CN103127959A - Carbon monoxide transformation catalyst carrier, preparation method of the carbon monoxide transformation catalyst carrier, and catalyst based on the carbon monoxide transformation catalyst carrier - Google Patents
Carbon monoxide transformation catalyst carrier, preparation method of the carbon monoxide transformation catalyst carrier, and catalyst based on the carbon monoxide transformation catalyst carrier Download PDFInfo
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- CN103127959A CN103127959A CN2011103782435A CN201110378243A CN103127959A CN 103127959 A CN103127959 A CN 103127959A CN 2011103782435 A CN2011103782435 A CN 2011103782435A CN 201110378243 A CN201110378243 A CN 201110378243A CN 103127959 A CN103127959 A CN 103127959A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a carbon monoxide transformation catalyst carrier for a high pressure technology. The carbon monoxide transformation catalyst carrier is prepared from 5 to 30 parts by weight of kaolin powder, 30 to 60 parts by weight of alumina powder and 10 to 40 parts by weight of magnesium oxide or magnesium hydroxide. Through utilization of kaolin powder, alumina powder and magnesium oxide or magnesium hydroxide having a certain ratio as raw materials, magnesium aluminate spinel structure compactness is effectively improved without increasing of a calcination temperature so that catalyst hydration resistance is improved; hydration under working conditions is avoided; high catalyst strength is kept in use; and crushing and wearing phenomenon is avoided.
Description
Technical field
The present invention relates to a kind of co surfer-resistant shift catalyst that is applicable to high-pressure process, be specifically related to a kind of carrier and use the Catalysts and its preparation method of this carrier, belong to the coal gasification field.
Background technology
Carbon monodixe conversion refers under the condition that catalyst exists, CO and steam reaction generation CO
2And H
2Process.In the technique of utilizing coal or residual oil for raw material synthetic ammonia, hydrogen manufacturing and oxo-synthesis gas processed, carbon monodixe conversion is an important operation, can improve H in unstripped gas by this operation
2Content, reduce simultaneously the concentration of CO, avoid causing because CO concentration is higher occuring the phenomenon of catalyst poisoning in post-order process.The carbon monoxide transformation catalyst that uses in early stage technology is Fe-Cr HTS catalyst (Fe
3O
4/ therefore Cr), because the Fe-Cr HTS catalyst has advantages of with low costly, obtained using comparatively widely.But the Fe in the Fe-Cr HTS catalyst
3O
4At H
2Following reaction: Fe easily occurs under the condition that S exists
3O
4+ H
2S+H
2=3FeS+4H
2O, thus cause the Fe-Cr HTS catalyst because of the sulfur poisoning inactivation.
In order to solve the problem of the sulfur poisoning that above-mentioned Fe-Cr HTS carbon monoxide transformation catalyst exists, those skilled in the art have developed some sulfur-resistant transformation catalysts, disclose a kind of sulfur-resistant CO conversion catalyst as Chinese patent literature CN101214442A, the active component of this catalyst is by with MoO
3The compound of the compound of the Mo of expression, the Co that represents with CoO and with K
2The compound of the K that O represents forms, and carrier is aluminum-spinel MgAl
2O
4, take the catalyst gross mass as benchmark, the consisting of of described catalyst: MoO
3, 2-10%; CoO, 0.2-5%; K
2O, 2-10%, surplus is carrier aluminum magnesia spinel MgAl
2O
4Wherein, the preparation method of described aluminum-spinel carrier is: be placed in kneading machine after light MgO and the moisture amorphous alumina of porous are taken according to the mol ratio of 1:1, add aqueous solution of nitric acid to mix and pinch pressure, form plastic, dry after extruded moulding, with strip roasting under 500-650 ℃ of condition of oven dry, namely obtain described aluminum-spinel carrier at last, this carrier has advantages of activity, good stability.
