CN101454078A - Loden nano metal catalyst and manufacture method thereof - Google Patents

Loden nano metal catalyst and manufacture method thereof Download PDF

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Publication number
CN101454078A
CN101454078A CNA2007800198557A CN200780019855A CN101454078A CN 101454078 A CN101454078 A CN 101454078A CN A2007800198557 A CNA2007800198557 A CN A2007800198557A CN 200780019855 A CN200780019855 A CN 200780019855A CN 101454078 A CN101454078 A CN 101454078A
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metal
catalyst
carrier
suspension
nano particle
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Inventor
格茨·布尔格费尔德
彼得·勒格尔
汉斯-约尔格·韦尔克
里夏德·菲舍尔
西比乐·翁加尔
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Sued Chemie AG
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Sued Chemie AG
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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B01J35/23—
    • B01J35/392—
    • B01J35/393—
    • B01J35/394—
    • B01J35/396—

Abstract

The present invention relates to a carried catalyst comprising a carrier on which a first catalytically active metal in the form of nano particles is applied, further comprising a second metal in the form of nano particles, and wherein the nano particles of the first and second metal are stabilized partly with S-donor ligands, and the second metal has a higher affinity to S-donor ligands than does the first metal.

Description

The metallic catalyst of load and manufacture method thereof
The metallic catalyst that the present invention relates to a kind of load with and manufacture method.
The metallic catalyst of load is particularly useful for synthetic chemistry and petrochemical industry processing, and wherein smaller metallic particles is deposited on the carrier surface of a solid.
The metallic catalyst of load is often used a method manufacturing that multistep is rapid.At this, in a first step with the metal salt solution impregnated carrier material of desired metal.In one second step, remove solute and a third step, calcine described carrier later on again, wherein, described metal is converted to oxide form by heat treatment from carrier.In one the 4th step, for example convert metal catalytic activity, highly dispersed to then by hydrogen, carbon monoxide or wet-chemical reducing agent.Then, generally in one the 5th step, for example stablize or the dried metallic catalyst that comes steady load of stablizing of metallic particles by depositing by means of oxidation (passivation) by wetting by means of oil.
The utilization rate of reduction between 70% to 90%, in other words, be deposited on metal on the carrier 10% to 30% not by catalyzing activation.
WO 2004/045767 discloses a kind of method of making the metallic catalyst of load, be when making catalyst, to constitute a kind of organic complex, after it constitutes described organic complex in the reducing metal with the formation catalyst before or partially or even wholly be decomposed.This catalyst has high metal spread value, and uniform distribution is arranged on carrier.This catalyst is especially effective at Fischer-Tropsch catalysis method and the conduct absorbent that the removal organosulfur compound is used from hydrocarbon.
DE 601 01 681 T2 disclose a kind of method of making a kind of precursor of co-based fischer-tropsch catalyst, wherein with carrier of a kind of cobalt salt dipping, and the carrier that flooded of calcining, and the material that has obtained mutually calcining with the catalytic activation cobalt oxidation of a correspondence wherein.
DE 690 10 321 T2 disclose a kind of method of making catalyst, wherein distribute on the outer periphery surface of the oxide carrier of the oxidation of the porous cobalt of a catalytically effective amount, wherein this catalyst can be used for forming gas is changed into hydrocarbon.
In order to reach the metallic particles of the least possible part that on a carrier, distributes as far as possible equably, also propose on common catalyst carrier, to lay metallic colloid or metal nanoparticle.
So DE 44 43 705 A1 have illustrated the monometallic and the bimetallic colloid of the tension stability of the VIII of a kind of manufacturing cycle table and Ib family metal, described colloid can be separated into powder shape and be used for the precursor compound of the eelctro-catalyst of fuel cell.
DE 197 53 464 A1 disclose palladium that a kind of colloid palladium with average particulate diameter 0.2 to 2nm makes bunch, and wherein at least 80% palladium cocooning tool has the particle diameter that departs from 0.2nm with this average particulate diameter at the most.At this, preferably stablize described palladium bunch with the phosphorus part.In addition, the disclosure document relate to contain be laid in a colloid palladium on the carrier contain the palladium heterogeneous catalyst.
DE 197 45 904 discloses a kind of by make the method for the colloidal metal solution of platinum, rhodium, rhotanium, iridium or palladium with the corresponding metallic compound of reduction conversion.In order to stablize this colloidal metal solution, use at least a cation exchange polymer.At this, preferably adopt the cation exchange polymer of sulfuration.The colloidal metal solution of this polymer stabilizing similarly is used as the catalyst of fuel cell.
Nano metal can be in water-borne glue body stabilisation, yet usually but can not be separated, and be merely able to higher dilution factor soluble in water, thereby be not suitable for catalyst precarsor.Be well known that equally water-soluble nano metallic colloid adopts hydrophilic P or N alms giver's part (J.S.Bradley in " Clusters and Colloids " (Herausgeber G.Schmid) VCH.Weinheim 1994).
The lewis base that P, N and S alms giver's part are considered to have the metal complex of transition metal definition to be connected, this is well known that the catalytic action that damages metal.Especially be well known that sulphur is catalyst toxicity (B.Cornils et.al. " catalysis from A-Z ", 2 Nd, Wiley VCH 2003), thus the part of sulfur-bearing seldom adopted, and because especially to cross metal or cation after so-called " soft ", for example platinum, palladium, gold and silver can produce the metal center of the non-activity that no longer shows catalytic activity.
