CN102527399B - Iron-based catalyst for process of preparing methane and co-generating petroleum products by synthesis gas, preparation and application of iron-based catalyst - Google Patents
Iron-based catalyst for process of preparing methane and co-generating petroleum products by synthesis gas, preparation and application of iron-based catalyst Download PDFInfo
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- CN102527399B CN102527399B CN201010610492.8A CN201010610492A CN102527399B CN 102527399 B CN102527399 B CN 102527399B CN 201010610492 A CN201010610492 A CN 201010610492A CN 102527399 B CN102527399 B CN 102527399B
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Abstract
The invention discloses a catalyst for reactions of preparing methane and co-generating petroleum products cogeneration by synthesis gas, preparation of the catalyst and technical conditions of methanation of and cogeneration of petroleum products of the synthesis gas. The catalyst has a formula of ABFeO/C, wherein an active component is FeO, and the content of metallic iron is 5.0-30.0 wt% of the total weight of the catalyst; an accessory ingredient A is composed of copper and manganese, and has the content of 0.01-5.0 wt% of the total weight of the catalyst; an accessory ingredient B comprises alkali metals of Li, Na, K and the like, and has the weight of 0.01-5.0 wt% of the total weight of the catalyst; and a carrier C comprises SiO2, ZrO, Al2O3, TiO2, active carbon and the like, and has the weight of 40.0 -95.0 wt% of the total weight of the catalyst. The catalyst is prepared by adopting an impregnation method through impregnating corresponding A, B, nitrates and ferric nitrate in a certain order on the carrier C, and roasting at 400-800 DEG C. The synthesis gas is adopted as the raw materials in the invention, and has wide resources; the catalyst has the advantages of low cost, simple preparation and high efficiency, can be adjusted according to requirements and is suitable for mass production.
Description
Technical field
The invention belongs to catalytic chemistry field, relate to synthesis gas and transform methane processed, and coproducing oil product, a kind of catalyst for low temperature synthesizing methane coproducing oil product provided especially, the preparation of catalyst and application thereof.
Background technology
Enforcement along with policies such as the domestic 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.Be based on the rich coal energy resource structure of China's oil starvation weak breath feature, Development of Coal preparing natural gas is one of feasible mode simultaneously.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, FE
2discharge, the pollution that alleviates environment.In addition, coal preparing natural gas can be carried on a large scale by pipeline, has increased its transportation and the security of using.
By gas reforming, be that methane (synthetic natural gas) is a mature technology, 1 ton of coal can be converted into 400m
3synthetic natural gas, ripe technique has Top's rope methanation circulation technology (TREMPTM) technology, DAVY company methanation technology (CRG) at present.Also there are ripe methanation technology in BASF AG and LURGI.Domestic comparatively familiar to methanation technology.
Whether at present, carrying out on a large scale preparing methane from coal has good economic benefit, need actual production checking.Preparing methane from coal industry has the features such as investment Risks is large.If can realize coal preparing natural gas, take coal as raw material with other, through the coproduction of the multiple Coal Chemical Industry product of synthesis gas system, can increase the ability to ward off risks of coal preparing natural gas project.Realize coal preparing natural gas and coal methyl alcohol processed, olefin hydrocarbon making by coal, coal liquefaction, the coproduction of the multiple coal-based product such as synthetic ammonia, will realize multiple coal-based product advantage complementary, effectively improves the economic benefit of coal preparing natural gas project and the ability of whole opposing risk.In addition, China's gas very unbalanced with gas, 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 Yong Mei preparing natural gas factory carry out peak regulation, that is to say that coal preparing natural gas factory produces natural gas winter, other seasons can coproduction part methyl alcohol, oil, alkene, the products such as synthetic ammonia.
Coal is through preparing methane by synthetic gas, and coproduction alcohol, oil, alkene, the technology catalyst of synthetic ammonia and the research and development of technique, has very large practicality and application prospect.
Summary of the invention
The object of the present invention is to provide a kind of preparing methane by synthetic gas coproducing oil product catalyst, its technology of preparing and application.
The present invention is except synthesis gas changes into methane, also coproduction is oily, and all synthesis gas are not converted into methane completely, also produce a certain amount of oil product, prior art is mainly converted into oil product synthesis gas, and this is the maximum difference that ferrum-based catalyst provided by the invention and prior art exist.
