CN102950006B - High-temperature-resistant synthetic natural gas methanation catalyst and preparation method thereof - Google Patents
High-temperature-resistant synthetic natural gas methanation catalyst and preparation method thereof Download PDFInfo
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- CN102950006B CN102950006B CN201210389570.5A CN201210389570A CN102950006B CN 102950006 B CN102950006 B CN 102950006B CN 201210389570 A CN201210389570 A CN 201210389570A CN 102950006 B CN102950006 B CN 102950006B
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Abstract
The invention discloses a high-temperature-resistant synthetic natural gas methanation catalyst and a preparation method thereof, belonging to the fields of catalysts and coal chemical industry. The ingredients of the catalyst comprise active constituents, carriers and stabilizers, wherein the active constituents are Ni and Mo, the carriers are Al2O3, ZrO2, TiO2 and SiO2, and auxiliaries are rare-earth metals and alkaline-earth metals. The preparation method comprises the following steps of: A, preparing the active constituents of a precipitate via the soluble salt solution of the active constituents and a precipitator; B, preparing the high-temperature carriers by means of high-temperature roasting; and C, uniformly mixing the active constituents, the carriers and the auxiliaries, forming by tabletting, and then preparing the high-temperature-resistant methanation catalyst after high-temperature calcining. The catalyst has the characteristics that cheap non-noble metals are used as the active constituents, the high-temperature-resistant materials prepared by mixing and calcining conventional carrier oxides are used as the carriers, and the activity, the selectivity and the high-temperature stability of the catalyst are further improved by adding proper amount of rare-earth metal auxiliaries and alkaline-earth metal auxiliaries, so that the catalyst can stably run for a long time at a high temperature and a high pressure.
Description
Technical field
The present invention relates to a kind of high temperature resistant synthetic natural gas methanation catalyst and preparation method thereof, belong to catalyst and coal chemical technology.
Background technology
The main component of natural gas is methane, the harmful substance such as sulfur-bearing, nitrogen hardly, and the carbon dioxide producing during burning is less than other fossil fuel, is green, the clear energy sources of generally acknowledging.The main application of natural gas is: make industry and domestic gas, generating, vehicle fuel and industrial chemicals etc.The energy resource structure feature of China is " rich coal, oil starvation, weak breath ", and wherein coal accounts for 97.7%, oil 1.6%, and natural gas only has 0.7%.Oil and natural gas proportion is far below world average level.
Rich coal resources in China, the coal of take is produced " synthetic natural gas " (SNG) as raw material, is Optimization of Energy Structure, the important channel of alleviating China's natural gas supply shortage.The low-grade coals such as brown coal are transformed on the spot, by pipe network, outwards carry, the utilization of resources is reasonable, freight is saved, and tallies with the national condition.In recent years, China starts the upsurge of synthetic natural gas, utilizes external more ripe technology, builds large-scale from coal synthetic natural gas enterprise.Once there was the experience of production city methanation coal gas in China, but to how to prepare high-temperature catalyst and synthesize expeditiously the natural gas of high concentration, also lacked ripe technology and experience.Research and development have high performance synthetic natural gas methanation catalyst and the reaction process of China's independent intellectual property right, and alternative foreign technology is the needs of development China synthetic natural gas industry.Existing catalyst performance is desirable not enough, and some catalyst resistances to elevated temperatures are poor, can only at lower temperature, move, and are unfavorable for the recycling of reaction heat, and stability is also good not.As Chinese patent CN1043639A, CN101468311A etc.BP GB 1546774 (A) " methanation catalyst " active component is nickel oxide and molybdenum oxide, employing is by nickel nitrate and nitric acid molybdenum and the mixed slurry of aluminium hydroxide, adopt precipitating reagent coprecipitated nickel hydroxide and molybdenum Kaolinite Preparation of Catalyst presoma, then through roasting, prepare methanation catalyst, this catalyst can stable operation at 600 ℃, but serviceability temperature is on the low side and the life-span is shorter.
