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CN116062782B - Spherical alumina carrier and preparation method thereof - Google Patents

Spherical alumina carrier and preparation method thereof Download PDF

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Publication number
CN116062782B
CN116062782B CN202111279544.2A CN202111279544A CN116062782B CN 116062782 B CN116062782 B CN 116062782B CN 202111279544 A CN202111279544 A CN 202111279544A CN 116062782 B CN116062782 B CN 116062782B
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oil
carrier
reaction
alumina
aluminum
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CN116062782A (en
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于秋莹
袁胜华
耿新国
隋宝宽
王永林
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/21—Attrition-index or crushing strength of granulates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a spherical alumina carrier and a preparation method thereof. The preparation method comprises the following steps: (1) preparing a pseudo-boehmite filter cake by a carbonization method; (2) Adding water into the filter cake obtained in the step (1) to prepare slurry, and then adding a peptizing agent to carry out peptization to obtain aluminum hydroxide sol; (3) Adding a curing agent solution, an emulsifying agent, a polyol and an organic phase into the aluminum hydroxide sol obtained in the step (2) respectively, and adding water into the mixture under stirring to prepare an oil-in-water emulsion; (4) And (3) dripping the oil-in-water emulsion obtained in the step (3) into an oil column for molding, washing, drying and roasting to obtain the carrier. The spherical alumina carrier prepared by the method has the characteristics of good roundness, low bulk density, high crushing strength and the like, is suitable for being used as a continuous reforming catalyst carrier, has no pollutant discharge, has no environmental pollution and is low in cost.

Description

Spherical alumina carrier and preparation method thereof
Technical Field
The invention relates to a spherical alumina carrier and a preparation method thereof, in particular to a spherical alumina carrier suitable for a boiling bed and a noble metal catalyst and a preparation method thereof.
Background
The shape and size of the catalyst particles are generally determined according to the reactor requirements used in industrial production. Currently, there are four types of reactors commonly used in industry: fixed bed, fluidized bed (ebullated bed), suspended bed, and moving bed. Fixed bed reactors are commonly used with spherical, cylindrical, clover and sheet catalysts. Moving bed reactors often employ large particle, spherical catalysts. Fluidized bed reactors typically employ small particle, spherical or bar catalysts.
The spherical catalyst has the advantages of good flow property, higher filling coefficient, uniform fluid distribution, low resistance, small pressure drop and the like. In recent years, spherical catalysts have been increasingly used.
The preparation method for the spherical particles mainly comprises spray drying molding, rotation molding, oil molding, spouting molding, melting molding and the like.
Spray drying forming is a method for producing powdery and microspherical products by utilizing the principle of spray drying, and is suitable for preparing microspheres with a diameter of several micrometers to tens of micrometers, such as catalytic cracking catalyst production; the rotary forming is to send powder and proper amount of water (or binder) into a container rotating at low speed, the powder particles are agglomerated together under the action of liquid bridge and capillary force to form micronuclei, and the micronuclei are continuously rotated and grown on a powder layer under the action of friction force and rolling impact generated by the rotation of the container, so that the rotary forming preparation process is simple, but the product has low particle density, poor strength and wider particle size distribution; spout molding is a molding method carried out in a device called a spouted bed, and can produce spherical particles having a particle diameter of 3 to 10 mm; the smelting forming is to put the raw materials for preparing the spherical catalyst into an electric smelting furnace for high-temperature smelting, the molten materials flow into a special spray nozzle positioned below the electric smelting furnace from a discharge hole of the electric smelting furnace, are quickly torn into liquid drops under the action of gravity or centrifugal force, and shrink and cool into balls depending on the self-cohesive force, and the ball forming mode is suitable for the metal catalyst; the shaping in oil is to make use of the gelation property of sol under proper pH value and concentration, drop the sol into medium such as kerosene, shrink to form balls due to the action of surface tension, and then gel to form balls. The gel pellets are aged, washed, dried and roasted to prepare the carrier.
Chinese patent CN104907103a discloses a method for preparing spherical alumina carrier. The method comprises the steps of preparing an aluminum sol A by a hydrochloric acid reflux method and preparing a wet filter cake B by an ammonia water precipitation method, mixing the aluminum sol A and the wet filter cake B to prepare a mixed aluminum sol, mixing the mixed aluminum sol with a hexamethylenetetramine solution, and then carrying out oil column molding, aging, drying and roasting to obtain the spherical alumina carrier. In the method, the raw materials generate flammable and explosive dangerous hydrogen in the process of preparing the aluminum sol by adopting a hydrochloric acid reflux method, and the process of preparing the wet filter cake B by adopting an ammonia precipitation method is also unfavorable for the environment.
