CN111375417B - Catalyst for preparing high-carbon alcohol by CO hydrogenation and preparation method thereof - Google Patents

Catalyst for preparing high-carbon alcohol by CO hydrogenation and preparation method thereof Download PDF

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CN111375417B
CN111375417B CN201811648072.1A CN201811648072A CN111375417B CN 111375417 B CN111375417 B CN 111375417B CN 201811648072 A CN201811648072 A CN 201811648072A CN 111375417 B CN111375417 B CN 111375417B
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catalyst
preparing
higher alcohols
hydrogenation according
hydrogenation
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CN111375417A (en
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张舒冬
宋永一
孙晓丹
张庆军
刘继华
方向晨
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract

The invention discloses a catalyst for preparing high-carbon alcohol by CO hydrogenation and a preparation method thereof, wherein the catalyst comprises an active component, an auxiliary agent and a carrier; the active component is Co, the auxiliary agent is one or more of rare earth elements, alkaline earth metals, ti, mn, zr, cu, al or B, and the carrier is silicon modified petroleum coke-based active carbon. The preparation method comprises the steps of (1) preparing silicon-containing petroleum coke; (2) Preparing a composite oxide containing an active component Co and an auxiliary agent element; (3) And (3) mixing the silicon-containing petroleum coke obtained in the step (1), the composite oxide obtained in the step (2) and an activating agent, uniformly mixing, activating, and finally washing and drying to obtain the catalyst for preparing the higher alcohol by CO hydrogenation. The catalyst prepared by the method has the advantages of large specific surface area, good dispersion of active components, high reaction activity, high selectivity of high-carbon alcohol and the like, and the preparation method is simple.

Description

Catalyst for preparing high-carbon alcohol by CO hydrogenation and preparation method thereof
Technical Field
The invention belongs to the field of petrochemical catalysis, and particularly relates to a catalyst for preparing high-carbon alcohol by CO hydrogenation and a preparation method thereof.
Background
The higher alcohol generally refers to monohydric alcohol containing more than 6 carbon atoms, which is an important raw material in modern fine chemical engineering and can be used for preparing detergents, surfactants, plasticizers and the like, and the derivatives thereof have the advantages of high unit yield value, large additional value and the like, and are widely applied in the fields of synthesis of three materials, industrial and agricultural production, manufacture of living goods, national defense and military and the like. Therefore, the production of higher alcohols plays an important role in national economy.
The current industrial production methods of high-carbon alcohol have two types: firstly, a conversion method using natural oil as a raw material is used for synthesizing high-carbon alcohol, which mainly comprises an oil hydrogenation method and a fatty acid hydrogenation method, but China does not have industrial oil source scale and cannot realize large-scale production. Secondly, the chemical synthesis method which takes petroleum derivative products as raw materials to produce the high-carbon alcohol comprises a Ziegler method and a oxo-synthesis method, but the two methods have the problems of long process flow, complex technology and high production cost. Therefore, there is a need to develop a production process with low raw material cost, simple synthetic route and environmental friendliness.
CO and hydrogen are one of the cheapest products in coal chemical industry and biomass chemical industry, and high-carbon alcohol is synthesized in one step by a catalytic method, so that the cost can be greatly saved, and good economic and social benefits are brought. The preparation of the high-carbon alcohol by CO hydrogenation is developed on the basis of the modified FT synthesis catalyst, the reaction conditions of the preparation are basically the same as those of the FT synthesis, and the selectivity of a byproduct, namely the high-carbon mixed alcohol oxygenated organic matter in the traditional FT synthesis catalyst can be improved by adjusting the auxiliary agent components of the catalyst, changing the type of the carrier or modifying the property of the carrier, introducing a new catalyst preparation method and the like.
CN103586060A discloses a high selectivity catalyst for synthesizing high carbon alcohol by CO hydrogenation, the carrier of the catalyst is active carbon, the active component is Co, the auxiliary agent is one or more of Al, B or Ga, the catalyst is prepared by an impregnation method, and the catalyst can improve the selectivity of high carbon primary alcohol in the mixed primary alcohol synthesized by CO hydrogenation.
CN105618051A discloses a catalyst for CO-production of naphtha and diesel oil by synthesizing high carbon alcohol through CO hydrogenation, and a preparation method and application thereof, wherein the catalyst is a cobalt-based catalyst which is loaded by active carbon and modulated by a Si auxiliary agent, so that the activity of the catalyst is improved, the selectivity of C1-C4 gaseous hydrocarbons is reduced, the selectivity of synthesized alcohol, naphtha and diesel oil is increased, and particularly the selectivity of C6-C18 high carbon alcohol with high added value is obviously improved. The catalyst is prepared by an impregnation method, and the active carbon carrier can be loaded with active components only after being boiled and washed by hydrochloric acid solution and boiled by deionized water.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a catalyst for preparing high carbon alcohol by CO hydrogenation and a preparation method thereof. The catalyst prepared by the method has the advantages of large specific surface area, good dispersion of active components, high reaction activity, high selectivity of high-carbon alcohol and the like, and the preparation method is simple.
The invention provides a catalyst for preparing high-carbon alcohol by CO hydrogenation, which comprises an active component, an auxiliary agent and a carrier; the catalyst comprises an active component and a carrier, wherein the active component is Co, the auxiliary agent is selected from one or more of rare earth elements, alkaline earth metals, ti, mn, zr, cu, al or B, preferably one or more of La, zr, al or B, the carrier is silicon-modified petroleum coke-based activated carbon, the content of the active component is 1-20%, preferably 5-15%, the content of the auxiliary agent elements is 1-10%, preferably 1-5%, and the content of the carrier is 71-97%, preferably 81-93%, based on the weight of the catalyst.
