JPH0724749B2 - Method for producing spherical agglomerates by selective agglomeration - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing small spherical formulations or particles that are agglomerates. More specifically, the present invention relates to a method for producing spherical solid agglomerates useful as absorbents, catalysts, or catalyst supports in various chemical processes by agglomeration operations from suspensions of solid particles. The method of the present invention provides formulations or particles that are substantially spherical agglomerates having a substantially uniform small diameter within a range.

BACKGROUND OF THE INVENTION [0002] Various types of inorganic tangible formulations are currently being made by chemical or similar operations. It is advantageous to make a spherical formulation. This is because the spherical preparation has preferable properties, for example, relatively good packing property, relatively high strength, relatively small amount of fine particles, and relatively good flow property. is there. Such spherical preparations are mainly used as catalysts, catalyst carriers, adsorbents and the like.

Various methods are already known for making tangible inorganic formulations. For example, U.S. Pat. No. 3,656,901 (Kumare) discloses that silica / alumina or silica is prepared by dropping an aqueous liquid of colloidal sodium silicate or colloidal silica / alumina into a solvent such as alcohol, ether-alcohol or amine. A method of gelling the particles of to make a tangible formulation is disclosed. However, this U.S. patent does not disclose a method of obtaining substantially spherical particles having a diameter within a predetermined range.

U.S. Pat. No. 3,844,978 (Hixson) discloses a hydrothermal crystallization (hys) using an aqueous slurry of an aqueous sol and salt.
A method of performing a drothermal crystallization operation and then dehydrating and drying the slurry to obtain a solid, which is then ground to obtain particles of a desired particle size is disclosed.
However, the Hixson US patent does not disclose any method for forming small, substantially spherical agglomerates.

US Patent Application No. 524,197 (Hixson; filing date 1
(August 18, 983), fine particles were dispersed in a non-aqueous medium, and then an aqueous phase was added in the presence of colloidal particles to agglomerate the dispersion to form a plastic mass. A method is disclosed for extruding or other operations on the mass to obtain small particles.

U.S. Pat. No. 3,258,311 (Bruzynski) discloses a method of making spherical beads of uniform size from alkali metal silicates. This method
(1) Particle forming raw material component, that is, (a) water,
(B) General formula xR ₂ O.ySiO ₂ [where R is an alkali and the x / y ratio is greater than 0.24 (the x / y ratio, which is the R ₂ O / SiO ₂ ratio, is defined by water-soluble sodium silicate and Is a value representing the compositional characteristics of a general water-soluble alkali silicate], (c) a dilute aqueous strong acid, (d) an emulsifier, and (2) the resulting mixture is stirred. This results in beads with a diameter of generally about 1 micron to 1.5 mm, which is not an advantageous method because the diameter is greater than 1.5 mm. This is because in the case of making a bead, a bead having a uniform size cannot be made by this method.

U.S. Pat. No. 3,140,251 (Planck et al.) Discloses a method for producing spheroidal formulations. In this method, in the hydrosol obtained by reacting an alkali metal silicate with an acidic or alkaline flocculant,
The aluminosilicate is dispersed. The hydrosol can be dispersed through a nozzle into a bath of oil or other water immiscible suspension medium, thereby forming catalyst particles which are bead particles in the form of spheroids. However, it is not possible with this known method to control the particle size of the small-sized aggregates to a constant value, and furthermore, this colloidal solution forms an emulsion when vigorously stirred. possible.

US Pat. No. 3,296,151 (Heinze et al.)
Wetting the solid zeolite particles with water to form a binder
There is disclosed a method which comprises mixing with, kneading into a paste, subjecting the paste to an extrusion molding operation or another operation to obtain a molded product, and drying the molded product.
Heinze et al. Also disclose another method of agglomeration,
That is, it discloses a method comprising dropping an aqueous sol into a water-immiscible liquid and gelling the sol in this liquid. In both cases, a molecular sieve consisting of spherical zeolite can be produced, but its diameter or other dimensions and its range are not disclosed.

US Pat. No. 3,515,684 (Matsukuevoi),
A method of making a fluidizable cracking catalyst is disclosed. In this method, a dispersion of a fine powder of kaolin in water is vigorously stirred in oil to condense kaolin particles,
It produces agglomerates with a particle size distribution on the order of 15-150 microns. This product is suitable as a catalyst for fluidized cracking reactions. The disadvantage of this catalyst manufacturing method is that
It is limited to the production of particles with diameters of the order of 15-150 microns.

U.S. Pat. No. 4,013,587 (Fisher et al.) Discloses that (a) an aluminum hydroxide hydrosol is mixed with a high molecular weight natural organic material to form a mixture, and (b) this mixture is dispersed in a water-insoluble form. Introducing into a miscible liquid to form gel particles at elevated temperature, (c) aging the particles in the above liquid and then in an aqueous ammonia solution,
A method for producing alumina-containing particles, which comprises (d) recovering the particles and (e) firing the particles, is disclosed. The disadvantage of this method is that high temperatures are required and that dangerous aqueous ammonia has to be used.

U.S. Pat. No. 2,474,911 (Pierce et al.) Discloses a method for continuously producing fine spherical gel particles.
In this method, the sol is introduced into a water immiscible liquid such as oil containing an emulsifier. The liquid is kept in a turbulent state only at the bottom of the mixing tower to form a turbulent zone. The flow rate of oil in the column is adjusted so that the gel droplets flow continuously. However, Pierce et al. Does not teach at all how to obtain spherical particles having a diameter of 1-5 mm.

