CN102626628A - Preparation method of synthetic gas methanation catalyst - Google Patents
Preparation method of synthetic gas methanation catalyst Download PDFInfo
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- CN102626628A CN102626628A CN201210064739XA CN201210064739A CN102626628A CN 102626628 A CN102626628 A CN 102626628A CN 201210064739X A CN201210064739X A CN 201210064739XA CN 201210064739 A CN201210064739 A CN 201210064739A CN 102626628 A CN102626628 A CN 102626628A
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Abstract
The invention discloses a preparation method of a synthetic gas methanation catalyst. The preparation method is characterized in that a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, one or more aluminum sources, nickel nitrate and one or more auxiliaries as raw materials undergo a one-step synthesis reaction according to a certain ratio by a solvothermal method to produce a desired product. The preparation method has simple processes. The synthetic gas methanation catalyst obtained by the preparation method has a mesoporous structure and controllable aperture sizes and catalyst particle dispersity, can show good sintering resistance, high activity at a low temperature, stability at a high temperature and high methane selectivity in methanation, and has important application values in synthesis of substitute natural gas and solution of the existing natural gas shortage problem.
Description
Technical field
The present invention relates to
OnePlant the preparation method of synthesis gas methanation catalyst; Be template specifically with the triblock copolymer; Aluminium source, nickel nitrate and slaine are the method for the methanation catalyst of synthetic hole material load of one step of raw material, can be used for the directly synthetic substitute natural gas of coal based synthetic gas.
Background technology
The core technology of coal preparing natural gas technology is a methanation catalyst.Methanation reaction is the strong exothermal reaction under catalyst action, necessarily requires methanation catalyst to keep stable performance at high temperature, and has higher activity at low temperatures.At present, methanation catalyst adopts nickel-base catalyst mostly, and carrier often is Al
2O
3,
Nickel just and aluminium oxide catalyst system that wherein representative methanation catalyst (US3988262 and US398826) uses.Industrialized methanation catalyst mainly from Britain Dai Wei company, German LURGI and rope company of Denmark Top [China and foreign countries the energy. 2010; 15 (6): 28]; Still there is high temperature active component easy-sintering in situation from existing catalyst operation and the problem of inactivation.
Publication number is that CN101380581A discloses " a kind of novel methanation catalyst and preparation method thereof ", and this catalyst consists of: Al
2O
3, NiO, La
2O
3, MgO, CeO
2, CaO, Na
2O, BaO, catalyst specific surface are 100-180m
2/ g; Reaction temperature is 300
oC, reaction pressure 1MPa, carbon monoxide conversion ratio 100%, methane selectively 99.9-100%.
Publication number is that CN102029162A discloses " a kind of wide temperature range type full methanation Catalysts and its preparation method "; Its active component is nickel (10-75%); Carrier is one or more and a zirconic composition of aluminium oxide and nickel aluminide; Auxiliary agent be lanthana or with the composition of nickel lanthanum compound, be suitable for temperature 280-650
oC, pressure 2-4MPa.
Publication number is that CN101786003A discloses " a kind of Catalysts and its preparation method that is used for preparing natural gas by methanation ", and its catalyst composition is: Ni, Sr, V, Ca, Cr and Al
2O
3Reaction temperature is 280-700
oC, pressure 2-6MPa, carbon monoxide conversion ratio 74.6-99 %, methane selectively 76.9-94.1%.
Publication number is that CN101844080A discloses " a kind of Catalysts and its preparation method that is used for preparing methane by synthetic gas ", and each component of catalyst is: Al
2O
3, NiO, MgO, La
2O
3, Na
2O.Reaction temperature is 450-500
oC, pressure 2.5MPa, carbon monoxide conversion ratio are greater than 94%, and methane selectively is greater than 88%, when temperature is lower than 300
oC or be higher than 700
oC, the carbon monoxide conversion ratio reduces greatly.
The preparation method of the nickel-base catalyst of above-mentioned public reported mostly adopts the method for salt solution impregnated carrier, and the high capacity amount needs repeatedly dipping; Catalyst particle size is with dispersed wayward, and catalyst carrier mainly is a conventional aluminium oxide, because the alumina material heat-transfer effect is poor; In the methanation reaction of strong heat release; Heat can not scatter and disappear fast, and the catalyst hot-spot causes the active component sintering easily.
Summary of the invention
The purpose of this invention is to provide
OneThe preparation method who kind is used for the synthesis gas methanation catalyst, solving existing catalyst active component easy-sintering and stability is low at high temperature, and the dispersed unmanageable problem of catalyst granules.
Problem based on above-mentioned methanation catalyst preparation method existence; The measure that the present invention taked is a kind of preparation method who is used for the synthesis gas methanation catalyst; The composition of its said method and content thereof are the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer in molar ratio: aluminium salt: nickel nitrate: auxiliary agent equals (0.003-0.02): 1: (0.1-0.3): (0.01-0.2) ratio; Earlier the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer is dissolved in the ethanol as template, after treating fully to dissolve, after adding aluminium salt continued stirs 4-6h; Add nickel nitrate and auxiliary agent, at 20-40
oC continues down to stir 3-5h, places 60-80 then
oIn the drying box of C behind the constant temperature 12-48h, at 400-600
oUnder the C, calcination process 2-4 h makes methanation catalyst.
In above-mentioned technical scheme, supplementary technology scheme of the present invention is that also said triblock copolymer is F127 or P123; Said aluminium salt is one or both in aluminium isopropoxide, aluminium chloride and the aluminum nitrate; Nickel content is the 10-20% of total catalyst weight in the said nickel nitrate; Said auxiliary agent is one or more mixing in cerium, lanthanum, copper and the iron; Said auxiliary agent content is the 1-10% of total catalyst weight.
The above-mentioned preparation method of the present invention, the specific area of its obtained methanation catalyst is: 200-400 m
2/ g; Pore volume is: 0.2-0.5 cm
3/ g; Average pore size is: 3-8 nm.
The above-mentioned preparation method of the present invention, its said method are through regulation and control proportioning raw materials, reaction condition, realize specific area, pore volume and the aperture parameters of control catalyst carrier; Through control aperture, the positioning of anchor of limiting catalyst particle.
The present invention is above-mentioned to be provided
OnePlant the preparation method who is used for the synthesis gas methanation catalyst, its said method is to be used for the process that synthesis gas is converted into methane, or is used for the methanation of carbon dioxide.
Embodiment of the present invention is above-mentioned described
OnePlant the preparation method who is used for the synthesis gas methanation catalyst,, can control specific area, pore volume and the pore-size distribution parameter of catalyst carrier through regulation and control proportioning raw materials, reaction condition.Simultaneously,, limited the positioning of anchor of catalyst granules, improved its dispersiveness through the control aperture.Simultaneously, the diffusion of the duct accelerated reaction heat that pore size is different reduces the carrier surface temperature, avoids the catalyst granules high temperature sintering, improves catalyst stability.
The prepared methanation catalyst of said method of the present invention; Directly taking a morsel is dispersed in ultrasonic 15 min in the absolute ethyl alcohol, it is dropped on the copper mesh that is coated with carbon film, in air after the air dry; Adopt the high explanation of JEM-2010 type Electronic Speculum (HRTEM; Accelerating potential 200kV) it is characterized, the result is that pore structure is orderly, the catalyst of metallic particles high dispersive, and its average pore size is 3-8 nm.
A kind of preparation method who is used for the synthesis gas methanation catalyst of the present invention, compared with prior art, its characteristics are that a step synthesized the hole material load Raney nickel, this preparation process is simple, mild condition, need be through the dipping or the process of dipping repeatedly; Synthetic methanation catalyst carrier hole Adjustable structure, catalyst good dispersion; The good heat conductivity of carrier own; Its duct helps that reaction heat transmits fast in the methanation reaction; Avoid high temperature active component sintering, had high activity and stable, be suitable for the directly synthetic instead of natural gas of coal based synthetic gas.
Description of drawings
Fig. 1 is the electromicroscopic photograph figure of mesoporous aluminas supported nickel catalyst of the present invention.The duct that shows among the figure is even, the catalyst granules high degree of dispersion.
The specific embodiment
The above-mentioned a kind of preparation method who is used for the synthesis gas methanation catalyst of the present invention can further specify through the specific embodiment; Said those skilled in the art are after having read this specific embodiment; Can understand and embodiment of the present invention, its said beneficial effect also can obtain through concrete embodiment embodying.
The specific embodiment 1
Take by weighing 1.5 g F127 and be dissolved in ethanol, after treating fully to dissolve, add 2 g aluminium isopropoxides, continue to stir 2h, take by weighing 0. 3 gram nickel nitrates and add in the above-mentioned solution 40
oAfter C constant temperature stirs 4 h, place 60 drying box freeze-day with constant temperature 48h, through 400
oC roasting 4h obtains load weight percentage and is 10% Raney nickel.The specific area of the catalyst that present embodiment is synthetic is 239 m
2/ g, pore volume 0.26 cm
3/ g, average pore size 8 nm.
