CN105344355A - Catalyst for preparing methane from coal-based synthetic gas, and preparation method thereof - Google Patents
Catalyst for preparing methane from coal-based synthetic gas, and preparation method thereof Download PDFInfo
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- CN105344355A CN105344355A CN201410410997.8A CN201410410997A CN105344355A CN 105344355 A CN105344355 A CN 105344355A CN 201410410997 A CN201410410997 A CN 201410410997A CN 105344355 A CN105344355 A CN 105344355A
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- catalyst
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Abstract
The present invention discloses a catalyst for preparing methane from coal-based synthetic gas, and a preparation method thereof, and belongs to the technical field of catalyst preparation. According to the present invention, the catalyst has characteristics of large inlet temperature operating range, high CO conversion rate under high space velocity, good high temperature thermal stability, high catalysis activity, and the like; during the catalyst preparation process, aluminum oxide, calcium oxide, or a calcium oxide or aluminum oxide composite carrier is adopted as the catalyst carrier, the particle size during the carrier preparation process can be controlled, nickel is adopted as the active component of the catalyst, and the rare earth element La is added so as to enhance the activity, the stability and the carbon deposition resistance of the catalyst; and the components of the finished product catalyst comprise, by mass, 65-70% of Al2O3, 15-23% of NiO, 0.3-5% of MgO, and 1-5% of La2O3, the specific surface area is 220-350 m<2>/g, and the pore volume is 0.16-0.30 mL/g.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, specifically a kind of Catalysts and its preparation method of coal based synthetic gas methane, belongs to catalyst preparation technical field.
Background technology
National energy distribution feature is rich coal, oil-poor (oil), weak breath (natural gas).Consumption of coal accounts for China's primary energy consumption proportion about 70%.Natural gas is a kind of energy of high-efficiency cleaning, and its advantage such as convenient transport, use safety receives much concern in recent years.Along with the quickening of China's industrialization, Development of China's Urbanization and the enforcement of energy-saving and emission-reduction policy, the consumption proportion of natural gas is increasing.Because conventional gas supply is not enough, supply breach also strengthens year by year, how to utilize the coal resources of China's relative abundance, and getting substitute natural gas by the synthesis gas methanation after coal gasification is the effective way solving natural gas imbalance between supply and demand.
The reaction that synthesis gas methanation occurs mainly comprises:
CO+3H
2→CH
4+H
2O+206.2KJ/mol⑴
CO
2+4H
2→CH
4+2H
2O+165KJ/mol⑵
From (1) (2) two formula, methanation reaction is strong exothermal reaction.In coal based synthetic gas, after coal gasification, CO content about 22%, CO
2content about 6%, if all CO, CO
2whole conversion, it reacts, and liberated heat is very fast rises to more than 1000 DEG C by in-furnace temperature.Under high temperature, activity and the stability of catalyst are greatly affected.
In synthesis gas methanation, the key component of its technology path is to control how reaction zone temperature rise basis improves CO, CO
2conversion ratio, the core improving conversion ratio is then the catalyst of methanation.Under methanation is in high temperature (about 650 DEG C) high pressure (about 3.0Mp) state, it requires that catalyst high temperatures is good, and under high pressure, mechanical strength is high.
At present, domestic natural gas catalyst manufactured by coal is also in development, under poor high temperature stability, high pressure, the easy efflorescence of catalyst, preparation technology adopts nitrate, and heat resolve generates nitride and pollutes the problems such as large.
Summary of the invention
At present, domestic coal based synthetic gas is methanation catalyst prepared is also in development.The subject matter occurred is easy efflorescence under catalyst poor high temperature stability, high pressure, operation entry temperature requirement harshness, the nitrate that preparation technology adopts, and the pollution of heat resolve generation nitride is large.
Under the object of the invention is to overcome above-mentioned not enough condition, provide a kind of coal based synthetic gas methanation catalyst prepared and preparation method.The present invention; Utilize the oxide of Al, Mg, La as the mixture preparing carrier, achieve efflorescence oxide by ball milling, control grain diameter size, and make Homogeneous phase mixing between each component, avoid occurring layering between component, after roasting carrier crystal formation good, free from admixture phase.Finished activated good, high temperature resistant, the intensity of impregnation-calcination rear catalyst is large, environmental friendliness, and preparation method is simply suitable for industrialization.
(1) by carrier A l
2o
3, auxiliary agent MgO, La
2o
3percentage by weight weighs powder; Al
2o
3percentage by weight is 65-70%, MgO percentage by weight: 0.3-5%; La
2o
3percentage by weight is: 1-5%.
(2) Al will weighed
2o
3, MgO, La
2o
3oxide mixed-powder, adds appropriate amount of deionized water as dispersant, is made into the suspension of solid content 40%.
(3) utilized by the suspension of preparation particle diameter 0.5-1.5mm zirconia ball to carry out ball milling 10-15 hour, obtain the slurry mixed; Ball milling gained slurry is moved in beaker, by electromagnetic agitation strong stirring, avoids density of fraction difference to form precipitated and separated; Carry out spraying dry while stirring, obtain mixing powder through cyclone collection.