The part that in above-mentioned patent application, illustrates, also attempt also to use simultaneously the compound of lithium salts and so on of sulphur betaine for example with surfactant.
Task of the present invention is to propose another kind of novel metallic catalyst, and wherein, described metal is in the good activity of demonstration in the catalysis method technology and optionally nano particle or colloidal form.
Finishing of this task is according to the present invention; a kind of catalyst that comprises a carrier is provided; on described carrier, lay first metal of a kind of nano particle or colloidal form; wherein said first metal is catalytic activity preferably; also comprise a kind of second metal of form of nanoparticles and regional stablize described first and second metals, and described second metal there be the compatibility to S alms giver part higher than first metal with S alms giver's part.
Find surprisingly, cause the poisoning and the inactivation of catalyst or its metal center although generally believe sulphur, but in the catalytic reaction as described in the present invention by means of sulphur alms giver (S alms giver) part stabilized nano particle a kind of good activity is arranged fully, provide catalyst as described in the present invention thereby can use with the stable metal nano dispersion of S alms giver's part.
" than high-affinity " notion refers to according to the present invention, second metal or metal cation constitute more stable metal-S alms giver's ligand complex on the thermokinetics with S alms giver's complex compound reaction (advantage on the Dui Ying complex compound dynamics in other words) and/or than first metal quickly than first metal.In the category of the Pierre of hard and soft acid and base (HSAB) pine notion, this refers to " soft " S alms giver part (soft lewis acid) and preferentially reacts with " soft " lewis base than late transition metal.
Observe surprisingly, add a kind of its compatibility of S alms giver's part second metal higher than " harder " metal of first caused first metal catalytic activation further, because sulphur alms giver part is preferentially swum second " softer " metal to non-activity in the catalysis category, and obtains stable combination.By said doping of another kind of expression way or selection " poisoning ", thereby enable to provide the high stability nano-colloid antigravity system of nano particle in other words to many catalytic reactions.
Preferably, described first metal is selected from the group that is made of Fan, Qiu, chromium, cobalt, ruthenium, rhodium, nickel, iron, platinum, palladium, iridium, copper and zinc or its mixture.At this, can adopt metal such as platinum, palladium, iridium and the copper of " soft " relatively according to the present invention.
According to the present invention, mixture is interpreted as or the mixture of the metal suspension thing that classical metal alloy or two kinds of S alms givers that only produce a kind of physical mixed have stablized.
At this, especially preferred is that described metal is cobalt, ruthenium, nickel, platinum, palladium and copper, very particularly preferably be cobalt, platinum, palladium and ruthenium.Thereby, can carry out many Catalytic processes, for example three times, the selective hydration of diplodization compound, Fischer-Tropsch catalysis, selective oxidation, the complete oxidation of hydrocarbon, the reformation of hydrocarbon.
Second metal is selected from silver and gold or it is as the defined mixture of preamble.Silver and gold are compared with above-mentioned " first " metal of " firmly " has very high compatibility to sulphur alms giver part, combines thereby described sulphur alms giver part preferentially enters one with silver-colored and gold.Thus, on the nano particle of the metal of first catalytic activity or nano-colloid, provide free binding site for catalysis.
Hereinafter, use the notion of nano particle and nano-colloid convertibly.According to the present invention, this notion both had been interpreted as that the single metal atom also can be understood as the cluster of metallic atom.
Preferably, sulphur alms giver part is selected from replacement and branch non-replacement and non-branch alkyl thionyl, alkenyl thionyl and acyl thiophene alkynes base thionyl and replacement and non-replacement.Especially preferredly be alkyl hydrosulfide branch, straight line, for example hexyl mercaptan, heptanthiol, spicy thioalcohol, decyl mercaptan, lauryl mercaptan or the like.
In a particularly preferred embodiment of the present invention, the weight ratio of first pair second metal is in the scope of 1:1 to 20:1, preferably in the scope of 1:1 to 7:1.If this weight ratio is less than 1:1, silver and gold participate in catalysis and damage activity of such catalysts in some cases or optionally have a big risk.Under the situation of the ratio that is higher than 20:1, no longer can provide enough silver atoms or gold atoms to use, thereby the metal center of the catalytic activity of first metal keep hidden by sulphur alms giver part, thereby limits activity of such catalysts of the present invention significantly.
The tenor of catalyst (amounts of first and second metals) is typically at 0.001 to 10 weight % as described in the present invention, and preferably between 0.01 to 7 weight %, especially preferred is 0.03 to 5 weight %, depends on the reaction of carrying out with this catalyst.
The size of nano particle is in 0.5 to 100nm scope, preferably in 0.5 to 50nm scope, it is most preferred that the scope 0.5 to 5nm, and wherein, described nano particle has a kind of uniform size distribution.
Metal surface area that is to say, the metal surface area of the carbonization activity of catalyst, for every gram 15 to 40m 2, measure by means of classic methods such as CO absorption process.
Preferably, the spread of described nano particle metal (no matter preferably be first or second metal, more preferably only first metal)〉40%." spread " of the metallic catalyst of load is interpreted as, all surfaces metallic atom of all metallic particles of first carrier is to the ratio of the sum of all metallic atoms of described particle.Generally preferably spread value than higher, because can obtain many metallic atoms to catalytic reaction in this case.That is to say, under the situation of the comparison high diffusive degree value of the metallic catalyst of a load, can reach certain catalytic activity with relatively more a small amount of metal that uses.