In addition, there are some interesting US patents. For example, US Pat. No. 2,384,946 (Marissik) discloses a method of making generally spherical hydrogel pellets. This pellet is obtained by spraying the hydrogel into a gaseous or liquid medium through an orifice.

U.S. Pat. No. 2,900,349 (Schwartz) discloses a method for producing a highly wear-resistant inorganic oxide gel.

In one embodiment of the Schwarz method, ellipsoidal hydrogels are produced by moving the gel down or up through a column of hydrocarbon solvent.

U.S. Pat. No. 3,004,929 (Lucas et al.) Discloses a method of producing a silica-alumina catalyst support and molding it by an extrusion operation. The catalyst carrier obtained by this method is generally a pellet, but it is not a spherical body having a uniform size, and the size range thereof is different from the value specified in the present invention.

Australian Patent No. 127,250 discloses a method of making fine gel particles which can be used for catalytic adsorbents or other applications. The size adjustment is performed as follows. By emulsifying the hydrosol as the internal phase of a water-immiscible liquid, stirring the resulting emulsion until the hydrosol has condensed to prevent phase separation and isolating the resulting gel particles. An inorganic gel in the form of fine particles is obtained. The disadvantage of this method is that the size of the particles is of the order of 60-100 microns, which is much smaller than the particles of the invention.

"Jeanal, Of, Catalysis", Vol. 18, No. 3, No. 35
Towster's article, pages 8-360 (1980), describes that particles are suspended in a water-immiscible liquid, which is then treated with an aqueous solution of a metal salt. , A method of impregnating voids of particles with a metal salt is disclosed.

The book "Agglomeration in liquid media" by CE Capes [Elsvia, Scientifik Publishing Company (Amsterdam, The Netherlands), 1980], Chapter 1, "Agglomeration in liquid media," describes various particle formation methods. It describes how to use water-immiscible liquids. However, Cape's book does not disclose any spherical product having a uniform diameter in the range of about 1-5 mm as described herein and its preparation.

AF Sirani's dissertation ("Canadian, Journal, Of, Chemical, Engineering" Vol. 47, p. 166-No. 1
On page 70 (1969), various methods for flocculating fine solids in suspension are discussed. In these methods, the solids can be separated as spheres, but they do not have substantially uniform dimensions.

Another example of literature on agglomeration is JE Browning's article "Agglomeration: Large Particle Growth and Its Technology in Various Fields"("Chemicals,Engineering," December 1967, 4).
J., pp. 147-170), HM Smith and IE Paddington's paper (Canadian, Journal, Of, Chemical, Engineering, Vol. 38, 1916, 1960), J.
A paper by R. Farand ("Canadian, Journal, Of, Chemical, Engineering" Vol. 39, p. 94, 1961)
,) And JP Sutherland's paper (“Canadian, Journal, Of, Chemical, Engineering”)
40, 268, 1962).

All the above-mentioned conventional methods have some drawbacks. For example, it is often difficult to vary the composition and size of solid particles. Moreover, the products of the conventional methods are often in the form of fine powder or flakes, which do not have sufficient mechanical properties under the conditions of use in their field of application.

On the other hand, the object of the present invention is to provide a method for producing small inorganic spheres which are particularly useful as catalysts and catalyst carriers. The spherical material of the present invention has advantages such as high strength, low fracture tendency, and good filling property. The average diameter of the spherules is in the range of about 1-5 mm and the diameter values are uniform.

SUMMARY OF THE INVENTION The present invention relates to a method for producing spherical agglomerates of substantially inorganic material having substantially uniform dimensions. When using a one-component solid, the method of the present invention comprises:
(A) A part of the inorganic substance is mixed at high speed with a water-immiscible liquid in the form of hydrophilic fine particles to form a dispersion, and (b) an aqueous phase is added to the dispersion while continuing high-speed mixing. The operation is continued until the formation of substantially spherical microaggregates in the water immiscible phase, optionally said aqueous phase containing an acidic substance, (c) then Mixing and stirring the fine agglomerates at a sufficiently low mixing speed to produce substantially uniform sized spherical agglomerates having diameters in the range of about 1-5 mm; Separating the agglomerates from the water-immiscible solvent described above, and (e) drying the agglomerates to produce spherical hardened agglomerates having substantially uniform dimensions. Is. Optionally, in step (b) of the process, the soluble metal salt in the aqueous phase is about 0.1-70.
% May be added, in which case the metal salt will enter the agglomerate. The final agglomerates generally have uniform dimensions and their diameters are in the range of about 1-5 mm.

In another aspect of the invention, this relates to a method of making a substantially spherical agglomerate comprising two or more components. In this case, two or more components are combined and the following operations are carried out: (a) A liquid reaction mixture comprising a water-immiscible solvent and hydrophilic inorganic particles is rapidly stirred to form a dispersion liquid. And (b) continuously stirring the reaction mixture at high speed while gradually adding an aqueous phase containing inorganic particles having colloidal dimensions, optionally the aqueous phase may step on an acidic substance. (C) then slowly mixing the products of step (b) above to produce spherical agglomerates of substantially uniform size, and (d) agglomerates obtained in step (c) above. The product is isolated from the solvent and (e) the agglomerates are dried to form spherical hardened agglomerates having substantially uniform dimensions. The process can optionally also use an aqueous phase containing about 0.1-70% by weight of soluble metal salt in step (b). The final agglomerates obtained are generally of uniform size and have diameters in the range of about 1-5 mm.

