CN105080569B - A kind of catalyst and its preparation method and application - Google Patents

Abstract

The present invention provides a kind of catalyst and its preparation method and application.The catalyst includes carrier and loads active component on this carrier and auxiliary agent, wherein, the carrier is that the particle diameter through overpickling oxidation is to the absorbent charcoal carrier for being less than 200 μm more than or equal to 30 μm, the active component is group VIII metal component, and the auxiliary agent is group ivb metal component.Low-carbon alcohols can not only be prepared at low temperature when catalyst provided by the invention is used in being reacted by low carbon alcohol by synthetic gas, and in oil-phase product low-carbon alcohols particularly methanol and ethanol content it is higher, mild condition, conversion per pass are high, energy consumption is low, are conducive to industrialization promotion.

Description

A kind of catalyst and its preparation method and application

technical field

The invention relates to a catalyst, a preparation method of the catalyst and an application of the catalyst in the reaction of producing low-carbon alcohols from synthesis gas.

Background technique

The preparation of low-carbon mixed alcohols (C ₁ -C ₅ mixed alcohols) from syngas is one of the important ways for the clean utilization of coal or natural gas. In recent years, the application value of low-carbon mixed alcohols in the fuel and chemical fields has gradually become prominent, and related research has become increasingly active . Low-carbon mixed alcohols have been positioned as gasoline additives for their good performance indicators. The preparation of low-carbon mixed alcohols from syngas can be used as a gasoline additive to replace the heavily polluting methyl tert-butyl ether (MTBE) to increase the octane number of gasoline. In the field of fuel, alcohol fuel has the advantages of complete combustion, high efficiency, and low emissions of CO, NOx and hydrocarbons. At present, "methyl fuel" mainly based on methanol and "ethyl fuel" mainly based on ethanol have been developed abroad. In addition, "hydrocarbon-alcohol mixed fuel" based on mixtures of different alcohols and hydrocarbons is also quite promising. The United States, Australia and other countries are currently using fuel blended with 5-20% ethanol, and some countries such as Brazil are already using 100% ethanol fuel. With the advancement of technology, the application advantages of alcohol fuel are very obvious. In addition, low-carbon alcohols have great value as chemical products and raw materials for bulk chemical production.

CN101249441A discloses a low-carbon mixed alcohol catalyst for synthesis gas production. The catalyst contains Co-Mo-K oxides and carbon nanotube-based nanomaterial accelerators. The carbon nanotube-based nanomaterial accelerators are multi-walled carbon nanotubes Or metal cobalt-modified multi-walled carbon nanotubes. The performance of the catalyst was evaluated on a pressurized fixed bed device under the process conditions of 5.0MPa, 290-320°C and 8000-10000h ^-1 . The catalyst had low activity, high alkane content and low yield of alcohol.

CN102008963A discloses a method for preparing a low-carbon mixed alcohol catalyst from synthesis gas, the method uses a surfactant (hexadecyltrimethylammonium bromide or polyethylene glycol-polypropylene glycol-polyethylene glycol embedded Segment copolymer) as auxiliary raw materials, copper, magnesium, cerium inorganic salts as raw materials to prepare CuO-MgO-CeO ₂ catalysts, using synthesis gas as raw material gas, in the presence of heating and pressure and CuO-MgO-CeO ₂ catalysts Preparation of C ₁ -C ₅ mixed alcohols under certain conditions. However, studies have shown that the yield of alcohol obtained by this method is low.

CN1390638A discloses a rhodium-based methanol synthesis catalyst supported by carbon nanotubes, which comprises rhodium supported on multi-walled carbon nanometer MWNTs and a metal oxide selected from Ti, Zn, Zr, Mn, Ce, Cr, Ca, Mg Rh-MxOy atomic clusters composed of substances, wherein the molar ratio Rh: M = 1: 2-8, and the weight ratio Rh: MWNTs = 1: 20-60. Although the catalyst has a very low alkane selectivity, the carbon nanotubes are very expensive and must be treated with concentrated nitric acid at high temperature for a long time before use. The conditions are relatively harsh and complicated, which makes the possibility of industrial application of the catalyst quite low.

Contents of the invention

The purpose of the present invention is to overcome the defect that the yield of alcohol obtained by the catalyst of the existing low-carbon alcohol reaction by synthesis gas is low, and to provide a new catalyst, the preparation method of the catalyst and the catalyst Application in the reaction of producing low-carbon alcohols from synthesis gas.

The invention provides a catalyst, which comprises a carrier, active components and auxiliary agents loaded on the carrier, wherein the carrier is an activated carbon carrier with a particle size greater than or equal to 30 μm to less than 200 μm after acid washing and oxidation, The active component is a Group VIII metal component, and the auxiliary agent is a Group IVB metal component.

The present invention also provides a method for preparing the above catalyst, the method comprising: loading the above active components and additives on the acid-washed and oxidized activated carbon carrier with a particle size greater than or equal to 30 μm to less than 200 μm.

The invention also provides the application of the above catalyst in the reaction of producing low-carbon alcohols from synthesis gas.

After in-depth research, the inventors of the present invention found that in the catalyst, acid-washed and oxidized activated carbon was used as a carrier, and the metal components of Group VIII and Group IVB were used as active components and auxiliary agents respectively. , when the catalyst is used in the reaction of producing low-carbon alcohols from syngas, it can not only prepare low-carbon alcohols at low temperature, but also have high content of low-carbon alcohols in the oil phase products, especially methanol and ethanol, with mild conditions and single-pass conversion High, low energy consumption, conducive to industrialization. It is speculated that the reason may be due to the fact that the activated carbon carrier can reduce the ash content in the activated carbon and remove other impurities after acid washing and oxidation, and change the number and distribution of oxygen-containing functional groups on the surface of the activated carbon carrier, so that the acid-washed and oxidized activated carbon catalyst is compatible with The combination of specific active components and additives has excellent catalytic performance. In addition, controlling the particle size of the activated carbon support to be greater than or equal to 30 μm to less than 200 μm can make the obtained catalyst particularly suitable for the reaction of producing low-carbon alcohols from syngas in a slurry bed reactor.

According to a preferred embodiment of the present invention, when the active component is a mixture of cobalt oxide and platinum oxide, the catalyst that can be obtained has Higher alcohol content.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The catalyst provided by the present invention includes a carrier and active components and additives loaded on the carrier, wherein the carrier is acid-washed and oxidized with a particle size greater than or equal to 30 μm to less than 200 μm, preferably 40-180 μm, most preferably It is an activated carbon carrier with a thickness of 50-150 μm, the active component is a group VIII metal component, and the auxiliary agent is a group IVB metal component. Wherein, the above-mentioned particle size refers to the particle size distribution of the carrier analyzed by a laser particle size analyzer (Saturn Digisizer5200 laser particle size analyzer of American Mike Company), and the mass fraction of the carrier whose particle size distribution is within the above-mentioned range is not less than 98% of the particle size range .

According to the catalyst provided by the invention, the acid-washed and oxidized activated carbon carrier is prepared by acid-washing and oxidizing the activated carbon carrier. The activated carbon carrier can be various existing amorphous carbons that can be used as catalyst carriers. The raw materials for forming activated carbon can be various existing carbon-rich organic materials, such as coal, wood, fruit shells, etc. These organic materials are converted into activated carbon through thermal decomposition in the activation furnace. Therefore, according to the production raw materials, the activated carbon carrier can be selected from one or more of coal activated carbon, wood activated carbon, fruit shell activated carbon, etc., especially preferably apricot shell activated carbon and/or coconut shell activated carbon. Using the above-mentioned preferred apricot shell activated carbon and/or coconut shell activated carbon as a carrier can not only minimize the adverse effects of harmful substances in the carrier such as sulfur-containing substances on the catalyst, but also the hardness of these two activated carbons is particularly suitable for use in slurry. Catalytic reactions in state-bed reactors.

The relevant parameters of the activated carbon carrier (such as specific surface area, pore volume, ^average pore size distribution, etc.) -1300m ² /g, most preferably 500-1200m ² /g; pore volume of 0.2-2cm ³ /g, more preferably 0.3-1.8cm ³ /g, most preferably 0.4-1cm ³ /g; average pore diameter of 0.5-5 nm, more preferably 0.8-4 nm, most preferably 1-3 nm. In the present invention, the specific surface area, pore volume and average pore diameter are all measured according to the nitrogen adsorption method, specifically, by _N at a constant temperature of 77K, the adsorption isotherm of the activated carbon carrier is measured, and then the specific surface area and pore size are calculated according to the BET formula Capacity, and calculate the average pore size according to the BJH method.

The present invention has no particular limitation on the method of pickling and oxidation. For example, the activated carbon carrier can be washed continuously with an acidic oxidizing solution, or the activated carbon carrier can be soaked in an acidic oxidizing solution. Preferably, the method of acid washing and oxidation is to reflux the activated carbon carrier in an acidic oxidation solution at a temperature of 40-100°C, preferably 50-90°C, more preferably 60-80°C. Wherein, the time of the reflux reaction can be 0.5-5h, preferably 0.8-4h, more preferably 1-3h, adopting this preferred acid washing and oxidation method can make the obtained catalyst used for the oil phase obtained during the reaction The product has a higher alcohol content.

The acidic oxidizing solution can be various existing acidic solutions with certain oxidation ability, for example, can be selected from nitric acid aqueous solution, concentrated sulfuric acid, hydrogen peroxide aqueous solution, ammonium persulfate aqueous solution, sodium hypochlorite aqueous solution and potassium hypochlorite aqueous solution one or more of. Wherein, the molar concentration of the nitric acid aqueous solution may be 0.5-15 mol/L, preferably 0.5-12 mol/L, more preferably 0.5-5 mol/L. The molar concentration of the concentrated sulfuric acid may be 0.5-10 mol/L, preferably 0.8-8 mol/L, more preferably 1-6 mol/L. The molar concentration of the aqueous hydrogen peroxide solution may be 2-20 mol/L, preferably 3-15 mol/L, more preferably 5-12 mol/L. The molar concentration of the ammonium persulfate aqueous solution may be 5-40 mol/L, preferably 10-35 mol/L, more preferably 15-30 mol/L. The molar concentration of the sodium hypochlorite aqueous solution may be 8-30 mol/L, preferably 10-25 mol/L, more preferably 12-20 mol/L. The molar concentration of the potassium hypochlorite aqueous solution may be 10-50 mol/L, preferably 13-40 mol/L, more preferably 15-30 mol/L.

The present invention does not specifically limit the content of the active components and additives, for example, in terms of oxides and based on the total weight of the catalyst, the content of the active components can be 8-40% by weight, It is preferably 10-30% by weight, more preferably 20-30% by weight; the content of the auxiliary agent may be 0.5-10% by weight, preferably 0.8-5% by weight, more preferably 2-5% by weight.

The active component is usually present in the form of its oxide, ie the active component is usually an oxide of a Group VIII metal. Wherein, examples of the oxides of the Group VIII metals include but are not limited to: one or more of iron oxide, cobalt oxide, nickel oxide, ruthenium oxide, rhodium oxide, palladium oxide, platinum oxide, etc., preferably oxide A mixture of cobalt and platinum oxide. When the active component is a mixture of cobalt oxide and platinum oxide, the obtained catalyst has a higher alcohol content in the oil phase product obtained when used for the reaction. In addition, the content of the cobalt oxide and platinum oxide can be conventionally selected in this field, but in order to make the two play a better coordinated catalytic effect, preferably, the weight ratio of the cobalt oxide to platinum oxide is 80-2000 :1, more preferably 500-1800:1.

The promoters are usually also present in the form of their oxides, ie the promoters are oxides of Group IVB metals. Wherein, examples of the oxides of Group IVB metals include, but are not limited to: one or more of titanium oxide, zirconium oxide, hafnium oxide, and the like. From the viewpoint of availability of raw materials, the auxiliary agent is preferably titanium oxide and/or zirconium oxide.

The preparation method of the catalyst provided by the present invention comprises loading the above-mentioned active components and auxiliary agents on an activated carbon carrier with a particle size greater than or equal to 30 μm to less than 200 μm, preferably 40-180 μm, most preferably 50-150 μm after acid washing and oxidation .

Wherein, the types and related parameters of the activated carbon carrier, the way of pickling and oxidation, the types and contents of active components and auxiliary agents have all been described above, and will not be repeated here.

In the present invention, the method of loading the active components and additives on the acid-washed and oxidized activated carbon carrier is not particularly limited, for example, it can be carried out by impregnation method, co-precipitation method, spraying method and other methods. Preferably, the method of loading the active components and additives on the acid-washed and oxidized activated carbon carrier is to impregnate the acid-washed and oxidized activated carbon carrier in a metal compound containing Group VIII and Group IVB metal compounds. dipping solution, followed by drying and roasting.

The present invention does not specifically limit the type of the Group VIII metal compound, which can be selected according to the type of active components in the catalyst to be obtained. As mentioned above, the active component may be one or more of iron oxide, cobalt oxide, nickel oxide, ruthenium oxide, rhodium oxide, palladium oxide, platinum oxide, etc., preferably a mixture of cobalt oxide and platinum oxide. Accordingly, the Group VIII metal compound may be a water-soluble iron salt, a water-soluble cobalt salt, a water-soluble nickel salt, a water-soluble ruthenium salt, a water-soluble rhodium salt, a water-soluble palladium salt, a water-soluble platinum salt, etc. One or more, preferably a mixture of water-soluble cobalt salts and water-soluble platinum salts. Wherein, the water-soluble cobalt salt may be one or more of cobalt nitrate, cobalt sulfate, cobalt oxide and the like. The water-soluble platinum salt may be one or more of platinum dichlorodiammine, chloroplatinic acid, platinum nitrate, tetraammineplatinum dichloride, and the like. The Group VIII metal compound may not contain water of crystallization, and may also contain water of crystallization. In addition, the amount of the Group VIII metal compound is such that in the obtained catalyst, the content of the active component may be 8-40% by weight, preferably 10% by weight, based on the total weight of the catalyst in terms of oxides. - 30% by weight, more preferably 20-30% by weight.

In the present invention, the usage amount of the Group IVB metal oxide is not particularly limited, and can be selected according to the type of the promoter in the catalyst to be obtained. As mentioned above, the auxiliary agent can be one or more of titanium oxide, zirconium oxide, hafnium oxide, etc., preferably titanium oxide and/or zirconium oxide. Therefore, correspondingly, the Group IVB metal oxide may be one or more of water-soluble titanium salt, water-soluble zirconium salt, water-soluble hafnium salt, etc., preferably water-soluble titanium salt and/or water-soluble zirconium salt Salt. Wherein, the water-soluble titanium salt may be one or more of titanium nitrate, titanium sulfate, titanium chloride and the like. The water-soluble zirconium salt may be one or more of zirconium nitrate, zirconium sulfate, zirconium chloride and the like. In addition, the amount of the Group IVB metal compound is such that in the obtained catalyst, in terms of oxides and based on the total weight of the catalyst, the content of the promoter can be 0.5-10% by weight, preferably 0.8- 5% by weight, more preferably 2-5% by weight.

In addition, the type of solvent in the immersion liquid can also be a conventional choice in the art, as long as it can dissolve the Group VIII metal compound and the Group IVB metal compound, for example, it can be water or water and alcohol, ether, aldehyde A mixed solvent composed of any one or more of ketones, preferably water. The amount of the solvent used can also be a conventional choice in the art, and will not be repeated here.

The conditions of the immersion are not particularly limited in the present invention. For example, the conditions of the immersion generally include that the immersion temperature can be 10-80°C, preferably 20-60°C; the immersion time can be 0.1-3h, preferably 0.5- 1h.