Though Chinese patent CN101890353A and CN101920208A be nickel-base catalyst and can at high temperature using both, need the checking of commercial Application.In view of above problem, to being sought after from the development of synthesis gas high-temperature methanation preparing natural gas catalyst.
Summary of the invention
In order to overcome problems of the prior art, the invention provides a kind of high temperature resistant synthetic natural gas methanation catalyst and preparation method thereof, this catalyst should be used cheap base metal to do active component, the exotic material of selecting conventional support oxide mixed calcining to make is done carrier, add appropriate rare earth oxide auxiliary agent and alkaline earth oxide auxiliary agent further to improve the activity of catalyst, selective and high-temperature stability, make the catalyst can be at long-time steady operation under high temperature and high pressure.
The technical solution used in the present invention is: it is that the active component of 15-60% is, the auxiliary agent of the carrier of 30-70% and 3-20% that a kind of high temperature resistant synthetic natural gas methanation catalyst comprises mass percent, active component is the oxide of Ni, Cr and Mo, wherein to account for the mass percent of catalyst be 12-50% to Ni oxide, the mass percent that Cr oxide accounts for catalyst is 2-8%, and the mass percent that Mo oxide accounts for catalyst is 2-8%; Carrier is Al
2o
3, ZrO
2, TiO
2and SiO
2, auxiliary agent is rare earth La
2o
3, CeO
2, Nd
2o
3, Sm
2o
3in one or more, or one or more in alkaline-earth metal MgO, CaO, SrO, BaO.
The preparation method of described a kind of high temperature resistant synthetic natural gas methanation catalyst comprises the following steps:
(1) prepare the soluble-salt solution of described active component Ni, Cr and Mo, concentration is 1.0-3.0 mol/L, adopts the active component of precipitating reagent preparation precipitation, then filters, dries, washing, roasting, sintering temperature is 400-800 ℃, preparation active component powder;
(2) by described carrier A l
2o
3, ZrO
2, TiO
2and SiO
2in two or more the powder of hydroxide, carbonate or bicarbonate mix, after 800-1100 ℃ of roasting as support powder;
(3) described active component powder, support powder, auxiliary agent are mixed, compression molding, then at 500-800 ℃ calcining after make high temperature resistant methanation catalyst.
Described precipitating reagent is NaOH, sodium carbonate, sodium acid carbonate, ammonium carbonate, ammoniacal liquor or oxalic acid.
Described auxiliary agent adds with the form of nitrate, carbonate, bicarbonate, acetate or oxalates.
The invention has the beneficial effects as follows: the feature of this high temperature resistant synthetic natural gas methanation catalyst and preparation method thereof is to do active component with cheap base metal, the exotic material of selecting conventional support oxide mixed calcining to make is done carrier, add appropriate rare earth oxide auxiliary agent and alkaline earth oxide auxiliary agent further to improve the activity of catalyst, selective and high-temperature stability, make the catalyst can be at long-time steady operation under high temperature and high pressure.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
By 73.2 grams of Ni (NO
3)
2, 12.52 grams of Cr (NO
3)
3, 9.4 grams of Mo (NO
3)
3be dissolved in 500 grams of water wiring solution-forming A; Prepare the sodium carbonate liquor B of 2 mol/L; B is splashed in A under stirring, to pH=10.0, then filter, wash, dry the active component powder that roasting obtained after 3 hours at 400 ℃.
Get 61.2 grams of Al (OH)
3, 12.9 grams of Zr (OH)
4after mixing, at 1000 ℃, roasting is 5 hours, makes catalyst carrier.
Get 11.9 grams of La (NO
3)
3, 17.6 grams of Ca (NO
3)
2be dissolved in suitable quantity of water, this solution is mixed with catalyst activity powder and the catalyst carrier of above-mentioned preparation, compressing tablet, dries, and at 600 ℃, roasting is 5 hours, makes high temperature resistant methanation catalyst sample 1.