The spread of a metallic catalyst depends on the average particulate diameter of described metal dispersion as described in the present invention.Yet be noted that the accumulation that may occur described metallic particles with the metallic particles supported catalyst agent carrier of nano particle the time at this, this can cause the decline of the spread.
The metal spread of catalyst for example can be determined by means of the chemical absorbing of catalyst samples as described in the present invention.At this, when calculating the spread based on total chemical absorbing of sample.
The carrier of catalyst preferably contains titanium dioxide, aluminium oxide, zirconia, silica, zinc oxide, magnesia, aluminium oxide-silicon oxide, carbonic acid silicon, magnesium silicate as described in the present invention, perhaps two or a plurality of mixtures.Described carrier is porous preferably, and is preferably the form of powder or formed body.At this, described formed body can also be got different geometries, for example a honeycomb shape that is called only stone toward contact.Said only stone or make or with a kind of metal or a kind of alloy manufacturing, described alloy is for example sold on market by Emitec and Alantum company with pottery.
Task of the present invention is similarly finished by the method for making a kind of metallic catalyst of the present invention, and described method comprises following steps:
A) the stable metal suspension thing of a kind of nano particle S alms giver part of a carrier and first metal and second metal is come in contact.Wherein, described second metal has higher compatibility than the described first metal pair S alms giver part;
B) remove the suspension media;
C) under certain situation, stablize the catalyst of described load.
At this, a kind of nano particle metal suspension thing or nano particle alloy suspended physical solution are to have the metallic particles of average particulate diameter≤100nm or the suspension of alloying pellet in this category.Metal nanoparticle is alloy nanoparticle in other words, for example can relate to the monocrystal of monocrystal or sintering.
Determine, the metallic catalyst of load or the alloy catalyst of load can be by means of a kind of simple three step method manufacturings, wherein, at first with a kind of metal suspension thing of nano particle or with a kind of metal suspension thing load carriers material of nano particle, wherein metallic atom is in oxidation state 0, and then removes the suspension media.
Yet,,, for example can also partly remove the suspension media at this if also will deposit or transport the catalyst (wet stable) that the metallic catalyst of described load or alloy catalyst and described suspension media are suitable for stablizing described load.For example can also fully remove described suspension media, and the catalyst of described load or be directly used in reaction, or, stablize, for example by wet stable or do stable carrying out with a special step in order to deposit or to transport.
The fact shows; under the situation about coming in contact at the metal suspension thing that makes a carrier and nano particle or with the alloy suspended thing of nano particle; described metallic particles or alloying pellet evenly and the highly dispersed degree be deposited on the carrier and do not change its oxidation grade; thereby, can make the metallic catalyst or the alloy catalyst of the wherein load of catalytically-active metals intimate 100% by means of the method for the invention.
In addition, the advantage of method also has as described herein, the method step of solid/liquid separation, described burning or described metallic reducing in the manufacture method of the metallic catalyst of the known load of prior art or alloy catalyst also can replace by comprising the single method step of removing the suspension media according to the present invention.
Compare with the prior art of making the metallic catalyst of load with the rapid method of a kind of high multistep that expends accordingly, according to the present invention, the metallic catalyst or the alloy catalyst of load be can make with a kind of simple three step method, thereby the metallic catalyst or the alloy catalyst of load advantageously made by means of method as described in the present invention on can method and technology on the simple and cost.
As mentioned before, under the situation of prior art known " classics " method, at first the metal salt solution dipping of catalyst carrier with desired metal.Slaine corresponding to adopting that is to say, corresponding to the ion that adopts, then the waste gas that is harmful to environment that appearance must be caught and remove in the oxidation step of following, for example nitrated gas, ammonia or hydrohalogenation compound.In method as described in the present invention, saved this oxidation step, and without slaine, thereby do not occur anyly must eliminating the waste gas that is harmful to environment expensively according to method of the present invention.
In method as described in the present invention, save the reduction step of using in the part common in the prior art, in described reduction step, for example metal oxide has been reduced into the metal of catalytic activity by means of hydrogen or carbon monoxide.In order to improve the utilization rate of reduction, that is to say that the ratio for the metal oxide of the metal pair catalytically inactive that improves catalytic activity often adopts so-called reduction to improve at this.This reduction improvement that for example often relates to gold and platinum, usually can be with the form of its salt together with the slaine of desirable catalyst metals attached on the carrier.According to the method as described in the present invention of having save the common reduction step of prior art, can cancel the use that reduction improves accordingly, thereby can advantageously implement method of the present invention by cost.
Because no longer require the reactions steps of oxidation or reducing metal corresponding to the method for the metallic catalyst of making load as described in the present invention or alloy catalyst, under the situation of method as described in the present invention, can also save corresponding equipment that carries out this reaction and device.At this, it is favourable especially saving consersion unit and device, because these security concepts of generally having relatively high expectations, and therefore equipping and keeping in repair and can occur more continually aspect its operating cost.
