CN1075961C - Double-function multi-metal-oxide catalyst - Google Patents
Double-function multi-metal-oxide catalyst Download PDFInfo
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- CN1075961C CN1075961C CN94192917A CN94192917A CN1075961C CN 1075961 C CN1075961 C CN 1075961C CN 94192917 A CN94192917 A CN 94192917A CN 94192917 A CN94192917 A CN 94192917A CN 1075961 C CN1075961 C CN 1075961C
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Abstract
A kind of double-function multi-metal-oxide catalyst, it is characterized in that: is 1 at silica and aluminium oxide with weight ratio: on the outer surface and/or inner surface of the carrier of 1.2-2.5 mixed-forming, be attached with and account for the active constituent metal oxide that this total catalyst weight is 3-30%, the metallic element in this metal oxide is selected from least two kinds of metallic elements in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relating to a kind of is the catalyst of active constituent with the metal oxide.
Background technology
Now; many countries are in aspects such as petrochemical industry, chemical industry, environmental protection, industrial waste gas improvement related chemical oxidation of gold and electronation process; generally adopted catalysis technique, but the active constituent of catalyst system therefor is mainly noble metals such as platinum, ruthenium, rhodium, palladium.In catalytic field, seek that raw material cheap, that resource is sufficient replaces costing an arm and a leg and the noble metal (as platinum) of resource scarcity, become an important topic of people's research.
Since this century the seventies, people begin to explore and use complex rare-earth oxidate containing valuable metal etc. as the activity of such catalysts component.Complex rare-earth oxidate containing valuable metal has special electro permanent magnetic, heat-resisting quantity and good catalytic oxidative, and these characteristics are early to cause people's extensive attention.For example, La
1-xSr
xCoO
3Propane, methane and carbon monoxide had very high oxidation activity (et al., Nippon Kagaku, Kaishi 1980,1679 for T.Nakamura, M.Misono).Other has the people just to propose to replace platinum as purification catalyst for automobile exhaust [R.J.H.Voorhoeve, Science, 177,353 (1972)] with complex rare-earth oxidate containing valuable metal at early seventies.
Though, disclose so far and multiplely replace the catalyst of noble metal as active component with composite oxides, but it is under the condition of practical application, the long-time stability of composite oxides structure, the problem of integrality are not resolved always, therefore, this class catalysis material fails to obtain well to use.So the research work of making the catalyst activity component with the alternative noble metal of composite oxides also rests on experimental stage at present, does not obtain ideal results.
Summary of the invention
The objective of the invention is to provide a kind of is the catalyst of active constituent with the poly-metal deoxide, this catalyst has good performance, can make various organic matter complete oxidations such as carbon monoxide, alkane, alkene, aromatic hydrocarbons, nitrogen oxide, sulfur oxide are decomposed.
Another object of the present invention is to provide the method for the above-mentioned catalyst of preparation and the product for preparing by this method.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of double-function multi-metal-oxide catalyst, so-called difunctional this catalyst that is meant both can be used as oxidation catalyst, can be used as reducing catalyst again.This catalyst is to be 1 at silica and aluminium oxide with weight ratio: on the outer surface and/or inner surface of the carrier of the mixed-forming of 1.2-2.5, be attached with and account for the metal oxide that this total catalyst weight is 3-30%, be preferably 5-20%, 8-15% more preferably, metallic element in this metal oxide is selected from least two kinds of metallic elements in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element, and element number is generally the 2-5 kind.Wherein, described metal oxide does not exist with the form of composite oxides.
Particularly, selected metal oxide can be: chromium oxide, manganese oxide, iron oxide, cupric oxide, cobalt oxide, nickel oxide, zinc oxide, vanadium oxide, titanium oxide, lanthana, cerium oxide.
It is that the microballoon of 60-100 μ is Powdered that carrier can be granularity, or particle diameter is the cylindrical shape of 3-5mm, circular, spherical, sheet, or cellular.