The catalyst for preparing the high-carbon alcohol by CO hydrogenation has the following properties: the specific surface area is 800-2800 m 2 A ratio of 1000 to 2500 m/g 2 (ii)/g; the catalyst has a pore size distribution with micropores less than 2nm greater than 60%, preferably greater than 80%.
In the catalyst for preparing high-carbon alcohol by CO hydrogenation, active components are embedded into petroleum coke-based activated carbon amorphous defects and an activated carbon graphite microchip layer, and the size of active component metal crystal grains is 0.5-4 nm, preferably 1-3 nm.
The second aspect of the present invention provides a preparation method of a catalyst for producing a higher alcohol by CO hydrogenation, the preparation method comprising the following steps:
(1) Preparing silicon-containing petroleum coke;
(2) Preparing a composite oxide containing an active component Co and an auxiliary agent element;
(3) Mixing the silicon-containing petroleum coke obtained in the step (1), the composite oxide obtained in the step (2) and an activating agent, and activating after uniformly mixing;
(4) And (4) washing and drying the sample obtained in the step (3) to obtain the catalyst for preparing the high-carbon alcohol by CO hydrogenation.
In the preparation method of the catalyst for preparing the high alcohol by CO hydrogenation, the preparation process of the silicon-containing petroleum coke in the step (1) is as follows: evenly mixing petroleum coke, a silicon-containing compound, water and a solvent, heating to 120-400 ℃ in a nitrogen atmosphere or an inert atmosphere, and keeping the temperature for 0.5-4 h to obtain silicon-containing petroleum coke; preferably, the petroleum coke, the silicon-containing compound, the water and the solvent are uniformly mixed, then the mixture is heated to 120-180 ℃ in nitrogen atmosphere or inert atmosphere, the temperature is kept constant for 0.5-1.5 h, then the mixture is continuously heated to 300-400 ℃, and the temperature is kept constant for 0.5-1.5 h, so that the silicon-containing petroleum coke is obtained.
In the above method, the inert atmosphere may be one or more of a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere, and a xenon atmosphere.
In the above method, the silicon-containing compound may be one or two of silica sol, water glass and tetraethoxysilane, preferably tetraethoxysilane;
in the above method, the solvent is one or more of methanol, ethanol, dioxane, ethylene glycol, glycerol, N-Dimethylformamide (DMF), acetone or tetrahydrofuran, preferably ethanol or acetone.
In the method, the weight ratio of the petroleum coke, the silicon-containing compound, the water and the solvent in the step (1) is 1:0.01 to 0.05:1 to 3:0.5 to 1.
In the preparation method of the catalyst for preparing higher alcohol by CO hydrogenation, the petroleum coke is preferably pretreated before the silicon-containing petroleum coke is prepared in the step (1), and the pretreatment comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) with water vapor-containing gas.
In the above method, the ammonium phosphate salt in step (1.1) is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, preferably ammonium phosphate.
In the above method, the method for introducing ammonium phosphate into petroleum coke in step (1.1) is performed according to a method known in the art, and comprises one or more of an equal volume impregnation method, a supersaturated impregnation method and a kneading method, and is preferably a supersaturated impregnation method.
In the method, the drying temperature in the step (1.1) is 60-120 ℃, preferably the drying temperature is 80-100 ℃, the drying time is 2-8 h, preferably the drying time is 4-6 h; the drying is further preferably carried out under vacuum conditions.
In the method, the weight ratio of the ammonium phosphate salt to the petroleum coke in the step (1.1) is 0.1-1: 1, preferably 0.3 to 0.8.
In the above method, in step (1.2), the vapor-containing gas is a mixture of vapor or vapor and a carrier gas, and the volume ratio of vapor to carrier gas in the mixture is 1; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the method, the pretreatment process in the step (1.2) comprises a first stage pretreatment, a second stage pretreatment and cooling, wherein the temperature of the first stage pretreatment is 150-250 ℃, preferably 180-220 ℃, and the pretreatment time is 1-6 hours, preferably 2-4 hours; the second-stage pretreatment temperature is 300-500 ℃, preferably 350-450 ℃, the pretreatment time is 1-6 hours, preferably 2-4 hours, and the second-stage pretreatment is followed by cooling to 20-100 ℃, preferably 40-80 ℃; the cooling process is preferably carried out under nitrogen protection.
In the method, the volume space velocity of the vapor-containing gas in the step (1.2) is 500 to 2000h -1 。
In the preparation method of the catalyst for preparing the higher alcohol by CO hydrogenation, the auxiliary agent in the step (2) is one or more selected from rare earth elements, alkaline earth metals, ti, mn, zr, cu, al or B, preferably one or more selected from La, zr, al or B.
In the preparation method of the catalyst for preparing the higher alcohol by CO hydrogenation, the composite oxide containing the active component Co and the auxiliary element in the step (2) is prepared by the following method:
(2.1) weighing a certain amount of soluble salt containing Co and soluble salt containing an auxiliary agent, dissolving in deionized water, and uniformly mixing to obtain a solution A;
(2.2) adding an organic acid solution into the solution A at the temperature of between 50 and 90 ℃, preferably between 70 and 90 ℃, mixing until the solution is viscous, and then drying and roasting to obtain the composite oxide.
In the above method, the soluble salt of Co in step (2.1) may be one or more of cobalt nitrate, cobalt sulfate and cobalt chloride, and is preferably cobalt nitrate.
