CN104226331A - Selective hydrogenation copper catalyst with core-shell structure and preparation method thereof - Google Patents
Selective hydrogenation copper catalyst with core-shell structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a selective hydrogenation copper catalyst with a core-shell structure and a preparation method thereof. The catalyst is composed of a copper core and an oxide shell layer which has a pore passage structure and is loaded with one or more of Ag, Co, Fe, Mn, Ni, Zn, Cr and Pd, wherein the diameter of the core is 5-500nm, the thickness of the oxide shell layer is 5-200nm, and the oxide shell layer is provided with pore passages with pore diameters being 0.1-20nm; the catalyst is prepared from the following ingredients by weight percent relative to the total weight of the catalyst: 5-90% of Cu, 5-90% of oxide shell layer, and 0.1-20% of one or more of Ag, Co, Fe, Mn, Ni, Zn, Cr and Pd; and the oxides of the oxide shell layer comprise one or more of silicon dioxide, aluminum oxide, titanium dioxide, stannic oxide, zirconium dioxide or ceric oxide. According to the selective hydrogenation copper catalyst, the operating period of the copper catalyst can be prolonged and the selectivity of the catalyst can be further improved.
Description
Technical field
The present invention relates to selective hydrogenation catalyst field, say further, relate to a kind of selective hydrogenation catalyst and the preparation method with nucleocapsid structure.
Background technology
Selective except alkynes, alkadienes field, mainly based on Pd catalyst, use copper catalyst little.Only have the KLP technology of Uop Inc. to use Cu to be main active component, it represents patent is US4101451, and its content is mainly to mixing C-4-fraction selec-tive hydrogenation de-carbon four alkynes, and only there is a few cover butadiene product equipment in the whole world in use KLP technology.The selective of Cu catalyst is better than Pd catalyst, and its subject matter is that the single cycle of operation is short, needs frequent regeneration.
Pd catalyst selective close to the limit, the improvement therefore for Pd catalyst is difficult to increase.In recent years, sight focuses on the body of Cu from new by some researchers, as (structures of copper-based catalysts such as Zhang Quanxin, physical property and the catalytic performance to the reflection of mixing carbon four selec-tive hydrogenation thereof, catalysis journal, 2002, 23:250-252) with Co, Ce modification Cu catalyst achieves the better selective and cycle of operation, (the Cooperative Effects in ternary Cu-Ni-Fe catalysts lead to enhanced alkene selectivity in alkyne hydrogenation such as Blaise Bridier, Journal of America Chemical society, 2010, 132, 4321-4327) achieve the almost propine-Propylene Selectivity of 100% and the acetylene-ethylene selectivity of 80% with Ni and Fe modification Cu catalyst.
Coating technology is mainly used to the reunion preventing catalyst granules, as (Thermally stable Pt/mesoporous silica core-shell nanocatalysts for high temperature reactions such as sang hoon joo, nature materials, 2009,8,126-131) available SiO is proposed
2shell stops Pt catalyst to be reunited when pyroreaction.So far, almost do not find that shell oxide can improve the report of catalyst choice.
How reducing the carbon distribution of selec-tive hydrogenation copper catalyst, improve its cycle of operation, is the current technical issues that need to address.
Summary of the invention
For solving produced problem in prior art, the invention provides a kind of selec-tive hydrogenation copper catalyst and the preparation method with nucleocapsid structure.The cycle of operation of copper catalyst can be improved, improve the selective of catalyst further.
An object of the present invention is to provide a kind of selec-tive hydrogenation copper catalyst with nucleocapsid structure.
Described catalyst is made up of core and the oxide shell layer with pore passage structure; The diameter of core is 5 ~ 500nm, is preferably 10 ~ 200nm; The thickness of oxide shell layer is 5 ~ 200nm, 5 ~ 30nm; It is 0.1 ~ 20nm that oxide shell layer has aperture, preferably the duct of 0.3 ~ 3nm;
Described core is made up of main active ingredient copper and auxiliary agent, and auxiliary agent is one or more in Ag, Co, Fe, Mn, Ni, Zn, Cr, Pd;
Oxide shell layer is: silica, aluminium oxide, titanium dioxide, tin ash, one or more in zirconium dioxide or ceria; Be preferably in silica, aluminium oxide or titanium dioxide one or more;
In the gross weight of catalyst for 100%:
(1) Cu, 5 ~ 90wt%; Be preferably 15-60wt%;
(2) oxide shell layer, 5 ~ 90wt%; Be preferably 30 ~ 80wt%;
(3) auxiliary agent, 0.1 ~ 20wt%.
