CN1074630A - Burning catalyst for composite oxide and method for making thereof and application - Google Patents
Burning catalyst for composite oxide and method for making thereof and application Download PDFInfo
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- CN1074630A CN1074630A CN 92100437 CN92100437A CN1074630A CN 1074630 A CN1074630 A CN 1074630A CN 92100437 CN92100437 CN 92100437 CN 92100437 A CN92100437 A CN 92100437A CN 1074630 A CN1074630 A CN 1074630A
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Abstract
The present invention relates to a kind of composite oxides (Complex Oxide) combustion catalyst, wherein directly to be carried on sillimanite and/or mullite be on the carrier of main thing phase to the composite oxides active component.The invention still further relates to the preparation method of above-mentioned combustion catalyst, this method comprises uses the aqueous metal salt that is mixed with by required metallic element of active component and mol ratio thereof to flood described carrier, after the drying, and calcination activation.What the invention still further relates to above-mentioned catalyst is the preparation method of the carrier of main thing phase with sillimanite and/or mullite.The invention still further relates to burning catalyst for composite oxide industry and civilian organic exhaust gas, contain carbon monoxide smoke catalytic combustion purification and energy-conservation aspect as the purposes of combustion catalyst.
Description
The present invention relates to a kind of composite oxides (Complex Oxide) combustion catalyst and preparation method thereof and the purposes of this catalyst as combustion catalyst; The invention still further relates to the preparation method of the carrier of this catalyst.More particularly, the present invention relates to directly to be carried on sillimanite and/or mullite is burning catalyst for composite oxide on the carrier of main thing phase and preparation method thereof, with and as the purposes of the combustion catalyst of industry and civilian organic exhaust gas, the catalytic combustion purification that contains carbon monoxide smoke and energy-conservation aspect.
Organic exhaust gas is one of a large amount of gas pollutants of discharging in process of production of a lot of industrial departments, especially ubiquity more in the production process of industries such as electronics, printing, process hides, paint, chemical industry.The carbon monoxide of Civil energy-saving cooking stove incomplete combustion discharging also is one of a large amount of gas pollutants in the air.The existence of organic exhaust gas and carbon monoxide jeopardizes production safety and health in the air.Catalytic combustion is a kind of effective ways of administering organic exhaust gas and carbon monoxide in the air.Up to now, be used for catalytic combustion handle organic exhaust gas and carbon monoxide with reach purify purpose the activity of such catalysts component mainly based on noble metal platinum, palladium.Because platinum is shortage of resources worldwide, costs an arm and a leg, seriously supply falls short of demand.Therefore, comprise that in the world China all makes great efforts to carry out the research to the composite oxides active component, attempt in order to replace noble metal platinum.But the loading problem of composite oxides active component is not well solved always, makes this class catalyst fail to be applied in the reality well to go.At present, the carrier of supported complex oxide catalyst is except using aluminium oxide, and great majority use cordierite (Cordierite) or mullite ceramic materials such as (Mullite).But, when adopting these ceramic materials to make carrier, often must carry out preliminary treatment to these ceramic materials, for example, in advance on the surface of potteries such as violet stone or mullite the dipping or be coated with other compound of last layer, these compounds generally are aluminium oxide, lanthana, zirconia, aluminium hydroxide, zirconium hydroxide or their mixture.Then, load composite oxides active component (Japan Patent, clear 60-51544 again; Chinese patent, 85109694).Another kind method is to pull an oar into slurries with materials such as composite oxides active component that prepared beforehand is good and oxidation aluminium glues, is coated in (Japan Patent, clear 60-175547 on the mullite carrier again; Japan Patent, clear 61-234947; United States Patent (USP), 4748143).Under these situations, cordierite or mullite only have been the effect of skeleton or substrate in carrier, and the active surface of carrier is to be provided by aluminium oxide, zirconia, lanthana or their compound.The characteristics of these methods all are by the third material, promptly use non-direct method the composite oxides active component attached on the carrier.These methods have increased the Preparation of catalysts step on the one hand, and cost is increased; On the other hand, the active component effective rate of utilization is low, influences activity of such catalysts.
In order to address the above problem, the inventor has carried out further investigation and a large amount of test, obtains finally to break through, and has finished the present invention.
Therefore, the present invention relates to a kind of burning catalyst for composite oxide, this catalyst is made up of following active component and carrier:
1, active component is main component with composite oxides, often is attended by a spot of metal oxide.Active component includes two or more metallic element.Described metallic element is transition metal, alkali earth metal and thulium;
2, be the carrier of main thing phase with sillimanite (Sillimanite) and/or mullite (Mullite); Described activity of such catalysts component is directly forming on the carrier situ and is directly loading on the described carrier.
