An alloy carbide catalyst, a preparation method thereof and an application thereof

Abstract

The present invention provides an alloy carbide catalyst, a preparation method thereof and an application thereof. The alloy carbide catalyst is an FeCoM1M2M3 alloy structure catalyst. By mass percentage, it comprises components with the following mass percentages: 4.8 wt% to 81.5 wt% of Fe element, 4.8 wt% to 81.5 wt% of Co element, 0.2 wt% to 11.2 wt% of a first metal promoter M1, 0 to 70 wt% of a second metal promoter M2, and 0 to 90 wt% of a carrier M3. The alloy carbide catalyst of the present invention is prepared by a co-precipitation method or an impregnation method. The preparation method is simple and can be scaled up. By forming a new active phase of the alloy carbide catalyst, the contact interface density of bifunctional sites is provided, realizing the high-activity and high-selectivity synthesis of higher alcohol aldehydes by the one-step method of syngas; and the alloy carbide catalyst has excellent comprehensive catalytic performance and good stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalyst synthesis, and particularly relates to an alloy carbide catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] The catalytic conversion of syngas is an important field of C1 chemical technology, providing a new route for the efficient conversion of non-petroleum resources into liquid fuels and chemicals. The catalytic conversion of syngas can produce methanol, liquid fuels, olefins, aromatics, higher alcohols and aldehydes, etc. At present, the main industrialized processes include methanol synthesis, Fischer-Tropsch synthesis, methanol-to-olefins, etc. As an important route for the catalytic conversion of syngas, the synthesis of higher alcohols and aldehydes from syngas has always been a key research field that has received continuous attention in the scientific community, but it has not been industrialized to date. Higher alcohols and aldehydes have high economic added value and practical application prospects. They can not only be directly used as fuels for modern transportation such as automobiles, but also as gasoline additives or intermediate products of fine chemicals, and are widely used in fields such as surfactants, plasticizers, detergents, and cosmetics.

[0003] In the reaction process of synthesizing higher alcohols and aldehydes from syngas, according to the mechanism of this reaction process, the reaction active center requires the synergistic action of bifunctional sites. One site is responsible for the dissociation of CO and the growth of carbon chains to generate unsaturated alkyl species, while the other site is responsible for the non-dissociative adsorption of CO. The two complete the migration and insertion of non-dissociative adsorbed CO at the interface of the bifunctional sites to generate higher alcohol and aldehyde products. The synergy of the bifunctional sites and the degree of interfacial contact determine the reaction activity and the selectivity of the target product. Therefore, if one wants to achieve the preparation of higher alcohols and aldehydes with high activity and high selectivity, the fine design of the interfacial structure is a very necessary and challenging method. Summary of the Invention

[0004] In view of the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide an alloy carbide catalyst, a preparation method thereof, and an application thereof, so as to improve the interfacial density of the bifunctional sites through the alloy carbide catalyst to achieve the high-activity and high-selectivity preparation of carbon alcohols and aldehydes from syngas.

[0005] To achieve the above object and other related objects, the present invention provides an alloy carbide catalyst, and the alloy carbide catalyst is an FeCoM1M2M3 alloy structure catalyst. Calculated according to the mass percentage of the FeCoM1M2M3 alloy structure catalyst, it includes the following components in mass percentage: 4.8 wt% - 81.5 wt% of Fe element, 4.8 wt% - 81.5 wt% of Co element, 0.2 wt% - 11.2 wt% of the first metal promoter M1, 0 - 70 wt% of the second metal promoter M2, and 0 - 90 wt% of the carrier M3.

[0006] Preferably, the first metal promoter M1 is selected from one or a combination of Li, Na, K, Rb, and Cs.

[0007] Preferably, the second metal promoter M2 is selected from one or a combination of Mg, Ca, Cu, Zn, Al, Zr, In, Mn, La, and Ce.

[0008] Preferably, the carrier M3 is selected from one or a combination of SiO 2 , Al 2 O 3 , TiO 2 , and carbon materials.

[0009] Preferably, in the alloy carbide catalyst, the molar ratio between the Fe element and the Co element is 1:10 to 10:1.

[0010] Preferably, in the alloy carbide catalyst, the molar ratio between the Co element and the M2 is 1:10 to 10:1.

[0011] A preparation method of the above alloy carbide catalyst, wherein the alloy carbide catalyst is obtained by at least one of the co-precipitation method and the impregnation method;

[0012] Among them, the method for preparing the alloy carbide catalyst by the co-precipitation method includes the following steps:

[0013] S1. Provide salts of Fe, Co, and the second metal promoter M2, and dissolve the salts of Fe, Co, and the second metal promoter M2 in water or ethanol according to the mass percentage to obtain a mixed metal salt solution;

[0014] S2. Dissolve the precipitant containing the first metal promoter M1 element in water or ethanol to obtain a precipitant solution;

[0015] S3. Disperse the carrier M3 in deionized water to obtain a mother liquor;

[0016] S4. Drop the mixed metal salt solution and the precipitant solution into the mother liquor simultaneously to perform co-precipitation to obtain a co-precipitation solution;

[0017] S5. After aging, centrifuging, washing, and drying the co-precipitation solution, obtain a solid powder precursor;

[0018] S6. Subject the solid powder precursor to carbonization treatment to obtain an alloy carbide catalyst;

[0019] The method for preparing the alloy carbide catalyst by the impregnation method includes the following steps:

[0020] A1. Provide salts of Fe, Co, and the second metal promoter M2. Dissolve the salts of Fe, Co, and the second metal promoter M2 in water or ethanol according to the mass percentage to obtain a mixed metal salt solution.

[0021] A2. Provide a salt of the first metal promoter M1 element and dissolve it in the mixed metal salt solution to obtain a mixed solution.

[0022] A3. Immerse the mixed solution on the carrier M3, and after standing and drying, obtain a solid powder.

[0023] A4. Subject the solid powder to carbonization treatment to obtain an alloy carbide catalyst.

[0024] Preferably, the Fe salt in step S1 is selected from one or a combination of Fe chloride salts, nitrate salts, sulfate salts, carbonate salts, and acetate salts.

[0025] Preferably, the Co salt in step S1 is selected from one or a combination of Co chloride salts, nitrate salts, sulfate salts, carbonate salts, and acetate salts.

[0026] Preferably, the salt of the second metal promoter M2 in step S1 is selected from one or a combination of chloride salts, nitrate salts, sulfate salts, carbonate salts, and acetate salts of the M2 element.

[0027] Preferably, the total molar concentration of the mixed metal salt solution in step S1 is 0.5 - 4 mol / L.

[0028] Preferably, the precipitating agent containing the first metal promoter M1 element in step S2 is Li 2 CO 3 、Na 2 CO 3 、K 2 CO 3 、Rb 2 CO 3 、Cs 2 CO 3 、LiOH, NaOH, KOH, RbOH, and CsOH.

[0029] Preferably, the precipitating agent containing the first metal promoter M1 element in step S2 is a mixture of the hydroxide and carbonate of the M1 element, where the M1 element is selected from one of Li, Na, K, Rb, and Cs.

[0030] Preferably, the molar concentration of the precipitating agent solution in step S2 is 0.5 - 4 mol / L.

[0031] Preferably, the temperature of the coprecipitation in step S4 is 10 - 80 °C.

[0032] Preferably, the pH value during the coprecipitation in step S4 is 6 to 12.

[0033] Preferably, the temperature of the aging in step S5 is 20 to 80 °C.

[0034] Preferably, the time of the aging in step S5 is 0.5 to 24 h.

[0035] Preferably, the number of times of centrifugation and washing in step S5 is 0 to 10 times.

[0036] Preferably, the temperature of the drying in step S5 is 50 to 120 °C.

[0037] Preferably, the time of the drying in step S5 is 6 to 48 h.

[0038] Preferably, the carbonization treatment in step S6 and step A4 specifically is: carbonization in a carbonization atmosphere at 200 to 400 °C for 2 to 48 h.

[0039] Preferably, before the carbonization treatment in step S6 and step A4, it further includes one or a combination of the steps of roasting and reduction.

[0040] Preferably, the carbonization atmosphere is a synthesis gas atmosphere, N 2 diluted synthesis gas atmosphere, CO 2 diluted synthesis gas atmosphere; wherein, the H 2 / CO ratio in the synthesis gas atmosphere is 0.5 to 3; in the N 2 diluted synthesis gas atmosphere, the content of N 2 is 5 wt% to 95 wt%; in the CO 2 diluted synthesis gas atmosphere, the content of CO 2 is 5 wt% to 95 wt%.

[0041] Preferably, the roasting step specifically includes: roasting in a static atmosphere or a flowing atmosphere at 200 to 600 °C for 0.5 to 10 h.

