CN104001556B - A kind of high-termal conductivity egg-shell catalyst carrier and preparation method and application - Google Patents
A kind of high-termal conductivity egg-shell catalyst carrier and preparation method and application Download PDFInfo
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Abstract
A kind of high-termal conductivity egg-shell catalyst carrier is metal ball, and metal ball average grain scope 1-5mm, specific surface is 70-600m
2/ g, average pore size 4-60nm, pore volume is 0.25-2.00cm
3/ g, metal ball corrosion layer thickness 0.05-0.25mm, corrosion layer is metal oxide.It is simple that the present invention has preparation process, and shell thickness is controlled, is applicable to the advantage of large-scale industrial production.
Description
Technical field
The present invention relates to a kind of catalyst carrier, specifically a kind of high-termal conductivity egg-shell catalyst carrier and preparation method and application.
Background technology
As everyone knows, the reactor used in the middle of industrial production has paste state bed reactor, fluidized-bed reactor, fixed bed reactors etc.Wherein fixed bed reactors have simplicity of design, easy and simple to handle, the segregative advantage of product and the system that the catalysis technical field that becomes the most often runs into.But in actual applications, also there is short slab in fixed bed reactors, the heat transfer namely in course of reaction and mass transfer problem.In fixed bed reactors, for high exothermic reaction, because the catalyst granules heat conductivility of filling is poor, very easily causes beds hot-spot, even occur " temperature runaway " phenomenon time serious, catalyst activity component is sintered, catalytic performance declines.On the other hand, in order to reduce pressure drop in suitability for industrialized production, the catalyst granules loaded in fixed bed reactors is greater than 1mm usually, and now in catalytic reaction, diffusion restriction becomes very serious, affects rate of catalysis reaction greatly, reduces the selective of product.At present, it is carrier Kaolinite Preparation of Catalyst and prepare egg-shell catalyst etc. that the method addressed these problems has with metal foam.
CN1939587A discloses a kind of integral catalyzer for synthesizing gas by reforming methane with co 2.Ni active component is assembled in mesoporous molecular sieve SBA-15, then loads to Al
2o
3for on the FeCrAl alloy sheet of transition vector, prepare the integral catalyzer of sheet metal as carrier.This catalyst has that heat conductivility is excellent, bed pressure drop is low, active component Ni high degree of dispersion and the not advantage such as easy-sintering, good stability.Simultaneously because load is thinner in the catalyst thickness of alumina layer, eliminate the interior diffusion restriction of reaction.But utilize catalyst prepared by the method, its Al
2o
3transition zone easily departs from course of reaction, causes catalyst activity component to run off, and integral catalyzer is also not easy to load in fixed bed reactors simultaneously.
CN1781595A discloses a kind of foam metal hydrogenating catalyst and its preparation method and application.Carrier adopts powder metallurgic method preparation, and active component adopts electroless plating method to carry out load, and it is high that the catalyst obtained has catalytic activity, the advantage of good heat conductivity.The porosity high due to foam metal and larger aperture, the interior diffusion restriction of reaction obtains elimination.But the catalyst carrier aperture that profit is prepared in this way is excessive, and specific surface is low, and reactor utilization ratio is low, catalyst preparation process is complicated, is difficult to large-scale production.
US5545674 discloses a kind of preparation method of egg-shell catalyst, by using the immersion with middle dry or combustion step or spray method to be repeatedly impregnated on bead-type substrate by cobalt nitrate solution, thus obtained egg-shell catalyst.But this method complicated operation, is difficult to large-scale industrial production, and repeatedly floods restive shell thickness.
CN1306459A disclose a kind of on cellular ceramic substrate preparation there is the technique of the noble metal lamella catalyst determining shell thickness, this technique is by depositing suitable noble metal precursor body on porous support with chemical vapour deposition technique, become metal by chemistry or thermal reduction and noble metal is fixed on carrier afterwards, thus obtained egg-shell catalyst.But egg-shell catalyst technical process prepared by this method is lengthy and jumbled, is difficult to large-scale application.
Summary of the invention
The object of the present invention is to provide a kind of preparation process simple, shell thickness is controlled, is applicable to high-termal conductivity egg-shell catalyst carrier and the preparation method and application of large-scale industrial production.