The present invention by the reactor reaction that supports ferrum-based catalyst is housed, produces methane coproducing oil product by synthesis gas.
Ferrum-based catalyst of the present invention consists of FeABO/C, and active component is iron oxide, and A, B are auxiliary agent, and C is carrier; Wherein:
Active component iron oxide, in metallic element, the content of Fe is 5.0-30.0wt%;
Auxiliary agent A is Cu and/or Mn, and in catalyst, its constituent content accounts for the 0.01-5.0wt% of total catalyst weight;
Auxiliary agent B is Li, Na, and any one in K or several mixing arbitrarily, in catalyst, its constituent content accounts for the 0.5-5.0wt% of total catalyst weight;
Support C is AL
2o
3, ZrO, SiO
2, TiO
2, any one in active carbon or several mixing arbitrarily, the content in catalyst is 40.0-95.0wt%.
The present invention uses the above-mentioned reaction condition that carries out preparing methane by synthetic gas coproducing oil product on ferrum-based catalyst that supports to be: reaction temperature T is 200≤T≤500 ℃, and reaction pressure P is 0.1≤P≤8.0MPa, and reaction volume air speed LHSV is 1000≤LHSV≤50000.
Before the present invention reacts, first use hydrogen, or the hydrogen of inert gas dilution, or synthesis gas reduces to catalyst, then react.
Hydrogen and carbon monoxide molar ratio: H in synthesis gas of the present invention
2/ CO=2-8.
In catalyst of the present invention, active component is transition metal oxide iron oxide FeO, and its ferro element accounts for the 15.0-25.0wt% of total catalyst weight.
In catalyst of the present invention, auxiliary agent A is copper, and copper content accounts for the 0.5-3.0wt% of total catalyst weight.
In catalyst of the present invention, auxiliary agent B is alkali metal K, and Determination of Potassium accounts for the 0.5-1.5wt% of total catalyst weight.
In catalyst of the present invention, support C is Al
2o
3, account for the 60.0-80.0wt% of total catalyst weight.
The preparation process of catalyst of the present invention adopts infusion process, uses corresponding A, B nitrate or liquid precursor, and in certain sequence, step impregnation, in support C, forms through 400-800 ℃ of roasting for 1～20 hour.
Catalyst of the present invention is mainly used in middle low temperature methanation reaction, produce oil in parallel, and reaction temperature T is 250 ℃≤T≤350 ℃.
Methane selectively of the present invention is 40.0-98%, regulates on demand.
In the oil product of coproduction of the present invention, the carbon number n of hydrocarbon is: 2≤n≤18.
In the oil product of coproduction of the present invention, the hydro carbons carbon number n=3-4 comprising, i.e. liquefied petroleum gas.
In the oil product of coproduction of the present invention, the hydro carbons carbon number n=5-12 comprising, i.e. gasoline.
In the oil product of coproduction of the present invention, the hydro carbons carbon number n=12-16 comprising, i.e. kerosene.
In the oil product of coproduction of the present invention, the hydro carbons carbon number n=15-18 comprising, i.e. diesel oil.
The present invention adopts cheap raw material, utilizes simple infusion process, has prepared the new catalyst of the methanation of a kind of synthesis gas part coproducing oil product.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 product advantage complementary, effectively improve the economic benefit of coal preparing natural gas project and the ability of whole opposing risk.
