CN108236939B - Alumina carrier containing mesopores/macropores and preparation method thereof - Google Patents

Alumina carrier containing mesopores/macropores and preparation method thereof Download PDF

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CN108236939B
CN108236939B CN201611228490.6A CN201611228490A CN108236939B CN 108236939 B CN108236939 B CN 108236939B CN 201611228490 A CN201611228490 A CN 201611228490A CN 108236939 B CN108236939 B CN 108236939B
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pore
acid
alumina carrier
macropores
parts
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CN108236939A (en
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董静
王廷海
李福崇
宋同江
鲁鸿
张华强
崔英
龚光碧
郑聚成
李晶
梁滔
丛日新
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Petrochina Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles

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Abstract

The invention relates to an alumina carrier containing mesopores/macropores, which has the pore size distribution of 10-200 nm, the total pore volume of 0.8-2.2 ml/g and bimodal distribution of pore sizes, wherein the mesoporous pore volume of 10-50 nm accounts for 10-50% of the total pore volume, the macroporous pore volume of 50-200 nm accounts for 50-90% of the total pore volume, and the carrier uses nitrile butadiene rubber emulsion as a pore-enlarging agent. The alumina carrier containing mesopores/macropores has the characteristics of adjustable pore size and effectively controllable mesopore/macropore ratio. The invention also relates to a preparation method of the alumina carrier containing mesopores/macropores.

Description

Alumina carrier containing mesopores/macropores and preparation method thereof
Technical Field
The invention relates to an alumina carrier containing mesopores/macropores and a preparation method thereof, in particular to an alumina carrier which takes nitrile rubber emulsion containing polarity as a pore-enlarging agent and has mesopore/macropore bimodal pore distribution, adjustable mesopore/macropore pore size distribution and effectively controllable mesopore/macropore proportion and a preparation method thereof.
Background
The catalytic science and process are taken as branches of important chemistry and chemical engineering, and are important means for improving the reaction conversion efficiency and the selectivity of target products, improving the economy of the reaction process and reducing the reaction severity. The catalyst is a core technology of a catalytic process, and the development of the high-efficiency catalyst is always a common pursuit of scientific researchers. The supported catalyst has the advantages of mature technology, simple production method, reliable quality and the like, and is always the first choice for catalyst development. The carrier is used as an important component of the supported catalyst, not only improves the utilization rate of active components and the dispersion performance of the active components, but also provides a channel for the diffusion process of reactants and products, and in recent years, macroporous carrier materials are widely used for improving the performance of the catalyst due to the fact that the mass transfer rate can be effectively improved.
The alumina is used as a traditional catalyst carrier material, has the characteristics of mature technology, adjustable pore structure, low use cost and easy processing and forming, and is widely used for preparing various catalysts. According to the requirements of different reactions on pore structure and surface acidity, a wide variety of alumina production processes and products are formed, such as: composite alumina products containing titanium, zirconium and the like for improving the action of alumina and active metals; alumina products containing fluorine, chlorine and the like for improving the acidity of the surface of the alumina carrier; and alumina products with high bulk ratio, low bulk ratio, high specific surface area, high purity and the like. The pore channel structure of the alumina comes from particles or stacking gaps among the particles, and the aperture of the gamma-alumina synthesized by the conventional method is generally less than 15nm, so researchers have conducted a great deal of research on the synthesis method of the alumina with the macroporous structure.
To obtain a product containing largeThe alumina carrier material with a pore structure is prepared by researchers through a pore-expanding agent, hydrothermal treatment and other methods. The pore-expanding agent method for synthesizing the macroporous alumina material has many related documents, and can be divided into the following steps according to different types of pore-expanding agents: hard pore-expanding agent and soft pore-expanding agent. Good macroporous alumina can be obtained by a hard pore-expanding agent method represented by activated carbon, and US19820384626 discloses that carbon black is used as a pore-expanding agent, macroporous alumina with pore size distribution of 15-300 nm can be obtained, but the macroporous alumina with concentrated pore size distribution is difficult to prepare due to non-uniform particle diameter distribution of the carbon black. CN201410347665.X discloses a preparation method of macroporous, high-strength alumina, which comprises adding pore-enlarging agent such as polyacrylamide, polyvinyl alcohol, alkyl cellulose, sesbania powder, starch and the like to obtain macroporous alumina carrier, wherein the usage amount of the pore-enlarging agent accounts for 10% -30% of that of the alumina, but a specific pore diameter range is not disclosed. Although a good macroporous alumina carrier can be obtained by the hard pore-expanding agent method, the dosage of the pore-expanding agent is preferably more than 20 percent, so that the processing cost is greatly increased, and the decomposition of a large amount of pore-expanding agent does not meet the development requirement of low carbon and environmental protection. CN201010509425.7 discloses a method for co-pore-enlarging by hydrothermal and pore-enlarging agent, which is used for preparing an alumina carrier containing a macroporous structure, wherein the dosage of the pore-enlarging agent can be reduced to 3% -10% by hydrothermal auxiliary pore-enlarging effect, but the energy consumption is increased by auxiliary hydrothermal. CN200310103035.X discloses a preparation method of macroporous alumina, which comprises expanding pores with polyvinyl alcohol, propanol, and polyethylene glycol soft