In above-mentioned technology, why select aluminum-spinel as carrier to be because, when carrying out the carbon monodixe conversion reaction, one of reactant is water, institute is so that in whole reaction system, water content is larger, when selecting carbon monoxide transformation catalyst, fully take into account the environment of such high water content to the hydration osmosis of catalyst like this, only have and select the carrier of crystal structure densification as aluminum-spinel so just can solve above-mentioned hydration infiltration problem.But, the compact texture of aluminum-spinel depends on the purity of itself, and the acquisition of highly purified aluminum-spinel, need to guarantee that its sintering temperature is more than 1100 ℃, although very fine and close by the magnesia-alumina spinel structure that obtains after calcination process more than 1100 ℃, but this specific area that also just means this structure is very little, can't use as the carrier of catalyst at all, if select the high temperature more than 1100 ℃ to carry out roasting in order to obtain highly purified magnesium aluminate spinel simply, energy consumption is large, and cost is high.Think the actual MgO of being of the catalyst carrier with magnesia-alumina spinel structure, aluminium oxide and MgAl if select such as what the sintering temperature of disclosed 500-650 in above-mentioned technology ℃ and preparation method obtained
2O
4Mixed oxide, just be easy to occur like this hydration phenomena in the environment of above-mentioned high water content, the alumina component that hydrone enters in carrier through carrier hole or duct and carrier does not form magnesium aluminate spinel is carried out combination, causes catalyst activity and strength decreased, easily the catalyst fracture phenomena occurs.
So, can't solve all the time the coordination problem between aluminum-spinel high-specific surface area, hydration stability and compact structure in prior art.
Summary of the invention
technical problem to be solved by this invention is that co surfer-resistant shift catalyst of the prior art selects aluminum-spinel as carrier, this carrier is owing to will guaranteeing that it has high-specific surface area and can only carry out roasting at 500-650 ℃ with stability, but the aluminum-spinel after this temperature roasting can't obtain high stability, make its hydration-resisting performance relatively poor, it is easy to occur hydration phenomena in catalytic process, thereby the strength decreased that further causes described catalyst, produce problems broken and wearing and tearing, and then provide a kind of and need not to carry out roasting at high temperature and can obtain to have high-specific surface area, the carbon monoxide transformation catalyst of the magnesium aluminate spinel carrier that can be used for co surfer-resistant shift catalyst of high stability and this carrier of use.
The carrier of carbon monoxide transformation catalyst described in the present invention and be based on the catalyst of carrier and preparation method's technical scheme:
A kind of carbon monoxide transformation catalyst carrier is prepared by following raw material at least:
Kaolin powder, the 5-30 weight portion;
Alumina powder, the 30-60 weight portion;
Magnesia or magnesium hydroxide, the 10-40 weight portion.
The particle diameter of described kaolin powder is the 40-80 order.
The particle diameter of described kaolin powder is the 50-60 order.
The specific surface area of described kaolin powder is 120-160m
2/ g.
The particle size range of described alumina powder is 40-200 orders.
Described raw material also comprises one or more in following component:
Peptizing agent, the 3-20 weight portion;
Pore creating material, the 1-6 weight portion;
Extrusion aid, the 2-5 weight portion;
Binding agent, the 1-6 weight portion.
Described peptizing agent is one or both in nitric acid and malonic acid; Described pore creating material is the mixture of a kind of in oxalic acid, citric acid or two kinds; Described extrusion aid is the mixture of a kind of in sesbania powder, stearic acid or two kinds; Described binding agent is the mixture of a kind of in cement, metatitanic acid fat or two kinds.
The preparation method of described carbon monoxide transformation catalyst carrier comprises:
(1) with kaolin powder, alumina powder and magnesia or the abundant kneading of magnesium hydroxide of specified weight part;
(2) mixture that obtains after abundant kneading is carried out extrusion;
(3) the extrusion product that obtains in step (2) is carried out drying, described baking temperature is 110-150 ℃, and be 120-240min drying time;
(4) product that obtains in step (3) is carried out roasting, described sintering temperature is 550-700 ℃, and roasting time is 2-6 hour.
Front in described step (2), one or more in peptizing agent, pore creating material, extrusion aid and the binding agent of specified weight part are joined in the mixture that step (1) kneading obtains, again abundant kneading.
Load has active component on described carrier.
Described active component is CoO and MoO
3, described CoO accounts for the 1-4wt% of described carrier quality, described MoO
3Account for the 3-15wt% of described carrier quality.