Accompanying drawing explanation
Fig. 1 is ferrum-based catalyst FeCuK/Al
2o
3under different reaction temperatures to H
2/ H
2the catalytic performance of=5: 1 synthesis gas methanation coproducing oil product.(catalyst quality: 1g FeCuK/Al
2o
3; Unstripped gas forms: H
2/ H
2/ Ar=80/16/4; Synthesis gas air speed: GHSV=6000hr
-1; Reaction pressure: P=3.0MPa; Activation condition: 5h at 400 ℃)
Fig. 2 is ferrum-based catalyst FeCuK/Al
2o
3under different reaction pressures to H
2/ CO=5: the catalytic performance of 1 synthesis gas methanation coproducing oil product.(catalyst quality: 1g FeCuK/Al2O3; Unstripped gas forms: H
2/ H2/Ar=80/16/4; Synthesis gas air speed: GHSV=6000hr
-1; Reaction temperature: T=300 ℃; Activation condition: 6h at 400 ℃)
Fig. 3 is ferrum-based catalyst FeCuK/Al
2o
3under different reaction velocity GHSV to H
2/ CO=3: the catalytic performance of 1 synthesis gas methanation coproducing oil product.(catalyst quality: 0.5g FeCuK/Al2O3; Unstripped gas forms: H
2/ H2/Ar=80/16/4; Reaction pressure: P=3.0MPa; Reaction temperature: T=300 ℃; Activation condition: 5h at 400 ℃)
The specific embodiment
The preparation method of embodiment 1 catalyst
In 10 grams of gamma-alumina carriers, in certain sequence, add successively ferric nitrate, the aqueous solution of manganese nitrate and potassium nitrate, the content of active component is the percentage composition of total catalyst weight, is respectively potassium 1.5%, iron 27%, 1.5%, 120 ℃, manganese is dry, and 400 to 600 ℃ of roastings obtain required catalyst.Before reaction, use pure hydrogen, or the hydrogen of inert gas dilution, or synthesis gas (gaseous mixture of H2 and CO) reduction, then react.
The preparation of embodiment .2 catalyst 1.5%K 1.5% Cu27% FeO/70%Al2O3
0.1801g KNO3 is dissolved in to 30ml deionized water, adopts equi-volume impregnating that this mixed aqueous solution is impregnated on 8.0gAl2O3 carrier.First roasting 4 hours at 550 ℃ of carrier.60 ℃ of water-baths evaporate excessive solvent.Again 14.4278g Fe (NO3) 39H2O and 1.2347g Cu (NO3) 23H2O are dissolved in 30ml deionized water, this mixed aqueous solution equal-volume is supported in above-mentioned sample, 60 ℃ of water-baths, evaporate excessive solvent.Gained sample is dry 12h in 120 ℃ of baking ovens, dry after sample be placed in Muffle furnace, with the heating rate of 2 ℃/min, be warmed up to 450 ℃, roasting 2h, obtains consisting of the catalyst of 1.5%K1.5%Cu27%FeO/70%/Al2O3.
Embodiment 3. product analysis methods
Products obtained therefrom is analyzed with Agilent 7890A.Chromatogram is furnished with dual detector FID and TCD, and has a ten-way valve, can be so that product enters respectively packed column and capillary column simultaneously.Data are processed with the Chemstation software of Agilent.
The concrete chromatographic condition of Agilent is as follows:
Chromatogram: Agilent 7890A
FID chromatographic column: HP-PONA 19091S-001,50m x 0.2mm (internal diameter), 0.5 μ m thickness
Carrier gas: helium, 2.5ml/min
Post case temperature: 35 ℃ keep 5min
35-150℃，5℃/min
150 ℃ keep 10min
Injection port: shunting (100: 1) temperature: 170 ℃
250 ℃ of detector: FID
TCD chromatographic column: carbon molecular sieve post, TDX-01 2m x 2mm (internal diameter)
Carrier gas: helium, 20ml/min
Post case temperature: 35 ℃ keep 5min
35-150℃，5℃/min
150 ℃ keep 10min
Injection port: temperature: 170 ℃
200 ℃ of detector: TCD
The catalytic perfomance of embodiment 4 preparing methane by synthetic gas produce oil in parallel
In tubular fixed-bed reactor, prepared catalyst has been carried out to the catalytic perfomance test evaluation of preparing methane by synthetic gas produce oil in parallel.According to requirement of the present invention, the technique initialization of preparing methane by synthetic gas produce oil in parallel as follows:
Raw material forms: H2/CO/Ar argon gas (Ar) is interior mark
Reaction pressure: 3.0MPa
The volume space velocity GHSV:6000hr of raw material
-1
The weight of catalyst: 1.0g
The granularity of catalyst: 40-60 order
The height of beds :～10mm
While starting to investigate, first by catalyst at 500 ℃, pure hydrogen, or add carrier gas, or reduce under the condition of synthesis gas 5 hours, then drops to the temperature of bed the temperature of appointment, passes into synthesis gas and reacts.Being heated by electric furnace of reactor, the control of reaction temperature is determined by the thermocouple that inserts beds.Unstripped gas and gas product form by Angilent7890 gas chromatographic detection, and this chromatogram has two detectors: hydrogen flame detector and thermal conductivity detector (TCD).The hydrocarbon that hydrogen flame detector detects in product distributes, and thermal conductivity detector (TCD) detects the hydrogen in raw material and product, carbon monoxide, carbon dioxide with, methane and interior mark argon gas.The composition of two detectors is usingd methane and is integrated as intermediary.Unless there is other explanation, the example below the present invention all carries out under above-mentioned experiment condition.