Can also comprise one or more in alkaline element in described oxide shell layer, the content of alkaline element is 0.05 ~ 5% of overall catalyst weight.Described alkaline element is preferably as one or more in K, Na, Cs, Mg, Ca, Ba.
The specific area of described catalyst is 10 ~ 300m
2/ g, pore volume is 0.1 ~ 1.2mL/g.
Find after deliberation, when the aperture of oxide coating is little of time to a certain degree, oxide coatedly on Cu particle can effectively improve the selective of catalyst, this is mainly because the micropore in oxide creates confinement effect on the surface of Cu particle, prevent the polymerization of alkynes molecule, thus improve the selective of catalyst and the cycle of operation.Except pore size, oxide coating also must have certain thickness, just can demonstrate such confinement effect.The duct of shell oxide is for carrying reaction mass to stratum nucleare surface, and the confinement effect in duct effectively can stop the polymerization on stratum nucleare of alkynes and alkadienes, thus effectively improves the selective of catalyst.The area load promoter metal with catalyst with core-casing structure of gained contributes to improving the selective of catalyst further.
Two of object of the present invention is to provide a kind of preparation method with the selec-tive hydrogenation copper catalyst of nucleocapsid mechanism.
Comprise:
(1) preparation of stratum nucleare: be dissolved in the protectant aqueous solution of dissolved organic matter by the salt of described consumption by soluble copper salt and solubility auxiliary agent, add reducing agent, make solution A;
(2) preparation of shell: by water-soluble for the precursor of shell oxide or organic solvent, make solution B;
(3) solution B is joined in solution A while stirring, add acid or subtract and regulate the pH value of mixed solution 9 ~ 12;
(4) mixed solution that step (3) obtains is reacted 4 ~ 72h at 25 ~ 200 DEG C of temperature, obtained described catalyst after centrifugation or filtration, washing, oven dry, calcining.
0.5 ~ 5 times of the total mole number that the protectant molal quantity of dissolved organic matter (as being polymer, then molal quantity is the molal quantity of monomer) is copper and auxiliary agent;
Dissolved organic matter protective agent is: polyvinylpyrrolidone, polyethylene glycol, according to ethyleneimine, amine dendrimer, crown ether, carboxymethyl cellulose, CMC, lauryl mercaptan, citric acid, , 4-propyl bromide, softex kw, TTAB, ethamine, propylamine, butylamine, lauryl amine, ethylenediamine tetra-acetic acid, triethanolamine, diethanol amine, monoethanolamine, ethylenediamine, butylamine, diethylamine, triethylamine, isopropylamine, aniline, N, accelerine, hexamethylene diamine, , triethylene diamine, cyclohexylamine, one in hexamethylenetetramine or combination,
Described reducing agent is sodium borohydride, potassium borohydride, hydrazine hydrate or inferior sodium phosphate;
The precursor of described oxide shell layer is: the one in sodium metasilicate, ethyl orthosilicate, methoxy silane, Ethoxysilane, sodium aluminate, aluminum nitrate, aluminium isopropoxide, butyl titanate, titanium tetrachloride, stannous chloride, butter of tin, stannous octoate, dibutyl tin, tetraphenyltin, zirconium oxychloride, zirconium nitrate, cerous nitrate or combination.
By the hydroxide of alkaline element or nitrate soluble in water, the catalyst that impregnation steps (4) obtains, the then obtained catalyst containing alkaline element after centrifugation or filtration, washing, oven dry, calcining.
Described soluble copper salt is preferably copper nitrate, copper chloride, copper sulphate or copper acetate;
The salt of solubility auxiliary agent is preferably the nitrate of auxiliary element, chloride or acetate.
