AU2009214560A1 - Iron-based Fischer-Tropsch catalyst and method for making the same - Google Patents

Iron-based Fischer-Tropsch catalyst and method for making the same Download PDF

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AU2009214560A1
AU2009214560A1 AU2009214560A AU2009214560A AU2009214560A1 AU 2009214560 A1 AU2009214560 A1 AU 2009214560A1 AU 2009214560 A AU2009214560 A AU 2009214560A AU 2009214560 A AU2009214560 A AU 2009214560A AU 2009214560 A1 AU2009214560 A1 AU 2009214560A1
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catalyst
solid substance
iron
catalysts
solution
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AU2009214560A
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Guozhu Bian
Peijun Cong
Hui Han
Huaping Mao
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Accelergy Shanghai R & D Center Co Ltd
BP International Ltd
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Accelergy Shanghai R & D Center Co Ltd
BP International Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00279—Features relating to reactor vessels
    • B01J2219/00306—Reactor vessels in a multiple arrangement

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

WO 2009/100663 PCT/CN2009/070241 1 Iron-based Fischer-Tropsch catalyst and method for making the same Field of the Invention 5 The present invention relates to a catalyst and methods for making the same, especially to an iron-based Fischer-Tropsch catalyst and methods for making the same. Background of the Invention A Fischer-Tropsch Synthesis process is known as a process for 10 catalytically producing hydrocarbons from syngas (a mixture of carbon monoxide gas and hydrogen gas as chief constituents). Iron-based catalysts are widely used in commercial Fischer-Tropsch Synthesis operations because of their high activity in a relative broad temperature range. Because a small change in the composition of a catalyst, or in the process 15 for making the catalyst, may cause significant changes on its catalytic properties, continued research efforts have been made to improve the catalytic properties of iron-based catalysts, such as their selectivity to certain reaction products, activities, lifetimes, etc. Summary of the Invention 20 An embodiment of the present invention provides an iron-based Fischer-Tropsch catalyst. The catalyst comprises Fe, Mn, K, and Cu. The Fe/Mn molar ratio is less than 7:3, the content of Cu is approximately 0.5 wt% and the content of K is equal to or less than lwt %. An embodiment of the present invention further provides an iron-based 25 Fischer-Tropsch catalyst. The catalyst comprises Fe, Mn, Cu, and K. The Fe/Mn molar ratio is between 5:5 and 6:4, the content of K is between 0.4 wt% and 2.2 wt%, and the content of Cu is approximately 0.5 wt%. A method for making an iron-based catalyst according to one embodiment, comprises selecting a content of K, between 0.4 wt%/0 and 1 wt%, of the iron-based 30 catalyst, preparing a K 2
CO
3 solution according to the selected content of K, adding a first solid substance, which includes Fe and Mn, to the K 2
CO
3 solution for impregnation to obtain a second solid substance, drying the second solid substance, preparing a Cu(NO 3
)
2 solution according to a 0.5 wt% content of Cu of the WO 2009/100663 PCT/CN2009/070241 2 iron-based catalyst, adding the dried second solid substance to the Cu(N0 3
)
2 solution for impregnation to obtain a third solid substance, drying the third solid substance, and calcining the third solid substance to obtain the iron-based catalyst. An embodiment of the present invention further provides a step for preparing 5 the first solid substance. The step includes preparing a mixture solution containing certain concentration of Fe(N0 3
)
3 and Mn(N0 3
)
2 according to a certain Fe/Mn molar ratio, adding a precipitator to the mixture solution to cause co-precipitation until the pH value of the mixture solution is equal to a predetermined number, keeping the solution in stillness until the co-precipitation stabilizes, separating the 10 precipitate, washing the precipitate, drying the washed precipitate, and calcining the dried precipitate to obtain the first solid substance. In one embodiment, the precipitator is an ammonia solution or a NH 4