[0042] Preferably, the reduction includes a high-temperature reduction method or a reduction-oxidation method. The high-temperature reduction method specifically includes: reducing at 200 to 600 °C for 2 to 10 h; the reduction-oxidation method specifically includes: performing reduction in sodium borohydride or hydrazine hydrate.

[0043] Preferably, in the roasting step, the static atmosphere is static air.

[0044] Preferably, in the roasting step, the flowing atmosphere includes flowing air, flowing N 2 gas, flowing Ar gas, flowing NO / Ar mixed gas, flowing H 2O / Ar mixed gas, flowing H 2 O / air mixed gas, flowing CO 2 / Ar mixed gas, flowing CO 2 One or a combination of / air mixed gases.

[0045] Preferably, in the high-temperature reduction method, the reducing atmosphere is pure H 2 gas, H 2 / Ar mixed gas, H 2 / CO 2 One or a combination of mixed gases.

[0046] Preferably, in step A1, the Fe salt is selected from one or a combination of Fe chloride, nitrate, sulfate, carbonate, acetate.

[0047] Preferably, in step A1, the Co salt is selected from one or a combination of Co chloride, nitrate, sulfate, carbonate, acetate.

[0048] Preferably, in step A1, the salt of the second metal promoter M2 is selected from one or a combination of chloride, nitrate, sulfate, carbonate, acetate of the M2 element.

[0049] Preferably, in step A1, the total molar concentration of the mixed metal salt solution is 0.5 - 4 mol / L.

[0050] Preferably, in steps A2 and A3, the salt of the first metal promoter M1 element is selected from one or a combination of carbonate, nitrate, chloride, sulfate, acetate of the M1 element.

[0051] Preferably, in steps A2 and A3, the temperature of the impregnation is 5 - 30 °C.

[0052] Preferably, in steps A2 and A3, the standing time is 4 - 48 h.

[0053] Preferably, in steps A2 and A3, the drying temperature is 50 - 120 °C.

[0054] Preferably, in steps A2 and A3, the drying time is 6 - 48 h.

[0055] An application of the above alloy carbide catalyst, where the alloy carbide catalyst is applied to directly synthesize higher alcohol aldehydes from syngas, and the higher alcohol aldehydes are straight-chain alcohol aldehydes with a carbon number greater than or equal to 2.

[0056] Preferably, in the application of the alloy carbide catalyst in directly synthesizing higher alcohol aldehydes from syngas, the alloy carbide catalyst is tableted and sieved to obtain particles with a mesh size of 40 - 60.

[0057] Preferably, in the application of the alloy carbide catalyst in the direct synthesis of higher alcohol aldehydes from syngas, the reaction conditions for the direct synthesis of higher alcohol aldehydes from syngas are as follows: the raw material gas is selected from one of the syngas with H 2 / CO = 0.5, H 2 / CO = 1, H 2 / CO = 2, the space velocity WHSV is 1000 - 20000 ml / (g cat ·h), the reaction temperature is 170 - 270 °C, and the reaction pressure is 0.5 - 6 MPa.

[0058] As described above, the alloy carbide catalyst, preparation method and application of the present invention have the following beneficial effects:

[0059] The present invention prepares a brand-new alloy carbide catalyst, and provides the contact interface density of bifunctional sites by forming a new active phase of the alloy carbide catalyst, realizing the high-activity and high-selectivity one-step synthesis of higher alcohol aldehydes from syngas.

[0060] The alloy carbide catalyst in the present invention has excellent comprehensive catalytic performance. In the application of directly synthesizing higher alcohol aldehydes from syngas, the CO conversion rate can reach up to 93.8%, the selectivity of higher alcohol aldehydes in the product distribution is relatively high, up to about 61.1% at most, and at the same time, the selectivity of hydrocarbons decreases correspondingly, and the product distribution is more economical.

[0061] The alloy carbide catalyst in the present invention has good stability. At the same time, the preparation method of the alloy carbide catalyst is relatively simple and can be scaled up to solve the problem that the synthesis of higher alcohol aldehydes from syngas cannot be industrialized. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 Shown is the XRD diffraction pattern of the FeCo spinel oxide, FeCo alloy, and FeCo alloy carbide catalyst obtained in Example 1 of the present invention.

[0063] Figure 2 Shown is the low-magnification transmission electron micrograph of the FeCo alloy carbide catalyst in Example 1 of the present invention.

[0064] Figure 3 Shown is the high-magnification transmission electron micrograph of the FeCo alloy carbide catalyst in Example 1 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0065] The following describes the embodiments of the present invention through specific examples. Those skilled in the art can easily understand the other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0066] The present invention provides an alloy carbide catalyst, which is an FeCoM1M2M3 alloy structure catalyst. Calculated by mass percentage of the FeCoM1M2M3 alloy structure catalyst, it includes the following components in mass percentage: 4.8 wt% - 81.5 wt% of Fe element, 4.8 wt% - 81.5 wt% of Co element, 0.2 wt% - 11.2 wt% of the first metal promoter M1, 0 - 70 wt% of the second metal promoter M2, and 0 - 90 wt% of the carrier M3.

[0067] Specifically, calculated by mass percentage of the FeCoM1M2M3 alloy structure catalyst, the mass percentage of the Fe element can include any value within the range such as 4.8 wt%, 10 wt%, 30 wt%, 50 wt%, 70 wt%, 80 wt%, 81.5 wt%, etc., and can be specifically adjusted according to the actual situation; the mass percentage of the Co element can include any value within the range such as 4.8 wt%, 10 wt%, 30 wt%, 50 wt%, 70 wt%, 80 wt%, 81.5 wt%, etc., and can be specifically adjusted according to the actual situation; the mass percentage of the first metal promoter M1 can include any value within the range such as 0.2 wt%, 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 7 wt%, 9 wt%, 10 wt%, 11 wt%, 11.2 wt%, etc., and can be specifically adjusted according to the actual situation; the second metal promoter M2 can include any value within the range such as 0 wt%, 1 wt%, 10 wt%, 30 wt%, 50 wt%, 60 wt%, 70 wt%, etc., and can be specifically adjusted according to the actual situation. When the mass percentage of the second metal promoter M2 is 0, it means that the alloy carbide catalyst does not include the second metal promoter M2; the carrier M3 can include any value within the range such as 0 wt%, 1 wt%, 10 wt%, 30 wt%, 50 wt%, 70 wt%, 85 wt%, 90 wt%, etc., and can be specifically adjusted according to the actual situation. When the mass percentage of the carrier M3 is 0, it means that the alloy carbide catalyst does not include the carrier M3.

[0068] As an example, the first metal promoter M1 is selected from one or a combination of Li, Na, K, Rb, and Cs.

[0069] Preferably, the first metal promoter M1 is one or a combination of Na and K.

[0070] As an example, the second metal promoter M2 is selected from one or a combination of Mg, Ca, Cu, Zn, Al, Zr, In, Mn, La, and Ce.

[0071] Preferably, the second metal promoter M2 is selected from one or a combination of Mg, Cu, Zn, Al, Zr, In, Mn, and Ce.

[0072] As an example, the carrier M3 is selected from 2 SiO 2 O 3 TiO 2 one or a combination of carbon materials.

[0073] Specifically, the carbon material can be activated carbon or carbon nanotubes CNTs.

[0074] As an example, in the alloy carbide catalyst, the molar ratio between the Fe element and the Co element is 1:10 to 10:1.

[0075] Specifically, in the alloy carbide catalyst, the molar ratio between the Fe element and the Co element can include any value within the range such as 1:10, 1:1, 3:1, 5:1, 7:1, 9:1, 10:1, etc., and can be specifically adjusted according to the actual situation.

[0076] Preferably, in the alloy carbide catalyst, the molar ratio between the Fe element and the Co element is 1:4 to 4:1 (which can include any value within the range such as 1:4, 1:2, 1:1, 2:1, 3:1, 4:1, etc.).

[0077] Preferably, in the FeCoM1M2M3 alloy structure catalyst, the mass percentage of the M1 element is 0.5 wt% to 5 wt%.

[0078] Specifically, in the FeCoM1M2M3 alloy structure catalyst, the mass percentage of the M1 element can include any value within the range such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, etc., and can be specifically adjusted according to the actual situation.

[0079] More preferably, in the FeCoM1M2M3 alloy structure catalyst, the mass percentage of the M1 element is 1 wt% to 2 wt% (which can include any value within the range such as 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, etc., and can be specifically adjusted according to the actual situation).

[0080] As an example, in the alloy carbide catalyst, the molar ratio between the Co element and M2 is 1:10 to 10:1.

