Process for the preparation of carbinols

Abstract

This invention provides a method for preparing carbon alcohols, in which syngas is reacted in the presence of a Co-Ag-based catalyst to produce carbon alcohols. The Co-Ag-based catalyst comprises active components Co and Ag, with the total mass of Co and Ag accounting for 10%-80% of the total mass of the catalyst, and the mass ratio of Co to Ag being (0.5-10):1. The preparation method provided by this invention enables one-step synthesis of carbon alcohols, and is particularly suitable for preparing C6+ higher carbon alcohols.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of synthesis gas, and particularly relates to a preparation method of carbinol. BACKGROUND

[0002] High carbinol refers to monohydric alcohol containing six carbon atoms or more, and is widely applied to synthesis of surfactants, plasticizers, detergents and other fine chemical products. High carbinol is mainly divided into plasticizer alcohol (C6-C11 alcohol) and detergent alcohol (C12-C20 alcohol). With the increasing demand for high carbinol and its derivative products year by year, how to prepare high-purity straight-chain aliphatic alcohol and reduce production cost is a research hotspot for those skilled in the art.

[0003] The existing methods for producing high carbinol include: (1) taking natural oil as raw material, esterifying with methanol and then hydrogenating to obtain straight-chain primary alcohol. In this method, the development time of natural oil is relatively long, the growth process is relatively complex, and is greatly affected by internal and external factors; (2) normal alkane oxidation method: taking C10-C16 normal alkane as raw material, and through processes such as oxidation, esterification, flash distillation, hydrolysis, saponification, water washing and rectification, secondary alcohol is obtained. The production process of this method is relatively long; (3) Alfol method: using Ziegler method to obtain oxygen-containing alkyl aluminum, and through hydrolysis, layering and refining, even carbon number straight-chain primary alcohol is obtained. The process of Alfol method is complex and requires high equipment; (4) carbonyl synthesis method: converting alpha-olefin, hydrogen and carbon monoxide into aldehyde compounds under the action of a catalyst, and then obtaining straight-chain and branched-chain mixed alcohol through high-pressure hydrogenation. The raw materials of carbonyl synthesis method and Alfol method are both alpha-olefin, which is relatively expensive.

[0004] Currently, the synthesis gas method is one of the potential carbon alcohol production technologies, which has the advantages of cheap and easy-to-obtain raw materials and short production process. The developed catalysts for directly synthesizing mixed alcohols from synthesis gas include Mo-based, Rh-based, modified methanol catalysts and modified Fischer-Tropsch synthesis catalysts. The Mo-based catalysts have MoS2 or Mo2C as the main active component and have good carbon deposition resistance, such as patent documents US4825013A and US4752622A. Researchers have improved this system by adding alkali metals, Co, Ni and other additives to improve the activity and the selectivity of high carbon alcohols in the product, represented by US835435A and CN107335444B. The main reaction products of this catalytic system are C1-C5 straight-chain alcohols; Rh-based catalysts have high activity and high selectivity for ethanol, but their weak carbon chain growth ability limits the selectivity of higher carbon alcohols, and their high price and weak sulfur poisoning resistance are not conducive to industrial application, represented by US4014913A and CN106268856A. The main components of the modified methanol catalysts are Cu, Zn, Cr and the like, and the main products are C1-C5 alcohols, represented by US5627295A and CN101185899A. The modified Fischer-Tropsch synthesis catalysts utilize the ability of the Fischer-Tropsch synthesis active components Co or Fe to dissociate and activate CO and promote carbon chain growth to control the active phase and improve the selectivity of alcohols, which is conducive to obtaining higher carbon number straight-chain primary alcohols. The French Petroleum Academy has developed a CoCu catalyst-based process, which is mainly used for producing C2-C6 alcohols, such as patent documents US4291126A, US4122110A and GB2118061A.

[0005] In the above disclosed carbon alcohol synthesis method, the synthesis product is mainly C1-C5 low carbon alcohol, but the technology for directly synthesizing C6+ high carbon alcohol from synthesis gas is not mature at present, and there are few research reports. SUMMARY

[0006] The present application provides a carbon alcohol preparation method, which can realize one-step synthesis of carbon alcohol, especially for preparing C6+ high carbon alcohol, and effectively overcomes the defects of the prior art.

[0007] The present application provides a carbon alcohol preparation method, which makes synthesis gas react under the action of a Co-Ag-based catalyst to prepare carbon alcohol, wherein the Co-Ag-based catalyst comprises active components Co and Ag, the total mass of Co and Ag accounts for 10%-80% of the total mass of the catalyst, and the mass ratio of Co to Ag is (0.5-10):1; preferably, the total mass of Co and Ag accounts for 20%-60% of the total mass of the catalyst, and the mass ratio of Co to Ag is (1-8):1.

[0008] According to an embodiment of the present application, the reaction is carried out under the conditions of a temperature of 160-360℃, a pressure of 0.5-8.0 MPa, and a volume space velocity of 400-10000 h-1. -1 -10000h -1 .

[0009] According to an embodiment of the present application, the reaction is carried out under the conditions of a temperature of 180-250℃, a pressure of 1-4 MPa, and a volume space velocity of 500-5000 h-1. -1 -5000h -1 .

[0010] According to an embodiment of the present application, the synthesis gas comprises H2 and CO, and the molar ratio of H2 to CO in the synthesis gas is (0.5-3.5):1.

[0011] According to an embodiment of the present application, the synthesis gas further comprises an inert gas in a volume fraction of 0-70%, and the inert gas comprises at least one of argon, carbon dioxide, helium, nitrogen, methane, ethane, propane, and butane.

[0012] According to an embodiment of the present application, the synthesis gas further comprises an inert gas in a volume fraction of 1-50%, and the inert gas comprises at least one of argon, carbon dioxide, helium, nitrogen, methane, ethane, propane, and butane.

[0013] According to an embodiment of the present application, before the reaction, the catalyst is further subjected to a pre-reduction treatment, and the pre-reduction treatment is carried out under a reducing atmosphere.

[0014] According to an embodiment of the present application, the reducing atmosphere comprises the following components in terms of volume fraction: H2: 20-100%, N2: 0-80%.

[0015] According to an embodiment of the present application, the pre-reduction treatment is carried out under the conditions of a temperature of 300-500℃, a pressure of 0.1-2 MPa, and a volume space velocity of 200-3000 h-1. -1 -3000h -1 , and a time of 3-30 h.

[0016] According to an embodiment of the present application, the Co-Ag-based catalyst further comprises an auxiliary agent and / or a carrier, the auxiliary agent comprises at least one of an alkali metal element, a transition metal element, and an element of Group IIA of the periodic table, and the carrier is an inorganic oxide; preferably, the auxiliary agent is selected from one or a combination of two or more of Li, Na, K, Cs, Mg, Sr, Zn, Mn, Mo, Ni, Ru, Rh, Pt, Ce, and La.

[0017] According to one embodiment of the present invention, the Co-Ag-based catalyst is prepared by any one of the following methods: co-precipitation, co-impregnation, stepwise impregnation, or a combination of precipitation and impregnation.

[0018] The implementation of this invention has at least the following beneficial effects:

[0019] The method for preparing carbon alcohols provided by this invention allows syngas to react under the action of a Co-Ag-based catalyst to produce carbon alcohols. This method not only enables one-step synthesis of carbon alcohols, simplifying the preparation process, but also achieves high total alcohol selectivity, reaching over 30%. Furthermore, it can suppress methanol selectivity and increase the yield of C6+ higher carbon alcohols. Specifically, the mass fraction of the main product, C6+ higher carbon alcohols, in the total alcohols can reach over 60%.

