WO2008146768A1

WO2008146768A1 - Method for filling silicon oxide-containing dry gel

Info

Publication number: WO2008146768A1
Application number: PCT/JP2008/059615
Authority: WO
Inventors: Tetsuo Suzuki
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2007-05-24
Filing date: 2008-05-20
Publication date: 2008-12-04
Also published as: JP2008290909A

Abstract

Disclosed is a method for filling a silicon oxide-containing dry gel into a liquid treatment container, wherein the silicon oxide-containing dry gel is expanded in advance by a liquid which is capable of expanding the gel, and then the expanded dry gel is filled into the liquid treatment container.

Description

Specification Method for filling silicon oxide-containing dry gel Technical Field

The present invention relates to a method for filling a silicon oxide-containing dry gel. More specifically, the present invention relates to silicon oxide containing a silicon oxide-containing dry gel that has been previously expanded with a liquid that expands the gel and then filled into the liquid processing container, or that has previously been filled with a liquid that causes the gel to expand. The present invention relates to a method for filling a material-containing dry gel, which is a method for filling a silicon oxide-containing dry gel having excellent characteristics such that the liquid can be fed without increasing the pressure loss in the liquid processing container.

Background art

Silicon oxide-containing gels are useful in applications where gases such as solid catalysts and gas chromatography column fillers are treated, but when used in the liquid phase, the gel in the dry state absorbs the solvent and expands in volume. May happen. To the best of our knowledge, there are no examples of methods for filling silicon oxide-containing dry gel that has the property of expanding. (See International Publication No. 2 0 0 5/0 2 8 1 0 1 A 1 Pamphlet)

Disclosure of the invention

Under such circumstances, the problem to be solved by the present invention is that a silicon oxide-containing dry gel is preliminarily expanded with a liquid that causes the gel to expand, and then filled into a liquid processing container, or a liquid that previously contains a liquid that causes the gel to expand. A method of filling a processing container with a silicon oxide-containing dry gel, which has an excellent feature such that a liquid can be fed without increasing the pressure loss in the liquid processing container. The point is to provide. That is, the present invention is to fill a liquid processing container after a silicon oxide-containing dry gel is expanded in advance with a liquid that expands the gel, or in a liquid processing container that contains a liquid that expands the gel in advance. The present invention relates to a method for filling a dry gel containing silicon silicate and filling the dry gel.

BEST MODE FOR CARRYING OUT THE INVENTION The expression “dry gel” used in the following description means a gel from which liquid has been removed by a drying operation such as decompression, heating, or blowing, and “wet gel” does not have a drying operation. It means a gel that contains a liquid or a gel that has been supplied with a liquid after the drying operation. The silicon oxide-containing gel represents a silicon oxide-containing dry gel and a silicon oxide-containing wet gel. The silicon oxide-containing dry gel used in the present invention is a silicon oxide-containing dry gel that expands to a volume of 1.1 times or more by absorbing the liquid that causes the gel to expand. It is a silicon oxide-containing dry gel prepared by the reaction represented by I), and more preferably a silylated silicon oxide-containing dry gel obtained by further silylating a silicon oxide-containing gel.

(Li) n (L ₂ ) o (L ₃ ) p (L4) q (L ₅ ) rM-X + (L ₆ ) s (L ₇ ) t (L ₈ ) u (L9) v (Lio) wM- OR

→ (Li) n (L ₂ ) o (L ₃ ) p (L4) q (L ₅ ) rM-0-M (L ₆ ) s (L7) t (L8) u (L9) v (Lio) + RX (I)

(Where M represents silicon alone or two or more elements consisting of silicon and Group 3 to 14 elements, X represents a halogeno group or a carboxylate group, R represents hydrogen or a hydrocarbon group, ~ ₀ represents an alkoxy group, a halogeno group, a carboxy group, hydrogen or a hydrocarbon group, and n, o, ρ, q, r, s, t, u, v and w are from 0 Represents an integer of 5, n + o + p + q + r and s + t + u + v + w are each 1 or more.)