Metal material has the characteristic being easy to be formed corrosion layer (composition is metal oxide) by corrosion such as soda acids, and the condition simultaneously regulating and controlling acid and alkali corrosion effectively can regulate and control the parameter such as specific surface, pore structure of the thickness of corrosion layer, material.Based on above characteristic, metal ball corrosion is formed one deck corrosion layer, then the load of catalyst activity component on corrosion layer, can egg-shell catalyst be obtained.Now active component is mainly positioned on metal ball corrosion layer, and inside is uncorroded metal material, egg-shell catalyst obtained in this way, diffusion in energy Effective Regulation.Meanwhile, metal material also has the good feature of thermal conductivity, utilize metal ball to prepare heat transfer efficiency that egg-shell catalyst can also improve bed, avoids being emerged of bed " focus ".In addition, metal ball also has its cheap market price, the sufficient advantage of raw material sources.Therefore, using metal ball as catalyst support preparation egg-shell catalyst, there is great actual application value and great commercial promise.
High-termal conductivity egg-shell catalyst carrier of the present invention is metal ball, metal ball average grain scope 1-5mm, and specific surface is 70-600m
2/ g, average pore size 4-60nm, pore volume is 0.25-2.00cm
3/ g, metal ball corrosion layer thickness 0.05-0.25mm, corrosion layer is metal oxide.
Metal ball as above is aluminium ball, magnesium ball or magnadure ball, albronze ball.
The preparation method of catalyst carrier of the present invention is as follows:
(1) be that the metal ball of 1-5mm is put into distilled water and boiled 6 ~ 10h by particle diameter, filter, by filter cake dry 10-20h at 60-100 DEG C;
(2) 1.0 × 10 are configured
-2-5.0mol/L acid or aqueous slkali 1-10L;
(3) when metal ball is aluminium ball, magnadure ball, albronze ball, by metal ball: acid or aqueous slkali=100g:1-10L, the solution of step (2) gained is added by l-10ml/min speed in the metal ball of step (1) gained, and electromagnetic agitation process 10-30h, filter, washing is extremely neutral, by filter cake dry 10-30h at 60-100 DEG C;
When metal ball is magnesium ball, by metal ball: acid solution=100g:1-10L, the solution of step (2) gained is added by l-10ml/min speed in the metal ball of step (1) gained, and electromagnetic agitation process 10-30h, filter, washing is extremely neutral, by filter cake dry 10-30h at 60-100 DEG C;
(4) by the material of step (3) gained roasting 6-10h under 300-600 DEG C of nitrogen atmosphere, obtaining outer is metal oxide, and internal layer is the catalyst carrier of uncorroded metal material.
Acid as above is the mixture of one or more in acetic acid, nitric acid, hydrochloric acid, oxalic acid, and alkali is the mixture of one or more in NaOH, potassium hydroxide, ammoniacal liquor.
Carrier of the present invention is used for the preparation of high heat release, high endothermic reaction catalyst agent, catalyst comprises reactive metal oxides and catalyst carrier, catalyst weight percent consists of: reactive metal oxides: 0.1%-40%, all the other are outer is metal oxide, and internal layer is the catalyst carrier of uncorroded metal material.
Reactive metal oxides as above is one or more mixtures in Co, Fe, Ni, Mn, Ru, Rh, Pt, Au, Pd, Cu oxide.
Egg-shell catalyst preparation method of the present invention is as follows:
Equi-volume impregnating is adopted to be dissolved in deionized water by reactive metal oxides soluble-salt, flood with catalyst carrier at ambient temperature, dip time is 6-10h, after dipping at 60-100 DEG C dry 10-20h, roasting is carried out in a nitrogen atmosphere after drying, sintering temperature is 200-600 DEG C, and roasting time is 3-10h, obtains egg-shell catalyst.Catalyst activity component is positioned on the outer field oxide of metal ball carrier, and internal layer is uncorroded metal material.
Reactive metal oxides soluble-salt as above is acetate, nitrate or oxalates.
Its specific surface of catalyst as above is 50-500m
2/ g.
