored in deionized water for use, and finally the catalyst has a Ni metal content of 50% by weight.
  • the catalyst reaction performance was evaluated using a fixed bed n-butyraldehyde liquid phase hydrogenation test. 20 ml of catalyst was charged into a fixed bed reactor, and the liquid phase hydrogenation of n-butyraldehyde was carried out under the conditions of a hydrogen flow rate of 50 ml/min, a reaction temperature of 90-130 ° C, a pressure of 4.0 MPa, and a n-butyraldehyde liquid hourly space velocity of 0.3 h -1 . test. The reaction product was quantified using gas chromatography and the chromatographic detector was FID.
  • Table 2 shows the results of conversion evaluation in the hydrogenation reaction of aldehyde, reflecting the activity of the catalyst. The higher the conversion rate, the higher the activity of the catalyst.
  • Table 3 shows the formation of n-butyl ether as a by-product in the hydrogenation of aldehyde, reflecting the selectivity of the catalyst. The smaller the amount of ether formed, the better the selectivity of the catalytic reaction.
  • Comparative Example 3 is a fixed bed Raney nickel catalyst containing alumina, which has a significantly lower aldehyde hydrogenation activity than the catalyst of the present invention, and which produces more n-butyl ether by-products than the catalyst of the present invention.
  • Comparative Example 4 was almost inactive, probably because the metal component was almost completely encapsulated or covered by the polymer, and the number of catalytically active sites was small, since the conversion rate of Comparative Example 4 was very low, and the by-product n-butyl ether was not detected.

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Abstract

本发明公开了一种复合型催化剂，其包含作为连续相的碳和作为分散相的雷尼合金颗粒，其中所述雷尼合金颗粒均匀或不均匀地分散在所述连续相碳中，并且其中所述作为连续相的碳是由至少一种可碳化的有机物碳化后得到的。该催化剂具有颗粒强度好、催化活性高和选择性好等优点。

Description

一种复合型催化剂及其制备方法
相关申请的交叉参考