[0081] Specifically, in the alloy carbide catalyst, the molar ratio between Co element and M2 can include values within any range such as 1:10, 1:1, 3:1, 5:1, 7:1, 9:1, 10:1, etc., and can be specifically adjusted according to the actual situation.

[0082] Preferably, in the alloy carbide catalyst, the molar ratio between Co element and M2 is 1:3 to 3:1 (values within any range such as 1:3, 1:2, 1:1, 2:1, 3:1, etc. can be included).

[0083] The present invention also provides a preparation method of the above alloy carbide catalyst, a method for preparing the alloy carbide catalyst by the co-precipitation method, including the following steps:

[0084] S1. Provide salts of Fe, Co, and the second metal promoter M2, and dissolve the salts of Fe, Co, and the second metal promoter M2 in water or ethanol according to the mass percentage to obtain a mixed metal salt solution;

[0085] S2. Dissolve the precipitant containing the first metal promoter M1 element in water or ethanol to obtain a precipitant solution;

[0086] S3. Disperse the carrier M3 in deionized water to obtain a mother liquor;

[0087] S4. Drop the mixed metal salt solution and the precipitant solution into the mother liquor simultaneously for co-precipitation to obtain a co-precipitation solution;

[0088] S5. After aging, centrifuging, washing, and drying the co-precipitation solution, obtain a solid powder precursor;

[0089] S6. Subject the solid powder precursor to carbonization treatment to obtain the alloy carbide catalyst.

[0090] As an example, in step S1, the Fe salt is selected from one or a combination of Fe chloride, nitrate, sulfate, carbonate, acetate.

[0091] As an example, in step S1, the Co salt is selected from one or a combination of Co chloride, nitrate, sulfate, carbonate, acetate.

[0092] As an example, in step S1, the salt of the second metal promoter M2 is selected from one or a combination of M2 element chloride, nitrate, sulfate, carbonate, acetate.

[0093] As an example, in step S1, the total molar concentration of the mixed metal salt solution is 0.5 to 4 mol / L.

[0094] Specifically, the total molar concentration of the mixed metal salt solution can include values within any range such as 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, etc., and can be specifically adjusted according to the actual situation.

[0095] As an example, the precipitant containing the first metal promoter M1 element in step S2 is Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , Rb 2 CO 3 , Cs 2 CO 3 , or one of LiOH, NaOH, KOH, RbOH, and CsOH.

[0096] As an example, the precipitant containing the first metal promoter M1 element in step S2 is a mixture of the hydroxide and carbonate of the M1 element, where the M1 element is selected from one of Li, Na, K, Rb, and Cs.

[0097] Specifically, when the M1 element is Li, the precipitant containing the first metal promoter M1 element is a mixture of LiOH and Li 2 CO 3 ; when the M1 element is Na, the precipitant containing the first metal promoter M1 element is a mixture of NaOH and Na 2 CO 3 ; and so on when the M1 element is one of K, Rb, and Cs, which will not be elaborated here.

[0098] As an example, the molar concentration of the precipitant solution in step S2 is 0.5 - 4 mol / L.

[0099] Specifically, the molar concentration of the precipitant solution can include values within any range such as 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, etc., and can be specifically adjusted according to the actual situation.

[0100] As an example, the temperature of the coprecipitation in step S4 is 10 - 80 °C.

[0101] Specifically, the temperature of the coprecipitation can include values within any range such as 10 °C, 20 °C, 40 °C, 60 °C, 80 °C, etc., and can be specifically adjusted according to the actual situation.

[0102] As an example, the pH value during the coprecipitation in step S4 is 6 - 12.

[0103] Specifically, the pH value at which coprecipitation occurs may include values within any range such as 6, 7, 8, 9, 10, 11, 12, etc., and can be specifically adjusted according to the actual situation.

[0104] As an example, the aging temperature in step S5 is 20 - 80 °C.

[0105] Specifically, the aging temperature may include values within any range such as 20 °C, 40 °C, 60 °C, 80 °C, etc., and can be specifically adjusted according to the actual situation.

[0106] As an example, the aging time in step S5 is 0.5 - 24 h.

[0107] Specifically, the aging time may include values within any range such as 0.5 h, 1 h, 5 h, 10 h, 15 h, 20 h, 22 h, 24 h, etc., and can be specifically adjusted according to the actual situation.

[0108] As an example, the number of centrifugation and washing times in step S5 is 0 - 10 times.

[0109] Specifically, the number of centrifugation and washing times may include 0 times, 1 time, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times. Among them, when the number of centrifugation and washing times is 0 times, it means that the steps of centrifugation and washing are not required.

[0110] As an example, the drying temperature in step S5 is 50 - 120 °C.

[0111] Specifically, the drying temperature may include values within any range such as 50 °C, 70 °C, 90 °C, 110 °C, 120 °C, etc., and can be specifically adjusted according to the actual situation.

[0112] As an example, the drying time in step S5 is 6 - 48 h.

[0113] Specifically, the drying time may include values within any range such as 6 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h, 48 h, etc., and can be specifically adjusted according to the actual situation.

[0114] As an example, the carbonization treatment in step S6 is specifically: carbonization in a carbonization atmosphere at 200 - 400 °C for 2 - 48 h.

[0115] Specifically, the temperature of the carbonization treatment may include values within any range such as 200 °C, 250 °C, 300 °C, 350 °C, 400 °C, etc., and can be specifically adjusted according to the actual situation; the carbonization time may include values within any range such as 2 h, 5 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h, 48 h, etc., and can be specifically adjusted according to the actual situation.

[0116] As an example, the carbonization atmosphere is a synthesis gas atmosphere, N 2 diluted synthesis gas atmosphere, CO 2 diluted synthesis gas atmosphere; wherein, in the synthesis gas atmosphere, the H 2 / CO ratio is 0.5 to 3; in the N 2 diluted synthesis gas atmosphere, the content of N 2 is 5 wt% to 95 wt%; in the CO 2 diluted synthesis gas atmosphere, the content of CO 2 is 5 wt% to 95 wt%.

[0117] Specifically, the H 2 / CO ratio in the synthesis gas atmosphere can include any value within the range such as 0.5, 1, 1.5, 2, 2.5, 3, etc., and can be specifically adjusted according to the actual situation; in the N 2 diluted synthesis gas atmosphere, the H 2 / CO ratio is 0.5 to 3, and the proportion of N 2 can include any value within the range such as 5 wt%, 15 wt%, 25 wt%, 35 wt%, 45 wt%, 55 wt%, 65 wt%, 75 wt%, 85 wt%, 95 wt%, etc., and can be specifically adjusted according to the actual situation; in the CO 2 diluted synthesis gas atmosphere, the H 2 / CO ratio is 0.5 to 3, and the proportion of CO 2 can include any value within the range such as 5 wt%, 15 wt%, 25 wt%, 35 wt%, 45 wt%, 55 wt%, 65 wt%, 75 wt%, 85 wt%, 95 wt%, etc., and can be specifically adjusted according to the actual situation; in the specific embodiments of the present invention, the dispersion degree of the alloy carbide catalyst to be prepared is adjusted by different carbonization atmospheres.

[0118] As an example, before the carbonization treatment in step S6, it further includes one or a combination of the steps of roasting and reduction.

[0119] Specifically, in step S6, the solid powder precursor is roasted and / or reduced and then carbonized.

[0120] As an example, the roasting step specifically includes: roasting for 0.5 to 10 h in a static atmosphere or a flowing atmosphere at 200 to 600 °C.

[0121] Specifically, the roasting temperature may include values within any range such as 200°C, 300°C, 400°C, 500°C, 600°C, etc., and can be specifically adjusted according to the actual situation; the roasting time may include values within any range such as 0.5 h, 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, etc., and can be specifically adjusted according to the actual situation.

[0122] As an example, in the roasting step, the static atmosphere is static air.

[0123] As an example, in the roasting step, the flowing atmosphere includes flowing air, flowing N 2 gas, flowing Ar gas, flowing NO / Ar mixed gas, flowing H 2 O / Ar mixed gas, flowing H 2 O / air mixed gas, flowing CO 2 / Ar mixed gas, flowing CO 2 / air mixed gas or a combination thereof.

[0124] Specifically, the content of NO in the flowing NO / Ar mixed gas is not overly restricted. Preferably, the content of NO in the flowing NO / Ar mixed gas is 5 wt%. As an example, reduction includes high-temperature reduction method or reduction oxidation method. The high-temperature reduction method specifically includes: reducing at 200 - 600°C for 2 - 10 h; the reduction oxidation method specifically includes: performing reduction in sodium borohydride or hydrazine hydrate.