Still another aspect of the present invention will be described. This concerns a continuous process for the production of substantially spherical condensates. In this method, the three or more components are mixed simultaneously rather than intermittently and the following operations are performed: (a) (i) a water immiscible liquid; (ii) a finely divided liquid. Continuous mixer constraining a reaction mixture comprising: hydrophilic hydrophilic inorganic particles; and (iii) an aqueous phase containing inorganic particles of colloidal size and optionally other additives (eg metal salts, acids, bases, etc.). (B) transfer the product obtained in step (a) above to a low speed mixer to produce spherical agglomerates of substantially uniform size; The agglomerates obtained in step (b) above are separated from the solvent and (d) the agglomerates are dried to form spherical hardened agglomerates having substantially uniform dimensions. According to the production method of this embodiment, spherical solid agglomerates of substantially uniform size substantially consisting of an inorganic substance are obtained, and the diameter thereof is a value within the range of about 2-5 mm.

The spheres are useful as catalysts, catalyst carriers, catalyst substrates, adsorbents and the like.

Definition of terms The terms "aggregate" and "aggregate" as used herein
Is a term that refers to the technique of collecting finely divided powders to form larger particles, and the product thus formed, respectively. The larger particles mentioned above are themselves retained by various physical and chemical forces.

The term "water-immiscible liquid" has a solubility in water of about 1.0% by weight.
It is a term meaning liquids such as hydrocarbons, fluorocarbons and halocarbons and mixtures thereof below.
Water-immiscible liquids that can be advantageously used in the present invention have a boiling point of about 35.
It is at -100 ° C. This liquid must not dissolve nor harm the hydrophobic material that is the lining material for the mixers and conduits in the apparatus used in the present invention.

The terms "hydrocarbon" and "hydrocarbon liquid" have a boiling point of about 35-100.
It is a term meaning a liquid hydrocarbon at ° C. Examples of this hydrocarbon are pentane, pentene, hexane, hexene, cyclohexane, heptane, heptene, boiling point 30-60 ° C petroleum ether, boiling point 50-80 ° C petroleum ether, boiling range approx.
Examples include petroleum fractions at 50-100 ° C. The hydrocarbon includes linear, branched, cyclic hydrocarbon compounds and mixtures thereof.

The term "fluorocarbon" refers to a straight chain, branched or cyclic, commercially available liquid aliphatic compound in which one or more protons have been replaced by fluorine. Generally, one or more additional protons are replaced with chlorine or bromine. Examples of this fluorocarbon are bromofluoromethane, 1,2-dichlorohexafluoro-cyclobutane, 1,1,2-trichloro-1,2,2-trifluoroethane, 1bromo-1,2-dichloro-1,2. 2,2-trifluoroethane, 2-fluoro-1,2,2-trichloroethane and the like can be mentioned. The boiling point of these liquids is about 35-100.
℃. Due to the low hydrogen bonds, the separation of these liquid fluorocarbons from the agglomerates can be carried out relatively easily by heating, ie this separation is easier than the separation of hydrocarbon liquids.

The "zeolite" used in the present invention has a skeletal structure composed of tetrahedral aluminosilicates, has a controlled porosity, contains large cations capable of ion exchange, and has loosely bound water molecules. It includes natural and synthetic hydrous tectosilicate minerals that have the property of being capable of reversible dehydration. Examples of hydrated aluminum silicate and calcium silicate, CaO.2 Al ₂ O ₃ .5SiO ₂ and Na ₂ O.2 Al
₂ O ₃ .5SiO _2, and the like. Usually there is some amount of water of hydration. These materials can be used very advantageously alone or with a catalyst support in petroleum refining and reforming processes. Examples of zeolites that can be used include natural zeolites such as erionite, chabazite, activated analsite, gmelinite, mordenite, and various synthetic or modified crystalline zeolites, and examples of synthetic zeolites include U.S. Patent 3,709,979. "ZSM-11" (trade name) described in the specification, U.S. Pat. No. 3,755,14
No. 5, "ZSM-5" and "ZSM-8" (trade name), U.S. Pat. No. 3,013,909, zeolite-A, X, Y, L, D, R, S and T. , "CZH-5-zeolite" described in U.S. Pat. No. 4,360,419, U.S. Pat.
"ZSM-43" described in 4,209,499, U.S. Pat. No. 4,0
86,186, "ZSM-34", U.S. Pat. No. 4,287,
"ZSM-39" described in Japanese Patent No. 166 is mentioned. These zeolites are listed solely for purposes of illustration, and each of the aforementioned U.S. patents is incorporated herein by reference.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram showing each step of the method of the present invention, namely, mixing, dispersion, aggregation, separation, drying and solvent recycling steps.

Detailed Description of the Preferred Embodiments of the Invention In FIG. 1, the vessel 1 is generally a high speed mixer [preferably a colloid mill, examples of which are Chem colloid, Laboratory Corp. (Heridex, Road 55; Garden City, New York, USA; 11040) mill (CHARLOTTE)
The mixture is used for high-speed and high-shear mixing to form a predetermined dispersion, and the aqueous phase is emulsified to form fine agglomerates. The container 1 may be provided with a high-speed stirring means (for example, a stirrer), or an equivalent means thereof, that is, a means capable of performing predetermined high shear force mixing may be provided. Another example of a high speed mixer (disperser) known in the art is a mixer made by Meyer's Engineering Co. (Bell, Salt, Lake, Avenyu, USA, 8376; 90201), and The homogenizer type mixer manufactured by Greeco (USA, New Hampshire, Hudson, Executive, Drive; 03051) can be mentioned.