HCO
3 solution. An embodiment of the present invention further provides a step for preparing the first solid substance. The step includes preparing a first mixture solution 15 containing certain concentration of Fe(N0 3
)
3 and Mn(N0 3
)
2 according to a certain Fe/Mn molar ratio of the catalyst, adding a second mixture solution to the first mixture solution to form a colloid including Fe and Mn by sol-gel method, drying and decomposing the colloid to obtain a fourth solid substance, and calcining the fourth substance to form the first solid substance. In one embodiment, the second 20 mixture solution includes glycolic acid and ammonia or citric acid and ammonia. The catalysts of the present invention have higher CO conversion and lower selectivity for CO 2 than conventional catalysts in Fischer-Tropsch Synthesis. Brief Description of the Drawings Figure 1 is a schematic flow chart of a method for making a catalyst in 25 accordance with one embodiment of the present invention. Figure 2 are plots of CO conversion data versus time taken from Fischer-Tropsch Synthesis processes using catalysts with different Fe/Mn molar ratios, respectively, which are prepared by using the method illustrated in Figure 1 and ammonium hydroxide as precipitator. 30 Figure 3 are plots of CO conversion data versus time taken from Fischer-Tropsch Synthesis processes using catalysts with different Fe/Mn molar ratios, respectively, which are prepared by using the method illustrated in Figure 1 and NH4HCO3 as precipitator. Figure 4 is a schematic flow chart of a method for making a catalyst in WO 2009/100663 PCT/CN2009/070241 3 accordance with an alternative embodiment of the present invention. Figure 5 are plots of CO conversion data versus time taken from Fischer-Tropsch Synthesis processes using catalysts with different Fe/Mn molar ratios, respectively, which are prepared by using the method illustrated in Figure 5 5 and a glycolic acid sol-gel process. Figure 6 are plots of CO conversion data versus time taken from Fischer-Tropsch Synthesis processes using catalysts with different Fe/Mn molar ratios, respectively, which are prepared by using the method illustrated in Figure 5 and a citric acid sol-gel process. 10 Figure 7 are plots of data taken from a set of Fischer-Tropsch processes using a set of selected catalysts, respectively, illustrating relationship between CO conversion and C02 selectivity in the Fischer-Tropsch Synthesis processes. Figure 8 are plots of data taken from a set of Fischer-Tropsch processes using a set of selected catalysts, respectively, illustrating relationship between CO 15 conversion and CO2 selectivity in the Fischer-Tropsch Synthesis processes. Figure 9 is a schematic block diagram of a reactor system for testing catalysts prepared in the embodiments of the present invention. Detailed Description of the Embodiments Example 1: 20 Referring to FIG. 1, a method 100 for making an iron-based Fischer-Tropsch catalyst comprises preparing a first mixture solution containing Fe and Mn (step 101), causing the first mixture solution to co-precipitate (step 103), aging the precipitate (step 105), separating and washing the precipitate (step 107), drying and calcining the precipitate to 25 obtain a solid substance (step 109), impregnating the solid substance (step 111), calcining the impregnated solid substance (step 113), and pressing, grinding and sieving the calcined solid substance to obtain the catalyst (step 115). In step 101, certain amounts of Fe(NO 3
)
3 -9H 2 0, Mn(NO 3
)
2 (in one embodiment, in the form of 50 wt% solution), and water are weighed according 30 to a selected Fe/Mn molar ratio, and then mixed to form the mixture solution containing Fe and Mn. The amounts of Fe(N0 3
)
3 -9H 2 0, Mn(N0 3
)
2 , and water used to prepare the mixture solutions for different Fe/Mn molar ratios can be calculated with reference to Table 1.