[0125] Specifically, the high-temperature reduction temperature may include values within any range such as 200°C, 300°C, 400°C, 500°C, 600°C, etc., and can be specifically adjusted according to the actual situation; the high-temperature reduction time may include values within any range such as 2 h, 4 h, 6 h, 8 h, 10 h, etc., and can be specifically adjusted according to the actual situation.

[0126] As an example, in the high-temperature reduction method, the reduction atmosphere is pure H 2 gas, H 2 / Ar mixed gas, H 2 / CO 2 mixed gas or a combination thereof.

[0127] The present invention also provides a preparation method of the above alloy carbide catalyst. The method for preparing the alloy carbide catalyst by the impregnation method includes the following steps:

[0128] A1. Provide salts of Fe, Co, and the second metal promoter M2, and dissolve the salts of Fe, Co, and the second metal promoter M2 in water or ethanol according to the mass percentage to obtain a mixed metal salt solution;

[0129] A2. Provide a salt of the first metal promoter M1 element and dissolve it in the mixed metal salt solution to obtain a mixed solution;

[0130] A3. Immerse the mixed solution in carrier M3, and obtain a solid powder after standing and drying;

[0131] A4. The solid powder is subjected to carbonization treatment to obtain an alloy carbide catalyst.

[0132] As an example, in step A1, the Fe salt is selected from one or a combination of chloride salts, nitrate salts, sulfate salts, carbonate salts, and acetate salts of Fe.

[0133] As an example, in step A1, the Co salt is selected from one or a combination of chloride salts, nitrate salts, sulfate salts, carbonate salts, and acetate salts of Co.

[0134] As an example, in step A1, the salt of the second metal promoter M2 is selected from one or a combination of chloride salts, nitrate salts, sulfate salts, carbonate salts, and acetate salts of element M2.

[0135] As an example, in step A1, the total molar concentration of the mixed metal salt solution is 0.5 - 4 mol / L.

[0136] Specifically, the total molar concentration of the mixed metal salt solution can include any value within the range such as 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, etc., and can be specifically adjusted according to the actual situation.

[0137] As an example, in step A2, the salt of the first metal promoter M1 element is selected from one or a combination of carbonate salts, nitrate salts, chloride salts, sulfate salts, and acetate salts of element M1.

[0138] As an example, in step A3, the impregnation temperature is 5 - 30 °C.

[0139] Specifically, the impregnation temperature can include any value within the range such as 5 °C, 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, etc., and can be specifically adjusted according to the actual situation.

[0140] As an example, in step A3, the standing time is 4 - 48 h.

[0141] Specifically, the refining time can include any value within the range such as 4 h, 8 h, 16 h, 24 h, 30 h, 36 h, 42 h, 48 h, etc., and can be specifically adjusted according to the actual situation.

[0142] As an example, in step A3, the drying temperature is 50 - 120 °C.

[0143] Specifically, the drying temperature can include any value within the range such as 50 °C, 60 °C, 80 °C, 100 °C, 120 °C, etc., and can be specifically adjusted according to the actual situation.

[0144] As an example, the drying time in step A3 is 6 to 48 hours.

[0145] Specifically, the drying time can include any value within the range such as 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, etc., and can be specifically adjusted according to the actual situation.

[0146] As an example, the carbonization treatment in step A4 is specifically: carbonization in a carbonization atmosphere at 200 to 400 °C for 2 to 48 hours.

[0147] Specifically, the temperature of the carbonization treatment can include any value within the range such as 200 °C, 250 °C, 300 °C, 350 °C, 400 °C, etc., and can be specifically adjusted according to the actual situation; the carbonization time can include any value within the range such as 2h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 48h, etc., and can be specifically adjusted according to the actual situation.

[0148] As an example, the carbonization atmosphere is one of a syngas atmosphere, a diluted syngas atmosphere, a CO 2 diluted syngas atmosphere; wherein, the H 2 / CO ratio in the syngas atmosphere is 0.5 to 3; in the N 2 diluted syngas atmosphere, the content of N 2 is 5 wt% to 95 wt%; in the CO 2 diluted syngas atmosphere, the content of CO 2 is 5 wt% to 95 wt%. 2 Specifically, the H

[0149] / CO ratio in the syngas atmosphere can include any value within the range such as 0.5, 1, 1.5, 2, 2.5, 3, etc., and can be specifically adjusted according to the actual situation; in the N 2 diluted syngas atmosphere, the H 2 / CO ratio is 0.5 to 3, and the proportion of N 2 can include any value within the range such as 5 wt%, 15 wt%, 25 wt%, 35 wt%, 45 wt%, 55 wt%, 65 wt%, 75 wt%, 85 wt%, 95 wt%, etc., and can be specifically adjusted according to the actual situation; in the CO 2 diluted syngas atmosphere, the H 2 / CO ratio is 0.5 to 3, and the CO 2 content can include any value within the range such as 5 wt%, 15 wt%, 25 wt%, 35 wt%, 45 wt%, 55 wt%, 65 wt%, 75 wt%, 85 wt%, 95 wt%, etc., and can be specifically adjusted according to the actual situation; in the CO 2The proportion may include any value within a range such as 5 wt%, 15 wt%, 25 wt%, 35 wt%, 45 wt%, 55 wt%, 65 wt%, 75 wt%, 85 wt%, 95 wt%, etc., and can be specifically adjusted according to the actual situation; in the specific embodiments of the present invention, different carbonization atmospheres are used to adjust the dispersion degree of the alloy carbide catalyst to be prepared.

[0150] As an example, before the carbonization treatment in step A4, it further includes one or a combination of the steps of roasting and reduction.

[0151] Specifically, in step A4, after the solid powder precursor is roasted and / or reduced, carbonization treatment is carried out.

[0152] As an example, the roasting step specifically includes: roasting for 0.5 - 10 h in a static atmosphere or a flowing atmosphere at 200 - 600 °C.

[0153] Specifically, the roasting temperature may include any value within a range such as 200 °C, 300 °C, 400 °C, 500 °C, 600 °C, etc., and can be specifically adjusted according to the actual situation; the roasting time may include any value within a range such as 0.5 h, 1 h, 2 h, 4 h, 6 h, 8 h, 10 h, etc., and can be specifically adjusted according to the actual situation.

[0154] As an example, in the roasting step, the static atmosphere is static air.

[0155] As an example, in the roasting step, the flowing atmosphere includes flowing air, flowing N 2 gas, flowing Ar gas, flowing NO / Ar mixed gas, flowing H 2 O / Ar mixed gas, flowing H 2 O / air mixed gas, flowing CO 2 / Ar mixed gas, flowing CO 2 / air mixed gas or a combination thereof.

[0156] As an example, reduction includes high-temperature reduction method or reduction oxidation method. The high-temperature reduction method specifically includes: reducing at 200 - 600 °C for 2 - 10 h; the reduction oxidation method specifically includes: carrying out reduction in sodium borohydride or hydrazine hydrate.

[0157] Specifically, the temperature of high-temperature reduction may include any value within a range such as 200 °C, 300 °C, 400 °C, 500 °C, 600 °C, etc., and can be specifically adjusted according to the actual situation; the time of high-temperature reduction may include any value within a range such as 2 h, 4 h, 6 h, 8 h, 10 h, etc., and can be specifically adjusted according to the actual situation.

[0158] As an example, in the high-temperature reduction method, the reduction atmosphere is pure H 2 gas, H2 / Ar mixed gas, H 2 / CO 2 One or a combination thereof in the mixed gas.

[0159] The present invention also provides an application of an alloy carbide catalyst, which is applied to directly synthesize higher carbon alcohol aldehydes from syngas, and the higher carbon alcohol aldehydes are straight-chain alcohol aldehydes with a carbon number greater than or equal to 2.

[0160] As an example, in the application of the alloy carbide catalyst in directly synthesizing higher carbon alcohol aldehydes from syngas, the alloy carbide catalyst is tableted and sieved to obtain particles with a mesh size of 40 - 60.

[0161] Specifically, the particles obtained by sieving can include any value within the range such as 40 mesh, 45 mesh, 50 mesh, 55 mesh, 60 mesh, etc., and can be specifically adjusted according to the actual situation.

[0162] As an example, in the application of the alloy carbide catalyst in directly synthesizing higher carbon alcohol aldehydes from syngas, the reaction conditions for directly synthesizing higher carbon alcohol aldehydes from syngas are as follows: the raw material gas is selected from one of the syngases with H 2 / CO = 0.5, H 2 / CO = 1, H 2 / CO = 2, the space velocity WHSV is 1000 - 20000 ml / (g cat ·h), the reaction temperature is 170 - 270 °C, and the reaction pressure is 0.5 - 6 MPa.