[0020] Furthermore, the method for preparing carbon alcohols provided by this invention has the advantages of mild reaction conditions, controllable process conditions, and ease of operation, which is conducive to industrial production and application. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0022] The present invention provides a method for preparing carbon alcohols by reacting syngas under the action of a Co-Ag-based catalyst to obtain carbon alcohols. The Co-Ag-based catalyst includes active components Co and Ag, the total mass of Co and Ag accounts for 10%-80% of the total mass of the catalyst, and the mass ratio of Co to Ag is (0.5-10):1.

[0023] The inventors, through research and analysis, concluded that different ratios of the active components Co and Ag in Co-Ag-based catalysts result in varying reaction performance and selectivity for alcohol products. This invention, by adjusting the Co / Ag ratio in the Co-Ag-based catalyst, can improve the catalyst activity and selectivity for C6+ higher alcohols. Applying this Co-Ag-based catalyst to the preparation of carbon alcohols from syngas can improve the selectivity for total alcohols while suppressing methanol selectivity, thereby increasing the yield of C6+ higher alcohols.

[0024] The above preparation process is a gas-solid phase reaction process, which can be carried out in a fixed-bed reactor or a fluidized-bed reactor. For example, a granular Co-Ag-based catalyst is packed into the reactor to form a fixed bed of a certain height. Syngas is then introduced into the reactor, and the reaction process is realized as the syngas flows through the fixed bed.

[0025] In this invention, the syngas comprises H2 and CO, and the molar ratio of H2 to CO in the syngas is (0.5-3.5):1. In some embodiments, the reaction conditions are: temperature of 160℃-360℃, pressure of 0.5MPa-8.0MPa, and volume hourly space velocity of 400 h⁻¹. -1 -10000h -1 Volumetric hourly space velocity (VHSV) refers to the volumetric hourly space velocity of syngas, which is the volume of syngas passing through a unit volume of catalyst per unit time.

[0026] In the above preparation method, the reaction conditions are: temperature 180℃-250℃, pressure 1MPa-4MPa, and volume hourly space velocity 500h⁻¹. -1 -5000h -1 .

[0027] In this invention, since the syngas contains H2 and CO, both of which are flammable gases, an inert gas can be added to the syngas to ensure the safety of the reaction. In some embodiments, the syngas also includes an inert gas with a volume fraction of 0-70%. The inert gas does not participate in the reaction, but the presence of the inert gas will cause a decrease in the partial pressure of H2 and CO in the syngas, thereby affecting the reaction rate. If the inert gas content is too high, it may reduce the reaction rate. Therefore, an appropriate amount of inert gas can be added according to the actual situation.

[0028] In some embodiments, the synthesis gas includes 1-50% by volume an inert gas, wherein the inert gas includes at least one of argon, carbon dioxide, helium, nitrogen, methane, ethane, propane, and butane.

[0029] In the preparation of the aforementioned carbon alcohols, a pre-reduction treatment of the Co-Ag-based catalyst is generally performed before the reaction. This pre-reduction treatment significantly affects the form of the active species Co and Ag, and the different forms of these active species directly influence the catalytic performance and selectivity for alcohols. The pre-reduction treated catalyst of this invention not only improves the selectivity for carbon alcohols but also significantly enhances the catalyst's stability.

[0030] In some embodiments, the pre-reduction treatment is carried out under a reducing atmosphere, which may consist of pure hydrogen or hydrogen and an inert gas that does not react with the catalyst, wherein the inert gas that does not react with the catalyst may be N2.

[0031] For example, the reducing atmosphere comprises the following components by volume fraction: H2: 20%-100%, N2: 0-80%.

[0032] In some embodiments, the pre-reduction treatment conditions are: temperature of 300℃-500℃, pressure of 0.1MPa-2MPa, and volumetric hourly space velocity of 200 h⁻¹. -1 -3000h -1 The time is 3h-30h. In the above embodiments, volume hourly space velocity (VHSV) refers to the VHSV of the reducing atmosphere, that is, the volume of reducing atmosphere passing through a unit volume of catalyst per unit time.

[0033] The carbon alcohols used in this invention are preferably C2-C18 alcohols, and the higher carbon alcohols of C6+ are preferably C6-C18 alcohols.

[0034] In the above preparation method, the Co-Ag-based catalyst uses active metals Co and Ag as active components, and the mass of active components Co and Ag refers to the mass of metal elements Co and Ag, respectively.

[0035] In the specific implementation of this invention, the Co-Ag-based catalyst also includes a support, on which the active metal is loaded.

[0036] In the above Co-Ag-based catalyst, the support is an inorganic oxide. For example, the support is selected from one or more combinations of Al2O3, SiO2, ZnO, MgO, WO3, TiO2, ZrO2, MnO2, and CeO2.

[0037] In the specific implementation of this invention, the Co-Ag-based catalyst also includes an auxiliary agent, which is supported on a carrier.

[0038] In the aforementioned Co-Ag-based catalyst, the promoter includes at least one alkali metal element, transition metal element, or element from Group IIA of the periodic table. For example, the promoter is selected from one or more combinations of Li, Na, K, Cs, Mg, Sr, Zn, Mn, Mo, Ni, Ru, Rh, Pt, Ce, and La. The amount of each promoter added is no more than 2% of the total mass of the catalyst.

[0039] In this invention, the Co-Ag-based catalyst can be prepared using conventional methods, such as co-precipitation, co-impregnation, stepwise impregnation, or a combination of precipitation and impregnation. First, Co... 2+ Ag + The catalyst is loaded onto a support, and according to actual needs, auxiliary metal ions can also be loaded onto the support, and then calcined at 300℃-800℃ for 2h-12h to obtain a Co-Ag-based catalyst.

[0040] In the specific implementation of this invention, the above-mentioned co-precipitation method includes the following steps: dispersing the carrier in water as a base liquid, preheating the base liquid to the temperature of the precipitation reaction, and simultaneously adding an alkaline solution and a solution containing Co to the base liquid under stirring conditions. 2+ Ag + The mixed salt solution was aged under the temperature conditions of the precipitation reaction after the addition was completed. The precipitated product was washed, dried and then calcined to obtain the catalyst.

[0041] In the above coprecipitation method, the total concentration of metal ions in the mixed salt solution is 0.2 mol / L-4 mol / L.

[0042] In the above coprecipitation method, the mixed salt solution may also contain auxiliary metal ions, such as Co. 2+ Ag + A mixed salt solution of auxiliary metal ions can be prepared by the following method: dissolving water-soluble salts of Co, Ag, and auxiliary metals in water to prepare a mixed salt solution with a total metal ion concentration of 0.2 mol / L to 4 mol / L.

[0043] In the above coprecipitation method, the alkaline solution can be prepared by the following method: weigh an excess of the water-soluble alkaline substance (solute) required for precipitating the above metal ions, dissolve it in water, and prepare an alkaline solution with a concentration of 0.2 mol / L-4 mol / L.

[0044] In the above coprecipitation method, the alkaline solution is the precipitant used to precipitate Co. 2+ Ag + The auxiliary metal ions precipitate simultaneously. The solute in the alkaline solution is selected from at least one of NaOH, Ba(OH)2, KOH, Na2CO3, and K2CO3, and the concentration of the alkaline solution is 0.2mol / L-4mol / L.

[0045] In the above coprecipitation method, the precipitation reaction temperature is 30℃-90℃, the aging temperature is 30℃-90℃, the aging time is 0.5-10h, and the dropping time is generally 0.5-5h.

[0046] In the coprecipitation method described above, washing the precipitate is to remove unreacted raw materials, and drying is to remove moisture from the surface of the precipitate.

[0047] In the above coprecipitation method, after calcination, the catalyst is naturally cooled to room temperature to obtain a Co-Ag-based catalyst, which can be kneaded and extruded or pressed into tablets.