WO 2009/100663 PCT/CN2009/070241 4 In step 103, a precipitator is added into the mixture solution until the pH value of the solution reaches a predetermined value to cause co-precipitation. In this example, 100 ml of 5.3 mol/1 ammonium hydroxide solution is used as the precipitator. 5 Table 1 amounts of precursors according to different Fe/Mn molar ratios Sample Fe/Mn molar ratio Fe(N03)3-9H20 (g) 50wtMn(NO3)2 (g) H20 (g) 1 9:1 81.8 8.1 94.3 2 7:3 63.6 24.2 96.0 3 6:4 54.5 32.2 96.9 4 5:5 45.5 40.3 97.7 5 4:6 36.4 48.3 98.5 6 3:7 27.3 53.4 99.4 7 2:8 18.2 64.4 100.4 In step 105, the precipitate is allowed to age for 1-4 hrs. In step 107, the precipitate is separated by, for example, centrifugal separation, and then washed using 600 ml de-ionized water for several times (e.g. 5 times). In step 10 109, the washed precipitate is dried at 110C for 16 hrs, and then calcined at 350 C for about 1hr to form a solid substance. In step 111, the solid substance obtained by step 109 is impregnated with K and Cu. In this example, impregnation is done by adding 9 grams of the solid substance to an 18 ml aqueous solution containing 0.16 grams K 2
CO
3 , which is afterwards dried at 15 110 C for 6 hrs. The dried solid substance thus obtained is then added to an 18 ml aqueous solution containing 0.28 grams Cu(NO 3
)
2 -3H 2 0, which is afterwards dried at 110 0 C for 16 hrs to result in the impregnated solid substance. In this example, the impregnated solid substance obtained from step 111 includes 1 wt% K and 0.5 wt% Cu. Catalysts with other K and Cu loadings 20 can be obtained similarly by adjusting the weight of the solid substance, the volume of the aqueous solution containing 0.16 grams K 2
CO
3 or the concentration of K 2
CO
3 in the solution, and/or the volume of the aqueous solution containing 0.28 grams Cu(NO 3
)
2 -3H 2 0 or the concentration of Cu(NO 3
)
2 -3H 2 0 in the solution. 25 In step 113, the impregnated solid substance obtained by step 111 is calcined at 400'C for 4 hrs. In step 115, the calcined solid substance is finally pressed and crushed in order to form catalyst particles with diameters in a WO 2009/100663 PCT/CN2009/070241 5 range of 20-40 meshes. The method 100 can also be used to prepare catalysts with different compositions. The catalysts prepared by method 100 can be used in Fischer-Tropsch Synthesis processes after reduction. The catalysts are 5 commonly loaded in an apparatus, such as a reduction reactor, to be activated by reduction under certain conditions before being used. Then, the reduced catalysts can be loaded in an appropriate reactor system to conduct Fischer-Tropsch Synthesis process at certain reaction conditions. The effluents of the Fischer-Tropsch Synthesis process can be analyzed, and thus some 10 properties of the catalysts can be determined. The catalysts can be loaded in a parallel reactor system, such as a parallel reactor system of Accelergy R&D Center (Shanghai) Co., Ltd. for carrying out both reduction and Fischer-Tropsch Synthesis reactions. FIG. 9 illustrates a schematic configuration of the parallel reactor system, which can be used to 15 test multiple catalysts of the same or different properties in parallel. The reactor system 900 includes a feed inlet module 910, a reactor module 920, a monitoring module 930 and an analysis module 940. The reactor module 920 comprises reactors 920-1, 920-2,..., 920-n (n '1), each of which has an inlet and an outlet. The feed inlet module 910 is connected to the inlets of each 20 reactor to feed H 2 and CO to the reactors. The monitoring module 930 is used to monitor and/or control the reactor system 