[0163] Specifically, the space velocity WHSV can include any value within the range such as 1000 ml / (g cat ·h), 5000 ml / (g cat ·h), 10000 ml / (g cat ·h), 15000 ml / (g cat ·h), 20000 ml / (g cat ·h), etc., and can be specifically adjusted according to the actual situation; the reaction temperature can include any value within the range such as 170 °C, 190 °C, 210 °C, 230 °C, 250 °C, 270 °C, etc., and can be specifically adjusted according to the actual situation; the reaction pressure can include any value within the range such as 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, etc., and can be specifically adjusted according to the actual situation.

[0164] To better understand the alloy carbide catalyst, preparation method and its application in the present invention, the alloy carbide catalyst, preparation method and its application in the present invention will be described below with reference to specific examples. It should be noted that these examples are merely descriptive and do not limit the present invention in any way.

[0165] Example 1

[0166] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 48.0 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0167] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, a method for preparing the FeCo alloy carbide catalyst by the co-precipitation method, including the following steps:

[0168] S1. Provide ferric nitrate and cobalt nitrate, weigh them according to the molar ratio of 1:1 between the Fe element and the Co element, and dissolve them in water to make a 1 mol / L mixed metal salt solution;

[0169] S2. Dissolve the precipitant containing the K element in water to make a 2 mol / L precipitant solution; wherein, weigh potassium carbonate and potassium hydroxide according to 1.5 wt% of the K element in the total mass of the catalyst, and the molar ratio of potassium carbonate to potassium hydroxide is 2;

[0170] S3. Measure 100 mL of deionized water, which is the mother liquor;

[0171] S4. Drop the mixed metal salt solution and the precipitant solution into the mother liquor simultaneously, and carry out co-precipitation at 60 °C. The pH during co-precipitation is 9.2 to obtain a co-precipitation solution;

[0172] S5. Age the co-precipitation solution at 60 °C for 2 h, centrifuge and wash it 6 times, and then place it in an oven at 100 °C to dry for 48 h to obtain a solid powder precursor;

[0173] S6. Calcinate the solid powder precursor in static air at 350 °C for 6 h to obtain an oxide powder (FeCo spinel oxide), and reduce the oxide powder in a hydrogen atmosphere at 300 °C for 5 h to obtain an alloy powder (FeCo alloy); Carbonize the alloy powder in a syngas atmosphere (H 2 / CO = 1) at 250 °C for 24 h to obtain the FeCo alloy carbide catalyst.

[0174] Refer to Figure 1XRD diffraction patterns of the FeCo spinel oxide, FeCo alloy, and FeCo alloy carbide catalysts obtained in step S6. As can be seen from the figure, the FeCo spinel oxide exhibits five main characteristic diffraction peaks with 2θ values of 31.0°, 36.5°, 44.2°, 58.6°, and 64.7°, respectively. All diffraction peaks are located between Fe 3 O 4 (JCPDS#03-0863) spinel and Co 3 O 4 spinel ((JCPDS#42-1467).

[0175] See Figure 2 、 Figure 3 Low-magnification and high-magnification transmission electron micrographs of the FeCo alloy carbide catalyst prepared in this example, respectively. As can be seen from Figure 2 it, the FeCo alloy carbide has a spherical-like morphology. As can be seen from Figure 3 it, the lattice spacing of the alloy carbide is 0.207 nm, corresponding to the (-101) crystal plane of the FeCo alloy carbide.

[0176] This example also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this example is applied to the direct synthesis of higher carbon alcohols and aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. Specifically:[[]]

[0177] Weigh 1.0 g of the alloy carbide catalyst and mix it with 3.0 g of quartz sand particles. Sieve the alloy carbide catalyst and quartz sand particles with 40-60 meshes respectively. In the syngas with H 2 / CO = 1, the space velocity WHSV is 3000 ml / (g cat ·h), the reaction pressure is 6 Mpa, heat up to 250 °C for reaction, and the performance results are shown in Table 1.

[0178] Example 2

[0179] This example provides an alloy carbide catalyst. The alloy carbide catalyst is a FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 4.8 wt% of Fe element, 5.1 wt% of Co element, 1.5 wt% of the first metal promoter K, and 88.6 wt% of the carrier SiO 2 ; among them, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0180] This embodiment also provides a preparation method of a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 lies in that: in step S3, an appropriate amount of carrier SiO 2 is dissolved in 100 mL of deionized water to obtain a mother liquor; in step S6, the solid powder precursor is calcined in a flowing NO / Ar mixed atmosphere (the content of NO is 5%) at 400 °C for 6 h to obtain an oxide powder, and the oxide powder is reduced in hydrazine hydrate to obtain an alloy powder; the alloy powder is carbonized in a syngas atmosphere (H 2 / CO = 1) at 300 °C for 18 h to obtain an alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0181] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for the direct synthesis of higher alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0182] Example 3

[0183] This embodiment provides an alloy carbide catalyst, which is a FeCo alloy structure catalyst. Calculated according to the mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 48.0 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0184] This embodiment also provides a preparation method of a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 lies in that: in step S6, the solid powder precursor is reduced in a hydrogen atmosphere at 250 °C for 5 h to obtain an alloy powder; the alloy powder is carbonized in a syngas atmosphere (H 2 / CO = 2) at 300 °C for 24 h to obtain an alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0185] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for the direct synthesis of higher alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0186] Example 4

[0187] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48.0 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0188] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is that: in step S6, the solid powder precursor is calcined in a flowing H 2 O / Ar mixed atmosphere at 350 °C for 6 h to obtain an oxide powder, and the oxide powder is carbonized in a syngas atmosphere (H 2 / CO = 0.5) at 250 °C for 24 h to obtain the alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0189] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed to directly synthesize higher carbon alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0190] Example 5

[0191] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48.0 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0192] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is that: in step S6, the solid powder precursor is carbonized in a syngas atmosphere (H 2 / CO = 1) at 250 °C for 24 h to obtain the alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0193] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed to directly synthesize higher carbon alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0194] Example 6

[0195] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0196] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is that: in step S6, the solid powder precursor is calcined in still air at 350 °C for 6 h to obtain an oxide powder, and the oxide powder is reduced in a hydrogen atmosphere at 300 °C for 5 h to obtain an alloy powder; the alloy powder is carbonized in a syngas atmosphere (H 2 / CO = 3) at 250 °C for 24 h to obtain the alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0197] This example also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this example is applied in a fixed bed to directly synthesize higher carbon alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0198] Example 7

[0199] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 64.5 wt% of Fe element, 34 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 2:1.

[0200] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is that: in step S1, ferric nitrate and cobalt nitrate are provided and weighed according to the molar ratio of 2:1 between the Fe element and the Co element, and dissolved in water to make a 1 mol / L mixed metal salt solution; in step S6, the solid powder precursor is calcined in still air at 250 °C for 6 h to obtain an oxide powder, and the oxide powder is reduced in a hydrogen atmosphere at 300 °C for 5 h to obtain an alloy powder; the alloy powder is carbonized in a syngas atmosphere (H 2Carbide for 24 h at 250 °C in a syngas atmosphere (H2 / CO = 1) to obtain an alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0201] This example also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this example is applied to the direct synthesis of higher alcohols and aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0202] Example 8

[0203] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 31.7 wt% of Fe element, 66.8 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:2.

[0204] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:2, and dissolved in water to form a 1 mol / L mixed metal salt solution; in step S6, the solid powder precursor is calcined in static air at 350 °C for 6 h to obtain an oxide powder, and the oxide powder is reduced in a hydrogen atmosphere at 250 °C for 5 h to obtain an alloy powder; the alloy powder is carbonized for 24 h at 250 °C in a syngas atmosphere (H2 / CO = 1) to obtain an alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here. 2 Carbide for 24 h at 250 °C in a syngas atmosphere (H2 / CO = 1) to obtain an alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0205] This example also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this example is applied to the direct synthesis of higher alcohols and aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0206] Example 9

[0207] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 78 wt% of Fe element, 20.5 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 4:1.

[0208] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 4:1, and dissolved in water to form a 1 mol / L mixed metal salt solution; in step S6, the solid powder precursor is calcined in static air at 350 °C for 6 h to obtain an oxide powder, and the oxide powder is reduced in a hydrogen atmosphere at 400 °C for 5 h to obtain an alloy powder; the alloy powder is carbonized in a syngas atmosphere (H 2 / CO = 1) at 250 °C for 24 h to obtain the alloy carbide catalyst; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0209] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed to directly synthesize higher carbon alcohols and aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0210] Example 10

[0211] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 18.9 wt% of Fe element, 79.6 wt% of Co element, and 1.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:4.

[0212] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:4, and dissolved in water to form a 1 mol / L mixed metal salt solution; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0213] This embodiment also provides an application of an alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for the direct synthesis of higher alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0214] Example 11

[0215] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 32.4 wt% of Fe element, 34.2 wt% of Co element, 1.5 wt% of the first metal promoter K, and 31.9 wt% of the second metal promoter Mn; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element, Co element, and Mn element is 1:1:1.

