CN112742397B

CN112742397B - Synthetic alcohol catalyst, preparation method and application thereof

Info

Publication number: CN112742397B
Application number: CN201911053364.5A
Authority: CN
Inventors: 侯朝鹏; 孙霞; 张荣俊; 徐润; 夏国富; 阎振楠
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2023-05-05
Anticipated expiration: 2039-10-31
Also published as: CN112742397A

Abstract

The invention provides a synthetic alcohol catalyst and a preparation method and application thereof, wherein the synthetic alcohol catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the active metal component is Cu or Cu-Co, the carrier is raspberry oxide microsphere, the raspberry oxide microsphere is a hollow microsphere with a large hole on the surface, the hollow microsphere is internally provided with a hollow structure, the large hole is communicated with the hollow structure to form a cavity with one end open, and the oxide in the raspberry oxide microsphere is one or more selected from aluminum oxide and silicon oxide. The CO conversion rate and the alcohol selectivity of the synthetic alcohol catalyst are obviously higher than those of solid catalysts due to the short diffusion distance and large macroscopic surface area, so that the synthetic alcohol catalyst has better synthetic alcohol performance.

Description

Synthetic alcohol catalyst, preparation method and application thereof

Technical Field

The invention relates to the field of catalysts, in particular to a synthetic alcohol catalyst and a preparation method and application thereof.

Background

In the past few decades, a great deal of literature has reported on inorganic hollow shell microsphere materials. Compared with the common compact spheres, the hollow materials have smaller density and larger specific surface area, are widely applied to various fields such as drug catalyst carriers, gas adsorbents and the like, and in recent years, the research and application of inorganic hollow microsphere materials are receiving more and more attention.

The hollow alumina composition ball is one new kind of high temperature heat insulating material, and is produced with industrial alumina and through smelting and blowing in electric furnace and has crystal form of a-Al ₂ O ₃ Microcrystals. The alumina cavity ball is used as main body to make products with various shapes, and the products have high mechanical strength which is several times of that of common light products, and the volume density is far less than that of solid products. The method is widely applied to high-temperature and ultra-high-temperature kilns such as petrochemical industry gasifiers, carbon black industry reaction furnaces, metallurgical industry induction furnaces and the like, and achieves quite satisfactory energy-saving effects. The existing preparation method of the alumina cavity material comprises a high-temperature melting and spraying reaction method, a template method, a layer-by-layer self-assembly method (L-b-L) and a microemulsion method.

The silica hollow microsphere has the advantages of good biocompatibility, easily available and cheap raw materials, and the like, and is widely applied to the fields of drug carriers, biological signal marks, coatings and the like, and the preparation technology of the inorganic hollow microsphere is also widely focused by researchers. The most widely reported method is to use polystyrene microspheres as templates, wrap the surfaces of the polystyrene microspheres with silicon oxide shells, and remove the polystyrene cores to obtain the silicon oxide hollow microspheres. The preparation methods reported in the prior literature mainly comprise (1) an electrostatic adsorption method; (2) silicon cross-linker modification; (3) Layer-by-Layer method.

The zirconia hollow spherical powder is a plasma spraying heat insulation material for surface modification of mechanical parts of aeroengines, gas turbines, heat treatment equipment and the like, and the coating prepared by the powder has the characteristics of good thermal shock resistance and high-temperature hot corrosion resistance, so that the powder can be sprayed on high-temperature parts of aeroengines and the like, not only can the mechanical properties of the engines be improved, but also the service life of the high-temperature parts can be prolonged. The hollow porous zirconia microsphere has stable chemical property, can be used as a miniature controlled release carrier (such as a drug sustained release agent) of an active substance, does not react with the loaded drug active ingredient, has good biocompatibility, does not pollute the environment, and can effectively control the size and the aperture of nano-scale pore channels. The current methods for producing hollow zirconia are a plasma spheroidization method and a spray drying granulation method. The plasma spheroidization method is a process method for preparing hollow sphere powder by adopting a plasma spray gun as a heat source and carrying out heat treatment on porous zirconia aggregate powder prepared in other modes.

The titanium dioxide hollow microsphere structure can enlarge the specific surface area of titanium dioxide, can provide more active sites for catalytic reaction, and the higher crystallinity can reduce the recombination rate of photo-generated electrons and active holes, thereby improving the catalytic activity. On the other hand, from the viewpoint of modification, the hollow structure can provide a space for further modification of the titania material. At present, various methods for synthesizing hollow titanium oxide, such as a template method, a flame combustion method, a template-free method and the like, are available, wherein the template method is easy to control the aperture of the microsphere and the thickness of the shell layer, and the dispersion is relatively uniform. However, the template method has complex steps, and the shell layer is easily damaged in the process of removing the template; the flame combustion method and the template-free method have the advantages of continuous preparation process, simple operation, no pollution and the like, but the prepared products are not regular.

Methanol is used as an important basic chemical raw material and clean fuel, and is widely applied to the fields of organic synthesis, medicines, pesticides, dyes, paints, plastics, synthetic rubber, synthetic fibers, automobiles, national defense and the like. The low-carbon mixed alcohol can be used as excellent clean vehicle fuel, and has the advantages of sufficient combustion, high efficiency, low emission of CO, NOx and hydrocarbon and the like because the alcohol contains oxygen. The fuel is a good clean fuel, and the research on low-carbon alcohols is also attracting attention due to the increasing market demands of higher alcohols with higher economic prices in recent years. Therefore, the CO hydrogenation catalytic synthesis of methanol and the low-carbon mixed alcohol reaction have important application prospects in the chemical field.