By performing silylation, the chemical stability of the gel can be improved.

The liquid that causes the gel to swell may be inert to the silicon-oxygen bond and silicon-carbon bond under immersion conditions. For example, water, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, Examples include oxides, ketones, epoxides, aldehydes, amines, amides, and mixtures thereof, preferably the components themselves contained in the liquid to be processed by being continuously supplied to the liquid processing container, or before and after the processing in the liquid processing container It is a liquid containing components. If the liquid that expands the gel and the liquid that is continuously supplied to the liquid processing container and processed are different, the volume of the silicon oxide-containing wet gel may change, causing pressure loss in the liquid processing container, or There is a problem when volumetric efficiency decreases. The liquid to be processed by being continuously supplied to the liquid processing container may be inert to the silicon-oxygen bond and the silicon-carbon bond under use conditions. Examples include water, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, hydroperoxides, ketones, epoxides, aldehydes, amines, amides and mixtures thereof. They may also contain acids, metal ions, ammonia and amino acids.

The liquid processing container only needs to have a liquid inlet / outlet so that the liquid to be processed can be continuously supplied to the liquid processing container. For example, a metal in which a tube is wound in a cylindrical shape or a spiral shape, Examples include glass and resin containers. A cylindrical container is preferable because of easy handling.

The preparation method of the silicon oxide containing gel of this invention is shown below.

First, in the liquid phase, a silicon oxide-containing gel is obtained by a condensation reaction represented by the formula (I). The raw materials in the formula (I) are the following formulas (1) and (2).

(Li) n (L ₂ ) o (L ₃ ) p (L4) q (L5) rM-X (1)

(L ₆ ) s (L7) t (L8) u (L ₉ ) v (Lio) wM-OR (2)

(Here, M represents silicon alone or two or more elements consisting of silicon and Group 3 to 14 elements, X represents a halogeno group or a carboxylate group, and R represents hydrogen or a hydrocarbon group. , ˜1 ^ ₁₀ represents any one of an alkoxy group, a halogeno group, a carboxy group, hydrogen or a carbonic acid hydrogen group, n, o, p, q, r, s, t, u, v and w represents an integer from 0 force to 5, n + o + p + Q + r and s + t + u + v + w are each 1 or more.)

Examples of X include an octagen group such as fluorine, chlorine, bromine and iodine, and a carboxylate group such as an acetate group. Among them, chlorine is preferable.

Examples of R include hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, and butyl group (which may include heteroatoms such as oxygen and nitrogen). From this viewpoint, an isopropyl group is preferable.

Examples of L! L HJ are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, fluorine, chlorine, bromine, iodine, acetate, cyclopentadienyl And a hydrocarbon group having 1 to 18 carbon atoms (which may contain a hetero atom such as oxygen, nitrogen and fluorine).

Examples of M include Aluminum, Yttrium, Titanium, Niopium, Vanadium, Zirconium, Chromium, Molypden, Tungsten, Manganese, Iron, Ruthenium, Cobalt, Nickel, Copper, Zinc, Gallium, Germanium, etc. Of these elements.

Specific compounds of formula (1) include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, aluminum chloride, yttrium chloride, titanium tetrachloride, cyclopentadienyl titanium chloride, salt ^: niobium, Vanadium chloride, Zirconium chloride, Zirconium butoxide, Chloride chrome, Molybdenum chloride, Tungsten chloride, Manganese chloride, Iron chloride, Iron acetate, Ruthenium chloride, Cobalt chloride, Nickel chloride, Copper chloride, Zinc chloride, Acetic acid Examples include zinc, gallium chloride, and germanium chloride.

Among the above compounds, it is preferable to prepare a gel using tetrahalogenosilane from the viewpoint of improving the chemical stability of the gel.