Under the method situation of the common five-stage of prior art, no matter be that oxidation step or reduction step are all carried out under than higher temperature.At this, especially use under the situation of pulverous carrier material and want the sintering carrier.In addition, also will carry out the sintering of metal precursor or metal in above-mentioned reactions steps, also be similarly for alloy.High temperature may cause that metal embeds in the carrier structure in addition, and the inactivation of described metal or undesirable article of the undesirable side reaction of formation catalysis may take place thus.In contrast, remove the suspension media corresponding to method as described in the present invention and can under lower temperature, carry out, thereby neither can cause the sintering of carrier material, also can not cause metal to embed in the carrier structure.
The advantage of method also has as described herein in addition, with metallic catalyst or the alloy catalyst that can make load with high catalytically-active metals load capacity, wherein, can need as described in the present invention method on the angle of step, to carry out in some cases to reach high load capacity multiplely.In this method as described in the present invention, cause described metal or alloy to be evenly distributed on the carrier simultaneously and the higher spread of metallic particles is arranged simultaneously.
By means of method as described in the present invention, can also make the metal or the alloy catalyst of the load of a plurality of different metals of deposition on it or alloy.For example can repeatedly carry out method as described in the present invention at this, wherein, when carrying out for the first time, on carrier, adhere to a kind of first metal, and when carrying out for the second time, on carrier, adhere to second metal.
The metallic catalyst of load often not with carrier material wherein with the state supply of material of the catalytically-active metals load of its form of having reduced.More be, often provide with corresponding slaine or metal oxide supported carrier that it must be by own redox of user or reduction by catalyst manufacturer.According to the method for the invention; the metal or the alloy catalyst of the load of making can conclude the business fairly simplely or deposit; for example under the protective gas condition; by means of method as described in the present invention make load with reactive metal or reactive alloys load the manufacturing of catalyst, just can transfer to catalyst manufacturer and locate.
According to method of the present invention, also has the advantage that deposit nanometric particles metal or alloying pellet do not require adhesive.
According to one of the method for the invention preferred embodiment, described carrier and nano particle metal suspension thing or come in contact with nano particle alloy suspended thing are by carrying out described metal suspension thing or the splash of alloy suspended thing on carrier.Thus, guarantee that described carrier lays nano particle metal suspension thing or alloy suspended thing to a great extent equably.Described carrier lays metal suspension thing or alloy suspended thing in fact equably, constitute to make the metallic catalyst of the load that as far as possible all even highly dispersed metal coating or alloy coat are arranged or the basis of alloy catalyst.For the metallic particles of getting rid of nano particle or the reaction of alloying pellet and composition of air, preferably, under a kind of protective gas environment, carry out the splash of described metal suspension thing or alloy suspended thing.This depends on metal or suitable nitrogen or the protection of inert gas do gas, for example helium, neon, argon or krypton.
If especially described carrier relates to the catalyst carrier of porous, method can be carried out in a reative cell as described in the present invention, makes and wherein is full of eddy current and negative pressure by sucking this reative cell.At this, the step a) of method comprises following steps as described herein:
1) catalyst carrier of porous is put in the reative cell, by sucking feasible eddy current and the negative pressure of wherein being full of of this reative cell;
2) described nano particle metal suspension thing or alloy suspended thing are introduced in the described reative cell;
3) constitute gas/metal suspension or alloy suspended thing mixture;
4) constantly the mixture band that obtains from step 3) is crossed described catalyst carrier.
Determine, especially the inner surface of the catalyst carrier of porous is by means of wherein being full of by sucking the reative cell of this described eddy current that causes and negative pressure, flood equably to a great extent by the metal suspension thing of introducing the nano particle in this reative cell or alloy suspended thing, just lay.In this regard importantly, the inner space of the catalyst carrier of described porous is interconnected at least in part, thereby can be through described catalyst carrier circulation said mixture.As to above-mentioned in a reative cell of being sucked splash or alternative replacement scheme of laying, according to the method for the invention another preferred embodiment, make described carrier and nano particle metal suspension thing or come in contact, undertaken by described carrier is immersed in the described metal suspension thing or in the described alloy suspended thing with nano particle alloy suspended thing.At this, described catalyst carrier is immersed in described nano particle suspension or the alloy suspended thing, remove the metal suspension thing or the alloy suspended thing that do not stick on the carrier surface, then carry out the step b) of method as described herein.
Preferably; the method step that is associated with immersion; for example remove unnecessary metal suspension thing or alloy suspended thing, under a protective gas environment, carry out, undesirable reaction takes place with the composition that prevents metal nanoparticle or alloy nanoparticle and air from carrier.Protective gas also can use for example inert gas helium, neon, argon and krypton, and, depend on metal that is adopted or the alloy that is adopted, can use nitrogen.
According to the method for the invention another preferred embodiment, make described carrier and nano particle metal suspension thing or come in contact with nano particle alloy suspended thing, carry out by means of the micropore completion method.At this, carrier is contacted with the suspension of its volume corresponding to the amount of the micropore volume of used carrier.With described suspension load after described carrier keep dry especially, from but loose.
Make the metallic catalyst of load as described in the present invention, can repeat above-mentioned alternative replacement scheme of method as described herein continually, up to described the catalyst cupport catalytically-active metals of desired amount or the catalytic activity alloy of desired amount to some extent.
Corresponding to another alternative replacement scheme of method as described herein, preferably, the metal suspension thing that described carrier is put into nano particle with the nano particle metal or the Nanoalloy particle of scheduled volume or the alloy suspended thing of nano particle are removed the suspension media according to the step b) of method as described herein then.Guaranteeing thus can be with metal or the alloy load described carrier of a single method flow with desired amount.