The methanation reaction evaluation result of catalyst is in Table 1.
Embodiment 2
By 146.4 grams of Ni (NO
3)
2, 6.28 grams of Cr (NO
3)
3, 18.8 grams of Mo (NO
3)
3be dissolved in 800 grams of water wiring solution-forming A; The sodium hydroxide solution B of preparation 1mol/L; In B being splashed into A under stirring, to pH=10.0, then filter, wash, dry, at 400 ℃, roasting obtains active component powder after 3 hours.
Get 24.5 grams of Al (OH)
3, 12.9 grams of Zr (OH)
4after mixing, at 1100 ℃, roasting is 5 hours, makes catalyst carrier.
Get 11.9 grams of La (NO
3)
3, 17.6 grams of Ca (NO
3)
2be dissolved in suitable quantity of water, this solution is mixed with catalyst activity powder and the catalyst carrier of above-mentioned preparation, compressing tablet, dries, and at 600 ℃, roasting is 5 hours, makes high temperature resistant methanation catalyst sample 2.Evaluation result is in Table 1.
Embodiment 3
By 73.2 grams of Ni (NO
3)
2, 12.9 grams of Cr (NO
3)
3, 9.4 grams of Mo (NO
3)
3be dissolved in 500 grams of water wiring solution-forming A; The sodium carbonate liquor B of preparation 2mol/L; In B being splashed into A under stirring, to pH=10.0, then filter, wash, dry, at 400 ℃, roasting obtains active component powder after 3 hours, standby;
Get 24.5 grams of Al (OH)
3, 25.8 grams of Zr (OH)
4, get 12 grams of Ti (OH)
3, 10 grams of SiO
2after mixing, at 1000 ℃, roasting is 5 hours, makes catalyst carrier, standby;
Get 11.9 grams of La (NO
3)
3, 17.6 grams of Ca (NO
3)
2be dissolved in suitable quantity of water, this solution is mixed with catalyst activity powder and the catalyst carrier of above-mentioned preparation, compressing tablet, dries, and at 700 ℃, roasting is 5 hours, makes high temperature resistant methanation catalyst sample 3.Evaluation result is in Table 1.
Embodiment 4
By 52.0 grams of NiCl
2, 8.34 grams of CrCl
3, 6.8 grams of MoCl
3be dissolved in 500 grams of water wiring solution-forming A; The ammonia spirit B of preparation 4mol/L; In B being splashed into A under stirring, to pH=10.0, then filter, wash, dry, at 450 ℃, roasting obtains active component powder after 3 hours.
Get 24.5 grams of Al (OH)
3, 12.9 grams of Zr (OH)
4, get 12.0 grams of Ti (OH)
3, 10.0 grams of SiO
2after mixing, at 900 ℃, roasting is 6 hours, makes catalyst carrier.
Get 5.81 grams of La (CH
3cOO)
3, 21.3 grams of Mg (NO
3)
2, 11.1 grams of Ce (CH
3cOO)
3be dissolved in suitable quantity of water, this solution is mixed with catalyst activity powder and the catalyst carrier of above-mentioned preparation, compressing tablet, dries, and at 600 ℃, roasting is 4 hours, makes high temperature resistant methanation catalyst sample 4.Evaluation result is in Table 1.
Evaluating catalyst condition:
Unstripped gas is H
2: CO:CO
2: CH
4: N
2: H
2o=52:6.5:4.2:16:5.2:20, reaction pressure is 3.0 MPa, air speed is 20000h
-1.
Table 1 catalyst performance evaluation
| Numbering | Light-off temperature ℃ | Hot(test)-spot temperature ℃ | CO conversion ratio % | CO 2Conversion ratio % |
| Sample 1 | 245 | 632 | 91.2 | 81.3 |
| Sample 2 | 228 | 641 | 89.9 | 82.6 |
| Sample 3 | 234 | 635 | 91.5 | 81.9 |
| Sample 4 | 238 | 645 | 88.9 | 79.8 |
From evaluating catalyst result, the catalyst that adopts the method to prepare has lower light-off temperature, and the activity of catalyst is higher, CO and CO
2conversion ratio approach the equilibrium conversion under hot(test)-spot temperature.Catalyst has good high temperature resistant methanation performance.
