CN105457622B - A kind of COxThe preparation method of methanation catalyst carrier - Google Patents
A kind of COxThe preparation method of methanation catalyst carrier Download PDFInfo
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- CN105457622B CN105457622B CN201410454585.4A CN201410454585A CN105457622B CN 105457622 B CN105457622 B CN 105457622B CN 201410454585 A CN201410454585 A CN 201410454585A CN 105457622 B CN105457622 B CN 105457622B
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Abstract
A kind of preparation method of high stability methanation catalyst carrier, step are as follows：1）Alumina powder or boehmite are added in a small amount of water simultaneously with magnesium nitrate and stirred, is dried after stirring；2) CrO is added in the material of drying3、SiO2, it is one or more of in CaO；3）Said mixture material is put into ball mill and is milled to below 200 mesh；4）Above-mentioned granular material is calcined；5）Added in granular material after above-mentioned roasting after cellulose is well mixed plus water is granulated, obtained particle drying；6）The particle of drying adds graphite and is well mixed, and is molded；7）Tablet is by drying, then is calcined to obtain catalyst carrier.Catalyst carrier prepared by the inventive method has good heat endurance, and the methane synthesizing catalyst prepared using the carrier has that heat-resistant stability is good, is applicable wide temperature region, the features such as being not easy carbon distribution under high CO contents.
Description
Technical field
The invention belongs to catalysis technical field, is related to a kind of preparation method of high stability methanation catalyst carrier.Tool
Body is related to a kind of method that high stability COx methanation catalyst carriers are prepared using hydrothermal synthesis method, and the carrier can be used for soaking
Stain method prepares catalyst, the carrier particularly suitable as COx methanation catalysts.
Background technology
With economic and society development, the demand of natural gas rapidly increases, and it is most fast will to turn into the growth of 21 century consumption figure
The energy.The deliverability of China's natural gas relatively lags behind, and causes natural gas imbalance between supply and demand to protrude.Natural gas disparities between supply and demand are asked
Topic, except existing resource of basing on our country, fully develop outside domestic natural gas resource, also to utilize the coal resources of China's abundant,
Positive Development of Coal substitute natural gas, to alleviate natural gas supply anxiety situation.Coal substitute natural gas technology can utilize China
The relatively large coal of resources advantage, the especially low-grade coal such as lignite, by coal gasification, methanation, produce substitute natural gas.
In recent years, the industrial investment project for producing synthetic natural gas increases, and the research for synthesizing methane course of reaction gradually obtains weight
Depending on.
One of the two big core technologies of methanation catalyst as coal to SNG, are researcher's emphasis in coal to SNG technique
The object of concern, substantial amounts of research work is carried out.More CO is usually contained in coal gas caused by coal gasificationX, it is necessary to pass through
Methanation reaction is by the CO in coal gasXMethane is converted into, because the thermal discharge of methanation reaction is very big, and coal based synthetic gas contains
The CO and CO of high level2, therefore methanation reaction can cause very big temperature rise, and this heat endurance to catalyst will be one
Huge test.
Coal to SNG is achieved that industrialization, but the hydrothermal stability of catalyst and anti-product early in the 1970s and 1980s in last century
Carbon governs the development of coal to SNG.Therefore the center of gravity of methanation catalyst development is placed on catalyst carrier by researcher
Selection and preparation technology aspect.
It is prepared by methanation catalyst generally use infusion process, dry pigmentation or coprecipitation in preparation technology, load Ni,
The transition metal such as Rh, Ru, Pd, carrier Al2O3、TiO2、ZrO2、SiO2, sepiolite etc., auxiliary agent is added in methanation catalyst to be had
La, Mo, Cr, Ce etc..Methanation catalyst is generally with Al in current existing patent2O3For carrier, such as Chinese patent
Methanation catalyst is with Al disclosed in CN88109760.82O3For carrier, nickel is active constituent, with rare earth metal, or alkaline earth gold
Category, or alkali metal is co-catalyst.Methanation catalyst disclosed in United States Patent (USP) US 3933883 using high purity aluminium oxide as carrier,
Supported active component nickel oxide and cobalt oxide.These catalyst are using aluminum oxide as carrier, in trace amounts of COXMethanation reaction in make
With reaction temperature is not high, and steam partial pressure is relatively low in reacting gas, and catalyst has good stability.But these catalyst
Carrier hydrothermal stability it is poor, and also face the carbon distribution problem in methanation reaction, be not suitable in coal based synthetic gas methane
Change and used in reaction.