In the above method, the soluble salt containing an auxiliary agent in step (2.1) may be one or more of nitrate, sulfate, hydrochloride and borate, and is preferably nitrate and/or borate containing an auxiliary agent metal.
In the above method, the organic acid in step (2.2) is a carboxyl group-containing organic acid, and the carboxyl group-containing organic acid is a hydroxycarboxylic acid composed of elements C, H, and O, and is preferably one or more of maleic acid, citric acid, and fumaric acid.
In the method, the mass ratio of the Co-containing soluble salt (calculated by Co element), the assistant-containing soluble salt (calculated by assistant element) and the organic acid is 1:0.03 to 16:1 to 5, preferably 1:0.05 to 1.25:1 to 3.
In the method, the drying temperature in the step (2.2) is 80-200 ℃, the drying time is 2-16 h, preferably the drying temperature is 120-180 ℃, and the drying time is 4-8 h.
In the method, the roasting temperature in the step (2.2) is 500-900 ℃, the roasting time is 2-12 h, preferably the roasting temperature is 600-800 ℃, and the roasting time is 4-8 h.
In the above method, the calcined sample in step (2.2) may be further ground into powder to obtain a powdered composite oxide.
In the preparation method of the catalyst for preparing the higher alcohol by CO hydrogenation, the activating agent in the step (3) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and preferably potassium hydroxide.
In the preparation method of the catalyst for preparing higher alcohol by CO hydrogenation, the mass ratio of the composite oxide (calculated by the mass of Co element), the activating agent and the silicon-containing petroleum coke in the step (3) is 0.004-0.2: 1 to 5:1, preferably 0.025 to 0.1:2 to 4:1.
in the preparation method of the catalyst for preparing the high-carbon alcohol by CO hydrogenation, the activation process in the step (3) is as follows: uniformly mixing silicon-containing petroleum coke, composite oxide and an activating agent, heating to an activation temperature in a nitrogen or inert atmosphere, and cooling to 20-100 ℃ after activation for subsequent treatment, wherein the inert atmosphere is one or more of helium or argon; the activation temperature is 400-1000 ℃, preferably 700-900 ℃, and the activation time is 5-240 min, preferably 10-120 min. The activation process is further preferably carried out under microwave irradiation conditions, the microwave frequency being 2450MHz or 915MHz; the microwave power is 1-10 kw, preferably 2-4 kw per kg of petroleum coke. When the activation is carried out under the microwave radiation condition, the activation is further preferably carried out in two sections, the first section is activated for 10 to 60min under the vacuum condition and at the temperature of between 400 and 600 ℃, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the activation is carried out for 10 to 30min after the temperature is raised to between 700 and 900 ℃ under the microwave radiation condition.
In the preparation method of the catalyst for preparing the higher alcohol by CO hydrogenation, the washing in the step (4) is water washing, and the sample obtained in the step (3) is mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral. The mass ratio of the sample obtained in the step (3) to the deionized water is 1.
In the preparation method of the catalyst for preparing the high-carbon alcohol by CO hydrogenation, the drying temperature in the step (4) is 100-200 ℃, the preferred drying temperature is 120-180 ℃, the drying time is 2-10 h, and the preferred drying time is 4-8 h; the drying is preferably carried out under vacuum conditions.
The third aspect of the invention provides a catalyst for preparing higher alcohols by CO hydrogenation obtained by the preparation method.
In the catalyst for preparing the high-carbon alcohol by CO hydrogenation, the catalyst comprises an active component, an auxiliary agent and a carrier; the catalyst comprises an active component and a carrier, wherein the active component is Co, the auxiliary agent is selected from one or more of rare earth elements, alkaline earth metals, ti, mn, zr, cu, al or B, preferably one or more of La, zr, al or B, the carrier is silicon-modified petroleum coke-based activated carbon, the content of the active component is 1-20%, preferably 5-15%, the content of the auxiliary agent elements is 1-10%, preferably 1-5%, and the content of the carrier is 71-97%, preferably 81-93%, based on the weight of the catalyst.
The catalyst for preparing the high-carbon alcohol by CO hydrogenation has the following properties: the specific surface area is 800 to 2800m 2 A ratio of 1000 to 2500 m/g 2 (ii)/g; the pore size distribution of the catalyst is such that the micropores smaller than 2nm are greater than 60%, preferably greater than 80%.
In the catalyst for preparing high-carbon alcohol by CO hydrogenation, active components are embedded into the petroleum coke-based activated carbon amorphous defects and the activated carbon graphite microchip layer, and the size of active component metal crystal grains is 0.5-4 nm, preferably 1-3 nm.
The fourth aspect of the present invention provides an application of the above catalyst in the preparation of higher alcohols by CO hydrogenation, wherein the hydrogenation reaction conditions are as follows: the pressure is 1 to 5MPa, preferably 2 to 4MPa; the temperature is 150 to 350 ℃, preferably 200 to 300 ℃; the feeding volume space velocity of the hydrogen and the CO is 500 to 3000h -1 ；H 2 The molar ratio of/CO is 0.5 to 3.
Compared with the prior art, the catalyst for preparing the high-carbon alcohol by CO hydrogenation and the preparation method thereof have the following advantages:
1. the catalyst for preparing the high carbon alcohol by CO hydrogenation takes the silicon modified petroleum coke-based active carbon as a carrier, and directly introduces the active component and the auxiliary agent in the petroleum coke activation process, so that the active component is highly dispersed in the carrier, and meanwhile, the existence of the silicon element can promote the generation of the pore wall of the graphite microcrystal structure, improve the connectivity of the pore channel of the carrier and be beneficial to improving the selectivity of the product. The catalyst prepared by the method has the advantages of large specific surface area, good dispersion of active components, high reaction activity, high selectivity of high-carbon alcohol and the like, and the preparation method is simple.
