WO2010013428A1 - Process for production of poly(aluminum-inorganic monobasic acid salt hydrate) and/or aqueous alumina sol, and poly(aluminum inorganic monobasic acid salt hydrate) and/or aqueous alumina sol obtained by the process - Google Patents

Process for production of poly(aluminum-inorganic monobasic acid salt hydrate) and/or aqueous alumina sol, and poly(aluminum inorganic monobasic acid salt hydrate) and/or aqueous alumina sol obtained by the process 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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French (fr)
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

A process for producing a poly(aluminum-inorganic monobasic acid salt hydrate) and/or an aqueous alumina sol which have high binder performance from a raw material alumina having ρ- and χ- crystal structures at a high degree of conversion to an objective product. A poly(aluminum-inorganic monobasic acid salt hydrate) and/or an aqueous alumina sol which have high binder performance can be produced at a high degree of conversion by subjecting a liquid preparation to aging and/or hydrothermal reaction at a temperature of 40 to 250°C, said liquid preparation being a preparation which consists of an alumina having ρ- and χ-structures and a median particle diameter (D50) of 5μm or below, water, and an inorganic monobasic acid or a salt thereof and in which the inorganic monobasic acid/alumina molar ratio is adjusted to 0.03 to 2.0 and the alumina concentration is adjusted to 3 to 50wt%.  Further, the particle shape of aqueous alumina sol can be controlled to a plate-, tape- or fiber-like shape.

Description

ポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法および該製造方法により得られたポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルMethod for producing polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol, and polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol obtained by the production method
　本発明は、ρ-およびχ-結晶構造を有するアルミナを用い、水熱反応を行うことによる、ポリ無機一塩基酸アルミニウム水和物及び水性アルミナゾルの製造する方法および該製造方法により得られたポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルに関する。特に、複数の特定粒子形状を有する水性アルミナゾルの製造方法に関するものである。 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 ρ- and χ- 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.
　ポリ無機一塩基酸アルミニウム水和物や水性アルミナゾルは、セラミック質バインダーとして用いられる。特に高表面積を有する水性アルミナゾルは触媒のバインダー機能材料として、ガソリンを製造するＲ－ＦＣＣ触媒のゼオライトのマトリックスとして用いることができる。 Polyinorganic monobasic aluminum hydrate and aqueous alumina sol are used as a ceramic binder. In particular, 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.
　例えば、特許文献１には、７０％のゼオライトと３０％のアルミナゾルからなるＦＣＣ触媒と、７０％のゼオライトと３０％のシリカゾルからなるＦＣＣ触媒が開示されている。 For example, 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.
　また、特許文献２には、ＦＣＣ触媒に触媒Ａと触媒Ｂを混合して使用し、触媒Ｂは1～３０重量％のゼオライト、１０～７０重量％のアルミナ、５～３０重量％のシリカ、及び残余カオリン組成を提案しており、アルミナ成分は酸性ベーマイト懸濁液の記載がある。 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.
　ところで、ポリ無機一塩基酸アルミニウム水和物の中で、ポリ塩酸アルミニウム水和物に関しては原料に水酸化アルミニウムやアルミニウム金属から製造している。しかしながら、ポリ硝酸アルミニウム水和物は同様な方法で製造できず、他原料から合成を試みた例が特許文献３で開示されているが、記載例の合成方法で作製したポリ硝酸アルミニウム水和物は不純分を含み商品化することは困難である。 By the way, among the poly inorganic monobasic aluminum hydrates, the poly aluminum hydrochloride hydrate is manufactured from aluminum hydroxide or aluminum metal as a raw material. However, 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.
　一方、水酸化アルミニウムを急速加熱脱水で得られるρ-およびχ-結晶構造を有するアルミナと無機一塩基酸を用い、水熱反応させてベーマイトの懸濁液を得る方法が特許文献４に記載されている。 On the other hand, Patent Document 4 describes a method for obtaining a boehmite suspension by hydrothermal reaction using alumina having inorganic ρ- and χ- crystal structures obtained by rapid thermal dehydration and inorganic monobasic acid. ing.
　特許文献４には、硝酸を用いた１８件の実施例について、原料からベーマイトへ変換して得られた生成物の特性の記載があり、比表面積の数値から判断する限り変換率が高くなる程生成するベーマイトの比表面積が低下している。また、同特許文献の方法では、ベーマイトの変換率はせいぜい８０％であり、工業的観点からは不十分である。 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. Moreover, in the method of the patent document, the conversion rate of boehmite is at most 80%, which is insufficient from an industrial viewpoint.
　また、本発明者出願の特許文献５では、ρ-およびχ-結晶構造を有するアルミナ原料を酸の存在下で水熱反応を行わせ、繊維状アルミナ粒子が単分散したアルミナゾルを経由して触媒用アルミナの製造方法が開示されている。　同特許文献で開示された製造方法では、高比表面積のアルミナを得ることができるものの、その製造には長時間要すると云う問題があった。 Further, in Patent Document 5 filed by the present inventor, an alumina raw material having a ρ- and χ- 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. In the manufacturing method disclosed in the patent document, although alumina having a high specific surface area can be obtained, there is a problem that the manufacturing takes a long time.
　また、本発明者出願の特許文献６には、酸含有水酸化アルミニウムまたはρ-およびχ-結晶構造を有するアルミナなどのアルミナ原料に、含酸素有機化合物または多価無機酸を添加する方法が開示されている。しかしながら、この方法では、ゲルを形成しやすく、水性アルミナゾルを得にくいのに加え、その液の性質は生成したベーマイト粒子同士は添加物で会合し粘着性が無く、バインダーとして不向きである。 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 ρ- and χ-crystal structure. Has been. However, 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.
特表２００４－５２５７６２号公報JP-T-2004-525762 特表２００４－５２８９６３号公報JP-T-2004-528963 特公昭４５－３８１２１号公報Japanese Examined Patent Publication No. 45-38121 特公昭５９－１３４４６号公報Japanese Patent Publication No.59-13446 国際公開１９９７／３２８１７号パンフレットInternational Publication No. 1997/32817 Pamphlet 国際公開２００１／５６９５１号パンフレットInternational Publication No. 2001/56951 Pamphlet
　以上のように従来の方法では、バインダーとしての機能を十分に備えた、ポリ無機一塩基酸アルミニウム水和物及び水性アルミナゾルを製造することができなかった。また、いずれの方法も煩雑な操作や長時間の処理を必要とするばかりでなく、原料アルミナの目的の生成物への変換率が低く、製造原価が高くなってしまうため、工業的に実施するには必ずしも適当なものとはいえなかった。 As described above, according to the conventional methods, it was not possible to produce a poly inorganic monobasic aluminum hydrate and an aqueous alumina sol having a sufficient function as a binder. In addition, both methods not only require complicated operations and long-time treatment, but also the conversion rate of raw material alumina to the target product is low, and the production cost is high, so that it is industrially implemented. It was not always appropriate.
　また、触媒用バインダーとしては、石油精製工業におけるガソリン製造用の接触分解用触媒にマトリックスとしてシリカゾルなどが使用されていたが、フィードオイル中に含有するニッケルとバナジウムの被毒対抗性が高く、バインダー力のあるアルミナ系マトリックスが求められている。 Moreover, as a catalyst binder, 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.
　かかる状況下、本発明の目的は、原料アルミナの目的生成物への変換率が高く、バインダーとしての性能が高いポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルを提供することである。 Under such circumstances, 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.
　本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、特定の平均粒子径（Ｄ50）以下のρ-およびχ-結晶構造を有する原料アルミナを使用し、特定の条件で熟成および／または水熱反応を行わせるという新規な製造法によって前記のような問題点を解決するものであることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have used raw material alumina having a ρ- and χ- 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.
