Preparation method of Fischer-Tropsch synthesis iron-based catalyst

Abstract

The invention provides a preparation method of a Fischer-Tropsch synthesis iron-based catalyst, Fe-Cu-K-M-Q-SiO2 is used as a basic formula, M element is selected from at least one of vanadium, tin, manganese, aluminum, cobalt, nickel, ruthenium, zinc and chromium, Q element is selected from at least one of cerium, zirconium, lanthanum, magnesium, calcium, barium, neodymium, strontium and boron, and the balance is Fe. According to the Fischer-Tropsch synthesis precipitation iron-based catalyst and the preparation method thereof, a coprecipitation reaction of a catalyst precursor is carried out by combining a supergravity rotating packed bed reactor, and then filtering, washing, drying and roasting are carried out, so that the finally prepared Fischer-Tropsch synthesis precipitation iron-based catalyst has high reaction activity, selectivity and stability and also has high wear resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of Fischer-Tropsch synthesis, particularly to the field of Fischer-Tropsch synthesis catalysts, and specifically relates to a preparation method of a Fischer-Tropsch synthesis iron-based catalyst. Background Art

[0002] The Fischer-Tropsch synthesis reaction can synthesize hydrocarbon compounds with different carbon numbers under appropriate temperature, pressure and the action of a catalyst using CO and H 2 and the products are further processed to obtain fuels and chemicals. The Fischer-Tropsch synthesis can be used to realize the energy conversion of coal, natural gas, biomass, etc. to oil through syngas. The low-temperature Fischer-Tropsch synthesis technology has a reaction temperature of less than 280 °C, usually using a fixed-bed or slurry-bed reactor, and the catalyst is a precipitated iron catalyst (suitable reaction temperature is 250 - 280 °C) or a supported cobalt catalyst (suitable reaction temperature is 200 - 230 °C), and the products are mainly diesel and wax. Due to different active phase structures and different main and side reaction paths, cobalt-based catalysts and iron-based catalysts have different formulation compositions and preparation methods. Iron-based catalysts with iron as the active component are more suitable for large-scale industrial applications due to their low price, strong anti-poisoning ability, and high content of linear α-olefins in the products.

[0003] Currently, in the preparation process of precipitated iron catalysts, the core co-precipitation reaction process is mainly completed in a stirred tank. Usually in a stirred tank, due to insufficient conventional stirring intensity, the mixing process of reactants is slow, and the mass transfer and mixing rate of molecules in the microscopic region is significantly slower than the nucleation reaction, directly affecting the nucleation and subsequent growth process of the precipitated colloid. The particle size distribution of the prepared catalyst precursor colloid is wide and the element distribution is uneven, resulting in problems such as low activity, low abrasion resistance, poor selectivity and stability of the finally prepared catalyst. In addition, the co-precipitation reaction process takes a long time and is not suitable for the feeding reaction of high-concentration reactant solutions, seriously restricting the production efficiency of Fischer-Tropsch precipitated iron catalysts.

[0004] For example, CN200410012349.3 discloses a microspherical Fischer-Tropsch synthesis iron-based catalyst, and its weight ratio composition is: Fe:Ce:Cu:K:SiO 2 = 100:(0.3 - 5):(1 - 10):(1 - 8):(5 - 40). Using a mixed solution of iron nitrate, cerium nitrate and copper acetate as raw materials, and sodium carbonate as the precipitant, co-precipitation is carried out in a precipitating dish with stirring to obtain a precipitated slurry, and then appropriate K 2 C 2 O 4The catalyst slurry is spray-dried and formed into a mixed solution with silica sol, and then placed in a tunnel kiln for calcination in an air atmosphere for 2 to 12 hours. It is said that the obtained catalyst has good sphericity and high wear resistance index, and can be directly used for slurry bed Fischer-Tropsch synthesis. The methane selectivity in the product is less than 4wt%, the C5+ selectivity is higher than 80wt%, and the olefin content is higher than 65%. This technology completes the precipitation reaction in a stirred sedimentation dish, and during the precipitation reaction, a certain amount of cerium is introduced into the catalyst formula to improve the catalyst activity and the selectivity of the product olefins, and the catalyst has a high wear resistance index. However, the methane selectivity of the catalyst prepared by this technology is still high, and there is still significant room for improvement in the catalyst activity, C5+ selectivity and olefin content in the product. In addition, this technology does not disclose the carbon dioxide selectivity of the catalyst.

[0005] Therefore, choosing a chemical process intensification equipment to provide a strong and uniform micro-mixing environment during the co-precipitation process of the precipitated iron catalyst to obtain a catalyst precursor with uniform morphology and surface structure, uniform element distribution and narrow particle size distribution is important for further improving the performance of the precipitated iron catalyst. In addition, by strengthening the co-precipitation reaction process, the entire catalyst production preparation time can be shortened, the reactant feed concentration can be increased, and the production efficiency of the Fischer-Tropsch precipitated iron catalyst can be significantly improved. Summary of the invention

[0006] In view of the problems existing in the prior art, one of the objects of the present invention is to provide a method for preparing an iron-based catalyst for Fischer-Tropsch synthesis, wherein the prepared precipitated iron-based catalyst for Fischer-Tropsch synthesis has high reaction activity, selectivity and stability while also having high anti-wear performance.

[0007] To achieve the purpose, the present invention provides the following technical solutions:

[0008] In one aspect of the present invention, it relates to a method for preparing a Fischer-Tropsch synthesis iron-based catalyst, wherein the Fischer-Tropsch synthesis iron-based catalyst comprises Fe element, Cu element, K element, M element, Q element and SiO 2 , wherein the M element is selected from at least one of vanadium, tin, manganese, aluminum, cobalt, nickel, ruthenium, zinc and chromium, and the Q element is selected from at least one of cerium, zirconium, lanthanum, magnesium, calcium, barium, neodymium, strontium and boron,

[0009] The preparation method comprises the following steps:

[0010] S1: forming a mixed iron salt solution with a water-soluble salt of Fe and a water-soluble salt of Cu, preparing a precipitant solution, and adding 0 to 100 wt % (e.g., about 10 wt %, about 20 wt %, about 30 wt %, about 40 wt %, about 50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, about 90 wt % or any combination of weight ratio intervals) of a silicon source to the precipitant solution;

[0011] S2: allowing the mixed iron salt solution and the precipitant solution to undergo a co-precipitation reaction in a high gravity rotating packed bed reactor, and collecting the precipitated slurry;

[0012] S3: separating the precipitation product from the precipitation slurry;

[0013] S4: mixing the precipitation product with the K element precursor aqueous solution and the remaining silicon source to form a mixed slurry and performing slurry treatment to obtain a catalyst precursor slurry; and

[0014] S5: drying and calcining the catalyst precursor slurry;

[0015] The method of adding the M element includes: adding the M element precursor aqueous solution to the mixed iron salt solution and / or the precipitant solution in step S1; or adding the M element precursor aqueous solution to the K element precursor aqueous solution and / or the mixed slurry in step S4;

[0016] The method of adding the Q element includes: adding the Q element precursor aqueous solution to the mixed iron salt solution and / or precipitant solution in step S1; or adding the Q element precursor aqueous solution to the K element precursor aqueous solution and / or mixed slurry in step S4.