Double-function multi-metal-oxide catalyst of the present invention prepares as follows, and this method comprises the following step:
1) will be 1: 1.2～2.5 mixed-formings with weight ratio as the silica and the aluminium oxide of carrier, in oxidizing atmosphere in 1000～1600 ℃ of temperature lower calcinations 2 to 8 hours;
2) get nitrate that is selected from a kind of metallic element in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element or the solution that acetate is made 0.3-2M, handle the carrier after the above-mentioned calcining;
3) will be through step 2) carrier handled is at 700-1200 ℃ and guaranteed under the condition of reducing atmosphere calcining 1-4 hour;
4) get the nitrate or the acetate that are selected from least two kinds of metallic elements in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element and make the mixed liquor that total concentration of metal ions is 1-2.5M, and in this mixed liquor, add the complexing agent be selected from one of oxalic acid, amion acetic acid, 2 hydroxy propanoic acid, succinic acid, hydroxysuccinic acid, tartaric acid, citric acid, phthalic acid, ortho-aminobenzoic acid and salicylaldoxime, the addition of complexing agent is 1/4～3/4 of a metal ion total concentration, makes maceration extract;
5) will through carrier impregnation that step 3) is handled in the maceration extract of step 4) preparation, obtain described double-function multi-metal-oxide catalyst after drying, the activation again.
Wherein said the 4th cycle transition metallic element and lanthanide transition metal element are selected from: chromium, manganese, iron, copper, cobalt, nickel, zinc, vanadium, titanium, lanthanum, cerium.
In step 1), carrier is plastic, and to become granularity be that the microballoon of 60-100 μ is Powdered, or particle diameter is the cylindrical shape of 3-5mm, circular, spherical, sheet, or cellular.
During the preparation maceration extract, can select the mixed liquor of manganese nitrate, cobalt nitrate, cerous nitrate for use, wherein the mol ratio of each metal ion species is 1: 1: 0.3～0.5, and the metal ion total concentration is 1～2.5M.
Maybe can select copper nitrate, chromic nitrate, cerous nitrate mixed solution for use, wherein the mol ratio of each metal ion species is 1: 1: 0.3～0.5, and the metal ion total concentration is 1～2.5M.
Or select the mixed solution of copper nitrate, chromic nitrate for use, wherein each metal ion species mol ratio is 1: 1-2, the metal ion total concentration is 1～2.5M.
Also can select the mixed solution of nickel nitrate, cobalt nitrate, cerous nitrate, chromic nitrate for use, wherein each metal ion species mol ratio is 0.5: 2.9: 3: 3.8, and the metal ion total concentration is 1～2.5M.
Can select the mixed solution of ferric nitrate, copper nitrate, cobalt nitrate, cerous nitrate, chromic nitrate for use, wherein each metal ion species mol ratio is 1.3: 2: 2.7: 3: 4, the metal ion total concentration was 1～2.5M.
Maybe can select the mixed solution of nickel nitrate, manganese nitrate, copper nitrate, cerous nitrate, cobalt nitrate for use, wherein each metal ion species mol ratio is 1: 2-4.7: 2.3: 3: 2-4.7, the metal ion total concentration is 1～2.5M.
Can select the mixed solution of nickel nitrate, cobalt nitrate, copper nitrate, cerous nitrate, chromic nitrate for use, wherein each metal ion species mol ratio is 1: 2: 2.3: 3: 4.7, the metal ion total concentration was 1～2.5M.
Also can select the mixed solution of cobalt acetate, manganese acetate and lanthanum acetate for use, wherein each metal ion species mol ratio is 1: 1: 0.04, and the metal ion total concentration is 1～2.5M.
The complexing agent that adds in mixed liquor is citric acid preferably.
Dipping described in the step 5) can be normal pressure dipping or decompression dipping.
Generally speaking, the number of metallic element is 2-5 in the mixed liquor.
Below describe the present invention in detail.