(4) what separated and collected obtained mixes the graphite that powder adds mass percent 1-3%, then adds mass percent 2-5% deionized water and carry out abundant mix and blend.
(5) by the powder compacting roasting of mix and blend: carrier compound is prepared into blank, by shaping blank dry 2-3 hour under 100-120 DEG C of condition, by dried blank at 800-1200 DEG C of roasting 5-8 hour.
(6) utilize the blank after nickel nitrate solution impregnation-calcination, immersion condition: nickel nitrate solution proportion 1.0-1.8, solution temperature 60-90 DEG C, dip time 1-5 hour, dipping 1-2 number.
(7) by the blank dry 2-3 hour under 150-200 DEG C of condition after dipping, by dried blank under 450-550 DEG C of condition, heating 4-9 hour, decomposes the catalyst that nickel nitrate obtains coal based synthetic gas methanation.
Detailed description of the invention
Below by embodiment, the present invention is elaborated.Following examples, just in order to explain the present invention, are not limitation of the present invention.
Embodiment 1
A preparation method for the catalyst of coal based synthetic gas methane, comprises the following steps:
(1) by 38gAl
2o
3, 1.7gMgO, 2.8gLa
2o
3powder adds 120ml deionized water and fully mixes, and to pour in ball mill ball milling into 10 hours, each component is fully mixed and be ground to average in granularity less than 1 μm.Solution after collection ball milling, is separated dry by solution, the powder mixed after obtaining drying through cyclone separator.
(2) 1.2ml deionized water and 0.55g graphite are added and mix in powder, fully stir, extruding is prepared into blank.
(3) by the blank of preparation at 110 DEG C of temperature dry 3 hours, dry blank is put into Muffle furnace with 4 DEG C/min heating rate, be warming up to 1100 DEG C, and be incubated 6 hours, obtain carrier solid solution.
(4) carrier of gained catalyst is flooded: put into by carrier and prepare, proportion is flood in the nickel nitrate aqueous solution of 1.45, dipping temperature is 90 DEG C, dip time 1 hour.The catalyst that flooded is taken out and under 180 DEG C of conditions dry 2.5 hours, then under 450 DEG C of conditions, carry out heat resolve 4 hours.
(5) by above-mentioned dipping Sum decomposition catalyst, in same concentrations nickel nitrate solution, carry out double-steeping Sum decomposition, finally obtain the catalyst of coal based synthetic gas methane.Ni mass percentage is 16.2%.
Embodiment 2
(1) by 54.72gAl
2o
3, 1.52gMgO, 1.52gLa
2o
3powder adds 200ml deionized water and fully mixes, and to pour in ball mill ball milling into 10 hours, each component is fully mixed and be ground to average in granularity less than 1 μm.Solution after collection ball milling, is separated dry by solution, the powder mixed after obtaining drying through cyclone separator.
(2) 2.3ml deionized water and 1.14g graphite are added and mix in powder, fully stir, extruding is prepared into blank.
(3) by the blank of preparation at 110 DEG C of temperature dry 3 hours, dry blank is put into Muffle furnace with 4 DEG C/min heating rate, be warming up to 1100 DEG C, be incubated 6 hours, obtain carrier solid solution.
(4) carrier of gained catalyst is flooded: put into by carrier and prepare, proportion is flood in the nickel nitrate aqueous solution of 1.67, dipping temperature is 90 DEG C, dip time 1 hour.The catalyst that flooded is taken out and under 180 DEG C of conditions dry 3 hours, then under 450 DEG C of conditions, carry out heat resolve 4 hours.
(5) by above-mentioned dipping Sum decomposition catalyst, in same concentrations nickel nitrate solution, carry out double-steeping Sum decomposition, finally obtain coal-based preparing natural gas catalyst.Ni mass percentage is 19.3%.
Embodiment 3
The performance of catalyst is evaluated, and loaded in stainless steel reactor by 30ml particle size 5mm circular catalyst, beds inlet temperature ensures at 260-330 DEG C, and pressure is 2.5-3.0Mpa, to catalyst reduction activation 6-8 hour.Then in reactor, pass into hydrogen, carbon monoxide and carbon dioxide gas mixture, control mol ratio C:H=1:3, air speed 9000h with flowmeter
-1, the results are shown in following table:
| Nickel Content In Catalyst (%) | CO（%） | CO 2（%） | H 2（%） | Inlet temperature (DEG C) | Reaction temperature (DEG C) | Outlet CH 4（%） |
| 16.2 | 22.3 | 2.8 | 75.6 | 280 | 632 | 95.8 |
| 15.8 | 21.4 | 3.0 | 73.5 | 300 | 648 | 95.3 |
Claims (6)
1., for a catalyst for coal based synthetic gas methane, its feature comprises: Al
2o
3as carrier, NiO as active component, auxiliary agent be in alkaline earth oxide, rare-earth oxide one or both; Prepared catalyst components mass percentage is respectively: carrier A l
2o
3: 65-70%; Active component NiO:15-23%; Alkali metal oxide: 0.3-5%; Rare-earth oxide 1-5%; Graphite 1-3%'s.