[0017] In some embodiments of the preparation method of the present invention, the water-soluble salt of Fe is a nitrate, a hydrochloride or a hydrate of each of Fe. Preferably, in the mixed aqueous solution, the concentration of Fe is 5 to 100 g / L (for example, about 10 g / L, about 20 g / L, about 30 g / L, about 40 g / L, about 50 g / L, about 60 g / L, about 70 g / L, about 80 g / L, about 90 g / L or any combination of concentration intervals).

[0018] In some embodiments of the preparation method of the present invention, the water-soluble salt of Cu is Cu nitrate, Cu hydrochloride or their respective hydrates.

[0019] In some embodiments of the preparation method of the present invention, the precipitant is selected from one or more of sodium carbonate, ammonia water, ammonium carbonate, sodium hydroxide, potassium hydroxide, and potassium carbonate. In a preferred embodiment of the preparation method of the present invention, the concentration of the precipitant is 50 to 150 g / L (for example, about 60 g / L, about 70 g / L, about 80 g / L, about 90 g / L, about 100 g / L, about 110 g / L, about 120 g / L, about 130 g / L, about 140 g / L, or any combination of concentration intervals).

[0020] In some embodiments of the preparation method of the present invention, the silicon source is selected from one or more of potassium silicate solution, sodium silicate solution, and silica sol solution, wherein SiO 2 The concentration is 10-50 wt % (for example, about 20 wt %, about 30 wt %, about 40 wt % or any combination of concentration ranges).

[0021] In some embodiments of the preparation method of the present invention, the K element precursor is one or more of potassium nitrate, potassium carbonate, potassium bicarbonate, potassium chloride, and potassium silicate.

[0022] In some embodiments of the preparation method of the present invention, when the M element is vanadium, the M element precursor is one or more metavanadates, preferably sodium metavanadate or potassium metavanadate; when the M element is ruthenium, the M element precursor is Ru(NO)(NO 3 ) x (OH) y , x+y=3; when the M element is other metal, the M element precursor is the nitrate, hydrochloride or their respective hydrates of the metal.

[0023] In some embodiments of the preparation method of the present invention, when the Q element is boron, the Q element precursor is one or more of boric acid, metaboric acid, boric oxide, and water-soluble borates; when the Q element is other metals, the Q element precursor is the nitrate, hydrochloride or their respective hydrates of the metal.

[0024] In some embodiments of the preparation method of the present invention, the co-precipitation reaction includes: adding the mixed iron salt solution into the cavity of the high-gravity rotating packed bed reactor from the acid feed port, so that the mixed iron salt solution is kept under the action of centrifugal force; when the rotor speed of the high-gravity rotating packed bed reactor is stable, adding the precipitant solution into the cavity of the high-gravity rotating packed bed reactor from the alkali feed port, so that the mixed iron salt solution and the precipitant solution undergo a co-precipitation reaction in the packing layer, and collecting the precipitated slurry.

[0025] In some preferred embodiments of the preparation method of the present invention, before the mixed iron salt solution is added to the high-gravity rotating packed bed reactor, the reactor temperature is maintained at 10-80°C (for example, it can be about 20°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C or any combination of temperature intervals).

[0026] In some preferred embodiments of the preparation method of the present invention, the rotor speed of the high gravity rotating packed bed reactor during the coprecipitation reaction is 500-2500 rpm (for example, it can be about 1000 rpm, about 1500 rpm, about 2000 rpm or any combination of speed ranges).

[0027] In some embodiments of the preparation method of the present invention, in the step S2, the precipitation temperature of the coprecipitation reaction is 5 to 95°C (for example, it can be about 20°C, about 40°C, about 60°C, about 80°C, or any combination of temperature intervals), the precipitation time is 5 to 100 min (for example, it can be about 10 min, about 20 min, about 30 min, about 40 min, about 50 min, about 60 min, about 70 min, about 80 min, about 90 min, or any combination of time intervals), and the pH value is controlled at 5 to 10 during the precipitation process (for example, it can be about 6, about 7, about 8, about 9, or any combination of pH value intervals).

[0028] In some embodiments of the preparation method of the present invention, the slurrying temperature of the slurrying treatment is 10-80°C (for example, it can be about 20°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, or any combination of temperature intervals), the slurrying time is 10-80min (for example, it can be about 20min, about 30min, about 40min, about 50min, about 60min, about 70min, or any combination of time intervals), and the concentration of the slurry during the slurrying treatment is controlled to be 5-40wt% (for example, it can be about 10wt%, about 15wt%, about 20wt%, about 25wt%, about 30wt%, about 35wt%, or any combination of concentration intervals).

[0029] In some embodiments of the preparation method of the present invention, in the step S5, the drying includes the following process: first, the catalyst precursor slurry is spray-dried, and the obtained powder is dried in an air atmosphere at 110-300°C (for example, about 150°C, about 200°C, about 250°C can be any combination of temperature intervals) for 1-12h (for example, about 2h, 4h, 6h, 8h, 10h or any combination of time intervals); preferably, the hot air inlet temperature of the spray drying is 180-400°C (for example, about 240°C, about 300°C, about 360°C or any combination of temperature intervals), and the exhaust outlet temperature is 100-220°C (for example, about 140°C, about 160°C, about 180°C, about 200°C or any combination of temperature intervals).

[0030] In some embodiments of the preparation method of the present invention, in the step S5, the calcination temperature is 400-600°C (for example, it can be about 450°C, about 500°C, about 550°C, or any combination of temperature intervals), and the calcination time is 1-15h (for example, it can be 2h, 4h, 6h, 8h, 10h, 12h, 14h, or any combination of time intervals).

