CN102527401B - Catalyst used in preparation of methane and coproduction of low-carbon olefin by conversion of syngas, preparation method for catalyst and application of catalyst - Google Patents
Catalyst used in preparation of methane and coproduction of low-carbon olefin by conversion of syngas, preparation method for catalyst and application of catalyst Download PDFInfo
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- CN102527401B CN102527401B CN201010613450.XA CN201010613450A CN102527401B CN 102527401 B CN102527401 B CN 102527401B CN 201010613450 A CN201010613450 A CN 201010613450A CN 102527401 B CN102527401 B CN 102527401B
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Abstract
The invention discloses a catalyst for reaction in the process of preparing methane and coproducing low-carbon olefin by using syngas, a preparation method for the catalyst and a process for synthesizing the methane. The composition of the catalyst is ACuFe2O3/B, wherein an active ingredient is ferric oxide, and the active ingredient accounts for 15.0 to 40.0 percent of the total weight of the catalyst; A is a cocatalyst, namely Mn, K, Zn or Fe, and the A accounts for 0.3 to 10.0 percent of the total weight of the catalyst; an aid Cu accounts for 1.5 to 8.0 percent of the total weight of the catalyst; and a carrier B is SiO2, Al2O3, ZrO or MgO, and the carrier B accounts for 40.0 to 85.0 percent of the total weight of the catalyst. The catalyst is prepared by an impregnation method and is obtained by the steps of: sequentially impregnating nitrates of the aid A, the aid Cu and the active ingredient Fe on the carrier B respectively, drying, and roasting at the temperature of between 400 and 800 DEG C. A raw material of the catalyst is the syngas, is wide in source and can be obtained from coal and biomass. The catalyst is low in cost and high in reaction activity, and is suitable for continuous large-scale production, and the preparation process is simple.
Description
Technical field
The invention belongs to catalytic chemistry field, relate to synthesis gas and transform methane processed, and co-producing light olefins, a kind of catalyst for low temperature synthesizing methane co-producing light olefins provided especially, the preparation of catalyst and application thereof.
Background technology
Along with the enforcement of the policies such as China's strategy of sustainable development and reinforcement environmental protection, the domestic demand to natural gas increases substantially, domestic natural gas is produced and can not be met the need of market completely, imbalance between supply and demand is outstanding, therefore must be by all kinds of means, multimode expands resource provision, meets the growing market demand.The energy resource structure feature of being simultaneously based on the rich coal of China's oil starvation weak breath, Development of Coal preparing natural gas is one of feasible mode.In the process transforming at coal, the highest coal utilization mode of energy efficiency of coal preparing natural gas, reaches 53%, not only can significantly reduce the consumption of coal, has also reduced SO simultaneously
2, CO
2discharge, alleviate environmental pollution.In addition, coal preparing natural gas on a large scale pipeline is carried, and has increased its transportation and the security using.
It is a mature technology that coal gasification is turned to methane (synthetic natural gas) through synthetic cyclostrophic, and 1 ton of coal can be converted into 400m
3synthetic natural gas, ripe technique has Top's rope methanation circulation technology (TREMPTM) technology at present, DAVY company methanation technology (CRG), also there are ripe methanation technology in BASF AG and LURGI.Domestic quite familiar to methanation technology.
Coal gasification will obtain good economic benefits through preparing methane by synthetic gas, need actual production checking.Coal synthetic natural gas industry processed has just started to have the features such as investment Risks is large, if realize the coproduction through multiple coal-based chemical products such as synthesising gas systeming carbinol, alkene, oil product, synthetic ammonia of coal synthetic natural gas processed and coal gasification, can increase the ability to ward off risks of coal synthetic natural gas project processed, realize multiple coal-based chemical products and have complementary advantages, effectively improve economic benefit and the overall ability to ward off risks of coal preparing natural gas project.In addition, China's gas use gas is very unbalanced, and northern area consumption in winter is large, and it is few that non-heating season is saved gas, and peaking problem is very serious.Except adopting the peak regulation means such as underground natural gas storage tank, gas peak regulation generating or LNG, also can carry out peak regulation with Mei Zhi synthetic natural gas factory, Ji Mei preparing natural gas factory produces natural gas winter, other seasons can coproduction the product such as part methyl alcohol, alkene, oil product, synthetic ammonia.
In sum, coal gasification is through preparing methane by synthetic gas coproduction alcohol, alkene, oil product, synthetic ammonia etc., and the research and development of catalyst and technique have very large practicality and application prospect.