At present, the production of industrial-scale methanol and low-carbon mixed alcohol is generally carried out by taking synthesis gas as a raw material and reacting the raw material under the conditions of a certain temperature, a certain pressure and the presence of a catalyst. With the high-speed development of social economy, the demand and the production capacity of the methanol and the low-carbon mixed alcohol at home and abroad are continuously increased, so that the development of the high-performance synthetic alcohol catalyst is promoted to be a research hot spot for the production of the methanol and the low-carbon mixed alcohol.

It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a synthetic alcohol catalyst with high CO conversion rate and high alcohol selectivity.

In order to achieve the above purpose, the present invention adopts the following technical scheme:

the active metal component is Cu or Cu-Co, the carrier is raspberry type oxide microsphere, the raspberry type oxide microsphere is a hollow microsphere with a large hole on the surface, the hollow microsphere is internally provided with a hollow structure, the large hole is communicated with the hollow structure to form a cavity with one open end, and the oxide in the raspberry type oxide microsphere is one or more selected from aluminum oxide, silicon oxide, zirconium oxide and titanium oxide, preferably one or more selected from aluminum oxide and silicon oxide.

In some embodiments, the support is present in an amount of from 30 to 98 weight percent and the active metal component is present in an amount of from 2 to 70 weight percent, on an oxide basis and based on the catalyst.

In some embodiments, the hollow structure has a diameter of 1 to 2000 μm, preferably 1 to 400 μm, and the hollow microsphere has a shell thickness of 0.2 to 1000 μm, preferably 0.5 to 200 μm.

In some embodiments, the macropores have a pore size of from 0.2 to 1000 μm, preferably from 0.5 to 200 μm.

In some embodiments, the raspberry oxide microspheres have a particle size of 3 to 2500 μm, preferably 10 to 500 μm, and a sphericity of 0.50 to 0.99.

In some embodiments, the raspberry oxide microspheres have a breakage rate of 0 to 1%.

In some embodiments, the synthetic alcohol catalyst further comprises an adjunct component selected from one or more of La, zr, ce, W, mn, ti, V, cr, fe, co, zn, sc, mg, ca, be, na, K, ru, ag, au, re, pt and Pd in an amount of 0.001 to 25 wt%, preferably 0.01 to 10 wt%, on an elemental basis and based on the catalyst

In another aspect, the present invention provides a method for preparing the above synthetic alcohol catalyst, comprising the steps of:

providing an impregnating solution of raspberry oxide microspheres and a compound containing the active metal component;

roasting the raspberry oxide microspheres to obtain the carrier; and

and (3) impregnating the carrier by using the impregnating solution, and drying, roasting and activating to obtain the synthetic alcohol catalyst.

In some embodiments, the step of providing raspberry-type oxide microspheres includes:

Adding nitrate, peptizing agent, pore-forming agent, oxide and/or precursor thereof into the dispersing agent, and stirring to obtain dispersed slurry;

aging the dispersion slurry;

feeding the aged dispersion slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃, and preferably 450-700 ℃; and (3) drying and forming at the air outlet temperature of 50-300 ℃, preferably 120-200 ℃ to obtain the raspberry oxide microspheres.

In some embodiments, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate, and yttrium nitrate.

In some embodiments, the peptizing agent is selected from one or more of acids, bases, and salts.

In some embodiments, the pore-forming agent is selected from one or more of starch, synthetic cellulose, a polymeric alcohol, and a surfactant.

In some embodiments, the oxide and/or precursor thereof is selected from one or more of an aluminum source selected from one or more of pseudoboehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, a silicon source selected from one or more of silicate, sodium silicate, water glass, and silica sol, a zirconium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium basic carbonate, and zirconium tetrabutoxide, and a titanium source selected from one or more of titanium dioxide, titanium meta-titanate, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate, and tetraisopropyl titanate.

In some embodiments, the dispersant is selected from one or more of water, alcohols, ketones, and acids.

In some embodiments, the nitrate, the peptizing agent, the pore former, and the oxide and/or precursor thereof are present in a mass ratio of (10-500): (1-10): (10-500): (10-1000).

In some embodiments, further comprising adding a blasting agent to the dispersant, the blasting agent selected from one or more of picric acid, trinitrotoluene, digested glycerol, nitrocotton, darner explosive, nikogold, and C4 plastic explosive, the blasting agent being added in an amount of 0-1% of the total dry basis weight of the nitrate salt, the peptizing agent, the pore former, and the oxide and/or precursor thereof.

In some embodiments, the drying device is a flash drying device or a spray drying device.

In some embodiments, the temperature of the aging process is from 0 to 90 ℃.

In some embodiments, the firing temperature is 400 ℃ to 1300 ℃, preferably 450 ℃ to 1100 ℃, more preferably 500 ℃ to 700 ℃, the drying temperature is 80 ℃ to 200 ℃, preferably 100 ℃ to 150 ℃, and the firing activation temperature is 200 ℃ to 800 ℃, preferably 300 ℃ to 600 ℃.

In yet another aspect, the present invention provides the use of the above-described synthetic alcohol catalyst in the preparation of methanol and/or lower alcohols from synthesis gas.

The cavity synthetic alcohol catalyst has high CO conversion rate and alcohol selectivity, and has high alcohol synthesizing performance. .

Drawings

FIGS. 1 to 4 are SEM photographs of raspberry type microsphere catalysts prepared in examples 1 to 4.

FIG. 5 is an SEM photograph of the microspheroidal catalyst of comparative example 1.

FIG. 6 is an SEM photograph of the microspheroidal catalyst of comparative example 2.

