CN104399501A - High-activity iron-based low-temperature Fischer-Tropsch synthesis catalyst and preparation method thereof - Google Patents

High-activity iron-based low-temperature Fischer-Tropsch synthesis catalyst and preparation method thereof Download PDF

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CN104399501A
CN104399501A CN201410623057.7A CN201410623057A CN104399501A CN 104399501 A CN104399501 A CN 104399501A CN 201410623057 A CN201410623057 A CN 201410623057A CN 104399501 A CN104399501 A CN 104399501A
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CN104399501B (en
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乔明华
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Fudan University
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Abstract

The invention belongs to the field of chemical catalysts, and specifically relates to a high-activity iron-based low-temperature Fischer-Tropsch synthesis catalyst and a preparation method thereof. The low-temperature Fischer-Tropsch synthesis iron-based catalyst is prepared by subjecting a skeleton iron material to low-temperature carbonization at a low temperature under a high carbon monoxide partial pressure and contains high-activity epsilon-Fe2C nano particles. The provided Fischer-Tropsch synthesis catalyst has an extremely high catalytic activity at a low temperature (less than 200 DEG C), wherein the catalytic activity is prominently higher than that of reported low-temperature iron-based Fischer-Tropsch synthesis catalysts. At the same time, the stability of the provided catalyst is high, and thus the catalyst can meet the production requirements.

Description

A kind of high activity iron-based Low Temperature Fischer Tropsch synthetic catalyst and preparation method thereof
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to a kind of highly active iron-based Low Temperature Fischer Tropsch synthetic catalyst and preparation method thereof.
Background technology
A kind of method of F-T synthesis to be the carbon monoxide that coal, natural gas, living beings obtained by catalysis and hydrogen gas be liquefied hydrocarbon, synthesized liquid fuel is made up of straight-chain hydrocarbons and alkene substantially, have without sulphur, without nitrogen, without metal, without advantages such as aromatic hydrocarbons, be clean, the fuel oil of environmental protection and chemicals, be therefore an important channel effectively solving day by day serious oil shortage and problem of environmental pollution.One of key factor of F-T synthesis develops the catalyst of high, active good, cheap, the wide material sources of stability.For this reason, domestic and international many oil companies and R&D institution have all dropped into huge financial resources and manpower is researched and developed, as (petrochemical technology economy such as Sasol company, Shell company, Exxon company, Shanxi coalification institute of the Chinese Academy of Sciences, Peking University, Xiamen University, Fudan University, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, Shenhua Groups, 2004,19,8; Chemical industry is in progress, and 2003,22,441).Need point out, the temperature of the Low Temperature Fischer Tropsch synthetic reaction of industrial indication is 200 omore than C.If can develop lower than 200 othe fischer-tropsch synthetic catalyst used under C, can not only make reaction condition gentleer, and can reduce energy consumption and equipment investment.Meanwhile, low temperature can improve the chain growth factor of Fischer-Tropsch synthesis product, and then improves the selective of the liquefied hydrocarbon such as vapour, diesel oil.