2. In the preparation method of the catalyst for preparing the high-carbon alcohol by CO hydrogenation, the composite oxide of the active metal and the auxiliary agent is introduced in the petroleum coke activation process, and the composite oxide enters a diffusion path generated by the petroleum coke phase through the activating agent and is combined with amorphous carbon defects or graphite carbon sheet layers under the action of microwave catalysis to form a high-dispersion and stable-state structure.
3. According to the preparation method of the catalyst for preparing the high carbon alcohol by CO hydrogenation, ammonium phosphate is introduced into petroleum coke firstly, and then the petroleum coke is treated by adopting steam-containing gas, so that the ammonium phosphate is promoted to be decomposed in the petroleum coke to generate ammonia gas and phosphoric acid, the generated ammonia gas provides more primary pores for further activation of the petroleum coke, and meanwhile, the generated phosphoric acid can also be used as an activating agent to carry out primary activation on the petroleum coke to form a developed pore structure. Solves the problems of serious equipment corrosion and higher production cost caused by the fact that petroleum coke has compact structure, high crystallinity and lacks initial pores required by activation and needs to be activated by strong alkali with large alkali-coke ratio under inert atmosphere to form pores.
4. In the preparation method of the catalyst for preparing the high-carbon alcohol by CO hydrogenation, phosphoric acid generated by decomposing ammonium phosphate salt plays a primary activation role on petroleum coke, and then the subsequent activation of the activating agent is carried out, and the two types of activation are combined, so that the activation effect is improved, the consumption of the alkali activating agent can be further reduced, the production cost of the catalyst is greatly reduced, and the environmental pollution is small.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples.
The specific surface and pore size distribution of the catalyst in the following examples and comparative examples are shown by using low temperature N 2 Measuring by an adsorption method; the grain size of the active component of the catalyst is measured by an X-ray broadening method.
Example 1
Grinding 100g of petroleum coke into powder, then uniformly mixing with 7.42g of tetraethyl orthosilicate, 200g of deionized water and 50g of absolute ethyl alcohol, heating to 260 ℃ in a nitrogen atmosphere, and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 49.08g of cobalt nitrate and 20.67g of lanthanum nitrate, and dissolving in 100mL of deionized water to obtain a solution A; weighing 30g of citric acid, and dissolving in 100mL of deionized water to obtain a solution B; and (2) placing the solution A in a water bath at 80 ℃, dropwise adding the solution B into the solution A under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-containing petroleum coke, 21.76g of composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the catalyst which comprises 15 percent of Co, 10 percent of La and 2 percent of Si in terms of the mass of elements, and is marked as C-1.
Example 2
Grinding 100g of petroleum coke into powder, then uniformly mixing with 7.42g of tetraethyl orthosilicate, 200g of deionized water and 50g of absolute ethyl alcohol, heating to 300 ℃ in a nitrogen atmosphere, and keeping the temperature for 0.5h to obtain the silicon-containing petroleum coke.
Weighing 12.44g of cobalt nitrate and 3.14g of lanthanum nitrate, and dissolving in 100mL of deionized water to obtain a solution A; weighing 10g of citric acid, and dissolving in 100mL of deionized water to obtain a solution B; and (2) placing the solution A in a water bath at 80 ℃, dropwise adding the solution B into the solution A under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-containing petroleum coke, 4.73g of composite oxide and 200g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 10min, then introducing nitrogen to the normal pressure, and continuously heating to 900 ℃ under the condition that the microwave power is 0.3kw to activate for 10min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 with deionized water, stirring thoroughly, then carrying out solid-liquid separation until the pH of the filtrate is neutral, placing the resulting solid sample in a vacuum oven, and drying at 150 ℃ for 6h under vacuum to obtain a catalyst which comprises, by mass as elements, 5% co, 2% la, 2% si, noted C-2, in terms of the percentage by weight of the catalyst.
Example 3
Grinding 100g of petroleum coke into powder, then uniformly mixing with 14.83g of tetraethyl orthosilicate, 200g of deionized water and 50g of absolute ethyl alcohol, heating to 300 ℃ in a nitrogen atmosphere, and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 27.86g of cobalt nitrate and 9.06g of lanthanum nitrate, and dissolving in 100mL of deionized water to obtain a solution A; weighing 20g of citric acid, and dissolving in 100mL of deionized water to obtain a solution B; and (2) placing the solution A in a water bath at 80 ℃, dropwise adding the solution B into the solution A under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-containing petroleum coke, 11.59g of composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 60min, introducing nitrogen to the normal pressure, and continuously heating to 700 ℃ under the condition that the microwave power is 0.3kw for activation for 30min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 by mixing with deionized water, stirring thoroughly, then carrying out solid-liquid separation until the pH of the filtrate is neutral, placing the resulting solid sample in a vacuum oven, and drying at 150 ℃ for 6 hours under vacuum conditions, to obtain a catalyst which comprises, by mass of elements in terms of the percentage of the catalyst, 10% Co, 5% La, 4% Si, noted C-3.