[0031] In another aspect of the present invention, it relates to an iron-based catalyst for Fischer-Tropsch synthesis obtained by the above preparation method.

[0032] In some embodiments of the Fischer-Tropsch synthesis iron-based catalyst of the present invention, the following weight ratios are used: Fe element: Cu element: K element: M element: Q element: SiO 2 =100: 0.2-5 (e.g., 0.4, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or any combination thereof): 0.5-8 (e.g., 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5 or any combination thereof): 0.5-10 (e.g., 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4 .5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 or any combination thereof): 0.5-10 (for example, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 or any combination thereof): 10-42 (for example, 15, 20, 25, 30, 35, 40 or any combination thereof).

[0033] Fe-Cu-KMQ-SiO 2The invention adopts a formula (M is at least one selected from vanadium, tin, manganese, aluminum, cobalt, nickel, ruthenium, zinc and chromium; Q is at least one selected from cerium, zirconium, lanthanum, magnesium, calcium, barium, neodymium, strontium and boron), and uses a supergravity method in combination to prepare a Fischer-Tropsch synthesis iron-based catalyst. On the basis of the above formula, a co-precipitation preparation process of a catalyst precursor is carried out in a supergravity reactor, and then after filtering, washing, drying and roasting processes, the Fischer-Tropsch synthesis precipitated iron-based catalyst finally obtained has high reactivity, selectivity and stability while also having high wear resistance. In addition, the co-precipitation unit in the catalyst preparation process is short in time, and the feed solubility of the raw material solution is high, which significantly improves the production efficiency of the Fischer-Tropsch precipitated iron catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a process schematic diagram of the co-precipitation reaction using a high gravity rotating packed bed reactor in the present invention. DETAILED DESCRIPTION

[0035] In order to facilitate the understanding of the present invention, the present invention will be further described below in conjunction with examples. It should be understood that the following examples are only for a better understanding of the present invention and do not mean that the present invention is limited to the following examples.

[0036] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in the art can be used. The reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained commercially. The percentages used in the examples and comparative examples of the present invention are all mass percentages unless otherwise specified.

[0037] The test methods used in the present invention include: (1) Catalyst composition: measured by X-ray fluorescence component analyzer (XRF); (2) Catalyst specific surface area (BET): measured by static low-temperature nitrogen adsorption method at 77K. 2 After the adsorption isotherm, BET was calculated using the BET model equation; (3) Pore volume (PV): N measured at 77K 2 The pore volume corresponds to the position of P / P0=0.98-0.99 on the adsorption isotherm. (4) Average pore diameter (PD): calculated according to PD=4*PV / BET.

[0038] In the preparation method of the present invention, the coprecipitation reaction of the mixed iron salt solution and the precipitant solution is carried out in a high gravity rotating packed bed reactor (referred to as high gravity reactor). Figure 1, the specific operation can be referred to as follows: prepare the supergravity reactor, continuously pass the constant temperature heat exchange medium into the temperature control jacket from the jacket inlet, and then flow out from the jacket outlet, so that the reactor temperature is maintained at 10-80°C; add the mixed iron salt solution into the cavity of the supergravity reactor through the acid feed port, and turn on the motor; the mixed iron salt solution is raised from the bottom to the inner wall of the rotor through the liquid lifter in the cavity of the supergravity reactor, and the rotor rotates under the drive of the motor to generate centrifugal force, so that the mixed iron salt solution passes through the packing layer and is thrown out from the outer wall of the rotor, and returns to the mixed iron salt solution storage container from the reactant outlet of the supergravity rotating packed bed reactor under the action of gravity; when the rotor reaches a speed of 500-2500rpm and stabilizes, add the precipitant solution into the cavity of the supergravity reactor from the alkali feed port, and the mixed iron salt solution and the precipitant solution undergo a co-precipitation reaction in the packing layer, and the precipitation slurry flows out from the discharge port into the precipitation slurry collection container.

[0039] I. Preparation Example

[0040] Example 1

[0041] 10kg Fe(NO 3 ) 3 9H 2 O, 137g Cu(NO 3 ) 2 ·3H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 5kg of ammonium carbonate, 1.84kg of silica sol solution with a silica mass concentration of 30% and 199g of sodium metavanadate were added to deionized water to prepare 40 liters of solution. The iron-copper mixed solution and the ammonia-silicon solution were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 1500rpm, the precipitation temperature was 30°C, the precipitation time was 20min, and the pH was controlled at 9.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 73g of potassium carbonate was fully dissolved in 1.5kg of deionized water to prepare an aqueous solution of K element precursor. 43g of Ce(NO 3 ) 3 6H 2O was fully dissolved in 1.5 kg of deionized water to prepare an aqueous solution of Ce element precursor. The aqueous solution of K element precursor and the aqueous solution of Ce element precursor were added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry was controlled to be 15%, the slurrying temperature was 25 °C, and the slurrying time was 20 min. After slurrying, a catalyst precursor slurry was obtained. Spray drying was carried out with the inlet temperature controlled at 380 °C and the outlet hot air temperature at 220 °C. The spray-dried product was collected, and the obtained product was dried in air at 120 °C for 12 h and calcined in air at 450 °C for 5 h to obtain the catalyst finished product, denoted as catalyst 1. The composition, specific surface area (BET), pore volume (PV), and average pore diameter (PD) of the catalyst were measured, and the results are shown in Table 1 below, and the same applies hereinafter.

[0042] Example 2

[0043] Dissolve 10 kg of Fe(NO 3 ) 3 ·9H 2 O, 137 g of Cu(NO 3 ) 2 ·3H 2 O in deionized water to make a 16.7-liter solution. Dissolve 5 kg of ammonium carbonate, 1.84 kg of silica sol solution with a mass concentration of 30% of silicon dioxide, and 199 g of sodium metavanadate in deionized water to make a 40-liter solution. The iron- and copper-containing mixed solution and the ammonia-silicon solution were introduced into a rotating packed bed reactor for co-current precipitation. The rotor speed was 1500 rpm, the precipitation temperature was 30 °C, the precipitation time was 60 min, and the pH was controlled at 9.0. After the precipitation reaction was completed, the precipitation slurry was filtered and washed several times to obtain a catalyst precursor filter cake. Dissolve 73 g of potassium carbonate fully in 1.5 kg of deionized water to prepare an aqueous solution of K element precursor. Dissolve 43 g of Ce(NO 3 ) 3 ·6H 2 O fully in 1.5 kg of deionized water to prepare an aqueous solution of Ce element precursor. The aqueous solution of K element precursor and the aqueous solution of Ce element precursor were added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry was controlled to be 15%, the slurrying temperature was 25 °C, and the slurrying time was 20 min. After slurrying, a catalyst precursor slurry was obtained. Spray drying was carried out with the inlet temperature controlled at 380 °C and the outlet hot air temperature at 220 °C. The spray-dried product was collected, and the obtained product was dried in air at 120 °C for 12 h and calcined in air at 450 °C for 5 h to obtain the catalyst finished product, denoted as catalyst 2.