At present, can be used for catalyst mainly ruthenium, iron, the cobalt metal nanoparticle of Low Temperature Fischer Tropsch synthetic reaction.Wherein, the activity of ruthenium nano-particle is high, but noble metal is expensive, does not have practical possibility.Ferrum-based catalyst have raw material sources extensive, cheap, the advantages such as different component synthesis gas can be adapted to, if prepare, there is highly active low temperature iron-base fischer-tropsch synthesis catalyst at low temperatures, tool be of great significance.Fan etc. adopt the ethylene glycol solution of frerrous chloride and the ethylene glycol water mixed solution of sodium borohydride to be raw material, adopt chemical preparation iron nano-particle catalyst.The particle diameter of this iron particle is about 8 nm, 150 oc take Macrogol 200 as the reactivity in dicyandiamide solution is 1.5 mol cOmol fe – 1h – 1, the thing of post catalyst reaction is SA mutually θ-Fe 3c and the metallic iron (Green Chem. 2010,12,795) of carbonization does not occur.Chen etc. adopt iron chloride and potassium borohydride to be raw material, by the ratio of water and ethylene glycol solvent in modulation ferric chloride solution, have prepared a series of iron nano-particle catalyst.Wherein, be that the iron nano-particle catalyst prepared of raw material is 200 by ferric chloride in aqueous solution oc is that in the reaction in dicyandiamide solution, activity is higher with PEG400, is 0.83 mol cOmol fe – 1h – 1, the dominant of post catalyst reaction is Fe mutually 3o 4, cementite ( χ-Fe 5c 2with ε＇-Fe 2.2c) 20.4%(J. Mol. Catal. A 2010,329,103 is only accounted for).There is no at present based on ε-Fe 2the report of the low temperature liquid phase fischer-tropsch synthetic catalyst of C thing phase.
Summary of the invention
One is the object of the present invention is to provide to contain ε-Fe 2fischer-tropsch synthetic catalyst of C thing phase and preparation method thereof, makes ferrum-based catalyst can show high catalytic activity under cryogenic.
What the present invention proposed contains ε-Fe 2the preparation method of the fischer-tropsch synthetic catalyst of C thing phase, concrete steps are as follows:
(1) preparation of skeletal iron catalyst presoma: under the protection of argon gas, adds the potassium hydroxide solution that volumetric concentration is 10 ~ 50% in a stirred vessel; Design temperature 20 ~ 90 is reached at stirred vessel oduring C, at 0 ~ 10 min(preferably 1 ~ 10 min) in potassium hydroxide solution, add ferroaluminium powder in time range, keep reaction 0 ~ 180 min(preferably 1 ~ 180 min after reinforced); Spend deionized water afterwards to neutral, then with absolute ethyl alcohol, water is replaced, finally replace absolute ethyl alcohol with polyethylene glycol solvent and this skeleton iron presoma is stored in wherein;
(2) contain ε-Fe 2the preparation of the efficient cryogenic fischer-tropsch synthetic catalyst of C thing phase
The skeletal iron catalyst presoma prepared by step (1) is in autoclave, and the addition of catalyst precursor is 2 ~ 6 mmol, and the consumption of solvent Macrogol 200 is 20 mL; Under normal temperature (room temperature), be filled with forming gas, forming gas consists of H 2, CO, H 2/ CO=0.67 ~ 2, pressure is 1.0 ~ 4.0 MPa; Afterwards autoclave is warming up to design temperature 120 ~ 200 oc, and to set stir speed (S.S.) be 500 ~ 1200 rpm, carries out low-temperature carbonization reaction; After 20 min ~ 4 h, stop reaction, and autoclave is cooled to room temperature.Catalyst granules collected after carburizing reagent turns out to be activity through sign ε-Fe 2c thing phase is highly active Low Temperature Fischer Tropsch synthetic catalyst.
In the present invention, described ferroaluminium can be cooling preparation naturally after alloy molten, also can prepare for Fast Cooling.
In the present invention, in described ferroaluminium, the weight ratio of Fe and Al can be 0.25 ~ 4, and granularity is 40 ~ 300 orders.
In the present invention, described potassium hydroxide solution concentration is 10 ~ 50%, and the mass ratio of ferroaluminium and potassium hydroxide is 1:1.5 ~ 1:5.
Compared with prior art, beneficial effect major embodiment of the present invention is in the following areas:
(1) preparation method of Fischer-Tropsch synthetic iron-based catalyst provided by the present invention is simple, is applicable to large-scale production;
(2) catalyst provided by the present invention has good mechanical strength and stability, is suitable for using in paste state bed reactor, and its even particle size distribution, there is suitable specific area and pore structure;
(3) proved by test, fischer-tropsch synthetic catalyst provided by the present invention (<200 at low temperatures oc) there is high catalytic activity (catalytic activity is significantly higher than the low temperature iron-base fischer-tropsch synthesis catalyst of contemporary literature report), also there is very high stability simultaneously, the needs of actual production can be met.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of the embodiment of the present invention 1 ~ 3 gained catalyst.