Chinese patent CN1068975A discloses a method for preparing low density, large pore volume, high strength alumina supports. The method comprises the steps of neutralizing an aluminum sulfate solution and a sodium hydroxide solution or a sodium metaaluminate solution with a certain proportion in the presence of soluble carbonate, controlling the reaction temperature to be 60-90 ℃, controlling the pH value to be 7-10, continuously stirring, and performing neutralization for 2-5 hours to obtain a precipitate, washing the precipitate with water and filtering. Adding dilute nitric acid into the filter cake, pulping uniformly, heating to 90 ℃, adding 15-30% (weight) of alumina powder with particles smaller than 200 meshes, which is equivalent to the content of alumina in the alumina sol, uniformly stirring, cooling to below 15 ℃, adding hexamethylenetetramine gelling agent which is equivalent to 30-50% of the content of alumina, continuously stirring, and keeping the temperature of the alumina sol below 15 ℃. The aluminum sol is molded in an oil column at the temperature of 95-110 ℃, the obtained pellets are aged for 2-5 hours at normal temperature, then dried at the temperature of 100-120 ℃, and baked at the temperature of 750-950 ℃ to obtain spherical gamma-Al 2O3 with the particle diameter of 1.0-3.0 mm, the specific surface of 120-280 m 2/g, the bulk density of 0.18-0.35 g/mL, the pore volume of 1.5-2.0 mL/g and the crushing strength of 5-30N/grain. The preparation process is complex, aluminum sulfate is adopted as an aluminum source in raw material preparation, sulfate ions are difficult to wash and are easy to be taken into a carrier as impurities, the performance of the catalyst is affected, and meanwhile, the crushing strength of the catalyst is low.
Chinese patent CN111905776a discloses a continuous reforming catalyst and a method for preparing the same. The method comprises the steps of uniformly mixing a first pseudo-boehmite powder, a second pseudo-boehmite powder and water to prepare a suspension, adding a peptizing agent to carry out peptization to obtain an aluminum hydroxide sol, adding a pore-expanding agent and a surfactant into the sol, dripping into an oil ammonia column to form balls, and drying and roasting to obtain the spherical alumina carrier. In order to adjust the pore structure of the carrier, the method adopts two pseudo-boehmite to be mixed, and the carrier has the condition of non-uniform proportion of two powders due to different peptization indexes of the two powders, and meanwhile, the preparation process of the method is complex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a spherical alumina carrier and a preparation method thereof. The spherical alumina carrier prepared by the method has the characteristics of good roundness, low bulk density, high crushing strength and the like, is suitable for being used as a continuous reforming catalyst carrier, has no pollutant discharge, has no environmental pollution and is low in cost.
The first aspect of the present invention provides a method for preparing a spherical alumina carrier, comprising the steps of:
(1) Preparing a pseudo-boehmite filter cake by a carbonization method;
(2) Adding water into the filter cake obtained in the step (1) to prepare slurry, and then adding a peptizing agent to carry out peptization to obtain aluminum hydroxide sol;
(3) Adding a curing agent solution, an emulsifying agent, a polyol and an organic phase into the aluminum hydroxide sol obtained in the step (2) respectively, and adding water into the mixture under stirring to prepare an oil-in-water (O/W) emulsion;
(4) And (3) dripping the oil-in-water emulsion obtained in the step (3) into an oil column for molding, washing, drying and roasting to obtain the carrier.
Further, in the step (1), the pseudo-boehmite filter cake method prepared by the carbonization method comprises the following steps:
(a) Respectively preparing a first aluminum-containing alkaline solution A and a second aluminum-containing alkaline solution B with two different alumina concentrations;
(b) Introducing mixed gas containing carbon dioxide into the first aluminum-containing alkaline solution A for reaction until the pH value is 4-6, and obtaining slurry;
(c) Adding bottom water into a reaction kettle, heating to the reaction temperature, adding the slurry obtained in the step (B) and the second aluminum-containing alkaline solution B into the reaction kettle in parallel flow, reacting, aging after the reaction is finished, washing, and filtering to obtain the pseudo-boehmite filter cake.
Further, in the step (a), the alkaline solution containing aluminum is one or two of sodium metaaluminate solution or potassium metaaluminate solution, preferably sodium metaaluminate solution.
Further, in the step (a), the concentration of the first aluminum-containing alkaline solution A is 40 to 100g Al 2O3/L, preferably 50 to 80g Al 2O3/L, in terms of Al 2O3. The caustic ratio of the first aluminum-containing alkaline solution A is 1.15 to 1.35, preferably 1.25 to 1.35; the concentration of the second aluminum-containing alkaline solution B is 130 to 350g Al 2O3/L, preferably 150 to 250g Al 2O3/L, in terms of Al 2O3. The caustic ratio of the second aluminum-containing alkaline solution B is 1.25 to 1.75, preferably 1.35 to 1.65.
Further, in the step (b), the carbon dioxide in the mixed gas containing carbon dioxide accounts for 50-90% of the volume fraction. The mixed gas containing carbon dioxide can be mixed gas of carbon dioxide and air; the reaction time is 1-5 min.
Further, in the step (b), the initial reaction temperature of the reaction carried out by introducing the mixed gas containing carbon dioxide is 15-65 ℃, the reaction is exothermic, the temperature of the system is gradually increased, the whole reaction process is not required to be cooled and kept at a low temperature, and the temperature of the slurry is 40-75 ℃ at the end of the reaction.
Further, in the step (c), before the parallel flow reaction, adding bottom water into the reaction kettle, wherein the bottom water accounts for 1/10-1/5 of the volume of the reaction container; the co-current reaction is carried out with stirring.
Further, in the step (c), the slurry obtained in the step (B) and the second aluminum-containing alkaline solution B are added into the reaction kettle in parallel flow, and the adding time is controlled to be 60-150 min.
Further, in the step (c), the slurry obtained in the step (B) is added into a reaction kettle, and meanwhile, a second aluminum-containing alkaline solution B is added, and the pH value of the slurry flow in the reaction kettle is controlled to be constant by adjusting the flow rate of the second aluminum-containing alkaline solution B. The temperature of the parallel flow reaction is 40-70 ℃, preferably 45-65 ℃, and the pH value of the reaction is controlled to be 8.5-9.5.
Further, in the step (c), aging is carried out for 30-120 min at the temperature of 85-100 ℃ after the reaction is finished; the washing can be carried out by a washing method conventional in the art, preferably by deionized water at 50-80 ℃.
Further, in the step (c), the mass content of alumina in the obtained filter cake is 35% -45%.
Further, in the step (2), the filter cake is mixed with water and pulped to obtain slurry; the peptizing agent is one or more of nitric acid, acetic acid and citric acid, preferably nitric acid; the mass concentration of the peptizing agent is 50% -70%.
Further, in the step (2), the addition amount of the peptizing agent is 1% -10% by mass of Al 2O3%, preferably 2% -8%.
Further, in the step (2), the mass content of the alumina in the aluminum hydroxide sol is 30-35%.
Further, in the step (3), the curing agent solution is one or more of hexamethylenetetramine and urea solution, preferably hexamethylenetetramine solution; the mass concentration of the curing agent solution is 30% -50%; the addition amount of the curing agent is 1 to 15 percent, preferably 2.5 to 12 percent of the mass of the alumina in the aluminum hydroxide sol.
Further, in the step (3), the emulsifier is preferably a nonionic emulsifier, and specifically is at least one selected from polyoxyethylene sorbitan monolaurate and fatty alcohol polyoxyethylene ethers; the hydrophilic-lipophilic balance (HLB) of the emulsifier is 13-20, preferably 15-18, and the adding amount of the emulsifier is 0.2-2.0% of the mass of the alumina, preferably 0.5-1.5%.
Further, in the step (3), the polyol is one or more of 1, 3-propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-propylene glycol, 1-amyl alcohol and polyethylene glycol (400), and the addition amount of the polyol is 0.1-1.0% of the mass of alumina in the aluminum hydroxide sol, preferably 0.2-0.8%.
Further, in the step (3), the organic phase is one or more of white oil or diesel oil; the addition amount of the organic phase is 7.0-13.0 percent, preferably 7.5-12.5 percent of the mass of the alumina in the aluminum hydroxide sol.
Further, in the step (3), the stirring revolution is 1000-4000 revolutions/min; the mass content of the alumina in the oil-in-water (O/W) emulsion is 15% -25%.
Further, in the step (4), the medium oil used in the oil column is one of white oil or diesel oil, preferably white oil, and the kinematic viscosity of the white oil at 40 ℃ is 20-40 mm 2/s, preferably 25-35 mm 2/s; the molding temperature is 90 ℃ to 110 ℃, preferably 95 ℃ to 105 ℃.
Further, in the step (4), the molding is performed in an oil column, and the oil-in-water emulsion in the step (3) is dripped into the oil column, wherein the inner diameter of a dripper is 0.4 mm-2.0 mm.
Further, in the step (4), the washing is performed in two steps, namely, at least one solvent selected from petroleum ether, cyclohexane or toluene and the like is adopted to be mixed with absolute ethyl alcohol in a volume ratio of 1: washing the molding material with the mixed solution of (1-3), removing medium oil of the molding material, and washing with deionized water at 70-90 ℃ to remove the mixed solution on the molding material.
Further, in the step (4), the drying temperature is 100-150 ℃ and the drying time is 6-10 hours; the roasting temperature is 550-750 ℃ and the roasting time is 1-4 hours.
In a second aspect, the present invention provides a spherical alumina carrier obtainable by the above-described process.
Further, the properties of the spherical alumina carrier are as follows: the pore volume is more than 0.65mL/g, preferably 0.68mL/g to 0.90mL/g; the specific surface area is 170m 2/g, preferably 180m 2/g～230m2/g; pore distribution: the pore volume of the pores with the pore diameter of less than 10nm accounts for less than 5.0 percent, preferably less than 4.5 percent, and the pore volume of the pores with the pore diameter of more than 20nm accounts for less than 8.0 percent, preferably less than 7.5 percent; the carrier particles have a diameter of 1.5-2.2 mm, preferably 1.6-2.0 mm, a bulk density of 0.62-0.68 g/mL, a crush strength of > 45N/granule, preferably 50-70N/granule; the volume of the micro spherical cavity is 5-30% of the volume of the carrier.
The invention has the advantages that:
(1) The invention adopts a preparation method of carbon neutralization to prepare a pseudo-boehmite wet filter cake, the first aluminum-containing alkaline solution and the mixed gas containing carbon dioxide are reacted rapidly, the pH value of the system is reduced to be acidic, then the system reacts with the second aluminum-containing alkaline solution in parallel flow, crystal grains in slurry can be used as seed crystals for the parallel flow reaction, the generated pseudo-boehmite particles are uniform, the prepared pseudo-boehmite wet filter cake has more concentrated pore size distribution, and meanwhile, the high-temperature aging is adopted, the crystallinity and peptization index of the pseudo-boehmite wet filter cake are improved, and the guarantee is provided for preparing the high-side pressure strength carrier.
(2) The carrier raw material is prepared into an oil-in-water (O/W) emulsion, an organic phase is dispersed in the emulsion in the form of fine liquid drops, the liquid drops of the emulsion enter medium oil during molding, the emulsion automatically shrink into a ball shape under the action of surface tension, a gelatinizing agent in the emulsion is decomposed by heating, the released alkaline gas enables the emulsion to be solidified into small balls, meanwhile, the emulsion is damaged in stability due to temperature, the organic phase is dissolved in the medium oil, fine spherical cavities with uniform size are formed on the surface and inside of the solidified small balls, and continuous phase aluminum hydroxide sol is not changed, so that the stacking ratio is reduced, and the strength is not affected.
(3) The polyalcohol is added in the process of preparing the oil-in-water (O/W) emulsion by the carrier raw material, so that the emulsifying capacity of the emulsifier is improved, the organic phase is promoted to be uniformly dispersed to form micro droplets, and the size and the quantity of the micro spherical cavities can be controlled by controlling the stirring revolution and the adding quantity of the organic phase.
(4) The preparation method of the invention has simple process and easy operation.
Drawings
FIG. 1 is an SEM image of a spherical alumina carrier prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a spherical alumina carrier prepared in example 3 of the present invention;
FIG. 3 is an SEM image of a spherical alumina carrier prepared in example 5 of the present invention;
FIG. 4 is an SEM image of a spherical alumina carrier prepared in comparative example 1 of the present invention;
FIG. 5 is an SEM image of a spherical alumina carrier prepared in comparative example 2 of the present invention;
FIG. 6 is an SEM image of a spherical alumina carrier prepared in comparative example 3 of the present invention.
Detailed Description
The preparation method and effect of the spherical alumina carrier of the present invention are further illustrated by the following examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
In the present invention, morphology and particle size of the carrier were observed by using a field emission Scanning Electron Microscope (SEM) of the type Hitachi S-4700.
In the invention, a nitrogen adsorption and desorption curve of a sample is tested by adopting an ASAP2020 type full-automatic physical adsorption instrument of Micromeritics company in the United states at the temperature of minus 196 ℃, and the specific surface area, pore volume and pore diameter distribution are measured.
In the invention, the crushing strength is tested by adopting a ZQJ-III intelligent particle strength tester manufactured by Dalian Chi taking tester, and the average value of ten crushed spherical carriers is tested.
In the invention, the bulk density is measured by loading 100mL measuring cylinders into the compacted weight of the spherical carrier.
According to the method for testing the volume of the carrier micro spherical cavity, solid spherical carriers with the same pore volume, the same particle size and the same true density as those of the micro spherical cavity carrier are prepared, 100mL of the micro spherical cavity carrier and 100mL of the solid spherical carrier are measured by a 100mL measuring cylinder, deionized water is added to a 100mL scale in the measuring cylinder and the water volume is measured, the total volume of the micro spherical cavity is the difference between the total pore volume of the solid spherical carrier added by 100mL and the total pore volume of the micro spherical cavity carrier subtracted by 100mL of the deionized water added by the measuring cylinder, and the occupied carrier volume of the micro spherical cavity is the total volume of the micro spherical cavity divided by the weight of the 100mL micro spherical cavity carrier and divided by the true density of the micro spherical cavity carrier.
Example 1
Introducing mixed gas containing 70% carbon dioxide and air by volume fraction into 3000mL sodium metaaluminate solution with the temperature of 35 ℃ and the concentration of 60gAl 2O3/L and the caustic ratio of 1.30 for reaction, carbonizing for 2min to reduce the pH value of the system to 4.5, adding the slurry into a 5000mL reaction kettle with the bottom water of 800mL at the flow rate of 35mL/min at the end of the reaction, simultaneously adding 200gAl 2O3/L sodium metaaluminate solution with the caustic ratio of 1.50 in parallel for reaction, controlling the reaction temperature to 55 ℃ and the reaction pH value to be 9.0 constantly, aging for 90min at the end of the reaction, washing with deionized water at 70 ℃ and filtering to obtain the pseudo-boehmite filter cake with the alumina mass content of 40%.
Taking 250g of the pseudo-boehmite filter cake, adding deionized water, stirring and pulping uniformly, then adding 10g of nitric acid solution with the mass concentration of 65% for peptization, and finally preparing aluminum hydroxide sol with the mass content of 32% of aluminum oxide;
30g of hexamethylenetetramine solution with the mass concentration of 35%, 1.0g of polyoxyethylene sorbitan monolaurate (Tween 20) with the HLB value of 16.7, 0.5g of 1, 3-propylene glycol and 10g of white oil are sequentially added into 312.5g of aluminum hydroxide sol, deionized water is added to adjust the stirring revolution to 3500 revolutions per minute for stirring, and the mass content of aluminum oxide in the finally prepared oil-in-water (O/W) emulsion is 22%.
The oil-in-water (O/W) emulsion is dripped into white oil with the kinematic viscosity of 30mm 2/s at 40 ℃ and the temperature of 97 ℃ by a dripper with the inner diameter of 0.8mm for molding, and the molding material is prepared by petroleum ether and absolute ethyl alcohol according to the volume ratio of 1:1, removing medium oil of the formed material, washing with deionized water at 85 ℃, drying at 130 ℃ for 8 hours, roasting at 650 ℃ for 3 hours to obtain the spherical alumina carrier A-1, wherein the analysis results are shown in table 1, the SEM analysis results are shown in figure 1, and the carrier of the invention can be seen to contain more uniform fine spherical cavities through figure 1, so that the bulk density of the carrier can be effectively reduced.
Example 2
Other conditions are the same as in example 1 except that the concentration of the sodium metaaluminate solution to be carbonized is changed to 75g Al 2O3/L, the pH value of the system is reduced to 4.0 by carbonizing for 4min, the concentration of the parallel flow sodium metaaluminate solution is changed to 160g Al 2O3/L, the parallel flow reaction temperature is changed to 65 ℃, the aging temperature is changed to 97 ℃, and the spherical alumina carrier A-2 is obtained, and the analysis results are shown in Table 1.
Example 3
The same conditions as in example 1 were followed except that the number of stirring revolutions at the time of preparing an oil-in-water (O/W) emulsion was changed to 1500 revolutions/min to obtain a spherical alumina carrier A-3 of the present invention, the analysis results thereof are shown in Table 1, and the SEM analysis results are shown in FIG. 2.
Example 4
The same conditions as in example 1 were followed except that the emulsifier was changed to fatty alcohol polyoxyethylene ether (MOA-15) having an HLB value of 15.0 and 1.0g of 1, 3-propanediol was changed to 1, 3-butanediol, to obtain a spherical alumina carrier A-4 of the present invention, and the analysis results thereof are shown in Table 1.
Example 5
Introducing mixed gas containing 80% of carbon dioxide and air by volume fraction into 2000mL of sodium metaaluminate solution with the temperature of 25 ℃ and the concentration of 55gAl 2O3/L and the caustic ratio of 1.25 for reaction, carbonizing for 1min to reduce the pH value of the system to 5.0, adding the slurry into a 5000mL reaction kettle with the bottom water of 1000mL at the flow rate of 25mL/min at the end of the reaction, simultaneously adding 220gAl 2O3/L sodium metaaluminate solution with the caustic ratio of 1.35 in parallel for reaction, controlling the reaction temperature to be 60 ℃ and the reaction pH value to be 8.6 constantly, aging for 120min at 85 ℃ after the reaction is ended, washing with deionized water at 70 ℃ and filtering to obtain the pseudo-boehmite filter cake with the alumina mass content of 40%.
Taking 250g of the pseudo-boehmite filter cake, adding deionized water, stirring and pulping uniformly, then adding 6.2g of nitric acid solution with the mass concentration of 65% for peptization, and finally preparing aluminum hydroxide sol with the mass content of 32% of aluminum oxide;
To the 312.5g of aluminum hydroxide sol, 21.4g of a hexamethylenetetramine solution with a mass concentration of 35%, 0.7g of polyoxyethylene sorbitan monolaurate (Tween 20) with an HLB value of 16.7, 0.3g of 1, 3-propanediol and 7.5g of white oil were sequentially added, and deionized water was added to adjust the stirring speed to 3500 rpm for stirring, so that the mass content of alumina in the finally prepared oil-in-water (O/W) emulsion was 18%.
The oil-in-water (O/W) emulsion is dripped into white oil with the kinematic viscosity of 27mm 2/s at 40 ℃ and the temperature of 102 ℃ by a dripper with the inner diameter of 1.2mm for molding, and the molding material is firstly prepared by the volume ratio of cyclohexane to absolute ethyl alcohol of 1:3, removing medium oil of the formed material, washing with deionized water at 75 ℃, drying at 120 ℃ for 10 hours, and roasting at 700 ℃ for 2 hours to obtain the spherical alumina carrier A-5, wherein the analysis results are shown in table 1, and the SEM analysis results are shown in figure 3.
Comparative example 1
Introducing mixed gas containing 70% carbon dioxide and air by volume fraction into 3000mL sodium metaaluminate solution with the temperature of 35 ℃ and the concentration of 60gAl 2O3/L and the caustic ratio of 1.30 for reaction, reducing the pH value of the system to 4.5 within 2min, adding the slurry into a 5000mL reaction kettle with the bottom water of 800mL at the flow rate of 35mL/min at the end of the reaction, simultaneously adding 200gAl 2O3/L sodium metaaluminate solution with the caustic ratio of 1.50 in parallel flow for reaction, controlling the reaction temperature to 55 ℃ and the reaction pH value to be 9.0 constantly, aging for 90min at the end of the reaction, washing with deionized water at 70 ℃ and filtering to obtain the pseudo-boehmite filter cake with the alumina mass content of 40%.
Taking 250g of the pseudo-boehmite filter cake, adding deionized water, stirring and pulping uniformly, then adding 10g of nitric acid solution with the mass concentration of 65% for peptization, and then adding deionized water, adjusting the stirring revolution to 3500 rpm for stirring, so that the mass content of alumina in the finally prepared aluminum hydroxide sol is 22%.
Dropwise adding the aluminum hydroxide sol into white oil with the kinematic viscosity of 30mm 2/s at 40 ℃ and the temperature of 97 ℃ by using a dripper with the inner diameter of 0.8mm for molding, wherein the volume ratio of petroleum ether to absolute ethyl alcohol is 1:1, removing medium oil of the molding materials, washing with deionized water at 85 ℃, drying at 130 ℃ for 8 hours, and roasting at 650 ℃ for 3 hours to obtain a spherical alumina carrier D-1, wherein the analysis results are shown in table 1, and the SEM analysis results are shown in fig. 4.
Comparative example 2
Introducing mixed gas containing 70% carbon dioxide and air by volume fraction into 3000mL sodium metaaluminate solution with the temperature of 35 ℃ and the concentration of 60gAl 2O3/L and the caustic ratio of 1.30 for reaction, reducing the pH value of the system to 4.5 within 2min, adding the slurry into a 5000mL reaction kettle with the bottom water of 800mL at the flow rate of 35mL/min at the end of the reaction, simultaneously adding 200gAl 2O3/L sodium metaaluminate solution with the caustic ratio of 1.50 in parallel flow for reaction, controlling the reaction temperature to 55 ℃ and the reaction pH value to be 9.0 constantly, aging for 90min at the end of the reaction, washing with deionized water at 70 ℃ and filtering to obtain the pseudo-boehmite filter cake with the alumina mass content of 40%.
Taking 250g of the pseudo-boehmite filter cake, adding deionized water, stirring and pulping uniformly, then adding 10g of 65% nitric acid solution for peptization, and finally preparing aluminum hydroxide sol with the mass content of aluminum oxide being 32%;
30g of hexamethylene tetramine solution with the mass concentration of 35%, 1.0g of polyoxyethylene sorbitan monolaurate (Tween 20) with the HLB value of 16.7 and 10g of white oil are sequentially added into the aluminum hydroxide sol, deionized water is added to adjust the stirring revolution to 3500 revolutions per minute for stirring, and the content of alumina in the finally prepared oil-in-water (O/W) emulsion is 22%.
The oil-in-water (O/W) emulsion is dripped into white oil with the kinematic viscosity of 30mm 2/s at 40 ℃ and the temperature of 97 ℃ by a dripper with the inner diameter of 0.8mm for molding, and the molding material is prepared by petroleum ether and absolute ethyl alcohol according to the volume ratio of 1:1, removing medium oil of the molding materials, washing with deionized water at 85 ℃, drying at 130 ℃ for 8 hours, and roasting at 650 ℃ for 3 hours to obtain a spherical alumina carrier D-2, wherein the analysis results are shown in table 1, and the SEM analysis results are shown in figure 5.
Comparative example 3
Introducing mixed gas containing 70% carbon dioxide and air by volume percent into 3000mL sodium metaaluminate solution with the temperature of 35 ℃ and the concentration of 60gAl 2O3/L and the caustic ratio of 1.30, reacting, finishing the reaction when the pH value of the system is reduced to 9.0, aging the slurry at 90 ℃ for 90min, washing with deionized water at 70 ℃ and filtering to obtain the pseudo-boehmite filter cake with the alumina mass content of 40%.
Taking 250g of the pseudo-boehmite filter cake, adding deionized water, stirring and pulping uniformly, then adding 10g of nitric acid solution with the mass concentration of 65% for peptization, and finally preparing aluminum hydroxide sol with the alumina content of 32%;
30g of hexamethylene tetramine solution with the mass concentration of 35%, 1.0g of polyoxyethylene sorbitan monolaurate (Tween 20) with the HLB value of 16.7, 0.5g of 1, 3-propylene glycol and 10g of white oil are sequentially added into the aluminum hydroxide sol, deionized water is added to adjust the stirring revolution to 3500 revolutions per minute for stirring, and the mass content of alumina in the finally prepared oil-in-water (O/W) emulsion is 22%.
The oil-in-water (O/W) emulsion is dripped into white oil with the kinematic viscosity of 30mm 2/s at 40 ℃ and the temperature of 97 ℃ by a dripper with the inner diameter of 0.8mm for molding, and the molding material is prepared by petroleum ether and absolute ethyl alcohol according to the volume ratio of 1:1, removing medium oil of the molding materials, washing with deionized water at 85 ℃, drying at 130 ℃ for 8 hours, and roasting at 650 ℃ for 3 hours to obtain a spherical alumina carrier D-3, wherein the analysis results are shown in table 1, and the SEM analysis results are shown in figure 6.