　すなわち、本発明は、以下の発明に係るものである。
　＜１＞　平均粒子径（Ｄ50）が５μｍ以下のρ-およびχ-結晶構造を有するアルミナ、水、および無機一塩基酸またはその塩からなり、無機一塩基酸/アルミナモル比を０．０１から２．０、アルミナ濃度を２重量％から５０重量％の範囲に調節した調整液を、４０℃から２５０℃の範囲で熟成および／または水熱反応を行うことを特徴とするポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。
　＜２＞　前記アルミナの熟成および／または水熱反応後のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルへの変換率が、９０％以上である前記＜１＞記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。
　＜３＞　前記ρ-およびχ-結晶構造を有するアルミナの平均粒子径（Ｄ50）が、１μｍ以下である前記＜１＞または＜２＞記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　＜４＞　前記ρ-およびχ-結晶構造を有するアルミナが、水と無機一塩基酸またはその塩との存在下で湿式粉砕することにより得られてなる前記＜１＞から＜３＞のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。
　＜５＞　調整液の無機一塩基酸／アルミナのモル比が０．５以上２．０以下の範囲であり、４０℃以上１３０℃未満の温度で熟成および／または水熱反応を行わせ、ポリ無機一塩基酸アルミニウム水和物を得る前記＜１＞から＜４＞のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　＜６＞　調整液の無機一塩基酸／アルミナのモル比が０．０３以上０．５未満の範囲であり、４０℃以上１３０℃未満の温度で熟成および／または水熱反応を行わせ、ポリ無機一塩基酸アルミニウム水和物と水性アルミナゾルの混合物を得る前記＜１＞から＜４＞のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　＜７＞　調整液の無機一塩基酸／アルミナのモル比が０．０３以上０．５以下の範囲であり、１３０℃以上２５０℃以下の温度で水熱反応を行わせ、水性アルミナゾルを得る前記＜１＞から＜４＞のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　＜８＞　前記調整液が下記の式で表されるｋ値の組成範囲を有する前記＜１＞から＜４＞のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。
　　0.000005≦ｋ≦0.30　　　ただし、ｋ＝(b／a)×(b／c)
（式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）
　＜９＞　調整液のｋ値が下記の式で表される組成範囲を有し、無機一塩基酸／アルミナのモル比が０．０３以上０．５以下の範囲を有する調製液を１３０℃以上２５０℃以下の温度で水熱反応を行わせ、板状、テープ状又は繊維状の粒子形状を有する水性アルミナゾルを得ることを特徴とする前記＜８＞記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　　0.000005≦ｋ≦0.03　　　ただし、ｋ＝(b／a)×(b／c)
（式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）
　＜１０＞　調整液のｋ値が下記の式で表される組成範囲であり、主に板状の粒子形状を有する水性アルミナゾルを得る前記＜８＞または＜９＞記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　　0.000005≦ｋ＜0.0005　　　ただし、ｋ＝(b／a)×(b／c)
（式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）
　＜１１＞　調整液のｋ値が下記の式で表される組成範囲であり、主にテープ状の粒子形状を有する水性アルミナゾルを得る前記＜８＞または＜９＞記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　　0.0005≦ｋ＜0.0015　　　ただし、ｋ＝(b／a)×(b／c)
（式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）
　＜１２＞　調整液のｋ値が下記の式で表される組成範囲であり、主に繊維状の粒子形状を有する水性アルミナゾルを得る前記＜８＞または＜９＞記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
　　0.0015≦ｋ≦0.03　　　ただし、ｋ＝(b／a)×(b／c)
（式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）
　＜１３＞　前記ポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの５５０℃、２時間焼成後の細孔容量が、０．４０ｍＬ／ｇ以下であり、かつ、平均細孔径が、１００Å以下である前記＜８＞から＜１２＞のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。
　＜１４＞　前記無機一塩基酸が、硝酸である前記＜１＞から＜１３＞のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。
　＜１５＞　前記＜１＞から＜１４＞のいずれかに記載の方法により製造されてなることを特徴とするポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾル。
　＜１６＞　前記＜８＞から＜１５＞のいずれかの製造方法により得られた水性アルミナゾルをバインダーとして用いてなるＲ－ＦＣＣ触媒。 That is, the present invention relates to the following inventions.
<1> Alumina, water, and an inorganic monobasic acid or salt thereof having an ρ- and χ-crystal structure with an average particle diameter (D 50 ) of 5 μm or less, and an inorganic monobasic acid / alumina molar ratio from 0.01 2.0, a polyinorganic monobasic acid characterized by aging and / or hydrothermal reaction of an adjustment solution in which the alumina concentration is adjusted to a range of 2 wt% to 50 wt% in a range of 40 ° C. to 250 ° C. A method for producing aluminum hydrate and / or aqueous alumina sol.
<2> Polyinorganic monobasic as described in <1> above, wherein the conversion rate to polyaluminum monobasic aluminum hydrate and / or aqueous alumina sol after aging and / or hydrothermal reaction of the alumina is 90% or more A method for producing aluminum hydrate and / or aqueous alumina sol.
<3> The polyinorganic monobasic aluminum hydrate according to the above <1> or <2>, wherein the average particle size (D 50 ) of the alumina having the ρ- and χ- crystal structures is 1 μm or less. A method for producing an aqueous arunamisol.
<4> Any one of <1> to <3>, wherein the alumina having the ρ- and χ- crystal structures is obtained by wet pulverization in the presence of water and an inorganic monobasic acid or a salt thereof. A method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous alumina sol as described in 1 above.
<5> 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 method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous arnamisol according to any one of <1> to <4>, wherein an inorganic monobasic aluminum hydrate is obtained.
<6> 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 method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous alnamisol according to any one of <1> to <4>, wherein a mixture of the inorganic monobasic aluminum hydrate and the aqueous alumina sol is obtained.
<7> 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 | water-based namimisol in any one of <4>.
<8> The poly inorganic monobasic aluminum hydrate and / or the aqueous alumina sol according to any one of <1> to <4>, wherein the adjustment liquid has a composition range of k value represented by the following formula: Production method.
0.000005 ≦ k ≦ 0.30 where 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> A prepared solution having a composition range in which the k value of the adjustment solution is represented by the following formula and the molar ratio of inorganic monobasic acid / alumina is 0.03 or more and 0.5 or less is 130 ° C. or more. The polyinorganic monobasic aluminum hydrate according to the above <8>, wherein a hydrothermal reaction is performed at a temperature of 250 ° C. or less to obtain an aqueous alumina sol having a plate-like, tape-like or fibrous particle shape. And / or a method for producing an aqueous arunamisol.
0.000005 ≦ k ≦ 0.03 where 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> The polyinorganic monobasic aluminum according to the above <8> or <9>, wherein the k value of the adjustment liquid is a composition range represented by the following formula, and an aqueous alumina sol mainly having a plate-like particle shape is obtained. A method for producing a hydrate and / or an aqueous alnamisol.
0.000005 ≦ k <0.0005 where 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> The polyinorganic monobasic aluminum according to the above <8> or <9>, wherein the k value of the adjustment liquid is a composition range represented by the following formula, and an aqueous alumina sol mainly having a tape-like particle shape is obtained. A method for producing a hydrate and / or an aqueous alnamisol.
0.0005 ≦ k <0.0015 where 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> The polyinorganic monobasic aluminum salt according to <8> or <9>, wherein the k value of the adjustment liquid is a composition range represented by the following formula, and an aqueous alumina sol mainly having a fibrous particle shape is obtained. A method for producing a hydrate and / or an aqueous alnamisol.
0.0015 ≦ k ≦ 0.03 where 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 μm 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.
　本発明の方法によれば、ポリ無機一塩基酸アルミニウム水和物、水性アルミナゾルまたはこれらの混合物を、低温の水熱反応条件で得ることが可能となり、さらに高い変換率で原料アルミナから目的の生成物を得ることができる。 According to the method of the present invention, it becomes possible to obtain a poly inorganic monobasic aluminum hydrate, an aqueous alumina sol or a mixture thereof under low-temperature hydrothermal reaction conditions. You can get things.
　本発明の方法で得られた、ポリ無機一塩基酸アルミニウム水和物、水性アルミナゾルまたはこれらの混合物はそれぞれ高いバインダー力を有しており、粉末の成型物のバインダーとして用いると、きわめて高い硬度を有する成型物を得ることができる。
　特に本発明の方法で製造される水性アルミナゾルは、バインダー力に優れ、石油精製工業におけるガソリン製造用の接触分解触媒（Ｒ－ＦＣＣ触媒）を初めとする各種触媒用マトリックスや吸着剤などのバインダーとして、または耐熱接着剤などにも好適である。 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 molding which has can be obtained.
In particular, 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.
各粒子形状の水性アルミナゾルの生成領域を示す図である。It is a figure which shows the production | generation area | region of the aqueous | water-based alumina sol of each particle shape. 実施例８（板状粒子）の透過型電子顕微鏡写真である。It is a transmission electron micrograph of Example 8 (plate-like particle). 実施例８の細孔径分布図である。10 is a pore size distribution diagram of Example 8. FIG. 実施例１４（テープ状粒子）の透過型電子顕微鏡写真である。It is a transmission electron micrograph of Example 14 (tape-like particles). 実施例２１（テープ粒子）の透過型電子顕微鏡写真である。It is a transmission electron micrograph of Example 21 (tape particles). 実施例２２（繊維状粒子）の透過型電子顕微鏡写真である。It is a transmission electron micrograph of Example 22 (fibrous particles).
