WO2015128983A1

WO2015128983A1 - Method for producing particulate inorganic porous material

Info

Publication number: WO2015128983A1
Application number: PCT/JP2014/054843
Authority: WO
Inventors: 利一宮本; 鴻志白
Original assignee: 株式会社エスエヌジー
Priority date: 2014-02-27
Filing date: 2014-02-27
Publication date: 2015-09-03
Also published as: JPWO2015128983A1; JP6068725B2

Abstract

　A method for producing a particulate inorganic porous material, having: a sol preparation step for preparing a precursor sol; a gelation step for filling the pores of a sol receptacle comprising a polymer compound having a series of pores in the form of a three-dimensional network with the precursor sol, inducing parallel sol-gel transition and phase separation of the precursor sol in the pores, and forming a co-continuous structure of a hydrogel phase and solvent phase in the pores; a removal step for separately or simultaneously removing the solvent phase and the sol receptacle from a first intermediate product comprising the co-continuous structure and the sol receptacle, and obtaining an aggregated inorganic porous material; and a crushing step for crushing the aggregated inorganic porous material and obtaining a particulate inorganic porous material. The aggregated inorganic porous material has a brittle structure in which remnant holes are formed in air gaps after the sol receptacle is removed, and is easily crushed and granulated.

Description

粒状無機多孔体の製造方法Method for producing granular inorganic porous material

　本発明は、ゾルゲル法による粒状無機多孔体の製造方法に関する。 The present invention relates to a method for producing a granular inorganic porous material by a sol-gel method.

　３次元階層的連続多孔構造を有する一体型（モノリス）の多孔体をゾルゲル法により作製する場合、一般的には、ゲル化を行う容器の形状及び大きさに応じた塊状の多孔体として作製される（例えば、下記特許文献１等参照）。従来ゾルゲル法により合成されていたモノリス多孔体は、高速液体クロマトグラフィーで使用されるような塊状多孔体を含め、長さ方向で１ｍｍ以上となる大きさのものが一般的であり、長さ方向で１ｍｍ未満の小さいモノリス多孔体は塊状多孔体として作成されていなかった。 When an integral (monolith) porous body having a three-dimensional hierarchical continuous porous structure is produced by the sol-gel method, it is generally produced as a massive porous body corresponding to the shape and size of the gelling container. (See, for example, Patent Document 1 below). Conventional monolithic porous bodies synthesized by the sol-gel method are generally those having a size of 1 mm or more in the length direction, including massive porous bodies used in high performance liquid chromatography. A small monolithic porous body of less than 1 mm was not prepared as a massive porous body.

　粒径が１ｍｍ未満の微小な粒状多孔体を作製する方法として、上記塊状のモノリス多孔体を単純に破砕して粒状化する方法が挙げられる。微小なモノリス多孔体をゾルゲル法により作製する他の方法として、直径０．１～１ｍｍのガラスキャピラリー管の微小空間でゾルゲル法によりモノリス多孔体を作製する例もある（下記非特許文献１参照）。 As a method for producing a fine granular porous body having a particle size of less than 1 mm, a method of simply crushing and granulating the massive monolithic porous body is mentioned. As another method for producing a fine monolithic porous body by a sol-gel method, there is an example of producing a monolithic porous body by a sol-gel method in a minute space of a glass capillary tube having a diameter of 0.1 to 1 mm (see Non-Patent Document 1 below). .

特開平７－４１３７４号公報JP 7-41374 A

　しかし、塊状のモノリス多孔体を単純に破砕して粒状化する方法の場合、破砕に大きな力が必要となり、更に、微細粉の発生が非常に多く、破砕により粒径分布が拡大して目的とする粒径範囲の粒子を効率よく得られないという問題がある。 However, in the case of a method of simply crushing and granulating a massive monolithic porous body, a large force is required for crushing, and furthermore, the generation of fine powder is very large, and the particle size distribution is expanded by crushing. There exists a problem that the particle | grains of the particle size range to be obtained cannot be obtained efficiently.

　また、ガラスキャピラリー管を用いた方法では、キャピラリー管壁とモノリスが結合してキャピラリーカラムが作製されるためモノリス成分のみを取り出すことはできず、粒状の無機多孔体の製造方法として利用できない。 Further, in the method using a glass capillary tube, the capillary tube wall and the monolith are combined to produce a capillary column, so that only the monolith component cannot be taken out and cannot be used as a method for producing a granular inorganic porous body.

　本発明は、上述の問題点に鑑みてなされたものであり、その目的は、ゾルゲル法による粒状の無機多孔体の製造方法であって、目的とする粒径範囲の粒子を効率良く作製可能な製造方法を提供することにある。 The present invention has been made in view of the above-described problems, and an object of the present invention is a method for producing a granular inorganic porous body by a sol-gel method, which can efficiently produce particles having a target particle size range. It is to provide a manufacturing method.

