WO2010013428A1 - Procédé de production de poly(hydrate) de sel d'acide monobasique d'aluminium inorganique et/ou de sol aqueux d'alumine, et sel d'acide monobasique d'aluminium inorganique et/ou sol aqueux d'alumine ainsi obtenus - Google Patents

Procédé de production de poly(hydrate) de sel d'acide monobasique d'aluminium inorganique et/ou de sol aqueux d'alumine, et sel d'acide monobasique d'aluminium inorganique et/ou sol aqueux d'alumine ainsi obtenus Download PDF

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WO2010013428A1
WO2010013428A1 PCT/JP2009/003498 JP2009003498W WO2010013428A1 WO 2010013428 A1 WO2010013428 A1 WO 2010013428A1 JP 2009003498 W JP2009003498 W JP 2009003498W WO 2010013428 A1 WO2010013428 A1 WO 2010013428A1
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alumina
aqueous
alumina sol
monobasic
inorganic
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PCT/JP2009/003498
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English (en)
Japanese (ja)
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佐藤護郎
佐藤正淳
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サトーリサーチ株式会社
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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
    • C01F7/66—Nitrates, with or without other cations besides aluminium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • 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
    • C01F7/447—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes
    • C01F7/448—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes using superatmospheric pressure, e.g. hydrothermal conversion of gibbsite into boehmite
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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

Definitions

  • the present invention relates to a method for producing a polyinorganic monobasic aluminum hydrate and an aqueous alumina sol by performing hydrothermal reaction using alumina having a ⁇ - and ⁇ - crystal structure, and a polycrystal obtained by the production method. It relates to inorganic monobasic aluminum hydrate and / or aqueous alumina sol. In particular, the present invention relates to a method for producing an aqueous alumina sol having a plurality of specific particle shapes.
  • Polyinorganic monobasic aluminum hydrate and aqueous alumina sol are used as a ceramic binder.
  • an aqueous alumina sol having a high surface area can be used as a binder functional material of a catalyst as a matrix of a zeolite of an R-FCC catalyst for producing gasoline.
  • Patent Document 1 discloses an FCC catalyst composed of 70% zeolite and 30% alumina sol, and an FCC catalyst composed of 70% zeolite and 30% silica sol.
  • Patent Document 2 uses FCC catalyst mixed with catalyst A and catalyst B, and catalyst B is 1 to 30 wt% zeolite, 10 to 70 wt% alumina, 5 to 30 wt% silica, And a residual kaolin composition, and the alumina component is described as an acidic boehmite suspension.
  • the poly aluminum hydrochloride hydrate is manufactured from aluminum hydroxide or aluminum metal as a raw material.
  • polyaluminum nitrate hydrate cannot be produced by the same method, and an example of synthesizing from other raw materials is disclosed in Patent Document 3, but polyaluminum nitrate hydrate produced by the synthesis method of the described example is disclosed. Is impractical and difficult to commercialize.
  • Patent Document 4 describes a method for obtaining a boehmite suspension by hydrothermal reaction using alumina having inorganic ⁇ - and ⁇ - crystal structures obtained by rapid thermal dehydration and inorganic monobasic acid. ing.
  • Patent Document 4 describes the characteristics of products obtained by converting raw materials to boehmite for 18 examples using nitric acid, and the higher the conversion rate as judged from the numerical value of the specific surface area.
  • the specific surface area of the produced boehmite is reduced.
  • the conversion rate of boehmite is at most 80%, which is insufficient from an industrial viewpoint.
  • Patent Document 5 filed by the present inventor, an alumina raw material having a ⁇ - and ⁇ - crystal structure is subjected to a hydrothermal reaction in the presence of an acid, and a catalyst is obtained via an alumina sol in which fibrous alumina particles are monodispersed.
  • a method for producing alumina for use in the field is disclosed.
  • alumina having a high specific surface area can be obtained, there is a problem that the manufacturing takes a long time.
  • Patent Document 6 of the present inventor discloses a method of adding an oxygen-containing organic compound or a polyvalent inorganic acid to an alumina raw material such as acid-containing aluminum hydroxide or alumina having a ⁇ - and ⁇ -crystal structure.
  • an alumina raw material such as acid-containing aluminum hydroxide or alumina having a ⁇ - and ⁇ -crystal structure.
  • this method is not suitable as a binder because it is easy to form a gel and it is difficult to obtain an aqueous alumina sol, and the resulting boehmite particles are associated with additives and are not sticky.
  • silica sol or the like was used as a matrix for a catalytic cracking catalyst for gasoline production in the oil refining industry, but the poisoning resistance of nickel and vanadium contained in feed oil is high, and the binder There is a need for a powerful alumina matrix.
  • an object of the present invention is to provide a poly inorganic monobasic aluminum hydrate and / or an aqueous alumina sol having a high conversion rate of raw material alumina to a target product and high performance as a binder.
  • the present inventors have used raw material alumina having a ⁇ - and ⁇ - crystal structure having a specific average particle size (D 50 ) or less and aged under specific conditions.
  • the inventors have found that the above-described problems can be solved by a novel production method in which a hydrothermal reaction is performed, and the present invention has been achieved.
  • the present invention relates to the following inventions.
  • ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the alumina having the ⁇ - and ⁇ - crystal structures is obtained by wet pulverization in the presence of water and an inorganic monobasic acid or a salt thereof.
