WO2008146768A1 - Method for filling silicon oxide-containing dry gel - Google Patents
Method for filling silicon oxide-containing dry gel Download PDFInfo
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- WO2008146768A1 WO2008146768A1 PCT/JP2008/059615 JP2008059615W WO2008146768A1 WO 2008146768 A1 WO2008146768 A1 WO 2008146768A1 JP 2008059615 W JP2008059615 W JP 2008059615W WO 2008146768 A1 WO2008146768 A1 WO 2008146768A1
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- gel
- silicon oxide
- liquid
- dry gel
- containing dry
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
Definitions
- 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.
- 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)
- 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.
- 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.
- 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
- n, o, ⁇ , q, r, s, t, u, v and w are from 0
- n + o + p + q + r and s + t + u + v + w are each 1 or more.
- 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.
- 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.
- 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.
- 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).
- 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.
- ⁇ 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.
- R examples 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.
- 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).
- M examples 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.
- 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.
- one or more compounds of the formula (1) and the formula (2) are mixed and used.
- 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 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.
- 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.
- the silicon oxide-containing gel obtained by the condensation reaction 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.
- 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.
- 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.
- the silicon oxide-containing dry gel used in the present invention can be obtained.
- 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.
- the silicon oxide-containing dry gel 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.
- 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.
- olefin compounds examples include 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.
- 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.
- a silicon oxide-containing gel was obtained by the following procedure.
- 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.
- 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.
- 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.
- 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.
- 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.
- a cylindrical stainless steel reactor filled with dry gel containing silylated silicon oxide 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.
- pressure loss occurred in the cylindrical stainless steel reactor and the feed could not be performed.
- 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.
- 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.
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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
明細書 珪素酸化物含有乾燥ゲルの充填方法 技術分野 Specification Method for filling silicon oxide-containing dry gel Technical Field
本発明は、 珪素酸化物含有乾燥ゲルの充填方法に関するものである。 更に詳しくは、 本発明は、 珪素酸化物含有乾燥ゲルを予めゲルを膨張せしめる液体で膨張させた後に液 体処理容器に充填する、 もしくは予めゲルを膨張せしめる液体を入れた液体処理容器に 珪素酸化物含有乾燥ゲルを充填する方法であって、 液体処理容器内の圧損を増加させず に液体をフィードできるといった優れた特徴を有する珪素酸化物含有乾燥ゲルの充填方 法に関するものである。 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.
背景技術 Background art
珪素酸化物含有ゲルは固体触媒、 ガスクロマトグラフィーカラム充填剤などの気体を 処理する用途において有用であるが、 液相中で使用される場合には乾燥状態のゲルが溶 媒を吸収し体積膨張が起こる場合がある。 膨張する性質を有する珪素酸化物含有乾燥ゲ ルの充填方法は、 我々の知る限りにおいてこれまでに例が無い。 (国際公開第 2 0 0 5 / 0 2 8 1 0 1 A 1パンフレツト参照) 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)
発明の開示 Disclosure of the invention
かかる現状において、 本発明が解決しょうとする課題は、 珪素酸化物含有乾燥ゲルを 予めゲルを膨張せしめる液体で膨張させた後に液体処理容器に充填する、 もしくは予め ゲルを膨張せしめる液体を入れた液体処理容器に珪素酸化物含有乾燥ゲルを充填する方 法であって、 液体処理容器内の圧損を増加させずに液体をフィードできるといった優れ た特徴を有する珪素酸ィヒ物含有乾燥ゲルの充填方法を提供する点に存するものである。 すなわち、 本発明は、 珪素酸化物含有乾燥ゲルを予めゲルを膨張せしめる液体で膨張 させた後に液体処理容器に充填する、 もしくは予めゲルを膨張せしめる液体を入れた液 体処理容器に珪素酸化物含有乾燥ゲルを充填する珪素酸ィヒ物含有乾燥ゲルの充填方法に 係るものである。 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.