[0048] In a specific implementation of the present invention, the above co-impregnation method includes the following steps: impregnating the pretreated carrier with a solution containing Co. 2+ Ag+ The catalyst is obtained by impregnating the catalyst in the impregnation solution, drying it after impregnation, and then calcining it.

[0049] In the above co-impregnation method, the pretreatment of the carrier includes: kneading and extruding the carrier, drying it at room temperature for 2h-24h, and calcining it at 300℃-800℃ for 2h-12h to obtain the shaped carrier, or pressing the carrier into tablets and crushing it to 10 mesh-40 mesh.

[0050] In the above co-impregnation method, the impregnation solution may also contain auxiliary metal ions, such as Co. 2+ Ag + The impregnation solution of auxiliary metal ions can be prepared by the following method: dissolving water-soluble salts of Co, Ag, and auxiliary metals in water to prepare an impregnation solution with a total metal ion concentration of 0.2 mol / L to 4 mol / L.

[0051] In the above co-impregnation method, impregnation can be either equal-volume impregnation or excessive impregnation. Generally, the water absorption rate of the pretreated support is measured, and equal-volume impregnation is performed. If the water absorption rate of the pretreated support is low or if a catalyst with a high metal loading is expected to be prepared, excessive impregnation can be performed. The impregnation time is 1-30 hours.

[0052] In the above co-impregnation method, drying is to remove excess water from the impregnation solution.

[0053] In the above coprecipitation and co-impregnation methods, the water-soluble salts of Co include, but are not limited to, cobalt nitrate and cobalt acetate; the water-soluble salts of Ag include, but are not limited to, silver nitrate, silver acetate, silver fluoride, and silver acetylacetone; and the water-soluble salts of the auxiliary metals include, but are not limited to, nitrates, acetates, fluorides, and acetylacetone salts.

[0054] In the specific implementation of this invention, the above-mentioned stepwise impregnation method includes the following steps:

[0055] (1) The pretreated carrier is impregnated with a solution containing Co. 2+ After impregnation in the solution, the product is dried and calcined to obtain a Co-loaded intermediate.

[0056] (2) Impregnate the intermediate with Ag + The catalyst is obtained by impregnation in a solution, followed by drying and secondary calcination.

[0057] In the above stepwise impregnation method, the pretreatment of the carrier includes: kneading the carrier, extruding it into strips and drying it, and then calcining it at 300-800℃ for 2-12 hours to obtain a shaped carrier, or pressing the carrier into tablets and then crushing it to 10-40 mesh.

[0058] In the above step-by-step impregnation method, the impregnation and secondary impregnation can be equal volume impregnation or excessive impregnation, and the impregnation or secondary impregnation time is 1h-30h.

[0059] In the above stepwise impregnation method, the firing and secondary firing temperatures can be the same or different. The secondary firing temperature can be 300℃-800℃, and the time can be 2h-12h.

[0060] In the specific implementation of this invention, the above precipitation-impregnation method includes the following steps:

[0061] (1) The carrier is dispersed in water as the base solution. After preheating to the precipitation reaction temperature, an alkaline solution and a solution containing Co are simultaneously added dropwise to the base solution under stirring. 2+ After the solution was added dropwise, it was aged at the precipitation reaction temperature. The precipitate was washed, dried and then calcined to obtain the Co-loaded intermediate.

[0062] (2) Impregnate the intermediate with Ag + The catalyst is obtained by impregnation in a solution, followed by drying and secondary calcination.

[0063] In the above precipitation-impregnation method, the calcination and secondary calcination temperatures are 300-800℃, and the time is 2-12h.

[0064] In the above precipitation-impregnation method, the precipitation reaction temperature is 30-90℃ and the aging time is 0.5-10h.

[0065] In the above precipitation-impregnation method, impregnation is either equal-volume impregnation or excessive impregnation, and the impregnation time is 1-30 hours.

[0066] In the above precipitation-impregnation method, Co is present. 2+ The solution may also contain auxiliary metal ions, which can be neutralized by adding an alkaline solution to Co. 2+ When metal ions precipitate simultaneously with the additives, the amount of alkaline solution added needs to be in excess of the water-soluble alkali required to precipitate all the metal ions.

[0067] In the above-mentioned distribution impregnation method and precipitation-impregnation method, Co is present 2+ The solution can be prepared by dissolving a water-soluble salt of Co in water to prepare a solution containing Co. 2+ The solution contains Ag. + The solution can be prepared by dissolving a water-soluble salt of Ag in water to prepare a solution containing Ag. + The solution.

[0068] In the above-mentioned distribution impregnation method and precipitation-impregnation method, the water-soluble salts of Co include, but are not limited to, cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt chloride, and cobalt bromide; the water-soluble salts of Ag include, but are not limited to, silver nitrate, silver acetate, silver fluoride, and silver acetylacetone; the water-soluble salts of the auxiliary metals include, but are not limited to, nitrates, acetates, fluorides, acetylacetone salts, chlorides, and bromides.

[0069] The catalyst preparation methods provided by this invention, including co-precipitation, impregnation, distribution impregnation, and precipitation-impregnation, are simple, reliable, and easy to scale up for industrial production.

[0070] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0071] Unless otherwise specified, the equipment and reagents used in this invention are commercially available products in this technical field. Reagents of industrial grade or higher purity can be used to achieve the technical solution of this invention.

[0072] Example 1

[0073] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0074] 15.75g of AgNO3 and 197.54g of Co(NO3)2·6H2O were dissolved in water to prepare a mixed salt solution with a total metal ion concentration of 2mol / L; 89.02g of Na2CO3 was dissolved in water to prepare a sodium carbonate aqueous solution with a concentration of 2mol / L.

[0075] 70.00 g of boehmite (with a weight loss of 30% during the preparation of alumina support) was stirred and dispersed in 150 mL of deionized water as a base solution. The base solution was preheated to 70 °C and maintained at the temperature. A prepared mixed salt solution and sodium carbonate solution were simultaneously and uniformly added dropwise to the base solution for 1-1.5 h. After the addition was completed, the solution was aged at 70 °C for 3 h. The resulting coprecipitate was washed 6 times and dried at 100 °C.

[0076] Add 3g of guar gum powder, 10g of dilute nitric acid (1mol / L), and 25g of deionized water to the dried coprecipitate. After mixing and extruding, the catalyst precursor was dried at room temperature for 20h and then calcined at 450℃ for 4h to obtain the CoAg / Al2O3 catalyst, denoted as catalyst A1. In catalyst A1, Co: 40wt%, Ag: 10wt%, Al2O3: 50wt%, and the mass ratio of Co to Ag was 4:1.

[0077] The preparation steps of carbon alcohols are as follows:

[0078] (1) Catalyst A1 was pre-reduced in a pure hydrogen atmosphere. The pre-reduction conditions were: volume hourly space velocity of 500 h⁻¹. -1 The pressure was 0.1 MPa, the temperature was 400℃, and the time was 6 hours.

[0079] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A1. The molar ratio of H2 to CO in the syngas was 1.6:1. The reaction reached steady state after 24 h. The products were collected between 24 h and 108 h and subjected to chromatographic analysis. The reaction conditions were: volume hourly space velocity of 600 h⁻¹. -1 The temperature was 188℃ and the pressure was 1.5MPa. The reaction evaluation results are shown in Table 1.

[0080] Example 2

[0081] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0082] 4.72 g of AgNO3 and 148.16 g of Co(NO3)2·6H2O were dissolved in water to prepare a mixed salt solution with a total metal ion concentration of 1 mol / L; 63.59 g of Na2CO3 were dissolved in water to prepare a sodium carbonate aqueous solution with a concentration of 1 mol / L.