本申请要求2014年3月7日提交的CN201410083872.9的优先权，通过引用并且为了所有的目的将所述文件整体结合在本申请中。
技术领域
本发明涉及一种复合型催化剂及其制备方法；更具体地涉及雷尼合金颗粒作为分散相分散在连续相中的催化剂及其制备方法。
背景技术
在催化领域中，“雷尼法”是一种活性金属催化剂的制备方法，该方法包括：i)先制备含有活性金属的二或更多组分的合金，和ii)然后将至少一种金属组分提取出来，剩下具有较高催化活性的、具有多孔结构的金属。步骤ii)也被称为“活化”。例如，M.Raney最早发明了雷尼镍催化剂(Industrial and Engineering Chemistry，1940，Vol.32，1199)，该催化剂通过如下方法制备：先制备镍铝合金，然后用强碱溶液溶去合金中的铝元素，剩下具有多孔结构的、具有很高的催化活性的镍金属。
雷尼催化剂包括雷尼镍催化剂、雷尼钴催化剂、雷尼铜催化剂等，其中以雷尼镍催化剂最为常见。雷尼镍催化剂通常以粉末形式出现，其易燃，操作不便，多用于精细化工领域中小规模催化加氢反应中，而无法用于一般固定床反应。
为了扩展雷尼镍催化剂的应用领域，采取一定的方法将其成 型，特别是将其加工成固定床催化剂，是近年来比较受关注的研究方向。
专利申请CN1557918公开了一种成型雷尼镍催化剂及其制备方法，该催化剂是由铝和Ni、Co、Cu、Fe中的一种或多种组成合金粉末，采用拟薄水铝石等无机物作为粘合剂，采用田菁粉、羧甲基纤维素等天然或合成的有机物质作为孔道模板剂，直接捏合、成型、焙烧，并经苛性碱溶液活化制得。所得催化剂具有一定的形状和强度，可以用作固定床催化剂。
专利US5536694公开了成型的、活化的雷尼金属固定床催化剂，其通过将至少一种催化剂合金粉末、作为粘结剂的纯雷尼法金属粉末、成型助剂和致孔剂成型，随后煅烧和碱液活化得到。
专利US4826799公开了一种成型的雷尼催化剂的制备方法，包括在一定温度下将雷尼合金与高分子聚合物、矿物油等充分均匀混合，然后采用挤出等方法成型，成型后将高分子聚合物烧去或者保留高分子聚合物，最后使用强碱溶去铝金属得到活化的催化剂。该方法能够容易地得到成型的催化剂，但若保留高分子聚合物则由于成型过程中雷尼合金被高分子聚合物包裹或覆盖，催化活性点少，其催化活性很低甚至无活性；若高温焙烧将高分子聚合物烧去会造成相当多的颗粒烧结，导致活性降低。
因此，仍需要一种活性高、选择性好且颗粒强度好的、可用于固定床的雷尼催化剂。
发明概述
本发明的一个目的是提供一种复合型催化剂，其包含作为连续相的碳和作为分散相的雷尼合金颗粒，其中所述雷尼合金颗粒均匀或不均匀地分散在所述连续相碳中，并且其中所述作为连续 相的碳是由至少一种可碳化的有机物碳化后得到的。该催化剂具有以下优点：制备过程简易，催化剂产品杂质少，活性金属的负载量高，催化剂颗粒强度好，用于加氢反应时活性高和选择性好。
本发明的另一个目的是提供一种制备所述催化剂的方法，其包括以下步骤：
a、配制可固化组合物，该可固化组合物或其固化产物包含可碳化的有机物，并且该可固化组合物可以为液体状、胶状、糊状或粉末状；
b、将雷尼合金颗粒与步骤a得到的可固化组合物混合，然后使所得到的混合物固化，并任选将固化的混合物粉碎，得到催化剂前体；
c、在惰性气体保护下，高温碳化由步骤b得到的催化剂前体，制得复合型催化剂。
本发明的又一个目的是提供一种活化所述复合型催化剂的方法，包括用苛性水溶液处理所述复合型催化剂。
本发明的又一个目的是提供一种活化的催化剂，其包含作为载体的、碳化的有机物和活化的雷尼合金颗粒。所述活化的催化剂通过上述活化方法得到。
本发明的又一个目的是提供所述活化的催化剂在加氢、脱氢、胺化、脱卤或脱硫反应中的应用。
附图简要说明
图1显示了实施例6制备的碳化后催化剂颗粒扫描电镜照片。
优选实施方案的描述
在第一个方面，本发明涉及一种复合型催化剂，其包含作为 连续相的碳和作为分散相的雷尼合金颗粒，其中所述雷尼合金颗粒均匀或不均匀地分散在所述连续相碳中，并且其中所述作为连续相的碳是由至少一种可碳化的有机物碳化后得到的。
在一个实施方案中，所述的雷尼合金包括至少一种雷尼金属和至少一种可被沥滤的元素。本文中使用的术语“雷尼金属”是指用雷尼法活化时不溶的、催化活性的金属。雷尼金属的实例包括但不限于镍、钴、铜和铁。本文中使用的术语“可被沥滤的元素”是指用雷尼法活化时可被溶解的元素。可被沥滤的元素的实例包括但不限于铝、锌和硅。
在一个优选的实施方案中，所述雷尼合金选自镍铝合金、钴铝合金和铜铝合金。
在一个实施方案中，所述雷尼合金中雷尼金属与可被沥滤的元素的重量比为1∶99-10∶1，优选为1∶10-4∶1，更优选为1∶3-2∶1，最优选约1∶1。
