CN103127959B - Carbon monoxide transformation catalyst carrier and preparation method and the catalyst based on carrier - Google Patents

Carbon monoxide transformation catalyst carrier and preparation method and the catalyst based on carrier Download PDF

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CN103127959B
CN103127959B CN201110378243.5A CN201110378243A CN103127959B CN 103127959 B CN103127959 B CN 103127959B CN 201110378243 A CN201110378243 A CN 201110378243A CN 103127959 B CN103127959 B CN 103127959B
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carbon monoxide
carrier
catalyst
weight portion
monoxide transformation
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CN103127959A (en
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江莉龙
魏可镁
曹彦宁
赵文涛
刘彦芳
谢红
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Beijing Haixin Energy Technology Co ltd
Fuzhou University
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Fuzhou University
Beijing SJ Environmental Protection and New Material Co Ltd
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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

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Abstract

The invention provides a kind of carbon monoxide transformation catalyst carrier being applicable to high-pressure process, it is characterized in that, at least prepared by following raw material: kaolin powder, 5-30 weight portion; Alumina powder, 30-60 weight portion; Magnesia or magnesium hydroxide, 10-40 weight portion.Present inventor finds by adopting the kaolin powder of special ratios, alumina powder and magnesia or magnesium hydroxide to prepare carrier as raw material, the compact structure of described magnesium aluminate spinel effectively can be improved under the prerequisite not improving sintering temperature, thus improve the hydration-resisting performance of described catalyst, avoid the hydration phenomena under working condition, make described catalyst in use can keep higher intensity, avoid generation that is broken and wear phenomenon.