[0083] 67.00 g of ZnO was dispersed in 150 mL of deionized water as the base solution. The base solution was preheated to 80 °C and maintained at that temperature. A prepared mixed salt solution and sodium carbonate solution were simultaneously and uniformly added dropwise to the base solution over a period of 3 h. After the addition was completed, the solution was aged at 80 °C for 8 h. The resulting coprecipitate was washed 6 times and dried at 100 °C. Then, it was calcined at 520 °C for 6 h, and after being pressed into tablets, it was crushed into 20-40 mesh to obtain CoAg / ZnO, denoted as catalyst A2. In catalyst A2, Co: 30 wt%, Ag: 3 wt%, ZnO: 70 wt%, and the mass ratio of Co to Ag was 10:1.

[0084] The preparation steps of carbon alcohols are as follows:

[0085] (1) Catalyst A2 was pre-reduced in a reducing atmosphere (where H2 volume percentage was 75% and N2 volume percentage was 25%). The pre-reduction conditions were: volume hourly space velocity (VHSV) of 1000 h⁻¹. -1 The pressure was 2 MPa, the temperature was 450℃, and the time was 14 hours.

[0086] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A2. The molar ratio of H2 to CO in the syngas was 2.5:1. The reaction reached steady state after 24 h. The products were collected between 24 h and 108 h and subjected to chromatographic analysis. The reaction conditions were: volume hourly space velocity of 3000 h⁻¹. -1 The temperature was 260℃ and the pressure was 6.5MPa. The reaction evaluation results are shown in Table 1.

[0087] Example 3

[0088] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0089] 41.17 g of AgF and 232.47 g of Co(Ac)2·4H2O were dissolved in water to prepare a mixed salt solution with a total metal ion concentration of 2.5 mol / L; 125.34 g of KOH was weighed and dissolved in water to prepare a potassium hydroxide solution with a concentration of 2.5 mol / L.

[0090] 5.00 g of ZrO2 and 15.00 g of TiO2 were stirred and dispersed in 80 mL of deionized water as the base solution. The base solution was preheated to 30 °C and maintained at the temperature. A prepared mixed salt solution and potassium hydroxide solution were simultaneously and uniformly added dropwise to the base solution for 4.5-5 h. After the addition was completed, the mixture was aged at 30 °C for 10 h. The resulting coprecipitate was washed 6 times, dried at 100 °C, and then calcined at 300 °C for 8 h. After being pressed into tablets and crushed to 20-40 mesh, CoAg / ZrO2-TiO2 was obtained, denoted as catalyst A3. In catalyst A3, Co: 55 wt%, Ag: 25 wt%, ZrO2-TiO2: 20 wt%, and the mass ratio of Co to Ag was 2.2:1.

[0091] The preparation steps of carbon alcohols are as follows:

[0092] (1) Catalyst A3 was pre-reduced in a reducing atmosphere (where H2 volume percentage was 50% and N2 volume percentage was 50%), and the volume hourly space velocity of the mixed gas was 200 h⁻¹. -1 The pressure was 1.2 MPa, the temperature was 300℃, and the time was 28 hours.

[0093] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A3. The syngas contained H2, CO, argon, and methane, with argon comprising 6% by volume, methane comprising 10% by volume, and the molar ratio of H2 to CO being 1:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: syngas volume hourly space velocity of 4000 h⁻¹. -1 The reaction temperature was 230℃ and the reaction pressure was 0.5MPa. The reaction evaluation results are shown in Table 1.

[0094] Example 4

[0095] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0096] 47.05 g of AgF, 98.77 g of Co(NO3)2·6H2O, and 100.90 g of Mn(NO3)2 were dissolved in water to prepare a mixed salt solution with a total metal ion concentration of 0.2 mol / L; 176.08 g of K2CO3 was weighed and dissolved in water to prepare a potassium carbonate aqueous solution with a concentration of 0.2 mol / L.

[0097] Using 50 mL of deionized water as the base solution, the base solution was preheated to 45 °C and maintained at that temperature. A prepared mixed salt solution and potassium carbonate solution were simultaneously and uniformly added dropwise to the base solution over a period of 3-3.5 h. After the addition was complete, the mixture was aged at 68 °C for 2 h. The resulting coprecipitate was washed 8 times, dried at 110 °C, calcined at 510 °C for 12 h, pressed into tablets, and then crushed to 20-40 mesh to obtain the CoAg / MnO catalyst, denoted as catalyst A4. In catalyst A4, Co: 20 wt%, Ag: 40 wt%, MnO: 40 wt%, and the mass ratio of Co to Ag was 0.5:1.

[0098] The preparation steps of carbon alcohols are as follows:

[0099] (1) Catalyst A4 was pre-reduced in a pure hydrogen atmosphere with a volume hourly space velocity of 400 h⁻¹. -1 The reaction pressure was 0.8 MPa, the temperature was 380℃, and the time was 30 h.

[0100] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A4. The molar ratio of H2 to CO in the syngas was 1.8:1. The reaction reached steady state after 24 h. The products were collected between 24 h and 108 h and subjected to chromatographic analysis. The reaction conditions were: syngas volume hourly space velocity of 7000 h⁻¹. -1 The reaction temperature was 235℃ and the pressure was 8.0MPa. The reaction evaluation results are shown in Table 1.

[0101] Example 5

[0102] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0103] Dissolve 10.83g of Ag(Ac), 63.40g of Co(Ac)2·4H2O, and 4.66g of Ce(NO3)3 in water to prepare a mixed salt solution with a total metal ion concentration of 4mol / L; weigh 27.13g of NaOH and dissolve it in water to prepare a sodium hydroxide aqueous solution with a concentration of 4mol / L.

[0104] 108.57 g of boehmite was stirred and dispersed in 80 mL of deionized water as the base solution. The base solution was preheated to 90 °C and maintained at the temperature. The prepared mixed salt solution and sodium carbonate solution were simultaneously and uniformly added dropwise to the base solution for 1-1.5 h. After the addition was completed, the solution was aged at 75 °C for 2.5 h. The resulting coprecipitate was washed 4 times and dried at 105 °C.

[0105] 3.5 g of guar gum powder, 12 g of dilute nitric acid (1.2 mol / L), and 28 g of deionized water were added to the dried coprecipitate. After mixing and kneading, the mixture was extruded into strips. The extruded catalyst precursor was dried at room temperature for 22 h and then calcined at 350 °C for 3 h to obtain the Ce-CoAg / Al2O3 catalyst, denoted as catalyst A5. In catalyst A5, Co: 15 wt%, Ag: 7 wt%, Al2O3: 76 wt%, Ce: 2 wt%, and the mass ratio of Co to Ag was 2.1:1.

[0106] The preparation steps of carbon alcohols are as follows:

[0107] (1) Catalyst A5 was pre-reduced in a reducing atmosphere (40% H2 and 60% N2 by volume). The pre-reduction conditions were: gas hourly space velocity (GHSV) of the mixed gas was 2000 h⁻¹. -1 The pressure was 0.5 MPa, the temperature was 470℃, and the time was 12 hours.

[0108] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A5, wherein the molar ratio of H2 to CO in the syngas was 2.2:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: syngas volume hourly space velocity 4000 h⁻¹. -1 The reaction temperature was 320℃ and the reaction pressure was 7MPa. The reaction evaluation results are shown in Table 1.

[0109] Example 6

[0110] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0111] 14.17 g of AgNO3, 190.20 g of Co(Ac)2·4H2O, 1.17 g of Sr(Ac)2, and 0.95 g of Ba(NO3)2 were dissolved in water to prepare a mixed salt solution with a total metal ion concentration of 2.2 mol / L; 122.4 g of K2CO3 was dissolved in water to prepare a potassium carbonate aqueous solution with a concentration of 1.5 mol / L.

[0112] 45g of SiO2 was dispersed in 70mL of deionized water as the base solution. The base solution was preheated to 55℃ and maintained at that temperature. A prepared mixed salt solution and potassium carbonate solution were simultaneously and uniformly added dropwise to the base solution over a period of 0.5-1h. After the addition was completed, the mixture was aged at 45℃ for 0.5h. The resulting coprecipitate was washed 8 times and dried at 105℃.

