CN102527401A - 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 PDF

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CN102527401A
CN102527401A CN201010613450XA CN201010613450A CN102527401A CN 102527401 A CN102527401 A CN 102527401A CN 201010613450X A CN201010613450X A CN 201010613450XA CN 201010613450 A CN201010613450 A CN 201010613450A CN 102527401 A CN102527401 A CN 102527401A
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catalyst
methane
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weight
reaction
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CN102527401B (en
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刘勇
刘中民
朱文良
刘洪超
孟霜鹤
李利娜
刘世平
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Dalian Institute of Chemical Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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

A kind of synthesis gas that is used for transforms catalyst, its preparation and the application of producing methane and co-producing light olefins
Technical field
The invention belongs to the catalytic chemistry field, relate to synthesis gas and transform system methane, and co-producing light olefins, a kind of catalyst that is used for low temperature synthesizing methane and co-producing light olefins, Preparation of catalysts and application thereof are provided especially.
Background technology
Enforcement along with policies such as China's strategy of sustainable development and reinforcement environmental protection; Domestic demand to natural gas increases substantially; Domestic gas production can not be met the need of market fully; Imbalance between supply and demand is outstanding, therefore must be by all kinds of means, multimode enlarges resource provision, satisfies the growing market demand.Be based on the energy resource structure characteristics of the rich coal of China's oil starvation weak breath simultaneously, development coal preparing natural gas is one of feasible mode.In the process that coal transforms, the highest coal utilization mode of the 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 2Discharging, alleviate environmental pollution.In addition, coal preparing natural gas pipeline is on a large scale carried, and has increased its transportation and the security of 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 at present technology has Top's rope methanation circulation technology (TREMPTM) technology, 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 benefit through synthesis gas system methane, is still waiting the actual production checking.Coal system synthetic natural gas industry has just begun to have characteristics such as investment has a big risk greatly; If can realize the coproduction of coal system synthetic natural gas and coal gasification through multiple coal-based chemical products such as synthesis gas system methyl alcohol, alkene, oil product, synthetic ammonia; Can increase the ability to ward off risks of coal system synthetic natural gas project; Realize multiple coal-based chemical products mutual supplement with each other's advantages, effectively improve the economic benefit and the whole ability to ward off risks of coal preparing natural gas project.In addition, China's gas usefulness gas is very unbalanced, and northern area consumption in winter is big, and it is few that non-heating season is saved gas, and peaking problem is very serious.Except adopting peak regulation means such as underground natural gas storage tank, gas peak regulation generating or LNG; Also can carry out peak regulation with coal system synthetic natural gas factory; Be that coal preparing natural gas factory produces natural gas winter, other seasons can coproduction products such as part methyl alcohol, alkene, oil product, synthetic ammonia.
In sum, coal gasification is through synthesis gas system methane and coproduction alcohol, alkene, oil product, synthetic ammonia etc., and the research and development of catalyst and technology have very big practicality and application prospect.
Summary of the invention
The object of the present invention is to provide a kind ofly, comprise Preparation of catalysts and application thereof, the screening of reaction condition from the catalyst and the reaction process of coal gasification through synthesis gas system methane and co-producing light olefins.
Main advantage of the present invention is: the present invention goes back the low-carbon alkene of coproduction high added value except synthesis gas is converted into methane.Compare with full methanation technology, can reduce the industry risk, operate more flexibly, can realize bigger economic and social benefit.This is the maximum difference that the catalyst based and existing full methanation technology of loading type iron provided by the invention exists.
The present invention through the reactor reaction of ferrum-based catalyst is housed, produces methane and co-producing light olefins with synthesis gas; Said ferrum-based catalyst consist of ACuFe 2O 3/ B, its active component is an 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 the perhaps any several kinds mixing among Mn, K, Ze, the Ce, in metal oxide, accounts for the 0.3-10.0wt% of total catalyst weight; Catalyst promoter Cu accounts for the 1.5-8.0wt% of total catalyst weight in metal oxide; Carrier B is SiO 2, Al 2O 3, any one or any several kinds mixing among the ZrO, MgO, content is the 40.0-85.0wt% of total catalyst weight.