発明を実施するための形態
以下の説明で用いられる表現の"乾燥ゲル" とは、 減圧、 昇温または送風等の乾燥操 作により液体を除去したゲルを意味し、 また "湿潤ゲル"とは乾燥操作が施されておらず液 体を保有しているゲルまたは乾燥操作後、 液体を供給し液体を保有した状態としたゲル を意味する。 また、 珪素酸化物含有ゲルとは珪素酸化物含有乾燥ゲルおよび珪素酸化物 含有湿潤ゲルを表す。 本発明で用いられる珪素酸化物含有乾燥ゲルは、 ゲルを膨張せしめる液体を吸収する ことで体積が 1 . 1倍以上に膨張する珪素酸化物含有乾燥ゲルであり、 好ましくは液相 中、 式 (I ) で表される反応によって調製された珪素酸化物含有乾燥ゲルであり、 さら に好ましくは珪素酸化物含有ゲルをさらにシリル化して得られたシリル化珪素酸化物含 有乾燥ゲルである。 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(L2)o(L3)p(L4)q(L5)rM-X + (L6)s(L7)t(L8)u(L9)v(Lio)wM-OR (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(L2)o(L3)p(L4)q(L5)rM-0-M(L6)s(L7)t(L8)u(L9)v(Lio) + RX ( I ) → (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)
(ここで、 Mは珪素単独または珪素と 3族から 1 4族の元素からなる 2種類以上の元素 を表し、 Xはハロゲノ基またはカルボキシレート基を表し、 Rは水素または炭化水素基 を表し、 〜 0はアルコキシ基、 ハロゲノ基、 カルポキシレート基、 水素または炭化 水素基のうちのいずれかを表し、 n、 o、 ρ、 q、 r、 s、 t、 u、 vおよび wは 0か ら 5の整数を表し、 n + o + p + q + rおよび s + t + u + v + wはそれぞれ 1以上で ある。 ) (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.)
シリル化を行うことでゲルの化学的な安定性を向上させることができる。 By performing silylation, the chemical stability of the gel can be improved.
ゲルを膨張せしめる液体は、 珪素一酸素結合および珪素一炭素結合に対して浸潰条件 下で不活性であれば良く、 例として水、 脂肪族炭化水素、 芳香族炭化水素、 アルコール、 ハイド口パーオキサイド、 ケトン、 ェポキサイド、 アルデヒド、 ァミン、 アミドおよび それらの混合物が挙げられ、 好ましくは液体処理容器に連続供給して処理される液体に 含まれる成分そのもの、 または液体処理容器での処理前後に含まれる成分を含有した液 体である。 ゲルを膨張せしめる液体と液体処理容器に連続供給して処理される液体が異 なる場合は、 珪素酸化物含有湿潤ゲルの体積が変化する場合があり、 液体処理容器内に 圧損が生じるか、 もしくは体積効率が低下するといつた問題がある。
液体処理容器に連続供給して処理される液体は、 使用条件で珪素一酸素結合および珪 素一炭素結合に対して不活性であれば良い。 例として、 水、 脂肪族炭化水素、 芳香族炭 化水素、 アルコール、 ハイドロパ一オキサイド、 ケトン、 ェポキサイド、 アルデヒド、 ァミン、 アミドおよびそれらの混合物が挙げられる。 また、 それらは酸、 金属イオン、 アンモニアおよびアミノ酸を含んでいても良い。 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.
液体処理容器は、 液体処理容器に連続供給して処理される液体を連続供給できるよう な、 液体の出入り口を有していれば良く、 例として円筒状またはらせん状に管が巻かれ た金属、 ガラスおよび樹脂製容器等が挙げられる。 好ましくは取り扱いの容易さから円 筒状の容器である。 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.
本発明の珪素酸化物含有ゲルの調製方法を以下に示す。 The preparation method of the silicon oxide containing gel of this invention is shown below.
まず、 液相中、 式 (I ) で表される縮合反応によって珪素酸化物含有ゲルを得る。 式 ( I ) における原料は下記式 (1 ) および (2 ) である。 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(L2)o(L3)p(L4)q(L5)rM-X (1) (Li) n (L 2 ) o (L 3 ) p (L4) q (L5) rM-X (1)
(L6)s(L7)t(L8)u(L9)v(Lio)wM-OR (2) (L 6 ) s (L7) t (L8) u (L 9 ) v (Lio) wM-OR (2)
(ここで、 Mは珪素単独または珪素と 3族から 1 4族の元素からなる 2種類以上の元素 を表し、 Xはハロゲノ基またはカルポキシレート基を表し、 Rは水素または炭化水素基 を表し、 〜1^ 10はアルコキシ基、 ハロゲノ基、 カルポキシレート基、 水素または炭ィ匕 水素基のうちのいずれかを表し、 n、 o、 p、 q、 r、 s、 t、 u、 vおよび wは 0力 ら 5の整数を表し、 n + o + p + Q + rおよび s + t + u + v +wはそれぞれ 1以上で ある。 ) (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.)
Xの例としてはフッ素、 塩素、 臭素、 ヨウ素等の八口ゲノ基やアセテート基等のカル ポキシレ一ト基があげられるが、 なかでも塩素が好ましい。 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.
Rの例としては、 メチル基、 ェチル基、 プロピル基、 イソプロピル基、 ブチル基等の 炭化水素基 (酸素や窒素等のへテロ原子を含んでもよい) をあげることができるが、 ゲ ル化速度の観点からイソプロピル基が好ましい。 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.
L ! L HJの例としては、 メトキシ基、 エトキシ基、 プロポキシ基、 イソプロポキシ基、 n—ブトキシ基、 フッ素、 塩素、 臭素、 ヨウ素、 アセテート基、 シクロペンタジェニル
基等の炭素数 1〜 1 8の炭化水素基 (酸素、 窒素およびフッ素等のへテロ原子を含んで もよい) をあげることができる。 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).
Mの例としては、 アルミニウム、 イットリウム、 チタン、 ニォピウム、 バナジウム、 ジルコニウム、 クロム、 モリプデン、 タングステン、 マンガン、 鉄、 ルテニウム、 コバ ルト、 ニッケル、 銅、 亜鉛、 ガリウム、 ゲルマニウム等の 3族から 1 4族の元素が挙げ られる。 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.
式 (1 ) の具体的な化合物としては、 四塩化珪素、 メチルトリクロロシラン、 ジメチ ルジクロロシラン、 トリメチルクロロシラン、 塩化アルミニウム、 塩化イットリウム、 四塩化チタン、 シクロペンタジェニルチタニウムクロライド、 塩^:二オビゥム、 塩化バ ナジゥム、 塩化ジルコニウム、 ジルコニウムブトキサイド、 塩ィ匕クロム、 塩化モリブデ ン、 塩化タングステン、 塩化マンガン、 塩化鉄、 酢酸鉄、 塩化ルテニウム、 塩化コバル ト、 塩化ニッケル、 塩化銅、 塩化亜鉛、 酢酸亜鉛、 塩化ガリウム、 塩化ゲルマニウム等 を例示することができる。 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.
上記化合物の中でも、 ゲルの化学的安定性を向上させるという観点からテトラハロゲ ノシランを使用してゲルを調製することが好ましい。 Among the above compounds, it is preferable to prepare a gel using tetrahalogenosilane from the viewpoint of improving the chemical stability of the gel.
式 (2 ) の具体的な化合物としては、 テトラメトキシシラン、 テトラエトキシシラン、 テトラー n—プロポキシシラン、 テトライソプロポシキシラン、 テトラブトキシシラン、 アルミニウムイソプロポキサイド、 チタンェトキサイド、 チタンイソプロポキサイド、 チタンメトキサイド、 チタンブトキサイド等を例示することができる。 上記化合物の中 でも、 ゲルの化学的安定性を向上させるという観点からテトラアルコシキシランを使用 してゲルを調製することが好ましい。 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.
珪素酸化物含有ゲルの調製には式 (1 ) および式 (2 ) の化合物をそれぞれ 1種類以 上混合して用いる。 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.
珪素酸化物含有ゲルの調製では溶媒を用いてもよいし、 用いなくてもよい。 溶媒は水 を含んでいても含んでいなくても良いが、 水が過剰に含まれる場合は縮合反応速度が加 速され、 得られる湿潤ゲルの均一性を低下させることがあるため、 溶媒には水が含まれ ていない方が好ましい。
溶媒の具体例はアルコール、 エーテルや炭化水素、 ハロゲン化炭化水素などがあげら れる。 またそれらは混合物として用いることもできる。 加えた溶媒が上記の原料と反応 しても構わない。 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.
ゲル調製時に 1〜 3級のアミンゃ 4級アンモニゥムイオン、 界面活性剤などの構造規 定剤 (型剤) を別途追加してもよいし、 用いなくてもよい。 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.
ゲル調製温度は通常一 3 0〜2 0 0 1であるが、 加熱を行った方が縮合反応が促進さ れる。 加熱する場合は、 原料および溶媒の気化を避けるために耐圧容器に移して密閉し て行うのが好ましい。 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.