[0113] 10g of polyethylene glycol PEG-2000 and 15g of deionized water were added to the dried coprecipitate and kneaded before extrusion. The extruded catalyst precursor was dried at room temperature for 24h and then calcined at 800℃ for 3h to obtain the SrBa-CoAg / SiO2 catalyst, denoted as catalyst A6. In catalyst A6, Co: 45wt%, Ag: 9wt%, SiO2: 45wt%, Sr: 0.5wt%, Ba: 0.5wt%, and the mass ratio of Co to Ag was 5:1.

[0114] The preparation steps of carbon alcohols are as follows:

[0115] (1) Catalyst A6 was pre-reduced in a reducing atmosphere (25% H2 and 75% N2 by volume). The pre-reduction conditions were: gas hourly space velocity (HHSV) of the mixture was 2400 h⁻¹. -1 The pressure was 0.8 MPa, the temperature was 400℃, and the time was 7 hours.

[0116] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A6. The syngas contained H2, CO, CO2 and ethane, with CO2 and N2 volume fractions of 30% and 40%, respectively, and the molar ratio of H2 to CO was 3.2:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity of 800 h⁻¹. -1 The temperature was 230℃ and the pressure was 3.5MPa. The reaction evaluation results are shown in Table 1.

[0117] Example 7

[0118] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0119] 25.00g MgO, 65.00g SiO2, 10g polyethylene glycol PEG-2000, and 20g deionized water were mixed and kneaded, then extruded into strips. The strips were dried at room temperature for 24 hours and then calcined at 800℃ for 3 hours to obtain the MgO-SiO2 support.

[0120] 24.69 g of Co(NO3)2·6H2O and 7.87 g of AgNO3 were dissolved in water to obtain an impregnation solution. The MgO-SiO2 support was impregnated with the impregnation solution in equal volume. After impregnation, the support was allowed to stand at room temperature for 18 h, dried at 110 °C for 3 h, and then calcined at 500 °C for 3 h to obtain a CoAg / MgO-SiO2 catalyst, denoted as catalyst A7. In catalyst A7, Co: 5 wt%, Ag: 5 wt%, MgO-SiO2: 90 wt%, and the mass ratio of Co to Ag was 1:1.

[0121] The preparation steps of carbon alcohols are as follows:

[0122] (1) Catalyst A7 was pre-reduced in a reducing atmosphere (20% H2 by volume and 80% N2 by volume). The pre-reduction conditions were: volume hourly space velocity 3000 h⁻¹. -1 The pressure was 1.4 MPa, the temperature was 420℃, and the time was 24 hours.

[0123] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A7, with a molar ratio of H2 to CO of 1.3:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity of 10000 h⁻¹. -1 The temperature was 200℃ and the pressure was 8MPa. The reaction evaluation results are shown in Table 1.

[0124] Example 8

[0125] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0126] 30.00 g of TiO2, 58.42 g of pseudoboehmite, 1.8 g of guar gum powder, 8 g of dilute nitric acid (1 mol / L), and 20 g of deionized water were mixed, kneaded, and extruded into strips. The strips were dried at room temperature for 22 h and then calcined at 450 °C for 3.5 h to obtain a TiO2-Al2O3 mixed support.

[0127] 101.44g of Co(Ac)2·4H2O, 7.67g of Ag(acac), and 0.55g of (NH4)6Mo7O were added. 243.39 g of Ni(Ac)2·4H2O was dissolved in water to prepare an impregnation solution. This impregnation solution was used to over-impregnate a TiO2-Al2O3 support. After impregnation, the solution was allowed to stand at room temperature for 30 h, and then dried at 120 °C for 8 h to remove excess water from the surface of the impregnated product. Finally, the product was calcined at 540 °C for 5 h to obtain a MoNi-CoAg / TiO2-Al2O3 catalyst, denoted as catalyst A8. In catalyst A8, Co, Ag, Mo, and Ni accounted for 24 wt%, 4 wt%, 0.3 wt%, and 0.8 wt%, respectively. The TiO2-Al2O3 mixed support accounted for 70.9 wt%, and the mass ratio of Co to Ag was 6:1.

[0128] The preparation steps of carbon alcohols are as follows:

[0129] (1) Catalyst A8 was pre-reduced in a reducing atmosphere (75% H2 and 25% N2 by volume). The pre-reduction conditions were: volume hourly space velocity (HHSV) of 1200 h⁻¹. -1 The pressure was 0.3 MPa, the temperature was 500℃, and the time was 9 hours.

[0130] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A8, with a molar ratio of H2 to CO of 0.5:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity of 2500 h⁻¹. -1 The temperature was 360℃ and the pressure was 1.2MPa. The reaction evaluation results are shown in Table 1.

[0131] Example 9

[0132] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0133] After ZrO2 powder is compressed into tablets, it is crushed to 20-40 mesh to obtain 64.00g of ZrO2 support;

[0134] 148.16 g of Co(NO3)2·6H2O, 4.72 g of AgNO3, 3.83 g of ruthenium(III) nitrite solution (ruthenium content 31.3%), and 5.61 g of La(NO3)3·6H2O were dissolved in water to prepare an impregnation solution. The ZrO2 support was over-impregnated with this impregnation solution. The solution was allowed to stand at room temperature for 1 h and then dried at 120 °C for 9 h to remove excess water from the surface of the impregnated product. The product was then calcined at 550 °C for 4 h to obtain the RuLa-CoAg / ZrO2 catalyst, denoted as catalyst A9. In the catalyst, Co: 30 wt%, Ag: 3 wt%, Ru: 1.2 wt%, La: 1.8 wt%, ZrO2 support: 64 wt%, and the mass ratio of Co to Ag was 10:1.

[0135] The preparation steps of carbon alcohols are as follows:

[0136] (1) Catalyst A9 was pre-reduced in a reducing atmosphere (where H2 volume percentage was 40% and N2 volume percentage was 60%). The pre-reduction conditions were: the volume hourly space velocity of the mixed gas was 1500 h⁻¹. -1 The pressure was 1.8 MPa, the temperature was 390℃, and the time was 6 hours.

[0137] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A9, wherein the molar ratio of H2 to CO in the syngas was 2.2:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity 800 h⁻¹. -1 The reaction was carried out at a temperature of 240℃ and a pressure of 4MPa. The evaluation results are shown in Table 1.

[0138] Example 10

[0139] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0140] 15.10g of CeO2, 33.00g of SiO2, 5g of polyethylene glycol PEG-2000, and 10g of deionized water were mixed and kneaded, then extruded into strips. The strips were dried at room temperature for 18h and then calcined at 400℃ for 4.5h to obtain CeO2-SiO2 support.

[0141] A mixing solution of 192.20 g of Co(Ac)2·4H2O, 9.45 g of AgNO3, 0.29 g of CsNO3, and 14 g of Rh(NO3)3 solution (containing 5 wt% Rh) was used to obtain an impregnation solution. This impregnation solution was used to over-impregnate a CeO2-SiO2 support. The mixture was allowed to stand at room temperature for 16 h, dried at 120 °C for 12 h, and then calcined at 300 °C for 6 h to obtain a CsRh-CoAg / CeO2-SiO2 catalyst, denoted as catalyst A10. In catalyst A10, Co: 45 wt%, Ag: 6 wt%, Cs: 0.2 wt%, Rh: 0.7 wt%, CeO2-SiO2 mixed support: 48.1 wt%, and the mass ratio of Co to Ag was 7.5:1.