　以下、本発明につき詳細に説明する。
　本発明は、平均粒子径（Ｄ50）が５μｍ以下のρ-およびχ-結晶構造を有するアルミナ、水、および無機一塩基酸またはその塩からなり、無機一塩基酸/アルミナモル比を０．０３から２．０、アルミナ濃度を３重量％から５０重量％の範囲に調節した調整液を、４０℃から２５０℃の範囲で熟成および／または水熱反応を行うことを特徴とするポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法（以下、「本発明の製造方法」と呼ぶことがある。）に係るものである。
　なお、本発明でいう平均粒子径（Ｄ50）（以下、単に「平均粒子径」と記載する場合がある。）は、例えばレーザ回折／散乱式粒度分布測定装置を用いて測定することができる。また、本発明における水性アルミナゾルとは、ρ-およびχ-結晶構造を有するアルミナから、Ｈ+を触媒として生成した結晶性ベーマイトを含んでなるアルミナゾルを意味する。
　また、アルミナ濃度は、調整液全体の重量を１００としたときのアルミナ（Ａｌ2Ｏ3換算）の割合（重量％）である。
　また、本発明において、熟成とは、調整液を６０℃未満の温度で保持することを意味し、水熱反応（「水熱合成」ともいう。）とは、調整液を容器へ密閉したまま６０℃以上で加熱することと定義する。 Hereinafter, the present invention will be described in detail.
The present invention comprises alumina having a ρ- and χ- crystal structure with an average particle size (D 50 ) of 5 μm 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 ρ- and χ- 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.
In the present invention, aging means holding the adjustment liquid at a temperature of less than 60 ° C., and 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.
　本発明の特徴の一つは、原料であるρ-およびχ-結晶構造を有するアルミナ（以下、「原料アルミナ」と呼ぶことがある。）として、平均粒子径（Ｄ50）が５μｍ以下の原料アルミナを使用することにある。
　目的の生成物であるポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルは、原料アルミナから以下の機構で生成すると考えられる。
　即ち、ρ-およびχ-結晶構造を有するアルミナ原料の表面が水と、無機一塩基酸由来のＨ+イオンとの反応で溶解し、アルミナ原料粉末の表面から分子量の異なる各種のポリ一塩基酸アルミニウム水和物が溶媒側へ溶出する。
　アルミナ原料からのポリ一塩基酸アルミニウム水和物の溶出が進行すると、その飽和溶解度の値を超える過飽和領域になる。この領域ではポリ一塩基酸アルミニウム水和物の溶解分子間の衝突や刺激（電気的や機械的）によりベーマイトの核が発生する。また、同時にＨ+イオンが副生する。なお、ベーマイトの核はa軸(bc面)、ｂ軸(壁開面のあるac面)、c軸(ab面)の３つの異なる結晶面を有しているが知られている。 One of the features of the present invention is that the raw material has an average particle diameter (D 50 ) of 5 μm or less as alumina having a ρ- and χ- crystal structure (hereinafter sometimes referred to as “raw material alumina”). The use of alumina.
The target product, polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol, is considered to be produced from raw alumina by the following mechanism.
That is, the surface of the alumina raw material having a ρ- and χ- 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. Aluminum hydrate is eluted to the solvent side.
As elution of the polymonobasic aluminum hydrate from the alumina raw material proceeds, the supersaturated region exceeds the saturation solubility value. In this region, boehmite nuclei are generated by collision or stimulation (electrical or mechanical) between dissolved molecules of polymonobasic aluminum hydrate. At the same time, 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).
　副生したＨ+イオンは再び原料アルミナを溶解してポリ一塩基酸アルミニウム水和物を生成し、溶液中へ拡散する。なお、すでにベーマイトの核が形成された後には、ポリ一塩基酸アルミニウム水和物は飽和溶解度以下の濃度であってもベーマイトの核と接近し、核の特定位置へ配位し次いで静電接合する。そして、ベーマイトの核とポリ一塩基酸アルミニウム水和物が反応することによって再びＨ+イオンを副生する。
　上記の反応サイクルを繰り返すことによって、ベーマイトが成長して、結果的に水性アルミナゾルを形成する。 The by-produced H + ions dissolve the raw material alumina again to form polymonobasic aluminum hydrate, and diffuse into the solution. After boehmite nuclei have already formed, 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. Then, the bo + ite nucleus reacts with the polymonobasic aluminum hydrate to regenerate H + ions as a by-product.
By repeating the above reaction cycle, boehmite grows, resulting in the formation of an aqueous alumina sol.
　そのため、原料アルミナの粒径が大きすぎると、生成物であるポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの他に、未溶解の原料アルミナが粉状物として多量に残存する。そこで、本発明では、原料アルミナを平均粒子径（Ｄ50）が５μｍ以下に限定することによって、未反応の原料アルミナを実質的になくし、また残存した場合においても、極めて微小径であるため、目的の生成物の品質を損なうことはない。
　特に、原料アルミナの平均粒子径（Ｄ50）を１μｍ以下とすることにより、反応速度を高め、最終品中の未反応の原料アルミナをなくすことができる。 Therefore, if 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 μm 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 μm or less, the reaction rate can be increased and unreacted raw material alumina in the final product can be eliminated.
　市販の原料アルミナは、通常、６μｍを超えている。例えば、住友化学株式会社より市販されているBK-540,BK-112,BK-105（品番）は、その平均粒子径（Ｄ50）は４８μｍ、１５μｍ、６．１μｍである。そのため、本発明の製造方法に使用する場合には、原料アルミナを粉砕することが好ましい。
　原料アルミナの粉砕は、原料アルミナの平均粒子径（Ｄ50）を５μｍ以下（好適には１μｍ以下）にできるならば、乾式粉砕、湿式粉砕のいずれでもよい。
　一方で、湿式粉砕であれば、Ｎａ成分の洗浄後の湿潤ケーキを乾燥させずに使用できる点で好ましい。特に湿式粉砕の中でも、水と無機一塩基酸またはその塩との存在下で原料アルミナを湿式粉砕すると、原料アルミナの内部に無機一塩基酸が浸透し、反応を促進するため好ましい。この場合、原料アルミナの反応が促進されるため、平均粒子径（Ｄ50）が１μｍ超５μｍ以下の場合でも、十分に原料アルミナが溶解する。 Commercial raw material alumina usually exceeds 6 μm. For example, BK-540, BK-112, and BK-105 (product numbers) commercially available from Sumitomo Chemical Co., Ltd. have an average particle diameter (D 50 ) of 48 μm, 15 μm, and 6.1 μm. Therefore, when using it for the manufacturing method of this invention, it is preferable to grind | pulverize raw material alumina.
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 μm or less (preferably 1 μm or less).
On the other hand, wet pulverization is preferred in that the wet cake after washing the Na component can be used without drying. Particularly in wet pulverization, 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 μm and not more than 5 μm.
　本発明の製造方法では、無機一塩基酸またはその塩の存在下で原料アルミナを湿式粉砕することが好ましく、この場合、まず原料アルミナ、水および無機一塩基酸の所定量を混合したスラリーを調製し、これを湿式粉砕機に供給する。このとき、無機一塩基酸は所定量を最初から加えてもよく、また当初は所定量より少なめに調製し、粉砕を始めたのちに残りの酸を加えてもよい。 In 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. In this case, first, a slurry in which a predetermined amount of raw material alumina, water and an inorganic monobasic acid are mixed is prepared. Then, this is supplied to a wet pulverizer. At this time, 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.
　粉砕が開始されると、粉砕機中のスラリーの粘度が上昇することがあるが、スラリーのｐＨ値を５．５以下に保持、若しくは水の希釈を行ない、粘度を１００ｍＰａ・ｓ未満に抑えて粉砕を継続することができる。このような湿式粉砕を行うには、強制攪拌付湿式微粉砕機が好ましく用いられる。 When pulverization is started, 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. In order to perform such wet pulverization, a wet pulverizer with forced stirring is preferably used.
　湿式微粉砕に於ける粉砕効率はアルミナ濃度が高い程高効率になるが、湿式粉砕機内の粉砕液の粘度限界の問題があり、濃度条件は粘度の制約を受ける。原料に対して無機一塩基酸が少ない場合には湿式微粉砕中のスラリーの粘度は高くなり易く、無機一塩基酸が多い場合にはスラリーの粘度は低くなり易いので、高効率粉砕を重視する場合には無機一塩基酸の比率を高めることが好ましい。 Grinding efficiency in wet pulverization increases as the alumina concentration increases, but there is a problem of the viscosity limit of the pulverized liquid in the wet pulverizer, and the concentration condition is limited by viscosity. When the amount of inorganic monobasic acid is small relative to the raw material, the viscosity of the slurry during wet pulverization tends to be high, and when the amount of inorganic monobasic acid is large, the viscosity of the slurry tends to be low. In some cases, it is preferable to increase the ratio of the inorganic monobasic acid.
　また、湿式粉砕の途中でスラリーを２相分離型遠心分離機により２相に分離し、小粒子部分を分離したのち再度粉砕を行うこともできる。これによって、粉砕中の粘度上昇に伴うトラブルの解消と粉砕効率の向上が期待される。
　なお、本発明の製造方法において、未反応の原料アルミナが比較的大きな粒子（粗粒）として残存する場合がある。
　このような原料アルミナの粗粒未反応物の分離は高速回転の遠心分離機を用い８０００-９０００回転／分の高速で行なうことができ、分離速度を高めるためにアルミナ濃度で１５％程度の濃度で行なうことが好ましい。 In addition, 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. This is expected to eliminate troubles associated with the increase in viscosity during grinding and improve grinding efficiency.