  • the inorganic monobasic acid / alumina molar ratio of the adjustment liquid is in the range of 0.5 to 2.0, and is subjected to aging and / or hydrothermal reaction at a temperature of 40 ° C. or more and less than 130 ° C.
  • the inorganic monobasic acid / alumina molar ratio of the adjustment liquid is in the range of 0.03 or more and less than 0.5, and is subjected to aging and / or hydrothermal reaction at a temperature of 40 ° C. or more and less than 130 ° C.
  • the inorganic monobasic acid / alumina molar ratio of the adjustment liquid is in the range of 0.03 to 0.5, and the hydrothermal reaction is performed at a temperature of 130 ° C. to 250 ° C. to obtain an aqueous alumina sol ⁇ 1> to the manufacturing method of the poly inorganic monobasic-acid aluminum hydrate and / or aqueous
  • k (b / a) ⁇ (b / c) (Wherein, a is the number of moles of alumina in the adjustment solution converted to Al 2 O 3 , b is the number of moles of inorganic monobasic acid or salt thereof, and c is the number of moles of water) ⁇ 9>
  • k (b / a) ⁇ (b / c) (Wherein, a is the number of moles of alumina in the adjustment solution converted to Al 2 O 3 , b is the number of moles of inorganic monobasic acid or salt thereof, and c is the number of moles of water) ⁇ 10>
  • k (b / a) ⁇ (b / c) (Wherein, a is the number of moles of alumina in the adjustment solution converted to Al 2 O 3 , b is the number of moles of inorganic monobasic acid or salt thereof, and c is the number of moles of water) ⁇ 11>
  • k (b / a) ⁇ (b / c) (Wherein, a is the number of moles of alumina in the adjustment solution converted to Al 2 O 3 , b is the number of moles of inorganic monobasic acid or salt thereof, and c is the number of moles of water) ⁇ 12>
  • k (b / a) ⁇ (b / c) (Wherein, a is the number of moles of alumina in the adjustment solution converted to Al 2 O 3 , b is the number of moles of inorganic monobasic acid or salt thereof, and c is the number of moles of water) ⁇ 13>
  • the pore volume of the poly inorganic monobasic aluminum hydrate and / or aqueous alumina sol after firing at 550 ° C. for 2 hours is 0.40 mL / g or less, and the average pore diameter is 100 ⁇ m or less.
  • the method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous alumina sol according to any one of ⁇ 8> to ⁇ 12>, wherein ⁇ 14> The method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous alumina sol according to any one of ⁇ 1> to ⁇ 13>, wherein the inorganic monobasic acid is nitric acid.
  • ⁇ 15> A polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol produced by the method according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 16> An R-FCC catalyst using the aqueous alumina sol obtained by the production method according to any one of ⁇ 8> to ⁇ 15> as a binder.
  • the polyinorganic monobasic aluminum hydrate, aqueous alumina sol, or a mixture thereof obtained by the method of the present invention has a high binder strength, and when used as a binder in a powder molded product, has extremely high hardness.
  • the aqueous alumina sol produced by the method of the present invention has excellent binder power, and is used as a binder for various catalytic matrices and adsorbents such as catalytic cracking catalysts (R-FCC catalysts) for gasoline production in the petroleum refining industry. Or a heat-resistant adhesive.
  • FIG. 8 It is a figure which shows the production
  • the present invention comprises alumina having a ⁇ - and ⁇ - crystal structure with an average particle size (D 50 ) of 5 ⁇ m or less, water, and an inorganic monobasic acid or a salt thereof, and has an inorganic monobasic acid / alumina molar ratio of 0.03.
  • a polyinorganic monobase characterized by aging and / or hydrothermal reaction of an adjustment solution in which the alumina concentration is adjusted in the range of 3 wt% to 50 wt% in the range of 40 ° C. to 250 ° C.
  • the present invention relates to a method for producing aluminum acid hydrate and / or aqueous alumina sol (hereinafter sometimes referred to as “production method of the present invention”).
  • the average particle diameter (D 50 ) referred to in the present invention (hereinafter sometimes simply referred to as “average particle diameter”) can be measured using, for example, a laser diffraction / scattering particle size distribution analyzer.
  • the aqueous alumina sol in the present invention means an alumina sol comprising crystalline boehmite produced from alumina having ⁇ - and ⁇ - crystal structures using H + as a catalyst.
  • the alumina concentration is a ratio (% by weight) of alumina (in terms of Al 2 O 3 ) when the weight of the whole adjustment liquid is 100.
  • aging means holding the adjustment liquid at a temperature of less than 60 ° C.
  • hydrothermal reaction also referred to as “hydrothermal synthesis” means that the adjustment liquid remains sealed in a container. It is defined as heating at 60 ° C. or higher.
  • the raw material has an average particle diameter (D 50 ) of 5 ⁇ m or less as alumina having a ⁇ - and ⁇ - crystal structure (hereinafter sometimes referred to as “raw material alumina”).
  • the use of alumina is considered to be produced from raw alumina by the following mechanism. That is, the surface of the alumina raw material having a ⁇ - and ⁇ - crystal structure is dissolved by the reaction of water and H + ions derived from an inorganic monobasic acid, and various polymonobasic acids having different molecular weights from the surface of the alumina raw material powder.