上記の方法によって得られた湿潤ゲルは式 (I ) 記載の R Xおよび Zまたは溶媒を含 むので乾燥によってそれらを除去し、 珪素酸化物含有乾燥ゲルを得る。 乾燥は減圧条件 下あるいは窒素等のガス流通下、 0〜2 0 0 °Cで実施できる。 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.
本発明では珪素酸化物含有ゲルの安定性を高める観点から、 縮合反応で得られた珪素 酸化物含有ゲルにシリル化処理を施すことが好ましい。 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.
シリル化処理は、 珪素酸化物含有ゲルをシリル化剤と接触させることにより行われる。 シリル化は湿潤ゲルおよび乾燥ゲルについて実施できるが、 シリル化の効率の点で乾燥 ゲルに実施することが好ましい。 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.
シリル化剤は、 有機八口ゲノシラン、 有機シリルアミン、 有機シリルアミドとその誘 導体、 及び有機シラザン等を使用することができる。 具体的にはクロロトリメチルシラ ン、 メトキシトリメチルシラン、 へキサメチルジシラザン等があげられる。 シリル化処 理は気相で行ってもよいし液相でおこなってもよい。 また溶媒を用いても良いし用いな くてもよい。 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.
液相でシリル化を実施した場合は、 乾燥により珪素酸化物含有乾燥ゲルを得るが、 乾 燥は減圧下あるいは窒素等のガス流通下、 0〜2 0 0 °Cで実施できる。 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.
かくして、 本発明に用いられる珪素酸化物含有乾燥ゲルを得ることができる。 Thus, the silicon oxide-containing dry gel used in the present invention can be obtained.
以下に、 珪素酸化物含有乾燥ゲルを予めゲルを膨張せしめる液体で膨張させた後に液 体処理容器に充填する珪素酸化物含有乾燥ゲルの液体処理容器への充填方法を説明する。 珪素酸化物含有乾燥ゲルを膨張させる方法は該ゲルとゲルを膨張せしめる液体を接触 させれば良く、 接触させる時間および温度の組み合わせは特に限定されないが、 湿潤ゲ
ルのかさ体積が乾燥ゲルの 1 . 1倍以上になる時間および温度の組み合わせが好ましく、 さらに好ましくは湿潤ゲルが膨張し到達する最大体積の 9 0 %以上となる時間および温 度の組み合わせである。 ゲルの膨張が不完全であると充填後にさらに膨張し、 許容でき ない程度の圧損が生ずる。 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.
予めゲルを膨張せしめる液体を入れた液体処理容器に珪素酸化物含有乾燥ゲルを充填 する場合は、 ゲルを膨張せしめる液体を予め液体処理容器に供給し、 次いで珪素酸化物 含有乾燥ゲルを供給する。 珪素酸化物含有乾燥ゲルの供給は予定量を一度に行っても良 いし、 膨張の度合いを確認しながら数回に分割して供給しても良い。 また、 2回目以降 の珪素酸化物含有乾燥ゲルの供給前にゲルを膨張せしめる液体を追加供給しても良い。 該珪素酸化物含有乾燥ゲルは液体処理容器へ充填後に液体処理に用いられるが、 液体 処理の例としては、 液相触媒反応、 液相分離、 吸着除去が挙げられる。 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.
液体処理の例として、 ォレフィン化合物とハイドロパ一ォキサイドを反応させるォキ シラン化合物の製造方法について以下に説明する。 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.
ォレフィン化合物は、 非環状化合物または環状化合物であってよく、 モノォレフィン、 ジォレフイン又はポリオレフインであってよい。 ォレフィン結合が 2以上ある場合には、 これは共役結合又は非共役結合であってよい。 炭素原子 2 ~ 6 0個のォレフィン化合物 が一般に好ましい。 ォレフィン化合物は置換基を有していてもよいが、 置換基は比較的 安定な基であることが好ましい。 置換基の例としてはハロゲン原子があげられ、 更にま た、 酸素、 硫黄、 窒素原子を、 水素及び/又は炭素原子と共に含有する種々の置換基が 存在してもよい。 このようなォレフィン化合物の例にはエチレン、 プロピレン、 ブテン ー 1、 イソプチレン、 へキセン一 1、 へキセン一 2、 へキセン一 3、 ォクテン一 1、 デ セン一 1、 スチレン、 シクロへキセン、 ブタジエン、 イソプレン、 ァリルアルコール、 クロチルアルコール、 塩化ァリルが挙げられるが、 プロピレンが好ましい。 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.
