CN102553609A - Ferrum-based catalyst applied to producing methane and co-producing petroleum products by converting syngas and preparation and application thereof - Google Patents

Ferrum-based catalyst applied to producing methane and co-producing petroleum products by converting syngas and preparation and application thereof Download PDF

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CN102553609A
CN102553609A CN2010106105136A CN201010610513A CN102553609A CN 102553609 A CN102553609 A CN 102553609A CN 2010106105136 A CN2010106105136 A CN 2010106105136A CN 201010610513 A CN201010610513 A CN 201010610513A CN 102553609 A CN102553609 A CN 102553609A
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catalyst
oil product
ferrum
based catalyst
component
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CN102553609B (en
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朱文良
刘中民
刘勇
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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Dalian Institute of Chemical Physics of CAS
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Abstract

Provided are a catalyst for applied to producing methane and co-producing petroleum products by converting syngas and process conditions for preparing the catalyst and producing the methane and the co-producing the petroleum products by converting the syngas. The catalyst is composed of ABFeO, the active component is ferric oxide, and the total content of ferrum accounts for 35.0-75.0wt% of the total weight of the catalyst. A promoter A is lithium (Li), sodium (Na), kalium (K), zinc (Zn) and/or zirconium (Zr), and the content of the promoter A accounts for 0.10-5.0wt% of the total weight of the catalyst. A promoter B is cuprum (Cu) and/or manganese (Mn), and the content of the promoter B accounts for 0.5-10.0wt% of the total weight of the catalyst. The preparation of the catalyst adopts a coprecipitation method, and the catalyst is obtained by aging, drying and roasting the precipitate. The promoter A is introduced into the roasted catalyst through an immersion method, and then the final catalyst with 20-40 meshes is obtained through drying, roasting and pelleting. The syngas serving as a raw material is wide in source and can be obtained from coal or biomass. The catalyst is low in cost, simple in preparation process, high in reaction activity and suitable for continuous large-scale production.