[0216] This embodiment also provides a preparation method of an FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is that in step S1, ferric nitrate, cobalt nitrate, and 50 wt% manganese nitrate aqueous solution are provided, weighed according to the molar ratio of Fe element, Co element, and Mn element of 1:1:1, and dissolved in water to form a 1 mol / L mixed metal salt solution; in step S4, the temperature of co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0217] This embodiment also provides an application of an alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for the direct synthesis of higher alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0218] Example 12

[0219] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 30.6 wt% of Fe element, 32.3 wt% of Co element, 1.5 wt% of the first metal promoter K, and 35.6 wt% of the second metal promoter Zn; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element, Co element, and Zn element is 1:1:1.

[0220] This embodiment also provides a method for preparing a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 lies in that: in step S1, an aqueous solution of iron nitrate, cobalt nitrate and zinc nitrate is provided, weighed according to the molar ratio of Fe element, Co element and Zn element of 1:1:1, and dissolved in water to form a 1 mol / L mixed metal salt solution; the temperature of co-precipitation in step S4 is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0221] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to directly synthesize higher alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0222] Example 13

[0223] This embodiment provides an alloy carbide catalyst, which is a FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 26.8 wt% of Fe element, 28.2 wt% of Co element, 1.5 wt% of the first metal promoter K, and 43.5 wt% of the second metal promoter Zr; among them, in the FeCo alloy structure catalyst, the molar ratio of Fe element, Co element and Zr element is 1:1:1.

[0224] This embodiment also provides a method for preparing a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 lies in that: in step S1, an aqueous solution of iron nitrate, cobalt nitrate and zirconium nitrate is provided, weighed according to the molar ratio of Fe element, Co element and Zr element of 1:1:1, and dissolved in water to form a 1 mol / L mixed metal salt solution; the temperature of co-precipitation in step S4 is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0225] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to directly synthesize higher alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0226] Example 14

[0227] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 38.9 wt% of Fe element, 40.9 wt% of Co element, 1.5 wt% of the first metal promoter K, and 18.7 wt% of the second metal promoter Al; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element, Co element, and Al element is 1:1:1.

[0228] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, an aqueous solution of iron nitrate, cobalt nitrate, and aluminum nitrate is provided, weighed according to the molar ratio of Fe element, Co element, and Al element of 1:1:1, and dissolved in water to form a 1 mol / L mixed metal salt solution; the temperature of co-precipitation in step S4 is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0229] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for directly synthesizing higher carbon alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0230] Example 15

[0231] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 24 wt% of Fe element, 25.3 wt% of Co element, 1.5 wt% of the first metal promoter K, and 49.2 wt% of the second metal promoter In; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element, Co element, and In element is 1:1:1.

[0232] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, an aqueous solution of iron nitrate, cobalt nitrate, and indium nitrate is provided, weighed according to the molar ratio of Fe element, Co element, and In element of 1:1:1, and dissolved in water to form a 1 mol / L mixed metal salt solution; the temperature of co-precipitation in step S4 is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0233] This embodiment also provides an application of an alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for the direct synthesis of higher alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0234] Example 16

[0235] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 30.8 wt% of Fe element, 32.5 wt% of Co element, 1.5 wt% of the first metal promoter K, and 35.2 wt% of the second metal promoter Cu; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element, Co element, and Cu element is 1:1:1.

[0236] This embodiment also provides a preparation method of an FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is that: in step S1, an aqueous solution of iron nitrate, cobalt nitrate, and copper nitrate is provided, weighed according to the molar ratio of Fe element, Co element, and Cu element of 1:1:1, and dissolved in water to form a 1 mol / L mixed metal salt solution; the temperature of co-precipitation in step S4 is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0237] This embodiment also provides an application of an alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for the direct synthesis of higher alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0238] Example 17

[0239] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter Na; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element and Co element is 1:1.

[0240] This embodiment also provides a method for preparing a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:1, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitant containing Na element is dissolved in water to form a 2 mol / L precipitant solution; among them, sodium carbonate and sodium hydroxide are weighed according to 1.5 wt% of the total mass of the catalyst by Na element, and the molar ratio of sodium carbonate to sodium hydroxide is 2; in step S4, the temperature of the co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0241] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to directly synthesize higher alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0242] Example 18

[0243] This embodiment provides an alloy carbide catalyst, which is a FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter Li; among them, in the FeCo alloy structure catalyst, the molar ratio of Fe element to Co element is 1:1.

[0244] This embodiment also provides a method for preparing a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:1, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitant containing Li element is dissolved in water to form a 2 mol / L precipitant solution; among them, lithium carbonate and lithium hydroxide are weighed according to 1.5 wt% of the total mass of the catalyst by Li element, and the molar ratio of lithium carbonate to lithium hydroxide is 2; in step S4, the temperature of the co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0245] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to directly synthesize higher alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0246] Example 19

[0247] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 48 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter Rb; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0248] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of 1:1 between the Fe element and the Co element, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitant containing the Rb element is dissolved in water to form a 2 mol / L precipitant solution; wherein, rubidium carbonate and rubidium hydroxide are weighed according to 1.5 wt% of the total mass of the catalyst for the Rb element, and the molar ratio of rubidium carbonate to rubidium hydroxide is 2; in step S4, the temperature of the co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0249] This example also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this example is applied to directly synthesize higher carbon alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0250] Example 20

[0251] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 48 wt% of Fe element, 50.5 wt% of Co element, and 1.5 wt% of the first metal promoter Cs; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0252] This embodiment also provides a preparation method of a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 lies in: in step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:1, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitant containing Cs element is dissolved in water to form a 2 mol / L precipitant solution; wherein, cesium carbonate and cesium hydroxide are weighed according to 1.5 wt% of the total mass of the catalyst by Cs element, and the molar ratio of cesium carbonate to cesium hydroxide is 2; in step S4, the temperature of co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0253] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to directly synthesize higher carbon alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0254] Example 21

[0255] This embodiment provides an alloy carbide catalyst. The alloy carbide catalyst is a FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48.6 wt% of Fe element, 51.2 wt% of Co element, and 0.2 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element to Co element is 1:1.

[0256] This embodiment also provides a preparation method of a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 lies in: in step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:1, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitant containing K element is dissolved in water to form a 2 mol / L precipitant solution; wherein, potassium carbonate and potassium hydroxide are weighed according to 0.2 wt% of the total mass of the catalyst by K element, and the molar ratio of potassium carbonate to potassium hydroxide is 2; in step S4, the temperature of co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0257] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to directly synthesize higher carbon alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0258] Example 22

[0259] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48.5 wt% of Fe element, 51 wt% of Co element, and 0.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0260] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of 1:1 between the Fe element and the Co element, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitant containing the K element is dissolved in water to form a 2 mol / L precipitant solution; wherein, potassium carbonate and potassium hydroxide are weighed according to 0.5 wt% of the total mass of the catalyst, and the molar ratio of potassium carbonate to potassium hydroxide is 2; in step S4, the temperature of the co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0261] This example also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this example is applied in a fixed bed for the direct synthesis of higher carbon alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0262] Example 23

[0263] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 48.2 wt% of Fe element, 50.8 wt% of Co element, and 1.0 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0264] This embodiment also provides a method for preparing a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between this preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:1, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitating agent containing K element is dissolved in water to form a 2 mol / L precipitating agent solution; wherein, potassium carbonate and potassium hydroxide are weighed according to 1.0 wt% of the total mass of the catalyst by K element, and the molar ratio of potassium carbonate to potassium hydroxide is 2; in step S4, the temperature of the co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0265] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to the direct synthesis of higher alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0266] Example 24

[0267] This embodiment provides an alloy carbide catalyst, which is a FeCo alloy structure catalyst. Calculated by mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 47.5 wt% of Fe element, 50.0 wt% of Co element, and 2.5 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio of Fe element to Co element is 1:1.

[0268] This embodiment also provides a method for preparing a FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between this preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of Fe element to Co element of 1:1, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitating agent containing K element is dissolved in water to form a 2 mol / L precipitating agent solution; wherein, potassium carbonate and potassium hydroxide are weighed according to 2.5 wt% of the total mass of the catalyst by K element, and the molar ratio of potassium carbonate to potassium hydroxide is 2; in step S4, the temperature of the co-precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0269] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied to the direct synthesis of higher alcohol aldehydes from syngas in a fixed bed, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0270] Example 25

[0271] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. By mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 46.3 wt% of Fe element, 48.7 wt% of Co element, and 5.0 wt% of the first metal promoter K; wherein, in the FeCo alloy structure catalyst, the molar ratio between the Fe element and the Co element is 1:1.