For this reason, for example at first the carrier of powder shape is suspended in the metal suspension thing or alloy suspended thing of nano particle.In the process of removing the suspension media; the content of the metal of nano particle or alloy rises in the suspension; carry out the thickening deposition of metal nanoparticle on the carrier or alloy nanoparticle thus; wherein by removing the suspension media till drying, the almost whole metal nanoparticles of former suspension or the content of alloy nanoparticle all are deposited on the catalyst carrier.
Preferably, the replacement scheme of the method for the invention also is to carry out under a kind of protective gas environment, especially for preventing described metallic particles of air oxygen or alloying pellet.
Nano particle metal suspension thing or alloy suspended thing often at high temperature are unsettled, because, may bump by having improved the motion of particle, and the accumulation of the nano particle of generation correspondence.In order to prevent the accumulation of nano particle, according to method as described herein another preferred embodiment, remove the suspension media and carry out in a vacuum, preferably in the protective gas environment, carry out.
In order to prevent the accumulation of metal nanoparticle or alloy nanoparticle; a particularly advantageous embodiment according to the method for the invention; removing the suspension media carries out under 120 ℃ temperature; advantageously under 100 ℃ temperature, carry out; preferably under 90 ℃ of temperature, carry out, more preferably under 80 ℃ of temperature, carry out, preferably under 70 ℃ of temperature, carry out again; particularly preferably be under 60 ℃ of temperature and carry out, most preferably under 50 ℃ of temperature, carry out.
If particularly the fact shows, metal nanoparticle does not have high compatibility to carrier material, and therefore can not be fixed on well on the carrier, can propose, after removing the suspension media, nano particle is fixed on the carrier by means of a specific method step.A particularly preferred embodiment according to the method for the invention; advantageously; if after the step b) of removing the suspension media; connect with stabilizing step fixing step c in other words); by means of this step; preferably under the protective gas environment, described metallic particles or alloying pellet are fixed on the carrier.
Said fixing step c) method is in every way carried out, for example by using adhesive.A simple and favourable embodiment of cost on method and technology according to the method for the invention; fixing step c) carrier of metallic particles by load or alloying pellet is heated to 120 ℃ to 700 ℃ temperature and carries out; preferably; under a kind of protective gas environment, carry out, undesirable reaction takes place with the composition that prevents described metallic particles or alloying pellet and air.
Another preferred implementation according to the method for the invention can propose; fixing step c) can be undertaken by load is heated to 300 ℃ to 650 ℃ temperature with the carrier of metallic particles or alloying pellet; preferably be heated to 350 ℃ to 600 ℃ temperature; more preferably be heated to 400 ℃ to 550 ℃ temperature, particularly preferably be the temperature that is heated to 450 ℃ to 500 ℃.
In order to deposit the metallic catalyst or the alloy catalyst of the load of making harmlessly in the long time according to the method for the invention; stablize described catalyst and under certain situation the described catalyst of aeroseal ground packing, the environment of a protective gas is wherein arranged in described packing.Thus, prevent that metal nanoparticle or alloy nanoparticle from can react away with the composition effect of air, this reaction may cause catalysqt deactivation.Corresponding to a particularly preferred embodiment of method as described herein; remove the step b) subsequent fixed step or the stabilizing step d of suspension media); this step is included under a kind of protective gas environment and deposits, with the carrier of metallic particles or alloying pellet load.
Determine; if described suspension media is water or a kind of organic solute, preferably a kind of aromatic series solute, preferably toluene, benzene; or the like, so described metal nanoparticle or alloy nanoparticle just can be especially equably and are laid on the carrier with the higher spread.At this, according to the method for the invention another preferred embodiment, described suspension media is water or a kind of organic solute, preferably toluene.At this, described suspension media can also contain with S alms giver's part other composition as the stabilizing agent of reply nano particle accumulation.
In the method, the carrier of use can be a kind of porous carrier as described herein, also can be the carrier of no porous.The carrier of porous is a feature with big surface area especially, and described big surface area almost is made of the micropore inwall entirely.In order can be fixed on catalytically-active metals as much as possible or catalytic activity alloy on the predetermined carrier volume, according to the method for the invention another preferred embodiment, described carrier is a kind of carrier of porous.
Preferably, described carrier adopts the mixture of titanium oxide, aluminium oxide, zirconia, silica, zinc oxide, magnesia, aluminium oxide-silicon oxide, carbonic acid silicon, magnesium silicate or above-mentioned two or more to constitute.At this, can be with mixed form, however especially use above-mentioned oxide, carbonate or silicate with the compound form of determining, preferably with TiO 2, Al 2O 3Form use, preferably with α-, β-, γ-or δ-Al 2O 3, ZrO 2, SiO 2, ZnO, MgO, Al 2O 3-SiO 2, SiC 2Perhaps Mg 2SiO 4Form use.
The kind of the carrier material that is adopted and character usually depend on the metal or the alloy that should be fixed on the described carrier.
According to of the present invention another preferred embodiment, preferred amorphous porous carrier, preferably, those have big mesopore and/or macropore ratio, wherein in category of the present invention, the conceptual understanding of macropore and mesopore is that diameter is 1 to 50nm hole greater than 50nm or diameter.