In the preferred embodiment of the continuous process for the production of spherical catalysts and / or adsorbents, the mixer 1 used is a high shear mixer, such as a colloid mill. The rotational speed of the rotating part of the mixer is generally about 2500-4000 rpm, preferably about 280.
At 0-3000 rpm, this gives a dispersion of fine agglomerates. The shear rate of the stirrer in this case can be calculated from the diameter of the stirrer or the mixer. For example, 6
In the case of a stirrer with an inch blade, about 2500-4000
A rotation speed of rpm corresponds to a peripheral speed of about 66.6-106.6 feet / second, and a rotation speed of about 2800-3000 rpm corresponds to a peripheral speed of about 74.6-80 feet / second.

A water-immiscible liquid is continuously supplied to the container 1 through a pipe 3 (in the case of a replenishing liquid) and a pipe 25 (in the case of a recirculating liquid).
Examples of water immiscible liquids include the hydrocarbons, fluorocarbons and halocarbons described. A preferred liquid is a fluorocarbon, an example of which has a boiling point of about 35-10.
Examples include fluoroalkanes and fluorohaloalkanes at 0 ° C. This fluorocarbon liquid also has the advantage that it has a high specific gravity. That is, the aggregates float on the liquid surface, and the aggregates can be easily removed from the liquid by a scooping operation on the liquid surface. Furthermore, since fluorocarbon has a high vapor pressure and does not have a hydrogen bond, it is easy to remove this solvent in the drying step. 1,1,2-trichloro-
1,2,2-Trifluoroethane and / or 1,2-dibromo-1,1,2,2-tetrafluoroethane are particularly useful as the liquid medium or solvent.

An inorganic substance in the form of hydrophilic fine-sized particles and an aqueous phase (which may optionally contain an acidic substance) are also simultaneously fed to the vessel 1 via tubes 4 and 5. In the high shear mixer, fine agglomerates consisting of the inorganic material and the aqueous phase are formed. The residence time of the fine agglomerates in the container 1 generally varies depending on the substances present therein, but is usually about 0.1-300 seconds. The diameter of the fine agglomerates at this stage is preferably less than 200 microns (0.2 mm). Inorganic salts or agents can be added to the aqueous phase to enhance the catalytic activity of the final product, such as Pt, Pd, Ni,
Salts of metals such as Co, Mo, Sn, W, Rh and Re; acids such as nitric acid, sulfuric acid, acetic acid and citric acid; bases such as sodium hydroxide, ammonia and organic amines can be added. Alternatively, the colloidally sized inorganic particles can be mixed with the aqueous phase, which can optionally contain acidic substances, and fed to the tube 1. According to this method, a homogeneous mixture of inorganic catalyst components (alumina, silica, zeolite, etc.), catalytic metal and chemical modifier can be produced by a high shear mixing operation.

Usage of water immiscible liquids, hydrophilic fine size particles, colloidal size inorganic particles and aqueous liquids (relative amount)
Should be in an amount sufficient to produce the desired agglomerates. The amount of hydrophilic fine size particles in a water immiscible liquid is generally about 1-25% by weight. The ratio of hydrophilic fine inorganic particles to particles of colloidal size is about 1: 5 to 5: 1.
It's okay. This ratio is preferably about 2 to 1 to 1.
It is a pair 2.

In the case of the continuous process, the dispersion of fine agglomerates is then piped 6
Add to container 7 through. Vessel 7 is a low speed mixer and generally has baffling means. This is equipped with a stirrer 8 or its equivalent means, in which mixing is carried out at a sufficiently low speed to carry out agglomeration, whereby the above-mentioned fine agglomerates are further grown, and within a range of about 1-5 mm. To produce substantially uniform sized spherical agglomerates having a diameter of .about.2 (preferably in the range of about 2-4 mm). The tube 6, container 7 and agitator 8 are preferably lined or coated with a hydrophobic material. Examples of the hydrophobic substance include hydrophobic plastic materials such as polyalkane (eg, polyethylene, polypropylene, polystyrene), polyvinyl chloride, polycarbonate, poly (methyl methacrylate), Teflon, and Viton. Polyethylene and Teflon are particularly preferred materials. If this agglomeration operation is carried out using a glass or metal (eg stainless steel) mixer, the inner surface of the mixer will be contaminated with the inorganic hydrogel, causing operational inconveniences such as tube clogging. Sometimes.

The speed of rotation of the vessel 7 or the mixing agitator 8 of the low speed aggregator is about 250-500 rpm, preferably about 300-400 rpm. The peripheral speed of this slow mixing stirrer can also be calculated. For example, in the case of a stirrer with 6-inch blades, about 25
A rotation speed of 0-500 rpm corresponds to a peripheral speed of about 6.6-13.3 feet / sec, and a rotation speed of about 300-400 rpm is about 8-10.6.
Equivalent to a peripheral velocity of feet / second. The residence time of the dispersion in the low speed aggregator will vary depending on the properties desired for the desired final agglomerate, but is generally about 1-30 minutes. When forming the agglomerates described above, the residence time is preferably about 5-10 minutes. Generally, when the rotation speed during the agglomeration operation in the container 7 is increased to about 350-500 rpm and the residence time is relatively short (less than about 5 minutes), it is relatively about 1 to 3 mm. Small aggregates will form.
On the other hand, when the rotation speed is lowered to about 250 rpm and the residence time is relatively long, aggregates having a diameter of about 3-5 mm will generally be formed.