[0044] Example 3

[0045] Dissolve 10 kg of Fe(NO 3) 3 9H 2 O, 137g Cu(NO 3 ) 2 ·3H 2 O was dissolved in deionized water to prepare 16.7 liters of solution, and 5 kg of ammonium carbonate, 1.84 kg of silica sol solution with a silica mass concentration of 30% and 199 g of sodium metavanadate were added to deionized water to prepare 40 liters of solution. The iron-copper mixed solution and the ammonia-silicon solution were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 1500 rpm, the precipitation temperature was 30°C, the precipitation time was 20 min, and the pH was controlled at 9.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 73 g of potassium carbonate was fully dissolved in 1.5 kg of deionized water to prepare an aqueous solution of K element precursor. 43 g of Ce(NO 3 ) 3 6H 2 O is fully dissolved in 1.5 kg of deionized water to prepare an aqueous solution of Ce element precursor. K element precursor aqueous solution and Ce element precursor aqueous solution are added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 25°C, and the slurrying time is 20 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 380°C and the outlet hot air temperature is controlled at 220°C for spray drying. The spray drying product is collected, and the obtained product is dried at 120°C in an air atmosphere for 12 hours, and calcined at 450°C in an air atmosphere for 5 hours to obtain a finished catalyst, which is recorded as catalyst 3.

[0046] Example 4

[0047] 10kg Fe(NO 3 ) 3 9H 2 O, 137g Cu(NO 3 ) 2 ·3H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 5kg of ammonium carbonate, 1.84kg of silica sol solution with a silica mass concentration of 30% and 199g of sodium metavanadate were added to deionized water to prepare 40 liters of solution. The iron-copper mixed solution and the ammonia-silicon solution were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 1500rpm, the precipitation temperature was 30°C, the precipitation time was 60min, and the pH was controlled at 9.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 73g of potassium carbonate was fully dissolved in 1.5kg of deionized water to prepare an aqueous solution of K element precursor. 43g of Ce(NO 3 ) 3 6H 2O is fully dissolved in 1.5 kg of deionized water to prepare an aqueous solution of Ce element precursor. K element precursor aqueous solution and Ce element precursor aqueous solution are added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 25°C, and the slurrying time is 20 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 380°C and the outlet hot air temperature is controlled at 220°C for spray drying. The spray drying product is collected, and the obtained product is dried at 120°C in an air atmosphere for 12 hours, and calcined at 450°C in an air atmosphere for 5 hours to obtain a finished catalyst, which is recorded as catalyst 4.

[0048] Example 5

[0049] 10kg Fe(NO 3 ) 3 9H 2 O, 137g Cu(NO 3 ) 2 ·3H 2 O and 306 g SnCl 4 ·5H 2 O was dissolved in deionized water to prepare 16.7 liters of solution, and 4 kg of sodium carbonate and 30 g of silica sol solution with a silica mass concentration of 20% were added to deionized water to prepare 40 liters of solution. The mixed solution containing iron, copper and tin and the ammonia silicon solution were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 1000 rpm, the precipitation temperature was 50 ° C, the precipitation time was 20 min, and the pH was controlled at 8.5. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 12 g of potassium carbonate was fully dissolved in 1.5 kg of deionized water to prepare an aqueous solution of K element precursor. 215 g of Zr(NO 3 ) 4 ·5H 2 O is fully dissolved in 1.5kg deionized water to prepare Zr element precursor aqueous solution. K element precursor aqueous solution, 660g silica sol solution with a silica mass concentration of 20%, and Zr element precursor aqueous solution are sequentially added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 30°C, and the slurrying time is 30min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 350°C and the outlet hot air temperature is controlled at 160°C for spray drying. The spray drying product is collected, and the obtained product is dried at 150°C in an air atmosphere for 10h, and calcined at 400°C in an air atmosphere for 15h to obtain a finished catalyst, which is recorded as catalyst 5.

[0050] Example 6

[0051] 10kg Fe(NO3 ) 3 9H 2 O, 137g Cu(NO 3 ) 2 ·3H 2 O and 306 g SnCl 4 ·5H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 4 kg of sodium carbonate and 30 g of silica sol solution with a silica mass concentration of 20% were added to deionized water to prepare 40 liters of solution. The mixed solution containing iron, copper and tin and the ammonia silicon solution were passed into the ultra-gravity reactor for co-current precipitation. The rotor speed was 1000 rpm, the precipitation temperature was 50 ° C, the precipitation time was 50 min, and the pH was controlled at 8.5. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 12 g of potassium carbonate was fully dissolved in 1.5 kg of deionized water to prepare an aqueous solution of K element precursor. 215 g of Zr(NO 3 ) 4 ·5H 2 O is fully dissolved in 1.5 kg of deionized water to prepare a Zr element precursor aqueous solution. The K element precursor aqueous solution, 660 g of silica sol solution with a silica mass concentration of 20%, and the Zr element precursor aqueous solution are sequentially added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 30°C, and the slurrying time is 30 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 350°C and the outlet hot air temperature is controlled at 160°C for spray drying. The spray drying product is collected, and the obtained product is dried at 150°C in an air atmosphere for 10 hours, and calcined at 400°C in an air atmosphere for 15 hours to obtain a finished catalyst, which is recorded as catalyst 6.