In the production method of the present invention, 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.
　無機一塩基酸/アルミナのモル比が低位の水性アルミナゾルの問題点として、湿式粉砕工程に於ける無機一塩基酸/アルミナのモル比が０．０９以下と低い場合には、湿式粉砕液の粘度が増加して粉砕液の硬化が起こし粉砕操作が困難になる。その場合、水で薄めて粘度を低下させることができるが、希釈による粉砕効率の低下、生成アルミナゾルの低濃度化を余儀なくされる問題点がある。
　その解消法として湿式粉砕工程に於ける無機一塩基酸/アルミナのモル比を０．１０以上の安定な組成領域で行い、粉砕工程の終了後無機一塩基酸/アルミナのモル比再調整工程に於いて、過剰の無機一塩基酸を、１．アンモニア等のアルカリ成分添加による中和、又は、２．乾式粉砕で得られたρ-およびχ-結晶構造を有するアルミナ添加による中和、又は、３．硝酸用陰イオン交換樹脂による吸着脱離、等の方法で除去することができる。 As a problem of aqueous alumina sol having a low molar ratio of inorganic monobasic acid / alumina, when the molar ratio of inorganic monobasic acid / alumina in the wet grinding process is as low as 0.09 or less, the viscosity of the wet grinding liquid Increases, the pulverized liquid is hardened, and the pulverization operation becomes difficult. In that case, 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.
In order to solve this problem, 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. Wherein an excess of inorganic monobasic acid is 1. Neutralization by adding alkaline components such as ammonia, or 2. Neutralization by addition of alumina having ρ- and χ- 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.
　上述のように本発明の製造方法で用いられる原料アルミナは、ρ-およびχ-結晶構造を有するアルミナであるが、この原料アルミナは、通常、水酸化アルミニウムを熱気流中で急速加熱して脱水することによって得ることができる。
　なお、水酸化アルミニウムは、バイヤー法で通常製造されるが、バイヤー法で製造された水酸化アルミニウム(欧米名：Bauxite Ore Concentration)を約１０００℃の急速加熱脱水で製造されたρ-およびχ-結晶構造を有するアルミナは、不純物としてＮａ2Ｏを約０．２５重量％含有している例が多い。
　そのため、バイヤー法で製造された水酸化アルミニウムを使用する場合には、事前に洗浄によって、Ｎａ濃度を減少させることが好ましい。Ｎａの洗浄には炭酸を含有する酸性水で濾過掛水洗浄することによって、Ｎａとして０．０６重量％程度に減少させることが可能である。 As described above, the raw material alumina used in the production method of the present invention is alumina having a ρ- and χ- 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 ρ- and χ- 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.
　無機一塩基酸としては、具体的には塩酸，硝酸等が挙げられ、硝酸が好ましく使用される。また、硝酸アルミニウムなどの無機一塩基酸の塩も用いることができる。 Specific examples of the inorganic monobasic acid include hydrochloric acid and nitric acid, and nitric acid is preferably used. In addition, a salt of an inorganic monobasic acid such as aluminum nitrate can also be used.
　本発明の製造方法において、上記原料アルミナからなる粉末と、水、および／または無機一塩基酸またはその塩とを混合（湿式粉砕を伴ってよい）することによって、無機一塩基酸/アルミナモル比が０．０３から２．０（好適には０．０５から１．５）、アルミナ濃度を３重量％から５０重量％（好適には５重量％から４０重量％）の範囲に調節した調整液を形成する。そして、この調整液を、４０℃から２５０℃の範囲で熟成および／または水熱反応させることにより、目的とする生成物を得ることできる。 In the production method of the present invention, 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). Form. The target product can be obtained by aging and / or hydrothermally reacting this adjustment liquid in the range of 40 ° C to 250 ° C.
　ここで、一塩基酸/アルミナモル比が０．０３未満の場合には、調整液の粘度が高すぎて操作が困難となり、２．０超であると反応に関与しない無機一塩基酸が増加することになる。
　また、アルミナ濃度が、３重量％未満であると、得られる生成物の濃度が小さすぎて、濃縮に余計なコストがかかり、５０重量％を超えると濃度が高すぎて、原料アルミナの粉砕や生成物のハンドリングが困難になる。 Here, when the monobasic acid / alumina molar ratio is less than 0.03, the viscosity of the adjustment liquid is too high, making the operation difficult, and if it exceeds 2.0, the amount of inorganic monobasic acid not involved in the reaction increases. It will be.
Further, if 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.
　本発明の製造方法の特徴の一つとして、原料アルミナの粒径、その他の成分の組成や熟成、水熱反応の温度を特定の範囲に調整することにより、原料アルミナが高効率に生成物に変換できるということが挙げられる。
　変換率は、反応時間にも依存するが、工業的観点からは、生成物の変換率は、９０％以上が好ましく、９５％以上が特に好ましい。 As one of the characteristics of the production method of the present invention, by adjusting the particle diameter of the raw material alumina, the composition and aging of other components, and the temperature of the hydrothermal reaction to a specific range, the raw material alumina can be converted into a product with high efficiency. It can be converted.
Although 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.
　本発明の製造方法において、得られる生成物は、原料アルミナ、水、無機酸またはその塩の濃度や、熟成および／または水熱反応の温度に依存する。 In the production method of the present invention, 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.
　すなわち、調整液の無機一塩基酸／アルミナのモル比が０．５以上２．０以下の範囲とし、４０℃以上１３０℃未満の温度で熟成および／または水熱反応を行わせ、ポリ無機一塩基酸アルミニウム水和物を得ることができる。
　また、調整液の無機一塩基酸／アルミナのモル比が０．０３以上０．５未満の範囲とし、４０℃以上１３０℃未満の温度で熟成および／または水熱反応を行わせ、ポリ無機一塩基酸アルミニウム水和物と水性アルミナゾルの混合物を得ることができる。
　さらに、調整液の無機一塩基酸／アルミナのモル比が０．０３以上０．５以下の範囲とし、１３０℃以上２５０℃以下の温度で水熱反応を行わせ、水性アルミナゾルを得ることができる。 That is, 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.
In addition, 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.
Furthermore, 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. .
　本発明の製造方法において、高品質な生成物を得るという観点から、上記調整液中のアルミナ、水および無機一塩基酸のモル比が、下記式（１）で定義されるｋ値が、0.000005≦ｋ≦0.30の範囲を有するような調整液を調製することが好ましい。
　　ｋ＝(b／a)×(b／c)　　（１）
（式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数） In the production method of the present invention, from the viewpoint of obtaining a high-quality product, the molar ratio of alumina, water and inorganic monobasic acid in the adjustment liquid is such that the k value defined by the following formula (1) is 0.000005. It is preferable to prepare an adjustment liquid having a range of ≦ k ≦ 0.30.
k = (b / a) x (b / c) (1)
(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)
　特に水性アルミナゾルを製造する条件において、水性アルミナゾルの形状は、原料アルミナ、水、無機酸またはその塩の濃度から上記式（１）により決定されるｋ値に依存する。すなわち、調整液のｋ値が0.000005≦ｋ≦0.03の組成範囲であり、熟成および／または水熱反応の温度が、１３０℃以上２５０℃以下であると、生成物として、水性アルミナゾルは、板状、テープ状又は繊維状の粒子形状を有する水性アルミナゾルが形成される。なお、水熱反応の温度が、１６０℃以上２５０℃以下であることが好ましく、この範囲であると効率的に水性アルミナゾルを製造することができる。 Especially in the conditions for producing 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.
　ここで、板状の粒子形状とは、ベーマイトにおけるa軸（bc面）とb軸（ac面）との均等な結合力で成長したもの、テープ状の粒子形状とは、ベーマイトにおけるa軸（bc面）とい結合し、b軸（ac面）と弱い結合力で配位して成長したもの、繊維状の粒子形状とは、ベーマイトにおけるa軸（bc面）へ強く配位して成長したものと推定される。具体的なそれぞれの形状は、後述する実施例における電子顕微鏡写真にて示す。 Here, 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, and 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, and 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.
　上記の水性アルミナゾルを形成する条件において、主に板状の粒子形状を有する水性アルミナゾルという観点では、調整液のｋ値が0.000005≦ｋ＜0.0005の組成範囲であることが好ましく、主にテープ状の粒子形状を有する水性アルミナゾルを得るという観点では、調整液のｋ値が0.0005≦ｋ＜0.0015の組成範囲であることが好ましく、主に繊維状の粒子形状を有する水性アルミナゾルを得るという観点では、調整液のｋ値が0.0015≦ｋ≦0.03の組成範囲であることが好ましい。図１に各粒子形状の水性アルミナゾルの生成領域を示す。 In the above-mentioned conditions for forming the aqueous alumina sol, from the viewpoint of an aqueous alumina sol having mainly a plate-like particle shape, the k value of the adjustment liquid is preferably within a composition range of 0.000005 ≦ k <0.0005, From the viewpoint of obtaining an aqueous alumina sol having a particle shape, 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.