pore-expanding agent, and adding 1% polyethylene glycol to make the pore volume of pore diameter larger than 100nm account for 26.2% of the total pore volume. The soft pore-expanding agent has the advantages of low consumption and good pore-expanding effect, but the higher molecular weight alcohol soft pore-expanding agent has poorer solubility in water, so that the application of the alcohol soft pore-expanding agent in expanding macroporous alumina is limited. CN201410148773.4 discloses a preparation method of alumina porous microspheres, which comprises the following steps: 1) dissolving a surfactant in deionized water, and stirring to obtain a water phase; 2) mixing a chelating agent, an alumina precursor and n-octanol, and stirring to obtain an oil phase; 3) adding Span80 and a pore-forming agent into the oil phase, and stirring; 4) subjecting the product obtained in step 3)Pouring the clear oil phase into the water phase, and continuously stirring and emulsifying; 5) and 4) carrying out vacuum filtration on the product obtained in the step 4), washing the obtained filter cake, and drying to obtain the alumina porous microspheres. The metal porous microsphere with the internally closed macroporous structure is obtained by utilizing a pore-foaming agent and a sol-gel process in emulsion, and the size of the metal porous microsphere is 1-100 mu m. The porous microspheres are prepared by utilizing the phase separation principle. The internal closed pore diameter is 50 nm-5 mu m. The pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or polyacrylic acid. The invention uses a large amount of surfactants, chelating agents and pore-forming agents, and has the advantages of more raw materials and complex synthesis process. CN201310748661.8 discloses a preparation method of an alumina/carbon aerogel composite material, which is to dissolve a water-soluble carbohydrate compound and a water-soluble polymer in water in a closed container, then add aluminum salt or aluminum hydroxide, react at 140-300 ℃, dry and calcine at 300-1500 ℃ in an inert atmosphere to obtain the alumina/carbon aerogel composite material. The alumina/carbon aerogel composite material with low density and high porosity is prepared by adopting a one-pot method, has the advantages of easily obtained raw materials, simple preparation process, low cost and the like, is light in weight and high in porosity, and can be used for catalyst carriers, gas sensitive elements, solid electrolytic diaphragms, molten steel oxygen probe materials and the like. CN201310499233.6 discloses a preparation method of an alumina carrier, which comprises the following steps: firstly, carrying out neutralization reaction on an alkaline precipitant aqueous solution and an acidic aluminum salt aqueous solution to obtain a precipitation slurry; then adding water-soluble resin into the precipitation slurry and carrying out aging treatment on the precipitation slurry by adopting microwave heating; and finally, filtering, washing, drying and molding the aged mixture to obtain the final alumina carrier. The alumina carrier prepared by the method has larger aperture and concentrated pore distribution, particularly the proportion of 10-20 nm pores in the total pore volume is large and reaches 60-80%, and the alumina carrier is suitable for serving as a carrier of a heavy oil hydrogenation catalyst. CN201310258011.5 relates to a tooth spherical alumina carrier, a tooth spherical alumina hydrotreating catalyst and a preparation method thereof, which comprises the following components: 0.5-4 parts by weight of peptizing agent; 0.2-2 parts by weight of a lubricant; 0.2-3 parts by weight of a dispersant; pore-expanding agent, 0.3-4 weight portions(ii) a 100 parts of aluminum hydroxide. The pore-expanding agent is one or a mixture of polyvinyl alcohol, sodium polyacrylate, starch derivatives or carbon black. The invention adds the anionic surfactant, reduces the addition amount of various auxiliary components and increases the specific surface area by 246m2(ii) in terms of/g. The dentiform spherical alumina carrier greatly reduces the content of various auxiliary agents such as peptizers, pore-expanding agents, dispersing agents, anionic surfactants and other components, thereby not only saving the cost, but also having the advantages of large specific surface area, high mechanical strength and the like. CN201110170283.0 discloses a three-dimensional ordered macroporous alumina and a preparation method thereof. The three-dimensional ordered macroporous alumina has a macroporous diameter of 50-1000 nm, a particle size of 1-50 mm and a mechanical strength of 80-280 g/mm. The method comprises the following steps: adding a carbohydrate compound and concentrated sulfuric acid into the monodisperse polymer microsphere emulsion to obtain a modified polymer microsphere colloidal crystal template, then filling alumina sol, and aging and roasting to obtain the three-dimensional ordered macroporous alumina. The method can greatly improve the adhesion of alumina precursors, enhance the mechanical strength of the material, ensure that the macroporous material is not easy to be broken into fine powder when the template is removed by high-temperature roasting, and still can keep higher integrity. CN201110116418.5 provides mesoporous spherical alumina and a method for preparing the mesoporous spherical alumina by adopting pore-enlarging agent guide. By adopting an oil column forming method, a pore-expanding agent with a guiding function is added into the aluminum sol in the process of preparing the aluminum sol, and a large amount of mesoporous structures are manufactured in the alumina spheres due to the existence of the pore-expanding agent with the guiding function in the forming and aging processes of the aluminum sol. The pore-expanding agent is an organic monomer or a linear polymer, the organic monomer is one of acrylic acid, ammonium acrylate, acrylamide and allyl alcohol, and the linear polymer is one of polyvinyl alcohol, polyacrylamide and polypropylene alcohol. The specific surface of the mesoporous spherical alumina is 150-300 m2The particles have a diameter of 0.1-5 mm, a pore volume of 0.7-1.5 ml/g, pores with a diameter of 2-40 nm of more than 97%, and a bulk density of 0.30-0.80 g/cm3The crushing strength is 70 to 250N/grain. The mesoporous spherical alumina prepared by the pore-expanding agent has concentrated pore diameter, and the mesoporous spherical oxygenThe aluminum oxide can be used as a catalyst or a catalyst carrier in petrochemical industry and fine chemical industry.