Organic solvent in step (2) is can the organic solvent of dissolved oxygen compound shell precursor, can be preferred: the one in methyl alcohol, ethanol, ethylene glycol, propane diols, isopropyl alcohol, glycerine, formic acid, acetic acid, acetone or combination.
Bronsted lowry acids and bases bronsted lowry in step (3) is in order to adjust pH value, and acid can adopt: sulfuric acid, hydrochloric acid, nitric acid, carbon dioxide, citric acid, acetic acid or oxalic acid; Alkali can adopt: NaOH, potassium hydroxide or ammoniacal liquor.
In step (4), preferably can dry 5 ~ 20h at 60 ~ 120 DEG C, 300 ~ 600 DEG C of calcining 2 ~ 10h;
Through compressing tablet, spin, extrusion molding, the catalyst powder obtained in step (4) can be that spherical, bar shaped, tooth are spherical, cloverleaf pattern or honeycombed.
Specifically can carry out according to the following steps:
(1) preparation of stratum nucleare: take dissolved organic matter protective agent and soluble copper salt respectively, wherein the molal quantity of dissolved organic matter protective agent (macromolecule is then in monomer in this way) is 0.5 ~ 5 times of copper and auxiliary agent total mole number.First dissolved organic matter protective agent and a certain amount of water are made into mixed solution, then lytic activity component and auxiliary agent, finally add reducing agent and make copper and auxiliary agent nucleation, make solution A;
(2) preparation of shell: by water-soluble for the precursor of shell oxide or organic solvent, make solution B;
(3) solution B is joined solution A, period use stirring make to mix, backward A and B mixed solution in add a certain amount of acid or alkali, its addition is as the criterion 9 ~ 12 to make the pH value of mixed solution;
(4) finally mixed solution is reacted 4 ~ 72h under uniform temperature (25 ~ 200 DEG C), then centrifugation or filtration, washing, dries 5 ~ 20h for 60 ~ 120 DEG C, 300 ~ 600 DEG C of calcining 2 ~ 10h;
By the hydroxide of alkaline element or nitrate soluble in water, flood catalyst obtained above, then the obtained catalyst containing alkaline element after centrifugation or filtration, washing, oven dry, calcining.
It is metallic forms that catalyst of the present invention needs Cu and aids reduction before use, can use H
2reductase 12 ~ 10h at 250 ~ 500 DEG C.
Invention effect:
Catalyst of the present invention for selec-tive hydrogenation except alkynes or/and butadiene time, owing to there is the confinement effect of shell, except alkynes or/and butadiene is greatly diminished in the polymerization of catalyst surface, not only increase the selective of catalyst, also can improve the cycle of operation of catalyst.
Accompanying drawing explanation
The Electronic Speculum figure of catalyst prepared by Fig. 1 embodiment 1
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
In embodiment raw materials used be commercially available, Beijing Yili Fine Chemicals Co., Ltd. produce
Catalyst stratum nucleare diameter, shell thickness, channel diameter are by the Autosorb-1-C instrument test of Kang Ta company, and specific surface, aperture and pore volume are by N
2de contamination method measures
Embodiment 1
Take polyvinylpyrrolidone 0.65g respectively, take the Cu (NO of 1.2g
3)
23H
2the AgNO of O, 0.05g
3with the Co (NO of 0.1g
3)
26H
2o, is first dissolved in polyvinylpyrrolidone in 200ml water, then adds Cu (NO
3)
23H
2o, AgNO
3with Co (NO
3)
26H
2o, after stirring, adds hydrazine hydrate 1ml, is mixed with solution A 1.
Ethyl orthosilicate 1ml is dissolved in 150ml ethanol, wiring solution-forming B1, solution B 1 is slowly added in solution A 1, to be added complete after, continue agitating solution 10min, in above-mentioned mixed solution, then add NaOH regulate pH value to 10.The last mixed solution 24h at room temperature stirring gained, after the centrifuge of 10000 turns are separated, put into baking oven and dries 6h in 100 DEG C, after 500 DEG C of calcinings, finally obtain the catalyst S iO with nucleocapsid structure in atmosphere by the sediment of gained
2cu+Ag+Co.
Copper content is 58.5%, Ag is 3.5%, Co is 8.0%, the content of oxide shell layer is 30.0%; The ratio 1.0 of polyvinylpyrrolidone monomer molar number and copper and auxiliary agent total mole number.
Obtained Catalysts Cu+Ag+Co nuclear diameter is 150nm, SiO
2shell thickness 30nm, SiO
2aperture 1nm.Specific surface 300m
2/ g, pore volume 1.2mL/g.
The electromicroscopic photograph of catalyst is shown in Fig. 1, can be found out by electromicroscopic photograph, and catalyst granules obviously has nucleocapsid mechanism.
Comparative example 1
Take polyvinylpyrrolidone 0.65g respectively, take the Cu (NO of 1.2g
3)
23H
2the AgNO of O, 0.05g
3with the Co (NO of 0.1g
3)
26H
2o, is first dissolved in polyvinylpyrrolidone in 200ml water, then adds Cu (NO
3)
23H
2o, AgNO
3with Co (NO
3)
26H
2o, after stirring, adds hydrazine hydrate 1ml, then at room temperature agitating solution 24h.After the centrifuge of 10000 turns are separated, the sediment of gained are put into baking oven and dry 6h in 100 DEG C, finally after 500 DEG C of calcinings, obtain typical catalyst Cu+Ag+Co in atmosphere.
Copper content is 83.7%, Ag is 5.0%, Co is 11.3%; The ratio 1.0 of polyvinylpyrrolidone monomer molar number and copper and auxiliary agent total mole number.
Obtained Catalysts Cu+Ag+Co is of a size of 200nm.
Embodiment 2
Take TTAB 4.0g respectively, take the Cu (NO of 1.2g
3)
23H
2ni (the NO of O, 0.1g
3)
26H
2cr (the NO of O and 0.05g
3)
39H
2o, is first dissolved in TTAB in 200ml water, then adds Cu (NO
3)
23H
2o, Ni (NO
3)
26H
2o and Cr (NO
3)
39H
2o, after stirring, adds hydrazine hydrate 1ml, is mixed with solution A 2.
5g sodium metasilicate is dissolved in 150ml water, wiring solution-forming B2, solution B 2 is slowly added in solution A 2, to be added complete after, continue agitating solution 10min, then in above-mentioned mixed solution, add HNO
3regulate pH value to 9.Finally stir the mixed solution 24h of gained at 60 DEG C, after the centrifuge of 10000 turns are separated, the sediment of gained are put into baking oven and dry 6h in 100 DEG C, the obtained catalyst S iO with nucleocapsid structure after finally calcining through 500 DEG C in atmosphere
2cu+Ni+Cr.
By 1.0gNaNO
3be dissolved in 10mL water, flood the SiO obtained
2cu+Ni+Cr catalyst, then through 5000 turns/min centrifugation, after deionized water washs 2 times, obtains the catalyst n a/SiO containing alkaline element Na at 60 DEG C after drying 3h, 350 DEG C of calcinings
2cu+Ni+Cr.
Copper content is 43.1%, Ni is 5.8%, Cr is 1.1%, the content of oxide shell layer is 47.9%; The content of alkaline element Na is 2.1%.The ratio 2.3 of TTAB molal quantity and copper and auxiliary agent total mole number.
Obtained Catalysts Cu+Ni+Cr nuclear diameter is 50nm, SiO
2shell thickness 10nm, SiO
2aperture 3nm.Specific surface 150m
2/ g, pore volume 0.7mL/g.
Comparative example 2
Take TTAB 0.8g respectively, take the Cu (NO of 1.2g
3)
23H
2ni (the NO of O, 0.1g
3)
26H
2cr (the NO of O and 0.05g
3)
39H
2o, is first dissolved in TTAB in 200ml water, then adds Cu (NO
3)
23H
2o, Ni (NO
3)
26H
2o and Cr (NO
3)
39H
2o, after stirring, adds hydrazine hydrate 1ml.Then at room temperature agitating solution 24h.After the centrifuge of 10000 turns are separated, the sediment of gained are put into baking oven and dry 6h in 100 DEG C, finally after 500 DEG C of calcinings, obtain typical catalyst Cu+Ni+Cr in atmosphere.
Copper content is 86.0%, Ni is 12.0%, Cr is 2.0%.The ratio 2.3 of TTAB molal quantity and copper and auxiliary agent total mole number.
Obtained Catalysts Cu+Ni+Cr core is of a size of 150nm.
Comparative example 3
Take the Cu (NO of 1.2g
3)
23H
2the AgNO of O, 0.05g
3with the Co (NO of 0.1g
3)
26H
2o is dissolved in 5ml water, and the solution impregnation 5g water absorption rate of gained is the SiO of 100%
2(specific surface is 320m
2/ g, pore volume 0.6ml/g), after completing, dry 6h at 100 DEG C, finally after 500 DEG C of calcinings, obtain Catalysts Cu+Ag+Co/SiO in atmosphere
2.
Comparative example 4
Take the Cu (NO of 1.2g
3)
23H
2the AgNO of O, 0.05g
3with the Co (NO of 0.1g
3)
26H
2o is dissolved in 200ml water, ethyl orthosilicate 12ml to be dissolved in 150ml ethanol and with above-mentioned aqueous solution, then adding NaOH regulates PH to 10 that inorganic elements is precipitated completely, continue under room temperature to stir 24h, rear centrifugation, then sediment is put into baking oven and dry 6h in 100 DEG C, finally after 500 DEG C of calcinings, obtain Catalysts Cu+Ag+Co+SiO in atmosphere
2.
Embodiment 3
Take ethylenediamine tetra-acetic acid 1.5g respectively, take the Cu (NO of 1.2g
3)
23H
2zn (the NO of O, 0.1g
3)
26H
2fe (the NO of O and 0.05g
3)
39H
2o, is first dissolved in ethylenediamine tetra-acetic acid in 200ml water, then adds Cu (NO
3)
23H
2o, Zn (NO
3)
26H
2o and Fe (NO
3)
39H
2o, after stirring, adds sodium borohydride 0.1g, is mixed with solution A 3.
Ethyl orthosilicate 12ml is dissolved in 20ml ethanol; By 2.5mL 4-propyl bromide and 0.4gAl (NO
3)
3be dissolved in 100mL water, by above-mentioned two solution mixing wiring solution-forming B3, solution B 3 slowly added in solution A 3, to be added complete after, continue agitating solution 10min, in above-mentioned mixed solution, then add NaOH regulate pH value to 10.The last mixed solution 24h stirring gained at 180 DEG C, after the centrifuge of 10000 turns are separated, the sediment of gained is put into baking oven and dry 6h in 100 DEG C, after 500 DEG C of calcinings, finally obtain the catalyst Z SM-5Cu+Zn+Fe with nucleocapsid structure in atmosphere.
Copper content is 17.1%, Zn is 1.2%, Fe is 0.7%, the content of oxide shell layer is 80.0%; The ratio 0.7 of ethylenediamine tetra-acetic acid molal quantity and copper and auxiliary agent total mole number.
Obtained Catalysts Cu+Zn+Fe nuclear diameter is 10nm, ZSM-5 shell thickness 5nm, ZSM-5 aperture 0.5nm.Specific surface 100m
2/ g, pore volume 0.4mL/g.
Embodiment 4
Take CMC 7.0g respectively, take the Cu (NO of 1.2g
3)
23H
2o, 1.2mL50% manganese nitrate solution, is first dissolved in CMC in 200ml water, then adds Cu (NO
3)
23H
2o, 50% manganese nitrate solution, after stirring, add inferior sodium phosphate 0.11g, is mixed with solution A 4.
Butyl titanate 12ml is dissolved in wiring solution-forming B4 in 150ml ethanol, solution B 4 is slowly added in solution A 4, to be added complete after, continue agitating solution 10min, in above-mentioned mixed solution, then add KOH regulate pH value to 10.The last mixed solution 24h stirring gained at 60 DEG C, after the centrifuge of 10000 turns are separated, put into baking oven and dries 6h in 100 DEG C, after 500 DEG C of calcinings, finally obtain the catalyst TiO with nucleocapsid structure in atmosphere by the sediment of gained
2cu+Mn.
Copper content is 31.4%, Mn is 18.6%, the content of oxide shell layer is 50.0%; The ratio 4.5 of CMC molal quantity and copper and auxiliary agent total mole number.
Obtained Catalysts Cu+Mn nuclear diameter is 170nm, TiO
2shell thickness 8nm, TiO
2aperture 1nm.Specific surface 10m
2/ g, pore volume 0.1mL/g.
Evaluate catalyst of the present invention, test condition is as follows:
Catalyst test carries out in fixed bed reactors, and loaded catalyst is 1mL, must replace, at 300 DEG C, uses hydrogen reducing 4h again before reaction with nitrogen, reactant composition lists in table 1, beds inlet temperature is 250 DEG C, and reaction pressure is normal pressure, and air speed is 5000h
-1.
Conversion ratio and optionally computational methods
1. the calculating of conversion of alkyne:
Conversion of alkyne (%)=(remaining the front acetylene content of acetylene content/reaction after 1-reaction) * 100
2. the calculating of ethylene selectivity
Ethylene selectivity (%)=(after reaction front acetylene content of ethylene contents/reaction) * 100
3. ethane optionally calculates
Ethane selective (%)=(after reaction front acetylene content of ethane content/reaction) * 100
4. the selective calculation of polymer
Acetylene content before selective (%)=(remaining the rear ethane content of the rear ethylene contents+reaction of acetylene content+reaction after 1-(the reaction)/reaction of polymer) * 100
Table 1 carbon two reactant forms
| Component | Content (at%) |
| Acetylene | 0.5 |
| Hydrogen | 1.5 |
| Nitrogen | 98% |
The evaluation result of the catalyst of embodiment and comparative example is in table 2.
The reaction evaluating result of table 2 catalyst
Can as apparent from the reaction evaluating result of catalyst, the copper catalyst with nucleocapsid structure of the present invention is selective is obviously better than other comparative catalysts, the polymer selective of catalyst with core-casing structure compares comparative catalyst all obvious decline, and this embodies the huge advantage of catalyst of the present invention.
Claims (13)
1. there is a selec-tive hydrogenation copper catalyst for nucleocapsid structure, it is characterized in that:
Described catalyst is made up of core and the oxide shell layer with pore passage structure; The diameter of core is 5 ~ 500nm, and the thickness of oxide shell layer is 5 ~ 200nm, and oxide shell layer has the duct that aperture is 0.1 ~ 20nm;
Described core is made up of main active ingredient copper and auxiliary agent, and auxiliary agent is one or more in Ag, Co, Fe, Mn, Ni, Zn, Cr, Pd;
Oxide shell layer is: silica, aluminium oxide, titanium dioxide, tin ash, one or more in zirconium dioxide or ceria;
In the gross weight of catalyst for 100%:
(1)Cu，5～90wt%;
(2) oxide shell layer, 5 ~ 90wt%;
(3) auxiliary agent, 0.1 ~ 20wt%.
2. there is the selec-tive hydrogenation copper catalyst of nucleocapsid structure as claimed in claim 1, it is characterized in that:
In the gross weight of catalyst for 100%:
(1)Cu，15～60wt%;
(2) oxide shell layer, 30 ~ 80wt%.
3. there is the selec-tive hydrogenation copper catalyst of nucleocapsid structure as claimed in claim 1, it is characterized in that:
The diameter of described core is: 10 ~ 200nm;
The thickness of described oxide shell layer is: 5 ~ 30nm;
The channel diameter of described oxide shell layer is 0.3 ~ 3nm.
4. there is the selec-tive hydrogenation copper catalyst of nucleocapsid structure as claimed in claim 1, it is characterized in that:
Described oxide shell layer is one or more in silica, aluminium oxide or titanium dioxide.