　本発明の生成物であるポリ無機一塩基酸アルミニウム水和物や水性アルミナゾルは、乾燥、焼成後、触媒、吸着剤等の成型物のバインダーとしても好適に用いられる。また、耐熱性接着剤などのバインダーとして好適に用いられる。 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.
　ここで、バインダー性能という観点では、熱処理後のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルを特定の温度で焼成後の細孔容量および平均細孔径を指標とすることができる。
　本発明のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの細孔容量は、５５０℃２時間焼成後の細孔容量が、０．４０ｍＬ／ｇ以下（特に０．３５ｍＬ／ｇ以下）であり、かつ、平均細孔径が１００Å以下（特に７５Å以下）であると、特に強いバインダー力が得られるため好適である。 Here, in terms of binder performance, 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 Å or less (particularly 75 Å or less) because a particularly strong binder force can be obtained.
　なお、本発明の生成物のうち、特に水性アルミナゾルは、Ｒ－ＦＣＣ触媒用バインダーとして好適に使用される。なお、Ｒ－ＦＣＣ触媒のゼオライトはフィードオイル中に含有しているニッケルとバナジウムの被毒で活性を失うが、そのパッシベーターとしてアルミナ質が有効である。そのため、本発明の製造方法に係る生成物をＲ－ＦＣＣ触媒用バインダーとして使用する場合、本発明に係る水性アルミナゾルのみならず、Ｒ－ＦＣＣ触媒の触媒活性などの諸特性を損なわない範囲で、ポリ無機一塩基酸アルミニウム水和物や原料アルミナであるρ-およびχ-結晶構造を有するアルミナを含有していてもよい。 Of the products of the present invention, 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 ρ- and χ- crystal structures.
　以下、実施例により本発明を更に詳細に説明するが、本発明の要旨を越えない限り以下の実施例に限定されるものではない。なお、実施例において、原料アルミナとなるρ-およびχ-結晶構造を有するアルミナは、住友化学株式会社製のBK-540,BK-112,BK-105（品番）を使用した。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. In the examples, BK-540, BK-112, and BK-105 (product numbers) manufactured by Sumitomo Chemical Co., Ltd. were used as the alumina having ρ- and χ- crystal structures as raw material alumina.
　なお、それぞれの測定法は次のとおりである。
(1)変換率
　アルミナ濃度１．０重量％に希釈した生成物試料１００ｇを、１００ｍｌのビーカーに入れ、２０時間静置する。静置後沈降物を採取して灼熱後の残留物の重量を秤り、測定試料の変換率を計算する。
(2)遠心沈降物
　アルミナ濃度1重量％に希釈した試料５ｍｌを、遠心分離機の遠心沈降管に採取し、３０００回転で５分間運転したのちの沈降物の量を測定する。
(3)比表面積
　測定試料を２００℃乾燥後、窒素ガス吸着法で測定する。
(4)細孔容積および平均細孔径
　水銀圧入法で細孔径４０～１００００Åの細孔を測定する。
(5)平均粒子径（Ｄ50）（重量平均粒子径）
　レーザ回折／散乱式粒度分布測定器（日機装社製 MT3300）で測定する。
(6)圧縮強度
　木屋式圧縮強度測定機で、円柱状成型物200個の側面の強度を測定し、その平均値を求める。
(7)生成物の形状
　ポリ無機一塩基酸アルミニウム水和物、水性アルミナゾルの２００℃乾燥物を透過型顕微鏡（日立製作所社製、型番：Ｈ－９０００ＮＡＲ）を使用して評価した。 In addition, each measuring method is as follows.
(1) 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.
(2) 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.
(3) Specific surface area A sample to be measured is dried at 200 ° C. and then measured by a nitrogen gas adsorption method.
(4) 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).
　実施例１
　平均粒子径（Ｄ50）が１５μｍのρ-およびχ-結晶構造を有するアルミナ１２００ｇを硝酸水溶液に添加し、アルミナ濃度２１重量％、硝酸／アルミナのモル比が０．１５のスラリーを調製した。このスラリーを０．３ｍｍのジルコニアビーズを用いた強制攪拌付湿式微粉砕機に供給して微粉砕を行った。粉砕の途中でスラリーのpH調整のため硝酸の追加添加を行い、ｐＨを５未満に維持して粉砕を続けた。粉砕後のスラリーは、平均粒子径（Ｄ50）が０．１１μｍ、アルミナ濃度２０重量％、硝酸／アルミナのモル比が０．２０、ｋ値が0.0018であった。 Example 1
1200 g of alumina having a ρ- and χ- crystal structure with an average particle size (D 50 ) of 15 μm 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. During the pulverization, 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 μm, an alumina concentration of 20% by weight, a nitric acid / alumina molar ratio of 0.20, and a k value of 0.0018.
　上記スラリー１０００ｇに硝酸を添加し、アルミナ濃度１９．３重量％、硝酸／アルミナのモル比が０．４０、ｋ値が０．００７２の調整液を調製した。
　この調整液を９８℃で１４時間水熱反応を行った結果、原料アルミナの変換率は９９．５％、遠心沈降物が２．６％であった。２００℃乾燥物の比表面積および８５０℃、５時間熱処理物の細孔容積を表１に示す。この生成物の電子顕微鏡観察によると、アルミナ粒子が多数観察されることおよび２００℃乾燥物の性状などから、ポリ無機一塩基酸アルミニウム水和物と水性アルミナゾルとの混合物と推定される。 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.
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. According to electron microscope observation of this product, it is presumed to be a mixture of poly inorganic monobasic aluminum hydrate and aqueous alumina sol from the fact that a large number of alumina particles are observed and the properties of the dried product at 200 ° C.
　また、ＵＳＹゼオライト、カオリンおよび本実施例の生成物を、酸化物基準で３０／４０／３０の重量比で混練し、ピストン式押出成形機で成形、乾燥後８５０℃、５時間焼成して得られた円柱状成型体の直径、細孔構造、側面圧縮強度を表１に併せて示した。 Further, 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.
　実施例２
　実施例１で得られたスラリーの１０００ｇに硝酸を添加し、アルミナ濃度１７．４重量％、硝酸／アルミナのモル比が１．００、ｋ値が０．０４３の調整液を調製した。
　この調整液を９８℃で１４時間水熱反応を行った結果、原料アルミナの変換率は９９．５％、遠心沈降物が３．８％であった。２００℃乾燥物の比表面積および850℃,5時間熱処理物の細孔容積を表１に示した。この生成物の電子顕微鏡観察によると、わずかのアルミナ粒子が観察されることおよび２００℃乾燥物の性状などから、主要生成物はポリ無機一塩基酸アルミニウム水和物と推定される。
　また、実施例１と同様の成型物の細孔構造、圧縮強度を表１に示した。 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. According to electron microscopic observation of this product, 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.
　比較例１
　市販のアルミナゾルの中でバインダー機能に優れていると見なされる、擬ベーマイトからなるアルミナゾル（商品名：カタロイド－ＡＰ）の２００℃乾燥物の比表面積および８５０℃、５時間熱処理物の細孔容積を測定し、結果を表１に示した。また、実施例１と同様の成型物を成型し、その細孔構造、圧縮強度を測定した結果を表１に示した。 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例３
　平均粒子径（Ｄ50）が１５μｍのρ-およびχ-結晶構造を有するアルミナを空気の旋回力で乾式粉砕し、平均粒子径（Ｄ50）が０．７μｍのアルミナ粉末を調製した。このアルミナ粉末５００ｇを硝酸水溶液に添加し、アルミナ濃度２０重量％、硝酸／アルミナのモル比が０．１５、ｋ値が０．００１０の調整液を調製した。
　この調整液を１４０℃で１４時間水熱反応を行った結果、原料アルミナの変換率は９６．３％、遠心沈降物が３．８％であった。この生成物の電子顕微鏡観察によると、繊維状粒子と板状粒子が混在する水性アルミナゾルであり、２００℃乾燥物の比表面積は、２９０ｍ2／ｇであった。 Example 3
Alumina having an average particle size (D 50 ) of 15 μm and having a ρ− and χ− 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 μm. 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.