Fig. 2 is the x-ray diffraction pattern of comparative example 1 ~ 2 gained catalyst of the present invention.
Detailed description of the invention
Further describe fischer-tropsch synthetic catalyst provided by the present invention and preparation method thereof below, but the present invention is not therefore subject to any restriction.
embodiment 1
(1) be that 50:50 adds in electric arc induction furnace by iron powder and aluminium powder with weight ratio, pass into argon gas after vacuumizing, excite electric arc heated with electric current, and under magnetic stirring action molten homogeneous, naturally cool afterwards or be quickly cooled to room temperature, ferroaluminium being ground to 100 ~ 200 orders;
(2) under the condition of argon shield, in stirred vessel, add the potassium hydroxide solution of 3 mL 30% mass fractions, treat that temperature rises to 70 oduring C, in alkali lye, add 0.5 g ferroaluminium powder, after reinforced, keep 1 h.Spend deionized water afterwards to neutral, then replace water with absolute ethyl alcohol, finally replace absolute ethyl alcohol with Macrogol 200, and skeletal iron catalyst presoma is stored wherein;
(3) skeletal iron catalyst presoma is dispersed in 20 mL Macrogol 200s, then catalysts and solvents is transferred in the lump in 50 mL autoclaves.At ambient temperature with consisting of H 23.0 MPa are inflated to after the synthesis gas displacement of/CO=2.The temperature of Fischer-Tropsch synthesis is set as 150 oc, mixing speed is set to 800 rpm.Under this Low Temperature Fischer Tropsch synthetic reaction condition, there is in-situ carburization in skeletal iron catalyst presoma simultaneously.When reaction pressure is down to 3.0 MPa, stop reaction and autoclave is cooled to room temperature.This catalyst called after A, its performance evaluation time is 30 minutes, and reaction result is shown in table 1.In this example, the x-ray diffraction pattern of gained catalyst is shown in Fig. 1, display ε-Fe 2c is the active phase of iron content in this catalyst, and its grain size is 8.3 nm.
embodiment 2
(1) with embodiment 1;
(2) with embodiment 1;
(3) skeletal iron catalyst presoma is dispersed in 20 mL Macrogol 200s, then catalysts and solvents is transferred in the lump in 50 mL autoclaves.At ambient temperature with consisting of H 23.0 MPa are inflated to after the synthesis gas displacement of/CO=2.The temperature of Fischer-Tropsch synthesis is set as 170 oc, mixing speed is set to 800 rpm.Under this Low Temperature Fischer Tropsch synthetic reaction condition, there is in-situ carburization in skeletal iron catalyst presoma simultaneously.When reaction pressure is down to 3.0 MPa, stop reaction and autoclave is cooled to room temperature.This catalyst called after B, its performance evaluation time is 20 minutes, and reaction result is shown in table 1.In this example, the x-ray diffraction pattern of gained catalyst is shown in Fig. 1, display ε-Fe 2c is the active phase of iron content in this catalyst, and its grain size is 8.1 nm.
embodiment 3
(1) with embodiment 1;
(2) with embodiment 1;
(3) skeletal iron catalyst presoma is dispersed in 20 mL Macrogol 200s, then catalysts and solvents is transferred in the lump in 50 mL autoclaves.At ambient temperature with consisting of H 23.0 MPa are inflated to after the synthesis gas displacement of/CO=2.The temperature of Fischer-Tropsch synthesis is set as 200 oc, mixing speed is set to 800 rpm.Under this Low Temperature Fischer Tropsch synthetic reaction condition, there is in-situ carburization in skeletal iron catalyst presoma simultaneously.When reaction pressure is down to 3.0 MPa, stop reaction and autoclave is cooled to room temperature.This catalyst called after C, its performance evaluation time is 15 minutes, and reaction result is shown in table 1.In this example, the x-ray diffraction pattern of gained catalyst is shown in Fig. 1, display ε-Fe 2c is the active phase of iron content in this catalyst, and its grain size is 8.4 nm.