According to another alternative alternate embodiments of the method for the invention, described carrier can be a kind of crystal carrier, preferably a kind of molecular screen material, for example a kind of zeolitic material or a kind zeolitic material.Preferred molecular sieve is silicate, alumina silicate, aluminum phosphate, SAPO.Phosphate metal aluminium or phosphorus silicic acid metallic aluminium.
What molecular screen material to make catalyst carrier with; depend on the metallic particles or the alloying pellet that will on carrier, deposit on the one hand, depend on the metallic catalyst of the load of making according to the method described in the present invention or the application that alloy catalyst should drop on the other hand.Such example application is separation, catalytic applications and catalytic applications and the combination that separates.
In the prior art, known many methods of pressing the characteristic of corresponding application purpose decision molecular sieve, for example structure type, chemistry association, ion-exchange capacity and activation characteristic.Yet generally preferably, the molecular sieve of one of corresponding following structure type: AFI, AEL, BEA, CHA, EUO, FAU, FER, KFI, LTA, LTL, MAZ, MOR, MEL, MTW, OFF, TON and MFI according to the present invention.Although some in the above-mentioned material are not real zeolites, on document, are often referred to zeolite, and in category of the present invention, also should belong to the zeolite notion.
The molecular screen material that preferably also has those to use amphipathic compound to make according to the present invention.For example preferred those at US 5,250, the material of explanation in 282, and should be merged into the present invention by reference.Amphipathic compound for example is also at the Chemical of Winsor Reviews, explanation in 68 (1), 1968.Other be suitable for and according to the present invention preferred this type of molecular screen material also in " Review of Ordered MesoporousMaterials " U.Ciesla and F.Schuth, Microporous and Mesoporous Materials, 27, (1999), explanation is arranged among the 131-49, and integrate with the present invention by reference.
According to the method for the invention another preferred embodiment, described catalyst carrier is a kind of powder, a kind of formed body or a kind of only stone.Preferred formed body for example is spheroid, annulus, cylinder, perforation cylinder, trilobal body, cone, and a preferred solely stone for example is a kind of honeycomb body.
In principle advantageously, the metallic particles or the alloying pellet that are deposited on the carrier are as much as possible little, because can reach a kind of very high spread thus.Be interpreted as in this spread, constitute the ratio of the sum of the quantity of metallic molecule of described nano grain surface and the metallic atom on carrier.
The nano particle metal suspension thing that uses or the average particulate diameter of alloy suspended thing also depend on the pore size distribution of the material and the carrier material of later Application of Catalyst, catalyst carrier.According to of the present invention one preferred embodiment, the particle of described nano particle metal or alloy suspended thing has 0.5 to 100nm average particulate diameter, preferably have 1 to 50nm, more preferably have 1 to 25nm, further preferably have 1 to 20nm, again preferably 1 to 15nm, and particularly preferably be 1 to 10nm average particulate diameter.
A particularly preferred embodiment according to method of the present invention, the particle of nano particle metal suspension thing or alloy suspended thing has 1 to 9nm, preferably 1 to 8nm, more preferably 1 to 7nm, further preferably 1 to 6nm, and particularly preferably is 1 to 5nm average particulate diameter.
By means of method of the present invention, the alloy catalyst that may make the metallic catalyst of load or load is together with metal or alloy.Yet prerequisite but is, can or be made the metal suspension thing or the alloy suspended thing of nano particle by described alloy by described metal.
The preferred metal according to the present invention for example is the 5th family (Va of family, Vb) metal, for example a vanadium; The 6th family (VIa, VIb) metal, for example chromium, molybdenum and tungsten; Seven races (VIIa, VIIb) metal, for example manganese and rhenium; Eight, nine and ten families (VIII, VIIIa) metal, for example iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum.
Particularly preferred alloy is the alloy of one of above-mentioned metal according to the present invention.
Determined,, can make to have and distribute very uniformly and the Co catalysts of the load of the very high spread of described metallic particles or the ruthenium catalyst of load by means of method as described in the present invention.According to of the present invention another preferred embodiment, at this, the metal suspension thing of described nano particle is the suspension of metallic cobalt or ruthenium.Said cobalt nano-particle or ruthenium nano-particle have 8 to 28nm average diameter.The spread of described cobalt granule or ruthenium particle is 0.5% to 20% advantageously, is preferably 1 to 15%, and particularly preferably is 1 to 10%.
Especially except iron, cobalt and ruthenium show a kind of very high catalytic activity in described Fischer-Tropsch is synthetic, and the mixture by carbon monoxide and hydrogen in described Fischer-Tropsch is synthetic synthesizes hydrocarbon.Accordingly, method also is applicable to the so-called fischer-tropsch catalysts of manufacturing as described herein.
In this regard preferably as carrier material especially titanium oxide (both can also can or use its mixed form), silica-Al with the anatase of modification with rutile 2O 3, modification α-, β-, γ-or δ-Al 2O 3In aluminium oxide and the mixture of titanium oxide and zirconium dioxide.At this, the especially preferred γ-Al that is based on 2O 3Carrier.