The content of the invention
Present invention aims at provide a kind of preparation method of high stability methanation catalyst carrier.
The preparation process of catalyst carrier of the present invention is as follows：1）By alumina powder or boehmite and magnesium nitrate
Add in a small amount of water and stir simultaneously, dried after stirring；2) CrO is added in the material of drying3、SiO2, it is a kind of in CaO or
It is several；3）Said mixture material is put into ball mill and is milled to below 200 mesh；4）Above-mentioned granular material is calcined；5）Above-mentioned
Added in granular material after roasting after cellulose is well mixed plus water is granulated, obtained particle drying；6）The particle of drying adds
Enter graphite to be well mixed, be molded；7）Tablet is by drying, then is calcined to obtain catalyst carrier.
The mol ratio of alumina content in alumina powder or boehmite and magnesium nitrate used in above-mentioned steps
Between 0.8 ~ 1.2.
The CrO added in above-mentioned steps3、SiO2, CaO total amount mass fraction in the carrier between 0.5% ~ 5%.
The sintering temperature of signified mixing granular material is 350 DEG C ~ 480 DEG C in above-mentioned steps 3, and roasting time is 1 ~ 3 small
When.
The mass fraction of the addition of signified cellulose in the carrier is between 1% ~ 4% in above-mentioned steps.
The sintering temperature of catalyst carrier is 800 DEG C ~ 1100 DEG C in above-mentioned steps 7.
Catalyst carrier prepared by the inventive method has good heat endurance, and the methane prepared using the carrier is synthesized
Catalyst has that heat-resistant stability is good, is applicable wide temperature region, the features such as being not easy carbon distribution under high CO contents.
Embodiment
The present invention is described in detail in reference to embodiment.
Embodiment 1：（1）By 800g magnesium nitrates, 300g alumina powders, add a certain proportion of water and mediate, after kneaded
Drying；（2）SiO is added in material drying222 grams, CaO33 grams；（3）Mixture made from step 2 is put into ball mill and ground
To 200 mesh；（4）Above-mentioned granular material is calcined 2 hours at 450 DEG C；（5）Added in granular material after above-mentioned roasting
After cellulose is well mixed plus water is granulated, obtained particle drying；（6）The particle of drying adds graphite and is well mixed, and is molded；7）
Tablet is by drying, then is calcined to obtain catalyst carrier I.
Embodiment 2：（1）By 800g magnesium nitrates, 300g alumina powders, add a certain proportion of water and mediate, after kneaded
Drying；（2）CrO is added in material drying311 grams；（3）Mixture made from step 2 is put into ball mill and is milled to 200 mesh
Below；（4）Above-mentioned granular material is calcined 2 hours at 400 DEG C；（5）Cellulose is added in granular material after above-mentioned roasting
After well mixed plus water is granulated, obtained particle drying；（6）The particle of drying adds graphite and is well mixed, and is molded；7）Tablet passes through
Drying is crossed, then is calcined to obtain catalyst carrier II.
Embodiment 3：（1）By 130 grams of magnesia, 500g boehmite aluminium powders, add a certain proportion of water and mediate, pinch
Dried after getting togather；（2）CrO is added in material drying36.5 grams, SiO213 grams, CaO19.5；（3）By the obtained mixing of step 2
Thing, which is put into ball mill, to be milled to below 200 mesh；（4）Above-mentioned granular material is calcined 2 hours at 400 DEG C；（5）After above-mentioned roasting
Granular material in add cellulose it is well mixed after plus water be granulated, obtained particle drying；（6）The particle of drying adds graphite
It is well mixed, shaping；7）Tablet is by drying, then is calcined to obtain catalyst carrier III.