Summary of the invention
The object of the present invention is to provide a kind of from coal gasification catalyst and the reaction process through preparing methane by synthetic gas co-producing light olefins, comprise preparation and the application thereof of catalyst, the screening of reaction condition.
Main advantage of the present invention is: the present invention, except synthesis gas is converted into methane, goes back the low-carbon alkene of coproduction high added value.Compared with full methanation technique, can reduce industry risk, operate more flexibly, can realize larger economic and social benefit.This is the maximum difference that loading type iron provided by the invention is catalyst based and existing full methanation technology exists.
The present invention by the reactor reaction of ferrum-based catalyst is housed, produces methane co-producing light olefins by synthesis gas; Described ferrum-based catalyst consist of ACuFe
2o
3/ B, its active component is iron oxide, component A and Cu are catalyst promoter, wherein, active component Fe
2o
3in metal oxide, account for the 15.0-40.0wt% of total catalyst weight; Component A is any one or the arbitrarily several mixing in Mn, K, Ze, Ce, in metal oxide, accounts for the 0.3-10.0wt% of total catalyst weight; Catalyst promoter Cu, in metal oxide, accounts for the 1.5-8.0wt% of total catalyst weight; Carrier B is SiO
2, Al
2o
3, any one or several mixing arbitrarily in ZrO, MgO, the 40.0-85.0wt% that content is total catalyst weight.
Ferrum-based catalyst of the present invention, before reaction, is first used CO and/or H
2gas reduces processing to it.
The condition of processing of reducing before ferrum-based catalyst reaction of the present invention is: temperature 250-500 ℃, pressure 0.1-1.5MPa, reduction processing time 5-18h.
H in synthesis gas of the present invention
2with the mol ratio of CO be 2.0-6.0.
The reaction temperature t that methane co-producing light olefins are produced in synthesis gas conversion of the present invention is 300 ℃≤t≤500 ℃, and reaction pressure P is 0.5MPa≤P≤4.0MPa, and reaction volume air speed GHSV is 800h-1≤GHSV≤15000h-1.
Low-carbon alkene of the present invention is that in molecule, carbon number is not more than any one or several mixing arbitrarily in 20 alkene.
Low-carbon alkene of the present invention is that in molecule, carbon number is not more than any one or several mixing arbitrarily in 4 alkene.
Selective in product of low-carbon alkene of the present invention is 5.0%-50.0%.
Selective in product of low-carbon alkene of the present invention is 5.0%-40.0%.
Active component Fe of the present invention
2o
3in metal oxide, account for the 20.0-30.0wt% of total catalyst weight.
Co-catalyst A of the present invention, in metal oxide, accounts for the 3.5-8.0wt% of total catalyst weight.
Auxiliary agent Cu content of the present invention, in metal oxide, accounts for the 2.5-5.0wt% of total catalyst weight;
The 50.0-75.0wt% that carrier B content of the present invention is total catalyst weight;
Catalyst of the present invention adopts infusion process preparation, comprises the following steps:
A) press each components by weight in catalyst, support in carrier B 40-100 ℃ of water bath method mother liquor by containing the aqueous solution of metal ion described in component A;
B) press each components by weight in catalyst, iron, copper mixed nitrate aqueous solution be impregnated in to a) gained sample of step, 40-100 ℃ of water bath method mother liquor, 80-150 ℃ of dry and 400-800 ℃ of calcination process 1-20 hour, obtains described catalyst
Advantage of the present invention is, adopts cheap raw material, utilizes simple infusion process, has prepared the catalyst of the methanation of a kind of synthesis gas part co-producing light olefins.Because synthesis gas can obtain from coal gasification, thereby can realize the coproduction of coal preparing natural gas and other multiple Coal Chemical Industry product, reach multiple coal-based chemical products and have complementary advantages, effectively improve the economic benefit of coal preparing natural gas project and the ability of entirety opposing risk.
Accompanying drawing explanation:
Fig. 1 is catalyst sample 1 (6.9% MnO-0.7% K
2o-3.3% CuO-23.4%Fe
2o
3/ 65.7%SiO
2) part methanation reaction performance under different temperatures.(350 ℃ of activation temperatures, soak time 12h, reaction pressure 1.5MPa, unstripped gas mole composition: Ar/CO/H
2=3.2/17.6/79.2, volume space velocity 1800h
-1);
Fig. 2 is catalyst sample 1 (6.9% MnO-0.7% K
2o-3.3% CuO-23.4%Fe
2o
3/ 65.7%SiO
2) part methanation reaction performance under different pressures.(350 ℃ of activation temperatures, soak time 12h, 400 ℃ of reaction temperatures, unstripped gas mole composition: Ar/CO/H
2=3.2/17.6/79.2, volume space velocity 1800h
-1);
Fig. 3 is catalyst sample 1 (6.9% MnO-0.7% K
2o-3.3% CuO-23.4%Fe
2o
3/ 65.7% SiO
2) part methanation reaction performance under different volumes air speed.(350 ℃ of activation temperatures, soak time 12h, 400 ℃ of reaction temperatures, reaction pressure 1.5MPa, unstripped gas mole composition: Ar/CO/H
2=3.2/17.6/79.2).
