CN105457622A - Preparation method for Cox methanation catalyst carrier - Google Patents
Preparation method for Cox methanation catalyst carrier Download PDFInfo
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- CN105457622A CN105457622A CN201410454585.4A CN201410454585A CN105457622A CN 105457622 A CN105457622 A CN 105457622A CN 201410454585 A CN201410454585 A CN 201410454585A CN 105457622 A CN105457622 A CN 105457622A
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Abstract
The invention relates to a preparation method for a methanation catalyst carrier with high stability. The preparation method comprises the steps of: 1) simultaneously adding aluminum oxide powder or pseudo-boehmite and magnesium nitrate into a small amount of water to be stirred, and after uniformly mixing the mixture, drying the mixture; 2) adding one or more of CrO3, SiO2 and CaO into the dried material; 3) putting the mixed material in a ball mill to be ground to be less than 200 meshes; 4) roasting the powdery material; 5) adding cellulose into the roasted powdery material to be uniformly mixed, adding water to granulate the mixture to obtain particles, and drying the particles; 6) adding graphite into the dried particles to be uniformly mixed and performing moulding; and 7) drying the tablets, and then roasting the tablets to obtain the catalyst carrier. The catalyst carrier prepared by the method has good thermal stability. A methanation catalyst prepared by using the carrier has the characteristics of being good in heat-resistant stability, wide in applicable temperature range, hard to deposit carbon with a high CO content and the like.
Description
Technical field
The invention belongs to catalysis technical field, relate to a kind of preparation method of high stability methanation catalyst carrier.Be specifically related to a kind of method adopting hydrothermal synthesis method to prepare high stability COx methanation catalyst carrier, this carrier can be used for preparation catalyst, is particularly suitable as the carrier of COx methanation catalyst.
Background technology
Along with development that is economic and society, the demand of natural gas rapidly increases, and will become the fastest-rising energy of 21 century consumption figure.The deliverability of China's natural gas relatively lags behind, and causes natural gas imbalance between supply and demand to be given prominence to.The problem of natural gas disparities between supply and demand, except existing resource of basing on our country, fully outside exploitation domestic natural gas resource, also will utilize the coal resources of China's abundant, develop actively coal substitute natural gas, to alleviate the nervous situation of natural gas supply.The low-grade coals such as the coal that coal substitute natural gas technology can utilize china natural resources advantage relatively large, especially brown coal, by coal gasification, methanation, production substitute natural gas.In recent years, the industrial investment project producing synthetic natural gas increases, and the research for synthesizing methane course of reaction is paid attention to gradually.
Methanation catalyst, as one of the two large core technologies of coal to SNG, is the object that in coal to SNG technique, researcher pays close attention to, has carried out a large amount of research work.Usually containing more CO in the coal gas that coal gasification produces
x, need the CO in coal gas by methanation reaction
xbe converted into methane, because the thermal discharge of methanation reaction is very large, and coal based synthetic gas contains CO and CO of high level
2, therefore methanation reaction can cause very large temperature rise, and this will be a huge test to the heat endurance of catalyst.
Coal to SNG just achieves industrialization as far back as the 1970s and 1980s in last century, but the hydrothermal stability of catalyst and anti-carbon govern the development of coal to SNG.Therefore researcher is placed on the center of gravity that methanation catalyst is developed selection and the preparation technology aspect of catalyst carrier.
Methanation catalyst usually adopts infusion process, dry pigmentation or coprecipitation to prepare in preparation technology, and the transition metal such as load Ni, Rh, Ru, Pd, carrier is Al
2o
3, TiO
2, ZrO
2, SiO
2, sepiolite etc., adding auxiliary agent in methanation catalyst has La, Mo, Cr, Ce etc.In current existing patent, methanation catalyst is usually with Al
2o
3for carrier, disclosed in Chinese patent CN88109760.8, methanation catalyst is with Al
2o
3for carrier, nickel is active constituent, with rare earth metal, or alkaline-earth metal, or alkali metal is co-catalyst.Methanation catalyst disclosed in US Patent No. 3933883 take high purity aluminium oxide as carrier, supported active component nickel oxide and cobalt oxide.These catalyst are carrier with aluminium oxide, at trace amounts of CO
xmethanation reaction in use, reaction temperature is not high, and in reacting gas, steam partial pressure is lower, and catalyst has good stability.But the carrier hydrothermal stability of these catalyst is poor, and be faced with the carbon distribution problem in methanation reaction, be not suitable for using in coal based synthetic gas methanation reaction.