Catalyst of the present invention is made of on the carrier that silica and aluminium oxide are formed activity component metal oxide carried.In years of researches, by the basic research to various composite oxide of metal and metal oxide, we recognize that the 4th cycle transition metallic element and lanthanide transition metal element are the components that generates the high activity metal oxide.
In addition, for make active component both can be firmly, be evenly distributed on the carrier, again not with carrier organizator compound mutually, special preparation method of the present invention has solved this problem, thereby makes the catalyst of preparation have long-term stability and integrality.At first calcine under the atmosphere of carrier material that the present invention has adopted elder generation that silica is made when the preparation carrier in oxidation; then with a kind of get the nitrate or acetate solution-treated that is selected from a kind of metal in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element after; calcining method prepares carrier under the atmosphere of guaranteeing to reduce again; here said processing is a method commonly known in the art, as soaking.Here also can use the nitrate or the acetate of two or more metal to handle carrier.
So among the preparation method of the present invention,, as citric acid, and make this SOLUTION PROPERTIES stable, and be very beneficial for active component attached to the uniformity on the carrier by in mixed liquor, adding complexing agent.And in the prior art, people generally believe and use the complexing agent citric acid that in the technology of preparation catalyst production safety is less than ensureing.
Need to prove that the existence form of double-function multi-metal-oxide catalyst active component of the present invention is used metallic element oxide separately, rather than with ABO
2, ABO
3, AB
2O
4Exist Deng the form of composite oxides.This active component distributes and firm outer surface and/or inner surface attached to catalyst carrier equably with the form of metallic element oxide.Prepared double-function multi-metal-oxide catalyst is a kind of loaded catalyst.
In principle, the various metal oxides that meet above-mentioned requirements all can be used as active component with the combination of arbitrary proportion, the difference that its best of breed requires according to various reactions and selecting.
Carrier adopts prior art in dynamically oven dry down behind dipping, as activate 1～4 hour under 200-800 ℃ of temperature, is prepared into final products.
Below will the present invention is described in more detail by embodiment, but do not limit the present invention.Wherein, agents useful for same is the commercially available prod.
Embodiment 1
Fluid catalytic cracking process used combustion supporting catalyst of when regeneration in the petroleum refining
1) get aluminium hydroxide and kaolin mixes by the weight ratio of silica and aluminium oxide at 1: 1.8; Spray-dried one-tenth microballoon powder; With this microballoon powder in the atmosphere of guaranteeing oxidation and 1400 ℃ calcining 4 hours down; After the cobalt nitrate solution immersion with 0.5M, the atmosphere of guaranteeing to reduce and 1000 ℃ of following calcinings 2 hours, make the microballoon dust carrier again.
2) getting molar concentration is that the cerous nitrate solution 200ml of cobalt nitrate solution 400ml, 2M of manganese nitrate solution 400ml, the 2M of 2M is made into mixed liquor, and wherein the mol ratio of each metal ion species is 1: 1: 0.5, adds citric acid 105 grams in mixed liquor, obtains maceration extract.
3) get above-mentioned microballoon dust carrier 100 and restrain, normal pressure floods 0.5 hour, 100 ℃ dynamically oven dry down in above-mentioned 60ml maceration extract, activates 2.5 hours behind the baking step under 300 ℃ temperature, gets the finished product combustion supporting catalyst.
Embodiment 2
Petrol engine exhaust gas purifying catalyst
1) get aluminium hydroxide and kaolin mixes by the weight ratio of silica and aluminium oxide at 1: 1.6; Through mechanical extrusion, cutting is shaped to spherical shape.Replace cobalt nitrate solution with the 0.5M copper nitrate solution, the method that repeats embodiment 1 step 1) prepares carrier.
2) getting molar concentration is that the cerous nitrate solution 130ml of chromium nitrate solution 435ml, 2M of copper nitrate solution 435ml, the 2M of 2M is made into mixed liquor, and wherein the mol ratio of each metal ion species is 1: 1: 0.3.In mixed liquor, add citric acid 105 grams, obtain maceration extract.