Carbon monoxide transformation catalyst carrier described in the present invention and being based on the advantage of the catalyst of this carrier:
(1) carbon monoxide transformation catalyst carrier of the present invention, the raw material of the described carrier of preparation comprises: kaolin powder, 5-30 weight portion; Alumina powder, the 30-60 weight portion; Magnesia or magnesium hydroxide, the 10-40 weight portion.The present inventor finds to prepare carrier by kaolin powder, alumina powder and the magnesia or the magnesium hydroxide that adopt special ratios as raw material, can effectively improve the compact structure of carrier, thereby improve the hydration-resisting performance of described catalyst, avoided the hydration phenomena under the working condition, make described catalyst in use can keep higher intensity, avoided the generation of broken and wear phenomenon.Simultaneously, also avoided utilizing the high temperature nuclear reactor carrier to carry out roasting in order to improve carrier structure compactness in prior art, make the little problem of carrier specific area for preparing, thereby provide better specific area loading condition and catalytic reaction condition for the load of active component.In addition, the present inventor finds, can also promote the activity of catalyst by adding kaolin, improves the conversion ratio of carbon monoxide.
(2) carbon monoxide transformation catalyst carrier of the present invention, the particle diameter that selection arranges the kaolin powder in raw material is the 40-80 order, reason is, if the particle diameter of described kaolin powder is excessive, easily cause the skewness of kaolin powder in raw mix, if and the particle diameter of described kaolin powder is too small, the phenomenon of reunion easily occurs, be unfavorable for that equally described kaolin powder evenly distributes in raw mix, the present invention is the 40-80 order by the particle diameter that limits described kaolin powder, effectively avoided above-mentioned two situations, in order to obtain better evenly distribution effect, the particle diameter that the present invention also preferably arranges described kaolin powder is the 50-60 order.
In addition, be similarly and obtained evenly distributing preferably effect, the particle size range that the present invention also arranges described alumina powder is the 40-200 order.
(3) carbon monoxide transformation catalyst carrier of the present invention, the specific surface area that described kaolin powder is set is 120-160m
2/ g.Why arrange like this, because if the specific surface area of described kaolin powder is too small, can have influence on the catalytic effect based on the catalyst of carrier, and the excessive kaolin powder of selection specific surface area, not only can increase the preparation cost of kaolin powder, also can cause the strength decreased of described carrier, broken phenomenon in use easily occurs.The present invention is 120-160m by the specific surface area that described kaolin powder is set
2/ g has effectively avoided above-mentioned two situations.
In order to make content of the present invention more be convenient to understand, below in conjunction with the specific embodiment, technical solutions according to the invention are described further.
The specific embodiment
Embodiment 1
Carbon monoxide transformation catalyst carrier in the present embodiment is prepared by following raw material:
Kaolin powder, 5 weight portions;
Alumina powder, 30 weight portions;
Magnesia, 10 weight portions;
The particle diameter of wherein said kaolin powder is 40 orders, and specific surface area is 100m
2/ g; The particle diameter of described alumina powder is 30 orders.
The preparation method of above-mentioned carbon monoxide transformation catalyst carrier in the present embodiment comprises:
(1) with the abundant kneading of kaolin powder, alumina powder and magnesia of above-mentioned weight portion;
(2) mixture that obtains after abundant kneading is carried out extrusion;
(3) the extrusion product that obtains in step (2) is carried out drying, described baking temperature is 110 ℃, and be 120min drying time;
(4) product that obtains in step (3) is carried out roasting, described sintering temperature is 550 ℃, and roasting time is 2 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on described carrier, the described active component in the present embodiment is CoO and MoO
3, the content of described CoO accounts for the 1wt% of described carrier, described MoO
3Content account for the 3wt% of described carrier.
Embodiment 2
Carbon monoxide transformation catalyst carrier in the present embodiment is prepared by following raw material:
Kaolin powder, 30 weight portions;
Alumina powder, 60 weight portions;
Magnesium hydroxide, 40 weight portions;
The particle diameter of wherein said kaolin powder is 80 orders, and specific surface area is 140m
2/ g; The particle diameter of described alumina powder is 40 orders.