Detailed Description

The technical scheme of the invention is further described below according to specific embodiments. The scope of the invention is not limited to the following examples, which are given for illustrative purposes only and do not limit the invention in any way.

In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.

All of the features disclosed in this invention may be combined in any combination which is understood to be disclosed or described in this invention unless the combination is obviously unreasonable by those skilled in the art. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

According to a first aspect of the present invention there is provided a synthetic alcohol catalyst comprising a support and an active metal component supported on the support.

In the synthetic alcohol catalyst, the active metal component is Cu or Cu-Co (mixture of Cu and Co), and when the target product is methanol, the preferable active metal component is Cu; when the target product is low-carbon mixed alcohol, the preferable active metal components are Cu and Co, wherein the molar ratio of Cu to Co is 0.05-50: 1, preferably in a molar ratio of 0.1 to 20:1.

In the synthetic alcohol catalyst, the carrier is raspberry oxide microsphere, the raspberry oxide microsphere has a hollow microsphere similar to raspberry structure, the surface of the raspberry oxide microsphere is provided with a large hole, the hollow microsphere is internally provided with a hollow structure, and the large hole and the hollow structure are communicated to form a cavity with one end open.

The oxide in the raspberry type oxide microsphere is an inorganic oxide and can be selected from one or more of aluminum oxide, silicon oxide, zirconium oxide and titanium oxide, preferably one or more of aluminum oxide, silicon oxide and titanium oxide.

The particle size of the raspberry type oxide microsphere is 3-500 mu m, preferably 10-500 mu m, the diameter of the hollow structure is 1-2000 mu m, preferably 1-400 mu m, and the pore diameter of the surface macropores is 0.2-1000 mu m, preferably 0.5-200 mu m. The raspberry type oxide microsphere has a shell layer surrounding the cavity and having a thickness of 0.2 to 1000 μm, preferably 0.5 to 200 μm.

The raspberry type oxide microsphere has an appearance similar to a sphere, and the sphericity is 0.50-0.99.

Sphericity of the bead blank is defined by

σ＝4πA/L ²

And (5) calculating to obtain the product. Wherein: sigma is sphericity; a is the projection area of the microsphere, and the unit is m ² The method comprises the steps of carrying out a first treatment on the surface of the L is the projected perimeter of the microsphere, and the unit is m; a and L were obtained from SEM pictures of microspheres, processed by the Image-Pro Plus picture processing software.

The raspberry oxide microsphere of the invention is roasted at 400-1300 ℃, preferably 450-1100 ℃ and more preferably 500-700 ℃ to obtain oxide with the specific surface of about 0.1-900 m ² Preferably 10 to 300m ² The pore volume per gram is about 0.01 to 3.6ml/g, preferably 0.1 to 0.9ml/g.

The raspberry oxide microsphere has a crushing rate of 0-1%, and the crushing rate is measured according to a method provided by a similar strength standard number Q/SH3360 226-2010, and the specific method is as follows:

firstly, selecting sieves S1 and S2 with the mesh numbers of M1 and M2 respectively, wherein M1 is less than M2, enabling microspheres to be tested to pass through the sieve S1 with the mesh number of M1 firstly, enabling the microsphere powder after sieving to pass through the sieve S2 with the mesh number of M2, and finally enabling the microsphere powder trapped by the sieve S2 to serve as a sample to be tested.

Adding a certain mass of sample to be tested into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure to the microspheres through a cylinder, continuously screening the pressed microsphere powder by using a screen S2 with the mesh number of M2, recording the mass of the microsphere powder under the screen, and dividing the mass of the microsphere powder under the screen by the total added mass of the microspheres to obtain the breakage rate of the microspheres.

In the present invention, M1 may be 100 mesh, M2 may be 150 mesh, the pressure may be 100N, and the time may be 10s.

The strength of the microsphere can be evaluated by utilizing the crushing rate; when the crushing rate is smaller, the strength of the microsphere is higher

The raspberry-shaped oxide microsphere has low crushing rate and obviously higher strength than the prior known oxide microsphere, such as the apple-shaped hollow molecular sieve microsphere disclosed by CN108404970A under the condition of pressurization, which is determined by the different raw materials and preparation methods. The high strength makes the raspberry oxide microsphere have larger porosity, greatly reduced pressure drop, excellent processability and wear resistance, short reaction diffusion distance in the catalyst field as a carrier, and wide application prospect, and can be made into high-temperature heat insulation materials, biological materials and photochemical materials.

In the synthetic alcohol catalyst of the present invention, the content of the active metal component is 2 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 30% by weight, and the content of the support is 30 to 98% by weight, preferably 50 to 95% by weight, more preferably 70 to 90% by weight, based on the oxide and based on the catalyst.

The synthetic alcohol catalysts of the present invention may also contain any material that improves the performance of the catalyst. For example, one or more auxiliary components selected from La, zr, ce, W, mn, ti, V, cr, fe, co, zn, sc, mg, ca, be, na or K may be incorporated, or one or more auxiliary components selected from Ru, ag, au, re, pt and Pd may be incorporated in an amount of 0.001 to 25% by weight, preferably 0.01 to 10% by weight, based on the element and based on the catalyst.

The synthetic alcohol catalyst can be applied to the production of methanol and/or low-carbon mixed alcohol by using synthesis gas.

The synthetic alcohol catalyst of the present invention can be prepared by a process comprising:

providing an impregnating solution of raspberry oxide microspheres and a compound containing an active metal component;

roasting the raspberry oxide microspheres to obtain a carrier; and

the carrier is impregnated with the impregnating solution, and the synthetic alcohol catalyst is obtained after drying, roasting and activating.