900. The analysis module 940 is connected to the outlets of each reactor and is used to analyze the effluents of the F-T reaction. The catalysts with different Fe/Mn molar ratios can be loaded in different 25 reactors of the reactor module 920 and be tested in parallel. In one embodiment, the reduction conditions are: atmospheric pressure, 270'C, a H 2 /CO ratio of 1.7, and a space velocity of 2000 h-1. After reduction, the catalysts can be used to carry out Fischer-Tropsch Synthesis processes, respectively. In one embodiment, although the reactors are loaded with different catalysts, the 30 reaction conditions for the Fischer-Tropsch Synthesis processes are the same for each reactor. In one example, the reaction conditions for the Fischer-Tropsch Synthesis processes are: pressure ~ 2.0 MPa, temperature ~ 240'C, H 2 /CO ratio ~ 1.7, and space velocity ~ 2000 h-'. Referring to FIG. 2, curves 201, 202, 203, 204, 205, 206, and 207 are plots of 35 CO conversion data versus time taken from reactions using catalysts with K WO 2009/100663 PCT/CN2009/070241 6 loading of 1 wt%, Cu loading of 0.5 wt%, and Fe/Mn molar ratios of 6:4, 5:5, 4:6, 7:3, 3:7, 2:8, and 9:1, respectively. As illustrated by FIG. 2, catalysts with the Fe/Mn molar ratios of 6/:4, 51:5, 4/:6, and 7/:3, result in higher CO conversions than other catalysts. After a short period of time in the beginning, the CO 5 conversions increase to higher than 70%, and keep relatively stable at about or above 70% for a long period of time (more than 120 hrs.). Especially, the catalyst with the Fe/Mn molar ratio of 6:4 results in a CO conversion higher than 80% after a short period of time in the beginning of the reaction. And fluctuation of the CO conversion for this catalyst is less than 10% in a long 10 period of time (more than 120 hrs.). The CO conversion of the catalysts with the Fe/Mn molar ratios of 5:5, 4:6, and 7:3 remains between 70%-80% during this period of time. The CO conversion of the catalyst with the Fe/Mn molar ratio of 5:5 is higher than the catalyst with the Fe/Mn molar ratio of 4:6, and the CO conversion of the catalyst with the Fe/Mn molar ratio of 4:6 is higher 15 than the catalyst with the Fe/Mn molar ratio of 7:3. The CO conversion of the catalyst with the Fe/Mn molar ratio of 3:7 stabilizes in the range of 60%- 7 0 %, which is lower than the CO conversion of the catalysts with the Fe/Mn molar ratios of 6:4, 5:5, and 4:6. The catalyst with the Fe/Mn molar ratio of 9/:1 has a high CO conversion at the beginning, but its CO conversion soon drops below 20 40%. The catalyst with the Fe/Mn molar ratio of 2:8 has a lower CO conversion that stabilizes at a level lower than 60%. Example 2: In this example, method 100 is also utilized to prepare catalysts. As shown in Figure 1, in one embodiment, compared with example 1, 400 ml of 1.3 mol/l 25 NH 4
HCO
3 solution is used as the precipitator, instead of 100 ml of 5.3 mol/l ammonia solution. In step 103, 1.3 mol/l NH 4
HCO
3 solution is added to a solution of Fe(N0 3
)
3 and Mn(N0 3
)
2 to cause co-precipitation until the pH value reaches 7.5. Other steps are similar to the corresponding steps described in example 1. 30 The catalysts prepared in example 2 are reduced and tested in the reactor system 900 under the same testing/reaction conditions as the conditions described in example 1, and the results are discussed below. Referring to FIG. 3, the curves 301, 302, 303, 304, 305, 306, and 307 are plots of CO conversion data versus time taken from reactions using the catalysts 35 with K loading of 1 wt%, Cu loading of 0.5 wt%, and Fe/Mn molar ratios of 6:4, WO 2009/100663 PCT/CN2009/070241 7 5:5, 4:6, 7:3, 3:7, 2:8, and 9:1 respectively. As illustrated in FIG. 3, CO conversions of catalysts with the Fe/Mn molar ratios of 6:4, 5:5, and 4:6 increase to higher than 70% in a short period of time start of the reactions, and then become relatively stable for a long period of time (more than 120 hrs.). 