The preparation method of above-mentioned carbon monoxide transformation catalyst carrier in the present embodiment comprises:
(1) with the abundant kneading of kaolin powder, alumina powder and magnesium hydroxide of above-mentioned weight portion;
(2) mixture that obtains after abundant kneading is carried out extrusion;
(3) the extrusion product that obtains in step (2) is carried out drying, described baking temperature is 150 ℃, and be 240min drying time;
(4) product that obtains in step (3) is carried out roasting, described sintering temperature is 700 ℃, and roasting time is 6 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on described carrier, the described active component in the present embodiment is CoO and MoO
3, the content of described CoO accounts for the 4wt% of described carrier, described MoO
3Content account for the 15wt% of described carrier.
Embodiment 3
Carbon monoxide transformation catalyst carrier in the present embodiment is prepared by following raw material:
Kaolin powder, 5 weight portions;
Alumina powder, 30 weight portions;
Magnesia, 10 weight portions.
Peptizing agent, 3 weight portions;
Pore creating material, 1 weight portion;
Extrusion aid, 2 weight portions;
Binding agent, 1 weight portion.
The particle diameter of wherein said kaolin powder is 50 orders, and specific surface area is 120m
2/ g; The particle diameter of described alumina powder is 120 orders.Described peptizing agent is nitric acid; Described pore creating material is oxalic acid; Described extrusion aid is the sesbania powder; Described binding agent is cement.
The preparation method of above-mentioned carbon monoxide transformation catalyst carrier in the present embodiment comprises:
(1) with the abundant kneading of kaolin powder, alumina powder and magnesia of above-mentioned weight portion;
Then peptizing agent, pore creating material, extrusion aid and the binding agent of above-mentioned weight portion joined in the mixture that step (1) kneading obtains, again abundant kneading;
(2) mixture that obtains after abundant kneading is carried out extrusion;
(3) the extrusion product that obtains in step (2) is carried out drying, described baking temperature is 120 ℃, and be 200min drying time;
(4) product that obtains in step (3) is carried out roasting, described sintering temperature is 600 ℃, and roasting time is 3 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on described carrier, the described active component in the present embodiment is CoO and MoO
3, the content of described CoO accounts for the 3wt% of described carrier, described MoO
3Content account for described carrier for the 10wt% weight portion.
Embodiment 4
Carbon monoxide transformation catalyst carrier in the present embodiment is prepared by following raw material:
Kaolin powder, 10 weight portions;
Alumina powder, 50 weight portions;
Magnesium hydroxide, 30 weight portions;
Peptizing agent, 20 weight portions;
Pore creating material, 6 weight portions;
Extrusion aid, 5 weight portions;
Binding agent, 6 weight portions.
The particle diameter of wherein said kaolin powder is 60 orders, and the specific surface area of described kaolin powder is 160m
2/ g; The particle diameter of described alumina powder is 200 orders.Described peptizing agent is malonic acid; Described pore creating material is citric acid; Described extrusion aid is stearic acid; Described binding agent is metatitanic acid fat.
The preparation method of the described carbon monoxide transformation catalyst carrier of the present embodiment comprises:
(1) with the abundant kneading of kaolin powder, alumina powder and magnesium hydroxide of above-mentioned weight portion;
Then peptizing agent, pore creating material, extrusion aid and the binding agent of above-mentioned weight portion joined in the mixture that step (1) kneading obtains, again abundant kneading;
(2) mixture that obtains after abundant kneading is carried out extrusion;
(3) the extrusion product that obtains in step (2) is carried out drying, described baking temperature is 140 ℃, and be 180min drying time;
(4) product that obtains in step (3) is carried out roasting, described sintering temperature is 600 ℃, and roasting time is 5 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on described carrier, the described active component in the present embodiment is CoO and MoO
3, the content of described CoO accounts for the 4wt% of described carrier, described MoO
3Content account for described carrier for the 15wt% weight portion.