According to the preparation method of the catalyst provided by the present invention, preferably, the method also includes washing the activated carbon carrier with water before acid-washing and oxidizing the activated carbon carrier, and after acid-washing and oxidizing the activated carbon carrier 1. Before loading active components and additives, the acid-washed and oxidized activated carbon carrier is washed to neutrality. The above-mentioned preferred treatment method can more fully remove the impurities in the activated carbon carrier and try to avoid the adverse effect of the acidic solution on the activity of the catalyst. Specifically, before the activated carbon carrier is acid-washed and oxidized, the method of washing the activated carbon carrier with water may be to mix the activated carbon with water, and then place the obtained mixture in an ultrasonic cleaner for cleaning for 20-40 minutes, wherein, relatively For 100g of activated carbon carrier, the amount of water can be 500-1000mL.

The present invention does not specifically limit the drying conditions, as long as the solvent attached to the carrier is removed. For example, the drying conditions generally include a drying temperature of 100-300°C, preferably 110-200°C; The drying time can be 2-12h, preferably 5-10h.

The present invention does not specifically limit the conditions of the calcination, as long as the metal compounds of the Group VIII and the metal compounds of the Group IVB are respectively converted into corresponding oxides, for example, the conditions of the calcination generally include that the calcination temperature can be 200-500°C, preferably 300-400°C; the firing time can be 2-8h, preferably 4-7h.

In addition, the drying and calcination are both carried out in an inert atmosphere. The inert atmosphere may be an atmosphere formed by various existing gases that do not react with reactants and products, for example, an atmosphere formed by nitrogen and/or group zero element gases.

In addition, the invention also provides the application of the catalyst in the reaction of producing low-carbon alcohols from synthesis gas.

In the present invention, the reaction of producing low-carbon alcohols from synthesis gas is particularly preferably carried out in a slurry bed reactor.

The present invention does not specifically limit the conditions for the reaction of producing low-carbon alcohols from syngas, for example, generally including the reaction temperature can be 190-250°C, preferably 200-240°C; the reaction pressure can be 1-5MPa, preferably 2-3MPa; the molar ratio of hydrogen to carbon monoxide can be 1.8-2.3:1, preferably 2.0-2.2:1; the volume space velocity of the feed gas can be 1000-12000h ^-1 , preferably 4000-10000h ^-1 .

In the present invention, the pressure refers to gauge pressure.

In addition, as mentioned above, catalyst precursors usually require reductive activation to become catalytically active. Therefore, it is generally necessary to reduce the catalyst at 300-450° C. for 1-24 h before carrying out the reaction. The reductive activation can be carried out in pure hydrogen, or in a mixed gas of hydrogen and inert gas. The inert gas may be nitrogen and/or argon. In the above mixture of hydrogen and inert gas, the pressure of hydrogen may be 0.1-2 MPa.

The present invention will be described in detail below by way of examples.

In the following examples and comparative examples:

The specific surface area, pore volume and average pore size distribution of the activated carbon carrier are all measured according to the nitrogen adsorption method. Specifically, the adsorption isotherm of the activated carbon carrier is measured at a constant temperature of 77K by _N , and then the specific surface area and pore volume are calculated according to the BET formula, and The average pore size distribution was calculated according to the BJH method. The content of active components and additives adopts X-ray fluorescence spectroscopic analysis method RIPP132-90 (petrochemical analysis method (RIPP experimental method), edited by Yang Cuiding, Gu Kanying, Wu Wenhui, the first edition in September 1990 of Science Press, No. 371- 379 pages) measured.

In the following examples and comparative examples:

CO conversion (X _CO ), _CH4 selectivity And the selectivity of hydrocarbons above C ₅ (C ₅₊ ) They are calculated by the following formulas respectively:

Among them, V ₁ and V ₂ respectively represent the volume of feed gas entering the reaction system and the volume of tail gas flowing out of the reaction system in a certain period of time under standard conditions; c _1,CO , c _2,CO represent the volume of feed gas and tail gas CO content. n _con is the number of moles of CO participating in the reaction, is the number of moles of CO that produces _CO2 , is the number of moles of CO that produces _CH4 , It is the sum of moles of CO that generate CH ₄ , C ₂ hydrocarbons, C ₃ hydrocarbons and C ₄ hydrocarbons.