5. there is the selec-tive hydrogenation copper catalyst of nucleocapsid structure as claimed in claim 1, it is characterized in that:
Described oxide shell layer comprises one or more in alkaline element, and the content of alkaline element is 0.05 ~ 5% of overall catalyst weight.
6. there is the selec-tive hydrogenation copper catalyst of nucleocapsid structure as claimed in claim 5, it is characterized in that:
Described alkaline element is one or more in K, Na, Cs, Mg, Ca, Ba.
7. the selec-tive hydrogenation copper catalyst with nucleocapsid structure as described in one of claim 1 ~ 6, is characterized in that:
The specific area of described catalyst is 10 ~ 300m
2/ g, pore volume is 0.1 ~ 1.2mL/g.
8. the preparation method with the selec-tive hydrogenation copper catalyst of nucleocapsid structure as described in one of Claims 1 to 4, is characterized in that described method comprises:
(1) preparation of stratum nucleare: be dissolved in the protectant aqueous solution of dissolved organic matter by the salt of described consumption by soluble copper salt and solubility auxiliary agent, add reducing agent, make solution A;
(2) preparation of shell: by water-soluble for the precursor of shell oxide or organic solvent, make solution B;
(3) solution B is joined in solution A while stirring, add the pH value of acid or alkali adjustment mixed solution 9 ~ 12;
(4) mixed solution that step (3) obtains is reacted 4 ~ 72h at 25 ~ 200 DEG C of temperature, obtained described catalyst after centrifugation or filtration, washing, oven dry, calcining;
The protectant molal quantity of dissolved organic matter is 0.5 ~ 5 times of copper and auxiliary agent total mole number;
Dissolved organic matter protective agent is: polyvinylpyrrolidone, polyethylene glycol, according to ethyleneimine, amine dendrimer, crown ether, carboxymethyl cellulose, CMC, lauryl mercaptan, citric acid, , 4-propyl bromide, softex kw, TTAB, ethamine, propylamine, butylamine, lauryl amine, ethylenediamine tetra-acetic acid, triethanolamine, diethanol amine, monoethanolamine, ethylenediamine, butylamine, diethylamine, triethylamine, isopropylamine, aniline, N, accelerine, hexamethylene diamine, triethylene diamine, cyclohexylamine, one in hexamethylenetetramine or combination,
Described reducing agent is sodium borohydride, potassium borohydride, hydrazine hydrate or inferior sodium phosphate;
The precursor of described oxide shell layer is: the one in sodium metasilicate, ethyl orthosilicate, methoxy silane, Ethoxysilane, sodium aluminate, aluminum nitrate, aluminium isopropoxide, butyl titanate, titanium tetrachloride, stannous chloride, butter of tin, stannous octoate, dibutyl tin, tetraphenyltin, zirconium oxychloride, zirconium nitrate, cerous nitrate or combination.
9. preparation method as claimed in claim 8, is characterized in that:
By the hydroxide of alkaline element or nitrate soluble in water, the catalyst that impregnation steps (4) obtains, the then obtained catalyst containing alkaline element after centrifugation or filtration, washing, oven dry, calcining.
10. preparation method as claimed in claim 8, is characterized in that:
Described soluble copper salt is copper nitrate, copper chloride, copper sulphate or copper acetate;
The salt of solubility auxiliary agent is the nitrate of auxiliary element, chloride or acetate.
11. preparation methods as claimed in claim 8, is characterized in that:
Organic solvent in step (2) is: the one in methyl alcohol, ethanol, ethylene glycol, propane diols, isopropyl alcohol, glycerine, formic acid, acetic acid, acetone or combination.
12. preparation methods as claimed in claim 8, is characterized in that:
Described in step (3), acid is: sulfuric acid, hydrochloric acid, nitric acid, carbon dioxide, citric acid, acetic acid or oxalic acid; Described alkali is: NaOH, potassium hydroxide or ammoniacal liquor.
13. preparation methods as claimed in claim 8, is characterized in that:
Through compressing tablet, spin, extrusion molding, the catalyst powder obtained in step (5) is that spherical, bar shaped, tooth are spherical, cloverleaf pattern or honeycombed.
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