所述的雷尼合金颗粒的颗粒大小可以在宽范围内选择。例如平均粒径可以为0.1-1000微米，优选为1-500微米，更优选为10-100微米。
在一个实施方案中，为了提高催化剂活性或者选择性，还可以将至少一种促进剂引入所述雷尼合金，形成多组分的雷尼合金。所述至少一种促进剂可以选自Mo、Cr、Ti、Pt、Pd、Rh和Ru。促进剂的量可以为雷尼合金总重量的0.01wt％-5wt％。
本文中使用的术语“可碳化的有机物”是指那些有机物，其可以通过在一定的温度和贫氧或无氧气氛下处理以使其中的氢、氧、氮、硫等非碳元素全部或大部挥发掉而转化成含碳量较高(例如至少80重量％)的合成材料。所得到的含碳合成材料具有耐高温、高强度、高模量、多孔等性能。
在一个实施方案中，所述可碳化的有机物优选是有机高分子化合物，包括天然有机高分子化合物和合成有机高分子化合物。天然有机高分子化合物的实例包括但不限于淀粉、改性淀粉、纤维素、羧甲基纤维素和木质素。合成有机高分子化合物的实例包括但不限于塑料和橡胶，其中塑料包括热固性塑料和热塑性塑料。在一个优选的实施方案中，所述可碳化的有机物为热固性塑料。
在一个实施方案中，所述可碳化的有机物是选自环氧树脂、酚醛树脂、呋喃树脂、聚苯乙烯、苯乙烯-二乙烯苯共聚物、聚丙烯腈、淀粉、改性淀粉、粘胶纤维、木质素、纤维素、羧甲基纤维素、丁苯橡胶、聚氨酯橡胶中的至少一种。
在另外的实施方案中，所述可碳化的有机物选自煤、天然沥青、石油沥青和煤焦沥青。
按照本发明，将可碳化的有机物与雷尼合金颗粒混合，然后对所得到的混合物进行碳化处理，以得到碳与雷尼合金颗粒的复合物，即本发明的复合型催化剂。不局限于任何特定的理论，据信所述雷尼合金对所述混合物的碳化起到促进作用，从而使碳化进行得更加完全。碳化后，雷尼合金颗粒分散在多孔碳连续相中，并与所述碳连续相牢固结合，使得复合催化剂具有很高强度。同时，由于雷尼合金颗粒分布在多孔碳连续相中，溶液可以容易地接触到雷尼合金颗粒。这样，在用碱液对复合催化剂进行活化时，雷尼合金颗粒可以被容易地活化以形成多孔的高活性雷尼金属。而且，据信在所述活化过程中所述复合催化剂中的少量的无定型碳也被洗去，从而所述连续相碳材料得以扩孔和更多的雷尼合金颗粒被暴露出来。因此，本发明的复合催化剂中几乎不含或者不含不能被碱液接近的雷尼合金颗粒，使得活化后的催化剂具有很高的催化活性。
本发明的复合催化剂中雷尼合金的含量可以在宽范围内变化，但优选为10-90重量％，优选为40-80重量％，基于复合催化剂的总重量计。
对本发明的复合催化剂的形状没有特殊的限制，只要其适合固定床或流化床工艺，特别是适合固定床工艺。合宜地，所述复合催化剂可以呈球体、半球体、环状体、半环状体、三叶草挤出物、圆柱体、半圆柱体、空心圆柱体、棱柱体、立方体、长方体、片粒、丸粒、不规则颗粒等的形式。
本发明的复合催化剂的颗粒大小可以在宽范围内变化，取决于制备方法和催化剂的预期的用途。所述复合催化剂颗粒的平均等量直径典型地在0.3mm-20mm范围内，优选在0.5mm-10mm范围内，更优选在1mm-8mm范围内。
在第二方面，本发明进一步提供了上述复合型催化剂的制备方法，其包括以下步骤：
a、配制可固化组合物，该可固化组合物或其固化产物包含可碳化的有机物，并且该可固化组合物可以为液体状、胶状、糊状或粉末状；
b、将雷尼合金颗粒与步骤a得到的可固化组合物混合，然后使所得到的混合物固化，并任选将固化的混合物粉碎，得到催化剂前体；
c、在惰性气体保护下，高温碳化由步骤b得到的催化剂前体，制得复合型催化剂。
在本发明的方法中，所述雷尼合金颗粒和所述可碳化的有机物如第一方面中所述。
所述可固化组合物的组成通常取决于所选择的可碳化的有机物。在一些实施方案中，当所选择的可碳化的有机物是热塑性塑 料时，所述可固化组合物可以基本上由所述热塑性塑料的粉料组成。这样的可固化组合物可以通过加热-冷却来固化。
在另一些实施方案中，所述可固化组合物可以包含可碳化的有机物以及溶剂和/或液体分散剂。这样的可固化组合物可以通过至少部分脱除所述溶剂和/或液体分散剂来固化。所述溶剂和液体分散剂的实例包括但不限于水；C1-C8的醇如甲醇、乙醇、异丙醇、正丁醇、2-乙基己醇；酯如乙酸乙酯、乙酸甲酯；酮如丙酮、甲乙酮、环己酮；C5-C30的烃，如戊烷、环戊烷、己烷、环己烷、庚烷、辛烷、癸烷、十二烷、苯、甲苯、二甲苯；C1-C10的卤代烃。这样的可固化组合物中可碳化的有机物的浓度的下限可以为5，10，15，20，25，30，35或40wt％，并且上限可以为20，30，40，45，50，55，60，65，70，75，80，85，90或95wt％。