　実施例４
　平均粒子径（Ｄ50）が１５μｍのρ-およびχ-結晶構造を有するアルミナ５００ｇを硝酸水溶液に添加し、アルミナ濃度３０重量％、硝酸／アルミナのモル比が０．１５、ｋ値が０．００１７７のスラリーを調製した。このスラリーを３．６Ｌの磁性ポットミルに供給し、１０ｍｍのジルコニアビーズを５ｋｇ挿入して６８時間湿式粉砕した。粉砕後のアルミナの平均粒子径（Ｄ50）は１．６μｍであった。
　これを調整液として１４０℃で１４時間水熱反応を行った結果、原料アルミナの変換率は９６．５％であり、生成物は電子顕微鏡観察によると、主として繊維状粒子からなる水性アルミナゾルであり、２００℃乾燥物の比表面積は、３１０ｍ2／ｇであった。 Example 4
500 g of alumina having a ρ- and χ- crystal structure with an average particle diameter (D 50 ) of 15 μm 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 μm.
As a result of carrying out a hydrothermal reaction at 140 ° C. for 14 hours using this as the adjustment liquid, the conversion rate of the raw material alumina was 96.5%, and 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.
　実施例５
　平均粒子径（Ｄ50）１２．８μｍの水酸化アルミニウム６００ｇを硝酸水溶液に添加し、アルミナ濃度２０重量％、硝酸／アルミナのモル比が１．００のスラリーを調製した。
　このスラリーを強制攪拌付湿式粉砕機に供給し、平均粒子径（Ｄ50）が１．４μｍになるまで微粉砕した。これを調整液とし、常温熟成後９８℃で１４時間水熱反応を行った結果、原料アルミナの変換率は９５．８％、遠心沈降物が３９．８％の白濁した粘凋な水性アルミナゾルおよびゲル状物が得られた。２００℃乾燥物の比表面積は、０ｍ2／ｇであったことからポリ硝酸アルミニウム水和物も含まれていることが推測された。 Example 5
600 g of aluminum hydroxide having an average particle size (D 50 ) of 12.8 μm 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 μm. This was used as an adjustment solution, and after hydrothermal reaction at 98 ° C. for 14 hours after aging at room temperature, 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.
　この調整液を、熟成あるいは水熱反応温度を６０℃、１４０℃、２００℃と変えてそれぞれ１４時間反応させた後の２００℃乾燥物の比表面積は、それぞれ０ｍ2／ｇ、０ｍ2／ｇ、６１ｍ2／ｇ、であった。このことから水熱反応が高温になるほどポリ硝酸アルミニウム水和物が減少して粒子成長が進むことがわかる。 The adjusted solution, 60 ° C. aging or temperature of the hydrothermal reaction, 140 ° C., a specific surface area of 200 ° C. dried product after the reaction, respectively 14 hours by changing a 200 ° C., respectively 0m 2 / g, 0m 2 / g 61 m 2 / g. From this, it can be seen that as the hydrothermal reaction becomes higher, the polyaluminum nitrate hydrate decreases and the particle growth proceeds.
　実施例６
　平均粒子径（Ｄ50）１５μｍのρ-およびχ-結晶構造を有するアルミナ５００ｇを塩酸水溶液に添加し、アルミナ濃度２０重量％、塩酸／アルミナのモル比が１．００、ｋ値が０．０５２のスラリーを調製した。このスラリーを３．６Ｌの磁性ポットミルに供給し、１０ｍｍのジルコニアビーズを5kg挿入して1週間湿式粉砕した。粉砕後のアルミナの平均粒子径（Ｄ50）は０．７μｍであった。 Example 6
500 g of alumina having a ρ- and χ- crystal structure with an average particle size (D 50 ) of 15 μm 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 μm.
　ポットミルからスラリーを取り出し、超遠心分離機で沈降物を分離して得られた液状物を分析した結果、［Al2(OH)nCl6-n］m （1≦n≦5, m≦10）の組成を有するポリ塩化アルミニウム水和物と同定された。 As a result of taking out the slurry from the pot mill and analyzing the liquid obtained by separating the sediment with an ultracentrifuge, [Al 2 (OH) n Cl 6-n ] m (1 ≦ n ≦ 5, m ≦ 10 ) Was identified as polyaluminum chloride hydrate.
　この生成物の水中懸濁物質に対する凝集試験を、カオリンの懸濁水で行った結果、良好な凝集効果があることが確認された。 As a result of conducting a coagulation test on the suspended substance in water with kaolin suspension water, it was confirmed that there was a good coagulation effect.
　実施例７
　平均粒子径（Ｄ50）が１５μｍのρ-およびχ-結晶構造を有するアルミナ（以下、「原料アルミナ」という。）を硝酸水溶液に添加し、アルミナ濃度１２．５重量％、硝酸／アルミナのモル比が０．０６のスラリーを調製した。このスラリーを０．３ｍｍのジルコニアビーズを用いた強制攪拌付湿式微粉砕機に供給して１時間３０分間、湿式粉砕を行った。粉砕後のスラリーは平均粒子径（Ｄ50）が０．３μｍであった。
　この粉砕液へ水を添加してアルミナ成分の濃度５％、硝酸／アルミナのモル比が０．０６、ｋ値を０．００００３４に調整した調整液を得た。調整液の一部をステンレス製1インチのガス管へ挿入し、エアバス中で１４０℃、１４時間水熱反応を行った。その結果、水性アルミナゾルの生成物を得た。
　反応条件、原料アルミナの変換率及び水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状の結果を表２に示す。 Example 7
Alumina having a ρ- and χ- crystal structure with an average particle size (D 50 ) of 15 μm (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 μm.
Water was added to the pulverized liquid to obtain an adjusted liquid in which the concentration of the alumina component was adjusted to 5%, the nitric acid / alumina molar ratio was adjusted to 0.06, and the k value was adjusted to 0.000034. A part of the adjustment liquid was inserted into a stainless steel 1-inch gas pipe, and hydrothermal reaction was performed in an air bath at 140 ° C. for 14 hours. As a result, an aqueous alumina sol product was obtained.
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.
　実施例８
　実施例７と同様の原料を使用し、アルミナ濃度１５重量％、硝酸／アルミナのモル比が０．０８８のスラリーを調製した。このスラリーは粉砕時間を３時間とした以外は、実施例７と同様に原料アルミナの微粉砕を行った。粉砕後のスラリーは平均粒子径（Ｄ50）が０．２μｍであった。得られた粉砕液へ水を添加してアルミナ成分の濃度１２．５％、ｋ値を０．００００２０とし、その一部をステンレス製１インチのガス管へ挿入し、エアバス中で昇温時間も含めて１４０℃、１４時間加熱して水熱反応を行い、微量の液状物質を含む水性アルミナゾルの生成物を得た。反応条件、原料アルミナの変換率及び水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ) 及び生成物の形状の結果を表２に示す。また、透過型顕微鏡写真を図２に示す。
　さらに水性アルミナゾルについて５５０℃、２時間焼成処理物の水銀圧入法による細孔径分布図を図３に示す。また、細孔径分布図から求めた細孔容量及び平均細孔径を表３に示す。 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 μm. 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. for 14 hours to obtain an aqueous alumina sol product containing a trace amount of liquid substance. 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.
Further, 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. In addition, Table 3 shows the pore volume and average pore diameter determined from the pore size distribution chart.
　実施例９
　実施例７と同様の原料アルミナを使用し、アルミナ濃度２５重量％、硝酸／アルミナのモル比が０．１０のスラリーを調製した。このスラリーに水を添加してアルミナ濃度１５％まで希釈しながら原料アルミナの微粉砕を行った。４時間粉砕したのちのスラリーは平均粒子径（Ｄ50）が０．１４μｍであった。得られた粉砕液へ水を添加してアルミナ成分の濃度１５％、ｋ値を０．０００４５とし、その一部をステンレス製１インチのガス管へ挿入し、エアバス中で昇温時間も含めて１４０℃、１４時間加熱して水熱反応を行い、微量の液状物質を含む水性アルミナゾルの生成物が得た。反応条件、原料アルミナの変換率及び水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状の結果を表２に示す。 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 μm. 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.
　実施例１０
　実施例７と同様の原料アルミナを使用し、アルミナ濃度２０重量％、硝酸／アルミナのモル比が０．１２のスラリーを調製した。このスラリーを粉砕時間を４時間とした以外は、実施例７と同様に原料アルミナの微粉砕を行った。粉砕後のスラリーは平均粒子径（Ｄ50）が０．１４μｍであった。得られた粉砕液へ水及び硝酸を添加してアルミナ成分の濃度１２．５％、硝酸／アルミナのモル比が０．１４、ｋ値を０．０００４２とし、その一部をステンレス製１インチのガス管へ挿入し、エアバス中で昇温時間も含めて１４０℃、１４時間加熱して水熱反応を行い、微量の液状物質を含む水性アルミナゾルの生成物を得た。反応条件、原料アルミナの変換率及び水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状の結果を表２に示す。 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 μm. 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.