Summary of the invention
The object of the invention is the preparation method providing a kind of high stability methanation catalyst carrier.
The preparation process of catalyst carrier of the present invention is as follows: 1) alumina powder or boehmite and magnesium nitrate are added in a small amount of water simultaneously and stir, stir post-drying; 2) in the material of drying, CrO is added
3, SiO
2, in CaO one or more; 3) said mixture material is put into ball mill and be milled to below 200 orders; 4) by above-mentioned granular material roasting; 5) add the granulation that to add water after cellulose mixes in the granular material after above-mentioned roasting, the particle obtained is dried; 6) particle of drying adds graphite and mixes, shaping; 7) tablet is through drying, then roasting obtains catalyst carrier.
Alumina content in the alumina powder used in above-mentioned steps or boehmite and the mol ratio of magnesium nitrate are between 0.8 ~ 1.2.
The CrO added in above-mentioned steps
3, SiO
2, CaO total amount mass fraction in the carrier between 0.5% ~ 5%.
In above-mentioned steps 3, the sintering temperature of indication mixing granular material is 350 DEG C ~ 480 DEG C, and roasting time is 1 ~ 3 hour.
In above-mentioned steps, the cellulosic addition of indication mass fraction is in the carrier between 1% ~ 4%.
In above-mentioned steps 7, the sintering temperature of catalyst carrier is 800 DEG C ~ 1100 DEG C.
Catalyst carrier prepared by the inventive method has good heat endurance, and it is good that the methane synthesizing catalyst adopting this carrier to prepare has heat-resistant stability, is suitable for wide temperature region, the not easily feature such as carbon distribution under high CO content.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:(1) by 800g magnesium nitrate, 300g alumina powder, add a certain proportion of water and mediate, kneaded post-drying; (2) in material drying, SiO is added
222 grams, CaO33 gram; (3) mixture that step 2 is obtained is put into ball mill and be milled to below 200 orders; (4) by above-mentioned granular material 450 DEG C of roastings 2 hours; (5) add the granulation that to add water after cellulose mixes in the granular material after above-mentioned roasting, the particle obtained is dried; (6) particle of drying adds graphite and mixes, shaping; 7) tablet is through drying, then roasting obtains catalyst carrier I.
Embodiment 2:(1) by 800g magnesium nitrate, 300g alumina powder, add a certain proportion of water and mediate, kneaded post-drying; (2) in material drying, CrO is added
311 grams; (3) mixture that step 2 is obtained is put into ball mill and be milled to below 200 orders; (4) by above-mentioned granular material 400 DEG C of roastings 2 hours; (5) add the granulation that to add water after cellulose mixes in the granular material after above-mentioned roasting, the particle obtained is dried; (6) particle of drying adds graphite and mixes, shaping; 7) tablet is through drying, then roasting obtains catalyst carrier II.
Embodiment 3:(1) by 130 grams of magnesia, 500g boehmite aluminium powder, add a certain proportion of water and mediate, kneaded post-drying; (2) in material drying, CrO is added
36.5 grams, SiO
213 grams, CaO19.5; (3) mixture that step 2 is obtained is put into ball mill and be milled to below 200 orders; (4) by above-mentioned granular material 400 DEG C of roastings 2 hours; (5) add the granulation that to add water after cellulose mixes in the granular material after above-mentioned roasting, the particle obtained is dried; (6) particle of drying adds graphite and mixes, shaping; 7) tablet is through drying, then roasting obtains catalyst carrier III.
Embodiment 4: get carrier I, II, III, impregnated in nickel nitrate solution respectively, the methane synthesizing catalyst I, II, III of obtained Ni content 15%.
Embodiment 8: by methane synthesizing catalyst I, II, III is loaded in the reactor of Φ 35mm respectively, and operating condition is: pressure 3.0MPa, reaction temperature 600 DEG C, CO:8%, CO
2: 3%, H
2: 40%, CH
4: all the other, react after 120 hours, result shows: methane synthesizing catalyst I, and the hotspot location of II remains unchanged, and detecting catalyst surface through materialization after stove torn open by catalyst does not have carbon distribution; And the hotspot location of methane synthesizing catalyst III has the trend that obviously moves down, detecting catalyst surface through materialization after stove torn open by catalyst has obvious carbon deposition phenomenon.