在另一些实施方案中，所述可固化组合物可以包含热固性树脂和如果需要的固化剂。这样的可固化组合物可以通过加热来固化。适用于不同热固性树脂的固化体系是本领域技术人员熟知的。
在配制所述可固化组合物时可以任选加入一种或多种选自以下的添加剂：粘结剂、固化促进剂、染料、颜料、着色剂、抗氧化剂、稳定剂、增塑剂、润滑剂、流动改性剂或助剂、阻燃剂、防滴剂、抗结块剂、助粘剂、导电剂、多价金属离子、冲击改性剂、脱模助剂、成核剂等。所用添加剂用量均为常规用量，或可以根据实际情况的要求进行调整。
配制的可固化组合物可以为液态体系、液-固体系、胶状体系或粉状固体体系。
在一些具体的实施方案中，本发明的复合型催化剂的制备方法包括以下步骤：
a、根据可碳化的有机物常用固化配方配制可固化体系，该可 固化体系可以为液体状或粉末状；
b、将雷尼合金颗粒与所述可固化体系均匀混合，然后模压固化，并任选将固化的混合物粉碎，得到催化剂前体；
c、在惰性气体保护下，高温碳化由步骤b得到的催化剂前体，制得复合型催化剂。
在本发明的方法中，所述雷尼合金颗粒和所述可碳化的有机物如第一方面中所述。
在步骤b中，所述的雷尼合金颗粒与可固化组合物的重量比为1∶99-99∶1，优选为10∶90-90∶10，更优选为25∶75-75∶25，仍更优选为40∶60-60∶40。
在步骤b中，通过将雷尼合金颗粒与可固化组合物的混合物固化并任选将固化的混合物粉碎，得到催化剂前体。固化方式和工艺条件取决于所述可固化组合物的组成，并且可以由本领域技术人员容易地确定。例如，如果热塑性树脂被用作可固化组合物中的可碳化有机物，则可以通过将所述雷尼合金颗粒与可固化组合物的混合物加热到所述热塑性树脂的软化温度以上和然后冷却来实现可固化组合物的固化；如果热固性树脂被用作可固化组合物中的可碳化有机物，则可以通过将所述雷尼合金颗粒与可固化组合物的混合物加热以引发固化反应来实现可固化组合物的固化；如果天然有机高分子化合物如淀粉、改性淀粉、纤维素、羧甲基纤维素和木质素被用作可固化组合物中的可碳化有机物，则可以通过脱除所述雷尼合金颗粒与可固化组合物的混合物中的液体介质和/或加热来实现可固化组合物的固化。如果需要，通过固化操作得到的固化的混合物可以采用任何本领域已知的方法如切割、裁剪、冲压或破碎等方法加工成具有所需要的形状和大小的颗粒。
所述催化剂前体的粒径大小和形状基本上与第一方面中针对复合催化剂所描述的那些相同。
在步骤c中，所述的碳化一般在管式加热炉中进行。碳化操作温度一般为400-1900℃，优选600-950℃，保护气体为氮气或者氩气等惰性气体，碳化1-12小时。例如，酚醛树脂在850℃碳化3小时，即可完全碳化，形成多孔的碳。更高碳化温度可以使得碳化后得到的碳更加规整。
本发明的复合催化剂可以很容易被活化。这构成了本发明的第三方面。
活化所述复合催化剂的方法和其采用的条件本质上是已知的。例如，所述复合催化剂可以通过用0.5-50重量％，优选1-40重量％，更优选5-30重量％浓度的苛性水溶液在25℃-95℃处理约5分钟-72小时，以溶出雷尼合金中的至少一部分可被沥滤的元素，例如铝、锌和硅中的至少一种，而被活化。在一个实施方案中，所述苛性水溶液是氢氧化钠水溶液或氢氧化钾水溶液。。
在第四方面，本发明涉及由上述活化方法制备的活化的雷尼催化剂。所述活化的雷尼包含作为载体的、碳化的有机物和活化的雷尼合金颗粒。本发明通过控制催化剂制备过程中雷尼合金颗粒的加入量和/或控制催化剂的活化程度，可以很容易地控制所述活化的催化剂中雷尼金属的负载量。在一个实施方案中，本发明的活化的催化剂的雷尼金属负载量为1-90重量％，优选10-90重量％，更优选40-80重量％，基于活化的催化剂的总重量计。
本发明的所述活化的催化剂具有好的强度，可以被用于固定床或者流化床催化反应。
本发明的所述活化的催化剂可以被用于加氢、脱氢、胺化、 脱卤、脱硫等化学反应，优选被用于加氢反应，如烯烃加氢、炔烃加氢、芳烃加氢、羰基加氢、硝基加氢、腈类加氢，更优选被用于醛加氢制备醇、CO加氢、苯加氢或硝基苯加氢制苯胺等反应。
因此，在第五方面，本发明提供了本发明的活化的催化剂在加氢、脱氢、胺化、脱卤或脱硫反应中的应用。
在一些实施方案中，本发明涉及有机化合物的转化方法，该方法包括使有机化合物原料与本发明的活化的催化剂在合适的转化条件下接触，和回收转化的有机化合物。
在一个具体的实施方案中，本发明涉及有机化合物的氢化方法，该方法包括使有机化合物原料与本发明的活化的催化剂在氢气存在下在合适的氢化条件下接触，和回收氢化的有机化合物。
在一个实施方案中，所述转化方法或者所述氢化方法是固定床或者流化床工艺。
所述转化方法的工艺条件是本领域技术人员公知的。
本发明催化剂为成型催化剂，颗粒强度好，具有很高活性，可用于固定床、移动床或者流化床反应。
本发明催化剂的制备方法简单，成本较低。
具体实施方式
下面实施例将对本发明做进一步的说明，但并不因此而限制本发明。
实施例1
(1)将液态环氧树脂(巴陵石化，CYD-128)100质量份、固化剂甲基四氢苯酐(MeTHPA)(广东盛世达科贸股份有限公司)85质量份、固化促进剂三乙醇胺(TEA)(天津市化学试剂一厂)1.5质量份搅拌均匀，提供可固化的环氧树脂体系。
(2)称取40g步骤(1)中配好的环氧树脂体系，并将其和180g 100目-200目的镍铝合金粉充分搅拌混合，镍铝合金中Ni含量为48％(重量)，铝含量52％(重量)。取适量上述混合料加入到具有Φ5mm的圆柱形孔的模具中，并将所述模具放入平板硫化仪中，在温度120℃、压力7MPa的条件下模压30mins，然后在温度150℃、压力7MPa的条件下模压90mins。在冷却后取出固化产物，得到颗粒状催化剂前体。
(3)量取100ml催化剂前体，放入管式高温电炉中。在200ml/min的氮气流量下，将温度以10℃/min的速率升高至600℃，在该温度保持3小时，然后冷却，得到复合型催化剂。
(4)用去离子水配置20％NaOH水溶液400g，并将其加入到50ml的步骤(3)所得催化剂中。将所得到的混合物在85℃保持4小时，然后过滤掉液体，并将固体物用去离子水洗涤至接近中性，得到活化的复合型催化剂。所述活化的催化剂存放于去离子水中备用。所述活化的催化剂被发现具有60％(重量)的镍含量，基于活化的催化剂的重量计。
实施例2
(1)将液态环氧树脂(巴陵石化，CYD-128)100质量份、固化剂甲基四氢苯酐(MeTHPA)(广东盛世达科贸股份有限公司)85质量份、固化促进剂三乙醇胺(TEA)(天津市化学试剂一厂)1.5质量份搅拌均匀，提供可固化的环氧树脂体系。
(2)称取50g步骤(1)中配好的可固化的环氧树脂体系，并将其和150g 100目-200目的镍铝合金粉充分搅拌混合，镍铝合金中Ni含量为48％(重量)，铝含量52％(重量)。取适量上述混合料加入到具有Φ5mm的圆柱形孔的模具中，并将所述模具放 入平板硫化仪中，在温度120℃、压力7MPa的条件下模压30mins，然后在温度150℃、压力7MPa的条件下模压90mins。冷却后取出固化产物，得到颗粒状催化剂前体。
(3)量取100ml催化剂前体，放入管式高温电炉中。在200ml/min的氮气流量下，将温度以10℃/min的速率升高至700℃，在该温度保持3小时，然后冷却，得到复合型催化剂。
(4)用去离子水配置20％NaOH水溶液400g，并将其加入到50ml的步骤(3)所得催化剂中。将所得到的混合物在85℃保持4小时，然后过滤掉液体，并将固体物用去离子水洗涤至接近中性，得到活化的复合型催化剂。所述活化的催化剂存放于去离子水中备用。所述活化的催化剂被发现具有50％(重量)的镍含量，基于活化的催化剂的重量计。
实施例3
(1)将液态环氧树脂(巴陵石化，CYD-128)100质量份、固化剂甲基四氢苯酐(MeTHPA)(广东盛世达科贸股份有限公司)85质量份、固化促进剂三乙醇胺(TEA)(天津市化学试剂一厂)1.5质量份搅拌均匀，提供可固化的环氧树脂体系。
(2)称取50g步骤(1)中配好的可固化的环氧树脂体系，并将其和130g 100目-200目的镍铝合金粉充分搅拌混合，镍铝合金中Ni含量为48％(重量)，铝含量52％(重量)。取适量上述混合料加入到具有Φ5mm的圆柱形孔的模具中，并将该模具放入平板硫化仪中，在温度120℃、压力7MPa的条件下模压30mins，然后在温度150℃、压力7MPa的条件下模压90mins。冷却后取出固化产物，得到颗粒状催化剂前体。
(3)量取100ml催化剂前体，放入管式高温电炉中。在 200ml/min的氮气流量下，将温度以10℃/min的速率升高至800℃，在该温度保持3小时，然后冷却，得到复合型催化剂。
(4)用去离子水配置20％NaOH水溶液400g，并将其加入到50ml的步骤(3)所得催化剂中。将所得到的混合物在85℃保持4小时，然后过滤掉液体，并将固体物用去离子水洗涤至接近中性，得到活化的复合型催化剂。所述活化的催化剂存放于去离子水中备用。所述活化的催化剂被发现具有45％(重量)的镍含量，基于活化的催化剂的重量计。
实施例4