  • boehmite nuclei are generated by collision or stimulation (electrical or mechanical) between dissolved molecules of polymonobasic aluminum hydrate.
  • H + ions are by-produced. It is known that boehmite nuclei have three different crystal planes: an a axis (bc plane), a b axis (ac plane with a wall opening), and a c axis (ab plane).
  • the by-produced H + ions dissolve the raw material alumina again to form polymonobasic aluminum hydrate, and diffuse into the solution.
  • polymonobasic aluminum hydrate approaches the boehmite nuclei even at a concentration below the saturation solubility, coordinates to a specific position of the nucleus, and then electrostatic bonding To do.
  • the bo + ite nucleus reacts with the polymonobasic aluminum hydrate to regenerate H + ions as a by-product.
  • boehmite grows, resulting in the formation of an aqueous alumina sol.
  • the particle diameter of the raw material alumina is too large, a large amount of undissolved raw material alumina remains as a powder in addition to the product poly inorganic monobasic aluminum hydrate and / or aqueous alumina sol. Therefore, in the present invention, by limiting the raw material alumina to an average particle diameter (D 50 ) of 5 ⁇ m or less, the unreacted raw material alumina is substantially eliminated, and even when it remains, it has a very small diameter. The quality of the intended product is not impaired. In particular, by setting the average particle diameter (D 50 ) of the raw material alumina to 1 ⁇ m or less, the reaction rate can be increased and unreacted raw material alumina in the final product can be eliminated.
  • the pulverization of the raw material alumina may be either dry pulverization or wet pulverization as long as the average particle diameter (D 50 ) of the raw material alumina can be 5 ⁇ m or less (preferably 1 ⁇ m or less).
  • wet pulverization is preferred in that the wet cake after washing the Na component can be used without drying.
  • wet pulverization of raw material alumina in the presence of water and an inorganic monobasic acid or a salt thereof is preferable because the inorganic monobasic acid penetrates into the raw material alumina and promotes the reaction. In this case, since the reaction of the raw material alumina is promoted, the raw material alumina is sufficiently dissolved even when the average particle diameter (D 50 ) is more than 1 ⁇ m and not more than 5 ⁇ m.
  • the production method of the present invention it is preferable to wet pulverize raw material alumina in the presence of an inorganic monobasic acid or a salt thereof.
  • a slurry in which a predetermined amount of raw material alumina, water and an inorganic monobasic acid are mixed is prepared.
  • this is supplied to a wet pulverizer.
  • the inorganic monobasic acid may be added in a predetermined amount from the beginning, or initially prepared to be less than the predetermined amount, and after the pulverization is started, the remaining acid may be added.
  • the viscosity of the slurry in the pulverizer may increase, but the pH value of the slurry is maintained at 5.5 or lower, or diluted with water, and the viscosity is suppressed to less than 100 mPa ⁇ s. Grinding can be continued.
  • a wet pulverizer with forced stirring is preferably used.
  • the slurry can be separated into two phases by a two-phase separation type centrifuge during the wet pulverization, and the pulverization can be performed again after separating the small particle portion.
  • unreacted raw material alumina may remain as relatively large particles (coarse particles). Separation of coarse unreacted material of such raw material alumina can be performed at a high speed of 8000-9000 revolutions / minute using a high-speed rotating centrifuge, and the alumina concentration is about 15% in order to increase the separation speed. Is preferable.
  • aqueous alumina sol having a low molar ratio of inorganic monobasic acid / alumina
  • the viscosity of the wet grinding liquid Increases, the pulverized liquid is hardened, and the pulverization operation becomes difficult.
  • the viscosity can be lowered by diluting with water, but there are problems that the pulverization efficiency is reduced by dilution and the concentration of the produced alumina sol is reduced.
  • the inorganic monobasic acid / alumina molar ratio in the wet pulverization process is performed in a stable composition region of 0.10 or more, and the inorganic monobasic acid / alumina molar ratio readjustment process is performed after the pulverization process is completed.
  • an excess of inorganic monobasic acid is 1. Neutralization by adding alkaline components such as ammonia, or 2. Neutralization by addition of alumina having ⁇ - and ⁇ - crystal structure obtained by dry grinding, or It can be removed by a method such as adsorption / desorption with an anion exchange resin for nitric acid.
  • the raw material alumina used in the production method of the present invention is alumina having a ⁇ - and ⁇ - crystal structure, and this raw material alumina is usually dehydrated by rapidly heating aluminum hydroxide in a hot air stream. Can be obtained.
  • Aluminum hydroxide is usually produced by the Bayer method, but ⁇ - and ⁇ - produced by rapid heating and dehydration of aluminum hydroxide (Bauxite Ore Concentration) produced by the Bayer method at about 1000 ° C.
  • Alumina having a crystal structure often contains about 0.25% by weight of Na 2 O as an impurity. Therefore, when using aluminum hydroxide produced by the Bayer method, it is preferable to reduce the Na concentration by washing in advance. Na can be reduced to about 0.06% by weight as Na by filtering and washing with acidic water containing carbonic acid.
  • the inorganic monobasic acid examples include hydrochloric acid and nitric acid, and nitric acid is preferably used.
  • a salt of an inorganic monobasic acid such as aluminum nitrate can also be used.