In the case of batch operation, one container having a hydrophobic inner surface as described above can be used instead of the two containers, container 1 and container 7, and the rotation speed can be increased or decreased over a predetermined time. By appropriately changing the above, substantially the same result as when using the above two containers can be obtained. In the case of batch operation, 2
All drugs and liquids can be added sequentially in any order to achieve substantially the same results as when using one container. In both the continuous and batch processes, the agglomerates are transferred to the solid-liquid separator 10 through the tube 9 after the low speed agglomeration operation. The tube 9 and separator 10 (ie screen) are preferably those having a hydrophobic surface as described above.
In this case, the agglomerates will never contaminate the surface and the agglomerates will not be destroyed in the separator.

After separating the agglomerates from the liquid phase in the separator 10, the water immiscible liquid (ie solvent) and residual water are transferred to the water / liquid separator 12 via line 11. Water is removed via line 13 and the water immiscible liquid is recirculated to vessel 1 via lines 14 and 25. The liquor can be dried before reuse in the agglomeration process in order to meet its water content requirements.

The spherical agglomerates (the diameter is generally about 1-5 mm or more, and preferably about 2-4 mm after separating and removing most of the solvent in this manner, but this value depends on the aggregating conditions. Which will vary) and is then placed in dryer 16 through tube 15. The dryer used is generally an industrial belt dryer, but equivalent means may be used. Optionally, a pipe 17 is provided through which air or an inert gas is fed from its source to the dryer 16
To facilitate removal of solvent and water. The dried spherical agglomerates are passed through a tube 18 to a sizer 19 where the dried agglomerates are separated into various smaller particles as needed. The useful particle size range is about 1-
It is 5 mm, more preferably about 2-4 mm. The agglomerates are collected and used as a catalyst or catalyst support, but can be calcined at elevated temperature to remove excess volatiles before use.

The water immiscible liquid and water (which may optionally contain acidic substances) separated in the dryer are passed through a pipe 21 to a liquid separator (separation tank) by a method similar to the separation method described above. ) 22 and separate the two liquids from each other. The water separated here is removed via line 22 and the water immiscible liquid is recycled to the vessel 1 via lines 24 and 25. The liquor can be dried to meet moisture requirements before reuse in the flocculation process.

More Preferred Embodiments Various embodiments of the present invention involve the production of spherical agglomerates, the agglomerates having a dried diameter of generally about 2-4 mm. Some examples include the preparation of spherical agglomerates of a single material such as zeolite, silica, alumina. These single component materials may subsequently be impregnated with metals and the like by impregnation methods known in the art of active catalyst manufacture. Referring to a preferred embodiment of the method for making a one-component agglomerate, this preferred method involves high speed mixing of about 2500-40.
Performed at a rotation speed of 00 rpm, and low speed mixing about 200-400r
It includes performing at a rotation speed of pm. In the case of batch operation, these two speeds of mixing operation can be sequentially performed in the same container.

Another preferred embodiment of the method of making the one-component agglomerates comprises that the water-immiscible liquid is a fluorocarbon, especially 1,1,2-trichloro-1,2,2-trifluoroethane. is there.

Yet another embodiment of the present invention involves the production of spherical agglomerates of two inorganic materials, the diameter of the uncured agglomerates after removal from a separator (eg separator 10 in FIG. 1). Is about 2-4 mm.

Yet another embodiment of the present invention is the two components of two or more components (eg fine size zeolite and colloidal size silica or alumina; the weight ratio of zeolite to silica or alumina is preferably about 40). : 60 to 60:40)
The production of spherical aggregates consisting of

Yet another embodiment provides high speed mixing of about 2500-4000 to produce agglomerates of two or more components.
It includes performing at a rotation speed of rpm (or performing a mixing operation equivalent thereto), and performing low-speed mixing at a rotation speed of about 200-400 rpm (or performing a mixing operation equivalent thereto). A preferred specific example of the method for producing a two-component aggregate is to use a fluorocarbon, particularly 1,2-dibromo-1,1,2,2-tetrafluoroethane, as a water-immiscible liquid (solvent). Includes.

A more preferred embodiment is a high speed mixing of about 2700-3500 rpm in producing the one-component or multi-component agglomerates described above.
At a rotation speed of about 250-350 rpm for low speed mixing (aggregation)
At a rotational speed of. The peripheral speed of a stirrer having a 6-inch blade can be calculated by the method described above.

One specific example of the present invention will be described in detail. First, particles such as fine zeolites (particles of non-colloidal size)
Are suspended in a water immiscible liquid and then flocculated using the aqueous phase. This agglomeration is carried out by the gradual addition of colloidal or smaller colloidal-sized particles and optionally water containing acidic substances. For example, in order to supply the substance to be contained in the final solid agglomerate, the following three modes are possible. (1) The above substances or their precursors can be present in suspended non-colloidal solid particles. (2) The substance or precursor may be present in the form of colloidal particles. Or (3) the substance may be present as sol particles in the aqueous phase, or the substance may be one or more chemicals completely dissolved in the aqueous phase. Alternatively, after the spherical solid product is produced, another substance can be attached to or on the solid by a vapor deposition operation or the like.

The amount (relative amount) of hydrated non-colloidal particles (fine sized particles) and colloidal particles can be adjusted accordingly. The exact ratio of the two particles will be determined in part by the desired properties of the product. Generally, at least 5-10% by weight of each type of particle is present. That is,
The ratio of these two particles (% by weight) is about 95: 5 to 5: 9
5, preferably about 40:60 to 60:40, more preferably about 6
It can be varied within the range of 5:35 to 35:65.

Acidic substances that can be added to the aqueous solution used in the method of the present invention include both organic and inorganic acids.