Description

Carbon monoxide transformation catalyst carrier and preparation method and the catalyst based on carrier
Technical field
The present invention relates to a kind of co surfer-resistant shift catalyst being applicable to high-pressure process, be specifically related to the Catalysts and its preparation method of a kind of carrier and this carrier of use, belong to coal gasification field.
Background technology
Carbon monodixe conversion refers under catalyst existent condition, and CO and steam react and generates CO 2and H 2process.Utilizing that coal or residual oil are Material synthesis ammonia, in the technique of 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 the concentration of CO simultaneously, avoid the phenomenon causing occurring in post-order process catalyst poisoning because CO concentration is higher.The carbon monoxide transformation catalyst used in earlier technique is Fe-Cr-Al electrical heating alloy (Fe 3o 4/ Cr), because Fe-Cr-Al electrical heating alloy has advantage with low cost, therefore obtain and apply comparatively widely.But the Fe in Fe-Cr-Al electrical heating alloy 3o 4at H 2following reaction is easily there is: Fe under S existent condition 3o 4+ H 2s+H 2=3FeS+4H 2o, thus cause Fe-Cr-Al electrical heating alloy because of 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, as Chinese patent literature CN101214442A discloses a kind of sulfur-resistant CO conversion catalyst, the active component of this catalyst is by with MoO 3the compound of the Mo represented, the compound of Co represented with CoO and with K 2the compound composition of the K that O represents, carrier is aluminum-spinel MgAl 2o 4, with catalyst gross mass for benchmark, 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 4.Wherein, the preparation method of described aluminum-spinel carrier is: be placed in kneading machine after light MgO and the moisture amorphous alumina of porous being taken according to the mol ratio of 1:1, add aqueous solution of nitric acid to carry out mixing and pinching pressure, form plastic, dry after extruded moulding, strip roasting under 500-650 DEG C of condition of finally will dry, namely obtain described aluminum-spinel carrier, this carrier has the advantage of activity, good stability.
In above-mentioned technology, why select aluminum-spinel as carrier be because, when carrying out CO shift reaction, one of reactant is water, so make water content in whole reaction system larger, like this when selecting carbon monoxide transformation catalyst, the hydration osmosis of environment to catalyst of such high water content be fully taken into account, only having and selecting 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 ensure that its sintering temperature is more than 1100 DEG C, although very fine and close by the magnesia-alumina spinel structure obtained after more than 1100 DEG C calcination process, but this also just means that the specific area of this structure is very little, cannot use as the carrier of catalyst at all, if select the high temperature of more than 1100 DEG C to carry out roasting to obtain highly purified magnesium aluminate spinel simply, energy consumption is large, and cost is high.If select the such as sintering temperature of 500-650 DEG C disclosed in above-mentioned technology and preparation method to obtain think the catalyst carrier with magnesia-alumina spinel structure actual be MgO, aluminium oxide and MgAl 2o 4mixed oxide, just be easy to like this occur hydration phenomena in the environment of above-mentioned high water content, hydrone enters through carrier hole or duct the alumina component not forming magnesium aluminate spinel in carrier with carrier and combines, and causes catalyst activity and intensity to reduce, easily occur catalyst down phenomenon.
So, aluminum-spinel high-specific surface area, coordination problem between aqueous stability and compact structure cannot be solved in prior art all the time.
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 can only carry out roasting at 500-650 DEG C due to it will be ensured to have high-ratio surface sum stability, but the aluminum-spinel after this temperature calcination cannot obtain high stability, make its hydration-resisting poor-performing, in catalytic process, it is easy to hydration phenomena occurs, thus cause the intensity of described catalyst to reduce further, produce problem that is broken and wearing and tearing, and then provide a kind of and can obtain without the need to carrying out roasting at high temperature there is high-specific surface area, the magnesia alumina spinel carrier that can be used for co surfer-resistant shift catalyst of high stability and the carbon monoxide transformation catalyst of 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 the technical scheme of preparation method:
A kind of carbon monoxide transformation catalyst carrier, is at least prepared by following raw material:
Kaolin powder, 5-30 weight portion;
Alumina powder, 30-60 weight portion;
Magnesia or magnesium hydroxide, 10-40 weight portion.
The particle diameter of described kaolin powder is 40-80 order.
The particle diameter of described kaolin powder is 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 order.
Described raw material also comprise in following component one or more:
Peptizing agent, 3-20 weight portion;
Pore creating material, 1-6 weight portion;
Extrusion aid, 2-5 weight portion;
Binding agent, 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, comprising:
(1) by the kaolin powder of specified weight part, alumina powder and magnesia or the abundant kneading of magnesium hydroxide;
(2) extrusion is carried out to the mixture obtained after abundant kneading;
(3) carry out drying to the extrusion product obtained in step (2), described baking temperature is 110-150 DEG C, and drying time is 120-240min;
(4) carry out roasting to the product obtained in step (3), described sintering temperature is 550-700 DEG C, and roasting time is 2-6 hour.
Front in described step (2), one or more in the peptizing agent of specified weight part, pore creating material, extrusion aid and binding agent are joined in the mixture that step (1) kneading obtains, again abundant kneading.
Load has active component on the 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 preparing described carrier comprises: kaolin powder, 5-30 weight portion; Alumina powder, 30-60 weight portion; Magnesia or magnesium hydroxide, 10-40 weight portion.Present inventor finds by adopting the kaolin powder of special ratios, alumina powder and magnesia or magnesium hydroxide to prepare carrier as raw material, effectively can improve the compact structure of carrier, thus improve the hydration-resisting performance of described catalyst, avoid the hydration phenomena under working condition, make described catalyst in use can keep higher intensity, avoid generation that is broken and wear phenomenon.Simultaneously, it also avoid in prior art utilizes high temperature nuclear reactor carrier to carry out roasting to improve carrier structure compactness, make the problem that the carrier specific area for preparing is little, thus provide better specific area loading condition and catalytic reaction condition for the load of active component.In addition, present inventor finds, can also the activity of promoting catalyst by adding kaolin, improves the conversion ratio of carbon monoxide.
(2) carbon monoxide transformation catalyst carrier of the present invention, the particle diameter selecting the kaolin powder arranged in raw material is 40-80 order, reason is, if the particle diameter of described kaolin powder is excessive, then easily cause the skewness of kaolin powder in raw mixture, if and the particle diameter of described kaolin powder is too small, then easily there is the phenomenon of reuniting, be unfavorable for that described kaolin powder is uniformly distributed in raw mixture equally, the present invention is 40-80 order by limiting the particle diameter of described kaolin powder, effectively avoided above-mentioned two situations, in order to be better uniformly distributed effect, the particle diameter that the present invention also preferably arranges described kaolin powder is 50-60 order.
In addition, also for ease of and be uniformly distributed effect preferably, the particle size range that the present invention also arranges described alumina powder is 40-200 order.