[0052] Example 7

[0053] 10kg Fe(NO 3 ) 3 9H 2 O, 263g Cu(NO 3 ) 2 ·3H 2 O and 379gMn(NO 3 ) 2 ·4H 2O was dissolved in deionized water to prepare 50 liters of solution, and 8 kg of 25% ammonia water and 140 g of potassium silicate solution with a silica mass concentration of 20% were added to the deionized water to prepare 40 liters of solution. The iron, copper and manganese mixed solution and the ammonia silicon solution were passed into the supergravity reactor for co-current precipitation. The rotor speed was 2500 rpm, the precipitation temperature was 70 ° C, the precipitation time was 30 min, and the pH was controlled at 5.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 104 g of potassium carbonate was dissolved in 1.0 kg of deionized water to prepare an aqueous solution of K element precursor. 224 g of La(NO 3 ) 4 6H 2 O is fully dissolved in 1.0 kg of deionized water to prepare a La element precursor aqueous solution. 2.63 kg of silica sol solution with a silica mass concentration of 20%, La element precursor aqueous solution and K element precursor aqueous solution are sequentially added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 50 ° C, and the slurrying time is 40 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 320 ° C and the outlet hot air temperature is controlled at 140 ° C for spray drying. The spray drying product is collected, and the obtained product is dried at 180 ° C in an air atmosphere for 8 hours, and calcined at 600 ° C in an air atmosphere for 6 hours to obtain a finished catalyst, which is recorded as catalyst 7.

[0054] Example 8

[0055] 10kg Fe(NO 3 ) 3 9H 2 O, 11g Cu(NO 3 ) 2 ·3H 2 O and 1115g Al(NO 3 ) 3 9H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 12 kg of 25% ammonia water was added to deionized water to prepare 40 liters of solution. The iron, copper and aluminum mixed solution and the ammonia solution were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 1000 rpm, the precipitation temperature was controlled at 90 ° C, the precipitation time was 20 min, and the endpoint pH was controlled at 6.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 25 g of potassium carbonate and 460 g of potassium silicate solution with a silicon dioxide content of 30% were fully dissolved in 1.0 kg of deionized water to prepare a K element precursor aqueous solution. 292 g of Mg(NO 3 ) 2 6H 2O is fully dissolved in 1.5 kg of deionized water to prepare an aqueous solution of Mg element precursor. K element precursor aqueous solution and Mg element precursor aqueous solution are added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 70°C, and the slurrying time is 50 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 290°C and the outlet hot air temperature is controlled at 120°C for spray drying. The spray drying product is collected, and the obtained product is dried at 200°C in an air atmosphere for 6 hours, and calcined at 600°C in an air atmosphere for 8 hours to obtain a finished catalyst, which is recorded as Catalyst 8.

[0056] Example 9

[0057] 10kg Fe(NO 3 ) 3 9H 2 O, 263g Cu(NO 3 ) 2 ·3H 2 O, 68g Co(NO 3 ) 2 6H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 3.5 kg of sodium carbonate and 1.73 kg of sodium silicate solution with a silica mass concentration of 20% were added to deionized water to prepare 40 liters of solution. The mixed solution containing iron, copper and cobalt and the ammonia silicon solution were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 500 rpm, the precipitation temperature was controlled at 10°C, the precipitation time was 90 min, and the endpoint pH was controlled at 7.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 12 g of potassium carbonate was fully dissolved in 0.5 kg of deionized water to prepare an aqueous solution of K element precursor. 635 g of Ca(NO 3 ) 2 ·4H 2 O is fully dissolved in 1.5 kg of deionized water to prepare a Ca element precursor aqueous solution. The K element precursor aqueous solution and the Ca element precursor aqueous solution are added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 10°C, and the slurrying time is 60 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 260°C and the outlet hot air temperature is controlled at 110°C for spray drying. The spray drying product is collected, and the obtained product is dried at 220°C in an air atmosphere for 4 hours, and calcined at 550°C in an air atmosphere for 10 hours to obtain a finished catalyst, which is recorded as catalyst 9.

[0058] Example 10

[0059] 10kg Fe(NO 3 )3 9H 2 O, 11g Cu(NO 3 ) 2 ·3H 2 O, 205g Ni(NO 3 ) 2 6H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 4.5 kg of ammonium carbonate and 120 g of sodium silicate solution with a silica mass concentration of 30% were added to deionized water to prepare 40 liters of solution. The mixed solution containing iron, copper and nickel and the ammonia silicon solution were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 1500 rpm, the precipitation temperature was controlled at 30 ° C, the precipitation time was 30 min, and the endpoint pH was controlled at 8.5. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 195 g of potassium carbonate was added to 1.5 kg of deionized water to prepare an aqueous solution of K element precursor. 263 g of Ba(NO 3 ) 2 Fully dissolve in 1.0 kg of deionized water to prepare an aqueous solution of Ba element precursor. Add the aqueous solution of K element precursor, 1.04 kg of silica sol solution with a silica mass concentration of 30%, and the aqueous solution of Ba element precursor to the catalyst precursor filter cake for slurrying. Control the mass concentration of the slurry to be 15%, the slurrying temperature to be 25°C, and the slurrying time to be 20 min. After the slurrying is completed, the catalyst precursor slurry is obtained. Control the inlet temperature at 230°C and the outlet hot air temperature at 105°C for spray drying, collect the spray drying product, dry the obtained product at 250°C in an air atmosphere for 3 hours, and calcine at 400°C in an air atmosphere for 12 hours to obtain a finished catalyst, recorded as catalyst 10.

[0060] Embodiment 11

[0061] 10kg Fe(NO 3 ) 3 9H 2 O, 263g Cu(NO 3 ) 2 ·3H2O and 109gRu(NO)(NO 3 ) x (OH) y, x+y=3 is dissolved in deionized water to make 50 liters of solution, 8kg of 25% ammonia water and 690g of potassium silicate solution with a silicon dioxide mass concentration of 20% are added to deionized water to make 40 liters of solution. The mixed solution containing iron, copper and ruthenium and the ammonia silicon solution are passed into an ultra-gravity reactor for co-current precipitation. The rotor speed is 2000rpm, the precipitation temperature is controlled at 50°C, the precipitation time is 60min, and the endpoint pH is controlled at 5.0. After the precipitation reaction is completed, the precipitated slurry is filtered and washed several times to obtain a catalyst precursor filter cake. 268g of potassium nitrate is fully dissolved in 1.0kg of deionized water to prepare an aqueous solution of K element precursor. 265g of Nd(NO 3 ) 3 6H 2 O is fully dissolved in 1.0 kg of deionized water to prepare an aqueous solution of Nd element precursor. The aqueous solution of K element precursor and the aqueous solution of Nd element precursor are sequentially added to the catalyst precursor filter cake for slurrying, and the mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 30°C, and the slurrying time is 30 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 200°C and the outlet hot air temperature is controlled at 105°C for spray drying, and the spray drying product is collected. The obtained product is dried at 280°C in an air atmosphere for 2 hours, and calcined at 500°C in an air atmosphere for 8 hours to obtain a finished catalyst, which is recorded as catalyst 11.