Specific compounds of formula (2) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetrabutoxysilane, aluminum isopropoxide, titanium ethoxide, titanium isopropoxide, Examples thereof include titanium methoxide and titanium butoxide. Among the above compounds, it is preferable to prepare a gel using tetraalkoxysilane from the viewpoint of improving the chemical stability of the gel.

For the preparation of the silicon oxide-containing gel, one or more compounds of the formula (1) and the formula (2) are mixed and used.

In the preparation of the silicon oxide-containing gel, a solvent may or may not be used. The solvent may or may not contain water. However, if water is contained excessively, the condensation reaction rate is accelerated and the uniformity of the resulting wet gel may be reduced. Is preferably free of water. Specific examples of the solvent include alcohol, ether, hydrocarbon, and halogenated hydrocarbon. They can also be used as a mixture. The added solvent may react with the above raw materials.

Structural preparation agents (molding agents) such as primary to tertiary amines, quaternary ammonium ions, and surfactants may be added separately or not during gel preparation.

The gel preparation temperature is usually from 30 to 200, but the condensation reaction is promoted by heating. When heating, it is preferable to transfer to a pressure-resistant vessel and seal in order to avoid vaporization of the raw materials and the solvent.

Since the wet gel obtained by the above method contains R X and Z described in formula (I) or a solvent, they are removed by drying to obtain a silicon oxide-containing dry gel. Drying can be performed at 0 to 200 ° C. under reduced pressure conditions or under a gas stream such as nitrogen.

In the present invention, from the viewpoint of improving the stability of the silicon oxide-containing gel, it is preferable to subject the silicon oxide-containing gel obtained by the condensation reaction to a silylation treatment.

The silylation treatment is performed by bringing the silicon oxide-containing gel into contact with a silylating agent. Silylation can be carried out on wet gels and dry gels, but is preferably carried out on dry gels in view of the efficiency of silylation.

As the silylating agent, organic eight-necked genosilane, organic silylamine, organic silylamide and its derivative, and organic silazane can be used. Specific examples include chlorotrimethylsilane, methoxytrimethylsilane, and hexamethyldisilazane. The silylation treatment may be performed in the gas phase or in the liquid phase. A solvent may or may not be used.

When silylation is carried out in the liquid phase, a silicon oxide-containing dry gel is obtained by drying. Drying can be carried out at 0 to 200 ° C. under reduced pressure or under a gas stream such as nitrogen.

Thus, the silicon oxide-containing dry gel used in the present invention can be obtained.

Hereinafter, a method for filling the liquid treatment container with the silicon oxide-containing dry gel that is filled in the liquid treatment container after the silicon oxide-containing dry gel has been expanded in advance with a liquid that causes the gel to expand will be described. The method for expanding the silicon oxide-containing dry gel is only to bring the gel into contact with the liquid that causes the gel to expand. The combination of time and temperature for contact is not particularly limited. Preferred is a combination of time and temperature at which the bulk volume of the gel is 1.1 times or more that of the dried gel, and more preferred is a combination of time and temperature at which the wet gel expands and reaches 90% or more of the maximum volume reached. . Incomplete gel expansion will result in further expansion after filling and unacceptable pressure loss.

When the silicon oxide-containing dry gel is filled in a liquid processing container in which a liquid that expands the gel in advance is supplied, the liquid that expands the gel is supplied to the liquid processing container in advance, and then the silicon oxide-containing dry gel is supplied. The silicon oxide-containing dry gel may be supplied in a predetermined amount at once, or may be supplied in several divided portions while confirming the degree of expansion. Further, a liquid for expanding the gel may be additionally supplied before the supply of the silicon oxide-containing dry gel for the second and subsequent times. The silicon oxide-containing dry gel is used for liquid treatment after filling into a liquid treatment container. Examples of liquid treatment include liquid phase catalytic reaction, liquid phase separation, and adsorption removal.