5 Especially, the catalyst with the Fe/Mn molar ratio of 6:4 results in a CO conversion higher than 80% after a short period of time in the beginning, and the fluctuation of CO conversion is less than 10% for a long period of time. The CO conversions of the catalysts with the Fe/Mn molar ratios of 5:5 and 4:6 are higher than 70% and lower than 80%, which is lower than the CO 10 conversion of the catalyst with the Fe/Mn molar ratio of 6:4. Catalyst with the Fe/Mn molar ratio of 3:7 shows a relatively stable CO conversion, which stays in a range of 60%-70%, and which is less than the CO conversion of the catalysts with the Fe/Mn molar ratios of 6:4, 5:5, and 4:6. Catalysts with the Fe/Mn molar ratios of 7:3 and 9:1 have high CO conversion at the beginning, 15 but the CO conversion drops below 40% indicating quick deactivation of the catalysts. The catalyst with the Fe/Mn molar ratio of 2:8 has a CO conversion lower than 60%. Example 3: Referring to FIG. 4, according to another embodiment of the present 20 invention, a method 400 for making an iron-based Fischer-Tropsch catalyst includes step 401 of preparing a mixture solution containing Fe and Mn, step 403 of making a colloid using sol-gel method, step 405 of drying and decomposing the colloid, step 407 of calcining, step 409 of impregnating and calcining, step 411 of calcining, and step 413 of pressing, grinding, and 25 sieving. In step 401, certain amounts of Fe(N0 3
)
3 -9H 2 0, Mn(N0 3
)
2 and water are weighed according to a selected Fe/Mn molar ratio, and then mixed to form a first mixture solution. The amounts of Fe(N0 3
)
3 -9H 2 0, Mn(N0 3
)
2 and water for different Fe/Mn molar ratios are given in Table 1. 30 In step 403, a second mixture solution is prepared and added to the first solution prepared by step 401 to form a colloid. In one embodiment, the second mixture solution is prepared by mixing 34.9 grams glycolic acid, 5.3 grams H 2 0, and 40 ml 25 wt% ammonia solution, which has a pH value of 6.5. In step 405, the colloid is dried in air at 100'C, and then decomposed at 130-180'C. In step 35 407, the substance obtained by step 405 is calcined in air at 300-450'C for 1 hr WO 2009/100663 PCT/CN2009/070241 8 to form a solid substance. In step 409, 9 grams of the solid substance obtained by step 407 is added into an 18 ml aqueous solution of 0.16 grams K 2
CO
3 for impregnation, and then the combination is dried at 110 C for 6 hrs. Subsequently the dried solid 5 substance is added into an 18 ml aqueous solution of 0.28 grams Cu(NO 3
)
2 -3H 2 0 for impregnation followed by drying at 110 C for 16 hrs. Thus, a solid substance obtained by step 409 includes about 1 wt% of K and about 0.5 wt% of Cu. In step 411, the solid substance obtained by step 409 is calcined at 400'C 10 for 4 hrs. In step 413, the solid substance obtained by step 411 is pressed and crushed to form catalyst particles with diameters in a range of 20-40 meshes. The method 400 can be used repeatedly to prepare catalysts with different compositions. The catalysts prepared in example 3 are reduced and tested in the reactor 15 system 900 under the same testing/reaction conditions as those described in example 1, and the results are discussed below. Referring to FIG. 5, the curves 501, 502, 503, 504, 505, 506, and 507 illustrate CO conversion