[0062] Example 12

[0063] 10kg Fe(NO 3 ) 3 9H 2 O, 11g Cu(NO 3 ) 2 ·3H 2 O and 327 g Zn(NO 3 ) 2 6H 2 O was dissolved in deionized water to make 50 liters of solution, and 9 kg of 25% ammonia water and 2.76 kg of sodium silicate solution with a silica mass concentration of 20% were added to deionized water to make 40 liters of solution. The ammonia silicon solution and the mixed solution of iron, copper and zinc were passed into the supergravity reactor for co-current precipitation. The rotor speed was 2500 rpm, the precipitation temperature was controlled at 70 ° C, the precipitation time was 40 min, and the endpoint pH was controlled at 6.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 300 g Sr(NO 3 ) 2Fully dissolve in 1.5 kg of deionized water to prepare an aqueous solution of Sr element precursor. Fully dissolve 18 g of potassium nitrate in 0.5 kg of deionized water to prepare an aqueous solution of K element precursor. Add the aqueous solution of Sr element precursor and the aqueous solution of K element precursor to the catalyst precursor filter cake in sequence for slurrying, control the mass concentration of the slurry to 15%, the slurrying temperature to 50°C, and the slurrying time to 40 min to obtain a catalyst precursor slurry. Control the inlet temperature at 180°C and the outlet hot air temperature at 100°C for spray drying, collect the spray drying product, dry the obtained product at 300°C in an air atmosphere for 1 h, and calcine at 550°C in an air atmosphere for 8 h to obtain a finished catalyst, recorded as catalyst 12.

[0064] Embodiment 13

[0065] 10kg Fe(NO 3 ) 3 9H 2 O, 137g Cu(NO 3 ) 2 ·3H 2 O, 638g Cr(NO 3 ) 3 9H 2 O is dissolved in deionized water to prepare 50 liters of solution, and 3kg of sodium carbonate and 1.73kg of sodium silicate solution with a silica mass concentration of 20% are added to deionized water to prepare 40 liters of precipitant solution. The mixed solution containing iron, copper and chromium and the precipitant solution are passed into the supergravity reactor for co-current precipitation, the rotor speed is 1000rpm, the precipitation temperature is 30°C, the precipitation time is 80min, and the pH is controlled at 7.0. After the precipitation reaction is completed, the precipitated slurry is filtered and washed several times to obtain a catalyst precursor filter cake. 152g of potassium nitrate and 316g of boric acid are fully dissolved in 1.5kg of deionized water to prepare a K element precursor aqueous solution. The K element precursor aqueous solution is added to the catalyst precursor filter cake for slurrying, and the mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 25°C, and the slurrying time is 50min. After the slurrying is completed, a catalyst precursor slurry is obtained. The inlet temperature was controlled at 380°C and the outlet hot air temperature was controlled at 220°C for spray drying, and the spray drying product was collected. The obtained product was dried at 120°C in an air atmosphere for 12 h and calcined at 600°C in an air atmosphere for 10 h to obtain a finished catalyst, which was recorded as catalyst 13.

[0066] Embodiment 14

[0067] 10kg Fe(NO 3 ) 3 9H 2 O, 11g Cu(NO 3) 2 ·3H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 4.5 kg of ammonium carbonate, 460 g of sodium silicate solution with a silica mass concentration of 30% and 116 g of sodium metavanadate were added to deionized water to prepare 40 liters of solution. The ammonia silicon solution and the mixed solution containing iron and copper were passed into an ultra-gravity reactor for co-current precipitation. The rotor speed was 500 rpm, the precipitation temperature was controlled at 50 ° C, the precipitation time was 50 min, and the endpoint pH was controlled at 8.5. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 18 g of potassium nitrate was fully dissolved in 0.5 kg of deionized water to prepare an aqueous solution of K element precursor. 507 g of Zr(NO 3 ) 4 ·5H 2 O is fully dissolved in 1.5 kg of deionized water to prepare a Zr element precursor aqueous solution. The K element precursor aqueous solution and the Zr element precursor aqueous solution are sequentially added to the catalyst precursor filter cake for slurrying, and the mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 30°C, and the slurrying time is 60 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 350°C and the outlet hot air temperature is controlled at 150°C for spray drying, and the spray drying product is collected. The obtained product is dried at 150°C in an air atmosphere for 10 hours, and calcined at 400°C in an air atmosphere for 9 hours to obtain a finished catalyst, which is recorded as catalyst 14.

[0068] Embodiment 15

[0069] 10kg Fe(NO 3 ) 3 9H 2 O, 263g Cu(NO 3 ) 2 ·3H 2 O and 505gMn(NO 3 ) 2 ·4H 2 O was dissolved in deionized water to prepare 50 liters of solution, and 8 kg of 25% ammonia water was added to deionized water to prepare 40 liters of solution. The ammonia solution and the mixed solution containing iron, copper and manganese were passed into the supergravity reactor for co-current precipitation. The rotor speed was 1500 rpm, the precipitation temperature was controlled at 90 ° C, the precipitation time was 20 min, and the end point pH was controlled at 5.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 26.3 g Ba(NO 3 ) 2and 79g boric acid are fully dissolved in 0.5kg deionized water to prepare a Ba element aqueous solution. 152g potassium nitrate is fully dissolved in 1.0kg deionized water to prepare a K element precursor aqueous solution. The Ba element aqueous solution, the K element precursor aqueous solution and 1.84kg silica sol solution with a silica mass concentration of 30% are sequentially added to the catalyst precursor filter cake for slurrying, and the mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 70°C, and the slurrying time is 20min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 320°C and the outlet hot air temperature is controlled at 130°C for spray drying, and the spray drying product is collected. The obtained product is dried at 180°C in an air atmosphere for 8h, and calcined at 600°C in an air atmosphere for 4h to obtain a finished catalyst, which is recorded as catalyst 15.