Catalyst as above is used for high heat release, the high endothermic reaction, such as F-T synthesis, methanation, methanol-fueled CLC, methane carbon dioxide reformation, alcohol Selective Oxidation aldehyde ketone, waste gas purification.
Not diluting during catalyst application as above is loaded in fixed bed reactors, after reduction, carries out catalytic reaction.
Compared with prior art, tool has the following advantages in the present invention:
1. by adopting metal ball as catalyst carrier, drastically increasing the heat transfer efficiency of beds, effectively prevent the generation with " temperature runaway " that emerged of fixed bed reactors bed " focus ".
2., compared with traditional egg-shell catalyst preparation method, energy Effective Regulation shell thickness of the present invention, is suitable for large-scale production.
3. catalyst preparation process is simple, cheap.
Detailed description of the invention
The present invention will be further described for embodiment below, and protection scope of the present invention is not by the restriction of these embodiments.
Embodiment 1:
Catalyst support preparation: metallic aluminium ball (particle diameter 2mm) is put into distilled water and boils 6h, filters, by filter cake dry 10h at 60 DEG C.By in 2L1.0mol/L sodium hydroxide solution instillation gained material, instillation speed is 2ml/min, and electromagnetic agitation process 10h, filter, washing to neutral, by filter cake dry 15h at 100 DEG C, 400 DEG C of roasting 8h in a nitrogen atmosphere after drying, obtaining outer is aluminium oxide, and internal layer is the metallic aluminium ball carrier of uncorroded metallic aluminium.The metallic aluminium ball diameter of carrier of gained is 2mm, and corrosion layer thickness is 0.15mm, and specific surface is 175m
2/ g, average pore size is 15nm, and pore volume is 0.36cm
3/ g.
Catalyst preparing: 15 (wt) % accounting for final catalyst by cobalt oxide takes Co (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in obtained above-mentioned carrier, dip time is 6h, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 350 DEG C, and roasting time is 6h, finally obtained egg-shell catalyst.The active component of catalyst is positioned on the aluminium oxide of metallic aluminium ectosphere, and inside is uncorroded metallic aluminium.Catalyst weight percent is: cobalt oxide 15%, and all the other are metallic aluminium ball carrier, and the catalyst specific surface obtained is 148m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, and the lower 400 DEG C of reduction 6h of hydrogen atmosphere are used for fischer-tropsch reaction.Reaction needed raw material is synthesis gas, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 220 DEG C, and reaction pressure is 2Mpa, and volume space velocity is 1000h
-1.Reaction result shows: CO conversion ratio 45%, CH
4selective 7.1%, C
5+selective 86%.
Embodiment 2:
Catalyst support preparation: metallic aluminium ball (particle diameter 3mm) is put into distilled water and boils 6h, filters, by filter cake dry 10h at 60 DEG C.By in 5L2.0mol/L sodium hydroxide solution instillation gained material, instillation speed is 5ml/min, and electromagnetic agitation process 10h, filter, washing is to neutral, by filter cake dry 15h at 100 DEG C, after drying at 400 DEG C roasting 8h, obtaining outer is the aluminium oxide inside metallic aluminium ball carrier that is uncorroded metallic aluminium.The metallic aluminium ball diameter of carrier of gained is 3mm, and corrosion layer thickness is 0.20mm, and specific surface is 260m
2/ g, average pore size is 12nm, and pore volume is 0.42cm
3/ g.
Catalyst preparing: 25 (wt) % and 5 (wt) % accounting for final catalyst by iron oxide and manganese oxide respectively, take Fe (NO
3)
39H
2o and Mn (NO
3)
24H
2o, measures deionized water according to equi-volume impregnating, and configuration mixing salt solution also impregnated in above-mentioned carrier, and dip time is 6h, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 350 DEG C, and roasting time is 4h.Final obtained egg-shell catalyst.The active component of catalyst is positioned on the aluminium oxide of metallic aluminium ectosphere, and inside is uncorroded metallic aluminium.Catalyst weight percent is iron oxide 25%, manganese oxide 5%, and all the other are metallic aluminium ball carrier.Final obtained egg-shell catalyst specific surface is 220m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, and the lower 400 DEG C of reduction 12h of hydrogen atmosphere are used for fischer-tropsch reaction.Reaction raw materials is synthesis gas, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 270 DEG C, and reaction pressure is 2Mpa, and volume space velocity is 3000h
-1.Reaction result shows: CO conversion ratio 85%, CH
4selective 8.6%, C
5+selective 82%.
Embodiment 3:
Catalyst support preparation: magnadure ball (mass percent: Mg5%Al95%, particle diameter 4mm) is put into distilled water and boils 6h, filters, by filter cake dry 10h at 60 DEG C.By in 5L1.0mol/L hydrochloric acid solution instillation gained material, instillation speed is 5ml/min, and electromagnetic agitation process 6h, filter, washing is to neutral, by filter cake dry 9h at 80 DEG C, after drying at 350 DEG C roasting 10h, obtaining outer is magnesia, the aluminium oxide inside magnesium metal aluminium alloy ball carrier that is uncorroded metal material.The particle diameter of magnesium metal aluminium alloy ball carrier is 4mm, and corrosion layer thickness is 0.22mm, and specific surface is 402m
2/ g, average pore size 6nm, pore volume is 0.71cm
3/ g.
Catalyst preparing: 3 (wt) % accounting for final catalyst by ruthenium-oxide takes Ru (NO) (NO
3)
3, measure deionized water according to equi-volume impregnating, configuration salting liquid also impregnated in above-mentioned carrier, dip time is 6h, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 350 DEG C, and roasting time is 4h, finally obtained egg-shell catalyst.The active component of catalyst is positioned on the oxide of magnesium metal aluminium alloy ectosphere, and inside is uncorroded metal material.Catalyst weight percent is: ruthenium-oxide 3%, and all the other are magnadure ball carrier.The catalyst specific surface obtained is 350m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, and the lower 300 DEG C of reduction 12h of hydrogen atmosphere are used for fischer-tropsch reaction.Reaction raw materials is synthesis gas, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 200 DEG C, and reaction pressure is 2Mpa, and volume space velocity is 1000h
-1.Reaction result shows: CO conversion ratio 80%, CH
4selective 5.1%, C
5+selective 90%.
Embodiment 4:
Catalyst support preparation: magnesium ball (particle diameter 5mm) is put into distilled water and boils 8h, filters, by filter cake dry 10h at 80 DEG C.By 10L1.0 × 10
-2in mol/L salpeter solution instillation gained material, instillation speed is 5ml/min, and electromagnetic agitation process 10h, filter, washing is extremely neutral, by filter cake dry 9h at 80 DEG C, after drying at 600 DEG C roasting 10h, obtaining outer is magnesia, and inside is the magnesium metal ball carrier of uncorroded magnesium metal.The magnesium metal ball diameter of carrier of gained is 5mm, and corrosion layer is 0.18mm, and specific surface is 360m
2/ g, average pore size 20nm, pore volume is 0.55cm
3/ g.
Catalyst preparing: 10 (wt) % accounting for final catalyst by nickel oxide takes Ni (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, dip time is 10h, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 400 DEG C, and roasting time is 4h, finally obtained egg-shell catalyst.The active component of catalyst is positioned on the magnesia of magnesium metal ectosphere, and inside is uncorroded magnesium metal.Catalyst weight percent is: nickel oxide 10%, and all the other are magnesium metal ball carrier.The catalyst specific surface obtained is 290m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, and the lower 600 DEG C of reduction 6h of hydrogen atmosphere are for the synthesis of gas methanation reaction.Reaction raw materials is H
2and CO, reaction condition is: H
2the mol ratio of/CO is 3, and reaction temperature is 600 DEG C, and reaction pressure is 2Mpa, and volume space velocity is 30000h
-1.Reaction result shows: CO conversion ratio 90%, CH
4selective 87%, all the other are CO
2.