Adding aluminum hydroxide or alumina to rubber is more common, for example, CN201110360481.3 provides a method for preparing an aluminum hydroxide-silicone rubber composite material, which is characterized in that: the composite heat-conducting silicon rubber is prepared by taking aluminum hydroxide as a filler and silicon rubber as a carrier in a direct-current electric field. The blending ratio of the aluminum hydroxide to the silicon rubber is 0: 100-40: 60. the composite heat-conducting silicone rubber prepared under the condition of an external direct-current electric field can improve the effective heat conductivity by 30 percent. CN97112353.5 discloses a diene rubber composition containing alumina as a reinforcing filler and a tire tread comprising the same. Rubber composition based on at least one diene elastomer comprising, as reinforcing filler, alumina having: the BET specific surface area is 30 to 400m2Per g, an average particle size of less than or equal to 500nm, a high proportion of Al-OH surface-reactive functional groups and a high dispersibility, the amount of coupling agent being 10 per square meter of alumina-7～10-5In particular, the composition is suitable for the manufacture of tires. CN200510113501.1 relates to a silicone rubber composition for high voltage insulators. More precisely, it relates to addition-or peroxide-crosslinking silicone rubber compositions which contain aluminum hydroxide as filler, the aluminum hydroxide used being untreated aluminum hydroxide.
CN102311134A discloses a spherical integral macroporous alumina, the specific surface area is 100-350 m2/g, the pore volume is 0.5-1.5 ml/g, the average pore diameter of the macropores is 0.05-1.0 μm, the invention also discloses a preparation method thereof, polymer microspheres, alumina sol and coagulant are uniformly mixed at a certain temperature, then the mixture is dispersed into an oil phase, the temperature is raised to a certain temperature, the alumina sol is gelled into spheres, and then the formed gel microspheres are treated from the oil phase, the polymer microspheres are polystyrene microspheres, polymethyl methacrylate microspheres, polyacrylate microspheres and the like, but the preparation method is the macroporous alumina with unimodal distribution, and the alumina carrier with bimodal distribution of pore diameters has great advantages in solid phase catalytic reaction: the macropores are beneficial to full contact of reactant molecules and active centers, larger storage space can be provided for deposition accommodation of impurities, meanwhile, convenience is provided for rapid diffusion and removal of product molecules, the small pore part provides larger specific surface area and reaction sites, and the dispersity of loaded active metals is also improved.
Macroporous alumina has been successfully applied to a plurality of catalyst systems, and has various improvements in the aspects of catalyst activity, selectivity and stability. Although the hard pore-expanding agent can obtain a better macroporous structure, the hard pore-expanding agent has certain defects in the aspect of adjusting the pore size, and the solubility of the polyvinyl alcohol soft pore-expanding agent in water is influenced by the degree of polymerization, so that the preparation of the super-macroporous alumina by using the polyvinyl alcohol soft pore-expanding agent is limited to a certain extent.
Disclosure of Invention
Aiming at the wide application of macroporous alumina in the field of catalysis, the invention adopts butadiene-acrylonitrile copolymer rubber (nitrile rubber) emulsion containing polarity as a pore-enlarging agent to synthesize the mesoporous/macroporous alumina carrier. The nitrile rubber has higher stability to non-polar or low-polar solvents due to the existence of polar nitrile groups, and is more suitable for pore-expanding agents of mesoporous/macroporous alumina carriers. The alumina carrier containing mesopores/macropores can be used in the fields of petrochemical industry and fine chemical industry. The mesopores of the invention are pores with the aperture between 2 and 50 nanometers, and the macropores are pores with the aperture larger than 50 nanometers.