(3) carbon monoxide transformation catalyst carrier of the present invention, the specific surface area arranging described kaolin powder is 120-160m 2/ g.Why arrange like this, because if the specific surface area of described kaolin powder is too small, then can have influence on the catalytic effect of the catalyst based on carrier, and the kaolin powder that Selection radio surface area is excessive, not only can increase the preparation cost of kaolin powder, the intensity of described carrier also can be caused to reduce, in use easily broken phenomenon occurs.The present invention is 120-160m by arranging the specific surface area of described kaolin powder 2/ g, effectively prevent above-mentioned two situations.
Accompanying drawing explanation
More being convenient to make content of the present invention understand, below in conjunction with detailed description of the invention, technical solutions according to the invention being described further.
Detailed description of the invention
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, comprising:
(1) by abundant to the kaolin powder of above-mentioned weight portion, alumina powder and magnesia kneading;
(2) extrusion is carried out to the mixture obtained after abundant kneading;
(3) carry out drying to the extrusion product obtained in step (2), described baking temperature is 110 DEG C, and drying time is 120min;
(4) carry out roasting to the product obtained in step (3), described sintering temperature is 550 DEG C, and roasting time is 2 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on the 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, comprising:
(1) by abundant to the kaolin powder of above-mentioned weight portion, alumina powder and magnesium hydroxide kneading;
(2) extrusion is carried out to the mixture obtained after abundant kneading;
(3) carry out drying to the extrusion product obtained in step (2), described baking temperature is 150 DEG C, and drying time is 240min;
(4) carry out roasting to the product obtained in step (3), described sintering temperature is 700 DEG C, and roasting time is 6 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on the 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 sesbania powder; Described binding agent is cement.
The preparation method of above-mentioned carbon monoxide transformation catalyst carrier in the present embodiment, comprising:
(1) by abundant to the kaolin powder of above-mentioned weight portion, alumina powder and magnesia kneading;
Then the peptizing agent of above-mentioned weight portion, pore creating material, extrusion aid and binding agent are joined in the mixture that step (1) kneading obtains, again abundant kneading;
(2) extrusion is carried out to the mixture obtained after abundant kneading;
(3) carry out drying to the extrusion product obtained in step (2), described baking temperature is 120 DEG C, and drying time is 200min;
(4) carry out roasting to the product obtained in step (3), described sintering temperature is 600 DEG C, and roasting time is 3 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on the 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 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 carbon monoxide transformation catalyst carrier described in the present embodiment, comprising:
(1) by abundant to the kaolin powder of above-mentioned weight portion, alumina powder and magnesium hydroxide kneading;
Then the peptizing agent of above-mentioned weight portion, pore creating material, extrusion aid and binding agent are joined in the mixture that step (1) kneading obtains, again abundant kneading;
(2) extrusion is carried out to the mixture obtained after abundant kneading;
(3) carry out drying to the extrusion product obtained in step (2), described baking temperature is 140 DEG C, and drying time is 180min;
(4) carry out roasting to the product obtained in step (3), described sintering temperature is 600 DEG C, and roasting time is 5 hours.
Adopt equi-volume impregnating namely to obtain carbon monoxide transformation catalyst after load active component on the 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 15wt% weight portion.
experimental example
In order to prove the technique effect of catalyst carrier described in the present invention and the catalyst based on this carrier, the present invention devises following experimental example to the catalyst carrier described in above-described embodiment 1-4 and measure based on the performance of the catalyst of this carrier:
1. catalyst carrier strength detection:
Extract 40 catalyst samples according to quartering, in the radial crushing strength of the upper detecting catalyst of ZQJ-II Intelligent testing machine for particle (national chemical catalyst inspection center supervises), represent the height of catalyst strength with the size of mean value.20.0g catalyst granules sample and 80mL water are placed in 150mL teflon-lined hydrothermal reaction kettle, 200 DEG C of constant temperature 4h.Then cool to room temperature, filter, 120 DEG C of dry 4h, obtain the catalyst sample after hydrothermal treatment consists.Radial crushing strength test is carried out to the sample after hydro-thermal reaction.The height of catalyst strength is represented with the size of mean value.
2. catalyst carrier hydration-resisting performance measurement:
20.0g catalyst granules sample and 80mL water are placed in 150mL teflon-lined hydrothermal reaction kettle, 200 DEG C of constant temperature 4h.Then cool to room temperature, filter, 120 DEG C of dry 4h, obtain the catalyst sample after hydrothermal treatment consists.Again the intensity of the catalyst sample after process is measured, and contrast with intensity before treatment, calculate strength retention ratio.
3. carbon monoxide transformation catalyst activity rating:
first carry out sulfuration to catalyst, conditions of vulcanization is:
H 2s concentration: 0.2-0.6(v/v%);
Curing temperature: 250-300 DEG C, cure time 10-20h;
Sulfide stress 1.0-2.0MPa, sulfuration air speed: 500-2000h -1.
simulation catalytic condition:
Analog raw material gas consists of: CO:40-45%, CO 2: 5-8%, H 2: 45-50%;
Load the catalyst after the extrusion of 30ml in a device, the diameter range of described catalyst is 3.1-3.5mm, and length range is 5-20mm.
Catalytic reaction condition is:
Air speed: 3000h -1, pressure is 3.0-8.0MPa, and temperature is: 300 DEG C, vapour/gas=0.4.
Adopt gas chromatography (GC-2014A type form and aspect chromatogram) to measure the content of CO, characterize CO shift activity with CO conversion ratio (V/V%):
，
In formula: carbon monoxide percentage by volume in-unstripped gas; Carbon monoxide percentage by volume in-conversion gas.
comparative example
In order to prove that the catalyst carrier described in the present invention and the catalyst based on this carrier compared with prior art have significant Substantial technical effect, the present invention is provided with comparative example:
Consisting of of the catalyst that this comparative example adopts: MoO 3, 10wt%; CoO, 3%; K 2o, 3%, surplus is carrier aluminum magnesia spinel MgAl 2o 4.The preparation method of wherein said aluminum-spinel carrier is: be placed in kneading machine after magnesia and the moisture amorphous alumina of porous being taken according to the mol ratio of 1:1, add aqueous solution of nitric acid to carry out mixing and pinching pressure, form plastic, dry after extruded moulding, strip roasting under 600 DEG C of conditions of finally will dry, namely obtains described aluminum-spinel carrier.
Step in reference experimental example is to intensity, the hydration-resisting performance of above-mentioned catalyst and carbon monodixe conversion activity carries out measuring also and in embodiment 1-4, the measurement result of catalyst and carrier thereof contrasts.
The result that experimental example and comparative example obtain is as follows:
as shown in the table with hydrothermal treatment consists rear catalyst support strength measurement result before hydrothermal treatment consists:
the measurement result of carbon monoxide transformation catalyst active appraisal experiment is as follows:
Above-mentioned experimental result shows, the footpath Compressive Strength of the catalyst carrier in comparative example 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 example, its CO conversion ratio is respectively 79.8,79.1 and 78.3 under 4.0,6.0 and 8.0MPa condition, also all lower than using the CO conversion ratio that described in the present invention, catalyst obtains under equal pressure condition.Therefore, the present invention, compared with prior art, has more excellent hydration-resisting performance, can increase substantially intensity and the activity of catalyst.
Although the present invention is elaborated it by detailed description of the invention; but; those skilled in the art should be understood that and made on this basis not exceed any form of claims and the change of details, all belong to invention which is intended to be protected.