[0272] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co - precipitation method. The difference between its preparation method and that of Example 1 is as follows: In step S1, ferric nitrate and cobalt nitrate are provided, weighed according to the molar ratio of 1:1 between the Fe element and the Co element, and dissolved in ethanol to form a 1 mol / L mixed metal salt solution; in step S2, a precipitant containing K element is dissolved in water to form a 2 mol / L precipitant solution; wherein, potassium carbonate and potassium hydroxide are weighed according to 5.0 wt% of the total mass of the catalyst, and the molar ratio of potassium carbonate to potassium hydroxide is 2; in step S4, the temperature of the co - precipitation is 30 °C; other methods and steps are the same as those in Example 1 and will not be elaborated here.

[0273] This example also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this example is applied in a fixed bed for the direct synthesis of higher - carbon alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0274] Example 26

[0275] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. By mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 6.7 wt% of Fe element, 7.3 wt% of Co element, 1.3 wt% of the first metal promoter K, and 84.7 wt% of the carrier SiO 2 。

[0276] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co - precipitation method. Its preparation method includes the following steps:

[0277] A1. Dissolve 6.83 g of ferric nitrate and 8.5 g of cobalt nitrate in water to obtain a mixed metal salt solution;

[0278] A2. Dissolve 0.79 g of potassium nitrate in the mixed metal salt solution to obtain a mixed solution;

[0279] A3. Immerse the mixed solution in 20 g of the carrier SiO 2 , and obtain a solid powder after standing and drying; wherein, the water absorption of SiO 2 is 2.5 mL / g;

[0280] A4. Calcinate the solid powder in static air at 350 °C for 6 h to obtain an oxide powder, and reduce the oxide powder in a hydrogen atmosphere at 300 °C for 5 h to obtain an alloy powder; Carbide the alloy powder in a syngas atmosphere (H 2 / CO = 1) at 250 °C for 24 h to obtain an alloy carbide catalyst.

[0281] This example also provides an application of the alloy carbide catalyst. Apply the alloy carbide catalyst in this example in a fixed bed to directly synthesize higher alcohol aldehydes from syngas, and then evaluate the catalytic performance of the catalyst. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0282] Example 27

[0283] This example provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated according to the mass percentage of the FeCo alloy structure catalyst, it includes the following components by mass percentage: 6.7 wt% of Fe element, 7.3 wt% of Co element, 1.3 wt% of the first metal promoter K, and 84.7 wt% of the carrier TiO 2 .

[0284] This example also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co-precipitation method. The difference between its preparation method and that of Example 26 is that in step A3, the mixed solution is immersed in 20 g of the carrier TiO 2 , and obtain a solid powder after standing and drying; wherein, the water absorption of TiO 2 is 1.5 mL / g; Other steps and methods are the same as those in Example 26 and will not be elaborated here.

[0285] This example also provides an application of the alloy carbide catalyst. Apply the alloy carbide catalyst in this example in a fixed bed to directly synthesize higher alcohol aldehydes from syngas, and then evaluate the catalytic performance of the catalyst. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0286] Example 28

[0287] The present embodiment provides an alloy carbide catalyst, which is a FeCo alloy structure catalyst, and includes the following components in mass percentage: 6.7wt% of Fe element, 7.3wt% of Co element, 1.3wt% of a first metal additive K and 84.7wt% of a carrier activated carbon.

[0288] This embodiment also provides a preparation method of a FeCo alloy carbide catalyst, which is prepared by a co-precipitation method. The difference between the preparation method and that of Example 26 is that in step A3, the mixed liquid is impregnated on 20 g of a carrier activated carbon, and a solid powder is obtained after standing and drying; wherein the water absorption capacity of the activated carbon is 4.5 mL / g; the other steps and methods are the same as those in Example 26 and will not be repeated here.

[0289] This embodiment also provides an application of an alloy carbide catalyst. The alloy carbide catalyst in this embodiment is used in a fixed bed to directly produce high-carbon alcohol aldehydes from synthesis gas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as the evaluation method in Example 1 and will not be repeated here. The performance results are shown in Table 1.

[0290] Embodiment 29

[0291] The present embodiment provides an alloy carbide catalyst, which is a FeCo alloy structure catalyst, and includes the following components by mass percentage: 6.7wt% of Fe element, 7.3wt% of Co element, 1.3wt% of the first metal additive K, and 84.7wt% of the carrier Al. 2 O 3 .

[0292] This embodiment also provides a method for preparing a FeCo alloy carbide catalyst, which is prepared by coprecipitation. The difference between the preparation method and that of embodiment 26 is that in step A3, the mixed solution is impregnated in 20 g of a carrier Al 2 O 3 After standing and drying, a solid powder is obtained; wherein Al 2 O 3 The water absorption capacity is 1.3 mL / g; the other steps and methods are the same as those in Example 26 and will not be repeated here.

[0293] This embodiment also provides an application of an alloy carbide catalyst. The alloy carbide catalyst in this embodiment is used in a fixed bed to directly produce high-carbon alcohol aldehydes from synthesis gas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as the evaluation method in Example 1 and will not be repeated here. The performance results are shown in Table 1.

[0294] Embodiment 30

[0295] This embodiment provides an alloy carbide catalyst, which is an FeCo alloy structure catalyst. Calculated by the mass percentage of the FeCo alloy structure catalyst, it includes the following components in mass percentage: 6.7 wt% of Fe element, 7.3 wt% of Co element, 1.3 wt% of the first metal promoter K, and 84.7 wt% of the carrier carbon nanotubes CNTs.

[0296] This embodiment also provides a preparation method of the FeCo alloy carbide catalyst, which is prepared by the co - precipitation method. The difference between its preparation method and that of Example 26 is that in step A3, the mixed solution is impregnated on 20 g of the carrier carbon nanotubes CNTs, and after standing and drying, a solid powder is obtained; wherein, the water absorption of the carbon nanotubes CNTs is 3.3 mL / g; other steps and methods are the same as those in Example 26 and will not be elaborated here.

[0297] This embodiment also provides an application of the alloy carbide catalyst. The alloy carbide catalyst in this embodiment is applied in a fixed bed for directly synthesizing higher - carbon alcohol aldehydes from syngas, and then the catalytic performance of the catalyst is evaluated. The evaluation method is the same as that in Example 1 and will not be elaborated here. The performance results are shown in Table 1.

[0298] Table 1 Reaction results of the alloy carbide catalyst in Examples 1 - 30 for directly synthesizing higher - carbon alcohol aldehydes from syngas

[0299]

[0300]

[0301] Examples 1, 3, 4, 5, and 6 compared the effects of different treatment atmospheres. It can be found that reduction in a pure hydrogen atmosphere at 250 °C and then H at 300 °C 2The alloy carbide catalyst obtained by carbonization under a syngas atmosphere with a / CO ratio of 1 has the best activity and selectivity. Examples 1, 8, 9, and 10 compared the effects of different Fe / Co ratios and found that the alloy carbide catalyst prepared with an Fe / Co ratio of 1 exhibited the best performance. Examples 11, 12, 13, 14, 15, and 16 compared the effects of different transition metals M2 and found that the Mn promoter can effectively improve the catalytic activity and the selectivity of alcohol and aldehyde products. Examples 1, 17, 18, 19, and 20 compared the effects of different alkali metals M1 and found that the promoting effect of the K promoter was the most obvious. Examples 1, 21, 22, 23, 24, and 25 compared the effects of different contents of K metal and found that the promoting effect of the K promoter with a content of 1.5 wt% was the best. Examples 2, 26, 27, 28, 29, and 30 compared the effects of different supported carriers and found that the prepared supported alloy carbide catalyst can maintain high catalytic activity and the selectivity of alcohol and aldehyde products while reducing the usage amounts of Fe and Co.

[0302] In summary, the present invention prepares a brand-new alloy carbide catalyst. By forming a new active phase of the alloy carbide catalyst, the contact interface density of bifunctional sites is provided, realizing the high-activity and high-selectivity synthesis of higher alcohol and aldehyde by the one-step method of syngas. The alloy carbide catalyst in the present invention has excellent comprehensive catalytic performance. In the application of directly synthesizing higher alcohol and aldehyde from syngas, the CO conversion rate can reach up to 93.8%, the selectivity of higher alcohol and aldehyde in the product distribution is relatively high, up to about 61.1% at most, and at the same time, the selectivity of hydrocarbons decreases accordingly, and the product distribution is more economical. The alloy carbide catalyst in the present invention has good stability. At the same time, the preparation method of the alloy carbide catalyst is relatively simple and can be scaled up to solve the problem that the synthesis of higher alcohol and aldehyde from syngas cannot be industrialized. Therefore, the present invention effectively overcomes various disadvantages in the prior art and has high industrial utilization value.