Description

A kind of synthesis gas that is used for transforms ferrum-based catalyst, its preparation and the application of producing methane and coproducing oil product
Technical field
The invention belongs to the catalytic chemistry field, relate to synthesis gas and transform system methane, and coproducing oil product, a kind of catalyst that is used for low temperature synthesizing methane and coproducing oil product, 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 energy efficiency of coal preparing natural gas is the highest coal utilization mode, reaches 53%, not only can significantly reduce the consumption of coal, also reduces 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, reaction condition from the catalyst and the reaction process of coal gasification through synthesis gas system methane and coproducing oil product.
Main advantage of the present invention is: the present invention goes back the oil product 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 precipitated iron-based catalyst provided by the invention and existing full methanation technology exist.
The present invention through the reactor reaction of ferrum-based catalyst is housed, produces methane and coproducing oil product with synthesis gas; This
Bright said ferrum-based catalyst consist of ABFeO, active component is an iron oxide, auxiliary agent is A and B; Wherein:
Component Fe, in metallic element, the weight percentage in catalyst is 35.0-75.0wt%;
Component A is Li, Na, and K, Zn, any one among the Zr or any several kinds mixing, in metallic element,
Content in catalyst is 0.1-5.0wt%;
B component is Cu and/or Mn, and in metallic element, the content in catalyst is 0.5-10.0wt%.
Ferrum-based catalyst according to the invention is used hydrogen before reaction, or the hydrogen of inert gas dilution, or the synthesis gas reduction, reacts then.
The condition of handling of reducing before the ferrum-based catalyst reaction according to the invention is: temperature 300-500 ℃, pressure 0.1-1.5MPa reduced processing time 5-18 hour.
Hydrogen and carbon monoxide molar ratio: H in the synthesis gas according to the invention 2/ CO=2-8.
The present invention utilizes above-mentioned catalyst to transform the condition of producing methane and coproducing oil product in said synthesis gas: reaction temperature t is 300 ℃≤t≤600 ℃, and reaction pressure P is 0.5MPa≤P≤5.0MPa, and reaction volume air speed GHSV is 1000h -1≤GHSV≤40000h -1
Oil product according to the invention is that carbon number is not more than any one or any several kinds mixing in 18 the hydro carbons in the molecule.
Ferrum-based catalyst according to the invention adopts the coprecipitation preparation, comprises following following steps:
A) in the ratio of each component in the said catalyst, will contain Fe 3+With the aqueous solution that contains the said metal ion of B component, add in 25-50 ℃ the ammonia spirit, stir the gained sediment to evenly, gained sediment pH value is 3.0-10.0;
B) gained sediment, 80-150 ℃ drying aging through 5-20 hour and 400-800 ℃ of roasting were handled in 1~10 hour in the step a), obtained the roasting sample;
C) place the aqueous solution that contains the said metal ion of component A to flood in gained roasting sample in the step b), dipping is accomplished after 80-150 ℃ of drying, 400-800 ℃ roasting obtained described ferrum-based catalyst in 1~20 hour.
The carbon number n of the hydrocarbon of oil product according to the invention is: 2≤n≤18.
In the oil product of coproduction according to the invention, the hydro carbons carbon number n=3-4 that comprises, i.e. liquefied petroleum gas.
In the oil product of coproduction according to the invention, the hydro carbons carbon number n=5-12 that comprises, i.e. gasoline.
In the oil product of coproduction according to the invention, the hydro carbons carbon number n=12-16 that comprises, i.e. kerosene.
In the oil product of coproduction according to the invention, the hydro carbons carbon number n=15-18 that comprises, i.e. diesel oil.
Advantage of the present invention is, adopts cheap raw material, utilizes simple coprecipitation, has prepared the catalyst of methanation of a kind of synthesis gas part and 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 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 the reactivity worth of catalyst 100Fe5.5Mn1.3K2Cu methanation parallel connection produce oil under different temperatures.(350 ℃ of activation temperatures, soak time 12h, reaction pressure 1.5MPa, the unstripped gas mole is formed: Ar/CO/H 2=4.0/24.0/72.0, volume space velocity 1800h -1);
Fig. 2 is the reactivity worth of catalyst 100Fe5.5Mn1.3K2Cu methanation parallel connection produce oil under different pressures.(350 ℃ of activation temperatures, soak time 12h, 400 ℃ of reaction temperatures, the unstripped gas mole is formed: Ar/CO/H 2=4.0/24.0/72.0, volume space velocity 1800h -1);
Fig. 3 is the reactivity worth of catalyst appearance 100Fe5.5Mn1.3K2Cu methanation parallel connection produce oil under the different volumes air speed.(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=4.0/24.0/72.0);
Fig. 4 is the reactivity worth of catalyst 100Fe5.5Mn1.3K2Cu with the methanation parallel connection produce oil of reaction time variation.(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=4.0/24.0/72.0, volume space velocity 6000h -1);
The specific embodiment
Embodiment 1: method for preparing catalyst
In the ratio of each component in the catalyst, with Fe, Mn, the nitrate of Cu is dissolved in the deionized water, and at room temperature the vigorous stirring ammonia spirit slowly adds the metal mixed nitrate aqueous solution in the ammonia spirit, about joining day 20min then.Regulate deposition pH value to 9.0 with ammonia spirit, continue to stir after the 150min, will precipitate age overnight.
The precipitate with deionized water washing to neutral, is centrifugalized.Gained is deposited in dry 12h in 120 ℃ of baking ovens, and dry back sample places Muffle furnace, is warmed up to 500 ℃ with the heating rate of 2 ℃/min, and roasting 2h obtains the sample after the roasting.
Potassium nitrate is dissolved in deionized water, adopts infusion process KNO 3The aqueous solution supports in the sample after the roasting, and 110 ℃ evaporate unnecessary solvent.Sample after adopting condition same as described above to dipping carries out drying, roasting.The catalyst that obtains, the mol ratio of catalyst are 100Fe5.5Mn1.3K2Cu.With the catalyst sample granulation, granularity is the 20-40 order.
Embodiment 2: the preparation of catalyst 100Fe5.5Mn1.3K2Cu
With 46.9664g Fe (NO3) 39H2O, 0.5521g Cu (NO3) 23H2O is dissolved in the 300ml deionized water, with 250ml deionized water dilution 37.3245g concentrated ammonia liquor.At room temperature the vigorous stirring ammonia spirit slowly adds the metal mixed nitrate aqueous solution in the ammonia spirit, about joining day 20min then.Regulate deposition pH value to 9.0 with ammonia spirit, continue to stir after the 150min, will precipitate age overnight.The precipitate with deionized water washing to neutral, is centrifugalized.Gained is deposited in dry 12h in 120 ℃ of baking ovens, and dry back sample places Muffle furnace, is warmed up to 500 ℃ with the heating rate of 2 ℃/min, and roasting 2h obtains the sample after the roasting.1.5924gMn (NO3) 24H2O just again, 0.1574g KNO3 is dissolved in the 20ml deionized water, adopts equi-volume impregnating to support potassium and copper aqueous metal salt in the sample after the roasting, and 80 ℃ evaporate unnecessary solvent.Dry 12h in 120 ℃ of baking ovens, dry back sample places Muffle furnace, is warmed up to 500 ℃ with the heating rate of 2 ℃/min, and roasting 2h obtains catalyst sample.Catalyst consists of 100Fe5.5Mn1.3K2Cu.
Embodiment 3: product analysis method
Products obtained therefrom is analyzed with Agilent 7890A.Chromatogram is furnished with dual detector FID and TCD, and a ten-way valve is arranged, can be so that product gets into packed column and capillary column simultaneously respectively.Data are with the Chemstation software processes of Agilent.
The concrete chromatographic condition of Agilent is following:
Chromatogram: Agilent 7890A
FID chromatographic column: HP-PONA 19091S-001,50m * 0.2mm (internal diameter), 0.5 μ m thickness
Carrier gas: helium, 2.5ml/min
Post oven temperature, degree: 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 * 2mm (internal diameter)
Carrier gas: helium, 20ml/min
Post oven temperature, degree: 35 ℃ keep 5min
35-150℃,5℃/min
150 ℃ keep 10min
Injection port: temperature: 170 ℃
200 ℃ of detector: TCD
Embodiment 4: 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=4.0/24.0/72.0), 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.Resulting result such as Fig. 1~shown in Figure 4.