  • the inorganic monobasic acid / alumina molar ratio can be adjusted by mixing the powder comprising the raw material alumina with water and / or an inorganic monobasic acid or a salt thereof (which may be accompanied by wet pulverization).
  • An adjustment liquid adjusted to 0.03 to 2.0 (preferably 0.05 to 1.5) and alumina concentration in the range of 3% to 50% by weight (preferably 5% to 40% by weight).
  • the target product can be obtained by aging and / or hydrothermally reacting this adjustment liquid in the range of 40 ° C to 250 ° C.
  • the alumina concentration is less than 3% by weight, the concentration of the resulting product is too small, and extra cost is required for concentration. If it exceeds 50% by weight, the concentration is too high, Product handling becomes difficult.
  • the raw material alumina can be converted into a product with high efficiency. It can be converted.
  • the conversion rate depends on the reaction time, from the industrial viewpoint, the conversion rate of the product is preferably 90% or more, particularly preferably 95% or more.
  • the product obtained depends on the concentration of raw material alumina, water, inorganic acid or a salt thereof, and the temperature of aging and / or hydrothermal reaction.
  • the molar ratio of the inorganic monobasic acid / alumina in the adjustment liquid is in the range of 0.5 or more and 2.0 or less, and aging and / or hydrothermal reaction is performed at a temperature of 40 ° C. or more and less than 130 ° C.
  • Aluminum basic acid hydrate can be obtained.
  • the molar ratio of the inorganic monobasic acid / alumina in the adjustment liquid is in the range of 0.03 or more and less than 0.5, and aging and / or hydrothermal reaction is performed at a temperature of 40 ° C. or more and less than 130 ° C.
  • a mixture of aluminum basic acid hydrate and aqueous alumina sol can be obtained.
  • the molar ratio of the inorganic monobasic acid / alumina in the adjustment liquid is in the range of 0.03 or more and 0.5 or less, and a hydrothermal reaction is performed at a temperature of 130 ° C. or more and 250 ° C. or less to obtain an aqueous alumina sol. .
  • the shape of the aqueous alumina sol depends on the k value determined by the above formula (1) from the concentrations of the raw material alumina, water, inorganic acid or salt thereof. That is, if the k value of the adjustment liquid is in the composition range of 0.000005 ⁇ k ⁇ 0.03, and the temperature of aging and / or hydrothermal reaction is 130 ° C. or higher and 250 ° C. or lower, the aqueous alumina sol is a plate-like product. An aqueous alumina sol having a tape-like or fibrous particle shape is formed. In addition, it is preferable that the temperature of hydrothermal reaction is 160 degreeC or more and 250 degrees C or less, and aqueous alumina sol can be efficiently manufactured as it is this range.
  • the plate-like particle shape means that the a-axis (bc surface) and b-axis (ac surface) in boehmite are grown with an equal bonding force
  • the tape-like particle shape means the a-axis (in the boehmite) bc-plane) and co-grown with b-axis (ac-plane) with weak bonding force
  • the fibrous particle shape is strongly coordinated with a-axis (bc-plane) in boehmite Estimated.
  • Each specific shape is shown in the electron micrograph in the Example mentioned later.
  • the k value of the adjustment liquid is preferably within a composition range of 0.000005 ⁇ k ⁇ 0.0005
  • the k value of the adjustment liquid is preferably in the composition range of 0.0005 ⁇ k ⁇ 0.0015, and in terms of obtaining an aqueous alumina sol having mainly a fibrous particle shape, adjustment is performed.
  • the k value of the liquid is preferably in the composition range of 0.0015 ⁇ k ⁇ 0.03.
  • FIG. 1 shows a region where aqueous alumina sol having various particle shapes is formed.
  • the polyinorganic monobasic aluminum hydrate and aqueous alumina sol which are the products of the present invention, are also suitably used as binders for molded products such as catalysts and adsorbents after drying and firing. Moreover, it is used suitably as binders, such as a heat resistant adhesive agent.
  • the pore volume and average pore diameter after firing the polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol after heat treatment at a specific temperature can be used as indices.
  • the pore volume of the polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol of the present invention is 0.40 mL / g or less (especially 0.35 mL / g or less) after calcination at 550 ° C. for 2 hours. It is preferable that the average pore diameter is 100 ⁇ or less (particularly 75 ⁇ or less) because a particularly strong binder force can be obtained.
  • the aqueous alumina sol is particularly preferably used as a binder for R-FCC catalysts.
  • the R-FCC catalyst zeolite loses its activity due to poisoning of nickel and vanadium contained in the feed oil, but alumina is effective as its passivator. Therefore, when the product according to the production method of the present invention is used as a binder for an R-FCC catalyst, not only the aqueous alumina sol according to the present invention but also various characteristics such as the catalytic activity of the R-FCC catalyst are not impaired.
  • Poly inorganic aluminum monobasic acid hydrate or raw material alumina may be contained which has alumina having ⁇ - and ⁇ - crystal structures.
  • each measuring method is as follows.
  • Conversion rate 100 g of a product sample diluted to an alumina concentration of 1.0% by weight is placed in a 100 ml beaker and allowed to stand for 20 hours. After standing, the sediment is collected, the weight of the residue after heating is weighed, and the conversion rate of the measurement sample is calculated.