An alumina carrier containing macropores, the pore size distribution is 10-200 nm, the pore size is bimodal distribution, wherein the mesoporous pore volume of 10-50 nm accounts for 10% -50% of the total pore volume, the macroporous pore volume of 50-200 nm accounts for 50% -90% of the total pore volume, preferably, the macroporous pore size distribution is 80-180 nm, and the macroporous pore volume accounts for 60% -80% of the total pore volume; the mesoporous aperture is 20-50 nm, the total pore volume is 0.8-2.2 ml/g, preferably 0.8-1.2 ml/g or preferably 1.8-2.2 ml/g, and the specific surface area is 260-290 m2The carrier uses nitrile rubber emulsion with the particle size range of 10-200 nm as a pore-enlarging agent, the particle size of the synthesized emulsion is controllable, and the stability is good, so that oxygen is used as the pore-enlarging agentThe aluminum oxide carrier can easily generate a mesoporous/macroporous structure, the mesoporous/macroporous pore size distribution can be adjusted, and the pore size distribution is in the range of 10-200 nm.
The pore diameter of the alumina carrier containing mesopores/macropores can be adjusted by changing the molecular weight, the particle size and the addition amount of the pore-enlarging agent. The pore size distribution can be changed between 10 nm and 200nm, for example, the pore size distribution of macropores is 80nm to 180nm, and the pore volume of the macropores accounts for 60 percent to 80 percent of the total pore volume; the mesoporous aperture is 20-50 nm. Preferably, the pore size distribution of the macropores is 80-100 nm or 100-130 nm or 150-180 nm, and the pore size distribution of the mesopores is 20-30 nm.
The invention also provides a preparation method of the mesoporous/macroporous alumina-containing carrier, which comprises the following steps:
firstly, preparing a nitrile rubber emulsion with the particle size of 10-200 nm, adding an organic acid or an inorganic acid into the nitrile rubber emulsion, wherein the addition amount of the organic acid or the inorganic acid is 0.2-3.4 wt% of the nitrile rubber emulsion, then adding the mixed powder of the pseudo-boehmite powder and the sesbania powder into a kneader to be uniformly mixed, adding the nitrile rubber emulsion containing the organic acid or the inorganic acid into the mixed powder to be uniformly kneaded, wherein the addition amount of the nitrile rubber emulsion containing the organic acid or the inorganic acid is 0.1-45 wt%, preferably 0.5-30 wt%, more preferably 5-20.0 wt% of the mixed powder, and obtaining the alumina carrier containing mesopores/macropores through extrusion-molding-drying-roasting.
The nitrile rubber emulsion is prepared by adopting an emulsion polymerization method, and comprises the following steps:
firstly, adding a polymer-grade butadiene monomer, a polymer-grade acrylonitrile monomer, deionized water, an emulsifier, an electrolyte and an auxiliary aid into a polymerization system, wherein the total mass of the polymer-grade butadiene monomer and the polymer-grade acrylonitrile monomer is 100 parts, and the using amount of the polymer-grade butadiene is 50-80 parts, preferably 58-75 parts; the using amount of the deionized water is 100-300 parts; the dosage of the emulsifier is 0.2-10 parts; the using amount of the electrolyte is 0.1-2 parts; the dosage of the auxiliary additive is 0.01-0.2 part;
under the condition of stirring, mixing and pre-emulsifying the materials for 20-40 min to obtain an emulsion, cooling to 5-8 ℃, adding an initiator and a regulator, wherein the amount of the initiator is 0.005-0.5 part by weight based on 100 parts by weight of the total monomers of polymerization-grade butadiene and polymerization-grade acrylonitrile; the dosage of the regulator is 0.1-2 parts;
controlling the temperature to be 5-8 ℃, the pressure to be 0.1-0.5 MPa, and the reaction time to be 10-12 h, and adding a terminator to terminate the polymerization reaction when the conversion rate of two monomers, namely polymerization-grade butadiene and polymerization-grade acrylonitrile, reaches 70-85%, thereby obtaining the nitrile-butadiene rubber emulsion.
The particle size of the synthesized nitrile-butadiene rubber emulsion is 10-200 nm, and is mainly controlled by the type of an emulsifier, the using amount of the emulsifier and the using amount of a regulator. Generally, the better the emulsifying effect of the emulsifier selected in the synthesis process, the more the emulsifier is used, the more the regulator is used, and the smaller the particle size of the synthesized nitrile rubber emulsion is.
The emulsifier is selected from one or more of anionic initiators (fatty acid soaps, long-chain alkyl sulfonates, long-chain alkyl sulfates and the like, preferably fatty acid soaps and long-chain alkyl sulfonates), amphoteric emulsifiers (carboxylic acids, sulfuric acid esters and sulfonic acids, preferably sulfonic acids), and high-molecular emulsifiers (carboxymethyl cellulose, p-styrene sulfonates and the like, preferably p-styrene sulfonates). The electrolyte is selected from one or more of potassium chloride, sodium bisulfate and sodium fluoride, and potassium chloride is preferred. The auxiliary agent is selected from pH regulator (KOH, Na)2CO3Etc., preferably Na2CO3) One or more of chelating agent (ethylene diamine tetraacetic acid and metal salt thereof, preferably, iron sodium Ethylene Diamine Tetraacetic Acid (EDTA)), wherein the initiator can be one or more of inorganic peroxide (potassium persulfate, ammonium persulfate and the like, preferably potassium persulfate), oxidation-reduction system (persulfate-mercaptan, chlorate-bisulfite, organic peroxide-ferrous salt, persulfate-bisulfite and the like, preferably organic peroxide-ferrous salt and the like), azo initiator (azodiisobutyronitrile). The regulator is also called chain transfer agent, and is selected from one or more of compounds containing sulfur, nitrogen, phosphorus or organic unsaturated bonds, preferably one or two of mercaptan and thiuram disulfide. The terminator can be one of p-phenylene diphenols, quinones and sulfur-containing compoundsOr several of them.
The addition amount of the nitrile rubber emulsion containing organic acid or inorganic acid is 0.1 wt% -45 wt%, preferably 0.5 wt% -30 wt%, more preferably 5 wt% -20.0 wt% of the mixed powder, the addition amount of the organic acid or inorganic acid is 0.2 wt% -3.4 wt% of the nitrile rubber emulsion, the used acid is various organic acids or inorganic acids commonly used in the field, and the organic acid is selected from acetic acid or citric acid; the inorganic acid is selected from nitric acid or hydrochloric acid. The source and property of the pseudo-boehmite powder are not limited, and the pseudo-boehmite powder can be a product produced by a carbonization method, a nitric acid method, a sulfuric acid method, an ammonium method and other processes. Is suitable for pseudo-boehmite with different ranges of specific surface area, pore volume and pore diameter.
The kneading or extruding process comprises the steps of adding the prepared pore-expanding agent containing the organic acid or the inorganic acid into the mixed powder of the pseudo-boehmite powder and the sesbania powder, uniformly mixing, extruding, forming, drying at the temperature of 80-200 ℃ for 2-8 hours, and roasting at the temperature of 550-700 ℃ for 4-6 hours to finally obtain the alumina carrier containing the mesopores/macropores.
The particle size of the synthesized nitrile-butadiene rubber emulsion can be adjusted to 10-200 nm by controlling the type and the dosage of the emulsifier, and the molecular weight of the nitrile-butadiene rubber emulsion can be adjusted from thousand to hundred thousand by controlling the dosage of the initiator and the regulator, so that the pore size and the ratio of the mesopore/macropore of the alumina can be controlled according to the different particle sizes of the nitrile-butadiene rubber emulsion and the addition amount of the nitrile-butadiene rubber emulsion.
Drawings
FIG. 1 is a graph of the aperture distribution of example 1.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
The main raw material sources for preparing the catalyst are as follows: the raw material reagents used in the invention are all commercial products.
Example 1
70 parts (mass ratio) of polymerization-grade butadiene monomer, 30 parts of polymerization-grade acrylonitrile monomer, 250 parts of deionized water, 4.5 parts of emulsifier sodium dodecyl benzene sulfonate and 4.5 parts of emulsifier fatty acid soap, 1.5 parts of electrolyte KCl and 0.12 part of chelating agent iron ethylene diamine tetraacetic acid sodium salt (EDTA) are added into a 10L polymerization kettle, pre-emulsification is carried out for 30min, after the temperature is cooled to 5 ℃, 0.4 part of initiator dicumyl peroxide-ferrous sulfate and 1.5 parts of regulator tert-dodecyl mercaptan are added, reaction is carried out for 12h at 5 ℃, the initial reaction pressure is controlled to be 0.1MPa, and the p-phenylene glycol terminator is added when the monomer conversion is controlled to be 80%, so that the nitrile-butadiene rubber emulsion with the particle size of 15nm is obtained.
260mL of deionized water is weighed into a beaker, 15.0g of acetic acid is added into the deionized water to be uniformly mixed, and the mixture is placed into a water bath kettle at 80 ℃. Weighing 15.0g of nitrile rubber emulsion, adding the nitrile rubber emulsion into the prepared deionized water acid solution, and uniformly stirring to obtain the acid solution containing the pore-expanding agent. Weighing 300g of pseudo-boehmite powder and 15.0g of sesbania powder, uniformly mixing in a kneader, adding acid liquor of the nitrile-butadiene rubber emulsion into the pseudo-boehmite and the sesbania powder, and kneading and extruding to form a clover shape. Drying at 150 deg.C for 6 hr, and calcining at 600 deg.C for 5 hr to obtain alumina carrier A-1 containing mesopores/macropores. The specific surface area and pore size distribution of the alumina carrier containing mesopores/macropores are shown in Table 1.