Because experiment is carried out under different reaction conditions, resulting oil product is selectively also different, and product can regulate on demand.Here the hydrocarbon carbon number n of gained oil product is: 2≤n≤20, except gasoline, diesel oil, outside kerosene, also comprises the liquefied gas of C3+C4.Concrete outcome as shown in FIG. 1 to 3.
Claims (9)
1. for the synthesis of cyclostrophic, produce a catalyst for methane coproducing oil product, it is characterized in that,
Described catalyst consists of FeABO/C, and active component is iron oxide, and A, B are auxiliary agent, and C is carrier; Wherein:
Active component iron oxide, in metallic element, content is 15.0-25.0wt%;
Auxiliary agent A is Cu and/or Mn, and in metallic element, the content in catalyst is 0.01-5.0wt%;
Auxiliary agent B is Li, Na, and any one in K or several mixing, in metallic element, the content 0.5-5.0wt% in catalyst;
Support C is Al
2o
3, ZrO, SiO
2, TiO
2, any one in active carbon or several mixing, the content in catalyst is 60.0-80.0wt%.
2. according to wooden fork profit, require the catalyst described in 1, described auxiliary agent A is copper, and in metallic element, content is 0.5-3.0wt%.
3. according to catalyst claimed in claim 1, in described catalyst, auxiliary agent B is alkali metal K, and Determination of Potassium accounts for the 0.5-1.5wt% of total catalyst weight.
4. according to catalyst claimed in claim 1, described support C is Al
2o
3.
5. a preparation method for catalyst described in claim 1, adopts infusion process, in the ratio of each component in described catalyst, uses corresponding A, B nitrate or liquid precursor, and step impregnation, in support C, forms through 400-800 ℃ of roasting for 1～20 hour.
6. a synthesis gas transforms the method for producing methane coproducing oil product, it is characterized in that, by synthesis gas by the reactor reaction that supports ferrum-based catalyst described in claim 1 is housed, produce methane coproducing oil product, supporting the reaction temperature T that carries out preparing methane by synthetic gas coproducing oil product on ferrum-based catalyst is 200≤T≤500 ℃, reaction pressure P is 0.1≤P≤8.0MPa, and reaction volume air speed LHSV is 1000≤LHSV≤50000.
7. in accordance with the method for claim 6, it is characterized in that, before reaction, first use hydrogen, or the hydrogen of inert gas dilution, or synthesis gas reduces to catalyst, then react hydrogen and carbon monoxide molar ratio: H in described synthesis gas
2/ CO=2-8.
8. in accordance with the method for claim 6, it is characterized in that, described methane selectively 40.0-98%, regulates on demand; In the oil product of described coproduction, the carbon number n of hydrocarbon is: 2≤n≤18.
9. in accordance with the method for claim 8, it is characterized in that, in the oil product of described coproduction, the hydro carbons carbon number n=3-4 comprising, i.e. liquefied petroleum gas; N=5-12, i.e. gasoline; N=12-16, i.e. kerosene; N=15-18, i.e. diesel oil.
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| CN102527401B (en) * | 2010-12-30 | 2014-06-25 | 中国科学院大连化学物理研究所 | Catalyst used in preparation of methane and coproduction of low-carbon olefin by conversion of syngas, preparation method for catalyst and application of catalyst |
| CN105289622B (en) * | 2015-11-11 | 2019-01-08 | 中国石油大学(华东) | Saturated alkane dehydrogenation prepares the application of the catalyst of monoolefine |
| CN109908909B (en) * | 2017-12-13 | 2021-10-08 | 中国石油化工股份有限公司 | Synthetic gas methanation catalyst and preparation method thereof |
| CN109908931B (en) * | 2017-12-13 | 2021-10-08 | 中国石油化工股份有限公司 | Catalyst with Al modified activated carbon as carrier and preparation method thereof |
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| 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 |
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