The specific embodiment
Embodiment 1: method for preparing catalyst
By 2.9872g Mn (NO
3)
24H
2o, 0.1801g KNO
3be dissolved in 30ml deionized water, adopt infusion process that this mixed aqueous solution is impregnated into 8.0g SiO
2on carrier, 60 ℃ of water-baths evaporate excessive solvent.By 14.4278g Fe (NO
3)
39H
2o, 1.2347g Cu (NO
3)
23H
2o is dissolved in 30ml deionized water, and this mixed aqueous solution is supported in above-mentioned sample, and excessive solvent is evaporated in 60 ℃ of water-baths.Gained sample is dry 12h in 120 ℃ of baking ovens, and dry rear sample is placed in Muffle furnace, is warmed up to 400 ℃ with the heating rate of 2 ℃/min, and roasting 2h, obtains final catalyst.Gained catalyst (sample 1) consists of 6.9% MnO-0.7% K
2o-3.3% CuO-23.4% Fe
2o
3/ 65.7%SiO
2.By catalyst sample granulation, granularity is 20-40 order.
Embodiment 2: the analytical method of product
Chromatogram: Agilent 7890A
FID chromatographic column: HP-PLOT-Q 19091P-Q04,30mx0.32mm (internal diameter), 20 μ m thickness
Carrier gas: helium, 2ml/min
Post case temperature: 50 ℃-150 ℃, 30 ℃/min
150 ℃ keep 5min
150℃-270℃，20℃/min
270 ℃ keep 11.5min
Injection port: shunting (30: 1); Temperature: 250 ℃
Detector: FID; Temperature: 300 ℃
TCD chromatographic column: carbon molecular sieve post, TDX-01 2mx2mm (internal diameter)
Carrier gas: helium, 23ml/min
Post case temperature: 50 ℃-150 ℃, 30 ℃/min
150 ℃ keep 5min
150℃-270℃，20℃/min
270 ℃ keep 11.5min
Injection port: dottle pin purges injection port; Temperature: 250 ℃
Detector: TCD; Temperature: 300 ℃
Embodiment 3: evaluating catalyst method
Reaction volume air speed of the present invention is defined as reacting gas raw material (butt) volume flow of reaction system that enters per hour divided by the volume of catalyst.Represent with GHSV, unit is h
-1.
0.5ml 20-40 order catalyst sample 1 is fully mixed with 0.5ml 25-50 object quartz sand, put into fixed bed reactors flat-temperature zone.Before reaction, catalyst is reduced online, reduction temperature is 350 ℃, pressure 0.1MPa, and reducing gas is unstripped gas synthesis gas (unstripped gas mole composition: Ar/CO/H
2=3.2/17.6/79.2), recovery time 12h.After reduction finishes, regulate temperature controller and counterbalance valve that reaction temperature and pressure are divided and be clipped to 400 ℃ and 1.5MPa, quality of regulation flowmeter flow is 30ml/min (status of criterion), starts reaction after temperature and pressure is stable.Product on-line analysis, sampling per hour once.From reactor outlet to gas-chromatography ten-way valve entrance, all pipelines and counterbalance valve all carry out heating and thermal insulation.Reaction result as shown in FIG. 1 to 3.
Claims (10)
1. a catalyst of producing methane co-producing light olefins for the synthesis of cyclostrophic, is characterized in that, is to form ACuFe
2o
3the ferrum-based catalyst that/B is represented, its active component is Fe
2o
3, component A and Cu are catalyst promoter, wherein,
Active component Fe
2o
3in metal oxide, account for the 15.0-40.0wt% of total catalyst weight;
Component A is the mixing of two kinds in Mn, K, in metal oxide, accounts for the 0.3-10.0wt% of total catalyst weight;
Catalyst promoter Cu, in metal oxide, accounts for the 1.5-8.0wt% of total catalyst weight;
Carrier B is SiO
2, Al
2o
3, any one or several mixing arbitrarily in ZrO, MgO, the 40.0-85.0wt% that content is total catalyst weight,
Described low-carbon alkene is that in molecule, carbon number is not more than any one or several mixing arbitrarily in 4 low-carbon alkene,
The content sum of all compositions of described catalyst is 100wt%.