　実施例１１
　実施例７と同様の原料アルミナを使用し、アルミナ濃度２５重量％、硝酸／アルミナのモル比が０．１６のスラリーを調製した。このスラリーを、粉砕時間を６時間とした以外は、実施例７と同様に原料アルミナの微粉砕を行った。粉砕後のスラリーは平均粒子径（Ｄ50）が０．１１μｍであった。得られた粉砕液へ水を添加してアルミナ成分の濃度１５．０％、硝酸／アルミナのモル比が０．１６、ｋ値を０．０００８１とし、その一部をステンレス製１インチのガス管へ挿入し、エアバス中で昇温時間も含めて１４０℃、１６時間加熱して水熱反応を行い、微量の液状物質を含む水性アルミナゾルの生成物を得た。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に示す。また、透過型顕微鏡写真を図３に示す。
　さらに水性アルミナゾルについて５５０℃、２時間焼成処理物の水銀圧入法による細孔径分布図から求めた細孔容量及び平均細孔径を表３に示す。 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 μm. 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. for 16 hours including the temperature rising time to perform a hydrothermal reaction to obtain an aqueous alumina sol product containing a small amount of liquid substance. 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. 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.
　実施例１２
　水熱反応の反応条件を、１５０℃、８時間とした以外は、実施例１１と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。 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.
　実施例１３
　水熱反応の反応条件を、１６０℃、４時間とした以外は、実施例１１と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。 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.
　実施例１４
　水熱反応の反応条件を、１７０℃、１時間３０分とした以外は、実施例１１と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。また、透過型顕微鏡写真を図４に示す。
　さらに水性アルミナゾルについて５５０℃、２時間焼成処理物の水銀圧入法による細孔径分布図から求めた細孔容量及び平均細孔径を表３に示す。 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. 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.
　実施例１５
　ステンレス製１インチのガス管に代わり、ステンレス製３／４インチのガス管を使用し、エアバスに代わり、オイルバスを使用し、水熱反応の反応条件を、１８０℃、３０分とした以外は、実施例１１と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。 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. In the same manner as in Example 11, 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.
　実施例１６
　水熱反応の反応条件を、１８０℃、１時間３０分とした以外は、実施例１５と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。 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.
　実施例１７
　水熱反応の反応条件を、１８０℃、２時間３０分とした以外は、実施例１５と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。 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.
　実施例１８
　水熱反応の反応条件を、２００℃、６分とした以外は、実施例１５と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。 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.
　実施例１９
　水熱反応の反応条件を、２００℃、１２分とした以外は、実施例１５と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。 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.
　実施例２０
　水熱反応の反応条件を、２２０℃、２分とした以外は、実施例１５と同様にして、微量の液状物質を含む水性アルミナゾルの生成物を製造した。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。さらに水性アルミナゾルについて５５０℃、２時間焼成処理物の水銀圧入法による細孔径分布図から求めた細孔容量及び平均細孔径を表３に示す。 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. 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.
　実施例２１
　実施例１１の平均粒子径（Ｄ50）が０．１１μｍの原料アルミナ粉砕物を用い、硝酸と水を添加してアルミナ成分の濃度１４．９％、硝酸／アルミナのモル比が０．２０、ｋ値を０．００１２７である調製液を添加した。１インチステンレス製ガス管に調整液を挿入し、エアバス中で１７０℃、２時間水熱反応を行った。結果を表２に示す。反応条件、原料アルミナの変換率、水性アルミナゾルの２００℃乾燥物の比表面積(ＳＡ)及び生成物の形状を表２に併せて示す。また、透過型顕微鏡写真を図５に示す。 Example 21
The raw material alumina pulverized product having an average particle diameter (D 50 ) of Example 11 of 0.11 μm 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.
　実施例２２
　実施例１１の平均粒子径（Ｄ50）が０．１１μｍの原料アルミナ粉砕物を用い、硝酸と水を添加してアルミナ成分の濃度１４．８％、硝酸／アルミナのモル比が０．２０、ｋ値を０．００１８４である調製液を添加した。１インチステンレス製ガス管に調整液を挿入し、エアバス中で１７０℃、２時間水熱反応を行った。結果を表２に示す。また、透過型顕微鏡写真を図６に示す。
　さらに水性アルミナゾルについて５５０℃、２時間焼成処理物の水銀圧入法による細孔径分布図から求めた細孔容量及び平均細孔径を表３に示す。 Example 22
The raw material alumina pulverized product having an average particle diameter (D 50 ) of Example 11 of 0.11 μm 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　比較例２
　平均粒子径（Ｄ50）が６．１μｍのρ-およびχ-結晶構造を有する原料アルミナを用い、アルミナ濃度を４５％、硝酸のモル比/アルミナのモル比を０．１６、ｋ値が0.0040としてステンレスパイプ中に充填し、１６０℃で８時間水熱反応を行なった結果、その生成物はその変換率が８５．３％と低位で、２００℃乾燥後の生成ベーマイトの比表面積は１８３ｍ2／ｇの低い値を示した。 Comparative Example 2
Raw material alumina having a ρ- and χ- crystal structure with an average particle diameter (D 50 ) of 6.1 μm 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.
　比較例３
　平均粒子径（Ｄ50）が０．７μｍのρ-およびχ-結晶構造を有する原料アルミナを用い、アルミナ濃度を１５％、硝酸のモル比/アルミナのモル比を０．０２、ｋ値が0.000012としてステンレスパイプ中に充填し、１５０℃で８時間水熱合成を行なった結果、その生成物は固化したゲル状物の性質を示し、バインダー性を示さないベーマイトゲルが得られた。 Comparative Example 3
Raw material alumina having a ρ- and χ- crystal structure with an average particle diameter (D 50 ) of 0.7 μm 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.
　比較例４
比較例３のアルミナ原料を用い、アルミナ濃度を５５％、硝酸のモル比/アルミナのモル比を０．１０、ｋ値が0.0023としてステンレスパイプ中に充填し、１６０℃で８時間水熱合成を行なった結果、生成物は固結した塊状物でハンドリングに著しく困難な物質となっていた。 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.
　比較例５
　実施例１１のアルミナ濃度１５％、硝酸のモル比/アルミナのモル比０．１６の湿式粉砕液を用い、これに蓚酸をアルミナに対して２重量％添加したあと、ステンレスパイプ中に充填し、１５０℃で８時間水熱合成を行なった結果、固化したゲル状物の性質を示す生成物（ベーマイトゲル）が得られた。表４に生成物の諸性質を示す。生成物は、比較的高い比表面積を示すもののバインダー性を示さなかった。 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.
　比較例６
　蓚酸の代わりにグリコール酸をアルミナに対して２重量％添加した以外は、比較例５と同様にして、生成物（ベーマイトゲル）を得た。表４に生成物の諸性質を示す。生成物は、比較的高い比表面積を示すもののバインダー性を示さなかった。 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.
　比較例７
　蓚酸の代わりにクエン酸をアルミナに対して２重量％添加した以外は、比較例５と同様にして、生成物（ベーマイトゲル）を得た。表４に生成物の諸性質を示す。生成物は、比較的高い比表面積を示すもののバインダー性を示さなかった。 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.
　比較例８
　蓚酸の代わりに燐酸（Ｐ2Ｏ5）をアルミナに対して２重量％添加した以外は、比較例５と同様にして、生成物（ベーマイトゲル）を得た。表４に生成物の諸性質を示す。生成物は、比較的高い比表面積を示すもののバインダー性を示さなかった。 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.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

Claims (16)

  1. 　平均粒子径（Ｄ50）が５μｍ以下のρ-およびχ-結晶構造を有するアルミナ、水、および無機一塩基酸またはその塩からなり、無機一塩基酸/アルミナモル比を０．０３から２．０、アルミナ濃度を３重量％から５０重量％の範囲に調節した調整液を、４０℃から２５０℃の範囲で熟成および／または水熱反応を行うことを特徴とするポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。 It consists of alumina having a ρ- and χ- crystal structure with an average particle size (D 50 ) of 5 μm or less, water, and an inorganic monobasic acid or a salt thereof, and has an inorganic monobasic acid / alumina molar ratio of 0.03 to 2.0. Polyhydric monobasic aluminum hydration characterized by aging and / or hydrothermal reaction of an adjustment liquid whose alumina concentration is adjusted in the range of 3 wt% to 50 wt% in the range of 40 ° C. to 250 ° C. And / or production method of aqueous alumina sol.
  2. 　前記アルミナの熟成および／または水熱反応後のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルへの変換率が、９０％以上である請求項１記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。 2. The polyinorganic monobasic aluminum hydrate according to claim 1, wherein the conversion rate to polyaluminum monobasic aluminum hydrate and / or aqueous alumina sol after aging and / or hydrothermal reaction of the alumina is 90% or more. And / or production method of aqueous alumina sol.
  3. 　前記ρ-およびχ-結晶構造を有するアルミナの平均粒子径（Ｄ50）が、１μｍ以下である請求項１または２記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。 The method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous arnamisol according to claim 1 or 2, wherein the alumina having the ρ- and χ- crystal structure has an average particle diameter (D 50 ) of 1 µm or less.