For such use, any water-soluble organic or inorganic acidic compound, preferably an inorganic acidic compound can be used. Examples of such water-soluble acidic substances are nitric acid, sulfuric acid,
Inorganic acids such as hydrofluoric acid, hydrochloric acid, phosphoric acid, boric acid, etc.,
And trifluoroacetic acid, trichloroacetic acid, oxalic acid,
Organic acids such as citric acid, tartaric acid, formic acid, etc. may be mentioned.

The following examples are provided to further illustrate the present invention.
However, these examples are merely exemplifications of the present invention, and the scope of the present invention is not limited only to the scope described in the examples.

Example 1 Spherical zeolite-silica catalyst (a) Potassium-L-form zeolite powder (crystal size 0.5-1 μm) was added to 1000 ml of 1,1,2-trichloro-1,2,2-trifluoroethane, High-speed mixing stirrer (Brinkman, "Polytron" manufactured by Instrument, type PT
-10/35) was used for dispersion.

The reactor was a 2-1 polyethylene container. Fused silica (Cab-O-Sil; particle size about 20 μm) was added and dispersed with the above zeolite. An aqueous solution (SiO ₂ = 30.1% by weight) of colloidal silica sol “Ludotux” and water were gradually added dropwise to the dispersion, and this addition was continued until fine agglomerates were formed. The rotation speed of the Polytron mixing stirrer was about 3000 rpm. The amount of solids in the total amount (amount was also connexion measured before) was 53%, Thus part of the solid, and 65 wt% zeolite, it has been made made of SiO ₂ 35 wt% (the SiO ₂ Was composed of half the amount of Cab-O-Sil and half the amount of Russox). The reaction mixture was transferred to a container equipped with a low speed stirrer. This container had a bare inner surface made entirely of polypropylene. The rotation speed of the stirrer was 300 rpm. This resulted in substantially spherical, uniformly sized small agglomerates. The aggregate was separated from the solvent and had a diameter of about 1-3 mm.

The particles are then vacuum dried at 110 ° C. for 16 hours,
It was then calcined in dry air at 1000 ° F for 10 hours. The dried agglomerate particles are classified with a standard sieve to have a diameter of 2
The -4 mm one was separated. It was able to withstand these treatments under extra ion exchange conditions with potassium solution and in the impregnation treatment step. After these treatments, small size and substantially spherical final agglomerates (catalysts) were obtained.

(B) It is also possible to use other water-immiscible liquids in place of 1,1,2-trichloro-1,2,2-trifluoroethane in the above production operation. Therefore,
In the above production method (a), 1,1,2-trichloro-1,2,2
The following liquids were used instead of trifluoroethane in the equivalents (volume units).

Pentane; Pentene; Cyclohexane; Hexane; Heptane; Octane; Pentane / Heptane (volume ratio 50/50); Petroleum ether (boiling point 30-60 ° C); Petroleum ether (boiling point 50-80 ° C); Methylene chloride; Chloroform; Ethylene dichloride; 1,2-dibromo-1,1,2,2-tetrafluoroethane; 1-bromo-1,2-dichloro-1,2,2-difluorohexane; pentane / chloroform (volume ratio 50/50 ); Octane / 1,1,2-trichloro-1,2,2-trifluoroethane (volume ratio 50/50); or a mixture thereof.

In these cases too, substantially spherical zeolite / silica agglomerates of similar size were obtained, which, after drying, could advantageously be used as catalysts.

(C) In the method of the present invention, it is possible to use another substance (in particular, another zeolite) instead of the potassium-L-form zeolite powder (fine-sized particles). Therefore, in the method (a) in the above-mentioned Examples, the following substances were used in place of Zeolite-L, and stoichiometric equivalents were used.

Zeolite-A Zeolite-D; Zeolite-R; Zeolite-S; Zeolite-T; Zeolite-X; Zeolite-Y; ZSM-5; ZSM-8; ZSM-11; ZSM-43; ZSM-34; ZSM-39 CZH-5; or a mixture thereof.

Substantially spherical, substantially spherical zeolite / silica agglomerates were obtained, similar to the previous case. After being dried, it can be advantageously used as a catalyst.

(D) Instead of the final silica and / or silica sol (particles of colloidal size) mentioned above, it is possible to use other substances. Therefore, in the method (a) in this Example, the following colloidal-sized substances were used in stoichiometric equivalents in place of the above-mentioned colloidal-sized fused silica and colloidal silica sol. .

Al ₂ O ₃ ; SiO ₂ ; TiO ₂ ; ZrO ₂ ; Atagel-50; TiO ₂ --Al ₂ O ₃ ; TiO ₂ --SiO ₂ ; SiO ₂ --Al ₂ O _{3 Of the} above potassium-L-zeolite / colloidal material As good as the agglomerates, good agglomerates were obtained, which after sieving and drying could be advantageously used as catalysts.

(E) When forming agglomerates of substantially spherical and uniform size according to the invention, of the previously mentioned solvents, fine size particles (zeolite) and sol particles (colloidal size particles). Alternatively, other substances can be used. Therefore, in the method (a) in this Example, an equivalent amount of the solvent or solvent mixture described in the method (b) is used instead of 1,1,2-trichloro-1,2,2-trifluoroethane. (Volume units), instead of Zeolite-L, an equivalent amount (volume unit) of the zeolite or zeolite mixture described in method (c) is used, and in place of the colloidal silica sol, the colloidal size of method (d) is used. The operation was carried out using equivalent weight (volume unit) of particles. Good agglomerates were obtained as with the agglomerates of zeolite / colloidal sized particles described above, which after drying were advantageously usable as catalysts. Some examples are shown below.