The invention still further relates to above-mentioned Preparation of catalysts method, this method comprises: the metallic element mol ratio preparing metal ion concentration required according to active component is the soluble-salt aqueous solution of 1.0～3.0M, if desired, can be 0～2.0 adding citric acid by the mol ratio of citric acid and total metal ion, mix, promptly get maceration extract.Flood described sillimanite and/or mullite is the carrier of main thing phase with this maceration extract, after the drying, in 400～800 ℃ of calcination activations 0.5～24 hour, reaction generates the composite oxides active component on carrier situ, it is on the carrier of main thing phase that active component directly loads on sillimanite and/or mullite, promptly makes described catalyst.The weight ratio of prepared catalyst activity component and described carrier is 5%～30%.
The invention still further relates to the preparation method of the carrier of above-mentioned catalyst, this method comprises:
1, the raw material of salic and silica is pressed Al
2O
3: SiO
2=1.40～2.30(weight ratio) ratio is mixed, and is mixed with compound;
2, in compound, add 0～10.0%(weight) binding agent, 0～20.0%(weight) pore creating material and suitable quantity of water, stir, mediate aftershaping;
3,2 article shaped is dried the back 1200～1600 ℃ of roastings 1～24 hour, promptly make described carrier; Wherein said pore creating material is made of materials such as being selected from active carbon, high molecular polymer, shuck, grass-seed, cereal; Described binding agent is carboxymethyl cellulose (CMC) or polyvinyl alcohol etc.
The invention still further relates to the purposes of above-mentioned catalyst as the combustion catalyst of industry and civilian organic exhaust gas, the catalytic combustion purification that contains carbon monoxide smoke and energy-conservation aspect.
This shows, the object of the present invention is to provide a kind of composite oxides active component directly to load on sillimanite and/or mullite is the raw catelyst that constitutes on the carrier of main thing phase, this catalyst is used for catalytic combustion to be handled organic exhaust gas and contains carbon monoxide smoke, can satisfy fully to reach catalytic combustion purification and purpose of energy saving; Another object of the present invention is that a kind of method for preparing this catalyst will be provided, and using this method can make the composite oxides active component directly load on sillimanite and/or mullite is on the carrier of main thing phase; Other purpose of the present invention will be easy to embody in consulting following explanation.
The x-ray diffraction pattern of the carrier that Fig. 1 makes for the present invention.
The x-ray diffraction pattern of the burning catalyst for composite oxide that Fig. 2 makes for the present invention.
As everyone knows, replace the noble metals such as platinum, palladium as the research of catalyst activity component with non-noble metal composite oxide, be an important topic in present catalyst research field, and the loading problem of composite oxides is key issues wherein, is not well solved always. The inventor finds that on the basis of being engaged in structural chemistry research sillimanite and mullite are suitable as the carrier of composite oxides. The chemical composition of sillimanite crystal is Al2SiO
5; Belong to rhombic system; Space group is D16 2h-Pbnm; Its cell parameter is roughly a=7.49
，b＝7.67
，c＝5.77
The chemical composition of mullite crystal is 3Al2O
3·2SiO
2～2Al
2O
3·SiO
2; Belong to rhombic system; Space group is D9 2h-Pbam; Its cell parameter is roughly a=7.55
，b＝7.66
，c＝2.88
Mullite is the disordered structure of sillimanite, and the structure of the two is close. Experimental result shows, the carrier take sillimanite and/or mullite as main phase is conducive to the composite oxides active component and disperses and firm attachment at its surface uniform. And this carrier Heat stability is good, not with the active component chemically reactive, can effectively bring into play the effect of composite oxides active component, and can save the preload step of carrier, directly load on problem on the carrier thereby solved for many years unsolved composite oxides active component always.
The active component that catalyst of the present invention is suitable for is made of the composite oxides of two or more metallic element, take composite oxides as main component, often is attended by a small amount of metal oxide. Described metallic element is transition metal, is selected from Ti, Cr, and Mn, Zn, Fe, Co, Ni, Cu, V, Mo and/or W; Alkali earth metal is selected from Mg, Ca, Sr and/or Ba; Thulium is selected from La, Ce or norium element; If be necessary, active component of the present invention also can be selected from the precious metal elements such as Pt, Pd and/or Rh. The content range of each metallic element counts 0～0.999 with molar fraction in the described active component, and need satisfy the condition that active component is made of two kinds of metallic elements at least, the molar fraction that two kinds of metallic elements are namely at least wherein arranged is not zero with the molar fraction of other metallic element simultaneously.