  • Centrifugal sediment 5 ml of a sample diluted to an alumina concentration of 1% by weight is collected in a centrifugal sedimentation tube of a centrifuge and measured for the amount of sediment after operating at 3000 rpm for 5 minutes.
  • Specific surface area A sample to be measured is dried at 200 ° C. and then measured by a nitrogen gas adsorption method.
  • Pore volume and average pore diameter A pore having a pore diameter of 40 to 10,000 mm is measured by a mercury intrusion method. (5) Average particle diameter (D 50 ) (weight average particle diameter) Measured with a laser diffraction / scattering particle size distribution analyzer (MT3300 manufactured by Nikkiso Co., Ltd.). (6) Compressive strength Measure the strength of the side surfaces of 200 cylindrical molded products with a Kiya-type compressive strength measuring device, and determine the average value. (7) Shape of Product A polyinorganic monobasic aluminum hydrate and an aqueous alumina sol dried at 200 ° C. were evaluated using a transmission microscope (manufactured by Hitachi, Ltd., model number: H-9000NAR).
  • Example 1 1200 g of alumina having a ⁇ - and ⁇ - crystal structure with an average particle size (D 50 ) of 15 ⁇ m was added to an aqueous nitric acid solution to prepare a slurry having an alumina concentration of 21% by weight and a nitric acid / alumina molar ratio of 0.15.
  • the slurry was supplied to a wet pulverizer with forced agitation using 0.3 mm zirconia beads and pulverized.
  • nitric acid was additionally added to adjust the pH of the slurry, and the pulverization was continued while maintaining the pH below 5.
  • the crushed slurry had an average particle diameter (D 50 ) of 0.11 ⁇ m, an alumina concentration of 20% by weight, a nitric acid / alumina molar ratio of 0.20, and a k value of 0.0018.
  • Nitric acid was added to 1000 g of the slurry to prepare an adjustment solution having an alumina concentration of 19.3% by weight, a nitric acid / alumina molar ratio of 0.40, and a k value of 0.0072.
  • this adjustment liquid As a result of hydrothermal reaction of this adjustment liquid at 98 ° C. for 14 hours, the conversion rate of the raw material alumina was 99.5%, and the centrifugal sediment was 2.6%.
  • Table 1 shows the specific surface area of the dried product at 200 ° C and the pore volume of the heat-treated product at 850 ° C for 5 hours.
  • USY zeolite, kaolin and the product of this example were kneaded at a weight ratio of 30/40/30 based on oxides, molded with a piston-type extruder, dried and then fired at 850 ° C. for 5 hours.
  • Table 1 also shows the diameter, pore structure, and side compression strength of the obtained cylindrical molded body.
  • Example 2 Nitric acid was added to 1000 g of the slurry obtained in Example 1, and an adjustment liquid having an alumina concentration of 17.4% by weight, a nitric acid / alumina molar ratio of 1.00, and a k value of 0.043 was prepared. As a result of hydrothermal reaction of this adjusted liquid at 98 ° C. for 14 hours, the conversion rate of the raw material alumina was 99.5%, and the centrifugal sediment was 3.8%. Table 1 shows the specific surface area of the dried product at 200 ° C and the pore volume of the heat-treated product at 850 ° C for 5 hours.
  • the main product is presumed to be polyinorganic monobasic aluminum hydrate from the fact that few alumina particles are observed and the properties of the 200 ° C. dried product.
  • Table 1 shows the pore structure and compressive strength of the molded product similar to Example 1.
  • Comparative Example 1 The specific surface area of a 200 ° C. dry product of alumina sol (trade name: Cataloid-AP) composed of pseudoboehmite, which is considered to have an excellent binder function among commercially available alumina sols, and the pore volume of the heat-treated product at 850 ° C. for 5 hours. The results are shown in Table 1. Table 1 shows the results of molding the same molded product as in Example 1 and measuring its pore structure and compressive strength.
  • Example 3 Alumina having an average particle size (D 50 ) of 15 ⁇ m and having a ⁇ and ⁇ crystal structure was dry-pulverized by a swirling force of air to prepare an alumina powder having an average particle size (D 50 ) of 0.7 ⁇ m. 500 g of this alumina powder was added to an aqueous nitric acid solution to prepare an adjustment solution having an alumina concentration of 20% by weight, a nitric acid / alumina molar ratio of 0.15, and a k value of 0.0010. As a result of hydrothermal reaction of this adjustment liquid at 140 ° C. for 14 hours, the conversion rate of raw material alumina was 96.3%, and the centrifugal sediment was 3.8%. According to electron microscope observation of this product, it was an aqueous alumina sol in which fibrous particles and plate-like particles were mixed, and the specific surface area of the 200 ° C. dried product was 290 m 2 / g.
  • Example 4 500 g of alumina having a ⁇ - and ⁇ - crystal structure with an average particle diameter (D 50 ) of 15 ⁇ m was added to an aqueous nitric acid solution, the alumina concentration was 30% by weight, the nitric acid / alumina molar ratio was 0.15, and the k value was 0.1.
  • a slurry of 00177 was prepared. This slurry was supplied to a 3.6 L magnetic pot mill, and 5 kg of 10 mm zirconia beads were inserted and wet pulverized for 68 hours. The average particle diameter (D 50 ) of the alumina after pulverization was 1.6 ⁇ m.
  • D 50 average particle diameter
  • the conversion rate of the raw material alumina was 96.5%
  • the product was an aqueous alumina sol mainly composed of fibrous particles according to electron microscope observation.