Drawn by above embodiment result, the methane synthesizing catalyst prepared with carrier prepared by the inventive method, compared with traditional alumina base catalyst, has better heat endurance, under high temperature, high CO content, have better anti-carbon performance.
Claims (6)
1. a CO
xthe preparation method of methanation catalyst carrier, is characterized in that it is obtained by following steps: 1) alumina powder or boehmite and magnesium nitrate are added in a small amount of water simultaneously and stir, stir post-drying; 2) in the material of drying, CrO is added
3, SiO
2, in CaO one or more; 3) said mixture material is put into ball mill and be milled to below 200 orders; 4) by above-mentioned granular material roasting; 5) add the granulation that to add water after cellulose mixes in the granular material after above-mentioned roasting, the particle obtained is dried; 6) particle of drying adds graphite and mixes, shaping; 7) tablet is through drying, then roasting obtains catalyst carrier.
2. the preparation method of catalyst carrier according to claim 1, is characterized in that the mol ratio of alumina content in alumina powder or boehmite and magnesium nitrate is between 0.8 ~ 1.2.
3. the preparation method of catalyst carrier according to claim 1, is characterized in that CrO
3, SiO
2, CaO add total amount mass fraction in the carrier between 0.5% ~ 5%.
4. the preparation method of catalyst carrier according to claim 1, it is characterized in that mixing granular material sintering temperature is 350 DEG C ~ 480 DEG C, roasting time is 1 ~ 3 hour.
5. the preparation method of catalyst carrier according to claim 1, is characterized in that cellulosic addition mass fraction is in the carrier between 1% ~ 4%.
6. the preparation method of catalyst carrier according to claim 1, is characterized in that the sintering temperature of catalyst carrier is 800 DEG C ~ 1100 DEG C.
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|---|---|---|---|
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|---|---|---|---|
| CN201410454585.4A CN105457622B (en) | 2014-09-09 | 2014-09-09 | A kind of COxThe preparation method of methanation catalyst carrier |
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| CN105457622A true CN105457622A (en) | 2016-04-06 |
| CN105457622B CN105457622B (en) | 2018-01-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114345363A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Preparation method of isothermal fixed bed methanation catalyst |
| CN115445598A (en) * | 2022-09-05 | 2022-12-09 | 浦江思欣通科技有限公司 | Modified alpha-alumina carrier and preparation method and application thereof |
| CN115475620A (en) * | 2022-09-05 | 2022-12-16 | 浦江思欣通科技有限公司 | Preparation method and application of methane multi-reforming catalyst |
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| US3962140A (en) * | 1975-03-10 | 1976-06-08 | The Harshaw Chemical Company | Nickel-copper-molybdenum methanation catalyst |
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2014
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| US3962140A (en) * | 1975-03-10 | 1976-06-08 | The Harshaw Chemical Company | Nickel-copper-molybdenum methanation catalyst |
| CN101380581A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Novel methanation catalyst and preparation method thereof |
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| CN102302936A (en) * | 2011-05-31 | 2012-01-04 | 神华集团有限责任公司 | Titanium-containing nickel-based catalyst, as well as preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114345363A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Preparation method of isothermal fixed bed methanation catalyst |
| CN115445598A (en) * | 2022-09-05 | 2022-12-09 | 浦江思欣通科技有限公司 | Modified alpha-alumina carrier and preparation method and application thereof |
| CN115475620A (en) * | 2022-09-05 | 2022-12-16 | 浦江思欣通科技有限公司 | Preparation method and application of methane multi-reforming catalyst |
| CN115445598B (en) * | 2022-09-05 | 2024-02-02 | 浙江思欣通氢能科技有限公司 | Modified alpha-alumina carrier and preparation method and application thereof |
| CN115475620B (en) * | 2022-09-05 | 2024-02-02 | 浙江思欣通氢能科技有限公司 | Preparation method and application of methane multiple catalyst |
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| CN105457622B (en) | 2018-01-30 |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |