CN105195160A - Isothermal methanation catalyst and preparation method thereof - Google Patents
Isothermal methanation catalyst and preparation method thereof Download PDFInfo
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- CN105195160A CN105195160A CN201510725468.1A CN201510725468A CN105195160A CN 105195160 A CN105195160 A CN 105195160A CN 201510725468 A CN201510725468 A CN 201510725468A CN 105195160 A CN105195160 A CN 105195160A
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- catalyst
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- methanation catalyst
- nitrate
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Abstract
The invention relates to an isothermal methanation catalyst and a preparation method thereof and belongs to the technical field of methanation catalysts. The methanation catalyst comprises components in parts by mass as follows: 50-80 parts of a shaping carrier, 1-16 parts of an auxiliary and 5-45 parts of an active component. A composite oxide formed by magnesium, aluminum and silicon is taken as the catalyst shaping carrier, so that the mechanical strength of the catalyst can be improved; the catalyst shaping carrier obtained through extrusion molding has huge outer surface area and rich channels, methanation reaction is facilitated, the heat transmission efficiency can be improved, and the bed layer temperature can be reduced; with addition of the auxiliary, the dispersity of the active component can be improved, and the anti-coking performance and the stability of the catalyst can be improved. The invention further relates to the preparation method of the catalyst. The preparation method is simple to operate, raw materials are cheap and easy to obtain, controllability of preparation conditions is high, industrial production is easy, and the preparation method of the isothermal methanation catalyst has the advantages of low cost, high operability, convenience in popularization and high yield.
Description
Technical field
The invention belongs to methanation catalyst technical field, be specifically related to one and be applicable to coke-stove gas, coal gas etc. containing H
2, CO, CO
2the isothermal methanation Catalysts and its preparation method of gas.
Background technology
Preparing natural gas by methanation reaction is as follows:
CO+3H
2＝CH
4+H
2O+206KJ/mol(1)
CO
2+4H
2＝CH
4+2H
2O+165KJ/mol(2)
Methanation reaction (1), (2) are strong heat release, and removing of reaction heat is the difficult point of preparing natural gas by methanation technique.Isothermal methanation process has small investment, takes up an area the advantages such as few, and the application in methanation synthetic natural gas is increased gradually, and general employing that remove of its reaction heat to become or tube side adds the mode of condensed water at the shell of reactor.But in real reaction running, its beds can present " non-isothermal " phenomenon, namely along with bed deeply presents huge temperature rise situation, mention reaction bed temperature in " samming methanation technology is used for coal preparing natural gas and inquires into " that Lou Ren etc. deliver and reach 460 ~ 470 DEG C, obvious temperature rise is there is compared with inlet temperature (250 ~ 280 DEG C), and methanation reaction is exothermic reaction, bed temperature is too high is unfavorable for the releasing of heat of reaction and the carrying out of methanation reaction.Therefore, need to develop the high catalyst of a kind of heat transfer efficiency to reduce bed temperature, promote the carrying out of reaction.
Summary of the invention
The object of the invention is to improve a kind of heat transfer efficiency high, be applicable to coke-stove gas, coal gas etc. containing H
2, CO, CO
2the catalyst of the isothermal methanation synthetic natural gas of gas.The present invention is achieved through the following technical solutions:
A kind of isothermal methanation catalyst, described catalyst comprises the component of following mass parts: 50 ~ 80 parts, integer carrier, auxiliary agent 1 ~ 16 part, active component 5 ~ 45 parts.Wherein, auxiliary agent and active component are counted in the form of an oxide.
Preferably a kind of as the present invention, described carrier is the integer composite oxides formed by silicon, aluminium and magnesium.The composite oxides formed by magnesium, aluminium and silicon extruded moulding, as the integer carrier of isothermal methanation catalyst, have good mechanical strength, external surface area, abundant duct, are convenient to methanation reaction and occur, improve heat transfer efficiency, reduce bed temperature.
As the present invention, a kind of preferably described auxiliary agent is one or more in magnesia, cerium oxide, lanthanum sesquioxide, calcium oxide, zirconium dioxide, aluminium oxide, auxiliary agent add the stability being conducive to improving catalyst carbon accumulation resisting ability, active component.
Preferably a kind of as the present invention, described active component is nickel oxide.Active component nickel oxide has high methanation activity.
Preferably a kind of as the present invention, the preparation method of described isothermal methanation catalyst, comprises the following steps:
1) magnesia, kaolin and aluminium oxide are mixed, and extruded moulding is integer carrier, then dry, roasting;
2) auxiliary agent be impregnated on integer carrier with the form of nitrate solution, and dry, roasting;
3) active component be impregnated in step 2 with the form of nickel nitrate solution) on the carrier that obtains, and dry, roasting;
4) step 3 is repeated) namely obtain isothermal methanation catalyst.
In isothermal methanation catalyst preparation process of the present invention, adopt the mode of extruded moulding to obtain integer catalyst carrier, integer carrier has huge external surface area, abundant duct, is conducive to the generation of methanation reaction, improves heat transfer efficiency, reduces bed temperature.In concrete preparation process, adopt the first impregnation aids of carrier, impregnated activated component mode again, acting as of first impregnation aids improves the anti-carbon nature of catalyst surface, the stability of active component and dispersiveness, thus improves quality and the methanation effect of isothermal methanation catalyst.
The present invention can repeat dipping in step 3, drying and pyrolytic process according to specific needs, to obtain the more excellent isothermal methanation catalyst of quality.
Preferred as one of the present invention, described magnesia, aluminium oxide, kaolinic mass ratio are 1 ~ 15:10 ~ 60:50 ~ 75, and wherein magnesia, aluminium oxide and kaolin are the raw material of integer carrier in catalyst preparation process.
Preferably a kind of as the present invention, described nitrate is one or more in magnesium nitrate, cerous nitrate, lanthanum nitrate, calcium nitrate, zirconium nitrate, aluminum nitrate.
As further preferred, the mass fraction 5 ~ 18% of described magnesium nitrate, aluminum nitrate, calcium nitrate, the mass fraction of lanthanum nitrate, cerous nitrate, zirconium nitrate is 0.5% ~ 4%, and the mass fraction of nickel nitrate solution is 20 ~ 50%.
Preferably a kind of as the present invention, the temperature of described drying is 80 ~ 120 DEG C, and the time is 4 ~ 12 hours.
Preferably a kind of as the present invention, the temperature of described roasting is 400 ~ 1200 DEG C, and the time is 2 ~ 12 hours.
A kind of preferably as the present invention, need to add one or both in carboxymethyl cellulose, tung oil in described extruded moulding process as lubricant.Carboxymethyl cellulose is 1 ~ 3% of solid mixture quality, and tung oil is 1 ~ 4% of solid mixture quality, and wherein, solid mixture is magnesia, aluminium oxide and kaolin mixture.
Beneficial effect of the present invention: the composite oxides that the present invention adopts magnesium, aluminium and silicon to be formed, as catalyst integer carrier, can improve the mechanical strength of catalyst; Adopt extruded moulding mode to obtain integer catalyst carrier, there is huge external surface area and abundant duct, be conducive to the generation of methanation reaction, improve heat transfer efficiency, reduce bed temperature; Be conducive to the adding of auxiliary agent the dispersiveness improving active component, improve anti-carbon nature and the stability of catalyst.Method for preparing catalyst of the present invention, simple to operate, cheaper starting materials is easy to get, preparation condition controlledization is strong, being easy to suitability for industrialized production, is that a kind of cost catalyst heat-transfer effect that is low, workable, that be convenient to promote, prepare is good, the isothermal methanation method for preparing catalyst that productive rate is high.
Accompanying drawing explanation
Fig. 1 is the evaluating apparatus structural representation that isothermal methanation catalyst of the present invention carries out methanation performance evaluation.
Reference numeral: 1-raw material gas cylinder, 2-pressure regulator valve, 3-pressure maintaining valve, 4-mass flowmenter, 5-electric heating cover, 6-fixed bed reactors, 7-temperature controller, 8-condensation separator, 9-gas-chromatography are in parallel with microanalyser.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Carry out the preparation of isothermal methanation catalyst according to scheme of the present invention, concrete preparation process is as follows:
1) by kaolin 120g, aluminium oxide 180g, magnesia 40g mixes, add the carboxymethyl cellulose of solid mixture quality 2% and the tung oil of solid mixture quality 2% and mix, by the mixing 4h of mixture obtained, and extruded moulding, at 90 DEG C of dry 12h, 800 DEG C of roasting 4h, obtain integer carrier;
2) will containing magnesium nitrate 15% (mass fraction, lower same), cerous nitrate 1%, lanthanum nitrate 1.5%, calcium nitrate 8%, zirconium nitrate 3%, on the integer carrier that the solution impregnation of aluminum nitrate 14% obtains in above-mentioned steps, at 100 DEG C of dry 12h, 500 DEG C of roasting 4h;
3) nickel nitrate solution being 50% by mass fraction impregnated on the carrier that step 2 obtains, and in 90 DEG C of dry 6h, 400 DEG C of Roasting Decomposition 4h;
4) repeat step 3 according to demand, finally obtain the product of isothermal methanation catalyst.
Embodiment 2
Carry out the preparation of isothermal methanation catalyst according to scheme of the present invention, concrete preparation process is as follows:
1) by kaolin 100g, aluminium oxide 200g, magnesia 40g mixes; Add the carboxymethyl cellulose of solid mixture quality 3% and the tung oil of solid mixture quality 1% and mix, by the mixing 4h of mixture obtained, and extruded moulding, at 90 DEG C of dry 12h, 1200 DEG C of roasting 2h, obtain integer carrier.
2) will containing magnesium nitrate 10% (mass fraction, lower same), lanthanum nitrate 1.5%, calcium nitrate 10%, zirconium nitrate 3%, on the integer carrier that the solution impregnation of aluminum nitrate 14% obtains in above-mentioned steps, at 90 DEG C of dry 12h, 600 DEG C of Roasting Decomposition 8h;
3) nickel nitrate solution being 45% by mass fraction impregnated on the carrier that step 2 obtains, and in 110 DEG C of dry 6h, 400 DEG C of Roasting Decomposition 6h;
4) repeat step 3 according to demand, finally obtain the product of isothermal methanation catalyst.
Embodiment 3
Carry out the preparation of isothermal methanation catalyst according to scheme of the present invention, concrete preparation process is as follows:
1) by kaolin 120g, aluminium oxide 180g, magnesia 40g mixes; Add the carboxymethyl cellulose of solid mixture quality 1% and the tung oil of solid mixture quality 4% and mix, by the mixing 4h of mixture obtained, and extruded moulding, at 100 DEG C of dry 8h, 1000 DEG C of roasting 6h, obtain integer carrier.
2) will containing magnesium nitrate 12% (mass fraction, lower with), cerous nitrate 1%, zirconium nitrate 3%, on the integer carrier that the solution impregnation of aluminum nitrate 16% obtains in above-mentioned steps, at 100 DEG C of dry 10h, 400 DEG C of Roasting Decomposition 12h;
3) nickel nitrate solution being 45% by mass fraction impregnated on the carrier that step 2 obtains, and in 120 DEG C of dry 4h, 600 DEG C of Roasting Decomposition 6h;
4) repeat step 3 according to demand, finally obtain the product of isothermal methanation catalyst.
Embodiment 4
Following experiment is adopted to be described isothermal methanation catalyst synthetic natural gas performance of the present invention and heat-transfer effect
By the isothermal methanation Catalyst packing prepared by example 1 ~ 3 in the fixed bed reactors 6 of evaluating apparatus shown in Fig. 1, test according to following condition: test unstripped gas adopts the preparation steel cylinder gas in raw material gas cylinder 1, unstripped gas is through pressure regulator valve 2, the decompression metering of pressure maintaining valve 3 and mass flowmenter 4 is laggard to be entered to react in fixed bed reactors 6, the gas temperature that fixed bed reactors 6 comprise electric heating cover 5 and the temperature controller 7 that is connected with electric heating cover 5 exports to adopt the form control of external heat, exit gas cools through cooler 8, be separated, after metering, part exit gas enters gas chromatographicanalyzer and CO
2carry out component analysis in microanalyser 9, remainder is emptying.
Wherein: the loadings of isothermal methanation catalyst: 30mL; Reactor inside diameter: Φ 19mm; Catalyst external diameter is consistent with reactor inside diameter, and bed height is 10.5mm.The concrete gas composition of unstripped gas is as shown in following table table 1.
The feed gas composition of table 1 methanation synthetic natural gas
| Component | CO | CO 2 | H 2 | N 2 | CH 4 |
| V％ | 3.63 | 1.3 | 44.90 | 4.78 | 44.88 |
Isothermal methanation catalyst reduction condition: pressure is 0.5MPa; Air speed is 2500h-1; Reducing medium: high-purity hydrogen.Test condition: inlet/outlet temperature is 400 DEG C; Steam-to-gas ratio: 0.1; Pressure: 2.0MPa; Air speed: 4000h
-1.Isothermal methanation catalyst synthetic natural gas performance and heat-transfer effect as shown in table 2 below:
Table 2 isothermal methanation catalyst synthetic natural gas performance and heat-transfer effect
| Isothermal methanation catalyst | N 2/％ | CO/％ | CH 4/％ | CO 2(*10 -6)％ | H 2/％ | Bed hot(test)-spot temperature (DEG C) |
| Example 1 | 5.65 | - | 59.42 | 44 | 34.65 | 404 |
| Example 2 | 5.72 | - | 59.35 | 67 | 34.70 | 404 |
| Example 3 | 5.74 | - | 59.39 | 40 | 34.63 | 404 |
As known from Table 2, the isothermal methanation catalyst activity prepared by example 1 ~ 3 of the present invention is excellent, reflects in armatine alkanisation gas and detects CO by chromatography, CO
2content is all less than 0.1%, and CO
2content is 10
-6magnitude, shows that catalyst low-temperature activity of the present invention is high, can significantly improve reaction efficiency and productive rate.
Due to CO, CO
2methanation reaction is strong exothermal reaction, along with the carrying out of reaction, reaction bed temperature can raise, but adopt the isothermal methanation catalyst prepared by example 1 ~ 3 of the present invention, in course of reaction, reaction bed temperature point (i.e. hot(test)-spot temperature) is 404 DEG C, with outlet temperature (400 DEG C) closely, illustrate that methanation catalyst of the present invention has excellent heat-transfer effect, can promote that reaction is carried out to heat release direction, improve reaction efficiency and productive rate, make reaction more complete.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an isothermal methanation catalyst, is characterized in that, described catalyst comprises the component of following mass parts: 50 ~ 80 parts, integer carrier, auxiliary agent 1 ~ 16 part, active component 5 ~ 45 parts.
2. a kind of isothermal methanation catalyst as claimed in claim 1, it is characterized in that, described carrier is the integer composite oxides formed by silicon, aluminium and magnesium.
3. a kind of isothermal methanation catalyst as claimed in claim 1, it is characterized in that, described auxiliary agent is one or more in magnesia, cerium oxide, lanthanum sesquioxide, calcium oxide, zirconium dioxide, aluminium oxide.
4. a kind of isothermal methanation catalyst as claimed in claim 1, it is characterized in that, described active component is nickel oxide.
5. a kind of preparation method of isothermal methanation catalyst as described in any one of Claims 1-4, is characterized in that, comprise the following steps:
1) magnesia, kaolin and aluminium oxide are mixed, and extruded moulding is integer carrier, then dry, roasting;
2) auxiliary agent be impregnated on integer carrier with the form of nitrate solution, and dry, roasting;
3) active component be impregnated in and step 2 with the form of nickel nitrate solution) on the carrier that obtains, and dry, roasting;
4) step 3 is repeated) namely obtain isothermal methanation catalyst.
6. the preparation method of a kind of isothermal methanation catalyst as claimed in claim 5, it is characterized in that, described magnesia, aluminium oxide, kaolinic mass ratio are 1 ~ 15:10 ~ 60:50 ~ 75.
7. the preparation method of a kind of isothermal methanation catalyst as claimed in claim 5, it is characterized in that, described nitrate is one or more in magnesium nitrate, cerous nitrate, lanthanum nitrate, calcium nitrate, zirconium nitrate, aluminum nitrate.
8. the preparation method of a kind of isothermal methanation catalyst as claimed in claim 5, it is characterized in that, the temperature of described drying is 80 ~ 120 DEG C, and the time is 4 ~ 12 hours.
9. the preparation method of a kind of isothermal methanation catalyst as claimed in claim 5, it is characterized in that, the temperature of described roasting is 400 ~ 1200 DEG C, and the time is 2 ~ 12 hours.
10. the preparation method of a kind of isothermal methanation catalyst as claimed in claim 5, is characterized in that, needs to add one or both in carboxymethyl cellulose, tung oil as lubricant in described extruded moulding process.
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Cited By (5)
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|---|---|---|---|---|
| CN105642372A (en) * | 2016-03-21 | 2016-06-08 | 中国华能集团清洁能源技术研究院有限公司 | Recycling method of deactivated methanation catalyst |
| CN108479787A (en) * | 2018-04-02 | 2018-09-04 | 西南化工研究设计院有限公司 | A kind of rare earth methanation catalyst and its preparation method and application |
| CN110479280A (en) * | 2019-07-17 | 2019-11-22 | 华南理工大学 | A kind of CO cryogenic selective methanation Ni-ZrO2/NiAl2O4Catalyst and its preparation method and application |
| CN113499763A (en) * | 2021-06-15 | 2021-10-15 | 中石化南京化工研究院有限公司 | Coke-oven gas isothermal methanation catalyst and preparation method thereof |
| 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642372A (en) * | 2016-03-21 | 2016-06-08 | 中国华能集团清洁能源技术研究院有限公司 | Recycling method of deactivated methanation catalyst |
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| CN110479280A (en) * | 2019-07-17 | 2019-11-22 | 华南理工大学 | A kind of CO cryogenic selective methanation Ni-ZrO2/NiAl2O4Catalyst and its preparation method and application |
| CN110479280B (en) * | 2019-07-17 | 2022-09-13 | 华南理工大学 | CO low-temperature selective methanation Ni-ZrO 2 /NiAl 2 O 4 Catalyst, preparation method and application thereof |
| 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 |
| CN113499763A (en) * | 2021-06-15 | 2021-10-15 | 中石化南京化工研究院有限公司 | Coke-oven gas isothermal methanation catalyst and preparation method thereof |
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Application publication date: 20151230 |