  • the specific surface area of the dried product at 200 ° C. was 310 m 2 / g.
  • Example 5 600 g of aluminum hydroxide having an average particle size (D 50 ) of 12.8 ⁇ m was added to an aqueous nitric acid solution to prepare a slurry having an alumina concentration of 20% by weight and a nitric acid / alumina molar ratio of 1.00. This slurry was supplied to a wet pulverizer with forced stirring and finely pulverized until the average particle size (D 50 ) became 1.4 ⁇ m. This was used as an adjustment solution, and after hydrothermal reaction at 98 ° C.
  • the conversion rate of the raw material alumina was 95.8%
  • the centrifugal sediment was 39.8%
  • a cloudy, viscous aqueous alumina sol and A gel was obtained. Since the specific surface area of the 200 ° C. dried product was 0 m 2 / g, it was estimated that polyaluminum nitrate hydrate was also contained.
  • Example 6 500 g of alumina having a ⁇ - and ⁇ - crystal structure with an average particle size (D 50 ) of 15 ⁇ m was added to an aqueous hydrochloric acid solution, the alumina concentration was 20% by weight, the molar ratio of hydrochloric acid / alumina was 1.00, and the k value was 0.052.
  • a slurry was prepared. This slurry was supplied to a 3.6 L magnetic pot mill, and 5 kg of 10 mm zirconia beads were inserted and wet pulverized for 1 week. The average particle size (D 50 ) of the pulverized alumina was 0.7 ⁇ m.
  • Example 7 Alumina having a ⁇ - and ⁇ - crystal structure with an average particle size (D 50 ) of 15 ⁇ m (hereinafter referred to as “raw alumina”) was added to an aqueous nitric acid solution, the alumina concentration was 12.5% by weight, and the nitric acid / alumina mole. A slurry with a ratio of 0.06 was prepared. This slurry was supplied to a wet pulverizer with forced stirring using 0.3 mm zirconia beads and wet pulverized for 1 hour 30 minutes. The slurry after pulverization had an average particle size (D 50 ) of 0.3 ⁇ m.
  • Example 8 The same raw material as in Example 7 was used, and a slurry having an alumina concentration of 15% by weight and a nitric acid / alumina molar ratio of 0.088 was prepared.
  • the raw material alumina was finely pulverized in the same manner as in Example 7 except that the pulverization time was 3 hours.
  • the slurry after pulverization had an average particle size (D 50 ) of 0.2 ⁇ m. Water was added to the obtained pulverized liquid so that the concentration of the alumina component was 12.5% and the k value was 0.000020, a part of which was inserted into a stainless steel 1-inch gas pipe, In addition, a hydrothermal reaction was performed by heating at 140 ° C.
  • FIG. 3 shows a pore size distribution diagram of the aqueous alumina sol by a mercury intrusion method for a product fired at 550 ° C. for 2 hours.
  • Table 3 shows the pore volume and average pore diameter determined from the pore size distribution chart.
  • Example 9 The same raw material alumina as in Example 7 was used to prepare a slurry having an alumina concentration of 25% by weight and a nitric acid / alumina molar ratio of 0.10.
  • the raw material alumina was finely pulverized while adding water to the slurry to dilute the alumina concentration to 15%.
  • the slurry after pulverization for 4 hours had an average particle diameter (D 50 ) of 0.14 ⁇ m. Water is added to the obtained pulverized liquid so that the concentration of the alumina component is 15% and the k value is 0.00045.
  • a part of the pulverized liquid is inserted into a stainless steel 1-inch gas pipe, and the temperature rise time is included in the air bath.
  • a hydrothermal reaction was carried out by heating at 140 ° C. for 14 hours to obtain an aqueous alumina sol product containing a small amount of liquid substance.
  • Table 2 shows the reaction conditions, the raw material alumina conversion rate, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • Example 10 The same raw material alumina as in Example 7 was used, and a slurry having an alumina concentration of 20% by weight and a nitric acid / alumina molar ratio of 0.12 was prepared.
  • the raw material alumina was finely pulverized in the same manner as in Example 7, except that the slurry was pulverized for 4 hours.
  • the slurry after pulverization had an average particle size (D 50 ) of 0.14 ⁇ m. Water and nitric acid were added to the pulverized liquid so that the concentration of the alumina component was 12.5%, the molar ratio of nitric acid / alumina was 0.14, and the k value was 0.00042.
  • the product was inserted into a gas pipe and subjected to a hydrothermal reaction by heating in an air bath at 140 ° C. for 14 hours including the temperature raising time to obtain a product of an aqueous alumina sol containing a trace amount of liquid substance.
  • Table 2 shows the reaction conditions, the raw material alumina conversion rate, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • Example 11 The same raw material alumina as in Example 7 was used, and a slurry having an alumina concentration of 25% by weight and a nitric acid / alumina molar ratio of 0.16 was prepared.
  • the raw material alumina was finely pulverized in the same manner as in Example 7 except that the pulverization time was 6 hours.
  • the slurry after pulverization had an average particle diameter (D 50 ) of 0.11 ⁇ m. Water was added to the pulverized liquid so that the concentration of the alumina component was 15.0%, the molar ratio of nitric acid / alumina was 0.16, and the k value was 0.00081. Then, the mixture was heated in an air bath at 140 ° C.
  • Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the shape of the product.
  • SA specific surface area
  • Table 3 shows the pore volume and average pore diameter of the aqueous alumina sol obtained from the pore diameter distribution chart of the calcinated product at 550 ° C. for 2 hours by the mercury intrusion method.
  • Example 12 A product of an aqueous alumina sol containing a small amount of liquid substance was produced in the same manner as in Example 11 except that the reaction conditions of the hydrothermal reaction were 150 ° C. and 8 hours.
  • Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • Example 13 A product of an aqueous alumina sol containing a trace amount of liquid substance was produced in the same manner as in Example 11 except that the reaction conditions of the hydrothermal reaction were 160 ° C. and 4 hours.
  • Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • Example 14 An aqueous alumina sol product containing a trace amount of liquid substance was produced in the same manner as in Example 11 except that the reaction conditions for the hydrothermal reaction were 170 ° C. and 1 hour 30 minutes.
  • Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • SA specific surface area
  • Table 3 shows the pore volume and average pore diameter of the aqueous alumina sol obtained from the pore diameter distribution chart of the calcinated product at 550 ° C. for 2 hours by the mercury intrusion method.
  • Example 15 Instead of using a stainless steel 1-inch gas pipe, a stainless steel 3 / 4-inch gas pipe is used, an oil bath is used instead of an air bath, and the reaction conditions of the hydrothermal reaction are 180 ° C. for 30 minutes.
  • a product of an aqueous alumina sol containing a small amount of liquid substance was produced.
  • Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • SA specific surface area
  • Example 16 An aqueous alumina sol product containing a trace amount of liquid substance was produced in the same manner as in Example 15 except that the reaction conditions for the hydrothermal reaction were 180 ° C. and 1 hour 30 minutes. Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • SA specific surface area
  • Example 17 An aqueous alumina sol product containing a trace amount of liquid substance was produced in the same manner as in Example 15 except that the reaction conditions for the hydrothermal reaction were 180 ° C. and 2 hours and 30 minutes. Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • SA specific surface area
  • Example 18 An aqueous alumina sol product containing a trace amount of liquid substance was produced in the same manner as in Example 15 except that the reaction conditions for the hydrothermal reaction were 200 ° C. and 6 minutes. Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • SA specific surface area
  • Example 19 An aqueous alumina sol product containing a trace amount of liquid substance was produced in the same manner as in Example 15 except that the reaction conditions of the hydrothermal reaction were 200 ° C. and 12 minutes. Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • SA specific surface area
  • Example 20 A product of an aqueous alumina sol containing a trace amount of liquid substance was produced in the same manner as in Example 15 except that the reaction conditions for the hydrothermal reaction were 220 ° C. and 2 minutes.
  • Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape.
  • SA specific surface area
  • Table 3 shows the pore volume and average pore diameter of the aqueous alumina sol obtained from the pore diameter distribution chart of the calcinated product at 550 ° C. for 2 hours by the mercury intrusion method.
  • Example 21 The raw material alumina pulverized product having an average particle diameter (D 50 ) of Example 11 of 0.11 ⁇ m was used, and nitric acid and water were added to obtain an alumina component concentration of 14.9%, a nitric acid / alumina molar ratio of 0.20, A preparation having a k value of 0.00127 was added. The adjustment liquid was inserted into a 1 inch stainless steel gas pipe, and a hydrothermal reaction was performed in an air bath at 170 ° C. for 2 hours. The results are shown in Table 2. Table 2 shows the reaction conditions, the conversion rate of the raw material alumina, the specific surface area (SA) of the 200 ° C. dry product of the aqueous alumina sol, and the product shape. A transmission micrograph is shown in FIG.
  • SA specific surface area
  • Example 22 The raw material alumina pulverized product having an average particle diameter (D 50 ) of Example 11 of 0.11 ⁇ m was used, and nitric acid and water were added to give an alumina component concentration of 14.8%, nitric acid / alumina molar ratio of 0.20, A preparation having a k value of 0.00184 was added. The adjustment liquid was inserted into a 1 inch stainless steel gas pipe, and a hydrothermal reaction was performed in an air bath at 170 ° C. for 2 hours. The results are shown in Table 2. A transmission micrograph is shown in FIG. Further, Table 3 shows the pore volume and average pore diameter of the aqueous alumina sol obtained from the pore diameter distribution chart of the calcinated product at 550 ° C. for 2 hours by the mercury intrusion method.
  • D 50 average particle diameter
  • Example 11 The raw material alumina pulverized product having an average particle diameter (D 50 ) of Example 11 of 0.11 ⁇ m was used, and nitric acid and water
  • Comparative Example 2 Raw material alumina having a ⁇ - and ⁇ - crystal structure with an average particle diameter (D 50 ) of 6.1 ⁇ m was used, the alumina concentration was 45%, the molar ratio of nitric acid / the molar ratio of alumina was 0.16, and the k value was 0.0040. As a result of performing a hydrothermal reaction at 160 ° C. for 8 hours, the product has a conversion rate as low as 85.3%, and the specific surface area of the resulting boehmite after drying at 200 ° C. is 183 m 2. A low value of / g was shown.