versus time for the catalysts with K loading of 1 wt%, Cu loading of 0.5wt%, and Fe/Mn molar ratios of 6:4, 5:5, 4:6, 7:3, 3:7, 2:8, and 9:1 20 respectively. As illustrated in FIG. 5, the catalyst with the Fe/Mn molar ratio of 6:4 results in a CO conversion higher than 80% after a short period of time in the beginning, and the fluctuation of the CO conversion is less than 10% for a long period of time (more than 120 hrs). The CO conversion of the catalyst with the Fe/Mn molar ratio of 7:3 is lower than that of the catalyst with the 25 Fe/Mn molar ratio of 6:4. Their CO conversion is about 80% after a short period of time in the beginning, and decreases below 70% after 140 hrs. CO conversion of the catalysts with the Fe/Mn molar ratios of 3:7, 4:6, 5:5, and 9:1 are higher than 60%, 60%, 60%, and 80% respectively at the beginning, and decrease below 50%, 60%, 30% and 20% in a short period of time respectively. 30 The catalyst with the Fe/Mn molar ratio of 2:8 is less active and its CO conversion never reaches 30%. Example 4: In this example, method 400 is also used to make catalysts. As shown in FIG 4, in one embodiment, in step 403, 29.4 grams glycolic acid and 40 ml 25 WO 2009/100663 PCT/CN2009/070241 9 wt% ammonia solution are mixed to form a complexing agent. Then, the complexing agent is added to the first mixture solution containing Fe and Mn to form a colloid, while the first solution is agitated. Other steps are similar to those described in example 3. 5 The catalysts prepared in example 4 are reduced and tested in the reactor system 900 under the same testing/reaction conditions as those applied in example 1, and the results are discussed below. Referring to FIG. 6, the curves 601, 602, 603, 604, 605, 606, and 607 illustrate CO conversion versus time for the catalysts with K loading of 1 wt%, Cu 10 loading of 0.5 wt%, and Fe/Mn molar ratios of 6:4, 5:5, 4:6, 7:3, 3:7, 2:8, and 9:1 respectively. As illustrated in FIG. 6, the catalyst with the Fe/Mn molar ratio of 6:4 shows a higher stability and activity than other catalysts in this embodiment. The CO conversion of the catalyst with the Fe/Mn molar ratio of 6:4 remains above 80% in a relatively long period of time (e.g. more than 15 100-140 hrs.), and the fluctuation of the CO conversion is lower than 10%. The activities of other catalysts are significantly lower than the catalyst with the Fe/Mn ratio of 6:4, and their CO conversion drops below 40% after about 80 hrs. Example 5: 20 In this example, method 100 is used to make catalysts. As shown in FIG 1, in one embodiment, in step 101, 23.7 grams Fe(NO 3
)
3 -9H 2 0 and 21 grams Mn(N0 3
)
2 are dissolved in 50.9 grams H 2 0 to form a solution. In step 103, 100 ml 5.3 mol/1 ammonia solution is used as a precipitator. In an alternative embodiment, 400 ml 1.3 mol/1 NH 4
HCO
3 solution instead of the 25 100 ml 5.3 mol/1 ammonia solution is used as the precipitator. In step 111, a solid substance obtained by step 109 is first impregnated with a K 2
CO
3 solution, which is prepared by dissolving 0.06 grams K 2
CO
3 in 10.8g H 2 0, 0.16 grams K 2 C0 3 in 10.8 grams H 2 0, 0.26 grams K 2
CO
3 in 10.8 grams H 2 0, or 0.35g K 2
CO
3 in 10.8g H 2 0, for a K loading of the catalyst at 0.4 30 wt%, 1 wt%, 1.6 wt%, and 2.2 wt% , respectively, and then dried at 110 C for 6 hrs. Subsequently, the dried solid substance is impregnated with a Cu(N0 3
)
2 solution, which is prepared by dissolving 0.28 grams Cu(NO 3
)
2 -3H 2 0 in 10.8g
H
2 0, for a Cu loading of the catalyst at about 0.5 wt%, and then dried at 110 C for 16 hrs. Other steps are similar to the corresponding steps in example 1.