[0142] The preparation steps of carbon alcohols are as follows:

[0143] (1) The catalyst A10 was pre-reduced in a reducing atmosphere (35% H2 and 65% N2 by volume). The pre-reduction conditions were: volume hourly space velocity (VHSV) of 500 h⁻¹. -1 Pressure 1.1 MPa, temperature 450℃, time 12h;

[0144] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A10, wherein the molar ratio of H2 to CO in the syngas was 2.4:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity 4000 h⁻¹. -1 The reaction was carried out at a temperature of 315℃ and a pressure of 2MPa. The evaluation results are shown in Table 1.

[0145] Example 11

[0146] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0147] After the WO3 powder was compressed into tablets, it was crushed to 20-40 mesh to obtain 82.00g of WO3 carrier;

[0148] 32.10 g of Co(NO3)2·6H2O, 11.76 g of AgF, 6.37 g of Zn(NO3)2·6H2O, and 0.65 g of Mn(NO3)2 solution (with a Mn(NO3)2 content of 50 wt%) were dissolved in deionized water to obtain an impregnation solution. This impregnation solution was used to impregnate an equal volume of WO3 support. The mixture was allowed to stand at room temperature for 4 h, dried at 110 °C for 2 h, and then calcined at 435 °C for 5.5 h to obtain a ZnMn-CoAg / WO3 catalyst, denoted as A11. In catalyst A11, the composition was: Co: 6.5 wt%, Ag: 10 wt%, Zn: 1.4 wt%, Mn: 0.1 wt%, WO3 support: 82 wt%, and the mass ratio of Co to Ag was 0.65:1.

[0149] The preparation steps of carbon alcohols are as follows:

[0150] (1) The catalyst A11 was pre-reduced under a pure hydrogen atmosphere. The pre-reduction conditions were: volume hourly space velocity 850 h⁻¹. -1 The pressure was 0.1 MPa, the temperature was 440℃, and the time was 8 hours.

[0151] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A11. The syngas contained H2, CO, and propane, with a propane volume fraction of 1% and an H2 to CO molar ratio of 3.5:1. The reaction reached steady state after 24 h. The products were collected between 24 h and 108 h and subjected to chromatographic analysis. The reaction conditions were: volume hourly space velocity of 5000 h⁻¹. -1 The temperature was 220℃ and the pressure was 5MPa. The reaction evaluation results are shown in Table 1.

[0152] Example 12

[0153] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0154] 15.00g of SiO2, 94.42g of boehmite, 3.5g of guar gum powder, 15g of dilute nitric acid (1mol / L), and 30g of deionized water were mixed and kneaded, then extruded into strips. The strips were dried at room temperature for 16h and then calcined at 300℃ for 4.5h to obtain 81.10g of SiO2-Al2O3 mixed support.

[0155] 76.32g of CoSO4·7H2O was dissolved in water to prepare a Co-containing impregnation solution. The SiO2-Al2O3 support was over-impregnated with this impregnation solution, allowed to stand at room temperature for 30h, dried at 120℃ for 14h, and then calcined at 300℃ for 7h to obtain Co / SiO2-Al2O3.

[0156] 3.09 g of Ag(Ac) and 5.96 g of LiNO3 were dissolved in deionized water to obtain an Ag-containing impregnation solution. Co / SiO2-Al2O3 was impregnated with this impregnation solution in equal volume. The mixture was allowed to stand at room temperature for 12 h, dried at 110 °C for 2 h, and then calcined at 300 °C for 5 h to obtain Li-CoAg / SiO2-Al2O3, denoted as catalyst A12. In catalyst A12, Co: 16 wt%, Ag: 2 wt%, Li: 0.6 wt%, Al2O3-SiO2 mixed support: 81.1 wt%, and the mass ratio of Co to Ag was 8:1.

[0157] The preparation steps of carbon alcohols are as follows:

[0158] (1) The catalyst Al2 was pre-reduced in a reducing atmosphere (90% H2 by volume and 10% N2 by volume). The pre-reduction conditions were: volume hourly space velocity 1300 h⁻¹. -1 Pressure 2.0 MPa, temperature 420℃, time 4 hours;

[0159] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A12. The syngas contained H2, CO, ethane, and methane, with a methane volume fraction of 5%, an ethane mass fraction of 5%, and an H2 to CO molar ratio of 1.3:1. The reaction reached steady state after 24 h. The products were collected between 24 h and 108 h and subjected to chromatographic analysis. The reaction conditions were: volume hourly space velocity (VHSV) of 5000 h⁻¹. -1 The reaction was carried out at a temperature of 320℃ and a pressure of 1.5MPa. The evaluation results are shown in Table 1.

[0160] Example 13

[0161] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0162] 32.00g of TiO2, 25.50g of pseudoboehmite, 0.6g of guar gum powder, 4g of dilute nitric acid (1mol / L), and 10g of deionized water were mixed and kneaded, then extruded into strips, dried at room temperature for 2h, and then calcined at 430℃ for 4h to obtain 49.50g of TiO2-Al2O3 mixed support.

[0163] 155.44 g of CoCl2·6H2O was used to prepare a Co-containing impregnation solution. The TiO2-Al2O3 support was over-impregnated with this impregnation solution, allowed to stand at room temperature for 6 h, dried at 120 °C for 15 h, and then calcined at 430 °C for 6 h to obtain Co / TiO2-Al2O3.

[0164] 12.94 g of AgF, 1.05 g of Mg(NO3)2·6H2O, 2.89 g of Fe(NO3)3·9H2O, and 2.27 g of Zn(NO3)2·6H2O were dissolved in deionized water and used to impregnate Co / TiO2-Al2O3 in equal volumes. After impregnation, the mixture was allowed to stand at room temperature for 13 h, dried at 110 °C for 3 h, and then calcined at 400 °C for 4.5 h to obtain the MgFeZn-CoAg / TiO2-Al2O3 catalyst, denoted as catalyst A13. In the catalyst, Co: 38.5 wt%, Ag: 11 wt%, Mg: 0.1 wt%, Fe: 0.4 wt%, Zn: 0.5 wt%, and TiO2-Al2O3 mixed support: 49.5 wt%, with a Co to Ag mass ratio of 3.5:1.

[0165] The preparation steps of carbon alcohols are as follows:

[0166] (1) The catalyst A13 was pre-reduced in a reducing atmosphere (95% H2 by volume and 5% N2 by volume). The pre-reduction conditions were: volume hourly space velocity 1100 h⁻¹. -1 Pressure 0.6 MPa, temperature 410℃, time 7 h;

[0167] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst Al3, wherein the molar ratio of H2 to CO in the syngas was 2.2:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity 10000 h⁻¹. -1 The reaction was carried out at a temperature of 240℃ and a pressure of 5.5MPa. The results of the reaction evaluation are shown in Table 1.

[0168] Example 14

[0169] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0170] After pressing the ZrO2 powder into tablets, it was crushed to 20-40 mesh to obtain 87.60g of ZrO2 support;

[0171] 59.90 g of CoBr2·6H2O and 1.06 g of H2PtCl6·6H2O were dissolved in deionized water to obtain a Co-containing impregnation solution. The ZrO2 support was impregnated with this impregnation solution, allowed to stand at room temperature for 14 h, dried at 120 °C for 2.5 h, and then calcined at 470 °C for 6 h to obtain Pd-Co / ZrO2.

[0172] 2.30 g of Ag(acac) was dissolved in deionized water to obtain an Ag-containing impregnation solution. Pt-Co / ZrO2 was isovolumetrically impregnated with this impregnation solution, allowed to stand at room temperature for 14 h, dried at 120 °C for 2.5 h, and then calcined at 420 °C for 4 h to obtain a Pt-CoAg / ZrO2 catalyst, denoted as catalyst A14. In catalyst A14, Co: 10.8 wt%, Ag: 1.2 wt%, Pt: 0.4 wt%, ZrO2 support: 87.6 wt%, and the mass ratio of Co to Ag was 9:1.