comparative example 1:the preparation of Fe – Cu – K – Si precipitated iron catalyst
(1) this method for preparing catalyst derives from bibliography (J. Catal. 2009,262,244).25 g nine water ferric nitrates and 1.2 g nitrate trihydrate copper are dissolved in 100 mL deionized waters.25 g natrium carbonicum calcinatums are dissolved in 100 mL deionized waters.After iron, copper nitrate mixed solution and sodium carbonate liquor being heated to closely boil, by iron, the copper nitrate mixed solution of sodium carbonate liquor instillation in strong agitation.The precipitation obtained is precipitated filter cake after filtering, washing.Precipitated filter cakes is scattered in again in 200 mL deionized waters, in these slurries, adds 1.9 g potassium silicates.After stirring and evenly mixing, add 1.5 mL red fuming nitric acid (RFNA) precipitated silicas, precipitation terminates rear filtration, washing obtains filter cake.By filter cake 105 odry 16 h under C, afterwards by the powder that obtains after drying 300 ounder C, roasting 5 h, is ground to 100 ~ 200 orders, obtains Fe – Cu – K – Si catalyst precursor;
(2) getting 0.43 g Fe – Cu – K – Si catalyst precursor loads in tube furnace, logical H 2/ Ar(volume ratio 5%) gaseous mixture is 400 oreduce 8 h under C, gas flow is 50 mL/min, and heating rate is 2 oc/min.After reduction terminates, at H 2under/Ar atmosphere, catalyst is transferred in Macrogol 200 and stores.In this example, the x-ray diffraction pattern of gained catalyst precursor is shown in Fig. 2, and the particle diameter of iron nano-particle is 8.6 nm;
(3) with embodiment 2.
comparative example 2:the preparation of crystalline state iron nano-particle catalyst
(1) this method for preparing catalyst derives from bibliography (J. Cryst. Growth 2005,275,548).2.42 g Iron trichloride hexahydrates are dissolved in 12.1 mL absolute ethyl alcohols.The hydrazine hydrate solution of 4.24 g potassium hydroxide powder and 6.1 mL 80% mass fractions is joined in ferric chloride solution.Be transferred to after at room temperature said mixture being stirred in 50 mL autoclaves.After the air in argon replaces autoclave, be warming up to 80 oc(autogenou pressure rises to 6.0 MPa) and keep 10 h.Autoclave is cooled to room temperature, spends deionized water crystalline state iron nano-particle afterwards to neutral, then replace water with absolute ethyl alcohol, finally replace absolute ethyl alcohol with Macrogol 200, and crystalline state iron nano-particle catalyst is stored wherein.In this example, the x-ray diffraction pattern of gained catalyst is shown in Fig. 2, and the particle diameter of iron nano-particle is 33.2 nm;
(2) with embodiment 2.