As its alternative replacement scheme, titanium oxide/zirconic carrier preferably.Preferred embodiment at first do not have chlorine ground and clean titanium dioxide according to one, use a kind of titanium dioxide precursor then, for example ZrO (NO 3) 2X 4H 2O, dipping, dry and calcining are to constitute a kind of ZrO 2/ TiO 2Carrier.At this, described carrier comprises the zirconium dioxide that reaches 50 weight % with respect to the gross weight of carrier, preferably reaches 35 weight %, more preferably reaches 20 weight %, preferably reaches 10 weight % again, most preferably reaches the zirconium dioxide of 0.1 to 5 weight %.May show, can add for example metals such as rhenium, zirconium, hafnium (Cer) and uranium, Fischer-Tropsch is synthesized the activity and the recyclability of the Co catalysts that improves load cobalt.Corresponding for example have on it metallic catalyst of load that both deposit cobalt nano particles also deposits the carrier of rhenium nano particle, equally can be by means of method manufacturing of the present invention.At this, what for example do is both to have contained the nano particle metal suspension thing that cobalt nano-particle also contains the rhenium nano particle and implement method as described in the present invention with a kind of.As its alternative replacement scheme, for example can at first use the cobalt nano-particle load carriers by means of method as described in the present invention.Co catalysts to consequent load reuses method as described in the present invention then, and the rhenium suspension of wherein using a kind of nano particle is as the metal suspension thing.
Except the Co catalysts or rhenium catalyst of load, using as described in the present invention, the Raney nickel of the load of method manufacturing also has a kind of very even and highly dispersed metal nanoparticle distribution.According to the method for the invention another preferred embodiment, at this, the metal suspension thing of nano particle is the suspension of metallic nickel.The Raney nickel of load especially can be used for the desulfurization of gas or liquid.
By means of method as described in the present invention, can make the metallic catalyst or the alloy catalyst of load with certain every gram metallic area.At this, described metal surface area or alloy surface are long-pending can be changed in the scope of a non-constant width.According to one of the method for the invention preferred embodiment, total metal surface area of the metallic catalyst of described load or alloy catalyst is 0.01 to 60m 2/ g metal, advantageously 10 to 55m 2/ g, preferably 12 to 50m 2/ g is more preferably 14 to 45m 2/ g, most preferably 15 to 40m 2/ g.
Corresponding to method of the present invention another preferred embodiment; make metallic catalyst or alloy catalyst by means of this embodiment; its metallic particles or alloying pellet have 1 to 10% the spread; advantageously be higher than 20%; advantageously be higher than 30% again, preferably be higher than 35%, preferably be higher than 40% again; more preferably be higher than 45%, especially preferred is to be higher than 50%.
The invention still further relates to a kind of metal suspension thing of nano particle or a kind of alloy suspended thing of nano particle and make the metallic catalyst or the alloy catalyst of load.
As described in the present invention in the method, the metal dispersion market of the nano particle that uses is on sale, and can or be directly used in method as described in the present invention, also can after regulating metal particle concentration or alloying pellet concentration accordingly, be used for method as described in the present invention.
Explain the present invention by means of unrestriced illustrative embodiment below.
Example 1: make a kind of palladium carried catalyst
The solution that in toluene, adds the palladium nano-particles contain 2.25 weight % (stable, Pd content 26.8%, granular size 1.2nm, Hamburg, Germany Nanosolutions Gmbh is on sale) with lauryl mercaptan.With the carrier of alumina coating at room temperature by the immersion solution impregnation.This α-Al 2O 3Coating has 16m 2BET value and the 225m of/g 3The microvoid content of/g.Adopt the coating of groove (Hamburg, Germany Linde AG) on alumina supporter by the ZrO that has 5% 2α-Al 2O 3Constitute.Then the carrier that has flooded at 120 ℃ temperature drying is one hour, then heats three hours 350 ℃ temperature.This catalyst has 0.2g/m 2Palladium.
Example 2: manufacturing has the palladium carried catalyst that silver mixes
In toluene, add the palladium nano-particles (palladium of 2.2 weight %, stable with lauryl mercaptan, Pd content 26.8%, granular size 1.2nm, Hamburg, Germany Nanosolutions Gmbh is on sale) and solution (the 0.187 weight % of silver nano-grain, stable with lauryl mercaptan, Ag content 47%, granular size 10nm).Carrier as the usefulness alumina coating in example 1 is at room temperature used solution impregnation.Then, the carrier that has flooded at 120 ℃ temperature dryings one hour, and heated three hours 350 ℃ temperature.This catalyst has 0.2g/m 2Palladium and 0.2g/m 2Silver (ratio Pd:Ag=1:1).
The prior art of comparative example (according to EP 686 615 A1)):
By splash oxide impregnation alumina supporter (α-Al 2O 3Sheet, 4 x 4mm, BET 15m 2/ g, micro-pore diameter: 97% micropore〉40nm, micropore volume 226m 3/ g).Follow temperature drying, and heated three hours 350 ℃ temperature at 120 ℃.Resulting catalyst has 0.2g/m 2Palladium and 0.2g/m 2Silver (ratio Pd:Ag=1:1).
Example 4: catalysis
For the catalyst of catalyst and prior art more as described in the present invention carries out the reduction of acetyl in an ethylene stream.
Condition is:
GHSV 7000h -1, pressure 30 crust
Feed:0.15mol% C 2H 2, all the other C of 0.03mol% Co 2H 4
Reference value is selected 20 ℃ activity
In a Berty reactor, detect, comparative to obtain sheet/coating.