[0173] The preparation steps of carbon alcohols are as follows:

[0174] (1) Catalyst A14 was pre-reduced in a reducing atmosphere (50% H2 and 50% N2 by volume). The pre-reduction conditions were: volume hourly space velocity (VHSV) 1800 h⁻¹. -1 Pressure 0.9 MPa, temperature 430℃, time 5 hours;

[0175] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst Al4, wherein the molar ratio of H2 to CO in the syngas was 1.6:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity 1000 h⁻¹. -1 The reaction was carried out at a temperature of 230℃ and a pressure of 5.5MPa. The reaction evaluation results are shown in Table 1.

[0176] Example 15

[0177] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0178] 87.6g of MgO, 16g of polyethylene glycol PEG-2000, and 30g of deionized water were mixed and extruded into strips, dried at room temperature for 20h, and then calcined at 600℃ for 4h to obtain the MgO support.

[0179] 29.63 g of Co(NO3)2·6H2O was dissolved in water to obtain a Co-containing impregnation solution. The MgO support was impregnated with this impregnation solution, allowed to stand at room temperature for 14 h, dried at 110 °C for 3.5 h, and then calcined at 450 °C for 3 h to obtain Co / MgO.

[0180] 19.90 g of AgNO3 and 4.07 g of NaNO3 were dissolved in deionized water to obtain an Ag-containing impregnation solution. Co / MgO was impregnated with this solution. The mixture was allowed to stand at room temperature for 14 h, dried at 110 °C for 4 h, and then calcined at 400 °C for 4 h to obtain a Na-CoAg / MgO catalyst, denoted as catalyst A15. In catalyst A15, Co: 6 wt%, Ag: 12 wt%, Na: 1.1 wt%, MgO support: 87.6 wt%, and the mass ratio of Co to Ag was 0.5:1.

[0181] The preparation steps of carbon alcohols are as follows:

[0182] (1) Catalyst A15 was pre-reduced in a reducing atmosphere (60% H2 and 40% N2 by volume). The pre-reduction conditions were: volume hourly space velocity (VHSV) of 900 h⁻¹. -1 Pressure 1.4 MPa, temperature 420℃, time 4 hours;

[0183] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A15. The syngas contained H2, CO, Ar, and N2, with volume fractions of Ar and N2 of 8% and 5%, respectively, and a molar ratio of H2 to CO of 2:1. The reaction reached steady state after 24 h. The products were collected between 24 h and 108 h and subjected to chromatographic analysis. The reaction conditions were: syngas volume hourly space velocity 3500 h⁻¹. -1 The temperature was 340℃ and the pressure was 1.8MPa. The reaction evaluation results are shown in Table 1.

[0184] Example 16

[0185] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0186] 214.65g of CoSO4·7H2O was dissolved in water to prepare a Co salt solution with a total metal ion concentration of 1.2mol / L; 86.92g of Na2CO3 was dissolved in water to prepare a sodium carbonate aqueous solution with a concentration of 1.2mol / L.

[0187] 5.00 g of ZnO and 35.72 g of boehmite were stirred and dispersed in 100 mL of deionized water as the base solution. The base solution was preheated to 70 °C and maintained at the temperature. A prepared Co salt solution and sodium carbonate solution were simultaneously and uniformly added dropwise to the base solution for 1-1.5 h. After the addition was completed, the mixture was aged at 55 °C for 3 h. The resulting coprecipitate was washed 6 times and dried at 105 °C. 2 g of guar gum powder, 4 g of nitric acid solution (1.5 mol / L), and 12 g of deionized water were added to the dried precipitate, kneaded, and extruded into strips. The strips were dried at room temperature for 15 h and then calcined at 430 °C for 3 h to obtain Co / ZnO-Al2O3.

[0188] 39.37 g of AgNO3 was dissolved in deionized water to prepare an Ag-containing impregnation solution. Co / ZnO-Al2O3 was over-impregnated with this impregnation solution, allowed to stand at room temperature for 12 h, dried at 120 °C for 2 h, and then calcined at 430 °C for 4 h to obtain a CoAg / ZnO-Al2O3 catalyst, denoted as catalyst A16. In catalyst A16, Co: 45 wt%, Ag: 25 wt%, Al2O3 support: 30 wt%, and the mass ratio of Co to Ag was 1.8:1.

[0189] The preparation steps of carbon alcohols are as follows:

[0190] (1) Catalyst A16 was pre-reduced in a reducing atmosphere (50% H2 and 50% N2 by volume). The pre-reduction conditions were: volume hourly space velocity (VHSV) 1700 h⁻¹. -1 Pressure 0.9 MPa, temperature 420℃, time 7 hours;

[0191] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A16. The syngas contained H2, CO, N2 and ethane, with N2 and ethane volume fractions of 16% and 24%, respectively, and the molar ratio of H2 to CO was 2.2:1. The reaction reached steady state after 24 h. The products were collected between 24 h and 108 h and subjected to chromatographic analysis. The reaction conditions were: volume hourly space velocity of 500 h⁻¹. -1 The temperature was 165℃ and the pressure was 8.0MPa. The reaction evaluation results are shown in Table 1.

[0192] Example 17

[0193] The preparation method of the Co-Ag-based catalyst in this embodiment is as follows:

[0194] 169.58g of CoCl2·6H2O was dissolved in water to prepare a Co-containing solution with a total metal ion concentration of 1.8mol / L; 62.07g of NaOH was dissolved in water to prepare a sodium hydroxide aqueous solution with a concentration of 1.8mol / L.

[0195] 50.1 g of TiO2 was dispersed in 100 mL of deionized water as the base solution. The base solution was preheated to 50 °C and maintained at that temperature. A prepared Co-containing solution and a sodium hydroxide solution were simultaneously and uniformly added dropwise to the base solution over a period of 2.5–3 h. After the addition was complete, the mixture was aged at 50 °C for 4 h. The coprecipitate was washed 6 times and dried at 105 °C.

[0196] Add 8g of methylcellulose, 3g of nitric acid solution (1mol / L), and 25g of deionized water to the dried precipitate, knead and extrude, dry at room temperature for 15h, and then calcine at 500℃ for 3h to obtain Co / TiO2.

[0197] 8.23 g of AgF and 2.82 g of La(NO3)3·6H2O were dissolved in deionized water to obtain an Ag-containing impregnation solution. Co / TiO2 was isovolumetrically impregnated with this impregnation solution, allowed to stand at room temperature for 12 h, dried at 120 °C for 2 h, and then calcined at 480 °C for 2.5 h to obtain a CoAg / TiO2 catalyst, denoted as catalyst A17. In the catalyst, Co: 42 wt%, Ag: 7 wt%, La: 0.9 wt%, TiO2 support: 50.1 wt%, and the mass ratio of Co to Ag was 6:1.

[0198] The preparation steps of carbon alcohols are as follows:

[0199] (1) The catalyst A17 was pre-reduced under a pure hydrogen atmosphere. The pre-reduction conditions were: volume hourly space velocity 2000 h⁻¹. -1 The pressure was 1.3 MPa, the temperature was 450℃, and the time was 5 hours.

[0200] (2) In a fixed-bed reactor, the syngas was reacted under the action of pre-reduced catalyst A17, wherein the molar ratio of H2 to CO in the syngas was 1.8:1. The reaction reached steady state after 24 h, and the products were collected between 24 h and 108 h for chromatographic analysis. The reaction conditions were: volume hourly space velocity 5000 h⁻¹. -1 The temperature was 245℃ and the pressure was 3.2MPa. The reaction evaluation results are shown in Table 1.