Example 2
75 parts (mass ratio) of polymerization-grade butadiene monomer, 25 parts of polymerization-grade acrylonitrile monomer, 250 parts of deionized water, 5.0 parts of emulsifier fatty acid soap, 1.5 parts of electrolyte KCl and 0.05 part of pH value regulator Na are added into a 10L polymerization kettle2CO3Pre-emulsifying for 30min, cooling to 5 ℃, adding 0.12 part of potassium sulfate as an initiator and 1.0 part of thiuram disulfide as a regulator, reacting for 10h at 5 ℃, controlling the initial reaction pressure to be 0.2MPa, and adding a mercaptan terminator when the conversion rate of the two monomers is controlled to be 70%, thereby obtaining the nitrile rubber emulsion with the particle size of 80 nm.
250mL of deionized water is measured in a beaker, 18.0g of nitric acid with the concentration of 68 percent is added into the deionized water and evenly mixed, and the mixture is placed in a water bath kettle at the temperature of 80 ℃. Weighing 30.0g of nitrile rubber emulsion, adding the nitrile rubber emulsion into the prepared deionized water nitric acid solution, and uniformly stirring to obtain the acid solution containing the pore-expanding agent. Weighing 300g of pseudo-boehmite powder and 15.0g of sesbania powder, uniformly mixing in a kneader, adding acid liquor of the nitrile-butadiene rubber emulsion into the pseudo-boehmite and the sesbania powder, and kneading and extruding to form a clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain alumina carrier A-2 containing mesopores/macropores. The specific surface area and pore size distribution of the alumina carrier containing mesopores/macropores are shown in Table 1.
Example 3
Adding 65 parts (by mass ratio) of polymer-grade butadiene monomer, 35 parts of polymer-grade acrylonitrile monomer, 150 parts of deionized water, 2.5 parts of emulsifier anhydrous sorbitol ester, 0.8 part of electrolyte NaCl, 0.10 part of pH value regulator KOH, pre-emulsifying for 40min, cooling to 12 ℃, adding 0.05 part of initiator azobisisobutyronitrile and 0.8 part of regulator tert-dodecyl mercaptan, reacting for 11h at 7 ℃, controlling the initial reaction pressure to be 0.2MPa, and adding a mercaptan terminator when the monomer conversion rate is controlled to be 70%, thereby obtaining the nitrile-butadiene rubber emulsion with the particle size of 100 nm.
260mL of deionized water is measured in a beaker, 12.0g of acetic acid is added into the deionized water and mixed evenly, and the mixture is placed in a water bath kettle at 80 ℃. 60.0g of nitrile rubber emulsion is weighed and added into the prepared deionized water acid solution, and the mixture is stirred uniformly to obtain the acid solution containing the pore-expanding agent. Weighing 300g of pseudo-boehmite powder and 15.0g of sesbania powder, uniformly mixing in a kneader, adding acid liquor of the nitrile-butadiene rubber emulsion into the pseudo-boehmite and the sesbania powder, and kneading and extruding to form a clover shape. Drying at 130 deg.C for 8 hr, and calcining at 700 deg.C for 4 hr to obtain alumina carrier A-3 containing mesopores/macropores. The specific surface area and pore size distribution of the alumina carrier containing mesopores/macropores are shown in Table 1.
Example 4
70 parts (mass ratio) of polymer-grade butadiene monomer, 30 parts of polymer-grade acrylonitrile monomer, 200 parts of deionized water, 1.8 parts of emulsifier fatty acid soap, 0.5 part of electrolyte KCl and 0.06 part of pH value regulator Na are added into a 10L polymerization kettle2CO3Pre-emulsifying for 30min, cooling to 5 ℃, adding 0.12 part of potassium sulfate as an initiator and 0.3 part of tert-dodecyl mercaptan as a regulator, reacting for 10h at 5 ℃, controlling the initial reaction pressure to be 0.3MPa and the conversion rate of the two monomers to be 70%, and adding a mercaptan terminator to obtain the nitrile rubber with the particle size of 150nmAn emulsion.
250mL of deionized water is measured in a beaker, 19.0g of nitric acid with the concentration of 68 percent is added into the deionized water and evenly mixed, and the mixture is placed in a water bath kettle at the temperature of 80 ℃. Weighing 45.0g of nitrile rubber emulsion, adding the nitrile rubber emulsion into the prepared deionized water nitric acid solution, and uniformly stirring to obtain the acid solution containing the pore-expanding agent. Weighing 300g of pseudo-boehmite powder and 15.0g of sesbania powder, uniformly mixing in a kneader, adding acid liquor of the nitrile-butadiene rubber emulsion into the pseudo-boehmite and the sesbania powder, and kneading and extruding to form a clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain alumina carrier A-4 containing mesopores/macropores. The specific surface area and pore size distribution of the alumina carrier containing mesopores/macropores are shown in Table 1.