　上記目的を達成するための本発明に係る粒状無機多孔体の製造方法は、前駆体ゾルを調製するゾル調製工程と、３次元網目状に連続した空孔を有する高分子化合物からなるゾル収容体の前記空孔内に、前記前駆体ゾルを充填し、前記空孔内の前記前駆体ゾルに対して、ゾルゲル転移と相分離を並行して発現させ、前記空孔内に、ヒドロゲル相と溶媒相の共連続構造体を形成するゲル化工程と、前記共連続構造体と前記ゾル収容体からなる第１中間生成物から前記溶媒相と前記ゾル収容体を個別或いは同時に除去し、塊状の無機多孔体を得る除去工程と、前記塊状の無機多孔体を破砕して粒状の無機多孔体を得る破砕工程と、を有し、
　前記塊状の無機多孔体が、前記ゾル収容体を除去した後の空隙に形成された残存孔、及び、前記残存孔に囲まれた３次元網目状の骨格体に形成された、前記骨格体内を貫通する３次元網目状に連続した貫通孔と前記骨格体の表面から内部に向けて延伸する細孔の少なくとも何れか一方を備えて構成される３次元網目状の階層的多孔構造を有し、前記粒状の無機多孔体が、破砕され粒状化した前記骨格体からなる多孔体であることを特徴とする。 In order to achieve the above object, the method for producing a granular inorganic porous material according to the present invention comprises a sol preparation step for preparing a precursor sol and a sol container comprising a polymer compound having pores continuous in a three-dimensional network. The sol is filled with the precursor sol, and sol-gel transition and phase separation are caused to occur in parallel with the precursor sol in the pore, and the hydrogel phase and the solvent are contained in the pore. A gelation step for forming a phase co-continuous structure, and removing the solvent phase and the sol container separately or simultaneously from the first intermediate product composed of the co-continuous structure and the sol container; A removing step for obtaining a porous body, and a crushing step for crushing the massive inorganic porous body to obtain a granular inorganic porous body,
In the skeleton body, the massive inorganic porous body is formed into a residual hole formed in a void after removing the sol container, and a three-dimensional network skeleton body surrounded by the residual hole. Having a three-dimensional network-like hierarchical porous structure comprising at least one of through-holes continuous in a three-dimensional network that penetrates and pores extending from the surface of the skeleton to the inside; The granular inorganic porous body is a porous body composed of the skeletal body that has been crushed and granulated.

　更に、上記特徴の製造方法は、前記粒状の無機多孔体の粒径を所定の範囲内に制御するために、前記空孔の孔径分布の平均孔径が前記所定の範囲内にある前記ゾル収容体を準備する工程を更に有することが好ましい。 Further, in the manufacturing method having the above characteristics, in order to control the particle diameter of the granular inorganic porous body within a predetermined range, the sol container in which the average pore diameter of the pore diameter distribution of the pores is within the predetermined range. It is preferable to further include the step of preparing

　更に、上記特徴の製造方法は、前記ゾル収容体が、前記空孔に囲まれた３次元網目状の骨格構造を有することが好ましい。 Furthermore, in the manufacturing method having the above characteristics, it is preferable that the sol container has a three-dimensional network skeleton structure surrounded by the pores.

　更に、上記特徴の製造方法は、前記除去工程が、前記第１中間生成物から前記溶媒相を除去して第２中間生成物を得る第１除去工程と、前記第２中間生成物から前記ゾル収容体を除去する第２除去工程を有することが好ましい。 Further, in the manufacturing method having the above characteristics, the removal step includes a first removal step of removing the solvent phase from the first intermediate product to obtain a second intermediate product, and the sol from the second intermediate product. It is preferable to have the 2nd removal process which removes a container.

　更に、上記特徴の製造方法は、上記第１及び第２除去工程を有する場合、例えば、前記第１除去工程は、前記第１中間生成物中の１ゲルを、洗浄する工程、乾燥する工程、または、洗浄して乾燥する工程であることが好ましい。更に、例えば、前記第２除去工程において、第２中間生成物中のゲルを焼結するとともに、前記ゾル収容体を燃焼して消失させることが好ましい。 Furthermore, when the manufacturing method having the above characteristics includes the first and second removal steps, for example, the first removal step includes a step of washing, drying, and drying one gel in the first intermediate product. Or it is preferable that it is the process of wash | cleaning and drying. Further, for example, in the second removal step, it is preferable that the gel in the second intermediate product is sintered and the sol container is burned and disappeared.