(1)将液态环氧树脂(巴陵石化，CYD-128)100质量份、固化剂甲基四氢苯酐(MeTHPA)(广东盛世达科贸股份有限公司)85质量份、固化促进剂三乙醇胺(TEA)(天津市化学试剂一厂)1.5质量份搅拌均匀，提供可固化的环氧树脂体系。
(2)称取50g步骤(1)中配好的可固化的环氧树脂体系，并将其和110g 100目-200目的镍铝合金粉充分搅拌混合，镍铝合金中Ni含量为48％(重量)，铝含量52％(重量)。取适量上述混合料加入到具有Φ5mm的圆柱形孔的模具中，并将该模具放入平板硫化仪，在温度120℃、压力7MPa的条件下模压30mins，然后在温度150℃、压力7MPa的条件下模压90mins。冷却后取出固化产物，得到颗粒状催化剂前体。
(3)量取100ml催化剂前体，放入管式高温电炉中。在200ml/min的氮气流量下，将温度以10℃/min的速率升高至600℃，在该温度保持3小时，然后冷却，得到复合型催化剂。
(4)用去离子水配置20％NaOH水溶液400g，并将其加入到50ml的步骤(3)所得催化剂中。将所得到的混合物在85℃保持 4小时，然后过滤掉液体，并将固体物用去离子水洗涤至接近中性，得到活化的复合型催化剂。所述活化的催化剂存放于去离子水中备用。所述活化的催化剂被发现具有40％(重量)的镍含量，基于活化的催化剂的重量计。
实施例5
(1)将粉状酚醛树脂与固化剂六次甲基四胺用高速搅拌机充分混合，其中六次甲基四胺与酚醛树脂的重量比为12/100。将100克上述混合料与300克100目-200目的镍铝合金粉用高速搅拌机充分混合，镍铝合金粉中Ni含量为48％(重量)，铝含量52％(重量)。
(2)将得自步骤(1)的物料放入模具中，然后在升温至90℃的压片机上进行模压，成型为2mm厚的片材。将所述片材进一步在压片机中在150℃和5MPa的压力下固化10min。将固化好的2mm厚片材机械切割成粒径大小约3-5mm的颗粒。
(3)量取100ml上述颗粒，放入管式高温电炉中。在200ml/min的氮气流量下，将温度以10℃/min的速率升高至650℃，在该温度保持3小时，然后冷却，得到复合催化剂。
(4)用去离子水配置20％NaOH水溶液400g，并将其加入到50ml的步骤(3)所得催化剂中。将所得到的混合物在85℃保持4小时，然后过滤掉液体，并将固体物用去离子水洗涤至接近中性，得到活化的复合型催化剂。所述活化的催化剂存放于去离子水中备用。所述活化的催化剂被发现具有40％(重量)的镍含量，基于活化的催化剂的重量计。
实施例6
(1)将粉状酚醛树脂与固化剂六次甲基四胺用高速搅拌机充分混合，其中六次甲基四胺与酚醛树脂的重量比为12/100。将100克上述混合料与350克100目-200目的镍铝合金粉用高速搅拌机充分混合，镍铝合金粉中Ni含量为48％(重量)，铝含量52％(重量)。
(2)将得自步骤(1)的物料放入模具中，然后在已升温至90℃的压片机上进行模压，成型为2mm厚的片材。将所述片材进一步在压片机中在150℃和5MPa的压力下固化10min。将固化好的2mm厚片材机械切割成粒径大小约3-5mm的颗粒；
(3)量取100ml上述颗粒，放入管式高温电炉中。在200ml/min的氮气流量下，将温度以10℃/min的速率升高至600℃，在该温度保持3小时，然后冷却，得到复合催化剂。
(4)用去离子水配置20％NaOH水溶液400g，并将其加入到50ml的步骤(3)所得催化剂中。将所得到的混合物在85℃保持4小时，然后过滤掉液体，并将固体物用去离子水洗涤至接近中性，得到活化的复合型催化剂。所述活化的催化剂存放于去离子水中备用。所述活化的催化剂被发现具有45％(重量)的镍含量，基于活化的催化剂的重量计。
对比例1
氧化铝负载镍金属低温甲烷化催化剂：
参照专利CN100490972C的实施例1，通过浸渍法制备得到氧化铝负载的镍金属催化剂。该催化剂中含40％(重量)镍金属，可用于低温甲烷化脱除氢气中微量CO的反应。
对比例2
氧化铝负载镍金属醛加氢催化剂：
将291g Ni(NO3)2·6H2O溶于150g去离子水中，再加入103g拟薄水铝石，搅拌条件下滴入5％NaOH溶液直至镍沉淀完全。过滤出拟薄水铝石和氢氧化镍的混合物，并洗涤至接近中性，120℃烘干，500℃焙烧，压片成型，得到氧化铝负载的镍金属催化剂。经450℃氢气还原后，该催化剂含45％(重量)镍金属，可用于醛加氢制备醇的反应。
对比例3
氧化铝作为粘合剂的固定床雷尼镍催化剂：
制备方法参照专利CN1557918，采用拟薄水铝石为粘合剂，加入田菁粉、稀硝酸等，混捏、挤出、切割成型为直径Φ3mm×3mm的圆柱形小颗粒，烘干、900℃焙烧后，碱洗活化，经去离子水洗涤至接近中性后，存放于去离子水中备用，最终催化剂中Ni金属含量为50％(重量)。