WO 2009/100663 PCT/CN2009/070241 10 Catalysts with different K loadings are prepared to investigate effects of the different K loadings on the properties of the iron-based catalysts. The catalysts prepared in example 5 are reduced and tested in the reactor system 900 under the same testing/reaction conditions as those described in 5 example 1. The reaction time is about 150 hrs. The reaction results are shown in Table 2. Table 2: The reaction results of the catalysts prepared in the examples 5-6 CO CH 4
CO
2 C=/C- C 5 + C 5 + Catalysts Conversion Selectivity Selectivity ratio Selectivity Productivity 5Fe-5Mn-NH 4 0H-0.4K-0.5Cu 52% 5.1% 27% 1.6 52% 107 5Fe-5Mn-NH 4 0H-IK-0.5Cu 74% 2.8% 35% 2.9 52% 147 5Fe-5Mn-NH 4 0H-1.6K-O.5Cu 21% 3.0% 30% 2.8 58% 47 5Fe-5Mn-NH 4 0H-2.2K-0.5Cu 17% 2.8% 27% 13.2 63% 40 5Fe-5Mn-NH 4
HCO
3 -0.4K-0.5Cu 48% 4 .0% 2 9 % 2.0 54% 100 5Fe-5Mn-NH 4
HCO
3 -IK-0.5Cu 69% 2.6% 36% 2.9 52% 139 5Fe-5Mn-NH 4
HCO
3 -1.6K-0.5Cu 19% 3.3% 28% 2.6 59% 39 5Fe-5Mn-NH 4
HCO
3 -2.2K-0.5Cu 14% 3.1% 29% 7.2 6 0 % 33 6Fe-4Mn-NH 4 0H-0.4K-0.5Cu 58% 3.9% 29% 2.0 53% 115 6Fe-4Mn-NH 4 0H-1K-0.5Cu 7 5 % 2.7% 3 5 % 3.1 53% 148 6Fe-4Mn-NH 4 0H-1.6K-0.5Cu 16% 2
.
6 % 2 6 % 6.7 65% 39 6Fe-4Mn-NH 4 0H-2.2K-0.5Cu 16% 2.8% 28% 8.0 62% 38 6Fe-4Mn-NH 4
HCO
3 -0.4K-0.5Cu 63% 3.3% 33% 2.2 52% 123 6Fe-4Mn-NH 4
HCO
3 -IK-0.5Cu 6 4 % 2
.
9 % 3 6 % 2.8 51% 121 6Fe-4Mn-NH 4
HCO
3 -1.6K-0.5Cu 15% 3 .5% 2 9 % 4.0 58% 32 6Fe-4Mn-NH 4
HCO
3 -2.2K-0.5Cu 16% 2.7% 29% 8.2 61% 36 Example 6: 10 In this example, method 100 is used to make catalysts. As shown in Figure 1, in one embodiment, in step 101, 28.4 grams of Fe(N0 3
)
3 -9H 2 0 and 16.7 grams Mn(N0 3
)
2 are dissolved in 50.4 grams H 2 0 to form a solution with Fe/Mn ratio of 6:4. The other steps are similar to the corresponding steps in example 5. Catalysts with Fe/Mn molar ratio of 6:4, Cu loading of 0.5 wt%, and K 15 loadings of 0.4 wto, 1 wt% 1.6 wt%, and 2.2 wto are each prepared using method 100.
WO 2009/100663 PCT/CN2009/070241 11 The catalysts are then reduced and tested in the reactor system 900 under the same testing/reaction conditions as those described in example 1. The reaction time is about 150hrs. The reaction results are shown in the Table 2. Referring to Table 2, catalysts with K loading of 0.4 wto and 1 wt% have 5 relatively higher CO conversion compared to catalysts with higher K loadings of 1.6 wt% and 2.2 wt
%
. Figures 7-8 illustrate the relationship between the CO conversion and the CO 2 selectivity in the Fischer-Tropsch Synthesis processes using catalysts with Fe/Mn molar ratios of 5:5 and 6:4, Cu loading of 0.5 wt%, and K loadings of 0.4 wt%, 1 10 wt%, 1.6 wt%, and 2.2 wt%, respectively. For convenience, the catalysts with K loadings of 0.4 wt%, 1 wt%, 1.6 wt%, and 2.2 wt% are referred as A, B, C, and D catalysts respectively. In Figures 7-8, the rectangular shaped data points 70 and 80 show the relationship between the CO conversion and the CO 2 selectivity using the D 15 catalyst measured at different times. Ellipse shaped data points 71 and 81 show the relationship between the CO conversion and the CO 2 selectivity using the C catalyst measured at different times. Triangular shaped data points 72 and 82 show the relationship between the CO conversion and the CO 2 using the B catalyst measured at different times. X shaped data points 73 and 83 show the relationship 20 between the CO conversion and the CO 2 selectivity using the A catalyst measured at different times. Referring to Figures 7-8, the beelines 74 and 84 approximately illustrate the relationship between the CO conversion and the CO 2 selectivity when using the A catalyst. The beelines 75 and 85 approximately illustrate the relationship between 25 the CO conversion and the CO 2 selectivity when using the B catalyst. The relationship between the CO conversion and the CO 2 selectivity using the A and B catalysts show certain regularity, indicating that the properties of the A and B catalysts are relatively stable. In contrast, the relationship between the CO conversion and the CO 2 selectivity using the C and D catalysts is more irregular, 30 indicating that the properties of the C and D catalysts are less stable. Therefore, the K loading range of 0.4 wt%-1 wt% is preferred, and the K loading of 0.4 wt% is more preferred.