　更に、上記特徴の製造方法は、前記除去工程において、前記第１中間生成物中のゲルを焼結するとともに、焼結時の加熱により、前記第１中間生成物中の前記溶媒相を除去し、前記ゾル収容体を燃焼して消失させることが好ましい。 Furthermore, in the manufacturing method having the above characteristics, in the removing step, the gel in the first intermediate product is sintered, and the solvent phase in the first intermediate product is removed by heating at the time of sintering. The sol container is preferably burned away.

　更に、上記特徴の製造方法は、前記塊状の無機多孔体の前記骨格体に前記貫通孔が形成され、前記粒状の無機多孔体が、前記貫通孔と前記細孔によって構成される３次元網目状の階層的多孔構造を有することが好ましい。 Further, in the manufacturing method having the above characteristics, the through-holes are formed in the skeleton of the massive inorganic porous body, and the granular inorganic porous body is formed by the through-holes and the pores. It is preferable to have a hierarchical porous structure of

　更に、上記特徴の製造方法は、前記塊状の無機多孔体の前記骨格体に前記貫通孔が形成される場合、前記塊状の無機多孔体の前記貫通孔の平均孔径が、前記ゾル収容体の前記空孔の平均孔径の５分の１未満であり、且つ、前記塊状の無機多孔体に形成された前記残存孔の平均孔径より小さいことが好ましい。更には、前記貫通孔の平均孔径が、ゾル収容体の前記空孔の平均孔径の１０分の１未満であり、且つ、前記塊状の無機多孔体に形成された前記残存孔の平均孔径の２分の１未満であることが、より好ましい。 Furthermore, in the manufacturing method of the above feature, when the through-hole is formed in the skeleton body of the massive inorganic porous body, the average pore diameter of the through-hole of the massive inorganic porous body is the same as that of the sol container. It is preferably less than one fifth of the average pore diameter of the pores and smaller than the average pore diameter of the remaining holes formed in the massive inorganic porous body. Furthermore, the average pore diameter of the through-hole is less than one-tenth of the average pore diameter of the pores of the sol container, and 2 of the average pore diameter of the remaining holes formed in the massive inorganic porous body. More preferably, it is less than a fraction.

　更に、上記特徴の製造方法は、前記前駆体ゾルに、ゾルゲル転移と相分離を並行して誘起する働きを有する共存物質を添加することが好ましい。 Furthermore, in the production method having the above characteristics, it is preferable to add a coexisting substance having a function of inducing sol-gel transition and phase separation in parallel to the precursor sol.

　上記特徴の製造方法によれば、微細粉の発生が少なく粒径分布範囲の狭い粒状の無機多孔体を高い収率で製造することができる。 According to the production method having the above characteristics, it is possible to produce a granular inorganic porous body with a small generation of fine powder and a narrow particle size distribution range in a high yield.

　上記特徴の製造方法では、使用するゾル収容体の空孔内に、塊状多孔体の骨格体が、３次元網目状に形成され、当該３次元網目状の骨格体の周囲に残存孔による空隙が分散して形成されるため、ゾル収容体を使用せずに作製された塊状多孔体に比べて、骨格体を容易に破砕することが可能である。 In the manufacturing method having the above characteristics, a massive porous skeleton is formed in a three-dimensional network in the pores of the sol container to be used, and voids due to residual holes are formed around the three-dimensional network skeleton. Since it is formed in a dispersed manner, the skeleton body can be easily crushed as compared to a massive porous body produced without using a sol container.

　また、塊状の無機多孔体を破砕して得られる粒状の無機多孔体の粒径は、塊状の無機多孔体の骨格体の直径、つまり、ゾル収容体の空孔の孔径で制御することができる。よって、ゾル収容体の空孔の孔径分布の平均孔径が所定の範囲内にあるゾル収容体を準備することで、粒状の無機多孔体の粒径を所定の範囲内に制御することが可能となる。 The particle diameter of the granular inorganic porous material obtained by crushing the massive inorganic porous material can be controlled by the diameter of the skeleton of the massive inorganic porous material, that is, the pore diameter of the pores of the sol container. . Therefore, it is possible to control the particle size of the granular inorganic porous body within a predetermined range by preparing a sol container in which the average pore diameter of the pore size distribution of the sol container is within a predetermined range. Become.