对比例4
将10g聚丙烯粉料，100g镍铝合金粉(其中镍铝合金中Ni含量为48重量％，铝含量为52重量％)在高速搅拌机中进行共混，然后从双螺杆挤出机挤出，挤出温度200℃。将挤出物切割为Φ3mm×3mm的圆柱形小颗粒。
用去离子水配置20wt％NaOH水溶液400g，并将其加入到40g上面制备的镍铝合金-聚丙烯圆柱形颗粒中。将所得到的混合物在85℃保持8小时，然后过滤掉液体，并将固体物用去离子水洗涤至接近中性，得到活化的催化剂。所述活化的催化剂存放于去离子水中备用。所述活化的催化剂被发现具有45重量％的镍含量， 基于活化的催化剂的重量计。
实施例7
CO甲烷化反应性能测试：
量取6ml催化剂装入不锈钢固定床反应器，通入高纯氮气，流量为300ml/min，加热升温至120℃，保持2小时；然后将高纯氮气切换为氢气，流量为300ml/min，升温至150℃，切入含有5800ppm CO的粗氢原料，开始反应，反应压力为2.8MPa，反应温度控制在170℃。改变粗氢流量以得到不同条件下反应结果。反应后气体组成使用气相色谱分析，色谱检测器为FID，CO含量可以精确到1ppm。
按照上述评价方法，对实施例4-5和对比例1催化剂分别进行了反应评价，表1给出了详细评价结果。出口CO含量(ppm)越小，表明催化剂的活性越高。
表1催化剂CO甲烷化反应评价结果
Figure PCTCN2015073783-appb-000001
由表1结果可见，本发明实施例的出口CO含量远低于对比例，表明本发明催化剂具有更好的低温甲烷化活性。
实施例8
醛加氢反应性能测试：
使用固定床正丁醛液相加氢试验评价催化剂反应性能。取催化剂20ml装入固定床反应器，在氢气流量为50ml/min，反应温度90-130℃，压力4.0MPa，正丁醛液时空速0.3h-1的条件下进行正丁醛液相加氢试验。反应产物使用气相色谱定量，色谱检测器为FID。
表2催化剂的醛加氢反应活性
Figure PCTCN2015073783-appb-000002
表3催化剂的醛加氢反应副产物醚生成量
Figure PCTCN2015073783-appb-000003
表2为醛加氢反应中转化率评价结果，反映催化剂活性大小，转化率越高表示催化剂活性越高；表3为醛加氢反应中副产物正丁醚生成情况，反映催化剂选择性好坏，醚生成量越小表示催化反应的选择性越好。
从表2和表3的评价结果可以看出，本发明催化剂的活性和选择性均显著优于对比例，这在工业生产中具有应用价值。对比例3是含氧化铝的固定床雷尼镍催化剂，其醛加氢活性明显低于本发明催化剂，且其生成的正丁醚副产物较多，选择性不如本发明催化剂。对比例4几乎无活性，原因可能是金属组分被高分子聚合物几乎完全包裹或覆盖，催化活性点数量很少，因对比例4转化率很低，副产物正丁醚未检出。
尽管已经特别地描述了本发明的说明性实施方案，应该理解的是，各种其它修改对于本领域技术人员来说是显而易见的，并且可以由本领域技术人员容易地做出，而不背离本发明的精神和范围。因此，不打算将所附权利要求书的范围限制在本文所陈述的实施例和说明中，而是权利要求书应被理解为包括存在于本发明中的所有具有专利新颖性的特征，包括将被本发明所属领域技术人员作为其等同物看待的所有特征。在上面已经结合许多实施方案和具体实施例描述了本发明。考虑到以上的详细描述，许多变例对本领域技术人员来说是显而易见的。所有这样的各种变例都在所附权利要求书的整个意图的范围内。
在本公开中，当组合物、要素或者要素组前有过渡短语“包含”时，应理解我们还想到了相同的组合物、要素或者要素组，其中所述组合物、要素或者要素组前由过渡短语“基本上由…组成”、“由…组成”、“选自由…组成的组”或者“是”引导，反之亦然。

Claims (21)

  1. 一种复合型催化剂，其包含作为连续相的碳和作为分散相的雷尼合金颗粒，其中所述雷尼合金颗粒均匀或不均匀地分散在所述连续相碳中，并且其中所述作为连续相的碳是由至少一种可碳化的有机物碳化后得到的。
  2. 权利要求1所述的催化剂，其具有以下特征中至少之一：
    -所述雷尼合金包含至少一种雷尼金属和至少一种可被沥滤的元素；
    -所述雷尼合金颗粒具有0.1-1000微米的平均粒径；
    -所述可碳化的有机物为有机高分子化合物；
    -所述复合型催化剂具有10-90重量％的雷尼合金含量，基于复合型催化剂的总重量计；
    -所述复合型催化剂呈球体、半球体、环状体、半环状体、三叶草挤出物、圆柱体、半圆柱体、空心圆柱体、棱柱体、立方体、长方体、片粒、丸粒、齿形物、不规则颗粒的形式；和