The preferred active component composite oxides that metallic element with following mol ratio consists of of serving as reasons among the present invention:
Cu∶Co＝1∶1
Cu∶Co＝1∶2
Cu∶Mn＝1∶2
Ni∶Co＝1∶2
Ni∶Mn＝1∶2
Co∶Mn＝1∶2
Zn∶Mn＝3∶14
Fe∶Cu∶Mn＝1∶1∶3
Fe∶Cu∶Mn＝1∶1∶14
Fe∶Ni∶Mn＝1∶2∶3
Fe∶Co∶Mn＝1∶1∶3
Ni∶Cu∶Mn＝1∶1∶3
La∶Ca∶Co＝33∶17∶50
Co∶Ni∶Cu∶Mn＝1∶2∶2∶4
Co∶Ni∶Cu∶Mn＝1∶1∶3∶5
Ni∶Co∶Cu∶Cr＝9∶18∶1∶2
La∶Sr∶Ce∶Co＝7∶2∶1∶10
Fe∶Co∶Ni∶Cu∶Mn＝1∶2∶2∶2∶6
Fe∶Co∶Ni∶Cu∶Mn＝1∶2∶3∶3∶6
Fe∶Co∶Ni∶Cu∶Mn＝1∶3∶3∶3∶6
Fe∶Co∶Ni∶Cu∶Mn＝2∶1∶2∶3∶6
Fe∶Co∶Ni∶Cu∶Mn＝3∶1∶3∶2∶6
Ni∶Co∶Cu∶Cr∶Ce＝7∶14∶3∶6∶3
The used carrier of burning catalyst for composite oxide of the present invention is to be main component with sillimanite and/or mullite, often is attended by the oxide of a spot of silicon, aluminium.In the process by the feedstock production carrier of siliceous, aluminium, sillimanite and mullite generate often together, and the two structural difference only is that sillimanite is an ordered structure, and mullite is a disordered structure; Ratio and the content of clearly distinguishing the two are difficult technically.And, because sillimanite has identical load effect in the present invention with mullite, so the present invention need not clearly to define the definite ratio and the content of sillimanite and mullite in the carrier of the present invention.For the foregoing reasons, used carrier of the present invention is referred to as sillimanite and/or mullite carrier.Experimental result shows, the present invention is that the carrier of main thing phase extremely helps composite oxides active component firm attachment thereon with sillimanite and/or mullite, and not with the active component chemically reactive, stably directly load is thereon and give full play to its catalytic activity and make active component.In addition, sillimanite of the present invention and/or mullite are that the carrier of main thing phase can be processed into Any shape as required, as sphere, cylindricality, hollow cylindrical or other abnormity.
The preparation method of sillimanite of the present invention and/or mullite carrier comprises:
(1) with the raw material of salic and silica by weight Al
2O
3: SiO
2=1.40～2.30, be preferably 1.55～1.90, mix, be mixed with compound;
(2) in compound, add 0～10%(weight), be preferably 1%～5%(weight) binding agent; In compound, add 0～20%(weight), be preferably 5%～15%(weight) pore creating material; And suitable quantity of water, stir, after the kneading, moulding on make-up machine;
(3) after the article shaped oven dry with (2), at 1200～1600 ℃, be preferably 1300～1500 ℃, roasting 1～24 hour is preferably 4～12 hours, promptly can be made into qualified carrier.
The specific surface of the carrier that makes according to the method described above is 1.0～10m
2/ g, pore volume are 0.1～0.7ml/g, and heap is than being 0.4～1.0g/ml.The X-ray diffraction measurement result shows that the main thing of the carrier that makes according to the method described above is sillimanite and/or mullite mutually.
Prepare the used pore creating material of carrier of the present invention and can be selected from materials such as active carbon, high molecular polymer, shuck, grass-seed, cereal; Preparing carrier of the present invention binding agent commonly used is materials such as carboxymethyl cellulose (CMC), polyvinyl alcohol.
Method for preparing catalyst of the present invention comprises:
To be mixed with aqueous metal salt with the corresponding raw material of active component, for example be mixed with the aqueous solution of nitrate or acetate etc., by required metallic element mol ratio preparing metal salt mixed aqueous solution, the metal ion total concentration is 1.0～3.0M, is preferably 1.5～2.5M, and the mol ratio by citric acid and total metal ion is 0～2.0 again, be preferably 0.3～0.6, add citric acid, mix, promptly get activity component impregnation liquid.With activity component impregnation liquid impregnated carrier, after the drying, in 400～800 ℃, be preferably 500～700 ℃, calcination activation 0.5～24 hour, be preferably 2～8 hours, promptly reaction generates the composite oxides active component on carrier situ, and directly to load on sillimanite and/or mullite be on the carrier of main thing phase, and said process can repeat for several times, reach required amount up to the active component that loads on the carrier, make composite oxide catalysts thus.The weight ratio of active component and carrier is 5%～30% in the catalyst of the present invention, but in fact, weight ratio is 8%～15% o'clock, and catalyst can reach good catalytic performance.