　ここで、塊状の無機多孔体の３次元網目状の骨格体に貫通孔と細孔の両方が形成されると、塊状の無機多孔体は、残存孔を含めて３段階の階層的多孔構造を有し、該骨格体の貫通孔と細孔の何れか一方のみが形成されると、塊状の無機多孔体は、２段階の階層的多孔構造を有する。そして、２または３段階の階層的多孔構造を有する塊状の無機多孔体は、残存孔に沿って破砕されるため、粒状の無機多孔体は、貫通孔と細孔の両方が形成される場合は、２段階の階層的多孔構造を有し、貫通孔と細孔の何れか一方のみが形成される場合は、１階層のみの多孔構造を有することになる。 Here, when both the through holes and the pores are formed in the three-dimensional network skeleton of the massive inorganic porous body, the massive inorganic porous body has a three-stage hierarchical porous structure including the remaining pores. And when only one of the through-holes and pores of the skeleton is formed, the massive inorganic porous body has a two-stage hierarchical porous structure. And since the massive inorganic porous body having a two- or three-stage hierarchical porous structure is crushed along the remaining pores, the granular inorganic porous body is formed when both through-holes and pores are formed. In the case of having a two-stage hierarchical porous structure and only one of the through-holes and pores is formed, the porous structure has only one layer.

本発明方法で作製された粒状無機多孔体の実施例１～７と、従来の製造方法で作製された粒状無機多孔体の比較例１，２の平均粒径、粒径範囲、収率、貫通孔及び細孔の平均孔径を対比して一覧表示する対照表。Average particle diameter, particle size range, yield, penetration of Examples 1 to 7 of the granular inorganic porous material produced by the method of the present invention and Comparative Examples 1 and 2 of the granular inorganic porous material produced by the conventional production method A comparison table listing and comparing the average pore size of pores and pores. 実施例１，２及び比較例１の粒状の無機多孔体の粒度分布を示す図。The figure which shows the particle size distribution of the granular inorganic porous body of Examples 1, 2 and Comparative Example 1. 実施例１，４の粒状の無機多孔体の微分細孔径分布を示す図。The figure which shows the differential pore diameter distribution of the granular inorganic porous body of Examples 1 and 4. 実施例１，３～７においてゾル収容体として使用したメラミンスポンジのＳＥＭ写真。SEM photographs of melamine sponges used as sol containers in Examples 1 and 3-7. 実施例２においてゾル収容体として使用したポリウレタンスポンジのＳＥＭ写真。4 is an SEM photograph of a polyurethane sponge used as a sol container in Example 2. FIG. 実施例１の破砕工程前の塊状の無機多孔体を示すＳＥＭ写真。The SEM photograph which shows the block-shaped inorganic porous body before the crushing process of Example 1. FIG. 実施例１の破砕工程後の粒状の無機多孔体を示すＳＥＭ写真。The SEM photograph which shows the granular inorganic porous body after the crushing process of Example 1. FIG. 実施例１の破砕工程後の粒状の無機多孔体を示す他のＳＥＭ写真。The other SEM photograph which shows the granular inorganic porous body after the crushing process of Example 1. FIG. 実施例２の破砕工程後の粒状の無機多孔体を示すＳＥＭ写真。The SEM photograph which shows the granular inorganic porous body after the crushing process of Example 2. FIG.

　本発明に係る粒状の無機多孔体の製造方法（以下、適宜「本発明方法」という。）の実施の形態につき、図面を参照して説明する。 Embodiments of a method for producing a granular inorganic porous material according to the present invention (hereinafter referred to as “the method of the present invention” as appropriate) will be described with reference to the drawings.

　本発明方法は、以下に説明するゾル調製工程、ゲル化工程、除去工程、及び、破砕工程を備えて構成される。以下、各工程の詳細につき説明する。尚、以下の説明では、一例として、無機多孔体がシリカゲルまたはシリカガラスの場合を想定する。 The method of the present invention includes a sol preparation step, a gelation step, a removal step, and a crushing step described below. Hereinafter, the details of each process will be described. In the following description, the case where the inorganic porous material is silica gel or silica glass is assumed as an example.

　ゾル調製工程では、酸またはアルカリ性水溶液中に、シリカゲルまたはシリカガラスの原料となるシリカ前駆体と、ゾルゲル転移と相分離を並行して誘起する働きを有する共存物質を添加して、例えば５℃以下のゾルゲル転移が進行し難い低温下で攪拌し、加水分解反応を起こさせて、均一な前駆体ゾルを調製する。 In the sol preparation step, a silica precursor as a raw material of silica gel or silica glass and a coexisting substance having a function of inducing sol-gel transition and phase separation in parallel are added to an acid or alkaline aqueous solution, for example, 5 ° C. or less. A uniform precursor sol is prepared by stirring at a low temperature at which the sol-gel transition hardly proceeds to cause a hydrolysis reaction.