Example 4
Grinding 100g of petroleum coke into powder, then uniformly mixing with 7.42g of tetraethyl orthosilicate, 200g of deionized water and 50g of absolute ethyl alcohol, heating to 300 ℃ in a nitrogen atmosphere, and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 43.79g of cobalt nitrate and 8.41g of zirconium nitrate, and dissolving in 100mL of deionized water to obtain a solution A; weighing 30g of citric acid, and dissolving in 100mL of deionized water to obtain a solution B; and (2) placing the solution A in a water bath at 80 ℃, dropwise adding the solution B into the solution A under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
The silicon-containing petroleum coke, 14.98g of composite oxide and 300g of sodium hydroxide are uniformly mixed, placed in a tube furnace, heated to 800 ℃ in nitrogen atmosphere and activated for 40min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the catalyst which comprises 15 percent of Co, 3 percent of Zr and 2 percent of Si by mass of elements, and is marked as C-4.
Example 5
Grinding 100g of petroleum coke into powder, then uniformly mixing with 7.42g of tetraethyl orthosilicate, 200g of deionized water and 50g of absolute ethyl alcohol, heating to 150 ℃ in a nitrogen atmosphere, keeping the temperature for 1h, then continuously heating to 350 ℃, and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 13.52g of cobalt nitrate and 38.06g of aluminum nitrate, and dissolving in 100mL of deionized water to obtain a solution A; weighing 10g of citric acid, and dissolving in 100mL of deionized water to obtain a solution B; and (2) placing the solution A in a water bath at 80 ℃, dropwise adding the solution B into the solution A under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
The silicon-containing petroleum coke, 9.02g of composite oxide, 100g of potassium bicarbonate and 200g of potassium hydroxide are uniformly mixed, placed in a microwave heating furnace with the microwave frequency of 2450MHz, and heated to 900 ℃ in a nitrogen atmosphere to be activated for 20min under the condition that the microwave power is 0.3 kw.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 by mixing with deionized water, stirring thoroughly, then carrying out solid-liquid separation until the pH of the filtrate is neutral, placing the resulting solid sample in a vacuum oven, and drying at 150 ℃ for 6 hours under vacuum to obtain a catalyst which comprises, by mass of elements in terms of the percentage of the catalyst, 5% Co, 5% Al, 2% Si, noted C-5.
Example 6
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; grinding 100g of petroleum coke to powder, adding the powder into the solution A, standing for 1.5h, and filtering to obtainThe solid sample is dried in an oven at 110 ℃ for 5h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 1500 h) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing with 14.83g of tetraethyl orthosilicate, 200g of deionized water and 50g of absolute ethyl alcohol, heating to 300 ℃ in a nitrogen atmosphere, and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 27.86g of cobalt nitrate and 9.06g of lanthanum nitrate, and dissolving in 100mL of deionized water to obtain a solution B; weighing 20g of citric acid, and dissolving in 100mL of deionized water to obtain a solution C; and (3) placing the solution B in a water bath at 80 ℃, dropwise adding the solution C into the solution B under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-containing petroleum coke, 11.59g of composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the catalyst which comprises 10 percent of Co, 5 percent of La and 4 percent of Si in terms of element mass, and is marked as C-6.
Example 7
Weighing 50g of ammonium dihydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke is ground into powder, then added into the solution A, placed for 1.5h and then filtered, and the solid sample obtained is dried in an oven at 110 ℃ for 5h. Drying at 200 deg.C with water vaporThe solid sample is pretreated for 3 hours (the volume space velocity of the vapor gas is 1200 hours) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing with 14.83g of tetraethyl orthosilicate, 200g of deionized water and 100g of absolute ethyl alcohol, heating to 150 ℃ in a nitrogen atmosphere, keeping the temperature for 1h, then continuously heating to 350 ℃ and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 28.81g of cobalt nitrate and 9.04g of cerium nitrate, and dissolving in 100mL of deionized water to obtain a solution B; weighing 30g of citric acid, and dissolving in 100mL of deionized water to obtain a solution C; and (3) placing the solution B in a water bath at 90 ℃, dropwise adding the solution C into the solution B under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into a drying oven to dry for 8 hours at 120 ℃, and roasting the obtained sample for 6 hours at 600 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-containing petroleum coke, 11.79g of composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 by mixing with deionized water, stirring thoroughly, then carrying out solid-liquid separation until the pH of the filtrate is neutral, placing the resulting solid sample in a vacuum oven, and drying at 150 ℃ for 6 hours under vacuum conditions, to obtain a catalyst which comprises, by mass of elements in terms of the percentage of the catalyst, 10% Co, 5% Ce, 4% Si, noted C-7.
Example 8
Weighing 50g of ammonium hydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 90 ℃ for 8h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 8)00h -1 ) And raising the temperature to 400 ℃, continuing to pretreat for 3 hours, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing with 14.83g of tetraethyl orthosilicate, 200g of deionized water and 80g of absolute ethyl alcohol, heating to 150 ℃ in a nitrogen atmosphere, keeping the temperature for 1h, then continuously heating to 350 ℃ and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 31.96g of cobalt nitrate and 24.18g of potassium tetraborate, and dissolving the cobalt nitrate and the potassium tetraborate in 100mL of deionized water to obtain a solution B; weighing 30g of citric acid, and dissolving in 100mL of deionized water to obtain a solution C; and (3) placing the solution B in a water bath at 80 ℃, dropwise adding the solution C into the solution B under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-containing petroleum coke, 19.53g of composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, then introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under the vacuum condition to obtain the catalyst which comprises 10 percent of Co, 5 percent of B and 2 percent of Si in terms of element mass, and is marked as C-8.