2. the catalyst for coal based synthetic gas methane according to claim 1, is characterized in that, described rare-earth oxide is La
2o
3, described alkaline earth oxide is MgO.
3. the catalyst for coal based synthetic gas methane according to claim 1, it is characterized in that in carrier granulation process, particle is tiny, grain diameter can be controlled in more than 300 orders.
4. the catalyst for coal based synthetic gas methane according to claim 1,3, is characterized in that described carrier specific area is 220-350m
2/ g.
5. the methanation catalyst prepared by synthetic gas according to claim 1,2, after it is characterized in that described catalyst carrier roasting, intensity is 200-450N/cm.
6. the catalyst for coal based synthetic gas methane according to claim 1-5, is characterized in that preparation method comprises the steps:
(1) by carrier A l
2o
3, auxiliary agent MgO, La
2o
3percentage by weight weighs powder; Al
2o
3mass percent is 65-70%, MgO percentage by weight: 0.3-5%; La
2o
3percentage by weight is: 1-5%;
(2) Al will weighed
2o
3, MgO, La
2o
3oxide powder, adds deionized water as dispersant, is made into the suspension of solid content 40%;
(3) utilized by the suspension of preparation particle diameter 0.5-1.5mm zirconia ball to carry out ball milling 10-15 hour, obtain the slurry mixed; Ball milling gained slurry is moved in beaker, by electromagnetic agitation strong stirring, avoids density of fraction difference to form precipitated and separated; Carry out spraying dry while stirring, obtain mixing powder through cyclone collection;
(4) what separated and collected obtained mixes the graphite that powder adds mass percent 1-3%, then adds mass percent 2-5% deionized water and carry out abundant mix and blend;
(5) by the powder compacting roasting of mix and blend: carrier compound is prepared into blank, by shaping blank dry 2-3 hour under 100-120 DEG C of condition, by dried blank at 800-1200 DEG C of roasting 5-8 hour;
(6) utilize the blank after nickel nitrate solution impregnation-calcination, immersion condition: nickel nitrate solution proportion 1.0-1.8, solution temperature 60-90 DEG C, dip time 1-5 hour, dipping 1-2 number;
(7) by the blank dry 2-3 hour under 150-200 DEG C of condition after dipping, by dried blank under 450-550 DEG C of condition, heating 4-9 hour, decomposes the catalyst that nickel nitrate obtains coal based synthetic gas methane.
Priority Applications (1)
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|---|---|---|---|
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944072A (en) * | 2017-02-15 | 2017-07-14 | 中国五环工程有限公司 | The preparation method of efficient isothermal coal based synthetic gas methanation catalyst |
| CN108620137A (en) * | 2017-03-15 | 2018-10-09 | 成都汇嘉春天科技有限公司 | The preparation process of organic compound depickling catalyst |
| CN108982288A (en) * | 2018-07-30 | 2018-12-11 | 杨晓梅 | Methyl acrylate adsorbent for methyl acrylate content detection sampling in plant gas |
| CN111111642A (en) * | 2019-12-26 | 2020-05-08 | 山东国瓷功能材料股份有限公司 | Denitration catalyst and preparation method and application thereof |
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| CN103706370A (en) * | 2013-12-17 | 2014-04-09 | 西南化工研究设计院有限公司 | High-temperature methanation catalyst for producing natural gas through coal and preparation method of catalyst |
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2014
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| CN101703934A (en) * | 2009-12-03 | 2010-05-12 | 熊世平 | Natural gas catalyst manufactured by coal and manufacturing method thereof |
| CN102513119A (en) * | 2011-12-15 | 2012-06-27 | 西南化工研究设计院 | Catalyst for natural gas from coal and preparation method thereof |
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|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944072A (en) * | 2017-02-15 | 2017-07-14 | 中国五环工程有限公司 | The preparation method of efficient isothermal coal based synthetic gas methanation catalyst |
| CN106944072B (en) * | 2017-02-15 | 2019-06-07 | 中国五环工程有限公司 | The preparation method of efficient isothermal coal based synthetic gas methanation catalyst |
| CN108620137A (en) * | 2017-03-15 | 2018-10-09 | 成都汇嘉春天科技有限公司 | The preparation process of organic compound depickling catalyst |
| CN108620137B (en) * | 2017-03-15 | 2021-03-19 | 成都汇嘉春天科技有限公司 | Preparation process of catalyst for deacidifying organic compound |
| CN108982288A (en) * | 2018-07-30 | 2018-12-11 | 杨晓梅 | Methyl acrylate adsorbent for methyl acrylate content detection sampling in plant gas |
| CN108982288B (en) * | 2018-07-30 | 2021-02-02 | 杨晓梅 | Methyl acrylate adsorbent for detecting and sampling methyl acrylate content in factory waste gas |
| CN111111642A (en) * | 2019-12-26 | 2020-05-08 | 山东国瓷功能材料股份有限公司 | Denitration catalyst and preparation method and application thereof |
| CN111111642B (en) * | 2019-12-26 | 2023-01-24 | 山东国瓷功能材料股份有限公司 | Denitration catalyst and preparation method and application thereof |
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