Embodiment 5:
Catalyst support preparation: magnadure ball (mass percent is magnesium 5% aluminium 95%, particle diameter 1mm) is put into distilled water and boils 8h, filters, by filter cake dry 10h at 80 DEG C.By 5L1.0 × 10
-2in mol/L acetum instillation gained material, instillation speed is 5ml/min, and electromagnetic agitation process 6h, filter, washing is to neutral, by filter cake dry 9h at 80 DEG C, after drying at 600 DEG C roasting 10h, obtaining outer is magnesia, the aluminium oxide inside magnesium metal aluminium alloy ball carrier that is uncorroded metal material.The magnesium metal aluminium alloy ball diameter of carrier of gained is 1mm, and corrosion layer thickness 0.05mm, specific surface is 360m
2/ g, average pore size 30nm, pore volume is 0.55cm
3/ g.
Catalyst preparing: 30 (wt) % accounting for final catalyst by cupric oxide takes Cu (NO
3)
23H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, dip time is 10h, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 400 DEG C, and roasting time is 4h, finally obtained egg-shell catalyst.The active component of catalyst is positioned on the oxide of magnesium metal aluminium alloy ectosphere, and inside is uncorroded metal material.Catalyst weight percent is cupric oxide 30%, and all the other are magnesium metal aluminium alloy ball carrier.The catalyst specific surface obtained is 290m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, and the lower 220 DEG C of reduction 6h synthesis gas of hydrogen atmosphere prepare methyl alcohol reaction.Reaction raw materials is synthesis gas, and reaction condition is: H
2the mol ratio of/CO is 2, and reaction temperature is 180 DEG C, and reaction pressure is 5Mpa, and volume space velocity is 10000h
-1.Reaction result shows: CO conversion ratio 75%, and methyl alcohol is selective is 82%.
Embodiment 6:
Catalyst support preparation: magnesium ball (particle diameter 2mm) is put into distilled water and boils 8h, filters, by filter cake dry 10h at 80 DEG C.By in 5L0.1mol/L acid of hydrochloric acid and nitric acid mixed solution instillation gained material, instillation speed is 1ml/min, and electromagnetic agitation process 6h, filter, washing is to neutral, by filter cake dry 9h at 80 DEG C, after drying at 600 DEG C roasting 10h, obtaining outer is the magnesia inside magnesium metal ball carrier that is uncorroded metal material.The magnesium metal ball carrier average grain scope 2mm of gained, corrosion layer thickness is 0.25mm, and specific surface is 580m
2/ g, average pore size 23nm, pore volume is 0.62cm
3/ g.
Catalyst preparing: 10 (wt) % accounting for final catalyst by nickel oxide takes Ni (NO
3)
26H
2o, measures deionized water according to equi-volume impregnating, and configuration salting liquid also impregnated in above-mentioned carrier, dip time is 10h, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 600 DEG C, and roasting time is 4h, finally obtained egg-shell catalyst.The active component of catalyst is positioned on the magnesia of magnesium metal ectosphere, and inside is uncorroded magnesium metal.Catalyst weight percent is nickel oxide 10%, and all the other are magnesium metal ball carrier, and the catalyst specific surface obtained is 370m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, and the lower 700 DEG C of reduction 6h of hydrogen atmosphere are used for methane carbon dioxide reformation.Reaction raw materials is CH
4and CO
2, reaction condition is: CH
4/ CO
2mol ratio be 1, reaction temperature is 700 DEG C, and reaction pressure is normal pressure, and volume space velocity is 2000h
-1.Reaction result shows: CH
4conversion ratio 94%, CO
2conversion ratio be 92%, CO selective be 89%.Embodiment 7:
Catalyst support preparation: magnesium ball (particle diameter 3mm) is put into distilled water and boils 8h, filters, by filter cake dry 10h at 80 DEG C.By 5L1.0 × 10
-2in mol/L salpeter solution instillation gained material, instillation speed is 5ml/min, and electromagnetic agitation process 8h, filter, washing is extremely neutral, by filter cake dry 9h at 80 DEG C, after drying at 600 DEG C roasting 10h, obtaining outer is the magnesia inside magnesium metal ball carrier that is uncorroded magnesium metal.The magnesium metal ball diameter of carrier of gained is 3mm, and corrosion layer thickness is 0.08mm, and specific surface is 360m
2/ g, average pore size 17nm, pore volume is 0.55cm
3/ g.