Ferrum-based catalyst according to the invention is before reaction, earlier with CO and/or H 2Gas reduces processing to it.
The condition of handling of reducing before the ferrum-based catalyst reaction according to the invention is: temperature 250-500 ℃, and pressure 0.1-1.5MPa, reduction processing time 5-18h.
H in the synthesis gas according to the invention 2With the mol ratio of CO be 2.0-6.0.
It is 300 ℃≤t≤500 ℃ that synthesis gas according to the invention transforms the reaction temperature t that produces methane and co-producing light olefins, 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 according to the invention is that carbon number is not more than any one or any several kinds mixing in 20 the alkene in the molecule.
Low-carbon alkene according to the invention is that carbon number is not more than any one or any several kinds mixing in 4 the alkene in the molecule.
The selectivity of low-carbon alkene according to the invention in product is 5.0%-50.0%.
The selectivity of low-carbon alkene according to the invention in product is 5.0%-40.0%.
Active component Fe according to the invention 2O 3In metal oxide, account for the 20.0-30.0wt% of total catalyst weight.
Co-catalyst A according to the invention accounts for the 3.5-8.0wt% of total catalyst weight in metal oxide.
Auxiliary agent Cu content according to the invention accounts for the 2.5-5.0wt% of total catalyst weight in metal oxide;
Carrier B content according to the invention is the 50.0-75.0wt% of total catalyst weight;
Catalyst according to the invention adopts immersion process for preparing, may further comprise the steps:
A) press each components by weight in the catalyst, the aqueous solution that will contain the said metal ion of component A supports on carrier B, 40-100 ℃ of water bath method mother liquor;
B) press each components by weight in the catalyst, iron, copper mixed nitrate aqueous solution impregnated in step a) gained sample, 40-100 ℃ of water bath method mother liquor, 80-150 ℃ of drying and 400-800 ℃ calcination process 1-20 hour obtain described catalyst
Advantage of the present invention is, adopts cheap raw material, utilizes simple infusion process, has prepared the catalyst of methanation of a kind of synthesis gas part and 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 and whole opposing risk ability of coal preparing natural gas project.
Description of drawings:
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) the methanation reaction performance in the different temperatures lower part.(350 ℃ of activation temperatures, soak time 12h, reaction pressure 1.5MPa, the unstripped gas mole is formed: 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) the methanation reaction performance in the different pressures lower part.(350 ℃ of activation temperatures, soak time 12h, 400 ℃ of reaction temperatures, the unstripped gas mole is formed: 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) the methanation reaction performance in different volumes air speed lower part.(350 ℃ of activation temperatures, soak time 12h, 400 ℃ of reaction temperatures, reaction pressure 1.5MPa, the unstripped gas mole is formed: Ar/CO/H 2=3.2/17.6/79.2).
The specific embodiment
Embodiment 1: method for preparing catalyst
With 2.9872g Mn (NO 3) 24H 2O, 0.1801g KNO 3Be dissolved in the 30ml deionized water, adopt infusion process to be impregnated into 8.0g SiO to this mixed aqueous solution 2On the carrier, 60 ℃ of water-baths evaporate excessive solvent.With 14.4278g Fe (NO 3) 39H 2O, 1.2347g Cu (NO 3) 23H 2O is dissolved in the 30ml deionized water, supports this mixed aqueous solution in the above-mentioned sample 60 ℃ of excessive solvents of water-bath evaporation.The gained sample is dry 12h in 120 ℃ of baking ovens, and dry back sample places 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 2With the catalyst sample granulation, granularity is the 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 oven temperature, degree: 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 oven temperature, degree: 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: the evaluating catalyst method
Reaction volume air speed according to the invention is defined as reacting gas raw material (butt) and per hour gets into the volume of the volume flow of reaction system divided by catalyst.Represent that with GHSV unit is h -1
0.5ml 20-40 order catalyst sample 1 is fully mixed with 0.5ml 25-50 purpose quartz sand, put into the fixed bed reactors flat-temperature zone.Before the reaction, catalyst is carried out online reduction, reduction temperature is 350 ℃, and pressure 0.1MPa, reducing gas are that the unstripped gas synthesis gas (form: Ar/CO/H by the unstripped gas mole 2=3.2/17.6/79.2), recovery time 12h.After reduction finishes, regulate temperature controller and counterbalance valve and make reaction temperature and pressure branch be clipped to 400 ℃ and 1.5MPa, quality of regulation flowmeter flow is 30ml/min (status of criterion), after temperature and pressure is stable, begins reaction.The product on-line analysis, per hour sampling once.The inlet from reactor outlet to the gas-chromatography ten-way valve, all pipelines and counterbalance valve all carry out heat tracing.Reaction result such as Fig. 1～shown in Figure 3.