As known from Table 1, ε-Fe 2the catalytic activity of C catalyst is 150 oc, 170 oc and 200 o2.8 mol are respectively during C cOmol fe – 1h – 1, 6.7 mol cOmol fe – 1h – 1and 9.0 mol cOmol fe – 1h – 1.Although 150 oactivity during C is lower, but still far above the best result of ferrum-based catalyst in low temperature liquid phase Fischer-Tropsch synthesis (Green Chem. 2010,12,795) of current bibliographical information, effectively describes ε-Fe 2c is the very outstanding active phase of Low Temperature Fischer Tropsch synthetic reaction.Along with the decline of reaction temperature, ε-Fe 2hydrocarbon product on C catalyst is selective to be moved to long-chain products direction, CO 2selective, decline, the effective rate of utilization of carrying out Fischer-Tropsch synthesis at low temperatures and being conducive to improving carbon atom is described.When reaction temperature is 170 oduring C, the advantage of reactivity and selectivity of product two aspect can be taken into account. ε-Fe 2c catalyst is 170 ocatalytic activity under C is significantly higher than the catalytic activity of crystalline state Fe nanometer particles and Fe – Cu – K – Si precipitated iron catalyst under same reaction temperature.Wherein the particle diameter of crystalline state Fe nanometer particles is excessive, hinder metallic iron to ε-Fe 2the transformation of C thing phase, therefore in Low Temperature Fischer Tropsch synthetic reaction, activity is very low, is only 0.7 mol cOmol fe – 1h – 1.Fe – Cu – K – Si precipitated iron catalyst may due to the existence of K hinder metallic iron at low temperatures to ε-Fe 2the transformation of C thing phase, activity is only 1.1 mol cOmol fe – 1h – 1.
As shown in Table 2, be separated and solvent wash by simple magnetic, ε-Fe 2in C catalyst, CO conversion ratio is applied mechanically in experiment continuously at five times and only be have dropped 4.2%, ascribes to ε-Fe 2caused by C catalyst is lost in separating, washing process, but selectivity of product remains unchanged, and illustrates that this catalyst has very high stability, has good prospects for commercial application.
Table 1 catalyst performance evaluation result
The estimation of stability result of table 2 catalyst B
。

Claims (4)

1. one kind contains ε-Fe 2the preparation method of the fischer-tropsch synthetic catalyst of C thing phase, concrete steps are as follows:
(1) preparation of skeletal iron catalyst presoma: under the protection of argon gas, adds the potassium hydroxide solution that volumetric concentration is 10 ~ 50% in a stirred vessel; Design temperature 20 ~ 90 is reached at stirred vessel oduring C, in 0 ~ 10 min time range, in potassium hydroxide solution, add ferroaluminium powder, after reinforced, keep reaction 0 ~ 180 min; Spend deionized water afterwards to neutral, then with absolute ethyl alcohol, water is replaced, finally replace absolute ethyl alcohol with polyethylene glycol solvent and this skeleton iron presoma is stored in wherein;
(2) contain ε-Fe 2the preparation of the efficient cryogenic fischer-tropsch synthetic catalyst of C thing phase
The skeletal iron catalyst presoma prepared by step (1) is in autoclave, and the addition of catalyst precursor is 2 ~ 6 mmol, and the consumption of solvent Macrogol 200 is 20 mL; At room temperature be filled with forming gas, forming gas consists of H 2, CO, H 2/ CO=0.67 ~ 2, pressure is 1.0 ~ 4.0 MPa; Afterwards autoclave is warming up to design temperature 120 ~ 200 oc, and to set stir speed (S.S.) be 500 ~ 1200 rpm, carries out low-temperature carbonization reaction; After 20 min ~ 4 h, stop reaction, and autoclave is cooled to room temperature.
2. preparation method according to claim 1, is characterized in that in described ferroaluminium, and the weight ratio of Fe and Al is 0.25 ~ 4, and granularity is 40 ~ 300 orders.
3. preparation method according to claim 1, is characterized in that the mass ratio of described ferroaluminium and potassium hydroxide is 1:1.5 ~ 1:5.
4. what prepared by preparation method described in claim 1-3 contains ε-Fe 2the fischer-tropsch synthetic catalyst of C thing phase.
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CN112569990B (en) * 2019-09-30 2023-07-11 国家能源投资集团有限责任公司 Composition containing supported epsilon/epsilon' iron carbide and theta iron carbide, preparation method, catalyst, application and Fischer-Tropsch synthesis method
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CN112569982B (en) * 2019-09-30 2023-08-18 国家能源投资集团有限责任公司 Precipitated epsilon/epsilon iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method

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