Example 5
58 parts (mass ratio) of polymerization-grade butadiene monomer, 42 parts of polymerization-grade acrylonitrile monomer, 300 parts of deionized water, 1.2 parts of emulsifier fatty acid soap, 1.5 parts of electrolyte NaCl and 0.07 part of pH value regulator Na are added into a 10L polymerization kettle2CO30.11 portion of chelating agent ethylene diamine tetraacetic acid ferric sodium salt (EDTA), pre-emulsifying for 20min, adding 0.03 portion of dicumyl peroxide-ferrous sulfate as an initiator and 0.5 portion of regulator tert-dodecyl mercaptan after the temperature is cooled to 7 ℃, reacting for 11h at 5 ℃, controlling the initial reaction pressure to be 0.35MPa, and adding a mercaptan terminator when the monomer conversion rate is controlled to be 70%, thereby obtaining the nitrile rubber emulsion with the particle size of 180 nm.
250mL of deionized water is measured in a beaker, 17.0g of nitric acid with the concentration of 68 percent is added into the deionized water and evenly mixed, and the mixture is placed in a water bath kettle at the temperature of 80 ℃. Weighing 16.0g of nitrile rubber emulsion, adding the nitrile rubber emulsion into the prepared deionized water acid solution, and uniformly stirring to obtain the acid solution containing the pore-expanding agent. Weighing 300g of pseudo-boehmite powder and 15.0g of sesbania powder, uniformly mixing in a kneader, adding acid liquor of the nitrile-butadiene rubber emulsion into the pseudo-boehmite and the sesbania powder, and kneading and extruding to form a clover shape. Drying at 130 deg.C for 8 hr, and calcining at 600 deg.C for 6 hr to obtain alumina carrier A-5 containing mesopores/macropores. The specific surface area and pore size distribution of the alumina carrier containing mesopores/macropores are shown in Table 1.
Example 6
75 parts (mass ratio) of polymerization-grade butadiene monomer, 25 parts of polymerization-grade acrylonitrile monomer, 300 parts of deionized water, 0.8 part of emulsifier fatty acid soap, 1.5 parts of electrolyte KCl and 0.05 part of pH value regulator Na are added into a 10L polymerization kettle2CO3Pre-emulsifying for 30min, cooling to 5 ℃, adding 0.10 part of potassium sulfate as an initiator and 0.10 part of tert-dodecyl mercaptan as a regulator, reacting for 10h at 5 ℃, controlling the initial reaction pressure to be 0.25MPa, and adding a mercaptan terminator when the conversion rate of the two monomers is controlled to be 70%, thereby obtaining the nitrile rubber emulsion with the particle size of 200 nm.
250mL of deionized water is measured in a beaker, 12.0g of nitric acid with the concentration of 68 percent is added into the deionized water and evenly mixed, and the mixture is placed in a water bath kettle at the temperature of 80 ℃. 42.0g of nitrile rubber emulsion is weighed and added into the prepared deionized water nitric acid solution, and the mixture is stirred uniformly to obtain acid solution containing the pore-expanding agent. Weighing 300g of pseudo-boehmite powder and 15.0g of sesbania powder, uniformly mixing in a kneader, adding acid liquor of the nitrile-butadiene rubber emulsion into the pseudo-boehmite and the sesbania powder, and kneading and extruding to form a clover shape. Drying at 120 deg.C for 8 hr, and calcining at 650 deg.C for 4 hr to obtain alumina carrier A-6 containing mesopores/macropores. The specific surface area and pore size distribution of the alumina carrier containing mesopores/macropores are shown in Table 1.
TABLE 1 specific surface area and pore size distribution of alumina carriers containing meso/macro pores
Figure BDA0001194081830000101
Figure BDA0001194081830000111
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.

Claims (10)

1. Oxidation containing mesopores/macroporesThe aluminum carrier is characterized in that the pore diameter distribution is 10-200 nm, the total pore volume is 0.8-2.2 ml/g, and the specific surface area is 260-290 m2The pore diameter is bimodal, wherein the mesoporous volume of 20-50 nm accounts for 10-50% of the total pore volume, the macroporous volume of 80-180 nm accounts for 60-80% of the total pore volume, and the carrier uses nitrile butadiene rubber emulsion as a pore-expanding agent.
2. The alumina carrier containing mesopores/macropores according to claim 1, wherein the pore size distribution of macropores is 80 to 100nm, 100 to 130nm or 150 to 180nm, and the pore size distribution of mesopores is 20 to 30 nm.
3. The alumina carrier containing mesopores/macropores according to claim 1, wherein the total pore volume is 0.8-1.2 ml/g or 1.8-2.2 ml/g.