TABLE 1 physicochemical Properties of spherical alumina Carrier
Numbering device A-1 A-2 A-3 A-4 A-5 D-1 D-2 D-3
Particle diameter, mm 1.71 1.71 1.71 1.71 1.91 1.71 1.71 1.71
Specific surface area, m 2/g 195 185 191 193 182 192 194 150
Pore volume, mL/g 0.853 0.792 0.849 0.851 0.785 0.851 0.839 0.621
Pore size distribution, percent
＜10nm 4.2 4.3 4.2 4.4 4.1 7.3 4.4 21.2
＞20nm 7.2 7.1 7.4 6.9 7.4 6.7 9.7 11.8
Bulk density, g/mL 0.630 0.655 0.631 0.628 0.675 0.980 0.630 0.715
Crush strength, N/grain 57 68 61 60 67 118 45 31
The volume of the cavity is% 26.2 26.4 26.1 26.0 12.0 0 25.1 26.1

Claims (9)

1. A method for preparing a spherical alumina carrier, comprising the following steps:
(1) Preparing a pseudo-boehmite filter cake by a carbonization method;
(2) Adding water into the filter cake obtained in the step (1) to prepare slurry, and then adding a peptizing agent to carry out peptization to obtain aluminum hydroxide sol;
(3) Adding a curing agent solution, an emulsifying agent, a polyol and an organic phase into the aluminum hydroxide sol obtained in the step (2) respectively, and adding water into the mixture under stirring to prepare an oil-in-water emulsion;
(4) The oil-in-water emulsion obtained in the step (3) is dripped into an oil column for molding, washing, drying and roasting to obtain the carrier;
Wherein in the step (3), the curing agent solution is one or more of hexamethylene tetramine solution and urea solution; the emulsifier is at least one selected from polyoxyethylene sorbitan monolaurate and fatty alcohol polyoxyethylene ether; the hydrophilic-lipophilic balance value of the emulsifier is 13-20;
the pseudo-boehmite filter cake method prepared by the carbonization method comprises the following steps:
(a) Respectively preparing a first aluminum-containing alkaline solution A and a second aluminum-containing alkaline solution B with two different alumina concentrations;
(b) Introducing mixed gas containing carbon dioxide into the first aluminum-containing alkaline solution A for reaction until the pH value is 4-5, and obtaining slurry;
(c) Adding bottom water into a reaction kettle, heating to the reaction temperature, adding the slurry obtained in the step (B) and a second aluminum-containing alkaline solution B into the reaction kettle in parallel flow for reaction, aging after the reaction is finished, and washing and filtering to obtain a pseudo-boehmite filter cake;
in the step (c), the temperature of the parallel flow reaction is 40-70 ℃, and the pH value of the reaction is controlled to be 8.5-9.0.
2. The preparation method according to claim 1, wherein in the step (2), the addition amount of the peptizing agent is 1% to 10% by mass of Al 2O3%; the mass content of alumina in the aluminum hydroxide sol is 30-35%.
3. The method according to claim 1, wherein in the step (3), the mass concentration of the curing agent solution is 30% to 50%; the adding amount of the curing agent is 1-15% of the mass of alumina in the aluminum hydroxide sol; the addition amount of the emulsifier is 0.2-2.0% of the mass of the alumina.
4. The preparation method according to claim 1, wherein in the step (3), the polyol is one or more of 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-propanediol, 1-pentanol and polyethylene glycol 400, and the addition amount of the polyol is 0.1% -1.0% of the mass of alumina in the aluminum hydroxide sol; the organic phase is one or more of white oil or diesel oil; the addition amount of the organic phase is 7.0-13.0% of the mass of the alumina in the aluminum hydroxide sol.
5. The method according to claim 1, wherein in the step (4), the medium oil used in the oil column is one of white oil and diesel oil; the molding temperature is 90-110 ℃.
6. The method according to claim 1, wherein in the step (4), the medium oil used in the oil column is white oil, and the kinematic viscosity of the white oil at 40 ℃ is 20-40 mm 2/s; the molding temperature is 95-105 ℃.
7. The process according to claim 1, wherein in step (4), the molding is carried out in an oil column, and the oil-in-water emulsion of step (3) is dropped into the oil column with a dripper having an inner diameter of 0.4mm to 2.0mm.
8. The spherical alumina carrier obtained by the preparation method according to any one of claims 1 to 7,
The spherical alumina carrier is characterized by comprising the following properties: pore volume >0.65mL/g; specific surface area >170m 2/g; pore distribution: the pore volume of the pores with the pore diameter smaller than 10nm accounts for less than 5.0 percent of the total pore volume, and the pore volume of the pores with the pore diameter larger than 20nm accounts for less than 8.0 percent of the total pore volume.
9. The spherical alumina carrier of claim 8, wherein the properties of the spherical alumina carrier further comprise: the diameter of the carrier particles is 1.5-2.2 mm; bulk density is 0.62-0.68 g/mL; crush strength > 45N/grain; the volume of the micro spherical cavity is 5% -30% of the volume of the carrier.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1250746A (en) * 1998-10-13 2000-04-19 中国石油化工集团公司 Process for preparing artificial diasporite and gamma-alumina
KR20030062164A (en) * 2002-01-16 2003-07-23 함영민 Process for preparation of alumina powder by using the w/o emulsion method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1250746A (en) * 1998-10-13 2000-04-19 中国石油化工集团公司 Process for preparing artificial diasporite and gamma-alumina
KR20030062164A (en) * 2002-01-16 2003-07-23 함영민 Process for preparation of alumina powder by using the w/o emulsion method

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