The specific embodiment 2
Take by weighing 1 g F127 and be dissolved in ethanol, after treating fully to dissolve, add 2 g aluminium isopropoxides, continue to stir 2h, take by weighing 0. 3 gram nickel nitrates and add in the above-mentioned solution 40
oC constant temperature stirs 4 h, places 60 drying box freeze-day with constant temperature 48h, through 500
oC roasting 4h obtains load weight percentage and is 10% Raney nickel.The specific area of catalyst is 324 m
2/ g, pore volume 0. 37 cm
3/ g, average pore size 6 nm.
The specific embodiment 3
Take by weighing 1 g F127 and be dissolved in ethanol, after treating fully to dissolve, add 2 g aluminum nitrates, continue to stir 2h, take by weighing 0. 3 gram nickel nitrates and add in the above-mentioned solution 40
oAfter C constant temperature stirs 4 h, place 60 drying box freeze-day with constant temperature 48h, through 500
oC roasting 4h obtains load weight percentage and is 10% Raney nickel.The specific area of catalyst is 254 m
2/ g, pore volume 0. 34 cm
3/ g, average pore size 3.5 nm.
The specific embodiment 4
Take by weighing 1 g P123 and be dissolved in ethanol, after treating fully to dissolve, add 2 g aluminium isopropoxides, continue to stir 2h, take by weighing 0. 3 gram nickel nitrates and add in the above-mentioned solution 40
oAfter C constant temperature stirs 4 h, place 60 drying box freeze-day with constant temperature 48h, through 400
oC roasting 4h obtains load weight percentage and is 10% Raney nickel.The specific area of catalyst is 329 m
2/ g, pore volume 0.43 cm
3/ g nm, average pore size 4.5 nm.
The specific embodiment 5
Take by weighing 1 g F127 and be dissolved in ethanol, after treating fully to dissolve, add 2 g aluminium isopropoxides, continuation stirring 2h takes by weighing 0. 3 gram nickel nitrates and 0.06 gram cerous nitrate adds in the above-mentioned solution 40
oAfter C constant temperature stirs 4 h, place 60 drying box freeze-day with constant temperature 48h, through 500
oC roasting 4h obtains load weight percentage and is 10% Raney nickel.The specific area of catalyst is 320 m
2/ g, pore volume 0. 35 cm
3/ g, average pore size 5.5 nm.
With this sample compression molding, obtain 40-60 purpose catalyst granules.Be used for the synthesis gas methanation reaction, reaction pressure 2 MPa, air speed is 9000 h
-1, H in the synthesis gas
2/ CO ratio is 3, reacts 200 h.When temperature is 190
oC, carbon monoxide conversion ratio are 90%, and methane selectively is 100 %; Temperature is 400
oC, carbon monoxide conversion ratio are 95%, and methane selectively is 100 %; Temperature is 500
oC, carbon monoxide conversion ratio are 92%, and methane selectively is 100 %.
According to the inventive method, can effectively regulate and control the catalyst carrier pore structure parameter, synthetic hole material load Raney nickel of a step through the embodiment explanation through regulation and control template, proportioning raw materials, reaction condition etc.Carrier aperture is different, and catalyst granules is anchored in the vestibule, and its migration on the surface is restricted, thereby has improved the dispersiveness of catalyst granules, and then has improved catalyst activity.Simultaneously, different duct, aperture helps the rapid diffusion of reaction heat and removes, and the carrier surface temperature is reduced, and has avoided the high temperature sintering of catalyst granules, has improved the stability of catalyst.
Claims (9)
1. preparation method who is used for the synthesis gas methanation catalyst; The composition of its said method and content thereof are to be the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer in molar ratio: aluminium salt: nickel nitrate: auxiliary agent equals (0.003-0.02): 1: (0.1-0.3): (0.01-0.2) ratio; Earlier the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer is dissolved in the ethanol as template; After treating fully dissolving; After adding aluminium salt continued stirring 4-6h, add nickel nitrate and auxiliary agent, at 20-40
oC continues down to stir 3-5h, places 60-80 then
oIn the drying box of C behind the constant temperature 12-48h, at 400-600
oUnder the C, calcination process 2-4 h makes methanation catalyst.
2. according to the described preparation method of claim 1, its said triblock copolymer is F127 or P123.
3. according to the described preparation method of claim 1, its said aluminium salt is one or both in aluminium isopropoxide, aluminium chloride and the aluminum nitrate.
4. according to the described preparation method of claim 1, nickel content is the 10-20% of total catalyst weight in its said nickel nitrate.