Claims (10)

1. one kind is used for the catalyst that methane and co-producing light olefins are produced in the synthesis gas conversion, it is characterized in that, is to form ACuFe 2O 3The ferrum-based catalyst that/B is represented, its active component are 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 any one the perhaps any several kinds mixing among Mn, K, Ze, the Ce, in metal oxide, accounts for the 0.3-10.0wt% of total catalyst weight;
Catalyst promoter Cu accounts for the 1.5-8.0wt% of total catalyst weight in metal oxide;
Carrier B is SiO 2, Al 2O 3, any one or any several kinds mixing among the ZrO, MgO, content is the 40.0-85.0wt% of total catalyst weight.
2. according to the described catalyst of claim 1, it is characterized in that: said active component Fe 2O 3In metal oxide, account for the 20.0-30.0wt% of total catalyst weight.
3. according to the described catalyst of claim 1, it is characterized in that: said co-catalyst A accounts for the 3.5-8.0wt% of total catalyst weight in metal oxide.
4. according to the described catalyst of claim 1, it is characterized in that: said auxiliary agent Cu content accounts for the 2.5-5.0wt% of total catalyst weight in metal oxide;
5. according to the described catalyst of claim 1, it is characterized in that: said carrier B content is the 50.0-75.0wt% of total catalyst weight;
6. according to the said Preparation of catalysts method of claim 1, it is characterized in that said catalyst adopts immersion process for preparing, may further comprise the steps:
A) by the weight ratio of each component in the said catalyst, the aqueous solution that will contain the said metal ion of component A supports on carrier B, 40-100 ℃ of water bath method mother liquor;
B) by the weight ratio of each component in the said catalyst, iron, copper mixed nitrate aqueous solution impregnated in step a) gained sample, 40-100 ℃ of water bath method mother liquor, 80-150 ℃ of drying and 400-800 ℃ of calcination process 1～20 hour obtain described catalyst.
7. a synthesis gas transforms the method for producing methane and co-producing light olefins, it is characterized in that, synthesis gas through the reactor reaction of the said ferrum-based catalyst of claim 1 is housed, is produced methane and co-producing light olefins; It is 300 ℃≤t≤500 ℃ that said synthesis gas transforms the reaction temperature t that produces methane and co-producing light olefins, and reaction pressure P is 0.5MPa≤P≤4.0MPa, and reaction volume air speed GHSV is 800h -1≤GHSV≤15000h -1
8. according to the described method of claim 1, it is characterized in that said low-carbon alkene is mixing that carbon number is not more than any one or several kinds in 4 the alkene in the molecule, the selectivity of said low-carbon alkene in product is 5.0%-40.0%.
9. according to claim 6,7 or 8 described methods, it is characterized in that said ferrum-based catalyst is before reaction, earlier with CO and/or H 2Gas reduces processing to it, and the condition that reduction is handled is: temperature 250-500 ℃, and pressure 0.1-1.5MPa, reduction processing time 5-18h.
10. according to claim 6,7 or 8 described methods, it is characterized in that H in the said synthesis gas 2With the mol ratio of CO be 2.0-6.0.
CN201010613450.XA 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 Expired - Fee Related CN102527401B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105080561A (en) * 2014-05-05 2015-11-25 中国石油化工股份有限公司 Supported iron-based catalyst and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2017518170A (en) * 2014-04-21 2017-07-06 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 Structured iron-based catalyst for the production of α-olefins from synthesis gas, and the preparation and use thereof
CN105080561A (en) * 2014-05-05 2015-11-25 中国石油化工股份有限公司 Supported iron-based catalyst and preparation method thereof

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