Embodiment 4：Take carrier I, II, III, it is impregnated in respectively in nickel nitrate solution, the methane synthesis of Ni contents 15% is made
Catalyst I, II, III.
Embodiment 8：Methane synthesizing catalyst I, II, III is loaded in Φ 35mm reactor respectively, operating condition is：
Pressure 3.0MPa, 600 DEG C of reaction temperature, CO：8%, CO2：3%, H2：40%, CH4：Remaining, after reacting 120 hours, as a result shows
Show：Methane synthesizing catalyst I, II hotspot location keep constant, and catalyst does not have after tearing stove open through materialization detection catalyst surface
Carbon distribution；And the hotspot location of methane synthesizing catalyst III have it is obvious move down trend, catalyst is torn open and detects catalyst through materialization after stove
There is obvious carbon deposition phenomenon on surface.
Drawn by above example result, methane synthesizing catalyst prepared by the carrier prepared with the inventive method and tradition
Alumina base catalyst compare, there is more preferable heat endurance, there is more preferable anti-carbon under high temperature, high CO contents
Energy.
Claims (6)
- A kind of 1. COxThe preparation method of methanation catalyst carrier, it is characterised in that it is made by following steps：1）Will oxidation Aluminium powder or boehmite are added in a small amount of water simultaneously with magnesium nitrate to be stirred, and is dried after stirring；2) in the material of drying Add CrO3；3）Said mixture material is put into ball mill and is milled to below 200 mesh；4）Above-mentioned granular material is calcined；5） Added in granular material after above-mentioned roasting after cellulose is well mixed plus water is granulated, obtained particle drying；6）The grain of drying Son adds graphite and is well mixed, and is molded；7）Tablet is by drying, then is calcined to obtain catalyst carrier.
- 2. the preparation method of catalyst carrier according to claim 1, it is characterised in that in alumina powder or boehmite Alumina content and magnesium nitrate mol ratio be 0.8 ~ 1.2 between.
- 3. the preparation method of catalyst carrier according to claim 1, it is characterised in that CrO3Add the matter of total amount in the carrier Fraction is measured between 0.5% ~ 5%.
- 4. the preparation method of catalyst carrier according to claim 1, it is characterised 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, it is characterised in that the addition of cellulose is in the carrier Mass fraction between 1% ~ 4%.
- 6. the preparation method of catalyst carrier according to claim 1, it is characterised in that the sintering temperature of catalyst carrier is 800℃~1100℃。
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| CN105457622B true CN105457622B (en) | 2018-01-30 |
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| CN114345363B (en) * | 2020-10-12 | 2024-10-25 | 中石化南京化工研究院有限公司 | Preparation method of isothermal fixed bed methanation 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102189004A (en) * | 2010-03-19 | 2011-09-21 | 中国石油化工股份有限公司 | Carrier for methanation catalyst of coal-based synthesis gas and preparation method thereof |
| 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 |
| CN103846108A (en) * | 2012-11-28 | 2014-06-11 | 中国石油化工股份有限公司 | Preparation method of catalyst carrier for preparing substitute natural gas from coal-based syngas |
| CN104016825A (en) * | 2014-06-05 | 2014-09-03 | 天津大学 | Technology for preparing organic fuel through directly converting carbon dioxide by using sunlight and photothermal catalyst |
-
2014
- 2014-09-09 CN CN201410454585.4A patent/CN105457622B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102189004A (en) * | 2010-03-19 | 2011-09-21 | 中国石油化工股份有限公司 | Carrier for methanation catalyst of coal-based synthesis gas and preparation method thereof |
| 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 |
| CN103846108A (en) * | 2012-11-28 | 2014-06-11 | 中国石油化工股份有限公司 | Preparation method of catalyst carrier for preparing substitute natural gas from coal-based syngas |
| CN104016825A (en) * | 2014-06-05 | 2014-09-03 | 天津大学 | Technology for preparing organic fuel through directly converting carbon dioxide by using sunlight and photothermal catalyst |
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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 |