3) get above-mentioned ball type carrier 100 and restrain, 0.5 hour, the 100 ℃ oven dry down of dipping of reducing pressure in above-mentioned maceration extract 80ml activate 3 hours behind the baking step under 300 ℃ temperature, get gasoline product engine exhaust gas purifying catalyst.
Embodiment 3
The purifying vehicle exhaust catalyst
With molar concentration is that 2M copper nitrate solution 40ml and molar concentration are that 2M chromium nitrate solution 40ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 1: 1, in this mixed liquor, add citric acid 8.5 grams, make maceration extract, under reduced pressure ball-type carrier 100 grams that use among the embodiment 2 are immersed in this maceration extract, flooded 0.4 hour, 100 ℃ of oven dry down, activate 4 hours down at 250 ℃, make the catalyst that can be used as purifying vehicle exhaust.
Embodiment 4
The purifying vehicle exhaust catalyst
With molar concentration is that 2M copper nitrate solution 15ml and molar concentration are that 2M chromium nitrate solution 30ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 1: 2, in this mixed liquor, add citric acid 5 grams, make maceration extract, under reduced pressure ball-type carrier 50 grams that use among the embodiment 2 are immersed in this maceration extract, dip time is 0.4 hour, 100 ℃ of oven dry, activate 2.5 hours down at 320 ℃, make the catalyst that can be used as purifying vehicle exhaust.
Embodiment 5
The purifying vehicle exhaust catalyst
With molar concentration is that 2M nickel nitrate solution 4ml, molar concentration are that 2M cobalt nitrate solution 23ml, molar concentration are that 2M cerous nitrate solution 24ml and molar concentration are that 2M chromium nitrate solution 30ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 0.5: 2.9: 3: 3.8, add citric acid 8 in this mixed liquor and restrain into maceration extract, under reduced pressure ball-type carrier 100 grams that use among the embodiment 2 are immersed in this maceration extract, dip time is 0.7 hour, 100 ℃ of oven dry, activation is 2 hours under 350 ℃ temperature, makes the catalyst that can be used as purifying vehicle exhaust.
Embodiment 6
The purifying vehicle exhaust catalyst
With molar concentration is 2M iron nitrate solution 12ml, molar concentration is 2M copper nitrate solution 19ml, molar concentration is 2M cobalt nitrate solution 25ml, molar concentration is that 2M cerous nitrate solution 28ml and molar concentration are that 2M chromium nitrate solution 37ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 1.3: 2: 2.7: 3: 4, in this mixed liquor, add citric acid 13 grams, make maceration extract, under reduced pressure ball-type carrier 150 grams that use among the embodiment 2 are immersed in this maceration extract, dip time is 0.7 hour, 100 ℃ of oven dry, activation is 2.5 hours under 320 ℃ temperature, makes the catalyst that can be used as purifying vehicle exhaust.
Embodiment 7
The purifying vehicle exhaust catalyst
With molar concentration is 2M nickel nitrate solution 12ml, molar concentration is 2M manganese nitrate solution 25ml, molar concentration is 2M copper nitrate solution 28ml, molar concentration is that 2M cerous nitrate solution 37ml and molar concentration are that 2M cobalt nitrate solution 58ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 1: 2: 2.3: 3: 4.7, in this mixed liquor, add citric acid 16 grams, make maceration extract, under reduced pressure ball-type carrier 200 grams that use among the embodiment 2 are immersed in this maceration extract, dip time is 0.5 hour, 100 ℃ of oven dry down, activation is 3.5 hours under 280 ℃ temperature, makes the catalyst that can be used as purifying vehicle exhaust.
Embodiment 8
The purifying vehicle exhaust catalyst
With molar concentration is 2M nickel nitrate solution 9ml, molar concentration is 2M cobalt nitrate solution 18ml, molar concentration is 2M copper nitrate solution 21ml, molar concentration is that 2M cerous nitrate solution 28ml and molar concentration are that 2M manganese nitrate solution 43ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 1: 2: 2.3: 3: 4.7, in this mixed liquor, add citric acid 13 grams, make maceration extract, under reduced pressure ball-type carrier 150 grams that use among the embodiment 2 are immersed in this maceration extract, dip time is 0.7 hour, 100 ℃ of oven dry, under 250 ℃ temperature, activate 4 hours again, make the catalyst that can be used as purifying vehicle exhaust.