Zeolite-X / Al ₂ O ₃ / Heptane; Zeolite-Y / SiO ₂ / Chloroform; ZSM-8 / SiO ₂ / Chloroform; ZSM-39 / Atagel-50 / 1,2-Dibromo-1,1,2,2 -Tetrafluoroethane.

Example 2 Simple solid system (a) Using a Polytron-high speed mixing stirrer, commercial grade pseudoboehmite (“catapal”; 0.1-1 μ)
M) 30 g were dispersed in 250 ml 1,1,2-trichloro-1,2,2-trifluoroethane.

To this dispersion, 15.5 g of an aqueous solution of 1.0 M nitric acid and 1.0 M ammonium nitrate was added dropwise. Mixing and stirring speed in the container is 3000r
It was pm. Then 3000 low speed mixing operations in the same container.
The rotation speed was rpm. This resulted in substantially spherical small size agglomerates. Remove the solvent by filtration,
The agglomerates were then dried in a vacuum oven at 110 ° C for 2 hours.

The average diameter of the spherical aggregates after drying was 3-5 mm.

(B) In performing the above-mentioned production operation, another water-immiscible solvent may be used instead of 1,1,2-trichloro-1,2,2-trifluoroethane. Therefore, in the method (a) in this Example, the following solvent was used in an equivalent amount (volume unit) instead of the 1,1,2-trichloro-1,2,2-trifluoroethane. I performed an operation.

Pentane; Pentene; Cyclohexane; Hexane; Heptane; Octane; Pentane / Heptane (volume ratio 50/50); Petroleum ether (boiling point 30-60 ° C); Petroleum ether (boiling point 50-80 ° C); Methylene chloride; Chloroform; Ethylene dichloride; 1,2-dibromo-1,1,2,2-tetrafluoroethane; 1-bromo-1,2-dichloro-1,2,2-difluorohexane; pentane / chloroform (volume ratio 50/50 ); Octane / 1,1,2-trichloro-1,2,2-trifluoroethane (volume ratio 50/50); or a mixture thereof.

In this case too, as good as the above-mentioned alumina agglomerates, good substantially spherical small-sized agglomerates were obtained, which, after drying, could be advantageously used as a catalyst substrate.

(C) Instead of the above nitric acid, other acids or bases can be used. Therefore, the method (a) of this example
The following operations were carried out using stoichiometric equivalents instead of the nitric acid used in.

HClO ₄ ; H ₂ SO ₄ ; HF; HBr; HI; or mixtures thereof.

Also in this case, good agglomerates were obtained as with the agglomerates described above. It could be advantageously used as a catalyst substrate after sieving and drying.

(D) In producing the substantially spherical small-sized agglomerates according to the present invention, it is possible to replace the above-mentioned solvent, fine-sized particles, and nitric acid with different substances.
Therefore, in performing the operation described in the method (a) in this Example, the solvent described in the method (b) was used instead of 1,1,2-trichloro-1,2,2-trifluoroethane. Alternatively, the solvent mixture was used in stoichiometric equivalents and the nitric acid was replaced with equivalent amounts of the acid or base described in method (c) in this example. As good as the alumina agglomerates described above, good agglomerates were obtained, which had a dry diameter in the range of 1-5 mm and could be advantageously used as catalyst substrate. Some examples of this case are shown below.

Zeolite-X / sulfuric acid / heptane; Zeolite-Y / hydrogen fluoride / chloroform; ZSM-8 / perchlorines / chloroform; or ZSM-39 / ammonium nitrate and nitric acid / 1,1,2-trichloro-1,2,2 -Trifluoroethane.

Example 3 Continuous flocculation method A suspension containing 10% by weight of catapal in 1,2-dibromo-1,1,2,2-tetrafluoroethane was pumped from a storage tank equipped with a stirrer at 100 ml / min. It was fed at a feed rate to a static mixer (Kenix, 1/4 inch static mixer; 21 elements). At the same time, an aqueous solution containing 1 M nitric acid and 1 M ammonium nitrate was fed to this mixer at a rate of 11 ml / min. Catapal was premixed with the aqueous phase so that the dispersion of uniform composition entered the high shear mixer. This high-stress mixer was a laboratory high speed mixer modified for continuous operation. The mixing chamber was a vertical type and was made by closing both ends of a stainless steel pipe having a diameter of 4 inches and a length of 5 inches with 1/8 inch stainless steel plates. A blade member for stirring was attached to the steel plate at the bottom. The raw material inlet was provided on the side wall of this cylindrical chamber 0.5 inch from the plate. Due to this structure, the raw material could be surely introduced directly into the high shear force zone near the rotary blade, and the rotation speed of the blade was 3000 rpm. The outlet is provided in the center of the uppermost flange, and this outlet and the adjacent low-speed flocculator are ID-
It was connected with a short tube (1/4 inch) made of Teflon.