The X-ray diffraction measurement result shows that the activity of such catalysts component that makes according to the method described above is mainly composite oxides.
Composite oxide catalysts of the present invention, to airborne n-hexane, normal heptane,
Table one is by the initiation temperature of combustion material
Quilt combustion material initiation temperature scope (℃)
Carbon monoxide 125～200
Saturated alkane (n-hexane, normal heptane) 210～300
Aromatic hydrocarbons (toluene, dimethylbenzene) 230～260
Alcohols (methyl alcohol, ethanol) 170～220
Ketone (rudimentary) 190～220
Aldehydes (furfural) 220～250
Phenols (phenol) 230～280
Acids (acetic acid, acetic anhydride) 230～260
Ester class (ethyl acetate, butyl acetate) 225～250
Amine (aniline, dimethyl formamide) 200～240
Organic compounds such as toluene, methyl alcohol, ethanol, butanone, furfural, phenol, glacial acetic acid, acetic anhydride, butyl acetate, nitrobenzene, aniline, dimethyl formamide, with the carbon monoxide in the flue gas is all had good catalytic combustion properties (seeing Table), at concentration 1500～15000mg/m
3, air speed 5000～20000h
-1The time initiation temperature be 125～300 ℃ (implication of initiation temperature is to make by combustion substance combustion conversion ratio to reach 90% when above, enters the catalytic combustion reactor beds before by the required minimum temperature of combustion gas body).The burning liberated heat can directly or by heat exchanger be used as the case may be.Therefore, this catalyst can be applied to industry and civilian organic exhaust gas, the burning purification that contains carbon monoxide smoke and energy-conservation aspect.
The present invention will be further described below in conjunction with embodiment, but be not to limit the scope of the invention with this.
10 kilograms of clays (are contained 30%Al
2O
3, 45%SiO
2) add 7.2 kilograms of Al(OH)
3, add 1.0 kilograms of CMC, add 0.2 kilogram of active carbon pore creating material, and suitable quantity of water, mix kneading thoroughly after, making diameter with make-up machine is 6 millimeters bead, after the drying, puts into high temperature furnace 1450 ℃ of roastings 12 hours, promptly makes carrier.
The specific surface of the carrier that makes according to the method described above is 5.3m
2/ g, pore volume are 0.45ml/g, and heap is than being 0.7g/ml.In Cu K α radiation, 40KV measures the above-mentioned carrier that makes under the condition of 150mA with Japan's D/MAX-RA type of science x-ray diffractometer, and it the results are shown in Fig. 1.This x-ray diffraction pattern proves that the main thing of obtained carrier is sillimanite and/or mullite mutually.
Get the above-mentioned ball type carrier of 50 grams, be with metal ion and mol ratio thereof
Fe: Co: Ni: Cu: Mn=1: 3: 3: 3: 6 maceration extract dipping (the solion total concentration is 2M, and citric acid is 0.4 with the mol ratio of total metal ion), activate 4 hours down at 520 ℃, promptly make composite oxide catalysts.
In Cu K α radiation, 40KV measures the above-mentioned composite oxide catalysts that makes under the condition of 150mA with Japan's D/MAX-RA type of science x-ray diffractometer, and it the results are shown in Fig. 2.This x-ray diffraction pattern proves that obtained catalyst contains composite oxides active component thing phase.
This catalyst is 5500mg/m to airborne toluene in concentration
3, air speed is 10000h
-1The time initiation temperature be 230 ℃; Is 6100mg/m to n-hexane in concentration
3, air speed is 10000h
-1The time initiation temperature be 246 ℃; Is 5600mg/m to methyl alcohol in concentration
3, air speed is 10000h
-1The time initiation temperature be 198 ℃; Is 10000mg/m to butanone in concentration
3, air speed is 10000h
-1The time initiation temperature be 198 ℃; Is 2.0%(v/v to carbon monoxide in concentration), air speed is 12000h
-1The time initiation temperature be 125 ℃.
9.9 kilograms of clays (are contained 35%Al
2O
3, 49%SiO
2) add 10.5 kilograms of Al(OH)
3, add 0.45 kilogram of CMC, add 0.5 kilogram of pore creating material (corn quarrel), and suitable quantity of water, mix kneading thoroughly after, making diameter with make-up machine is that 5 millimeters long are 6 millimeters garden post, after the drying, puts into high temperature furnace 1500 ℃ of roastings 8 hours, promptly makes carrier.The specific surface of the carrier that said method makes is 4.5m
2/ g, pore volume are 0.40ml/g, and heap is than being 0.75g/ml.Get the above-mentioned garden of 50 grams cylindricality carrier, with metal ion and mol ratio thereof is La: Sr: Ce: Co=7: (the solion total concentration is 2.7M to 2: 1: 10 maceration extract dipping, citric acid is 0.5 with the mol ratio of total metal ion), activate 3.5 hours down at 540 ℃, promptly make composite oxide catalysts.
This catalyst is 5500mg/m to airborne toluene in concentration
3, air speed is 10000h
-1The time initiation temperature be 290 ℃.
Embodiment 3
15 kilograms of clays (are contained 27%Al
2O
3, 57%SiO
2) add 18 kilograms of Al(OH)
3, add 0.75 kilogram of CMC, add 0.6 kilogram of pore creating material (active carbon) and suitable quantity of water, after mixing kneading thoroughly, making external diameter with make-up machine is that 6 millimeters long are that 6 millimeters internal diameters are 2 millimeters open tubular column, after the drying, put into high temperature furnace 1400 ℃ of roastings 10 hours, promptly make carrier.The specific surface of the carrier that makes according to the method described above is 7.5m
2/ g, pore volume are 0.55ml/g, and heap is than being 0.75g/ml.
Get the above-mentioned hollow cylindrical carrier of 50 grams, with metal ion and mol ratio thereof is Co: Ni: Cu: Mn=1: (the solion total concentration is 2.5M to 2: 2: 4 maceration extract dipping, citric acid is 0.4 with the mol ratio of total metal ion total concentration), activate 5 hours down at 500 ℃, promptly make composite oxide catalysts.
This catalyst is 5500mg/m to airborne toluene in concentration
3, air speed is 10000h
-1The time initiation temperature be 230 ℃; Is 6700mg/m to normal heptane in concentration
3, air speed is 10000h
-1The time initiation temperature be 283 ℃; Is 3400mg/m to butyl acetate in concentration
3, air speed is 10000h
-1The time initiation temperature be 225 ℃; The Pyrogentisinic Acid is 13300mg/m in concentration
3, air speed is 10700h
-1The time initiation temperature be 241 ℃; Is 2.0%(v/v to carbon monoxide in concentration), air speed is 12000h
-1The time initiation temperature be 125 ℃.
Embodiment 4
Get the ball type carrier among the 50 gram embodiment 1, with metal ion and mol ratio thereof is Cu: Co=1: (the solion total concentration is 2.5M to 2 maceration extract dipping, citric acid is 0.35 with the mol ratio of total metal ion), activate 2 hours down at 550 ℃, promptly make composite oxide catalysts.
This catalyst is 5500mg/m to airborne toluene in concentration
3, air speed is 10000h
-1The time initiation temperature be 230 ℃; Is 5600mg/m to methyl alcohol in concentration
3, air speed is 10000h
-1The time initiation temperature be 170 ℃; Is 6600mg/m to glacial acetic acid in concentration
3, air speed is 15000h
-1The time initiation temperature be 230 ℃; Is 10200mg/m to dimethyl formamide in concentration
3, air speed is 12000h
-1The time initiation temperature be 200 ℃; Is 3600mg/m to furfural in concentration
3, air speed is 10000h
-1The time initiation temperature be 245 ℃.
Embodiment 5
Get the garden cylindricality carrier among the 50 gram embodiment 2, with metal ion and mol ratio thereof is Ni: Co: Cu: Cr: Ce=7: 14: 3: 6: (the solion total concentration is 1.5M to 3 maceration extract dipping, citric acid is 0.5 with the mol ratio of total metal ion), activate 2 hours down at 600 ℃, promptly make composite oxide catalysts.
This catalyst to airborne be 6100mg/m to n-hexane in concentration
3, air speed is 10000h
-1The time initiation temperature be 268 ℃.
Claims (32)
1, a kind of burning catalyst for composite oxide, form by following active component and carrier:
Active component is main component with composite oxides, and described active component includes two or more metallic element, and described metallic element is a transition metal, alkali earth metal, thulium;
Carrier is a main component with sillimanite and/or mullite;
It is characterized in that, the directly preparation generation on carrier situ of described activity of such catalysts component, and directly load on the described carrier.