Claims (10)

1. one kind is used for synthesis gas and transforms the ferrum-based catalyst produce methane and coproducing oil product, it is characterized in that, said ferrum-based catalyst consist of ABFeO, active component is an iron oxide, auxiliary agent is A and B;
Wherein:
The active component iron oxide, in metallic element, the content in catalyst is 35.0-75.0wt%;
Component A is Li, Na, and K, Zn, any one among the Zr be several kinds mixing perhaps, and in metallic element, the content in catalyst is 0.1-5.0wt%;
B component is Cu and/or Mn, and in metallic element, the content in catalyst is 0.5-10.0wt%.
2. the said Preparation of catalysts method of claim 1 is characterized in that, said ferrum-based catalyst adopts the coprecipitation preparation, comprises following following steps:
A) in the ratio of each component in the said catalyst, will contain Fe 3+With the aqueous solution that contains the said metal ion of B component, add in 25-50 ℃ the ammonia spirit, stir the gained sediment to evenly, gained sediment pH value is 3.0-10.0;
B) gained sediment, 80-150 ℃ drying aging through 5-20 hour and 400-800 ℃ of roasting were handled in 1~10 hour in the step a), obtained the roasting sample;
C) gained roasting sample in the step b) is placed the ratio that contains in said each component of catalyst; Flood in the aqueous solution of the said metal ion of component A; Dipping accomplishes after 80-150 ℃ of drying, 400-800 ℃ roasting 1~20 hour obtain described ferrum-based catalyst.
3. a synthesis gas transforms the method for producing methane and coproducing oil product, 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 coproducing oil product; Said synthesis gas transforms the reaction condition of producing methane and coproducing oil product: reaction temperature t is 300 ℃≤t≤600 ℃, and reaction pressure P is 0.5MPa≤P≤5.0MPa, and reaction volume air speed GHSV is 1000h -1≤GHSV≤40000h -1
4. according to the described method of claim 3, it is characterized in that said ferrum-based catalyst is before reaction; Use hydrogen, or the hydrogen of inert gas dilution, or the synthesis gas reduction; React then; The condition that said reduction is handled is: temperature 300-500 ℃, pressure 0.1-1.5MPa reduced processing time 5-18 hour.
5. according to claim 3 or 4 described methods, it is characterized in that hydrogen and carbon monoxide molar ratio: H in the said synthesis gas 2/ CO=2-8.
6. according to the described method of claim 3, the carbon number n of the hydrocarbon of said oil product is: 2≤n≤18.
7. according to the described method of claim 6, it is characterized in that, in the oil product of said coproduction, the hydro carbons carbon number n=3-4 that comprises, i.e. liquefied petroleum gas.
8. according to the described method of claim 6, it is characterized in that, in the oil product of said coproduction, the hydro carbons carbon number n=5-12 that comprises, i.e. gasoline.
9. according to the described method of claim 6, it is characterized in that, in the oil product of said coproduction, the hydro carbons carbon number n=12-16 that comprises, i.e. kerosene.
10. according to the described method of claim 6, it is characterized in that, in the oil product of said coproduction, the hydro carbons carbon number n=15-18 that comprises, i.e. diesel oil.
CN201010610513.6A 2010-12-29 2010-12-29 Ferrum-based catalyst applied to producing methane and co-producing petroleum products by converting syngas and preparation and application thereof Expired - Fee Related CN102553609B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105435807A (en) * 2014-07-22 2016-03-30 北京化工大学 Non-supported catalyst and preparation method and application thereof

Citations (1)

* 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

Patent Citations (1)

* 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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105435807A (en) * 2014-07-22 2016-03-30 北京化工大学 Non-supported catalyst and preparation method and application thereof
CN105435807B (en) * 2014-07-22 2018-10-23 北京化工大学 A kind of unsupported catalyst and its preparation method and application

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