ォレフィン化合物との反応に用いられる八ィドロパーォキサイド類としては有機ハイ ドロパ一オキサイドおよび過酸化水素をあげることができるが、 有機ハイド口パーォキ サイドが好ましい。
有機ハイドロパ一ォキサイドとしてはクメンハイドロパーォキサイド、 ェチルベンゼ ン八ィドロパ一ォキサイド、 t一プチル八ィドロパ一ォキサイド等を例示することがで 含る。 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.
原料物質として使用される有機八ィドロパーォキサイド及び過酸化水素は、 希薄又は 濃厚な精製物又は非精製物であってよい。 The organic octaperoxide and hydrogen peroxide used as raw materials may be diluted or concentrated purified or non-purified.
本反応は、 溶媒の存在下あるいは非存在下に液相中で実施できる。 溶媒は反応時の温 度及び圧力のもとで液体であり、 かつ反応体及び生成物に対して実質的に不活性なもの が好ましい。 溶媒は使用されるノ\ィドロパ一ォキサイド溶液中に存在する物質からなる ものであってよい。 たとえばクメンハイドロパーォキサイドがクメンハイドロパ一ォキ サイドとその原料であるクメンとからなる混合物である場合には、 特に溶媒を添加する ことなく、 これを溶媒の代用とすることも可能である。 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.
エポキシ化反応温度は一般に 0〜 2 0 0 °Cであるが、 2 5〜 2 0 0 °Cの温度が好まし レ^ 圧力は、 反応混合物を液体の状態に保つのに充分な圧力でよい。 一般に圧力は 1 0 0〜: 1 0 0 0 0 k P aであることが有利である。 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.
本発明の方法は、 スラリー、 固定床の形で行うことができる。 本反応は、 回分法、 半 連続法又は連続法によつて実施できるが、 液体処理容器の体積効率を有効に利用する観 点からは固定床による連続法が好ましい。 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.
以下、 実施例により本発明を説明する。 Hereinafter, the present invention will be described by way of examples.
実施例 1 Example 1
珪素酸化物含有ゲルの調製 Preparation of gel containing silicon oxide
珪素酸化物含有ゲルを以下の手順で得た。 A silicon oxide-containing gel was obtained by the following procedure.
4 . 0 gの四塩化珪素、 6 . 7 gのテトライソプロポキシ珪素、 1 . 3 gのテトライ ソプロポキシチタニウム、 2 . 7 gのトリメチルシリルクロライドおよび 3 3 . 5 gの ジクロロメタンを窒素雰囲気下で混合し、 耐圧製のテフロン (登録商標) 容器に封入後、 1 1 0 °Cで 2 1 9時間加熱することにより調製直後の珪素酸化物含有湿潤ゲルを得た。 さらに 1 5 0 で 4時間、 1 0 mmH gの減圧下で乾燥し、 珪素酸化物食有乾燥ゲルを 得た。 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.
シリル化
得られた珪素酸化物含有乾燥ゲルの重量に対してへキサメチルジシラザンを 0. 67 倍量およびトルエンを 10倍量、 珪素酸化物含有乾燥ゲルに添加し、 1 10でで1. 5 時間加熱した。 デカンテーシヨンにてシリルイ匕後の反応液を除いた後に 1 1 0°〇で1. 5時間減圧乾燥することによりシリル化珪素酸化物含有乾燥ゲルを得た。 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.
かさ体積測定 Bulk volume measurement
珪素酸化物含有乾燥ゲルのかさ体積の測定は 0. 5〜 1. 0 mmにサイズを揃えた後、 メスシリンダ一で測定した。 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.
珪素酸化物含有湿潤ゲルの体積の測定は、 0. 5〜1. 0mmにサイズを揃えた珪素 酸化物含有乾燥ゲルをゲルを膨張せしめる液体に室温で 30分間浸漬させ、 ろ過によつ て回収した珪素酸化物含有湿潤ゲルをメスシリンダ一で測定した。 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.