Example 1

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

100g particle diameter is 50-150 μ m apricot shell activated carbon carrier AC-1 (specific surface area is 1136m ² /g, pore volume is 0.42cm ³ /g, and average pore diameter is 2.5nm, and component and content are as shown in table 1, The same below) was added to 500mL distilled water and stirred evenly for 5min, then the obtained mixed solution was placed in an ultrasonic cleaner for cleaning for 30min, and filtered to obtain water-washed activated carbon. Afterwards, add the activated carbon after washing with water and 500 mL of aqueous nitric acid solution with a molar concentration of 0.7 mol/L into the flask of the condensing reflux device, heat the reflux device to 80° C. for reflux reaction for 2 h, and then filter, and wash the solid components with deionized water to neutral, and then dried in an oven to obtain acid-washed and oxidized activated carbon carrier AC-11.

Dissolve 56 g of cobalt nitrate hexahydrate in 12.5 mL of deionized water to obtain an aqueous solution of cobalt nitrate, and mix this solution with 9.89 g of an aqueous solution of zirconium nitrate with a concentration of 7.3% by weight and 0.2 g of an aqueous solution of platinum dichlorodiammine with a concentration of 1.25% by weight Evenly, to obtain the impregnating liquid. Disperse 50 g of the above acid-washed and oxidized activated carbon carrier AC-11 into the impregnation solution, then stir at room temperature 30 ° C for 1 h, then filter with suction, and transfer the filter cake to a tube furnace, and flow N ₂ (flow rate is 50 mL /min) and heated to 120°C (heating rate of 2°C/min) for drying for 2h, and then calcined at 350°C for 4h, and were protected by _N2 during drying and calcining to obtain catalyst A. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst A is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

13 g of the above-mentioned catalyst A was weighed, and the catalyst was activated by reduction at 350° C. for 3 h in a pure hydrogen atmosphere. Then transfer it to an autoclave containing 150 grams of medium wax. After the airtight inspection is completed, the temperature is raised to 110°C and stirring is started. At the same time, the synthesis gas is introduced. The volume space velocity of the synthesis gas is controlled to be 10000h ^-1 and the pressure is 2.5 MPa, the synthesis gas composition is H ₂ :CO:N ₂ =56:28:16, continue to heat up to 220°C, and then react at 220°C for 55h. The product composition is analyzed by online chromatography, and the results are shown in Table 2.

Example 2

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

Prepare the catalyst according to the method of Example 1, the difference is that 500mL molar concentration of 0.7mol/L nitric acid aqueous solution is replaced by 1.4mol/L nitric acid aqueous solution with 500mL molar concentration, and 9.89g concentration is 7.3% by weight of nitric acid The aqueous zirconium solution was replaced with 14.84 g of an aqueous zirconium nitrate solution having a concentration of 7.3% by weight to obtain a catalyst B. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst B is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 4.05% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced with catalyst B in the same weight part, and the results are shown in Table 2.

Example 3

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

Prepare the catalyst according to the method of Example 1, the difference is that 500mL molar concentration of 0.7mol/L nitric acid aqueous solution is replaced with 500mL molar concentration of 2.1mol/L nitric acid aqueous solution, and 9.89g concentration is 7.3% by weight of nitric acid The aqueous zirconium solution was replaced with 19.78 g of an aqueous solution of zirconium nitrate having a concentration of 7.3% by weight to obtain catalyst C. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst C is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 5.4% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced with catalyst C in the same weight part, and the results are shown in Table 2.

Example 4

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

Catalyst was prepared according to the method of Example 1, except that 500 mL molar concentration of 0.7 mol/L nitric acid aqueous solution was replaced with 500 mL molar concentration of 4.2 mol/L nitric acid aqueous solution to obtain catalyst D. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst D is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced with catalyst D in the same weight part, and the results are shown in Table 2.