Claims (16)

1. An iron-based Fischer-Tropsch catalyst comprising Fe, Mn, K, and Cu, and having an Fe/Mn molar ratio less than 7:3, a Cu loading about 0.5 wt%, and a K 5 loading equal to or less than about 1 wt%.
2. The iron-based catalyst according to claim 1, wherein the Fe/Mn molar ratio is equal to or greater than 3:7, and less than 7:3.
3. The iron-based catalyst according to claim 2, wherein the Fe/Mn molar ratio is equal to or greater than 4:6, and less than 7:3. 10
4. The iron-based catalyst according to claim 3, wherein the Fe/Mn molar ratio is in a range of about 4:6 to about 6:4.
5. The iron-based catalyst according to claim 4, wherein the Fe/Mn molar ratio is in a range of about 5:5 to about 6:4.
6. An iron-based Fischer-Tropsch catalyst comprising 15 Fe, Mn, Cu, and K, and having an Fe/Mn molar ratio in a range of about 5:5 to about 6:4, a K loading in a range of about 0.4 wt/o to about 2.2 wt%, and a Cu loading approximately 0.5 wt%.
7. The iron-based catalyst according to claim 6, wherein the K loading is between 0.4 wt% and 1 wt%. 20
8. The iron-based catalyst according to claim 7, wherein the K loading is approximately 1 wt%.
9. The iron-based catalyst according to claim 7, wherein the K loading is approximately 0.4 wt%.
10. A method for making an iron-based Fischer-Tropsch catalyst comprising: 25 preparing a K 2 CO 3 solution according to a K loading in a range of about 0.4 wt% to about 1 wt% for the catalyst impregnating a first solid substance including Fe and Mn using the K 2 C0 3 solution to form a second solid substance; preparing a Cu(N0 3 ) 2 solution according to a Cu loading of about 0.5 wt% for 30 the catalyst; impregnating the second solid substance with the Cu(N0 3 ) 2 solution to form a WO 2009/100663 PCT/CN2009/070241 13 third solid substance; and calcining the third solid substance to form the catalyst.
11. The method according to claim 10, further comprising preparing the first solid substance, which comprises: 5 preparing a mixture solution including Fe(NO 3 ) 3 and Mn(NO3)2 according to a predetermined Fe/Mn molar ratio for the catalyst; adding a precipitator to the mixture solution until a pH value of the mixture solution is equal to a predetermined number so as to cause co-precipitation; and aging the mixture solution for a predetermined period of time. 10
12. The method according to claim 11, wherein the precipitator is an ammonia solution of a pH value equal to 9.0.
13. The method according to claim 11, wherein the precipitator is a N H 4HC0 3 solution of a pH value equal to 7.5.
14. The method according to claim 10, further comprising preparing the first 15 solid substance, which comprises: preparing a first mixture solution including Fe(N0 3 ) 3 and Mn(NO 3 ) 2 according to a predetermined Fe/Mn molar ratio for the catalyst; adding a second mixture solution to the first mixture solution to form a colloid including Fe and Mn by a sol-gel method; 20 drying and decomposing the colloid to form a fourth solid substance; and calcining the fourth solid substance to form the first solid substance.
15. The method according to claim 14, wherein the second mixture solution includes glycolic acid and ammonia.
16. The method according to claim 14, wherein the second mixture solution 25 includes citric acid and ammonia.
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