As an example of liquid treatment, a method for producing an oxysilane compound in which an olefin compound and a hydroperoxide are reacted will be described below.

The olefin compound may be an acyclic compound or a cyclic compound, and may be monoolefin, diolephin or polyolefin. If there are two or more olefin bonds, this may be a conjugated bond or a non-conjugated bond. Olefin compounds having 2 to 60 carbon atoms are generally preferred. The olefin compound may have a substituent, but the substituent is preferably a relatively stable group. Examples of the substituent include a halogen atom, and various substituents containing oxygen, sulfur, and nitrogen atoms together with hydrogen and / or carbon atoms may be present. Examples of such olefin compounds are ethylene, propylene, butene-1, isoptylene, hexene-1, hexene-1, hexene-3, octene-1, decene-1, styrene, cyclohexene, butadiene. , Isoprene, allylic alcohol, crotyl alcohol, gallic chloride, and propylene is preferred.

Examples of the octaperoxides used for the reaction with the olefin compound include organic hydroxide oxide and hydrogen peroxide, and organic hydroxide is preferred. Examples of the organic hydroxoxide include cumene hydropoxide, ethylbenzen octahydropoxide, and t-peptyl octapoxide.

The organic octaperoxide and hydrogen peroxide used as raw materials may be diluted or concentrated purified or non-purified.

This reaction can be carried out in the liquid phase in the presence or absence of a solvent. The solvent is preferably a liquid under the temperature and pressure during the reaction and substantially inert to the reactants and products. The solvent may consist of substances present in the used nanopoxide solution. For example, if cumene hydroperoxide is a mixture of cumene hydroperoxide and its raw material, cumene, it can be used as a substitute for solvent without any additional solvent. is there.

The epoxidation reaction temperature is generally 0 to 200 ° C, but a temperature of 25 to 200 ° C is preferred. The pressure may be sufficient to keep the reaction mixture in a liquid state. . In general, the pressure is advantageously from 1 0 0 to: 1 0 0 0 0 0 k Pa.

The method of the present invention can be carried out in the form of a slurry or a fixed bed. Although this reaction can be carried out by a batch method, a semi-continuous method or a continuous method, the continuous method using a fixed bed is preferable from the viewpoint of effectively utilizing the volumetric efficiency of the liquid treatment container.

Hereinafter, the present invention will be described by way of examples.

Example 1

Preparation of gel containing silicon oxide

A silicon oxide-containing gel was obtained by the following procedure.

4.0 g of silicon tetrachloride, 6.7 g of tetraisopropoxy silicon, 1.3 g of tetrisopropoxytitanium, 2.7 g of trimethylsilyl chloride and 33.5 g of dichloromethane mixed under nitrogen atmosphere After sealing in a pressure-resistant Teflon (registered trademark) container, the silicon oxide-containing wet gel immediately after preparation was obtained by heating at 110 ° C. for 2 19 hours. Further, it was dried at 150 mm for 4 hours under a reduced pressure of 10 mmHg to obtain a silicon oxide-containing dried gel.

Silylation Hexamethyldisilazane 0.67 times the amount of toluene and 10 times the amount of toluene to the weight of the silicon oxide-containing dry gel obtained were added to the silicon oxide-containing dry gel, and 1 10 for 1.5 hours. Heated. The reaction solution after silylation was removed by decantation, and then dried under reduced pressure at 110 ° C. for 1.5 hours to obtain a silylated silicon oxide-containing dry gel.

Bulk volume measurement

The bulk volume of the silicon oxide-containing dry gel was measured with a graduated cylinder after aligning the size to 0.5 to 1.0 mm.

The volume of the silicon oxide-containing wet gel is measured by immersing the silicon oxide-containing dry gel with a size of 0.5 to 1.0 mm in a liquid that swells the gel for 30 minutes at room temperature and collecting it by filtration. The silicon oxide-containing wet gel was measured with a measuring cylinder.