Example 5

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

Catalyst is prepared according to the method for embodiment 1, and the difference is that the coconut shell activated carbon carrier AC-2 (specific surface area is 923m3) that 100g particle diameter is 50-150 μ m is the apricot shell activated carbon carrier AC-1 of 50-150 μ m with 100 g particle diameter ² /g, the pore volume is 0.41cm ³ /g, the average pore diameter is 1.99nm, the components and contents are shown in Table 1, the same below) to obtain catalyst E. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst E is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced with catalyst E in the same weight part, and the results are shown in Table 2.

Example 6

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

Catalysts were prepared according to the method of Example 5, except that 500 mL of aqueous nitric acid with a molar concentration of 0.7 mol/L was replaced with 500 mL of aqueous nitric acid with a molar concentration of 1.4 mol/L to obtain catalyst F. Based on the total weight of the catalyst, the content of cobalt oxide in the catalyst F is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced with catalyst F in the same weight part, and the results are shown in Table 2.

Example 7

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

The catalyst was prepared according to the method of Example 5, except that 500 mL of an aqueous solution of nitric acid with a molar concentration of 0.7 mol/L was replaced with 500 mL of an aqueous solution of nitric acid with a molar concentration of 2.1 mol/L to obtain catalyst G. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst G is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced by catalyst G in the same weight part, and the results are shown in Table 2.

Example 8

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

Catalysts were prepared according to the method of Example 5, except that 500 mL of aqueous nitric acid with a molar concentration of 0.7 mol/L was replaced with 500 mL of aqueous nitric acid with a molar concentration of 4.2 mol/L to obtain catalyst H. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst H is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced with catalyst H in the same weight part, and the results are shown in Table 2.

Example 9

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

Catalyst is prepared according to the method for embodiment 1, and difference is, be that the apricot shell activated carbon carrier AC-1 of 50-150 μ m is used the coal-based activated carbon carrier AC-3 (specific surface area of 971 μm) of 50-150 μ m with 100 g particle diameter ² /g, the pore volume is 0.52cm ³ /g, the average pore diameter is 2.11nm, the components and contents are shown in Table 1, the same below) to obtain catalyst I. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst I is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

According to the method of Example 1, the reaction of producing low-carbon alcohols from synthesis gas was carried out, except that catalyst A was replaced with catalyst I in the same weight part, and the results are shown in Table 2.

Example 10

This embodiment is used to illustrate the catalyst provided by the present invention and its preparation method and application.

(1) Preparation of catalyst:

The catalyst was prepared according to the method of Example 1, except that 0.2 g of 1.25% by weight diammine platinum aqueous solution was replaced by 0.2 g of 1.25% by weight cobalt nitrate aqueous solution to obtain catalyst J. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst J is 25% by weight, and the content of zirconia is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced with catalyst J in the same weight part, and the results are shown in Table 2.

Comparative example 1

This comparative example is used to illustrate the reference catalyst and its preparation method and application.

(1) Preparation of catalyst:

Prepare the catalyst according to the method of Example 1, the difference is that before the active components and additives are loaded, the activated carbon carrier AC-1 is not subjected to pickling and oxidation treatment, but 50 g of activated carbon AC-1 that has not been acid-washed and oxidized is directly -1 was dispersed in the impregnating solution to obtain catalyst K. Based on the total weight of the catalyst, the content of cobalt oxide in catalyst K is 25% by weight, the content of platinum oxide is 0.015% by weight, and the content of zirconium oxide is 2.7% by weight.

(2) Reaction of producing low-carbon alcohols from synthesis gas:

The reaction of producing low-carbon alcohols from syngas was carried out according to the method of Example 1, except that catalyst A was replaced by catalyst K in the same weight part, and the results are shown in Table 2.