[0201] Comparative Example 1

[0202] The preparation method of the Co-Cu-based catalyst in this comparative example is as follows:

[0203] Compared with Example 1, 15.75g of AgNO3 was replaced with 38.02g of Cu(NO3)2·3H2O, and 89.02g of Na2CO3 was replaced with 98.02g of Na2CO3, while other conditions remained unchanged, to obtain a CoCu / Al2O3 catalyst, denoted as C1; in catalyst C1, Co: 40wt%, Cu: 10wt%, alumina: 50wt%, and the mass ratio of Co to Cu was 4:1;

[0204] The preparation steps of carbon alcohols are as follows:

[0205] Compared with Example 1, catalyst A1 was replaced with catalyst C1, while other conditions remained unchanged. The reaction results are shown in Table 1.

[0206] Comparative Example 2

[0207] The preparation method of the Co-Ag-based catalyst in this comparative example is as follows:

[0208] Compared with Example 12, 76.32g of CoSO4·7H2O was replaced with 81.09g of CoSO4·7H2O, and 3.09g of Ag(Ac) was replaced with 1.55g of Ag(Ac), while other conditions remained unchanged, to obtain Li-CoAg / SiO2-Al2O3, denoted as catalyst C2. In catalyst C2, Co: 17wt%, Ag: 1wt%, Li: 0.6wt%, Al2O3-SiO2 mixed support: 81.1wt%, and the mass ratio of Co to Ag was 17:1.

[0209] The preparation steps of carbon alcohols are as follows:

[0210] Compared with Example 12, catalyst A12 was replaced with catalyst C2, while other conditions remained unchanged. The reaction evaluation results are shown in Table 1.

[0211] Comparative Example 3

[0212] The preparation method of the Co-Ag-based catalyst in this comparative example is as follows:

[0213] Compared with Example 11, 32.10 g of Co(NO3)2·6H2O and 11.76 g of AgF were replaced with 22.22 g of Co(NO3)2·6H2O and 14.11 g of AgF, respectively, while keeping other conditions unchanged, to obtain a ZnMn-CoAg / WO3 catalyst, denoted as C3. In catalyst C3, Co: 4.5 wt%, Ag: 12 wt%, Zn: 1.4 wt%, Mn: 0.1 wt%, WO3 support: 82 wt%, and the mass ratio of Co to Ag was 0.375:1.

[0214] The preparation steps of carbon alcohols are as follows:

[0215] Compared with Example 11, catalyst A11 was replaced with catalyst C3, while other conditions remained unchanged. The reaction evaluation results are shown in Table 1.

[0216] Comparative Example 4

[0217] The preparation method of the Cu-Ag-based catalyst in this comparative example is as follows:

[0218] Compared with Example 2, 148.16g of Co(NO3)2·6H2O was replaced with 114.06g of Cu(NO3)2·3H2O, while other conditions remained unchanged, to obtain a CuAg / ZnO catalyst, denoted as C4. In catalyst C4, Cu: 30wt%, Ag: 3wt%, ZnO: 70wt%, and the mass ratio of Cu to Ag was 10:1.

[0219] The preparation steps of carbon alcohols are as follows:

[0220] Compared with Example 2, catalyst A2 was replaced with catalyst C4, while other conditions remained unchanged. The reaction evaluation results are shown in Table 1.

[0221] In this invention, CO conversion rate X co Methods for calculating the carbon number selectivity of Si:

[0222]

[0223]

[0224] in, For the number of moles of CO supplied, The number of unreacted CO moles; N i C represents the number of moles of alcohols or hydrocarbons with carbon number i in the product. i The number of carbon atoms.

[0225] The products after the reaction were analyzed online by gas chromatography, and the conversion rate and selectivity of the corresponding products were calculated.

[0226] Table 1

[0227]

[0228] According to the results in Table 1 (A1-A17), the CO conversion rate can reach over 44% using the carbon alcohol preparation method provided in this embodiment, the selectivity of oxygen-containing compounds in the product can reach over 30%, and the selectivity of C6+ higher alcohols (C6+OH) can reach over 60%.

[0229] Comparing A1 and C1, catalyst C1, obtained by replacing the active component Ag with Cu, produces methanol and C2-C5 low-carbon alcohols as the main products when preparing carbon alcohols, with low selectivity for C6+ high-carbon alcohols. Comparing A2 and C4, catalyst C4, obtained by replacing the active component Co with Cu, produces methanol as the main product when preparing carbon alcohols, with virtually no C6+ high-carbon alcohols generated. In Comparative Examples 2 and 3, the Co-Ag mass ratio of the selected Co-Ag-based catalysts falls outside the scope of this invention. Comparing A12 and C2, when the Co-Ag mass ratio is greater than the scope of this invention (i.e., the amount of Ag added is too small), the main products are hydrocarbons, with low selectivity for oxygen-containing compounds. Comparing A11 and C3, when the Co-Ag mass ratio is less than the scope of this invention (i.e., the amount of Co added is too small), the main product is CO2, and the catalyst activity is significantly reduced.

[0230] This invention selects a specific Co-Ag-based catalyst and adjusts the ratio of active components Co and Ag to improve the catalyst activity and selectivity for C6+ higher alcohols. Applying this specific Co-Ag-based catalyst to the preparation of carbon alcohols from syngas can improve the selectivity of total alcohols, while suppressing the selectivity of methanol and increasing the yield of C6+ higher alcohols.

[0231] The preferred embodiments and experimental verifications of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A method for preparing carbon alcohols, characterized in that, Syngas is reacted under the action of a Co-Ag-based catalyst to produce carbon alcohols, wherein the Co-Ag-based catalyst includes active components Co and Ag, the total mass of Co and Ag accounts for 20%-60% of the total mass of the catalyst, and the mass ratio of Co to Ag is (1-8):1; The Co-Ag-based catalyst also includes an additive and a support; The carrier is an inorganic oxide; The auxiliary agent is selected from one or more combinations of Li, Na, K, Cs, Mg, Sr, Zn, Mn, Mo, Ni, Ru, Rh, Pt, Ce, and La.

2. The preparation method according to claim 1, characterized in that, The reaction conditions were: temperature 160℃-360℃, pressure 0.5 MPa-8.0 MPa, and volume hourly space velocity (VHSV) 400 h⁻¹. -1 -10000h -1 .

3. The preparation method according to claim 2, characterized in that, The reaction conditions are as follows: temperature 180℃-250℃, pressure 1MPa-4MPa, and volume hourly space velocity (VHSV) 500 h⁻¹. -1 -5000h -1 .

4. The method according to claim 1 or 2, characterized in that, The synthesis gas includes H2 and CO, and the molar ratio of H2 to CO in the synthesis gas is (0.5-3.5):

1.

5. The preparation method according to claim 1, characterized in that, The synthesis gas also includes an inert gas with a volume fraction of 0-70%, wherein the inert gas includes at least one of argon, carbon dioxide, helium, nitrogen, methane, ethane, propane, and butane.

6. The preparation method according to claim 4, characterized in that, The synthesis gas also includes an inert gas with a volume fraction of 1-50%, wherein the inert gas includes at least one of argon, carbon dioxide, helium, nitrogen, methane, ethane, propane, and butane.

7. The preparation method according to claim 1 or 2, characterized in that, Prior to the reaction, the catalyst is subjected to a pre-reduction treatment, which is carried out under a reducing atmosphere.

8. The preparation method according to claim 7, characterized in that, The reducing atmosphere comprises the following components by volume fraction: H2: 20%-100%, N2: 0-80%.

9. The preparation method according to claim 7, characterized in that, The pre-reduction treatment conditions are: temperature 300℃-500℃, pressure 0.1MPa-2MPa, and volumetric hourly space velocity (VHSV) 200 h⁻¹. -1 -3000h -1 The time is 3 hours to 30 hours.

10. The preparation method according to claim 1, characterized in that, The Co-Ag-based catalyst is prepared by any one of the following methods: co-precipitation, co-impregnation, stepwise impregnation, or a combination of precipitation and impregnation.

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