Filling liquid processing containers

The silicon oxide-containing dry gel was pulverized, classified into a size between 0.5 mm and 1.0 mm, and collected. Dilute the silylated silicon oxide-containing dry gel (bulk volume 1.3 ml) recovered after classification in liquid (cumyl alcohol; 25 wt%, propylene oxide; 7 wt% and cumene; 68 wt%) at room temperature for 30 minutes. Inflated. When the liquid that expands the gel was removed by filtration, the bulk volume became 2.5 ml, and the silylated silicon oxide-containing dry gel expanded to a volume of 1.9 times by absorbing the liquid that expanded the gel. The obtained silylated silicon oxide-containing wet gel was filled into a cylindrical stainless steel reactor having an inner diameter of 8 mm.

Epoxidation of propylene

Propylene continuous feed was started into a cylindrical stainless steel reactor filled with silylated silicon oxide-containing wet gel, and in addition, cumene hydroperoxide cumene solution was continuously fed to synthesize propylene oxide. Went. At this time, no pressure loss was observed in the cylindrical stainless steel reactor due to the liquid feed.

Comparative Example 1

A cylindrical stainless steel reactor having an inner diameter of 8 mm was filled with a silylated silicon oxide-containing dry gel in the same manner as in Example 1 except that the gel was not soaked in a liquid that caused the gel to expand in advance. Put into a cylindrical stainless steel reactor filled with dry gel containing silylated silicon oxide. A continuous feed of lopyrene was started, and in addition to that, an attempt was made to continuously feed cumene hydroperoxide cumene solution. However, pressure loss occurred in the cylindrical stainless steel reactor and the feed could not be performed. When the silylated silicon oxide-containing gel was recovered from the cylindrical stainless steel reactor, the gel on the liquid inlet side became dusty and closed one inlet of the cylindrical stainless steel reactor.

Industrial applicability

According to the present invention, the silicon oxide-containing dry gel is previously expanded with a liquid that causes the gel to expand, and then filled into the liquid processing container, or the silicon oxide-containing dry gel is added to the liquid processing container that previously contains the liquid that causes the gel to expand. It is possible to provide a method for filling a silicon oxide-containing dry gel, which has an excellent characteristic that the liquid can be fed without increasing the pressure loss in the liquid processing container.

Claims

The scope of the claims

1. A method of filling a silicon oxide-containing dry gel into a liquid treatment container, wherein the silicon oxide-containing dry gel is expanded in advance with a liquid that causes the gel to expand, and then filled in the liquid treatment container A method for filling the liquid processing container with the contained dry gel.

2. A method of filling a silicon oxide-containing dry gel in a liquid treatment container, wherein the silicon oxide-containing dry gel is filled in a liquid treatment container in which a liquid for pre-expanding the gel is placed. A method for filling a liquid processing container.

3. The filling method according to claim 1 or 2, wherein the silicon oxide-containing dry gel is prepared by a reaction represented by the following formula (I) in a liquid phase.

(Li) n (L ₂ ) o (L3) p (L4) q (L ₅ ) rM-X + (L ₆ ) s (L ₇ ) t (L ₈ ) u (L ₉ ) v (L ₁₀ ) wM -OH

→ (Li) n (L ₂ ) o (L3) p (L4) q (L5) rM-OM (L6) s (L7) t (L8) u (L ₉ ) v (Li ₀ ) w + RX (I (Here, M represents silicon alone or two or more elements consisting of silicon and Group 3 to 14 elements, X represents a halogeno group or a carboxylate group, and R represents a hydrogen or hydrocarbon group.) represents, 1 ^ ~ Party B ₁₀ alkoxy group, a halogeno group, a force Rupokishire Ichitomoto represents any one of hydrogen or a hydrocarbon group, n, o, p, Q , r, s, t, u, v And w represents an integer of 0 to 5, and n + o + p + q + r and s + t + u + v + w are each 1 or more.)