2. according to catalyst claimed in claim 1, it is characterized in that: described active component Fe
2o
3in metal oxide, account for the 20.0-30.0wt% of total catalyst weight.
3. according to catalyst claimed in claim 1, it is characterized in that: described co-catalyst A, in metal oxide, accounts for the 3.5-8.0wt% of total catalyst weight.
4. according to catalyst claimed in claim 1, it is characterized in that: described auxiliary agent Cu content, in metal oxide, accounts for the 2.5-5.0wt% of total catalyst weight;
5. according to catalyst claimed in claim 1, it is characterized in that: the 50.0-75.0wt% that described carrier B content is total catalyst weight;
6. according to the preparation method of catalyst described in claim 1, it is characterized in that, described catalyst adopts infusion process preparation, comprises the following steps:
A), by the weight ratio of each component in described catalyst, support in carrier B 40-100 ℃ of water bath method mother liquor by containing the aqueous solution of metal ion described in component A;
B) by the weight ratio of each component in described catalyst, iron, copper mixed nitrate aqueous solution be impregnated in to step a) gained sample, 40-100 ℃ of water bath method mother liquor, 80-150 ℃ of dry and 400-800 ℃ of calcination process 1～20 hour, obtains described catalyst.
7. synthesis gas transforms the method for methane co-producing light olefins produced, and it is characterized in that, synthesis gas, by the reactor reaction of ferrum-based catalyst described in claim 1 is housed, is produced to methane co-producing light olefins; The reaction temperature t that methane co-producing light olefins are produced in described synthesis gas conversion is 300 ℃≤t≤500 ℃, and reaction pressure P is 0.5MPa≤P≤4.0MPa, and reaction volume air speed GHSV is 800h
-1≤ GHSV≤15000h
-1.
8. in accordance with the method for claim 7, it is characterized in that, described low-carbon alkene is that in molecule, carbon number is not more than any one or several mixing in 4 alkene, and selective in product of described low-carbon alkene is 5.0%-40.0%.
9. according to the method described in claim 6,7 or 8, it is characterized in that, described ferrum-based catalyst, before reaction, is first used CO and/or H
2gas reduces processing to it, and the condition that reduction is processed is: temperature 250-500 ℃, pressure 0.1-1.5MPa, reduction processing time 5-18h.
10. according to the method described in claim 6,7 or 8, it is characterized in that H in described synthesis gas
2with the mol ratio of CO be 2.0-6.0.
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|---|---|---|---|
| CN201010613450.XA CN102527401B (en) | 2010-12-30 | 2010-12-30 | Catalyst used in preparation of methane and coproduction of low-carbon olefin by conversion of syngas, preparation method for catalyst and application of catalyst |
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|---|---|---|---|
| CN201010613450.XA CN102527401B (en) | 2010-12-30 | 2010-12-30 | Catalyst used in preparation of methane and coproduction of low-carbon olefin by conversion of syngas, preparation method for catalyst and application of catalyst |
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| CN102527401B true CN102527401B (en) | 2014-06-25 |
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| CN103949262A (en) * | 2014-04-21 | 2014-07-30 | 武汉凯迪工程技术研究总院有限公司 | Structured iron-based catalyst for preparing alpha-alkene by synthesis gas as well as preparation method and application of structured iron-based catalyst |
| CN105080561B (en) * | 2014-05-05 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of load-type iron-based catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559373A (en) * | 2008-01-23 | 2009-10-21 | 亚申科技研发中心（上海）有限公司 | Iron-based catalyst used for Fischer-Tropsch synthesis and preparation method thereof |
| CN101733121A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing hydrocarbon from carbon dioxide-containing synthesis gas, preparation method and application |
| CN102527399A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Iron-based catalyst for process of preparing methane and co-generating petroleum products by synthesis gas, preparation and application of iron-based catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559373A (en) * | 2008-01-23 | 2009-10-21 | 亚申科技研发中心（上海）有限公司 | Iron-based catalyst used for Fischer-Tropsch synthesis and preparation method thereof |
| CN101733121A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing hydrocarbon from carbon dioxide-containing synthesis gas, preparation method and application |
| CN102527399A (en) * | 2010-12-29 | 2012-07-04 | 中国科学院大连化学物理研究所 | Iron-based catalyst for process of preparing methane and co-generating petroleum products by synthesis gas, preparation and application of iron-based catalyst |
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