  • Comparative Example 3 Raw material alumina having a ⁇ - and ⁇ - crystal structure with an average particle diameter (D 50 ) of 0.7 ⁇ m was used, the alumina concentration was 15%, the molar ratio of nitric acid / the molar ratio of alumina was 0.02, and the k value was 0.000012. As a result of filling in a stainless steel pipe and hydrothermal synthesis at 150 ° C. for 8 hours, the product showed the properties of a solidified gel, and a boehmite gel showing no binder property was obtained.
  • Comparative Example 4 Using the alumina raw material of Comparative Example 3, the alumina concentration was 55%, the molar ratio of nitric acid / alumina molar ratio was 0.10, and the k value was 0.0023, which was filled into a stainless steel pipe, and hydrothermal synthesis was performed at 160 ° C. for 8 hours. As a result, the product was a hardened mass and became a material that was extremely difficult to handle.
  • Comparative Example 5 Using the wet pulverized liquid of Example 11 having an alumina concentration of 15% and a molar ratio of nitric acid / alumina molar ratio of 0.16, oxalic acid was added in an amount of 2% by weight to the alumina, and then filled in a stainless steel pipe. As a result of hydrothermal synthesis at 150 ° C. for 8 hours, a product (boehmite gel) showing the properties of the solidified gel was obtained. Table 4 shows the properties of the product. Although the product showed a relatively high specific surface area, it did not show binder properties.
  • Comparative Example 6 A product (boehmite gel) was obtained in the same manner as in Comparative Example 5 except that 2% by weight of glycolic acid was added to alumina instead of oxalic acid. Table 4 shows the properties of the product. Although the product showed a relatively high specific surface area, it did not show binder properties.
  • Comparative Example 7 A product (boehmite gel) was obtained in the same manner as in Comparative Example 5 except that citric acid was added in an amount of 2% by weight based on alumina instead of oxalic acid. Table 4 shows the properties of the product. Although the product showed a relatively high specific surface area, it did not show binder properties.
  • Comparative Example 8 A product (boehmite gel) was obtained in the same manner as in Comparative Example 5 except that phosphoric acid (P 2 O 5 ) was added in an amount of 2% by weight based on alumina instead of oxalic acid. Table 4 shows the properties of the product. Although the product showed a relatively high specific surface area, it did not show binder properties.

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Abstract

La présente invention concerne un procédé permettant de produire, à partir d'alumine constituant la matière première du procédé, un poly(hydrate) de sel d'acide monobasique d'aluminium inorganique et/ou de sol aqueux d'alumine. Ce procédé donne des produits qui constituent un liant très efficace, et présentent des structures cristallines de types ρ- et χ-. Le degré de conversion en produit final est élevé. L'invention concerne également un poly(hydrate) de sel d'acide monobasique d'aluminium inorganique et/ou un sol aqueux d'alumine qu'il est possible de produire à un degré élevé de conversion en soumettant une préparation liquide à un vieillissement et/ou à une réaction hydrothermale à une température allant de 40°C à 250°C, laquelle préparation liquide est une préparation constituée, d'une part d'une alumine présentant des structures de types ρ- et χ- et un diamètre particulaire médian (D50) n'excédant pas 5µm, d'autre part d'eau, et enfin d'un acide monobasique inorganique ou de l'un de ses sels. Dans cette préparation, le rapport molaire [acide inorganique monobasique]/[alumine] est calé entre 0,03 et 2,0, la teneur en alumine étant calée entre 3% et 50% du poids. En outre, la forme des particules du sol aqueux d'alumine peut être gérée de façon à obtenir une forme en plaque, en bande ou en fibre.
PCT/JP2009/003498 2008-07-28 2009-07-24 Procédé de production de poly(hydrate) de sel d'acide monobasique d'aluminium inorganique et/ou de sol aqueux d'alumine, et sel d'acide monobasique d'aluminium inorganique et/ou sol aqueux d'alumine ainsi obtenus WO2010013428A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659149A (zh) * 2012-02-28 2012-09-12 山东大学 单分散高纯α-Al2O3粉的制备方法
CN111233490A (zh) * 2020-02-21 2020-06-05 鞍山腾泰耐火材料有限公司 一种烧结高铝砖用铝基粘结剂及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07256100A (ja) * 1994-03-24 1995-10-09 Agency Of Ind Science & Technol 触媒燃焼用耐熱性アルミナ担体の製造法
JPH10231120A (ja) * 1996-12-20 1998-09-02 Asahi Glass Co Ltd アルミナゾル、アルミナ水和物粉末及び記録媒体
WO2001056951A1 (fr) * 2000-01-06 2001-08-09 Goro Sato Composition d'alumine, procede de preparation et utilisation associes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07256100A (ja) * 1994-03-24 1995-10-09 Agency Of Ind Science & Technol 触媒燃焼用耐熱性アルミナ担体の製造法
JPH10231120A (ja) * 1996-12-20 1998-09-02 Asahi Glass Co Ltd アルミナゾル、アルミナ水和物粉末及び記録媒体
WO2001056951A1 (fr) * 2000-01-06 2001-08-09 Goro Sato Composition d'alumine, procede de preparation et utilisation associes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659149A (zh) * 2012-02-28 2012-09-12 山东大学 单分散高纯α-Al2O3粉的制备方法
CN111233490A (zh) * 2020-02-21 2020-06-05 鞍山腾泰耐火材料有限公司 一种烧结高铝砖用铝基粘结剂及制备方法

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