Embodiment 9
The purifying vehicle exhaust catalyst
With molar concentration is the nickel nitrate solution 6ml of 2M, molar concentration is 2M cobalt nitrate solution 52ml, molar concentration is 2M copper nitrate solution 14ml, molar concentration is that 2M cerous nitrate solution 19ml and molar concentration are that 2M chromium nitrate solution 29ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 1: 2: 3: 2.3: 4.7, in this mixed liquor, add citric acid 9 grams, under reduced pressure ball-type carrier 100 grams that use among the embodiment 2 are immersed in this maceration extract, dip time is 0.5 hour, 100 ℃ of oven dry, activation is 2.5 hours under 300 ℃ temperature, makes the catalyst that can be used as purifying vehicle exhaust.
Embodiment 10
Fluid catalytic cracking process used combustion supporting catalyst of when regeneration in the petroleum refining
With molar concentration is that the molar concentration of 2M is that 2M cobalt acetate solution 25ml, molar concentration are that 2M Schweinfurt green solution 25ml and molar concentration are that 2M lanthanum acetate solution 10ml is made into mixed liquor, wherein the mol ratio of each metal ion species is 1: 1: 0.04, in this mixed liquor, add citric acid 4 grams, under normal pressure, microballoon dust carrier 100 grams that use among the embodiment 1 are immersed in this maceration extract, dip time is 0.5 hour, 100 ℃ of dynamically oven dry, activation is 2 hours under 300 ℃ temperature, makes combustion supporting catalyst.
Industrial applicability
Adopt above-mentioned technical scheme, make catalyst of the present invention under suitable condition, can fully impel various organic complete oxidations such as carbon monoxide, alkane, alkene, aromatic hydrocarbons, be applicable to that petroleum refining, industrial waste gas handle, have the gas purification of specific (special) requirements; And can fully impel nitrogen oxide, sulfur oxide to decompose; Be applicable to the processing that contains nitrogen oxide and sulfur oxide gas; Impel nitrogen oxide fully to reduce when can impel the abundant oxidation of carbon monoxide, hydrocarbon; Catalyst of the present invention is specially adapted to petrol engine and discharges gas cleaning; In addition, in above-mentioned field, catalyst of the present invention is alternative with the catalyst of noble metals such as platinum, rhodium, ruthenium, palladium as active component, and than noble metal catalyst more perfect catalytic performance is arranged.
Following experimental example illustrates industrial applicability of the present invention.
Experimental example 1
The combustion supporting catalyst of getting by embodiment 1 preparation 5 restrains the sample that diluted by 1: 10, the small fixed flowing bed of packing into.Reacting gas is formed: O
23%; CO 4%; All the other are N
2, 300 ℃ of reaction temperatures (reaction bed temperature); Air speed (volume) 5000hr
-1Reaction condition under, CO conversion ratio 100%.
And the CO conversion ratio of commercial platinum catalyst under similarity condition is lower than 20%.
Experimental example 2
Get the catalyst 30g of embodiment 2 preparation, in the reactor of the φ 30m/m that packs into, the consisting of of reacting gas: CO 3%, HC 1500ppm, NO
x500ppm, O
21.5%, all the other are N
2Air speed (volume) 20000hr
-1Under the reaction condition of 250 ℃ of temperature (reaction bed temperature): CO conversion ratio＞95%; HC conversion ratio＞70%, NO
xConversion ratio＞70%.
The catalyst that promises to be commodity is thought by Japan, under above-mentioned reaction condition, and CO, HC, NO
xConversion ratio should be greater than 50%.