Table 1: the result of acetyl reduction
Conversion Selectivity A Temperature ℃
Compare catalyst 28.4 0.95 20.9
Example 1 30 0.95 20.3
Example 2 36 0.97 20.3
As above show shownly, from example 2, obtain optimum with the catalyst as described in the present invention that mixes of silver.With example 1 need not be that catalyst that silver mixes compares and reaches 20% activity and raise, that is to say, reach 20% conversion and raise.
Conventional catalyst with a prior art compares again, reaches 30% conversion rising.
Other catalyst as described in the present invention for example is the Pd/Au catalyst of selective hydration and partial oxidation.Pd, Pt, Pu, Rh individually combine with Ag or Au, are used for the complete oxidation of hydrocarbon, and Ni or Rh combine the reformation that is used for hydrocarbon with Ag and Au.

Claims (26)

1, the catalyst that comprises a carrier, on described carrier, lay a kind of first metal of form of nanoparticles, wherein said first metal is a catalytic activity, also comprise a kind of second metal of form of nanoparticles and wherein partly stablize described first and second metals, and described second metal there be the compatibility to sulphur alms giver part higher than first metal with sulphur alms giver part.
2, catalyst as claimed in claim 1 is characterized in that, described first metal be selected from by tungsten, vanadium, chromium, cobalt, ruthenium, rhodium, nickel, iron, platinum, palladium, iridium, copper and zinc with and composition thereof the group that constitutes.
3, catalyst as claimed in claim 2 is characterized in that, described second metal is selected from silver and gold or its mixture.
4, catalyst as claimed in claim 3 is characterized in that, sulphur alms giver part is selected from replacement and branch non-replacement and non-branch alkyl thionyl, alkenyl thionyl and acyl thiophene alkynes base thionyl and replacement and non-replacement.
5, catalyst as claimed in claim 4 is characterized in that, the weight ratio of first pair second metal is in the scope of 1:1 to 20:1.
6, catalyst as claimed in claim 5 is characterized in that, described nano particle has 0.5 to 5nm diameter.
7, catalyst as claimed in claim 6 is characterized in that, described metal load is the % of 0.001 to 10 weight with respect to total catalyst weight.
8, catalyst as claimed in claim 7 is characterized in that, the metal surface area of described catalyst is 15 to 40m 2/ g.
9, catalyst as claimed in claim 8 is characterized in that, the spread of described metal〉40%.
10, catalyst as claimed in claim 9, it is characterized in that, the carrier of described catalyst contains a kind of titanium dioxide, aluminium oxide, zirconia, silica, zinc oxide, magnesia, aluminium oxide-silicon oxide, carbonic acid silicon, magnesium silicate of being selected from, perhaps the material of two or a plurality of mixture.
11, catalyst as claimed in claim 10 is characterized in that, preferably a kind of powder of described carrier or a kind of formed body.
12, make the method for the catalyst of load according to any one of the preceding claims, described method comprises following steps:
A) the stable metal suspension thing of a kind of nano particle S alms giver part of a carrier and first metal and second metal is come in contact.Wherein, described second metal has higher compatibility than the described first metal pair S alms giver part;
B) remove the suspension media;
C) stablize the catalyst of described load.
13, method as claimed in claim 12; it is characterized in that; described carrier and nano particle metal suspension thing or come in contact with nano particle alloy suspended thing; undertaken by a kind of method; this method be selected from the splash of described metal suspension thing on carrier, be immersed in described carrier in the metal suspension thing or by means of the micropore completion method, all methods are preferably carried out under a kind of protective gas environment.
14, method as claimed in claim 13 is characterized in that, removes the suspension media and carries out under vacuum, preferably carries out under a kind of protective gas environment.
15, as claim 13 or 14 described methods, it is characterized in that, remove the suspension media and undertaken by drying under 120 ℃ temperature.
16, method as claimed in claim 15 is characterized in that, stabilizing step c) undertaken by the temperature that the carrier of carried metal particle is heated to 200 ℃ to 500 ℃, preferably, under a kind of protective gas environment, carry out.
17, method according to any one of the preceding claims is characterized in that, described suspension media is water or a kind of organic solute or its mixture.
18, method as claimed in claim 17 is characterized in that, described organic solution adopts a kind of aromatic series solute.
19, method according to any one of the preceding claims is characterized in that, a kind of porous carrier of carrier.
20, method as claimed in claim 19 is characterized in that, adopts the carrier of a kind of powder, a kind of formed body or a kind of only stone form.
21, method as claimed in claim 20 is characterized in that, the particle of described nano particle metal or alloy suspended thing has 0.5 to 100nm average particulate diameter.
22, method according to any one of the preceding claims is characterized in that, described nano metal suspension adopts and is selected from the metal suspension thing that is made of group cobalt, zinc, copper, iridium, vanadium, nickel, rhenium, tungsten, palladium, chromium, platinum, iron or its mixture.
23, method as claimed in claim 22 is characterized in that, the nano particle metal suspension thing of second metal adopts the suspension of argent, gold or its mixture.
As claim 21 or 22 described methods, it is characterized in that 24, first metal adopts the suspension of palladium, second metal adopts the suspension of silver.
As claim 21 or 22 described methods, it is characterized in that 25, first metal adopts the suspension of cobalt or ruthenium.
As claim 21 or 22 described methods, it is characterized in that 26, first metal adopts the suspension of nickel.
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