2, catalyst according to claim 1 is characterized in that, the weight ratio of described active component and described carrier is 5%～30%; And the content of each metallic element is expressed as 0～0.999 with molar fraction in the described active component.
3, catalyst according to claim 1 is characterized in that, the weight ratio of described active component and described carrier is 8%～15%.
4, catalyst according to claim 1, wherein said transition metal is selected from Ti, Cr, Mn, Zn, Fe, Co, Ni, Cu, V, Mo, W, Pt and/or Pd; Described alkali earth metal is selected from Mg, Ca, Sr and/or Ba; Described thulium is selected from La, Ce or norium element.
5, catalyst according to claim 1, each metallic element and mol ratio thereof are in the wherein said active component
Fe∶Co∶Ni∶Cu∶Mn＝（0～3）∶（0～3）∶（0～3）∶（0～3）∶（0～16）。
6, catalyst according to claim 1, each metallic element and mol ratio thereof are in the wherein said active component
Fe∶Co∶Ni∶Cu∶Mn＝（1～3）∶（1～3）∶（1～3）∶（1～3）∶（6～8）。
7, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Co: Ni: Cu: Mn=1 in the wherein said active component: 2: 2: 2: 6.
8, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Co: Ni: Cu: Mn=1 in the wherein said active component: 2: 3: 3: 6.
9, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Co: Ni: Cu: Mn=1 in the wherein said active component: 3: 3: 3: 6.
10, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Co: Ni: Cu: Mn=2 in the wherein said active component: 1: 2: 3: 6.
11, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Co: Ni: Cu: Mn=3 in the wherein said active component: 1: 3: 2: 6.
12, catalyst according to claim 1, each metallic element and mol ratio thereof are Ni: Co: Cu: Cr: Ce=7 in the wherein said active component: 14: 3: 6: 3.
13, catalyst according to claim 1, each metallic element and mol ratio thereof are Co: Ni: Cu: Mn=1 in the wherein said active component: 2: 2: 4.
14, catalyst according to claim 1, each metallic element and mol ratio thereof are Co: Ni: Cu: Mn=1 in the wherein said active component: 1: 3: 5.
15, catalyst according to claim 1, each metallic element and mol ratio thereof are Ni: Co: Cu: Cr=9 in the wherein said active component: 18: 1: 2.
16, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Cu: Mn=1 in the wherein said active component: 1: 3.
17, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Cu: Mn=1 in the wherein said active component: 1: 14.
18, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Ni: Mn=1 in the wherein said active component: 2: 3.
19, catalyst according to claim 1, each metallic element and mol ratio thereof are Fe: Co: Mn=1 in the wherein said active component: 1: 3.
20, catalyst according to claim 1, each metallic element and mol ratio thereof are Ni: Cu: Mn=1 in the wherein said active component: 1: 3.
21, catalyst according to claim 1, each metallic element and mol ratio thereof are Cu: Co=1 in the wherein said active component: 1.
22, catalyst according to claim 1, each metallic element and mol ratio thereof are Cu: Co=1 in the wherein said active component: 2.
23, catalyst according to claim 1, each metallic element and mol ratio thereof are Cu: Mn=1 in the wherein said active component: 2.
24, catalyst according to claim 1, each metallic element and mol ratio thereof are Ni: Co=1 in the wherein said active component: 2.
25, catalyst according to claim 1, each metallic element and mol ratio thereof are Ni: Mn=1 in the wherein said active component: 2.
26, catalyst according to claim 1, each metallic element and mol ratio thereof are Co: Mn=1 in the wherein said active component: 2.
27, the method for preparing each described burning catalyst for composite oxide of claim 1 to 26, it is characterized in that, the metallic element mol ratio preparing metal saline solution required according to active component, the metal ion total concentration is 1.0～3.0M in the aqueous metal salt, mixes promptly to get maceration extract; Flood described sillimanite and/or mullite is the carrier of main thing phase with this maceration extract, after the drying, in 400～800 ℃ of calcination activations 0.5～24 hour, reaction generates the composite oxides active component on carrier situ, and directly loading on sillimanite and/or mullite is on the carrier of main thing phase, promptly makes described catalyst.
28, method according to claim 27, wherein said aqueous metal salt metal ion total concentration is 1.5～2.0M, slaine is nitrate, acetate etc., and be 0～2.0 to add citric acid by the mol ratio of citric acid and total metal ion, the calcination activation temperature is 500～700 ℃, and the calcination activation time is 0.5～24 hour.