Experimental example 3
That gets embodiment 2 preparation gets catalyst 30g, in the reactor of the φ 30m/m that packs into, and the consisting of of reacting gas: CO 1%, HC 100ppm, NO
x2000ppm, O
20.5%, all the other are N
2Air speed (volume) 20000hr
-1Under the reaction condition of 650 ℃ of temperature (reaction bed temperature): CO conversion ratio＞95%; HC conversion ratio＞75%; NO
xConversion ratio 75%.
Claims (20)
1, a kind of double-function multi-metal-oxide catalyst is characterized in that; Is 1 at silica and aluminium oxide with weight ratio: on the outer surface and/or inner surface of the carrier of 1.2-2.5 mixed-forming, be attached with and account for the active constituent metal oxide that this total catalyst weight is 3-30%, the metallic element in this metal oxide is selected from least two kinds of metallic elements in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element.
2, double-function multi-metal-oxide catalyst as claimed in claim 1 is characterized in that described metal oxide is selected from: chromium oxide, manganese oxide, iron oxide, cupric oxide, cobalt oxide, nickel oxide, zinc oxide, vanadium oxide, titanium oxide, lanthana, cerium oxide.
3, double-function multi-metal-oxide catalyst as claimed in claim 1 is characterized in that described metal oxide accounts for the 5-20% of total catalyst weight.
4, double-function multi-metal-oxide catalyst as claimed in claim 1 is characterized in that described carrier is the powdered that granularity is 60-100 μ, or particle diameter is the cylindrical shape of 3-5mm, circular, spherical, sheet, or cellular.
5, it is 2-5 kind in the transition metal that double-function multi-metal-oxide catalyst as claimed in claim 1, the metallic element that it is characterized in that described active constituent metal oxide are selected from the periodic table of chemical element the 4th cycle transition metallic element and billows.
6, a kind of preparation method of double-function multi-metal-oxide catalyst is characterized in that comprising following steps:
1) will be 1: 1.2～2.5 mixed-formings with weight ratio as the silica and the aluminium oxide of carrier, in oxidizing atmosphere in 1000～1600 ℃ of temperature lower calcinations 2 to 8 hours;
2) get nitrate that is selected from a kind of metallic element in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element or the solution that acetate is made 0.3-2M, handle the carrier after the above-mentioned calcining;
3) will be through step 2) carrier handled is at 700-1200 ℃ and guaranteed under the condition of reducing atmosphere burning 1-4 hour;
4) get the nitrate or the acetate that are selected from least two kinds of metallic elements in the periodic table of chemical element the 4th cycle transition metallic element and the lanthanide transition metal element and make the mixed liquor that total concentration of metal ions is 1-2.5M, and in this mixed liquor, add the complexing agent be selected from one of oxalic acid, amion acetic acid, 2 hydroxy propanoic acid, succinic acid, hydroxysuccinic acid, tartaric acid, citric acid, phthalic acid, ortho-aminobenzoic acid and salicylaldoxime, the addition of complexing agent is 1/4～3/4 of a metal ion total concentration, makes maceration extract;
5) will through carrier impregnation that step 3) is handled in the maceration extract of step 4) preparation, obtain described double-function multi-metal-oxide catalyst after drying, the activation again.
7, method as claimed in claim 6 is characterized in that described the 4th cycle transition metallic element and lanthanide element are selected from: chromium, manganese, iron, copper, cobalt, nickel, zinc, vanadium, titanium, lanthanum, cerium.
8, method as claimed in claim 6 is characterized in that it is that the microballoon of 60-100 μ is Powdered that described carrier is molded into granularity, or particle diameter is the cylindrical shape of 3-5mm, circular, spherical, sheet, or cellular.
9, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the 4th cycle transition metallic element and the lanthanide transition metal element be the mixed liquor of manganese nitrate, cobalt nitrate, cerous nitrate, wherein each metal ion species mol ratio is 1: 1: 0.3～0.5, and the metal ion total concentration is 1～2.5M in this mixed liquor.
10, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the 4th cycle transition metallic element and the lanthanide transition metal element be copper nitrate, chromic nitrate, cerous nitrate mixed solution, wherein each metal ion species mol ratio is 1: 1: 0.3～0.5, and the total mole of metal ion is 1～2.5M in this mixed liquor.
11, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the mat woven of fine bamboo strips 4 cycle transition metallic elements and the lanthanide transition metal element be the mixed solution of copper nitrate, chromic nitrate, wherein each metal ion species mol ratio is 1: 1-2, the metal ion total concentration is 1～2.5M in this mixed liquor.
12, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the 4th cycle transition metallic element and the lanthanide transition metal element be the mixed solution of nickel nitrate, cobalt nitrate, cerous nitrate, chromic nitrate, wherein each metal ion species mol ratio is 0.5: 2.9: 3: 3.8, and the metal ion total concentration is 1～2.5M in this mixed liquor.
13, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the 4th cycle transition metallic element and the lanthanide transition metal element be the mixed solution of ferric nitrate, copper nitrate, cobalt nitrate, cerous nitrate, chromic nitrate, wherein each metal ion species mol ratio is 1.3: 2: 2.7: 3: 4, the metal ion total concentration was 1～2.5M in this mixed liquor.
14, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the 4th cycle transition metallic element and the lanthanide transition metal element be the mixed solution of nickel nitrate, manganese nitrate, copper nitrate, cerous nitrate, cobalt nitrate, wherein each metal ion species mol ratio is 1: 2-4.7: 2.3: 3: 2-4.7, the metal ion total concentration is 1～2.5M in this mixed liquor.
15, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the 4th cycle transition metallic element and the lanthanide transition metal element be the mixed solution of nickel nitrate, cobalt nitrate, copper nitrate, cerous nitrate, chromic nitrate, wherein each metal ion species mol ratio is 1: 2: 2.3: 3: 4.7, the metal ion total concentration was 1～2.5M in this mixed liquor.
16, method as claimed in claim 6, it is characterized in that described to get the nitrate or the acetate solution that are selected from least two kinds of metallic elements in the 4th cycle transition metallic element and the lanthanide transition metal element be the mixed solution of cobalt acetate, manganese acetate and lanthanum acetate, wherein each metal ion species mol ratio is 1: 1: 0.04, and the metal ion total concentration is 1～2.5M in this mixed liquor.
17, method as claimed in claim 6 is characterized in that described complexing agent is a citric acid.
18, method as claimed in claim 6 is characterized in that the dipping method described in the step 5) can be normal pressure dipping or decompression dipping.
19, method as claimed in claim 6 is characterized in that the nitrate of described metallic element or the metallic element of acetate are the 2-5 kind that is selected from the 4th cycle transition metallic element and the lanthanide transition metal element.
20, a kind of catalyst for preparing by the method for claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94192917A CN1075961C (en) | 1993-07-29 | 1994-07-29 | Double-function multi-metal-oxide catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93109023A CN1083742A (en) | 1993-07-29 | 1993-07-29 | Double-function multi-metal-oxide catalyst |
| CN93109023.7 | 1993-07-29 | ||
| CN94192917A CN1075961C (en) | 1993-07-29 | 1994-07-29 | Double-function multi-metal-oxide catalyst |
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Cited By (3)
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| CN104923236A (en) * | 2015-05-25 | 2015-09-23 | 常州大学 | Preparation method of catalyst for promoting conversion of ortho-xylene in chemical waste gases |
| CN104941647A (en) * | 2015-06-18 | 2015-09-30 | 四川之江高新材料股份有限公司 | Method for synthetizing N-methylmorpholine and supported catalyst used in synthesis of N-methylmorpholine |
| CN112403487A (en) * | 2020-11-22 | 2021-02-26 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium-free desulfurization and denitrification catalyst and preparation method thereof |
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| CN1074630C (en) * | 1997-11-24 | 2001-11-07 | 鸿友科技股份有限公司 | Built-in long tube scanner |
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