Experimental example
In order to prove catalyst carrier described in the present invention and based on the technique effect of the catalyst of this carrier, the present invention has designed following experimental example and has measured to the catalyst carrier described in above-described embodiment 1-4 and based on the performance of the catalyst of this carrier:
1. catalyst carrier strength detection:
Extract 40 catalyst samples according to quartering, in the radially crushing strength of the upper detecting catalyst of ZQJ-II Intelligent testing machine for particle (national chemical catalyst inspection center supervise), represent the height of catalyst strength with the size of mean value.20.0 g catalyst granules sample and 80mL water are placed in 150mL teflon-lined hydrothermal reaction kettle, 200 ℃ of constant temperature 4 h.Then cool to room temperature filters, and 120 ℃ of drying 4 h namely get the catalyst sample after hydrothermal treatment consists.Sample after hydro-thermal reaction is carried out radially crushing strength test.The height that represents catalyst strength with the size of mean value.
2. catalyst carrier hydration-resisting performance is measured:
20.0 g catalyst granules samples and 80mL water are placed in 150 mL teflon-lined hydrothermal reaction kettles, 200 ℃ of constant temperature 4 h.Then cool to room temperature filters, and 120 ℃ of drying 4 h namely get the catalyst sample after hydrothermal treatment consists.Again the intensity of the catalyst sample after processing is measured, and compared with processing front intensity, calculate strength retention ratio.
3. carbon monoxide transformation catalyst activity rating:
H
2S concentration: 0.2-0.6(v/v%);
Curing temperature: 250-300 ℃, cure time 10-20 h;
Sulfide stress 1.0-2.0MPa, sulfuration air speed: 500-2000h
-1
Analog raw material gas consists of: CO:40-45 %, CO
2: 5-8 %, H
2: 45-50 %;
Catalyst in device after the extrusion of filling 30ml, the diameter range of described catalyst is 3.1-3.5mm, length range is 5-20mm.
Catalytic reaction condition is:
Air speed: 3000h
-1, pressure is 3.0-8.0MPa, temperature is: and 300 ℃, vapour/gas=0.4.
Adopt gas chromatography (GC-2014A type form and aspect chromatogram) to measure the content of CO, (V/V%) characterizes the CO shift activity with the CO conversion ratio:
In formula: carbon monoxide percentage by volume in-unstripped gas; Carbon monoxide percentage by volume in-conversion gas.
Comparative Examples
In order to prove that the catalyst that the catalyst carrier described in the present invention reaches based on this carrier compared with prior art has significant substantive technique effect, the present invention is provided with Comparative Examples:
Consisting of of the catalyst that this Comparative Examples adopts: MoO
3, 10wt%; CoO, 3%; K
2O, 3%, surplus is carrier aluminum magnesia spinel MgAl
2O
4The preparation method of wherein said aluminum-spinel carrier is: be placed in kneading machine after magnesia and the moisture amorphous alumina of porous are taken according to the mol ratio of 1:1, add aqueous solution of nitric acid to mix and pinch pressure, form plastic, dry after extruded moulding, with strip roasting under 600 ℃ of conditions of oven dry, namely obtain described aluminum-spinel carrier at last.
With reference to the step in experimental example, intensity, hydration-resisting performance and the carbon monodixe conversion activity of above-mentioned catalyst are measured and with embodiment 1-4 in the measurement result of catalyst and carrier thereof compare.
The result that experimental example and Comparative Examples obtain is as follows:
Above-mentioned experimental result shows, the footpath Compressive Strength of the catalyst carrier in Comparative Examples before hydrothermal treatment consists is 108N/cm, and the footpath Compressive Strength after hydrothermal treatment consists is 76N/cm, and strength retention ratio is 70.3%, all lower than catalyst carrier of the present invention;
When using the catalyst in Comparative Examples, its CO conversion ratio 4.0,6.0 and the 8.0MPa condition under be respectively 79.8,79.1 and 78.3, also all lower than the CO conversion ratio that uses catalyst described in the present invention to obtain under equal pressure condition.Therefore, compare in the present invention and prior art, have better hydration-resisting performance, can increase substantially intensity and the activity of catalyst.
Although the present invention elaborates it by the specific embodiment; but; those skilled in the art should be understood that any form that does not exceed the claim protection domain made on this basis and the variation of details, all belong to invention which is intended to be protected.
Claims (11)
1. a carbon monoxide transformation catalyst carrier, is characterized in that, prepared by following raw material at least:
Kaolin powder, the 5-30 weight portion;
Alumina powder, the 30-60 weight portion;
Magnesia or magnesium hydroxide, the 10-40 weight portion.
