Supported ε/ε′ iron carbide catalyst for Fischer-Tropsch synthesis reaction, preparation method thereof and Fischer-Tropsch synthesis process
The present disclosure relates to the technical field of Fischer-Tropsch synthesis reaction catalysts, and discloses a supported ε/ε′ iron carbide catalyst for Fischer-Tropsch synthesis reaction, preparation method thereof and Fischer-Tropsch synthesis process, wherein the method comprises the following steps: (1) dipping a catalyst carrier in a ferric salt aqueous solution, drying and roasting the dipped carrier to obtain a catalyst precursor; (2) subjecting the catalyst precursor and H 2 to a precursor reduction at the temperature of 300-550° C.; (3) pretreating the material obtained in the step (2) with H 2 and CO at the temperature of 90-185° C., wherein the molar ratio of H 2 /CO is 1.2-2.8:1; (4) preparing carbide with the material obtained in the step (3), H 2 and CO at the temperature of 200-300° C., wherein the molar ratio of H 2 /CO is 1.0-3.2:1. The preparation method has the advantages of simple and easily obtained raw materials, simple and convenient operation steps, being capable of preparing the catalyst with 100% pure phase ε/ε′ iron carbide as the active phase, the catalyst has lower selectivity of CO 2 and CH 4 and higher selectivity of effective products.
1. A method of preparing a supported ε/ε′ iron carbide catalyst for Fischer-Tropsch synthesis reaction, wherein the preparation method comprises the following steps:
(1) dipping a catalyst carrier in a ferric salt aqueous solution, drying and roasting the dipped carrier to obtain a catalyst precursor;
(2) subjecting the catalyst precursor and H 2 to a precursor reduction at the temperature of 300-550° C.;
(3) pretreating the material obtained in the step (2) with H 2 and CO at the temperature of 90-185° C., wherein the molar ratio of H 2 /CO is 1.2-2.8: 1;
(4) preparing carbide with the material obtained in the step (3), H 2 and CO at the temperature of 200-300° C., wherein the molar ratio of H 2 /CO is 1.0-3.2: 1.
2. The method of claim 1 , wherein the ferric salt is at least one selected from the group consisting of iron nitrate, iron chloride and ferrous ammonium sulfate.
3. The method of claim 1 , wherein the dipping is performed such that the iron content in the dipped carrier after drying is within a range of 10-30 wt %.
4. The method of claim 1 , wherein the drying and roasting process comprises: firstly drying the dipped carrier at 20-30° C. for 0.5-4h, then stoving the dipped carrier at 35-80° C. and the vacuum degree of 250-1,200 Pa for 6-10h, drying the stoved material at 110-150° C. for 3-24h, and then roasting the obtained material at 300-550° C. for 1-10h.
5. The method of claim 1 , wherein the catalyst carrier is at least one selected from the group consisting of silica, alumina and titania.
6. The method of claim 1 , wherein the catalyst carrier has a particle size within a range of 30-200 μm.
7. The method of claim 1 , wherein in the step (2), the pressure of the precursor reduction is within a range of 0.1-15 atmospheric pressure; the time is within a range of 0.7-15h; the gas velocity of H 2 in the step (2) is within a range of 600-25,000 mL/h/g.
8. The method of claim 7 , wherein in the step (2), the pressure of the precursor reduction is within a range of 0.3-2.6 atmospheric pressure; the time is within a range of 1-12h; the gas velocity of H 2 in the step (2) is within a range of 2,800-22,000 mL/h/g.
9. The method of claim 1 , wherein in the step (3), the pressure of the pretreatment process is within a range of 0.05-7 atmospheric pressure; the time is within a range of 15-120 min; the total gas velocity of H 2 and CO in the step (3) is within a range of 300-12,000 mL/h/g.
10. The method of claim 9 , wherein in the step (3), the pressure of the pretreatment process is within a range of 0.08-4.5 atmospheric pressure; the time is within a range of 20-90 min; the total gas velocity of H 2 and CO in the step (3) is within a range of 1,500-9,000 mL/h/g.
11. The method of claim 1 , wherein in the step (4), the pressure of the carbide preparation in step (4) is within a range of 0.1-10 atmospheric pressure; the time is within a range of 1.5-15h; the total gas velocity of H 2 and CO in the step (4) is within a range of 500-30,000 mL/h/g.
12. The method of claim 11 , wherein in the step (4), the pressure of the carbide preparation in step (4) is within a range of 0.2-4.5 atmospheric pressure; the time is within a range of 2.5-12h; the total gas velocity of H 2 and CO in the step (4) is within a range of 3,000-25,000 mL/h/g.
13. The method of claim 1 , wherein the method further comprises: the system temperature after the pretreatment is increased to 200-300° C. at the heating rate of 0.2-5° C./min.
14. The method of claim 13 , wherein the system temperature after the pretreatment is increased to 210-290° C. at a heating rate of 0.2-2.5° C./min.
15. The method of claim 1 , wherein the precursor reduction, pretreatment and carbide preparation process is carried out in a Fischer-Tropsch synthesis reactor.
16. A supported ε/ε′ iron carbide catalyst for Fischer-Tropsch synthesis reaction obtained with the method of claim 1 .
17. A Fischer-Tropsch synthesis process comprising: contacting a synthesis feed gas with a catalyst under the Fischer-Tropsch synthesis reaction conditions, wherein the catalyst is the supported ε/ε′ iron carbide catalyst for the Fischer-Tropsch synthesis reaction of claim 9 .
18. The process of claim 17 , wherein the Fischer-Tropsch synthesis is carried out in a high temperature and high pressure continuous reactor.