Catalyst preparing: 0.3 (wt) % accounting for final catalyst by Au takes Au (OAC)
2, measure deionized water according to equi-volume impregnating, configuration salting liquid also impregnated in above-mentioned carrier, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 400 DEG C, and roasting time is 2h, final obtained egg-shell catalyst copper.The active component of catalyst is positioned on the magnesia of magnesium metal ectosphere, and inside is uncorroded magnesium metal.Percentage by weight is Au0.3%, and all the other are magnesium metal ball carrier.The catalyst specific surface obtained is 340m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, prepares benzaldehyde under oxygen atmosphere for benzyl alcohol oxidation.Reaction raw materials is phenmethylol and oxygen, and reaction condition is: the mol ratio of oxygen hydroxyl is 0.6, and reaction temperature is 350 DEG C, and volume space velocity is 200h
-1.Reaction result shows: phenmethylol conversion ratio 95%, and the selective of benzaldehyde is 94%.
Embodiment 8:
Catalyst support preparation: albronze ball (mass percent Cu5%Al95%, particle diameter 2mm) is put into distilled water and boils 8h, filters, by filter cake dry 10h at 80 DEG C.By in 8L4.0mol/L potassium hydroxide solution instillation gained material, instillation speed is 2ml/min, and electromagnetic agitation process 6h, filter, washing is to neutral, by filter cake dry 9h at 80 DEG C, after drying at 600 DEG C roasting 10h, obtain outer for aluminium oxide internal layer be the metallic copper aluminium alloy ball carrier of uncorroded metal material.Metallic copper aluminium alloy ball diameter of carrier is 3mm, and corrosion layer thickness is 0.21mm, and specific surface is 580m
2/ g, average pore size 11nm, pore volume is 0.82cm
3/ g.
Catalyst preparing: 0.2 (wt) % accounting for final catalyst by platinum takes Pt (NO
3)
2, measure deionized water according to equi-volume impregnating, configuration salting liquid also impregnated in above-mentioned carrier, dip time is 10h, after dipping at 60 DEG C dry 10h, carry out roasting in a nitrogen atmosphere after drying, sintering temperature is 400 DEG C, and roasting time is 1h, finally obtained egg-shell catalyst.The active component of catalyst is positioned on the aluminium oxide of metallic copper aluminium alloy ectosphere, and inside is uncorroded metal material.Catalyst weight percent is Pt2%, and all the other are metallic copper aluminium alloy ball carrier.The catalyst specific surface obtained is 550m
2/ g.
In fixed bed reactors, (Ф 15 × 1000mm) does not dilute the above-mentioned catalyst of filling 100ml, for similar diesel engine exhaust purification.Reaction condition is: reaction temperature is 180 DEG C, reaction pressure 0.1Mpa, and volume space velocity is 10000h
-1.Reaction result shows: the clean conversion ratio 99%, NO of CO
xconversion ratio 98%.
Claims (7)
1. a high-termal conductivity egg-shell catalyst carrier, it is characterized in that high-termal conductivity egg-shell catalyst carrier is metal ball, metal ball average grain scope 1-5mm, specific surface is 70-600m
2/ g, average pore size 4-60nm, pore volume is 0.25-2.00cm
3/ g, metal ball corrosion layer thickness 0.05-0.25mm, corrosion layer is metal oxide;
And prepared by following steps:
(1) be that the metal ball of 1-5mm is put into distilled water and boiled 6 ~ 10h by particle diameter, filter, by filter cake dry 10-20h at 60-100 DEG C;
(2) 1.0 × 10 are configured
-2-5.0mol/L acid or aqueous slkali 1-10L;
(3) when metal ball is aluminium ball, magnadure ball, albronze ball, by metal ball: acid or aqueous slkali=100g:1-10L, the solution of step (2) gained is added by l-10mL/min speed in the metal ball of step (1) gained, and electromagnetic agitation process 10-30h, filter, washing is extremely neutral, by filter cake dry 10-30h at 60-100 DEG C;
When metal ball is magnesium ball, by metal ball: acid solution=100g:1-10L, the solution of step (2) gained is added by l-10mL/min speed in the metal ball of step (1) gained, and electromagnetic agitation process 10-30h, filter, washing is extremely neutral, by filter cake dry 10-30h at 60-100 DEG C;
(4) by the material of step (3) gained roasting 6-10h under 300-600 DEG C of nitrogen atmosphere, obtaining outer is metal oxide, and internal layer is the catalyst carrier of uncorroded metal material;
Described metal ball is aluminium ball, magnesium ball, magnadure ball or albronze ball.