[0070] Example 16

[0071] 10kg Fe(NO 3 ) 3 9H 2 O, 137g Cu(NO 3 ) 2 ·3H 2 O and 1057gAl(NO 3 ) 3 9H 2 O was dissolved in deionized water to make 50 liters of solution, and 9 kg of 25% ammonia water and 630 g of potassium silicate solution with a silica mass concentration of 30% were added to the deionized water to make 40 liters of solution. The mixed solution containing iron, copper and aluminum and the ammonia silicon solution were passed into the supergravity reactor for co-current precipitation. The rotor speed was 2000 rpm, the precipitation temperature was 90 ° C, the precipitation time was 20 min, and the pH was controlled at 6.0. After the precipitation reaction was completed, the precipitated slurry was filtered and washed several times to obtain a catalyst precursor filter cake. 214 g Ce(NO 3 ) 3 6H 2 O and 325g Zr(NO 3 ) 4 ·5H 2O is fully dissolved in 1.5 kg of deionized water to prepare Ce and Zr element precursor aqueous solutions. Ce element precursor aqueous solution and 530 g of potassium silicate solution with a modulus of 3.5 and a silica mass concentration of 30% are sequentially added to the catalyst precursor filter cake for slurrying. The mass concentration of the slurry is controlled to be 15%, the slurrying temperature is 70°C, and the slurrying time is 30 min. After the slurrying is completed, the catalyst precursor slurry is obtained. The inlet temperature is controlled at 290°C and the outlet hot air temperature is controlled at 120°C for spray drying. The spray drying product is collected, and the obtained product is dried at 200°C in an air atmosphere for 6 hours, and calcined at 600°C in an air atmosphere for 4 hours to obtain a finished catalyst, which is recorded as catalyst 16.

[0072] Comparative Example 1

[0073] The method was carried out in accordance with Example 1, except that the iron-copper mixed solution and the ammonia-silicon solution were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 1500 rpm, the precipitation temperature was 30° C., the precipitation time was 20 min, and the pH was controlled at 9.0. The finished product was recorded as comparative agent 1. The composition, specific surface area (BET), pore volume (PV) and average pore diameter (PD) of the comparative agent were measured, and the results are shown in Table 2, the same below.

[0074] Comparative Example 2

[0075] The method was carried out in accordance with Example 2, except that the iron-copper mixed solution and the ammonia-silicon solution were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 1500 rpm, the precipitation temperature was 30° C., the precipitation time was 60 min, and the pH was controlled at 9.0. The finished product was recorded as Comparative Agent 2.

[0076] Comparative Example 3

[0077] The method was carried out in accordance with Example 3, except that the iron-copper mixed solution and the ammonia-silicon solution were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 1500 rpm, the precipitation temperature was 30° C., the precipitation time was 20 min, and the pH was controlled at 9.0. The finished product was recorded as Comparative Agent 3.

[0078] Comparative Example 4

[0079] The same method was used as in Example 4, except that sodium metavanadate was not added. The finished product was recorded as Comparative Agent 4.

[0080] Comparative Example 5

[0081] The method was carried out in accordance with Example 5, except that the mixed solution containing iron, copper and tin and the ammonia silicon solution were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 1000 rpm, the precipitation temperature was 50° C., the precipitation time was 20 min, and the pH was controlled at 8.5. The finished product was recorded as Comparative Agent 5.

[0082] Comparative Example 6

[0083] The same method was used as in Example 6, except that no Zr element precursor aqueous solution was added. The finished product was recorded as Comparative Agent 6.

[0084] Comparative Example 7

[0085] The method was carried out according to Example 7, except that no Mn(NO 3 ) 2 ·4H 2 O. The finished product was recorded as Comparative Agent 7.

[0086] Comparative Example 8

[0087] The same method was used as in Example 8, except that no Mg element precursor aqueous solution was added. The finished product was recorded as Comparative Agent 8.

[0088] Comparative Example 9

[0089] The same method as in Example 9 was used except that no Co(NO 3 ) 2 6H 2 O and Ca elemental precursor aqueous solution. The finished product is recorded as comparative agent 9.

[0090] Comparative Example 10

[0091] The method was carried out in accordance with Example 10, except that the mixed solution containing iron, copper and nickel and the ammonia silicon solution were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 1500 rpm, the precipitation temperature was controlled at 30° C., the precipitation time was 30 min, and the endpoint pH was controlled at 8.5. The finished product was recorded as Comparative Agent 10.

[0092] Comparative Example 11

[0093] The method was carried out in accordance with Example 11, except that the mixed solution containing iron, copper and ruthenium and the ammonia silicon solution were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 2000 rpm, the precipitation temperature was controlled at 50°C, the precipitation time was 60 min, and the endpoint pH was controlled at 5.0. The finished product was recorded as Comparative Agent 11.

[0094] Comparative Example 12

[0095] The method was carried out in accordance with Example 12, except that the ammonia silicon solution and the mixed solution of iron, copper and zinc were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 2500 rpm, the precipitation temperature was controlled at 70°C, the precipitation time was 40 min, and the endpoint pH was controlled at 6.0. The finished product was recorded as Comparative Agent 12.

[0096] Comparative Example 13

[0097] The method was carried out in accordance with Example 13, except that the mixed solution containing iron, copper and chromium and the precipitant solution were introduced into a stirred tank reactor for co-current precipitation, the stirring speed was 1000 rpm, the precipitation temperature was 30° C., the precipitation time was 80 min, and the pH was controlled at 7.0. The finished product was recorded as Comparative Agent 13.

[0098] II. Performance Test

[0099] After the catalyst and the comparison agent were prepared, the performance test was carried out by the following method:

[0100] Test equipment: 1L stirred tank;

[0101] Test conditions: 10g of catalyst was mixed with 300mL of liquid paraffin and placed in a 1L stirred tank device. After reduction activation, the reaction conditions were switched to conduct the reaction. The corresponding reduction activation and Fischer-Tropsch synthesis reaction process conditions are as follows:

[0102] (1) Reduction activation: use H 2 The synthesis gas with a CO / CO ratio of 20:1 was reduced by heating (4 h at 30-200 °C, 10 h at 200-265 °C, and 24 h at 265 °C), and the space velocity of the synthesis gas was 8000 h -1 , the reduction gauge pressure is 3.0MPa.

[0103] (2) Fischer-Tropsch synthesis: After the reduction is completed, the synthesis gas H 2 The / CO ratio was adjusted to 3:1 and stabilized for a period of time until the gas phase composition in the reaction tail gas basically did not change with time, which was recorded as the reaction 0 point.

[0104] (3) Data calculation: The molar number of CO in the feed was measured at the feed port of the stirred tank, and the molar number of CO and CO in the discharge was measured at the discharge port. 2 , CH 4 The molar number of C5+ and CO conversion rate % [X(CO)], CO 2 Selectivity % [S(CO 2 )], CH 4 Selectivity % [S(CH 4 )] and C5+ selectivity % [S(C5+)]:

[0105] CO conversion rate % = [(CO moles in feed - CO moles in discharge) / CO moles in feed] × 100%;

[0106] CO 2 Selectivity % = [CO in the discharge 2 mole number / (mole number of CO in feed - mole number of CO in discharge)] × 100%;

[0107] CH 4 Selectivity % = [CH 4 Number of moles / (number of moles of CO in feed × CO conversion % × (1-CO2 selectivity %))] × 100%.