　シリカ前駆体の主成分として、水ガラス（ケイ酸ナトリウム水溶液）、或いは、無機または有機シラン化合物が使用できる。無機シラン化合物の一例として、テトラメトキシシラン、テトラエトキシシラン、テトラ－イソプロポキシシラン、テトラ－ｎ－ブトキシシラン、テトラ－ｔ－ブトキシシラン等のテトラアルコキシシラン類が挙げられる。また、有機シラン化合物の一例として、メチル、エチル、プロピル、ブチル、ヘキシル、オクチル、デシル、ヘキサデシル、オクタデシル、ドデシル、フェニル、ビニル、ヒドロキシル、エーテル、エポキシ、アルデヒド、カルボキシル、エステル、チオニル、チオ、アミノ等の置換基を有するトリメトキシシラン、トリエトキシシラン、トリイソプロポキシシラン、トリフェノキシシラン等のトリアルコキシシラン類、メチルジエトキシシラン、メチルジメトキシシラン、エチルジエトキシシラン、エチルジメトキシシラン等のジアルコキシシラン類、ジメチルエトキシシラン、ジメチルメトキシシラン等のモノアルコキシシラン類等が挙げられる。また、モノアルキル、ジアルキル、フェニルトリエトキシ等の架橋反応速度制御基置換体を含むアルコキシシリケートやその二量体であるジシラン、三量体であるトリシランといったオリゴマー等もシリカ前駆体として想定される。上述の加水分解性シランは、種々の化合物が市販されており、容易且つ安価に入手可能であり、ケイ素－酸素結合からなる３次元架橋体を形成するゾルゲル反応を制御することも容易である。 As the main component of the silica precursor, water glass (sodium silicate aqueous solution) or an inorganic or organic silane compound can be used. Examples of the inorganic silane compound include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, and tetra-t-butoxysilane. Examples of organic silane compounds include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, hexadecyl, octadecyl, dodecyl, phenyl, vinyl, hydroxyl, ether, epoxy, aldehyde, carboxyl, ester, thionyl, thio, amino Trialkoxysilanes such as trimethoxysilane, triethoxysilane, triisopropoxysilane, and triphenoxysilane having a substituent such as dialkoxy such as methyldiethoxysilane, methyldimethoxysilane, ethyldiethoxysilane, and ethyldimethoxysilane Examples thereof include monoalkoxysilanes such as silanes, dimethylethoxysilane, and dimethylmethoxysilane. Further, alkoxysilicates containing a cross-linking reaction rate controlling group substituent such as monoalkyl, dialkyl, and phenyltriethoxy, disilanes that are dimers thereof, and oligomers such as trisilane that are trimers are also assumed as silica precursors. As the above-mentioned hydrolyzable silane, various compounds are commercially available and can be obtained easily and inexpensively, and it is also easy to control the sol-gel reaction for forming a three-dimensional crosslinked body composed of silicon-oxygen bonds.

　酸またはアルカリ性水溶液は、溶媒である水にシリカ前駆体の加水分解反応を促進する触媒として機能する酸または塩基が溶解した水溶液である。上記酸の具体例として、酢酸、塩酸、硫酸、硝酸、ギ酸、シュウ酸、及び、クエン酸等が、また、上記塩基の具体例として、水酸化ナトリウム、水酸化カリウム、アンモニア水、炭酸ナトリウム、炭酸水素ナトリウム、トリメチルアンモニウム等のアミン類、ｔｅｒｔ－ブチルアンモニウムヒドロキシド等のアンモニウムヒドロキシド類、及び、ソディウムメトキシド等のアルカリ金属アルコキシド類等が想定される。また、上記共存物質の具体例として、ポリエチレンオキシド、ポリプロピレンオキシド、ポリアクリル酸、ポリエチレンオキシドポリプロピレンオキシドブロック共重合体等のブロック共重合体、セチルトリメチルアンモニウムクロリド等の陽イオン性界面活性剤、ドデシル硫酸ナトリウム等の陰イオン性界面活性剤、及び、ポリオキシエチレンアルキルエーテル等のノニオン系界面活性剤等が想定される。尚、溶媒として水を使用するが、メタノールやエタノール等のアルコール類としても良い。 The acid or alkaline aqueous solution is an aqueous solution in which an acid or base functioning as a catalyst for promoting the hydrolysis reaction of the silica precursor is dissolved in water as a solvent. Specific examples of the acid include acetic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, and citric acid. Specific examples of the base include sodium hydroxide, potassium hydroxide, aqueous ammonia, sodium carbonate, Amines such as sodium hydrogen carbonate and trimethylammonium, ammonium hydroxides such as tert-butylammonium hydroxide, and alkali metal alkoxides such as sodium methoxide are envisaged. Specific examples of the coexisting substances include polyethylene oxide, polypropylene oxide, polyacrylic acid, block copolymers such as polyethylene oxide polypropylene oxide block copolymers, cationic surfactants such as cetyltrimethylammonium chloride, dodecyl sulfate. Anionic surfactants such as sodium and nonionic surfactants such as polyoxyethylene alkyl ether are envisaged. Although water is used as a solvent, alcohols such as methanol and ethanol may be used.

　ゲル化工程では、ゾル調製工程で調製された前駆体ゾルを、３次元網目状に連続した空孔を有する高分子化合物からなるゾル収容体を収容したゲル化容器内に注入して、ゾル収容体の空孔内に充填し、例えば４０℃程度のゾルゲル転移が進行し易い温度下でゲル化させる。ここで、前駆体ゾル内には、ゾルゲル転移と相分離を並行して誘起する働きを有する共存物質が添加されているため、スピノーダル分解が誘起され、３次元連続網目状の骨格構造を有するシリカヒドロゲル（湿潤ゲル）相と溶媒相の共連続構造体が、ゾル収容体の空孔内に徐々に形成される。シリカヒドロゲル相の３次元連続網目状構造は、当該シリカヒドロゲル相の骨格体内を貫通する３次元連続網目状の貫通孔の周囲に形成される。シリカヒドロゲル相は、当該貫通孔と、骨格体の表面から内部に向けて延伸する細孔の２段階の階層的多孔構造とすることができる。尚、貫通孔と細孔は、夫々、マクロポア、メソポアと呼ばれることもある。以下、便宜的に、ゲル化工程で生成されたシリカヒドロゲル相と溶媒相の共連続構造体とゾル収容体とを含めて「第１中間生成物」と称する。 In the gelation process, the precursor sol prepared in the sol preparation process is injected into a gelation container containing a sol container made of a polymer compound having pores that are continuous in a three-dimensional network, and the sol is stored. It fills in the pores of the body and gels at a temperature at which the sol-gel transition at about 40 ° C. is likely to proceed. Here, since a coexisting substance having a function of inducing the sol-gel transition and the phase separation in parallel is added in the precursor sol, the spinodal decomposition is induced and the silica having a three-dimensional continuous network skeleton structure. A co-continuous structure of a hydrogel (wet gel) phase and a solvent phase is gradually formed in the pores of the sol container. The three-dimensional continuous network structure of the silica hydrogel phase is formed around the three-dimensional continuous network through-holes that penetrate through the skeleton of the silica hydrogel phase. The silica hydrogel phase can have a two-stage hierarchical porous structure including the through-holes and pores extending from the surface of the skeleton to the inside. Note that the through hole and the fine hole may be referred to as a macropore and a mesopore, respectively. Hereinafter, for convenience, the co-continuous structure of the silica hydrogel phase and the solvent phase produced in the gelation step and the sol container will be referred to as “first intermediate product”.

　ゾル収容体として、樹脂を溶融状態または重合前に発泡させ泡状とし、凝固または重合させ固化させた発泡樹脂体を利用でき、一例として、市販のポリウレタン或いはメラミン製のスポンジを利用できる。ゾル収容体の空孔は、当該空孔内に前駆体ゾルを浸漬させるため、３次元網目状の連続空孔である必要がある。また、ゾル収容体の骨格構造も、空孔と同様に、３次元連続網目状構造を有しているのが望ましい。 As the sol container, a foamed resin body in which the resin is foamed or foamed before polymerization or in the form of a foam and solidified or polymerized and solidified can be used. For example, a commercially available polyurethane or sponge made of melamine can be used. The holes of the sol container need to be three-dimensional network-like continuous holes in order to immerse the precursor sol in the holes. The skeleton structure of the sol container preferably has a three-dimensional continuous network structure as well as the pores.