2. a kind of high-termal conductivity egg-shell catalyst carrier as claimed in claim 1, is characterized in that described acid is the mixture of one or more in acetic acid, nitric acid, hydrochloric acid, oxalic acid.
3. a kind of high-termal conductivity egg-shell catalyst carrier as claimed in claim 1, is characterized in that alkali is the mixture of one or more in NaOH, potassium hydroxide, ammoniacal liquor.
4. the application of a kind of high-termal conductivity egg-shell catalyst carrier as described in any one of claim 1-3, it is characterized in that reactive metal oxides and catalyst carrier composition catalyst, catalyst weight percent consists of: reactive metal oxides: 0.1%-40%, all the other are outer is metal oxide, internal layer is the catalyst carrier of uncorroded metal material, and the specific surface of catalyst is 50-500m
2/ g.
5. the application of a kind of high-termal conductivity egg-shell catalyst carrier as claimed in claim 4, is characterized in that described reactive metal oxides is one or more mixtures in Co, Fe, Ni, Mn, Ru, Rh, Pt, Au, Pd, Cu oxide.
6. the application of a kind of high-termal conductivity egg-shell catalyst carrier as described in claim 4 or 5, is characterized in that the preparation method of described reactive metal oxides and catalyst carrier composition catalyst comprises the steps:
Equi-volume impregnating is adopted to be dissolved in deionized water by reactive metal oxides soluble-salt, flood with catalyst carrier at ambient temperature, dip time is 6-10h, after dipping at 60-100 DEG C dry 10-20h, roasting is carried out in a nitrogen atmosphere after drying, sintering temperature is 200-600 DEG C, and roasting time is 3-10h, obtains egg-shell catalyst.
7. the application of a kind of high-termal conductivity egg-shell catalyst carrier as claimed in claim 6, is characterized in that described reactive metal oxides soluble-salt is acetate, nitrate or oxalates.
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| CN108187691B (en) * | 2017-12-26 | 2019-08-30 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of preparation method and applications of the filled composite structure catalyst for CO gas phase coupling synthesis of oxalate |
| CN109205681B (en) * | 2018-09-12 | 2021-04-09 | 嘉兴学院 | Three-dimensional hierarchical structure metal oxide and preparation method thereof |
| CN114308061B (en) * | 2020-09-29 | 2023-08-22 | 中国科学院大连化学物理研究所 | NiAu bimetallic alloy nano-catalyst and synthesis and application thereof |
| CN115845854A (en) * | 2022-11-28 | 2023-03-28 | 高潞空气化工产品(上海)能源科技有限公司 | High-thermal-conductivity high-temperature-resistant catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1542265A (en) * | 2003-04-30 | 2004-11-03 | 比亚迪股份有限公司 | Vehicle tail-gas catalytic converter |
| CN101062484A (en) * | 2006-04-27 | 2007-10-31 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN101298049A (en) * | 2008-05-29 | 2008-11-05 | 清华大学 | Method for preparing Pd/foamed metal catalyst for hydrogenolysis dechlorination |
| CN101648137A (en) * | 2009-09-18 | 2010-02-17 | 华东师范大学 | Metal carrier load gold catalyst and application thereof in preparing aldehyde or ketone by selectively oxidizing catalytic alcohol |
-
2014
- 2014-06-10 CN CN201410255022.2A patent/CN104001556B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1542265A (en) * | 2003-04-30 | 2004-11-03 | 比亚迪股份有限公司 | Vehicle tail-gas catalytic converter |
| CN101062484A (en) * | 2006-04-27 | 2007-10-31 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN101298049A (en) * | 2008-05-29 | 2008-11-05 | 清华大学 | Method for preparing Pd/foamed metal catalyst for hydrogenolysis dechlorination |
| CN101648137A (en) * | 2009-09-18 | 2010-02-17 | 华东师范大学 | Metal carrier load gold catalyst and application thereof in preparing aldehyde or ketone by selectively oxidizing catalytic alcohol |
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