Table 1

Table 2

In Table 1, * the wear index is obtained according to the ASTM5757-00 standard method on the Mixtrol 8920 abrasion instrument by air jet abrasion method test, specifically, the fine powder blown out by the Mixtrol 8920 abrasion instrument in the first hour is different, and the collected The fine powder blown out in the last four hours (that is, within the first 2-5 hours), and the wear index is calculated according to the following formula. Among them, the smaller the wear index, the better the anti-wear performance of the catalyst.

Air jet wear index (%)=(m ₅ -m ₁ )/m _s ;

m ₁ is the total weight of the fine powder collection bag in the first hour;

m ₅ is the total weight of the fine powder collection bag in the fifth hour;

m _s is the total filling capacity of the test sample.

As can be seen from the above results, when the catalyst provided by the invention is used for the reaction of producing lower alcohols from synthesis gas, lower alcohols can not only be prepared at low temperature, but also the content of lower alcohols, especially methyl alcohol and ethanol, is relatively low in the oil phase product. High, mild conditions, high single-pass conversion rate, good wear resistance, which is conducive to industrialization. In addition, the catalyst provided by the invention also has good wear resistance.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (10)

1. a kind of catalyst, which includes carrier and load active component on this carrier and auxiliary agent, its feature exist In the carrier is that the particle diameter through overpickling oxidation is to the absorbent charcoal carrier for being less than 200 μm, the activity more than or equal to 30 μm Component is cobalt oxide and the mixture of platinum oxide, and the weight ratio of the cobalt oxide and platinum oxide is 500-1800：1, the auxiliary agent For titanium oxide and/or zirconium oxide, the specific surface area of the absorbent charcoal carrier is 300-1500m²/ g, pore volume 0.2-2cm³/ g, puts down Equal aperture is 0.5-5nm.

2. catalyst according to claim 1, wherein, the absorbent charcoal carrier through overpickling oxidation is by by absorbent charcoal carrier Carry out pickling oxidation to be made, the absorbent charcoal carrier is apricot shell activated carbon and/or cocoanut active charcoal.

3. according to the catalyst described in any one in claim 1-2, wherein, the mode of the pickling oxidation is by the work Property high-area carbon back flow reaction 0.5-5h in 40-100 DEG C of acidic oxidation liquid.

4. catalyst according to claim 3, wherein, the acidic oxidation liquid is selected from aqueous solution of nitric acid, molar concentration is The concentrated sulfuric acid, aqueous hydrogen peroxide solution, ammonium persulfate aqueous solution, aqueous sodium hypochlorite solution and the postassium hypochlorite water of 0.5-10mol/L One or more in solution.

5. catalyst according to claim 4, wherein, the molar concentration of the aqueous solution of nitric acid is 0.5-15mol/L；Institute The molar concentration for stating the concentrated sulfuric acid is 0.8-8mol/L；The molar concentration of the aqueous hydrogen peroxide solution is 2-20mol/L；The mistake The molar concentration of ammonium sulfate solution is 5-40mol/L；The molar concentration of the aqueous sodium hypochlorite solution is 8-30mol/L；Institute The molar concentration for stating postassium hypochlorite aqueous solution is 10-50mol/L.

6. according to the catalyst described in any one in claim 1-2, wherein, in terms of oxide and with the total of the catalyst On the basis of weight, the content of the active component is 8-40 weight %, and the content of the auxiliary agent is 0.5-10 weight %.

7. the preparation method of the catalyst in claim 1-6 described in any one, this method include：By the active component and Auxiliary agent is supported on the particle diameter through overpickling oxidation as on the absorbent charcoal carrier more than or equal to 30 μm extremely less than 200 μm.

8. application of the catalyst in claim 1-6 described in any one in being reacted by low carbon alcohol by synthetic gas.

9. application according to claim 8, wherein, it is described by low carbon alcohol by synthetic gas reaction in paste state bed reactor into OK.

10. application according to claim 8, wherein, the condition by low carbon alcohol by synthetic gas reaction includes reaction temperature Spend for 190-250 DEG C, reaction pressure 1-5MPa, the molar ratio of hydrogen and carbon monoxide is 1.8-2.3：1, the volume of unstripped gas Air speed is 1000-12000h^-1。