    -所述复合型催化剂呈颗粒状，并且具有在0.3mm-20mm范围内的平均等量直径。
  3. 权利要求1所述的催化剂，其中所述雷尼合金包含至少一种雷尼金属和至少一种可被沥滤的元素，所述雷尼金属选自镍、钴、铜和铁，所述可被沥滤的元素选自铝、锌和硅。
  4. 权利要求1所述的催化剂，其中所述雷尼合金包含至少一种雷尼金属和至少一种可被沥滤的元素，其中所述至少一种雷尼金属与所述至少一种可被沥滤元素的重量比为1∶99-10∶1，优选为1∶10-4∶1。
  5. 权利要求1所述的催化剂，其中所述雷尼合金包含至少 一种雷尼金属、至少一种可被沥滤的元素和至少一种选自Mo、Cr、Ti、Pt、Pd、Rh和Ru的促进剂，其中所述至少一种促进剂占雷尼合金总重量的0.01重量％-5重量％。
  6. 权利要求1所述的催化剂，其中所述可碳化的有机物为选自橡胶、热固性塑料和热塑性塑料的合成高分子化合物。
  7. 权利要求6所述的催化剂，其中所述可碳化的有机物是选自环氧树脂、酚醛树脂和呋喃树脂中的至少一种热固性塑料。
  8. 权利要求6所述的催化剂，其中所述可碳化的有机物是选自聚苯乙烯、苯乙烯-二乙烯苯共聚物和聚丙烯腈中的至少一种热塑性塑料。
  9. 权利要求6所述的催化剂，其中所述可碳化的有机物是选自丁苯橡胶和聚氨酯橡胶的至少一种橡胶。
  10. 权利要求1所述的催化剂，其中所述可碳化的有机物为选自淀粉、改性淀粉、粘胶纤维、木质素、纤维素和羧甲基纤维素中的至少一种天然有机高分子化合物。
  11. 权利要求1所述的催化剂，其中所述可碳化的有机物选自煤、天然沥青、石油沥青、煤焦沥青和它们的混合物。
  12. 权利要求1所述的催化剂，其具有以下特征中至少之一：
    -所述雷尼合金颗粒具有1-500微米的平均粒径；
    -所述复合型催化剂呈球体、环状体、三叶草挤出物、圆柱体、棱柱体、长方体、齿形物、不规则颗粒的形式；
    -所述复合型催化剂具有40-80重量％的雷尼合金含量，基于复合型催化剂的总重量计；和
    -所述复合型催化剂呈颗粒状，并且具有在0.5mm-10mm范围内的平均等量直径。
  13. 一种活化权利要求1-12中任一项所述的复合型催化剂的 方法，包括用苛性水溶液处理所述复合型催化剂。
  14. 权利要求13所述的方法，其中所述处理如下进行：用0.5-50重量％浓度的苛性水溶液在25℃-95℃处理所述复合催化剂约5分钟-72小时。
  15. 一种制备权利要求1所述催化剂的方法，其包括以下步骤：
    a、配制可固化组合物，该可固化组合物或其固化产物包含可碳化的有机物；
    b、将雷尼合金颗粒与步骤a得到的可固化组合物混合，然后使所得到的混合物固化，并任选将固化的混合物粉碎，得到催化剂前体；
    c、在惰性气体保护下，高温碳化由步骤b得到的催化剂前体，制得复合型催化剂。
  16. 权利要求15所述的方法，其包括以下步骤：
    a、根据可碳化的有机物常用固化配方配制可固化体系，该可固化体系为液体状或粉末状；
    b、将雷尼合金颗粒与所述可固化体系均匀混合，然后模压固化，并任选将固化的混合物粉碎，得到催化剂前体；
    c、在惰性气体保护下，高温碳化由步骤b得到的催化剂前体，制得复合型催化剂。
  17. 权利要求15或16所述的方法，其具有以下特征中至少之一：
    -所述雷尼合金包含至少一种雷尼金属和至少一种可被沥滤的元素；
    -所述雷尼合金颗粒具有0.1-1000微米的平均粒径；
    -所述可碳化的有机物为有机高分子化合物；
    -在步骤c中，碳化温度为400-1900℃，碳化时间为1-24小时；
    -在步骤c中，惰性气体是氮气或者氩气；
    -在步骤b中，雷尼合金颗粒与步骤a得到的可固化混合物/可固化体系的重量比为1∶99-99∶1，优选为10∶90-90∶10，更优选为25∶75-75∶25。
  18. 活化的雷尼催化剂，其包含作为载体的、碳化的有机物和活化的雷尼合金颗粒，并且其可以通过权利要求13或14的方法得到。
  19. 权利要求18所述的活化的催化剂在加氢、脱氢、胺化、脱卤或脱硫反应中的应用。
  20. 权利要求19所述的应用，其中所述反应是烯烃加氢反应、炔烃加氢反应、芳烃加氢反应、羰基加氢反应或腈类加氢反应。
  21. 权利要求19或20所述的应用，其中所述反应在固定床或流化床工艺中进行。
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