29, method according to claim 27, wherein said carrier prepares as follows:
(1) salic and raw material silica are pressed Al
2O
3: SiO
2=1.40～2.30 ratio (weight) is mixed, and is mixed with compound;
(2) in compound, add 0～10%(weight) binding agent, 0～20%(weight) pore creating material and suitable quantity of water, after stirring, kneaded and formed;
(3) after the article shaped oven dry with (2), promptly made described carrier in 1～24 hour 1200～1600 ℃ of roastings;
Wherein said pore creating material can be selected from materials such as active carbon, high molecular polymer, shuck, grass-seed, cereal; Described binding agent is materials such as carboxymethyl cellulose (CMC), polyvinyl alcohol.
30, method according to claim 29, raw material wherein salic and silica is Al by weight
2O
3: SiO
2=1.55～1.90, binding agent is 1%～5% of a compound weight, and pore creating material is 5%～15% of a compound weight, and sintering temperature is 1300～1500 ℃, and roasting time is 4～12 hours.
31, method according to claim 29, wherein carrier can be processed into sphere, cylindricality, hollow cylindrical or other abnormity; The specific surface of carrier is 1.0～10m
2/ g, pore volume are 0.1～0.7ml/g, and heap is than being 0.4～1.0g/ml.
32, any one described catalyst of claim 1 to 26 is as the purposes of the combustion catalyst of industry and civilian organic exhaust gas, the catalytic combustion purification that contains carbon monoxide smoke and energy-conservation aspect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100437A CN1034790C (en) | 1992-01-24 | 1992-01-24 | Burning catalyst for composite oxide and preparing process and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100437A CN1034790C (en) | 1992-01-24 | 1992-01-24 | Burning catalyst for composite oxide and preparing process and application |
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| Publication Number | Publication Date |
|---|---|
| CN1074630A true CN1074630A (en) | 1993-07-28 |
| CN1034790C CN1034790C (en) | 1997-05-07 |
Family
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| Application Number | Title | Priority Date | Filing Date |
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| CN92100437A Expired - Fee Related CN1034790C (en) | 1992-01-24 | 1992-01-24 | Burning catalyst for composite oxide and preparing process and application |
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Cited By (16)
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| WO1995003886A1 (en) * | 1993-07-29 | 1995-02-09 | Hongxing Zhou | Bifunctional catalyst containing multimetal oxides |
| CN1055491C (en) * | 1993-12-17 | 2000-08-16 | 林科 | Base metal oxide carbon monoxide combustion-supporting agent and its preparation method and use |
| CN1068036C (en) * | 1998-01-23 | 2001-07-04 | 中国科学院山西煤炭化学研究所 | Catalyst for combustion of natural gas and preparing process thereof |
| CN101940932A (en) * | 2010-09-25 | 2011-01-12 | 东华大学 | Diatomite catalyst for processing hydrocarbons and preparation method thereof |
| CN101954285A (en) * | 2010-09-25 | 2011-01-26 | 东华大学 | Diatomite fine-desulfurization catalyst and preparation method thereof |
| CN101954283A (en) * | 2010-09-25 | 2011-01-26 | 东华大学 | Kieselguhr catalyst for eliminating carbon monoxide at normal temperature and preparation method thereof |
| CN102259034A (en) * | 2011-06-24 | 2011-11-30 | 淄博齐茂催化剂有限公司 | Method for producing finished product of supported catalyst |
| CN105413704A (en) * | 2014-09-22 | 2016-03-23 | 中国石化扬子石油化工有限公司 | Preparation method for CuCoMnFe/TiO2 catalyst for carboxylate catalytic combustion |
| CN106040205A (en) * | 2016-07-23 | 2016-10-26 | 芜湖长启炉业有限公司 | Combination based on activated carbon modification and used for purifying tail gas of grain dryer and preparation method and application thereof |
| CN106215886A (en) * | 2016-07-23 | 2016-12-14 | 芜湖长启炉业有限公司 | Based on diatomite modified for compositions purifying grain-drying tail gas and its preparation method and application |
| CN106540739A (en) * | 2015-09-16 | 2017-03-29 | 中国石化扬子石油化工有限公司 | A kind of preparation method of supported catalyst burning catalyst |