Example 9
Weighing 50g of ammonium hydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke is ground into powder, then added into the solution A, placed for 1.5h and then filtered, and the solid sample obtained is dried in an oven at 90 ℃ for 8h. And (2) pretreating the dried solid sample for 3h at 200 ℃ by using a mixed gas with the volume ratio of water vapor to nitrogen being 1 -1 ) Then will beAnd (3) raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 40 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing with 14.83g of tetraethyl orthosilicate, 200g of deionized water and 80g of absolute ethyl alcohol, heating to 150 ℃ in a nitrogen atmosphere, keeping the temperature for 1h, then continuously heating to 350 ℃ and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Weighing 31.96g of cobalt nitrate and 24.18g of potassium tetraborate, and dissolving in 100mL of deionized water to obtain a solution B; weighing 30g of citric acid, and dissolving in 100mL of deionized water to obtain a solution C; and (3) placing the solution B in a water bath at 80 ℃, dropwise adding the solution C into the solution B under the stirring condition, continuously stirring until the solution is viscous after dropwise adding, then placing the solution into an oven to dry for 6 hours at 150 ℃, and roasting the obtained sample for 6 hours at 700 ℃ to obtain the composite oxide.
Uniformly mixing the silicon-containing petroleum coke, 19.53g of composite oxide and 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 by mixing with deionized water, stirring thoroughly, then carrying out solid-liquid separation until the pH of the filtrate is neutral, placing the resulting solid sample in a vacuum oven, and drying at 150 ℃ for 6h under vacuum conditions, to obtain a catalyst which comprises 10% co, 5% b, 2% si, by mass of the element, as C-9.
Comparative example 1
Grinding 100g of petroleum coke into powder, then uniformly mixing with 14.83g of tetraethyl orthosilicate, 200g of deionized water and 50g of absolute ethyl alcohol, heating to 300 ℃ in a nitrogen atmosphere, and keeping the temperature for 1h to obtain the silicon-containing petroleum coke.
Grinding the petroleum coke into powder, then uniformly mixing the powder with 300g of potassium hydroxide, placing the mixture in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, then introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1:15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition.
Weighing 27.86g of cobalt nitrate and 9.06g of lanthanum nitrate, dissolving in 100mL of deionized water, adding into the sample after vacuum drying in the step, uniformly stirring, aging for 2h, then placing in a vacuum drying oven, drying at 150 ℃ for 6h under a vacuum condition, and roasting the dried sample at 700 ℃ for 6h under a nitrogen atmosphere to obtain the catalyst which accounts for 10 percent of Co, 5 percent of La and 4 percent of Si in terms of element mass, and marking as D-1.
Evaluation conditions were as follows: the catalyst of the invention is reduced with hydrogen at 400 ℃ for 4 hours before reaction. Reacting in a quartz reactor of a continuous sample injection fixed bed at 250 ℃ and 3MPa, wherein the raw material gas consists of H 2 /CO = 2, space velocity 2000h -1 The tail gas is analyzed on line by gas chromatography, the liquid phase product is sampled once every 20h, the oil phase and the water phase are analyzed off line by an FID detector, and the evaluation result is shown in table 1.
TABLE 1 catalyst Properties and reaction Performance
Figure 197796DEST_PATH_IMAGE001

Claims (62)

1. A catalyst for preparing high-carbon alcohol by CO hydrogenation comprises an active component, an auxiliary agent and a carrier; the catalyst comprises an active component, an auxiliary agent and a carrier, wherein the active component is Co, the auxiliary agent is selected from one or more of rare earth elements, alkaline earth metals, ti, mn, zr, cu, al or B, and the carrier is silicon-modified petroleum coke-based active carbon, wherein the content of the active component is 1-20%, the content of the auxiliary agent element is 1-10% and the content of the carrier is 71-97% based on the weight of the catalyst; the preparation method of the catalyst for preparing the high-carbon alcohol by CO hydrogenation comprises the following steps:
(1) Preparing silicon-containing petroleum coke;
(2) Preparing a composite oxide containing an active component Co and an auxiliary agent element;
(3) Mixing the silicon-containing petroleum coke obtained in the step (1), the composite oxide obtained in the step (2) and an activating agent, and activating after uniformly mixing;
(4) And (4) washing and drying the sample obtained in the step (3) to obtain the catalyst for preparing the high-carbon alcohol by CO hydrogenation.
2. The catalyst for producing higher alcohols by CO hydrogenation according to claim 1, wherein: the auxiliary agent is selected from one or more of La, zr, al or B, and based on the weight of the catalyst, the content of the active component is 5-15%, the content of the auxiliary agent element is 1-5%, and the content of the carrier is 81-93%.
3. The catalyst for producing higher alcohols by CO hydrogenation according to claim 1, wherein: the catalyst properties were as follows: the specific surface area is 800 to 2800m 2 In the pore size distribution of the catalyst, the micropores smaller than 2nm are larger than 60 percent.
4. The catalyst for producing higher alcohols by CO hydrogenation according to claim 1, wherein: the catalyst properties were as follows: the specific surface area is 1000-2500 m 2 (ii)/g; in the pore size distribution of the catalyst, micropores smaller than 2nm are larger than 80%.
5. The catalyst for producing higher alcohols by CO hydrogenation according to claim 1, wherein: in the catalyst for preparing high-carbon alcohol by CO hydrogenation, active components are embedded into the amorphous defects of petroleum coke-based activated carbon and the activated carbon graphite microchip layer, and the size of active component metal crystal grains is 0.5-4 nm.
6. The catalyst for preparing higher alcohols by CO hydrogenation according to claim 1, wherein: in the catalyst for preparing high-carbon alcohol by CO hydrogenation, active components are embedded into the amorphous defects of petroleum coke-based active carbon and the active carbon graphite microchip layer, and the size of active component metal crystal grains is 1.5-2.5 nm.