In the preparation method of the invention, the raspberry oxide microsphere can be prepared by the following method, which comprises the following steps:

adding nitrate, peptizing agent, pore-forming agent, aluminum source and/or silicon source into the dispersing agent, and stirring to obtain dispersed slurry;

aging the dispersion slurry; and

In the preparation method of the invention, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate and yttrium nitrate. Nitrate ions in the nitrate can promote the oxidant which can be used as a pore-forming agent under the high temperature condition, and the oxidant can perform self-propagating combustion reaction at the high temperature to generate gas and steam so that the oxide material forms a cavity.

In the preparation method of the invention, the peptizing agent is selected from one or more of acids, alkalis and salts. The acid can be selected from: inorganic acid (such as hydrochloric acid, sulfuric acid, nitric acid, etc.), organic acid (formic acid, acetic acid, oxalic acid, etc.), inorganic acid or a combination of one or more of the organic acids; the alkali can be selected from: inorganic base (sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, sodium carbonate (anhydrous sodium carbonate), sodium carbonate (monohydrate, heptahydrate, decahydrate), sodium bicarbonate (baking soda), potassium carbonate, potassium bicarbonate, etc.), organic base (such as amine compound, alkali metal salt of alcohol, alkaloid, alkyl metal lithium compound, etc.), inorganic acid or combination of several kinds of organic acid; the salts can be selected from: inorganic acid salts (e.g., hydrochloric acid, sulfate, nitrate, etc.), organic acid salts (formate, acetate, oxalate, etc.), and one or a combination of inorganic acid salts or organic acid salts.

In the preparation method of the invention, the pore-forming agent is one or more selected from starch, synthetic cellulose, polyalcohol and surfactant. The synthetic cellulose is preferably one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polyalcohol is preferably one or more of polyethylene glycol, polypropylene alcohol, polyvinyl alcohol and polypropylene alcohol PPG; the surfactant is preferably one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and its derivatives, and acrylic acid copolymer and maleic acid copolymer with molecular weight of 200-2000000.

In the preparation method of the invention, the oxide and/or the precursor thereof can be directly alumina, silica, zirconia and titanium oxide, or can be precursor for forming the oxide, and can be specifically selected from one or more of an aluminum source, a silicon source, a zirconium source and a titanium source, wherein the aluminum source is selected from one or more of pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate, the silicon source is selected from one or more of silicate, sodium silicate, water glass and silica sol, the zirconium source is selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium basic carbonate and zirconium tetrabutoxide, and the titanium source is selected from one or more of titanium dioxide, meta-titanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate and tetraisopropyl titanate.

When the above aluminum source, silicon source, zirconium source and titanium source are used, chemical agents for precipitating or gelling them, such as acids (e.g., inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, etc., or organic acids such as acetic acid, etc.), and/or bases (e.g., sodium carbonate, sodium hydroxide, etc.), are also included.

When it is desired to prepare an oxide composition containing other components, oxides such as vanadium oxide, chromium oxide, manganese oxide, molybdenum oxide, tungsten oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and the like may be added, and precursors capable of forming these oxides may be added.

In the preparation method of the invention, the dispersing agent is selected from one or more of water, alcohols, ketones and acids, wherein the alcohols can be methanol, ethanol, propanol and the like, the ketones can be acetone, butanone and the like, and the acids can be formic acid, acetic acid, propionic acid and the like. Preferably, the dispersing agent is a mixture of water and a small amount of ethanol, the small amount of ethanol can achieve better dispersing effect in water and can serve as a boiling point regulator, and the water evaporation effect and the liquid drop shrinkage effect are matched and matched better through the adjustment of the dispersing agent, so that the microsphere appearance effect is more regular and smoother.

In the preparation method, the mass ratio of nitrate to peptizing agent to pore-forming agent to oxide and/or precursor thereof is (10-500): (1-10): (10-500): (10-1000).

In the preparation method, nitrate, peptizing agent, pore-forming agent, oxide and/or precursor thereof can be added into the dispersing agent in sequence, or can be added simultaneously, or can be added sequentially according to the dissolution condition of each raw material, and the raw materials are stirred while being added so as to be uniformly mixed.

The preparation method of the invention can further comprise adding a blasting agent to the dispersing agent, wherein the blasting agent can be added before or after the oxide. The blasting agent is one or more selected from picric acid, trinitrotoluene, digested glycerol, nitrocotton, dana explosive, heisuojin and C4 plastic explosive. Before drying and shaping, the blasting agent is uniformly mixed with other materials. The addition amount of the blasting agent is 0-1% of the total dry basis weight of nitrate, peptizing agent, pore-forming agent and oxide and/or precursor thereof.

In the preparation method, nitrate, peptizing agent, pore-forming agent and precursor of oxide are sequentially added into a dispersing agent for pulping, and after the slurry is stirred uniformly, the slurry is pumped into a sand mill or a colloid mill for grinding, so that dispersed slurry is obtained. The solid content of the slurry is generally 5-60 wt% during beating, and the grinding time is 1-30 minutes. After mixing and grinding, the average particle size of the aluminum source, silicon source, zirconium source and titanium source particles in the slurry may be ground to 0.01-10 μm.

After the raw materials are mixed and ground, the mixture is fully dissolved and dispersed, so that the dispersion slurry is uniform. The milling equipment used may be a colloid mill, sand mill or other equipment, the criteria being that the catalyst fines after milling thereof reach the desired average particle size, i.e. less than 10 μm.

Then the dispersion slurry is aged at 0-90 ℃ for 0.1-24 hours, preferably 0.5-2 hours.