[0303] The above embodiments are only illustrative of the principles and effects of the present invention and are not used to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. An alloy carbide catalyst, characterized in that, The alloy carbide catalyst is an FeCoM1M2M3 alloy structure catalyst. Calculated by the mass percentage of the FeCoM1M2M3 alloy structure catalyst, it includes the following components in mass percentages: 4.8 wt% to 81.5 wt% of Fe element, 4.8 wt% to 81.5 wt% of Co element, 0.2 wt% to 11.2 wt% of the first metal promoter M1, 0 to 70 wt% of the second metal promoter M2, and 0 to 90 wt% of the carrier M3; the first metal promoter M1 is selected from one or a combination of Li, Na, K, Rb, and Cs; the second metal promoter M2 is selected from one or a combination of Mg, Ca, Zn, Al, Zr, In, Mn, La, and Ce; the carrier M3 is selected from one or a combination of TiO 2 , and carbon materials.

2. The alloy carbide catalyst according to claim 1, characterized in that, including one or a combination of the following conditions: In the alloy carbide catalyst, the molar ratio between the Fe element and the Co element is 1:10 to 10:1; in the alloy carbide catalyst, the molar ratio between the Co element and M2 is 1:10 to 10:

1.

3. A preparation method of the alloy carbide catalyst according to any one of claims 1 to 2, characterized in that: The alloy carbide catalyst is obtained by using at least one of the coprecipitation method and the impregnation method; Among them, the method for preparing the alloy carbide catalyst by the coprecipitation method includes the following steps: S1. Provide salts of Fe, Co and the second metal promoter M2, and dissolve the salts of Fe, Co and the second metal promoter M2 in water or ethanol according to the mass percentage to obtain a mixed metal salt solution; S2. Dissolve the precipitant containing the first metal promoter M1 element in water or ethanol to obtain a precipitant solution; S3. Disperse the carrier M3 in deionized water to obtain a mother liquor; S4. Drop the mixed metal salt solution and the precipitant solution into the mother liquor simultaneously to carry out coprecipitation to obtain a coprecipitation solution; S5. After aging, centrifuging, washing and drying the coprecipitation solution, a solid powder precursor is obtained; S6. The solid powder precursor is subjected to carbonization treatment to obtain an alloy carbide catalyst; The method for preparing the alloy carbide catalyst by the impregnation method includes the following steps: A1. Provide salts of Fe, Co and the second metal promoter M2, and dissolve the salts of Fe, Co and the second metal promoter M2 in water or ethanol according to the mass percentage to obtain a mixed metal salt solution; A2. Provide a salt of the first metal promoter M1 element and dissolve it in the mixed metal salt solution to obtain a mixed solution; A3. Immerse the mixed solution on the carrier M3, and obtain a solid powder after standing and drying; A4. The solid powder is subjected to carbonization treatment to obtain an alloy carbide catalyst.

4. The preparation method of the alloy carbide catalyst according to claim 3, characterized in that: Step S1 includes one or a combination of the following conditions: The Fe salt is selected from one or a combination of Fe chloride, nitrate, sulfate, carbonate, acetate; The Co salt is selected from one or a combination of Co chloride, nitrate, sulfate, carbonate, acetate; The salt of the second metal promoter M2 is selected from one or a combination of chloride, nitrate, sulfate, carbonate, acetate of M2 element; The total molar concentration of the mixed metal salt solution is 0.5 to 4 mol / L.

5. The preparation method of the alloy carbide catalyst according to claim 3, characterized in that: Step S2 includes one or a combination of the following conditions: The precipitant containing the first metal promoter M1 element is Li 2 CO 3 、Na 2 CO 3 、K 2 CO 3 、Rb 2 CO 3 、Cs 2 CO 3 、or one of LiOH, NaOH, KOH, RbOH, and CsOH; The precipitant containing the first metal promoter M1 element is a mixture of hydroxide and carbonate of M1 element, wherein the M1 element is selected from one of Li, Na, K, Rb, Cs; The molar concentration of the precipitant solution is 0.5 to 4 mol / L.

6. The preparation method of the alloy carbide catalyst according to claim 3, wherein: In step S4, one or a combination of the following conditions is included: The temperature of the coprecipitation is 10 to 80 °C; The pH value during the coprecipitation is 6 to 12.

7. The preparation method of the alloy carbide catalyst according to claim 3, wherein: In step S5, one or a combination of the following conditions is included: The temperature of the aging is 20 to 80 °C; The time of the aging is 0.5 to 24 h; The number of centrifugation and washing is 0 to 10 times; The temperature of the drying is 50 to 120 °C; The time of the drying is 6 to 48 h.

8. The preparation method of the alloy carbide catalyst according to claim 3, wherein: In both step S6 and step A4, one or a combination of the following conditions is included: The carbonization treatment is specifically: carbonization in a carbonization atmosphere at 200 to 400 °C for 2 to 48 h; Before the carbonization treatment, one or a combination of the steps of roasting and reduction is also included.

9. The preparation method of the alloy carbide catalyst according to claim 8, wherein: One or a combination of the following conditions is included: The carbonization atmosphere is one of a syngas atmosphere, a diluted syngas atmosphere, and a CO 2 diluted syngas atmosphere; wherein, the H 2 / CO ratio in the syngas atmosphere is 0.5 to 3; in the N 2 diluted syngas atmosphere, the content of N 2 is 5 wt% to 95 wt%; in the CO 2 diluted syngas atmosphere, the content of CO 2 is 5 wt% to 95 wt%; 2 ​ The roasting step specifically includes: roasting in a static atmosphere or a flowing atmosphere at 200 to 600 °C for 0.5 to 10 h; The reduction includes a high-temperature reduction method or a reduction-oxidation method. The high-temperature reduction method specifically includes: reduction at 200 to 600 °C for 2 to 10 h; The reduction-oxidation method specifically includes: reduction in sodium borohydride or hydrazine hydrate.

10. The preparation method of the alloy carbide catalyst according to claim 9, wherein: One or a combination of the following conditions is included: In the roasting step, the static atmosphere is static air; In the roasting step, the flowing atmosphere includes flowing air, flowing N 2 gas, flowing Ar gas, flowing NO / Ar mixed gas, flowing H 2 O / Ar mixed gas, flowing H 2 O / air mixed gas, flowing CO 2 / Ar mixed gas, flowing CO 2 / air mixed gas, or a combination thereof; In the high-temperature reduction method, the reducing atmosphere is pure H 2 gas, H 2 / Ar mixed gas, H 2 / CO 2 mixed gas, or a combination thereof.

11. The preparation method of the alloy carbide catalyst according to claim 3, wherein: In step A1, one or a combination of the following conditions is included: The Fe salt is selected from one or a combination of Fe chloride, nitrate, sulfate, carbonate, acetate; The Co salt is selected from one or a combination of Co chloride, nitrate, sulfate, carbonate, acetate; The salt of the second metal promoter M2 is selected from one or a combination of the chloride, nitrate, sulfate, carbonate, acetate of the M2 element; The total molar concentration of the mixed metal salt solution is 0.5 to 4 mol / L.

12. The preparation method of the alloy carbide catalyst according to claim 3, wherein: In step A2 and step A3, one or a combination of the following conditions is included: The salt of the first metal promoter M1 element is selected from one or a combination of the carbonate, nitrate, chloride, sulfate, acetate of the M1 element; The temperature of the impregnation is 5 to 30 °C; The time of the static placement is 4 to 48 h; The temperature of the drying is 50 to 120 °C; The time of the drying is 6 to 48 h.

13. An application of the alloy carbide catalyst according to any one of claims 1 to 2, wherein, The alloy carbide catalyst is applied to the direct synthesis of higher alcohol aldehydes from syngas, and the higher alcohol aldehydes are straight-chain alcohol aldehydes with a carbon number of 2 or more.

14. The application of the alloy carbide catalyst according to claim 13, wherein, in the application of the alloy carbide catalyst in the direct synthesis of higher alcohol aldehydes from syngas, it includes one or a combination of the following technical features: tabletting the alloy carbide catalyst and sieving to obtain particles with a mesh size of 40 - 60; The reaction conditions for directly synthesizing higher carbon alcohols and aldehydes from syngas are as follows: The feed gas is selected from one of the syngases with H 2 / CO = 0.5, H 2 / CO = 1, H 2 / CO = 2, the space velocity WHSV is 1000 - 20000 ml / (g cat ·h), the reaction temperature is 170 - 270 °C, and the reaction pressure is 0.5 - 6 MPa.

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