| CN107376929A (en) * | 2017-08-09 | 2017-11-24 | 南京工业大学 | A kind of catalyst for catalytic combustion and preparation and application |
| CN107486215A (en) * | 2017-08-09 | 2017-12-19 | 南京工业大学 | Supported catalyst combustion catalyst and preparation and application |
| CN115007166A (en) * | 2022-06-23 | 2022-09-06 | 山东亮剑环保新材料有限公司 | Preparation method of granular CO catalyst for catalytic combustion |
| CN115430431A (en) * | 2022-08-19 | 2022-12-06 | 河南农业大学 | Mn-doped Co-based catalyst, and preparation method and application thereof |
| CN115739106A (en) * | 2022-11-10 | 2023-03-07 | 南开大学 | Preparation method and application of composite oxide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103200A (en) * | 1986-05-06 | 1987-11-18 | 华东化工学院 | Non-noble metal combustion catalyst and manufacture method thereof |
| JPH0813686B2 (en) * | 1988-06-01 | 1996-02-14 | 松下電器産業株式会社 | Metal complex oxide |
| IT1229572B (en) * | 1989-04-17 | 1991-09-04 | S S T Solid State Technology S | PLANT FOR THE PURIFICATION OF AIR POLLUTED BY ORGANIC INDUSTRIAL PRODUCTS BY CATALYTIC COMBUSTION. |
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1992
- 1992-01-24 CN CN92100437A patent/CN1034790C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1995003886A1 (en) * | 1993-07-29 | 1995-02-09 | Hongxing Zhou | Bifunctional catalyst containing multimetal oxides |
| CN1055491C (en) * | 1993-12-17 | 2000-08-16 | 林科 | Base metal oxide carbon monoxide combustion-supporting agent and its preparation method and use |
| CN1068036C (en) * | 1998-01-23 | 2001-07-04 | 中国科学院山西煤炭化学研究所 | Catalyst for combustion of natural gas and preparing process thereof |
| CN101940932A (en) * | 2010-09-25 | 2011-01-12 | 东华大学 | Diatomite catalyst for processing hydrocarbons and preparation method thereof |
| CN101954285A (en) * | 2010-09-25 | 2011-01-26 | 东华大学 | Diatomite fine-desulfurization catalyst and preparation method thereof |
| CN101954283A (en) * | 2010-09-25 | 2011-01-26 | 东华大学 | Kieselguhr catalyst for eliminating carbon monoxide at normal temperature and preparation method thereof |
| CN101954283B (en) * | 2010-09-25 | 2012-06-13 | 东华大学 | Kieselguhr catalyst for eliminating carbon monoxide at normal temperature and preparation method thereof |
| CN101954285B (en) * | 2010-09-25 | 2012-06-13 | 东华大学 | Diatomite fine-desulfurization catalyst and preparation method thereof |
| CN101940932B (en) * | 2010-09-25 | 2012-07-25 | 东华大学 | Diatomite catalyst for processing hydrocarbons and preparation method thereof |
| CN102259034A (en) * | 2011-06-24 | 2011-11-30 | 淄博齐茂催化剂有限公司 | Method for producing finished product of supported catalyst |
| CN105413704A (en) * | 2014-09-22 | 2016-03-23 | 中国石化扬子石油化工有限公司 | Preparation method for CuCoMnFe/TiO2 catalyst for carboxylate catalytic combustion |
| CN106540739A (en) * | 2015-09-16 | 2017-03-29 | 中国石化扬子石油化工有限公司 | A kind of preparation method of supported catalyst burning catalyst |
| CN106040205A (en) * | 2016-07-23 | 2016-10-26 | 芜湖长启炉业有限公司 | Combination based on activated carbon modification and used for purifying tail gas of grain dryer and preparation method and application thereof |
| CN106215886A (en) * | 2016-07-23 | 2016-12-14 | 芜湖长启炉业有限公司 | Based on diatomite modified for compositions purifying grain-drying tail gas and its preparation method and application |
| CN106215886B (en) * | 2016-07-23 | 2018-08-21 | 芜湖长启炉业有限公司 | The composition and its preparation method and application for purifying grain-drying tail gas based on diatomite modified |
| CN107376929A (en) * | 2017-08-09 | 2017-11-24 | 南京工业大学 | A kind of catalyst for catalytic combustion and preparation and application |
| CN107486215A (en) * | 2017-08-09 | 2017-12-19 | 南京工业大学 | Supported catalyst combustion catalyst and preparation and application |
| CN115007166A (en) * | 2022-06-23 | 2022-09-06 | 山东亮剑环保新材料有限公司 | Preparation method of granular CO catalyst for catalytic combustion |
| CN115430431A (en) * | 2022-08-19 | 2022-12-06 | 河南农业大学 | Mn-doped Co-based catalyst, and preparation method and application thereof |
| CN115739106A (en) * | 2022-11-10 | 2023-03-07 | 南开大学 | Preparation method and application of composite oxide |
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