After aging treatment, the dispersion slurry is sent into a drying device, and is dried and molded at the air inlet temperature of 400-1200 ℃, preferably 450-700 ℃, the air outlet temperature of 50-300 ℃, preferably 120-200 ℃, and the pressure in a spray tower is similar to that of conventional spraying, so that the raspberry oxide microspheres can be obtained.

The drying apparatus used in the present invention may be a flash drying apparatus and a spray drying apparatus, preferably a spray drying apparatus. Flash drying and spray drying are common methods applied to material drying. After the wet material is dispersed in a drying tower, the moisture is quickly vaporized in contact with hot air, and a dried product is obtained. The spray drying method can directly dry the solution and emulsion into powder or granular products, and can omit the procedures of evaporation, crushing and the like.

The working principle of spray drying is that the materials to be dried are dispersed into very fine particles like fog through mechanical action (such as pressure, centrifugation and airflow spraying), the evaporation area of moisture is increased, the drying process is accelerated, and most of moisture is removed in a short time by contacting with hot air, so that solid matters in the materials are dried into powder.

The spray drying apparatus used in the present invention is a conventional apparatus in the existing flow, and the present invention is not particularly limited thereto. Spray drying apparatus generally comprises: the device comprises a feeding system, a hot air system, a drying tower system, a material receiving system and a sealing system. The feeding system is connected with the drying tower system in the middle of the top end, the hot air system is connected with the side surface of the top end of the drying tower system, the material receiving system is connected with the bottom end of the drying tower system, and the sealing system is connected with the hot air system. In the spray drying process, it is basically necessary to provide a spray of the stock solution; drying tiny liquid drops in spraying; the separation and recovery of the fine powder products. In the spray drying apparatus, an atomizer, a drying chamber, and a fine powder recoverer are generally equipped corresponding to the above functions.

Because of the more control parameters and complex factors in the spray drying process, the particle size and particle shape after spray drying are very complex. It is a difficulty to selectively shape the product into a desired single shape, such as a cavity, typically in the size range of microns, and typically in a mixture of shapes including spheres, discs, apples, grapes, cavities, and meniscus.

One method in the prior art is to form spherical emulsion under the surface tension of surfactant, then spray forming at a lower temperature instantly, gasifying or pyrolyzing pore-forming agent in the spherical emulsion, and the gas generated by the vaporization and pyrolysis can cause the cavity in the microsphere emulsion; the slow release of the gas causes the formation of macropores on the surface to communicate with the hollow structure in the interior, and the molecular sieve particles form secondary stacking holes to become mesopores on the surface of the molecular sieve microspheres in the spray forming process, and the subsequent roasting process is combined to obtain the large-particle hollow molecular sieve microspheres.

The method is characterized in that under the high temperature of 400-1200 ℃ of air inlet temperature, the oxide and the reducing agent in the slurry undergo strong oxidation-reduction self-propagating combustion reaction, and a large amount of gas is instantaneously generated; at the same time, the spray of droplets enters a high temperature zone, where it evaporates strongly, and the surface tension of the thickened slurry results in a sharp contraction of the droplets. The internal strong explosion and the external strong shrinkage form a raspberry type hollow material with good strength. The prepared raspberry oxide microsphere has high strength, high sphericity and high yield.

The raspberry oxide microsphere can be used as a carrier after being roasted, and can be prepared into various catalysts after corresponding active components are loaded. The roasting temperature can be 400-1300 ℃, preferably 450-1100 ℃, and more preferably 500-700 ℃; the calcination time may be 1 to 12 hours, preferably 2 to 8 hours, and more preferably 3 to 4 hours.

In the impregnation solution of the active metal component-containing compound, the active metal component-containing compound is selected from one or more of their soluble compounds, such as one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and soluble complexes of cobalt, preferably cobalt nitrate, basic cobalt carbonate.

The loading method of the present invention is preferably an impregnation method comprising preparing an impregnation solution of the active metal component-containing compound, and thereafter impregnating the support with the solution. The impregnation method is a conventional method, and for example, may be an excess liquid impregnation method or a pore saturation method impregnation method. Wherein the specified level of catalyst can be prepared by adjusting and controlling the concentration, amount or amount of the impregnation solution containing the active metal component, as will be readily understood and effected by those skilled in the art.

The active metal component and the auxiliary component may be co-impregnated or may be separately impregnated, preferably co-impregnated.

The product is dried after impregnation at a temperature of 80 to 200 c, preferably 100 to 150 c, and the drying apparatus used and the operating conditions thereof are conventional equipment and operating parameters in the existing drying technology, and the present invention is not particularly limited thereto.

The dried product is roasted and activated to obtain the catalyst, wherein the roasting and activating temperature is 200-800 ℃, and preferably 300-600 ℃. The firing apparatus used and its operating conditions are conventional equipment and operating parameters in the prior art firing, and the present invention is not particularly limited thereto.

The application of the raspberry oxide microspheres can reduce the waste of the carrier and the catalyst and save materials; meanwhile, due to the improvement of the shape efficiency factor, the diffusion can be promoted, and the reaction efficiency and the selectivity of target products are improved. In the reaction with larger heat effect, the hollow carrier can also reduce the generation of hot spots, and has good intrinsic safety.

The CO conversion rate and the alcohol selectivity of the synthetic alcohol catalyst are obviously higher than those of solid catalysts due to the short diffusion distance and large macroscopic surface area, so that the synthetic alcohol catalyst has better synthetic alcohol performance. In addition, the preparation method of the invention has lower cost and can be applied to large-scale industry.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

Examples

Reagents, instruments and tests

In the following examples, preparations and comparative examples, the specifications of some of the raw materials used were as follows:

Pseudo-boehmite powder (produced by Kaolin catalyst plant, solid content 69.5% by weight, gamma-Al) ₂ O ₃ Content is not less than 98% by weight);

aluminum sol (manufactured by Zhoucun catalyst plant, containing 22 wt% of Al ₂ O ₃ )；

Sodium silicate (Jinan Huifeng chemical industry Co., ltd., modulus 3.1-3.4, insoluble less than 0.4%)

Ammonia, hydrochloric acid, nitric acid, sulfuric acid, aluminum sulfate, aluminum chloride, zirconium hydroxide, zirconium oxychloride, titanium tetrachloride, titanium dioxide (national pharmaceutical group chemical reagent limited, industrial grade);

polyethylene glycol PEG4000 powder (double howl rubber plastic materials Co., ltd.);

methylcellulose (Hubei Jiang Mintai chemical Co., ltd.);

ethyl orthosilicate (TEOS, jinan hua chemical company limited, content about 99%);

aluminum nitrate, titanium nitrate, zirconium nitrate, yttrium nitrate, magnesium nitrate (fish table Ji Xin chemical industry Co., ltd., industrial grade)

The breakage rate of the support and the catalyst can be measured as follows:

and (3) enabling the microspheres to be tested to pass through a 100-mesh sieve, enabling the microsphere powder after sieving to pass through a 150-mesh sieve, and finally enabling the microsphere powder trapped by the 150-mesh sieve to serve as a sample to be tested. Adding a certain mass of microspheres (with granularity of 100-150 meshes) into a cylindrical steel container with a section diameter of 10mm, applying a certain pressure (100N) to the microspheres through a cylinder for a certain time (10 seconds), sieving the pressed microsphere powder by a 150-mesh sieve, recording the mass of the sieved microsphere powder, and dividing the mass of the sieved microsphere powder by the total added mass of the microspheres to obtain the breakage rate of the microspheres.

Preparation example 1

20kg of water is added into a reaction kettle, 0.5kg of zirconium nitrate is added into the reaction kettle, 175g of concentrated nitric acid is added into the reaction kettle, 2kg of PEG4000 and 5g of digested glycerol are added into the reaction kettle, and finally 4.6kg of pseudo-boehmite powder is added into the reaction kettle, and the reaction kettle is uniformly stirred and ground to obtain dispersion slurry.

The dispersion slurry was aged for 0.5 hours with stirring at 25 ℃.

Drying and molding the aged dispersion slurry in a spray drying device to obtain raspberry oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010 to-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the final air outlet temperature of drying is 140 ℃.

Preparation example 2

40kg of water was added to the reaction vessel, 0.5kg of cerium nitrate was added thereto, then 200g of concentrated sulfuric acid was added thereto, then 1kg of PEG4000 and 5g of picric acid were added thereto, and finally 3kg of sodium silicate was added thereto, and the mixture was stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 25℃with stirring for 1 hour.

Drying and molding the aged dispersion slurry in a spray drying device to obtain raspberry oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010 to-0.0090 MPa; the initial air inlet temperature of drying is 600 ℃, and the final air outlet temperature of drying is 180 ℃.

Preparation example 3

30kg of water was added to the reaction vessel, 0.7kg of zirconium nitrate was added thereto, then 2L of concentrated aqueous ammonia was added thereto, and further 1.5kg of PEG4000 and 8g of picric acid were added thereto, and finally 7kg of zirconium hydroxide was added thereto, and the mixture was stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 25 ℃ with stirring for 2 hours.

Preparation example 4

30kg of water was added to the reaction vessel, 0.7kg of titanium nitrate was added thereto, then 2.6L of concentrated aqueous ammonia was added thereto, then 1.5kg of PEG4000 and 6g of picric acid were added thereto, and finally 500g of concentrated nitric acid and 7kg of titanium nitrate were added thereto, and the mixture was stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 25 ℃ with stirring for 2 hours.

Drying and molding the aged dispersion slurry in a spray drying device to obtain raspberry oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010 to-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the final air outlet temperature of drying is 141 ℃.

Example 1

The raspberry oxide microspheres obtained in preparation example 1 were calcined at 600 ℃ to obtain a carrier ZT1, and the physical properties are shown in Table 1.

The carrier ZT1 is immersed in copper nitrate and zinc nitrate solution for multiple times to prepare a catalyst with Cu content of 40.0% and Zn content of 20.0%, the catalyst is dried at 120 ℃ and baked at 420 ℃, and the catalyst CAT1 is obtained, and the physical properties are shown in Table 2.

An SEM photograph of the catalyst prepared in example 1 is shown in fig. 1.

Example 2

The raspberry oxide microspheres obtained in preparation example 2 were calcined at 500 ℃ to obtain a carrier ZT2, the physical properties of which are shown in Table 1.

The carrier ZT2 is immersed in copper nitrate and zinc nitrate solution for multiple times to prepare a catalyst with Cu content of 40.0% and Zn content of 20.0%, and the catalyst is dried at 110 ℃ and baked at 350 ℃ to obtain the catalyst CAT2, and the physical properties of the catalyst CAT2 are shown in Table 2.

SEM photograph of the catalyst prepared in example 2 is shown in fig. 2.

Example 3

The raspberry oxide microsphere obtained in preparation example 3 was calcined at 550 ℃ to obtain a carrier ZT3, and the physical properties are shown in Table 1.

The carrier ZT3 is immersed in a copper nitrate and cobalt nitrate solution for multiple times to prepare a catalyst with Cu content of 12.0% and Co content of 6.0%, the catalyst is dried at 120 ℃ and baked at 420 ℃, and the catalyst CAT3 is obtained, and the physical properties of the catalyst CAT3 are shown in Table 2.

SEM photograph of the catalyst prepared in example 3 is shown in fig. 3.

Example 4

The raspberry oxide microspheres obtained in preparation example 4 were calcined at 700 c to obtain carrier ZT4, the physical properties of which are shown in table 1.

The carrier ZT4 is immersed in a copper nitrate and cobalt nitrate solution for multiple times to prepare a catalyst with Cu content of 12.0% and Co content of 6.0%, the catalyst is dried at 130 ℃ and baked at 370 ℃ to obtain the catalyst CAT4, and the physical properties of the catalyst CAT4 are shown in Table 2.

An SEM photograph of the catalyst prepared in example 4 is shown in fig. 4.

Comparative example 1

Adding 20kg of water into a reaction kettle, adding 4.5kg of pseudo-boehmite powder, and uniformly stirring and mixing; adding 200g of concentrated hydrochloric acid, mixing and grinding; adding 2.3kg of PEG4000, pulping continuously, stirring and ageing for 1 hour at 25 ℃, and drying and forming by using a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010 to-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the final air outlet temperature of drying is 145 ℃.

The microscopic photograph of the obtained oxide microsphere is shown in fig. 5, and it can be seen that the oxide microsphere is basically solid, and the hollow structure communicated with the outside is rarely present in the central part.

The oxide microspheres were calcined at 600 ℃ to give the support DBZT1, the physical properties of which are shown in table 1.

The carrier DBZT1 is dipped with copper nitrate and zinc nitrate solution for multiple times to prepare a catalyst with Cu content of 40.0% and Zn content of 20.0%, and the catalyst is dried at 120 ℃ and baked at 420 ℃ to obtain the catalyst DBCAT-Zn-1, and the physical properties are shown in Table 2.

The carrier DBZT1 is dipped with copper nitrate and cobalt nitrate solution for multiple times to prepare a catalyst with Cu content of 12.0 percent and Co content of 6.0 percent, and the catalyst is dried at 130 ℃ and baked at 370 ℃ to obtain the catalyst DBCAT-Co-1, and the physical properties of the catalyst are shown in Table 2.

Comparative example 2

Adding 30kg of water and 5.5kg of sodium silicate into a reaction kettle, and uniformly stirring and mixing; adding 200g of concentrated hydrochloric acid; the resulting dispersion was filtered and the precipitate was washed 2 times with ethanol and deionized water, respectively, to remove unreacted inorganic and organic impurities.

Adding 20kg of water and 2.0kg of PEG4000, pulping continuously, stirring and ageing for 1 hour at 25 ℃, and drying and forming by using a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010 to-0.0090 MPa; the initial air inlet temperature of drying is 450 ℃, and the final air outlet temperature of drying is 120 ℃.

The structure is also basically solid as shown in fig. 6, and the hollow structure communicating with the outside is not present in the center part when observed under a microscope.

The oxide microspheres were calcined at 600 ℃ to give the support DBZT2, the physical properties of which are shown in table 1.

The carrier DBZT2 is dipped with copper nitrate and zinc nitrate solution for multiple times to prepare a catalyst with Cu content of 40.0 percent and Zn content of 20.0 percent, and the catalyst is dried at 120 ℃ and baked at 420 ℃ to obtain the catalyst DBCAT-Zn-2, and the physical properties of the catalyst are shown in Table 2.

The carrier DBZT2 is dipped with copper nitrate and cobalt nitrate solution for multiple times to prepare a catalyst with Cu content of 12.0 percent and Co content of 6.0 percent, and the catalyst is dried at 120 ℃ and baked at 420 ℃ to obtain the catalyst DBCAT-Co-2, and the physical properties of the catalyst are shown in Table 2.

TABLE 1 physical Properties of the vector

TABLE 2 physical Properties of the catalysts

The catalysts of the examples and comparative examples of the present invention were tested for their performance in the synthesis of alcohols by the following application examples.

Application example

The catalysts of examples 1-8 and comparative examples 1-2 were evaluated for their synthetic reaction properties of methanol and lower mixed alcohols in a fixed bed reactor, wherein a Cu-based catalyst was used for methanol synthesis and a Cu-Co-based catalyst was used for lower mixed alcohol synthesis.

The synthetic alcohol catalyst needs to be reduced prior to use to reduce the catalyst to a metallic state. Catalyst reduction reaction conditions: the pressure is normal pressure, the heating rate is 5 ℃/min, and the hydrogen airspeed is 600h ^-1 The reduction temperature was 300℃and the reduction time was 5 hours.

After reduction, a reaction performance test was performed under the following specific reaction conditions:

reaction conditions of Cu-based catalyst: composition H of raw material gas ₂ /CO/N ₂ =70%/20%/10% (volume percent) pressure 5.0MPa, temperature 230 ℃, syngas (feed gas) space velocity 9600h-1, respectively. Each reaction temperature point was chromatographed by taking a gas sample after 24 hours of operation. The main indexes of the reaction performance are as follows: conversion of CO, methanol selectivity and methanol yield. The results of the reactivity test are shown in Table 3.

Reaction conditions for Cu-Co based catalysts: composition H of raw material gas ₂ /CO/N ₂ =60%/30%/10% (volume percent) pressure 5.0MPa, temperature 275 ℃, syngas (feed gas) space velocity 4000h, respectively ^-1 . Each reaction temperature point was chromatographed by taking a gas sample after 24 hours of operation. The main indexes of the reaction performance are as follows: conversion of CO, methanol selectivity, c2+ alcohol selectivity and total alcohol yield. The results of the reactivity test are shown in Table 4.

Table 3 results of test of reactivity of Cu-based catalyst

Table 4 results of test of reactivity of Cu-Co-based catalyst

The test results in tables 3 and 4 show that the synthetic alcohol catalyst prepared by using the raspberry oxide microspheres as the catalyst carrier has higher CO conversion rate and higher alcohol selectivity than those of the catalyst of the comparative example under the same other conditions, and shows that the raspberry oxide microspheres have better synthetic alcohol performance.

It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.

Claims

1. The synthetic alcohol catalyst is characterized by comprising a carrier and an active metal component loaded on the carrier, wherein the active metal component is Cu or Cu-Co, the carrier is raspberry oxide microspheres, the raspberry oxide microspheres are hollow microspheres with a large hole on the surface, the hollow microspheres are internally provided with a hollow structure, the large hole and the hollow structure are communicated to form a cavity with an opening at one end, and the oxide in the raspberry oxide microspheres is one or more of aluminum oxide, silicon oxide, zirconium oxide and titanium oxide;

the diameter of the hollow structure is 1-2000 mu m, and the thickness of the shell layer of the hollow microsphere is 0.2-1000 mu m; the pore diameter of the macropores is 0.2-1000 mu m;

the preparation method of the raspberry oxide microsphere comprises the following steps:

Aging the dispersion slurry;

sending the aged dispersion slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃; drying and forming at the air outlet temperature of 50-300 ℃ to obtain the raspberry oxide microspheres;

the method further comprises the step of adding a blasting agent into the dispersing agent, wherein the blasting agent is one or more selected from picric acid, trinitrotoluene, nitroglycerin, nitrocotton, darna explosive, black cable gold and C4 plastic explosive, and the addition amount of the blasting agent is 0-1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or the precursor thereof; the content of the blasting agent is not 0.

2. The synthetic alcohol catalyst according to claim 1, characterized in that the carrier is present in an amount of 30 to 98% by weight and the active metal component is present in an amount of 2 to 70% by weight, calculated on oxide basis and based on the catalyst.

3. The synthetic alcohol catalyst according to claim 1, wherein the hollow structure has a diameter of 1 to 400 μm and the hollow microsphere has a shell thickness of 0.5 to 200 μm.

4. The synthetic alcohol catalyst according to claim 1, characterized in that the macropores have a pore size of 0.5-200 μm.

5. The synthetic alcohol catalyst according to claim 1, wherein the raspberry oxide microspheres have a particle size of 3 to 2500 μm and a sphericity of 0.50 to 0.99.

6. The synthetic alcohol catalyst according to claim 5 wherein the raspberry oxide microspheres have a particle size of 10 to 500 μm.

7. The synthetic alcohol catalyst according to claim 1, wherein the raspberry oxide microspheres have a breakage rate of 0 to 1%.

8. The synthetic alcohol catalyst according to any one of claims 1 to 7 further comprising an adjunct component selected from one or more of La, zr, ce, W, mn, ti, V, cr, fe, co, zn, sc, mg, ca, be, na, K, ru, ag, au, re, pt and Pd in an amount of 0.001 to 25 wt% on an elemental basis and based on the catalyst.

9. The synthetic alcohol catalyst according to claim 8 wherein the adjunct component is present in an amount of 0.01 to 10% by weight.

10. Process for the preparation of a catalyst for the synthesis of alcohols according to any one of claims 1 to 9, characterized in that it comprises the following steps:

Roasting the raspberry oxide microspheres to obtain the carrier; and

impregnating the carrier by using the impregnating solution, and drying, roasting and activating to obtain the synthetic alcohol catalyst;

aging the dispersion slurry;

11. The method according to claim 10, wherein the inlet air temperature is 450-700 ℃ and the outlet air temperature is 120-200 ℃.

12. The method of claim 10, wherein the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate, and yttrium nitrate.

13. The method of claim 10, wherein the peptizing agent is selected from one or more of acids, bases, and salts.

14. The method of claim 10, wherein the pore-forming agent is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and surfactant.

15. The method according to claim 10, wherein the oxide and/or a precursor thereof is selected from one or more of an aluminum source selected from one or more of pseudoboehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, a silicon source selected from one or more of silicate, sodium silicate, water glass, and silica sol, and a titanium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium basic carbonate, and zirconium tetrabutoxide, and a titanium source selected from one or more of titanium dioxide, meta-titanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate, and tetraisopropyl titanate.

16. The method of claim 10, wherein the dispersant is selected from one or more of water, alcohols, ketones, and acids.

17. The method according to claim 10, wherein the mass ratio of the nitrate, the peptizing agent, the pore-forming agent, and the oxide and/or the precursor thereof is (10-500): (1-10): (10-500): (10-1000).

18. The method of claim 10, wherein the drying device is a flash drying device or a spray drying device.

19. The method according to claim 10, wherein the temperature of the aging treatment is 0 to 90 ℃.

20. The method according to claim 10, wherein the calcination temperature is 400 to 1300 ℃, the drying temperature of the synthetic alcohol catalyst is 80 to 200 ℃, and the calcination activation temperature is 200 to 800 ℃.

21. The method according to claim 20, wherein the calcination temperature is 450 to 1100 ℃, the drying temperature of the synthetic alcohol catalyst is 100 to 150 ℃, and the calcination activation temperature is 300 to 600 ℃.

22. The method of claim 21, wherein the firing temperature is 500-700 ℃.

23. Use of a synthetic alcohol catalyst according to any one of claims 1 to 9 in the production of methanol and/or lower alcohols from synthesis gas.