Claims (9)

1. a carbon monoxide transformation catalyst carrier, is characterized in that, is at least prepared by following raw material:
Kaolin powder, 5-30 weight portion;
Alumina powder, 30-60 weight portion;
Magnesia or magnesium hydroxide, 10-40 weight portion;
Wherein, the particle diameter of described kaolin powder is 40-80 order, and the specific area of described kaolin powder is 120-160m 2/ g;
The preparation method of described carbon monoxide transformation catalyst carrier, comprising:
(1) by the kaolin powder of specified weight part, alumina powder and magnesia or the abundant kneading of magnesium hydroxide;
(2) extrusion is carried out to the mixture obtained after abundant kneading;
(3) carry out drying to the extrusion product obtained in step (2), described baking temperature is 110-150 DEG C, and drying time is 120-240min;
(4) carry out roasting to the product obtained in step (3), described sintering temperature is 550-700 DEG C, and roasting time is 2-6 hour.
2. carbon monoxide transformation catalyst carrier according to claim 1, is characterized in that, the particle diameter of described kaolin powder is 50-60 order.
3. carbon monoxide transformation catalyst carrier according to claim 1, is characterized in that, the particle size range of described alumina powder is 40-200 order.
4. the carbon monoxide transformation catalyst carrier according to any one of claim 1-3, is characterized in that, described raw material also comprise in following component one or more:
Peptizing agent, 3-20 weight portion;
Pore creating material, 1-6 weight portion;
Extrusion aid, 2-5 weight portion;
Binding agent, 1-6 weight portion.
5. carbon monoxide transformation catalyst carrier according to claim 4, 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.
6. the preparation method of the carbon monoxide transformation catalyst carrier described in any one of claim 1-3, comprising:
(1) by the kaolin powder of specified weight part, alumina powder and magnesia or the abundant kneading of magnesium hydroxide;
(2) extrusion is carried out to the mixture obtained after abundant kneading;
(3) carry out drying to the extrusion product obtained in step (2), described baking temperature is 110-150 DEG C, and drying time is 120-240min;
(4) carry out roasting to the product obtained in step (3), described sintering temperature is 550-700 DEG C, and roasting time is 2-6 hour.
7. the preparation method of carbon monoxide transformation catalyst carrier according to claim 6, it is characterized in that, front in described step (2), one or more in the peptizing agent of specified weight part, pore creating material, extrusion aid and binding agent are joined in the mixture that step (1) kneading obtains, again abundant kneading.
8. based on the carbon monoxide transformation catalyst of carrier described in any one of claim 1-5, it is characterized in that, load has active component on the carrier.
9. carbon monoxide transformation catalyst according to claim 8, 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.
CN201110378243.5A 2011-11-24 2011-11-24 Carbon monoxide transformation catalyst carrier and preparation method and the catalyst based on carrier Active CN103127959B (en)

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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
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
CN112844388B (en) * 2021-02-02 2022-11-29 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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