  4. 　前記ρ-およびχ-結晶構造を有するアルミナが、水と無機一塩基酸またはその塩との存在下で湿式粉砕することにより得られてなる請求項１から３のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。 4. The polyinorganic one according to claim 1, wherein the alumina having the ρ- and χ- crystal structures is obtained by wet grinding in the presence of water and an inorganic monobasic acid or a salt thereof. A method for producing an aluminum basic acid hydrate and / or an aqueous alumina sol.
  5. 　調整液の無機一塩基酸／アルミナのモル比が０．５以上２．０以下の範囲であり、４０℃以上１３０℃未満の温度で熟成および／または水熱反応を行わせ、ポリ無機一塩基酸アルミニウム水和物を得ることを特徴とする請求項１から４のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。 The inorganic monobasic acid / alumina molar ratio of the adjustment liquid is in the range of 0.5 or more and 2.0 or less, and is subjected to aging and / or hydrothermal reaction at a temperature of 40 ° C. or more and less than 130 ° C. The method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous arnamisol according to any one of claims 1 to 4, wherein aluminum hydrate is obtained.
  6. 　調整液の無機一塩基酸／アルミナのモル比が０．０３以上０．５未満の範囲であり、４０℃以上１３０℃未満の温度で熟成および／または水熱反応を行わせ、ポリ無機一塩基酸アルミニウム水和物と水性アルミナゾルの混合物を得ることを特徴とする請求項１から４のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。 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. A method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous arnamisol according to any one of claims 1 to 4, wherein a mixture of aluminum hydrate and aqueous alumina sol is obtained.
  7. 　調整液の無機一塩基酸／アルミナのモル比が０．０３以上０．５以下の範囲であり、１３０℃以上２５０℃以下の温度で水熱反応を行わせ、水性アルミナゾルを得ることを特徴とする請求項１から４のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。 The molar ratio of the inorganic monobasic acid / alumina in the adjustment liquid is in the range of 0.03 to 0.5, and a hydrothermal reaction is performed at a temperature of 130 ° C. to 250 ° C. to obtain an aqueous alumina sol. A method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous arnamisol according to any one of claims 1 to 4.
  8. 　前記調整液が下記の式で表されるｋ値の組成範囲を有する請求項１から４のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。
    　　0.000005≦ｋ≦0.30　　　ただし、ｋ＝(b／a)×(b／c)
    （式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）     The method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous alumina sol according to any one of claims 1 to 4, wherein the adjustment liquid has a composition range of k value represented by the following formula.
    0.000005 ≦ k ≦ 0.30 where 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. 　調整液のｋ値が下記の式で表される組成範囲を有し、無機一塩基酸／アルミナのモル比が０．０３以上０．５以下の範囲を有する調製液を１３０℃以上２５０℃以下の温度で水熱反応を行わせ、板状、テープ状又は繊維状の粒子形状を有する水性アルミナゾルを得ることを特徴とする請求項８記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
    　　0.000005≦ｋ≦0.03　　　ただし、ｋ＝(b／a)×(b／c)
    （式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）     A prepared liquid having a composition range in which the k value of the adjustment liquid is represented by the following formula and the molar ratio of inorganic monobasic acid / alumina is 0.03 or more and 0.5 or less is 130 ° C. or more and 250 ° C. or less. 9. A polyinorganic monobasic aluminum hydrate and / or aqueous solution according to claim 8, wherein a hydrothermal reaction is carried out at a temperature of to obtain an aqueous alumina sol having a plate-like, tape-like or fibrous particle shape. Arnamisol production method.
    0.000005 ≦ k ≦ 0.03 where 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. 　調整液のｋ値が下記の式で表される組成範囲であり、主に板状の粒子形状を有する水性アルミナゾルを得ることを特徴とする請求項８または９記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
    　　0.000005≦ｋ＜0.0005　　　ただし、ｋ＝(b／a)×(b／c)
    （式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）     10. The polyinorganic monobasic aluminum aqueous solution according to claim 8, wherein an aqueous alumina sol having a k value of the adjustment liquid represented by the following formula and having mainly a plate-like particle shape is obtained. A method for producing a hydrate and / or an aqueous anamisol
    0.000005 ≦ k <0.0005 where 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. 　調整液のｋ値が下記の式で表される組成範囲であり、主にテープ状の粒子形状を有する水性アルミナゾルを得ることを特徴とする請求項８または９記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
    　　0.0005≦ｋ＜0.0015　　　ただし、ｋ＝(b／a)×(b／c)
    （式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）     10. The polyinorganic monobasic aluminum aqueous solution according to claim 8, wherein an aqueous alumina sol having a k value of the adjustment liquid represented by the following formula and mainly having a tape-like particle shape is obtained. A method for producing a hydrate and / or an aqueous arnamisol.
    0.0005 ≦ k <0.0015 where 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. 　調整液のｋ値が下記の式で表される組成範囲であり、主に繊維状の粒子形状を有する水性アルミナゾルを得ることを特徴とする請求項８または９記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルナミゾルの製造方法。
    　　0.0015≦ｋ≦0.03　　　ただし、ｋ＝(b／a)×(b／c)
    （式中、aは調整液中のアルミナをＡｌ2Ｏ3に換算したモル数、bは無機一塩基酸またはその塩のモル数、cは水のモル数）     10. The polyinorganic monobasic aluminum aqueous solution according to claim 8, wherein an aqueous alumina sol having a k value of the adjustment liquid represented by the following formula and mainly having a fibrous particle shape is obtained. A method for producing a hydrate and / or an aqueous arnamisol.
    0.0015 ≦ k ≦ 0.03 where 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. 　前記ポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの５５０℃、２時間焼成後の細孔容量が、０．４０ｍＬ／ｇ以下であり、かつ、平均細孔径が、１００Å以下である請求項１から１２のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。 The poly inorganic monobasic aluminum hydrate and / or the aqueous alumina sol has a pore volume after firing at 550 ° C. for 2 hours of 0.40 mL / g or less and an average pore diameter of 100 μm or less. Item 13. A method for producing a polyinorganic monobasic aluminum hydrate and / or an aqueous alumina sol according to any one of Items 1 to 12.
  14. 　前記無機一塩基酸が、硝酸である請求項１から１３のいずれかに記載のポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾルの製造方法。 The method for producing a poly inorganic monobasic aluminum hydrate and / or an aqueous alumina sol according to any one of claims 1 to 13, wherein the inorganic monobasic acid is nitric acid.
  15. 　請求項１から１４のいずれかに記載の方法により製造されてなることを特徴とするポリ無機一塩基酸アルミニウム水和物および／または水性アルミナゾル。 A polyinorganic monobasic aluminum hydrate and / or aqueous alumina sol produced by the method according to any one of claims 1 to 14.
  16. 　請求項８から１５のいずれかの製造方法により得られた水性アルミナゾルをバインダーとして用いてなるＲ－ＦＣＣ触媒。 An R-FCC catalyst using the aqueous alumina sol obtained by the production method according to any one of claims 8 to 15 as a binder.
PCT/JP2009/003498 2008-07-28 2009-07-24 Process for production of poly(aluminum-inorganic monobasic acid salt hydrate) and/or aqueous alumina sol, and poly(aluminum inorganic monobasic acid salt hydrate) and/or aqueous alumina sol obtained by the process WO2010013428A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659149A (en) * 2012-02-28 2012-09-12 山东大学 Preparation method for monodisperse high-purity alpha-Al2O3 powder
CN111233490A (en) * 2020-02-21 2020-06-05 鞍山腾泰耐火材料有限公司 Aluminum-based binder for sintering high-alumina bricks and preparation method thereof

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JPH07256100A (en) * 1994-03-24 1995-10-09 Agency Of Ind Science & Technol Production of heat-resistant alumina carrier for catalytic combustion
JPH10231120A (en) * 1996-12-20 1998-09-02 Asahi Glass Co Ltd Alumina sol, alumina hydrate powder, and recording medium
WO2001056951A1 (en) * 2000-01-06 2001-08-09 Goro Sato Alumina composition, method for preparation thereof and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07256100A (en) * 1994-03-24 1995-10-09 Agency Of Ind Science & Technol Production of heat-resistant alumina carrier for catalytic combustion
JPH10231120A (en) * 1996-12-20 1998-09-02 Asahi Glass Co Ltd Alumina sol, alumina hydrate powder, and recording medium
WO2001056951A1 (en) * 2000-01-06 2001-08-09 Goro Sato Alumina composition, method for preparation thereof and use thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102659149A (en) * 2012-02-28 2012-09-12 山东大学 Preparation method for monodisperse high-purity alpha-Al2O3 powder
CN111233490A (en) * 2020-02-21 2020-06-05 鞍山腾泰耐火材料有限公司 Aluminum-based binder for sintering high-alumina bricks and preparation method thereof

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