　ゾル収容体の成分は、後述する除去工程で除去されることが前提となるため、一例として、焼結過程により燃焼して消失するものが望ましい。また、ゾル収容体が無機多孔体と水素結合等の強い相互作用を起こす材質であれば、前駆体ゾルがゾル収容体と接触したうえでゲル化すると、無機多孔体の微細構造が、ゾル収容体との接触界面で乱れる可能性がある。そのため、無機多孔体とゾル収容体は、化学的に相互作用しない材質であることが望ましい。また、ゾル収容体は、ゲル化工程において、前駆体ゾルに溶解しない程度の適度な重合度のポリマーであれば良い。以上の要件に適したゾル収容体の材質として、高分子の炭化水素系化合物であるポリオレフィン系を主体とし、その酸化物・窒化物などが挙げられ、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアクリル、ポリウレタン、ポリエステル、ＥＶＡ架橋体、ポリフェノール、ポリ塩化ビニル、ポリユリア、ポリアミド、エチレンプロピレンジエン、メラミン等をはじめとする樹脂やその共重合体を発泡させたものが挙げられる。 Since the components of the sol container are premised on being removed in a removing step described later, as an example, it is desirable that the components be burnt and disappear during the sintering process. In addition, if the sol container is a material that causes strong interaction such as hydrogen bonding with the inorganic porous body, the microstructure of the inorganic porous body becomes a sol-containing structure when the precursor sol is gelled after contacting the sol container. There is a possibility of disturbance at the contact interface with the body. Therefore, it is desirable that the inorganic porous body and the sol container are materials that do not interact chemically. The sol container may be a polymer having an appropriate degree of polymerization that does not dissolve in the precursor sol in the gelation step. The material of the sol container suitable for the above requirements mainly comprises a polyolefin which is a high molecular weight hydrocarbon compound, and examples thereof include oxides and nitrides thereof, for example, polyethylene, polypropylene, polystyrene, polyacryl, Examples include foamed resins and copolymers thereof such as polyurethane, polyester, EVA crosslinked product, polyphenol, polyvinyl chloride, polyurea, polyamide, ethylene propylene diene, and melamine.

　ゲル化工程において、シリカヒドロゲル層が形成された後も、当該湿潤ゲルの重縮合反応が緩やかに進行して、ゲルの収縮が起こるため、ゲル化工程の後工程（ゲル化後工程）として、ゲル化工程でゾル収容体の空孔内に形成されたシリカヒドロゲル相と溶媒相の共連続構造体を、アンモニア水等の塩基性水溶液に浸漬し、加圧容器内で加熱処理することにより、シリカヒドロゲル相の加水分解反応、重縮合反応、及び、溶解再析出反応を更に進行させ、シリカヒドロゲル相の骨格構造をより強固なものにすることが可能となる。尚、当該ゲル化後工程は、必要に応じて行えば良い。尚、当該加熱処理は、必ずしも加圧容器や密閉容器内で行わなくても差し支えないが、加熱によりアンモニア成分等が生成または揮発する場合があるので、密閉容器内、或いは、耐圧性を有する加圧容器内で処理するのが好ましい。 In the gelation step, even after the silica hydrogel layer is formed, the polycondensation reaction of the wet gel proceeds slowly and the gel shrinks. Therefore, as a subsequent step of the gelation step (post-gelation step), By immersing the co-continuous structure of the silica hydrogel phase and the solvent phase formed in the pores of the sol container in the gelation step in a basic aqueous solution such as ammonia water, and heat-treating in a pressure vessel, It is possible to further advance the hydrolysis reaction, polycondensation reaction, and dissolution reprecipitation reaction of the silica hydrogel phase, and to further strengthen the skeleton structure of the silica hydrogel phase. In addition, what is necessary is just to perform the said post-gelation process as needed. Note that the heat treatment is not necessarily performed in a pressurized container or a sealed container, but an ammonia component or the like may be generated or volatilized by heating. Therefore, the heat treatment may be performed in a sealed container or a pressure resistant container. Processing in a pressure vessel is preferred.

　シリカヒドロゲル相の骨格体を形成するシリカ微粒子の溶解再析出反応の進行により、当該骨格体に形成される細孔径が拡大される。更に、水熱処理により、当該溶解再析出反応を繰り返すことにより、細孔径を更に拡大する制御が可能となる。尚、細孔径の制御は、前駆体ゾル内に上記触媒及び共存物質以外に尿素を添加することによっても実現できる。尿素は６０℃以上の温度下で加水分解してアンモニアを生成し、当該アンモニアにより、ゲル化工程で合成された湿潤ゲルの骨格体に形成される細孔の孔径が拡張されるため、尿素の添加により当該細孔径の制御が可能となる。一方、貫通孔の構造及び孔径の制御は、ゾル調製工程で前駆体ゾルに添加する水やシリカ前駆体の量、或いは、共存物質の組成及び添加量等の調整により可能となる。 The progress of the dissolution and reprecipitation reaction of the silica fine particles that form the skeleton of the silica hydrogel phase enlarges the pore diameter formed in the skeleton. Furthermore, by repeating the dissolution reprecipitation reaction by hydrothermal treatment, it is possible to control to further enlarge the pore diameter. The control of the pore diameter can also be realized by adding urea to the precursor sol in addition to the catalyst and the coexisting substance. Urea hydrolyzes at a temperature of 60 ° C. or higher to produce ammonia, and the ammonia expands the pore diameter of the pores formed in the skeleton of the wet gel synthesized in the gelation process. The pore diameter can be controlled by addition. On the other hand, the structure of the through-hole and the pore diameter can be controlled by adjusting the amount of water or silica precursor added to the precursor sol in the sol preparation step, or the composition and addition amount of coexisting substances.