[0108] C5+ selectivity % = [C5+ moles in the output / (CO moles in the feed × CO conversion % × (1-CO 2 Selectivity %))]×100%.

[0109] The deactivation rate of the catalyst refers to the rate at which the catalyst activity (carbon monoxide conversion rate) decreases from the reaction plateau to the end of the reaction, and the unit is % / h.

[0110] The wear rate is measured by the spray cup method, referring to the standard ASTM D5757-95.

[0111] The composition, physical structure, wear rate and reaction performance results of the catalyst are shown in Table 1 below.

[0112] Table 1

[0113]

[0114] The composition, physical structure, wear rate and reaction performance results of the contrast agent are shown in Table 2 below.

[0115] Table 2

[0116]

[0117] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A method for preparing a Fischer-Tropsch synthesis iron-based catalyst, wherein the Fischer-Tropsch synthesis iron-based catalyst comprises Fe element, Cu element, K element, M element, Q element and SiO 2 , in, The M element is at least one selected from vanadium, tin, manganese, aluminum, cobalt, nickel, ruthenium, zinc and chromium, the Q element is at least one selected from cerium, zirconium, lanthanum, magnesium, calcium, barium, neodymium, strontium and boron, The preparation method comprises the following steps: S1: forming a mixed iron salt solution with a water-soluble salt of Fe and a water-soluble salt of Cu, preparing a precipitant solution, and adding 0 to 100 wt % of a silicon source to the precipitant solution; S2: allowing the mixed iron salt solution and the precipitant solution to undergo a co-precipitation reaction in a high gravity rotating packed bed reactor, and collecting the precipitated slurry; S3: separating the precipitation product from the precipitation slurry; S4: mixing the precipitation product with the K element precursor aqueous solution and the remaining silicon source to form a mixed slurry and performing slurry treatment to obtain a catalyst precursor slurry; and S5: drying and calcining the catalyst precursor slurry; The method of adding the M element includes: adding the M element precursor aqueous solution to the mixed iron salt solution and / or the precipitant solution in step S1; or adding the M element precursor aqueous solution to the K element precursor aqueous solution and / or the mixed slurry in step S4; The method of adding the Q element includes: adding the Q element precursor aqueous solution to the mixed iron salt solution and / or precipitant solution in step S1; or adding the Q element precursor aqueous solution to the K element precursor aqueous solution and / or mixed slurry in step S4.

2. The preparation method according to claim 1, It is characterized in that The water-soluble salt of Fe is nitrate, hydrochloride or hydrate of Fe; preferably, the concentration of Fe in the mixed iron salt solution is 5-100 g / L; and / or The water-soluble salt of Cu is Cu nitrate, Cu hydrochloride or their respective hydrates; and / or The precipitant is selected from one or more of sodium carbonate, ammonia water, ammonium carbonate, sodium hydroxide, potassium hydroxide, and potassium carbonate; preferably, the concentration of the precipitant is 50-150 g / L.

3. The preparation method according to claim 1 or 2, It is characterized in that The silicon source is selected from one or more of potassium silicate solution, sodium silicate solution and silica sol solution, wherein SiO 2 The concentration is 10 to 50 wt%; and / or The K element precursor is one or more of potassium nitrate, potassium carbonate, potassium bicarbonate, potassium chloride, and potassium silicate; and / or When the M element is vanadium, the M element precursor is one or more metavanadates, preferably sodium metavanadate or potassium metavanadate; when the M element is ruthenium, the M element precursor is Ru(NO)(NO 3 ) x (OH) y , x+y=3; when M element is other metal, the M element precursor is the nitrate, hydrochloride or hydrate of the metal; and / or When the Q element is boron, the Q element precursor is one or more of boric acid, metaboric acid, boric oxide, and water-soluble borates; when the Q element is other metals, the Q element precursor is the nitrate, hydrochloride, or hydrate of the metal.

4. The preparation method according to any one of claims 1 to 3, It is characterized in that The co-precipitation reaction comprises: adding the mixed iron salt solution into the cavity of the high-gravity rotating packed bed reactor from the acid feed port, so that the mixed iron salt solution is kept under the action of centrifugal force; when the rotor speed of the high-gravity rotating packed bed reactor is stable, adding the precipitant solution into the cavity of the high-gravity rotating packed bed reactor from the alkali feed port, so that the mixed iron salt solution and the precipitant solution undergo a co-precipitation reaction in the packing layer, and collecting the precipitated slurry; and / or Preferably, before adding the mixed iron salt solution to the high gravity rotating packed bed reactor, the reactor temperature is maintained at 10-80°C; and / or Preferably, the rotor speed of the high gravity rotating packed bed reactor during the coprecipitation reaction is 500 to 2500 rpm.

5. The preparation method according to any one of claims 1 to 4, It is characterized in that In the step S2, the precipitation temperature of the coprecipitation reaction is 5 to 95° C., the precipitation time is 5 to 100 min, and the pH value of the precipitation slurry is controlled at 5 to 10 during the precipitation process.

6. The preparation method according to any one of claims 1 to 5, It is characterized in that In the step S4, the slurrying temperature of the slurrying treatment is 10-80° C., the slurrying time is 10-80 min, and the concentration of the slurry is controlled to be 5-40 wt % during the slurrying treatment.

7. The preparation method according to any one of claims 1 to 6, It is characterized in that In the step S5, the drying includes the following process: firstly, the catalyst precursor slurry is spray-dried, and the obtained powder is dried in an air atmosphere at 110-300° C. for 1-12 hours; Preferably, the hot air inlet temperature of the spray drying is 180-400°C, and the exhaust air outlet temperature is 100-220°C.

8. The preparation method according to any one of claims 1 to 7, It is characterized in that In the step S5, the calcination temperature is 400-600° C. and the calcination time is 1-15 hours.

9. The Fischer-Tropsch synthesis iron-based catalyst obtained by the preparation method according to any one of claims 1 to 8.

10. The Fischer-Tropsch synthesis iron-based catalyst according to claim 9, It is characterized in that By mass ratio, Fe element:Cu element:K element:M element:Q element:SiO 2 =100:0.2~5:0.5~8:0.5~10:0.5~10:10~42.

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