2. carbon monoxide transformation catalyst carrier according to claim 1, is characterized in that, the particle diameter of described kaolin powder is the 40-80 order.
3. carbon monoxide transformation catalyst carrier according to claim 2, is characterized in that, the particle diameter of described kaolin powder is the 50-60 order.
4. according to claim 1 and 2 or 3 described carbon monoxide transformation catalyst carriers, is characterized in that, the specific surface area of described kaolin powder is 120-160m
2/ g.
5. according to claim 1 and 2 or 3 described carbon monoxide transformation catalyst carriers, is characterized in that, the particle size range of described alumina powder is 40-200 orders.
6. according to claim 1-5 arbitrary described carbon monoxide transformation catalyst carriers, is characterized in that, described raw material also comprises one or more in following component:
Peptizing agent, the 3-20 weight portion;
Pore creating material, the 1-6 weight portion;
Extrusion aid, the 2-5 weight portion;
Binding agent, the 1-6 weight portion.
7. carbon monoxide transformation catalyst carrier according to claim 6, is characterized in that, described peptizing agent is one or both in nitric acid and malonic acid; Described pore creating material is the mixture of a kind of in oxalic acid, citric acid or two kinds; Described extrusion aid is the mixture of a kind of in sesbania powder, stearic acid or two kinds; Described binding agent is the mixture of a kind of in cement, metatitanic acid fat or two kinds.
8. the preparation method of the arbitrary described carbon monoxide transformation catalyst carrier of claim 1-7 comprises:
(1) with kaolin powder, alumina powder and magnesia or the abundant kneading of magnesium hydroxide of specified weight part;
(2) mixture that obtains after abundant kneading is carried out extrusion;
(3) the extrusion product that obtains in step (2) is carried out drying, described baking temperature is 110-150 ℃, and be 120-240min drying time;
(4) product that obtains in step (3) is carried out roasting, described sintering temperature is 550-700 ℃, and roasting time is 2-6 hour.
9. the preparation method of carbon monoxide transformation catalyst carrier according to claim 8, it is characterized in that, front in described step (2), one or more in peptizing agent, pore creating material, extrusion aid and the binding agent of specified weight part are joined in the mixture that step (1) kneading obtains, again abundant kneading.
10. based on the carbon monoxide transformation catalyst of the described carrier of claim 1-9, it is characterized in that, load has active component on described carrier.
11. carbon monoxide transformation catalyst according to claim 10 is characterized in that, described active component is CoO and MoO
3, described CoO accounts for the 1-4wt% of described carrier quality, described MoO
3Account for the 3-15wt% of described carrier quality.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435859A (en) * | 2016-01-14 | 2016-03-30 | 洛阳三睿宝纳米科技有限公司 | Modification method of nanocrystalline for surface of ceramic carrier of vehicle exhaust processor |
| CN112844388A (en) * | 2021-02-02 | 2021-05-28 | 新地能源工程技术有限公司 | Magnesium aluminate spinel type composite oxide carrier, preparation method thereof and steam reforming catalyst |
| CN114100624A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Kaolin modified sulfur-resistant transformation catalyst and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435859A (en) * | 2016-01-14 | 2016-03-30 | 洛阳三睿宝纳米科技有限公司 | Modification method of nanocrystalline for surface of ceramic carrier of vehicle exhaust processor |
| CN105435859B (en) * | 2016-01-14 | 2017-10-17 | 洛阳三睿宝纳米科技有限公司 | Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying |
| CN114100624A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Kaolin modified sulfur-resistant transformation catalyst and preparation method thereof |
| CN114100624B (en) * | 2020-08-31 | 2023-08-11 | 中国石油化工股份有限公司 | Kaolin modified sulfur-tolerant shift catalyst and preparation method thereof |
| CN112844388A (en) * | 2021-02-02 | 2021-05-28 | 新地能源工程技术有限公司 | Magnesium aluminate spinel type composite oxide carrier, preparation method thereof and steam reforming catalyst |
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| Publication number | Publication date |
|---|---|
| CN103127959B (en) | 2016-03-30 |
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