Claims (3)
1. the preparation method of a high temperature resistant synthetic natural gas methanation catalyst, it is that the active component of 15-60% is, the auxiliary agent of the carrier of 30-70% and 3-20% that described catalyst comprises mass percent, active component is the oxide of Ni, Cr and Mo, wherein to account for the mass percent of catalyst be 12-50% to Ni oxide, the mass percent that Cr oxide accounts for catalyst is 2-8%, and the mass percent that Mo oxide accounts for catalyst is 2-8%; Carrier is Al
2o
3, ZrO
2, TiO
2, SiO
2in two or more, auxiliary agent is rare earth La
2o
3, CeO
2, Nd
2o
3, Sm
2o
3in one or more, and one or more in alkaline-earth metal MgO, CaO, SrO, BaO; It is characterized in that: described preparation method comprises the following steps:
(1) prepare the soluble-salt solution of described active component Ni, Cr and Mo, concentration is 1.0-3.0 mol/L, adopts the active component of precipitating reagent preparation precipitation, then filters, dries, washing, roasting, sintering temperature is 400-800 ℃, preparation active component powder;
(2) by described carrier A l
2o
3, ZrO
2, TiO
2, SiO
2in two or more the powder of hydroxide, carbonate or bicarbonate mix, after 800-1100 ℃ of roasting as support powder;
(3) described active component powder, support powder, auxiliary agent are mixed, compression molding, then at 500-800 ℃ calcining after make high temperature resistant methanation catalyst.
2. the preparation method of a kind of high temperature resistant synthetic natural gas methanation catalyst according to claim 1, is characterized in that: described precipitating reagent is NaOH, sodium carbonate, sodium acid carbonate, ammonium carbonate, ammoniacal liquor or oxalic acid.
3. the preparation method of a kind of high temperature resistant synthetic natural gas methanation catalyst according to claim 1, is characterized in that: described auxiliary agent adds with the form of nitrate, carbonate, bicarbonate, acetate or oxalates.
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| WO2014158095A1 (en) * | 2013-03-28 | 2014-10-02 | Agency For Science, Technology And Research | Methanation catalyst |
| CN104107715B (en) * | 2013-04-16 | 2017-10-27 | 华东理工大学 | Mix metal and/or the silica composite of its oxide and application thereof in original position |
| SG2013050877A (en) | 2013-06-28 | 2015-01-29 | Agency Science Tech & Res | Methanation catalyst |
| CN103480381A (en) * | 2013-09-22 | 2014-01-01 | 大连瑞克科技有限公司 | Methanation catalyst with high nickel oxide content and preparation method thereof |
| CN103706370B (en) * | 2013-12-17 | 2015-09-09 | 西南化工研究设计院有限公司 | A kind of coal gas high-temperature methanation catalyst and preparation method thereof |
| CN103721720B (en) * | 2013-12-25 | 2016-04-20 | 南京国昌化工科技有限公司 | Methane synthesizing catalyst that double rare-earth elements promotes and preparation method thereof and application |
| CN105344355A (en) * | 2014-08-20 | 2016-02-24 | 中国石油化工股份有限公司 | Catalyst for preparing methane from coal-based synthetic gas, and preparation method thereof |
| CN105854889B (en) * | 2016-04-15 | 2019-01-15 | 西安向阳航天材料股份有限公司 | A kind of high temperature resistant methanation catalyst and preparation method thereof |
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| CN114931942B (en) * | 2022-05-09 | 2024-01-19 | 太原理工大学 | Preparation method and application of coal mine ventilation air methane combustion catalyst |
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