液体処理容器への充填 Filling liquid processing containers
珪素酸化物含有乾燥ゲルを粉碎し、 0. 5mmから 1. 0mmの間のサイズに分級し 回収した。 分級後回収したシリル化珪素酸化物含有乾燥ゲル (かさ体積 1. 3m l) を 液体 (クミルアルコール; 25wt %、 プロピレンオキサイド; 7wt %およびクメ ン; 68wt %) に室温で 30分浸漬することにより膨張させた。 ろ過によりゲルを膨 張せしめる液体を除去したところかさ体積は 2. 5mlとなり、 シリル化珪素酸化物含 有乾燥ゲルはゲルを膨張せしめる液体を吸収することにより 1. 9倍の体積に膨張した。 得られたシリル化珪素酸化物含有湿潤ゲルを内径 8 mmの円筒状ステンレス製リアクタ 一に充填した。 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.
プロピレンのエポキシ化反応 Epoxidation of propylene
シリル化珪素酸化物含有湿潤ゲルを充填した円筒状ステンレス製リアクターにプロピ レンの連続フィードを開始し、 それに追加してクメンハイドロパーォキサイドのクメン 溶液を連続フィードし、 プロピレンォキサドの合成を行った。 この時液フィードによる 円筒状ステンレス製リアクターに圧損は観測されなかつた。 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.
比較例 1 Comparative Example 1
事前にゲルを膨張せしめる液体に浸溃して膨張させないこと以外は実施例 1と同様に、 内径 8 mmの円筒状ステンレス製リアクターにシリル化珪素酸化物含有乾燥ゲルを充填 した。 シリル化珪素酸化物含有乾燥ゲルを充填した円筒状ステンレス製リアクターにプ
ロピレンの連続フィードを開始し、 それに追加してクメンハイドロパーォキサイドのク メン溶液の連続フィードを試みたが、 円筒状ステンレス製リアクターに圧損が生じ、 フ ィ―ドできなかった。 円筒状ステンレス製リアクターからシリル化珪素酸化物含有ゲル を回収したところ、 液入り口側のゲルが粉ィ匕し円筒状ステンレス製リアクタ一入り口を 閉塞させていた。 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.
産業上の利用可能性 Industrial applicability
本発明により、 珪素酸化物含有乾燥ゲルを予めゲルを膨張せしめる液体で膨張させた 後に液体処理容器に充填する、 もしくは予めゲルを膨張せしめる液体を入れた液体処理 容器に珪素酸化物含有乾燥ゲルを充填する方法であつて、 液体処理容器内の圧損を増加 させずに液体をフィードできるといった優れた特徴を有する珪素酸化物含有乾燥ゲルの 充填方法を提供することができる。
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
1 . 珪素酸化物含有乾燥ゲルを液体処理容器に充填する方法であって、 該珪素酸化物含 有乾燥ゲルを予めゲルを膨張せしめる液体で膨張させた後に液体処理容器に充填する珪 素酸化物含有乾燥ゲルの液体処理容器への充填方法。 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 . 珪素酸化物含有乾燥ゲルを液体処理容器に充填する方法であって、 予めゲルを膨張 せしめる液体を入れた液体処理容器に珪素酸化物含有乾燥ゲルを充填する珪素酸化物含 有乾燥ゲルの液体処理容器への充填方法。 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 . 珪素酸化物含有乾燥ゲルが、 液相中、 下記式 (I ) で表される反応によって調製さ れたものである請求項 1又は請求項 2記載の充填方法。 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(L2)o(L3)p(L4)q(L5)rM-X + (L6)s(L7)t(L8)u(L9)v(L10)wM-OH (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(L2)o(L3)p(L4)q(L5)rM-O-M(L6)s(L7)t(L8)u(L9)v(Li0)w + RX ( I ) (ここで、 Mは珪素単独または珪素と 3族から 1 4族の元素からなる 2種類以上の元素 を表し、 Xはハロゲノ基またはカルポキシレート基を表し、 Rは水素または炭化水素基 を表し、 1^〜乙10はアルコキシ基、 ハロゲノ基、 力ルポキシレ一ト基、 水素または炭化 水素基のうちのいずれかを表し、 n、 o、 p、 Q、 r、 s、 t、 u、 vおよび wは 0か ら 5の整数を表し、 n + o + p + q + rおよび s + t + u + v + wはそれぞれ 1以上で ある。 )
→ (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.)
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