7. The method for preparing a catalyst for the hydrogenation of CO to produce higher alcohols according to any of the claims 1-6, which comprises the following steps:
(1) Preparing silicon-containing petroleum coke;
(2) Preparing a composite oxide containing an active component Co and an auxiliary agent element;
(3) Mixing the silicon-containing petroleum coke obtained in the step (1), the composite oxide obtained in the step (2) and an activating agent, and activating after uniformly mixing;
(4) And (4) washing and drying the sample obtained in the step (3) to obtain the catalyst for preparing the high-carbon alcohol by CO hydrogenation.
8. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 7, wherein the method comprises the following steps: the preparation process of the silicon-containing petroleum coke in the step (1) is as follows: evenly mixing petroleum coke, a silicon-containing compound, water and a solvent, heating to 120-400 ℃ in an inert atmosphere, and keeping the temperature for 0.5-4 h to obtain the silicon-containing petroleum coke.
9. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: the preparation process of the silicon-containing petroleum coke in the step (1) is as follows: evenly mixing petroleum coke, a silicon-containing compound, water and a solvent, heating to 120-180 ℃ in an inert atmosphere, keeping the temperature for 0.5-2 h, continuing to heat to 300-400 ℃, and keeping the temperature for 0.5-2 h to obtain the silicon-containing petroleum coke.
10. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 8 or 9, wherein the method comprises the steps of: the inert atmosphere is one or more of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere.
11. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 8 or 9, wherein the method comprises the steps of: the silicon-containing compound is one or two of silica sol, water glass and tetraethoxysilane.
12. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 11, wherein: the silicon-containing compound is ethyl orthosilicate.
13. The method for producing a higher alcohol catalyst by CO hydrogenation according to claim 8 or 9, characterized in that: the solvent is one or more of methanol, ethanol, dioxane, ethylene glycol, glycerol, DMF, acetone or tetrahydrofuran.
14. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 13, wherein: the solvent is ethanol or acetone.
15. The method for producing a higher alcohol catalyst by CO hydrogenation according to claim 8 or 9, characterized in that: the weight ratio of the petroleum coke, the silicon-containing compound, the water and the solvent is 1:0.15 to 0.6:0.3 to 0.6:0.5 to 2.
16. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: before preparing the silicon-containing petroleum coke, pretreating the petroleum coke, wherein the pretreatment comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) with water vapor-containing gas.
17. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 16, wherein the method comprises the following steps: and (3) the ammonium phosphate in the step (1.1) is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
18. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 16 or 17, wherein: and (3) the ammonium phosphate in the step (1.1) is ammonium phosphate.
19. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 16, wherein: the drying temperature of the step (1.1) is 60-120 ℃, and the drying time is 2-8 h.
20. The method for producing a higher alcohol catalyst by CO hydrogenation according to claim 16 or 19, characterized in that: the drying temperature of the step (1.1) is 80-100 ℃, and the drying time is 4-6 h.
21. The method for producing a higher alcohol catalyst by CO hydrogenation according to claim 16 or 19, characterized in that: the drying of step (1.1) is carried out under vacuum.
22. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 16, wherein: in the step (1.1), the weight ratio of ammonium phosphate to petroleum coke is 0.1-1: 1.
23. the method for producing a higher alcohol catalyst by CO hydrogenation according to claim 16 or 22, wherein: in the step (1.1), the weight ratio of the ammonium phosphate to the petroleum coke is 0.3-0.8.
24. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 16, wherein the method comprises the following steps: the vapor-containing gas in the step (1.2) is vapor or a mixed gas of the vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
25. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 24, wherein the method comprises the following steps: the volume ratio of the water vapor to the carrier gas in the mixed gas is 1.
26. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 16, wherein: the pretreatment process of the step (1.2) comprises a first section of pretreatment, a second section of pretreatment and cooling, wherein the temperature of the first section of pretreatment is 150-250 ℃, and the pretreatment time is 1-6 h; the second stage of pretreatment is carried out at the temperature of 300-500 ℃ for 1-6 h, and then the second stage of pretreatment is cooled to 20-100 ℃.
27. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 16, wherein: the pretreatment process of the step (1.2) comprises a first section of pretreatment, a second section of pretreatment and cooling, wherein the temperature of the first section of pretreatment is 180-220 ℃, and the pretreatment time is 2-4 h; the temperature of the second stage of pretreatment is 350-450 ℃, the pretreatment time is 2-4 h, and the second stage of pretreatment is cooled to 40-80 ℃.
28. The method for producing a higher alcohol catalyst by CO hydrogenation according to claim 26 or 27, wherein: cooling was carried out under nitrogen.
29. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 16, wherein: the volume space velocity of the vapor-containing gas in the step (1.2) is 500 to 2000h -1 。
30. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: the composite oxide containing the active component Co and the auxiliary agent element in the step (2) is prepared by the following method:
(2.1) weighing soluble salt containing Co and soluble salt containing auxiliary agent, dissolving in deionized water, and uniformly mixing to obtain solution A;
(2.2) adding an organic acid solution into the solution A at the temperature of between 50 and 90 ℃, mixing until the solution is viscous, and then drying and roasting to obtain the composite oxide.
31. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: adding organic acid solution into the solution A at 70-90 ℃, mixing until the solution is viscous, and then drying and roasting to obtain the composite oxide.
32. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: the additive element in the step (2) is one or more selected from rare earth elements, alkaline earth metals, ti, mn, zr, cu, al or B.
33. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 7, wherein the method comprises the following steps: and (3) the auxiliary agent element in the step (2) is selected from one or more of La, zr, al or B.
34. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: and (3) the Co soluble salt in the step (2.1) is one or more of cobalt nitrate, cobalt sulfate and cobalt chloride.
35. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the following steps: and (3) the Co soluble salt in the step (2.1) is cobalt nitrate.
36. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: the soluble salt containing the auxiliary agent in the step (2.1) is one or more of nitrate, sulfate, hydrochloride and borate.
37. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: and (3) the soluble salt containing the auxiliary agent in the step (2.1) is nitrate and/or borate.
38. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: and (3) the organic acid in the step (2.2) is carboxyl group-containing organic acid, and the carboxyl group-containing organic acid is hydroxycarboxylic acid consisting of elements C, H and O.
39. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 30 or 38, wherein: and (3) the organic acid in the step (2.2) is one or more of maleic acid, citric acid and fumaric acid.
40. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: the mass ratio of the Co-containing soluble salt to the auxiliary agent-containing soluble salt is 1:0.1 to 0.5: 2 to 10.
41. The process for producing a higher alcohol catalyst by CO hydrogenation according to claim 30 or 40, wherein: the mass ratio of the Co-containing soluble salt to the auxiliary agent-containing soluble salt is 1:0.2 to 0.4:5 to 8.
42. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: the drying temperature of the step (2.2) is 80-200 ℃, and the drying time is 2-16.
43. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the following steps: the drying temperature of the step (2.2) is 120-180 ℃, and the drying time is 4-8 h.
44. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the steps of: the roasting temperature of the step (2.2) is 500-900 ℃, and the roasting time is 2-12 h.
45. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 30, wherein the method comprises the following steps: the roasting temperature of the step (2.2) is 600-800 ℃, and the roasting time is 4-8 h.
46. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: the activating agent in the step (3) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate.
47. The process for producing a higher alcohol catalyst by CO hydrogenation according to claim 7 or 46, wherein: the activating agent in the step (3) is potassium hydroxide.
48. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 7, wherein the method comprises the following steps: the composite oxide in the step (3) is calculated by the mass of Co element, and the mass ratio of the activating agent to the silicon-containing petroleum coke is 0.004-0.2: 1 to 5:1.
49. the method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 7, wherein the method comprises the following steps: the mass ratio of the activating agent to the silicon-containing petroleum coke, calculated by the mass of the Co element, of the composite oxide in the step (3), is 0.025-0.12: 2 to 4:1.
50. the method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: the activation process of the step (3) is as follows: uniformly mixing the silicon-containing petroleum coke, the composite oxide and the activating agent, heating to an activation temperature in an inert atmosphere, cooling to 20-100 ℃ after activation is completed, and performing subsequent treatment, wherein the activation temperature is 400-1000 ℃, and the activation time is 5-240 min.
51. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: the activation process of the step (3) is as follows: uniformly mixing the silicon-containing petroleum coke, the composite oxide and the activating agent, heating to the activation temperature in an inert atmosphere, cooling to 20-100 ℃ after activation is finished, and performing subsequent treatment, wherein the activation temperature is 700-900 ℃, and the activation time is 10-120 min.
52. The process for producing a higher alcohol catalyst by CO hydrogenation according to claim 48 or 49, wherein: the activation process is carried out under the microwave radiation condition, and the microwave frequency is 2450MHz or 915MHz; the microwave power is 1-10 kW per kg of petroleum coke.
53. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 52, wherein the method comprises the following steps: the microwave power is 2-4 kW in terms of petroleum coke per kg.
54. The process for producing a higher alcohol catalyst by CO hydrogenation according to claim 50 or 51, wherein: when the activation is carried out under the microwave radiation condition, the activation is carried out in two sections, the first section is activated for 10 to 60min under the vacuum condition at the temperature of between 400 and 600 ℃, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to between 700 and 900 ℃ under the microwave radiation condition for activation for 10 to 30min.
55. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 7, wherein: and (4) washing is water washing, firstly, mixing the sample obtained in the step (3) with deionized water, uniformly mixing, and then carrying out solid-liquid separation until the pH value of the filtrate is neutral, wherein the mass ratio of the sample obtained in the step (3) to the deionized water is 1-5.
56. The method for preparing a catalyst for producing higher alcohols by CO hydrogenation according to claim 55, wherein the method comprises the following steps: the mass ratio of the sample obtained in the step (3) to the deionized water is 1.
57. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 7, wherein the method comprises the following steps: the drying temperature of the step (4) is 100-200 ℃, and the drying time is 2-10 h.
58. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 7, wherein the method comprises the following steps: the drying temperature of the step (4) is 120-180 ℃, and the drying time is 4-8 h.
59. The method for preparing a catalyst for higher alcohols by CO hydrogenation according to claim 7, wherein the method comprises the following steps: and (4) drying under a vacuum condition.
60. Use of the catalyst for producing higher alcohols by CO hydrogenation according to any of claims 1 to 6 in the production of higher alcohols by CO hydrogenation.
61. The use of claim 60, wherein: the hydrogenation reaction conditions are as follows: the pressure is 1-5 MPa, the temperature is 150-350 ℃, and the feeding volume space velocity of hydrogen and CO is 500-3000 h -1 ，H 2 The mol ratio of/CO is 0.5-3.
62. The use of claim 61, wherein: the hydrogenation reaction conditions are as follows: the pressure is 2-4 MPa; the temperature is 200-300 ℃.
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