4. A method for preparing the alumina carrier containing mesopores/macropores according to any one of claims 1 to 3, comprising the steps of:
firstly, preparing a nitrile butadiene rubber emulsion with the particle size of 10-200 nm as a pore-enlarging agent, adding an organic acid or an inorganic acid into the nitrile butadiene rubber emulsion, wherein the addition amount of the organic acid or the inorganic acid is 0.2-3.4 wt% of the nitrile butadiene rubber emulsion, then adding the mixed powder of the pseudo-boehmite powder and the sesbania powder into a kneader to be uniformly mixed, adding the nitrile butadiene rubber emulsion containing the organic acid or the inorganic acid into the mixed powder to be uniformly kneaded, and the addition amount of the nitrile butadiene rubber emulsion containing the organic acid or the inorganic acid is 0.1-45 wt% of the mixed powder, and obtaining the alumina carrier containing the mesoporous/macroporous structure through extrusion, molding, drying and roasting.
5. The method for preparing the alumina carrier containing mesopores/macropores according to claim 4, wherein the organic acid is acetic acid or citric acid; the inorganic acid is nitric acid or hydrochloric acid.
6. The preparation method of the alumina carrier containing mesopores/macropores according to claim 4, wherein the nitrile rubber emulsion is prepared by an emulsion polymerization method, and comprises the following steps:
firstly, adding a polymer-grade butadiene monomer, a polymer-grade acrylonitrile monomer, deionized water, an emulsifier, an electrolyte and an auxiliary aid into a polymerization system, wherein the total mass of the polymer-grade butadiene monomer and the polymer-grade acrylonitrile monomer is 100 parts, and the using amount of the polymer-grade butadiene is 50-80 parts; the using amount of the deionized water is 100-300 parts; the dosage of the emulsifier is 0.2-10 parts; the using amount of the electrolyte is 0.1-2 parts; the dosage of the auxiliary additive is 0.01-0.2 part;
under the condition of stirring, mixing and pre-emulsifying the materials for 20-40 min to obtain an emulsion, cooling to 5-8 ℃, adding an initiator and a regulator, wherein the amount of the initiator is 0.005-0.5 part by weight based on 100 parts by weight of the total mass of a polymer-grade butadiene monomer and a polymer-grade acrylonitrile monomer; the dosage of the regulator is 0.1-2 parts;
controlling the temperature to be 5-8 ℃, the pressure to be 0.1-0.5 MPa, and the reaction time to be 10-12 h, and adding a terminator to terminate the polymerization reaction when the conversion rate of two monomers, namely polymerization-grade butadiene and polymerization-grade acrylonitrile, reaches 70-85%, thereby obtaining the nitrile-butadiene rubber emulsion.
7. The method for preparing the alumina carrier containing the meso/macropores according to claim 6, wherein the amount of the polymer-grade butadiene is 58-75 parts.
8. The method for preparing the alumina carrier containing the mesopores/macropores according to claim 4, wherein the addition amount of the nitrile rubber emulsion containing the organic acid or the inorganic acid is 0.5 wt% -30 wt% of the mixed powder.
9. The method for preparing the alumina carrier containing mesopores/macropores according to claim 6 or 7, wherein the emulsifier is selected from one or more of an anionic initiator, an amphoteric emulsifier or a polymeric emulsifier; the electrolyte is selected from one or more of potassium chloride, sodium bisulfate or sodium fluoride; the auxiliary agent is selected from one or two of pH value regulator or chelating agent, and the initiator is selected from one or more of inorganic peroxide, oxidation-reduction system or azo initiator; the regulator is selected from one or more compounds containing sulfur, nitrogen, phosphorus or organic unsaturated bonds, and the terminator is selected from one or more compounds of p-phenylene, quinones or sulfur-containing compounds.
10. The method for preparing alumina carrier containing mesopores/macropores according to claim 9, wherein the emulsifier is fatty acid soap, the electrolyte is potassium chloride, the chelating agent is ethylenediamine tetraacetic acid or metal salt of ethylenediamine tetraacetic acid, and the pH regulator is KOH, NaOH or Na2CO3One or more of the initiator, the regulator and the terminator, wherein the initiator is potassium persulfate, the regulator is one or two of mercaptan and thiuram disulfide, and the terminator is mercaptan.
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CN101337186A (en) * 2008-08-27 2009-01-07 云南大学 Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone
CN103706408A (en) * 2013-12-18 2014-04-09 宁波金远东工业科技有限公司 Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent
CN105983443A (en) * 2015-01-27 2016-10-05 中国石油天然气股份有限公司 Double-peak-pore-structured aluminum oxide supporter and preparation method thereof

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CN101337186A (en) * 2008-08-27 2009-01-07 云南大学 Preparation method of meso-porous alumina and catalytic synthesis of alpha-tetralone
CN103706408A (en) * 2013-12-18 2014-04-09 宁波金远东工业科技有限公司 Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent
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