5. according to the described preparation method of claim 1, its said auxiliary agent is one or more mixing in cerium, lanthanum, copper and the iron.
6. according to claim 1 or 4 described preparation methods, the 1-10% that its said auxiliary agent content is total catalyst weight.
7. according to the described preparation method of claim 1, the specific area of its obtained methanation catalyst is: 200-400 m
2/ g; Pore volume is: 0.2-0.5cm
3/ g; Average pore size is distributed as: 3-8 nm.
8. according to the described preparation method of claim 1, its said method is through regulation and control proportioning raw materials, reaction condition, realizes specific area, pore volume and the aperture parameters of control catalyst carrier; Through control aperture, the positioning of anchor of limiting catalyst particle.
9. according to the described preparation method of claim 1, its said method is to be used for the process that synthesis gas is converted into methane, or is used for the methanation of carbon dioxide.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801306A (en) * | 2014-02-27 | 2014-05-21 | 太原理工大学 | Nano nickel-based methanation catalyst as well as preparation method and applications thereof |
| CN104549291A (en) * | 2014-12-05 | 2015-04-29 | 天津大学 | Nickel-aluminum catalyst as well as preparation method and application thereof to carbon monoxide methanation |
| CN107803203A (en) * | 2016-09-08 | 2018-03-16 | 神华集团有限责任公司 | Methanation catalyst and preparation method thereof |
| CN108355668A (en) * | 2018-03-09 | 2018-08-03 | 壹碳环投(北京)科技有限公司 | A kind of methanation catalyst and its preparation method and application |
| CN111855537A (en) * | 2020-08-21 | 2020-10-30 | 太原理工大学 | HRTEM-based method for measuring micro-pore diameter in coal |
| CN113134356A (en) * | 2021-04-25 | 2021-07-20 | 内蒙古工业大学 | Aluminum-based MOFs-derived Ni-based catalyst, preparation method and application in CO methanation reaction |
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| CN101450312A (en) * | 2007-11-29 | 2009-06-10 | 南化集团研究院 | Natural gas steam reforming catalyst and preparation method thereof |
| CN101884927A (en) * | 2010-06-29 | 2010-11-17 | 清华大学 | Catalyst for full methanation of carbon dioxide and preparation method thereof |
| CN102319574A (en) * | 2011-05-17 | 2012-01-18 | 太原理工大学 | Synthesis gas methanation catalyst and preparation thereof |
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| CN101450312A (en) * | 2007-11-29 | 2009-06-10 | 南化集团研究院 | Natural gas steam reforming catalyst and preparation method thereof |
| CN101884927A (en) * | 2010-06-29 | 2010-11-17 | 清华大学 | Catalyst for full methanation of carbon dioxide and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801306A (en) * | 2014-02-27 | 2014-05-21 | 太原理工大学 | Nano nickel-based methanation catalyst as well as preparation method and applications thereof |
| CN103801306B (en) * | 2014-02-27 | 2016-01-06 | 太原理工大学 | A kind of nano nickel methylmethane catalyst and preparation method and application |
| CN104549291A (en) * | 2014-12-05 | 2015-04-29 | 天津大学 | Nickel-aluminum catalyst as well as preparation method and application thereof to carbon monoxide methanation |
| CN107803203A (en) * | 2016-09-08 | 2018-03-16 | 神华集团有限责任公司 | Methanation catalyst and preparation method thereof |
| CN107803203B (en) * | 2016-09-08 | 2021-01-22 | 神华集团有限责任公司 | Methanation catalyst and preparation method thereof |
| CN108355668A (en) * | 2018-03-09 | 2018-08-03 | 壹碳环投(北京)科技有限公司 | A kind of methanation catalyst and its preparation method and application |
| CN108355668B (en) * | 2018-03-09 | 2021-01-26 | 壹碳环投(北京)科技有限公司 | Methanation catalyst and preparation method and application thereof |
| CN111855537A (en) * | 2020-08-21 | 2020-10-30 | 太原理工大学 | HRTEM-based method for measuring micro-pore diameter in coal |
| CN113134356A (en) * | 2021-04-25 | 2021-07-20 | 内蒙古工业大学 | Aluminum-based MOFs-derived Ni-based catalyst, preparation method and application in CO methanation reaction |
| CN113134356B (en) * | 2021-04-25 | 2023-05-02 | 内蒙古工业大学 | Aluminum-based MOFs derived Ni-based catalyst, preparation method and application thereof in CO methanation reaction |
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Application publication date: 20120808 |