This low speed agglomerator is horizontal and has a diameter of 4 inches,
Made from 12 inch long stainless steel pipe. Both ends were sealed with 1/8 inch stainless steel plates (with flanges). This steel plate had a rotary shaft sealing portion, and a bearing was provided on the outside thereof. The impeller has a shaft with a diameter of 0.5 inch, and four sets of pegs were inserted into this shaft. The pegs were evenly spaced and had a peg diameter of 0.25 inches and a length of 3 inches. The pegs were able to ensure the agitation necessary to favor aggregation. The power source of the low speed agglomerator
A 1/4 horsepower DC-motor with a rotational speed of 50-1
It could be adjusted within the range of 800 rpm. In the case of catapal / nitric acid / ammonium nitrate system, the rotation speed for optimum aggregation is 30.
It was 0 rpm. All inner surfaces are 1 mm thick fluoropolymer films (“Fluoroshield Coatings”, WL
Gore, And, Associates). The inlet of the low speed agglomerator was located in the bottom of the cylindrical chamber, one inch away from the end of the flange closest to the motor. The inlet diameter was 0.25 inch. The outlet of this agglomerator was located 1 cm away from the flange end of the other end of the cylindrical chamber. The outlet consists of a stainless steel pipe with an inner diameter of 1 inch and a length of 3 inches, and the inside is thick
Coated with 0.5 mm fluoroshield layer. The outlet pipe is located on the upper surface of the cylindrical chamber and is 30 degrees in the radial direction (reference to the vertical axis)
Tilted. This allowed successful operation of discharging the agglomerates and the organic liquid onto the separating screen (which was also coated). With this device, a diameter of 2
Spherical aggregates of -4 mm could be formed continuously.

After vacuum drying the aggregate at 100 ° C. for 2 hours,
Baking for 4 hours at 950 ° F in a stream of dry air. Hard, hard spheres suitable as catalyst substrates were obtained.

Example 4 (Comparative Example) (a) 1 quart capacity polyethylene bottle with hexane
270 g, 10 g of water and 30 g of alumina were added. After adding alumina, a shaking operation was performed. A mixture of spherical agglomerates of size 1-7 mm was obtained. This agglomerate was difficult to break and was not easily deformed, but a sieving operation had to be performed in order to obtain an agglomerate having a predetermined narrow size range.

(B) The procedure was repeated under exactly the same conditions as in (a) above, but this time non-spherical aggregates within the range of 1-20 mm were obtained.

As described above, the method described in this comparative example cannot reliably control the particle size to a necessary degree, and accordingly,
It was not possible at all to obtain agglomerates of uniform size as in the present invention.

Example 5 Aggregate Preparation This Example 5-11 illustrates some embodiments of the present invention. Examples 5, 6 and 7 relate to single-component agglomerates, and these were operated in a manner substantially similar to that of Example 2 (a). Examples 8, 9, 10 and 11 were operated in a manner substantially similar to that of Example 1 with the following exceptions. That is, the mixing and aggregating operations were carried out in one polyethylene lined tank, and only the speed of the mixing stirrer was changed.
Variously changed to high speed or low speed. The water-immiscible liquid used was 1,2-dibromo-1,1,2,2-tetrafluoroethane. The results obtained are shown in Table 1.

Although some specific examples of the present invention are described in detail herein, it will be apparent to those skilled in the art that the method for producing a small spherical agglomerate according to the present invention is not limited to the gist and scope of the present invention. It can be implemented in various modes without departing from the above. It is to be understood that all such changes in form fall within the technical scope of the present invention as set forth in the claims below.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C01B 39/02 7202-4G C01F 7/02 G 9040-4G

Claims (18)

[Claims] 1. Particles of a hydrophilic, non-colloidal, micron-sized inorganic material dispersed in a water-immiscible liquid are contacted with an aqueous phase under conditions of high-speed shearing, and the inorganic material and the aqueous phase are separated from each other. Forming a fine agglomerate, which is formed in a container having a hydrophobic inner surface, and the thus obtained fine agglomerate is formed at a sufficiently low speed to form a substantially spherical agglomerate having an average uniform diameter of 1 mm to 5 mm. Agitating, separating the agglomerates obtained from the water-immiscible liquid and the aqueous phase, characterized by the fact that they are substantially inorganic from particles of hydrophilic, non-colloidal micron-sized inorganic substances. A method of producing a substantially spherical solid agglomerate of a substance. 2. The aqueous phase contains an acidic substance,
The method according to claim 1. 3. A process according to claim 1 or 2 wherein the aqueous phase contains about 0.1-70% by weight of soluble metal salt. 4. The method according to claim 1 or 2, wherein the aqueous phase contains an inorganic substance having a colloidal size.
Item 4. The method according to Item 3 or Item 3. 5. The method according to any one of claims 1, 2, 3, or 4, wherein the inorganic particles contain zeolite. 6. The method according to any one of claims 1, 2, 3, or 4, wherein the inorganic particles contain silica. 7. The method according to any one of claims 1, 2, 3, or 4, wherein the inorganic particles contain alumina. 8. The method according to claim 4, wherein the non-colloidal inorganic substance particles contain zeolite, and the colloidal inorganic substance particles contain silica. The method described. 9. The method according to claim 8, wherein the weight ratio of zeolite to silica is 40:60 to 60:40. 10. The non-colloidal inorganic substance particle contains zeolite, and the inorganic substance particle having the size of the colloid contains alumina. The method described. 11. The weight ratio of zeolite to alumina is 40: 6.
The method of claim 10 wherein the method is 0 to 60:40. 12. The high-speed shearing condition is about 2500-4000 rpm.
A method according to any one of the claims, which comprises the rotational speed of 13. The method according to claim 1, wherein the low speed is performed at a rotation speed of about 200 to 400 rpm. 14. The method according to claim 1, wherein the water-immiscible liquid used is a fluorocarbon. 15. The fluorocarbon is 1,2-dibromo-1,
The method according to claim 14, which is 1,2,2, -tetrafluoroethane. 16. The method according to claim 14, wherein the fluorocarbon is 1,1,2-trichloro-1,2,2-trifluoroethane.
The method described in the section. 17. The method according to claim 1, wherein the separated agglomerates are dried to form hardened agglomerates having a uniform particle size. 18. The method according to claim 17, wherein the diameter of the hardened agglomerate is 2 to 4 mm.