　除去工程は、ゲル化工程またはゲル化後工程に引き続いて、上記第１中間生成物から溶媒相とゾル収容体を個別或いは同時に除去し、塊状の無機多孔体を得る工程である。塊状の無機多孔体は、前記ゾル収容体を除去した後の空隙に形成された残存孔、当該残存孔に囲まれた骨格体内を貫通する３次元網目状に連続した貫通孔、及び、前記骨格体の表面から内部に向けて延伸する細孔の３段階の階層的多孔構造を有する。尚、貫通孔と細孔は、必ずしも両方が同時に形成される必要はなく、塊状の無機多孔体は、前記残存孔と、貫通孔と細孔の何れか一方だけが形成された２段階の階層的多孔構造であっても良い。 The removal step is a step of removing the solvent phase and the sol container from the first intermediate product individually or simultaneously after the gelation step or the post-gelation step to obtain a massive inorganic porous body. The massive inorganic porous body includes residual holes formed in voids after removing the sol container, three-dimensional network-like through holes penetrating through the skeleton surrounded by the residual holes, and the skeleton It has a three-stage hierarchical porous structure of pores extending from the body surface to the inside. It should be noted that both the through holes and the pores do not necessarily have to be formed at the same time, and the massive inorganic porous body has a two-stage hierarchy in which only one of the remaining holes, the through holes and the pores is formed. It may be a porous structure.

　本実施形態では、除去工程は、上記第１中間生成物から溶媒相を除去する第１除去工程と、第１除去工程により生成される第２中間生成物からゾル収容体を除去する第２除去工程の２段階の除去工程を有する。 In the present embodiment, the removal step includes a first removal step of removing the solvent phase from the first intermediate product and a second removal of removing the sol container from the second intermediate product generated by the first removal step. It has a two-stage removal process.

　第１除去工程では、湿潤ゲルの洗浄と乾燥或いは乾燥のみを行い、添加剤や未反応物等を含む溶媒相を除去する。溶媒相除去後の空間が貫通孔及び細孔となる。洗浄液は、有機溶剤や水溶液等の液体が望ましい。また、有機化合物や無機化合物を溶解させた液体を用いることもできる。更に、洗浄液として酸やアルカリ等のゲルの等電点と異なるｐＨの溶液を用いても、ゲル内に残留した添加材等を容易に除去することができる。具体的には、塩酸、硫酸、硝酸、フッ酸、酢酸、ギ酸、炭酸、クエン酸、リン酸を始めとする各種の酸、及び、水酸化ナトリウム、水酸化カリウム、アンモニア、水溶性アミン、炭酸ナトリウム、炭酸水素ナトリウムを始めとする各種の塩基を用いることができる。湿潤ゲルの乾燥は、自然乾燥を採用しても良く、真空下での減圧乾燥、電気オーブン等を用いた加温下での乾燥、湿潤ゲル内の溶媒を、イソプロパノール、アセトン、ヘキサン、ハイドロフルオロカーボン等の水より表面張力が低い低表面張力溶媒に置換してから行う乾燥、凍結昇華による乾燥、更に、湿潤ゲル内の溶媒を超臨界状態の二酸化炭素に交換してから無表面張力状態で行う超臨界乾燥等を採用するのも好ましい。 In the first removal step, the wet gel is washed and dried or only dried to remove the solvent phase containing additives and unreacted substances. The space after removal of the solvent phase becomes through holes and pores. The cleaning liquid is preferably a liquid such as an organic solvent or an aqueous solution. A liquid in which an organic compound or an inorganic compound is dissolved can also be used. Furthermore, even if a solution having a pH different from the isoelectric point of the gel such as acid or alkali is used as the cleaning liquid, the additive remaining in the gel can be easily removed. Specifically, various acids including hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, acetic acid, formic acid, carbonic acid, citric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, ammonia, water-soluble amine, carbonic acid Various bases including sodium and sodium bicarbonate can be used. Drying of the wet gel may adopt natural drying, drying under reduced pressure under vacuum, drying under heating using an electric oven, etc., and solvent in the wet gel as isopropanol, acetone, hexane, hydrofluorocarbon Drying after substituting with a low surface tension solvent whose surface tension is lower than that of water, etc., drying by freezing sublimation, and replacing the solvent in the wet gel with carbon dioxide in a supercritical state, followed by no surface tension. It is also preferable to employ supercritical drying or the like.

　引き続き、第２除去工程において、乾燥後のゲル（第２中間生成物）からゾル収容体を除去して、塊状の無機多孔体を得る。ゾル収容体除去後の空間が残存孔となる。第２除去工程は、例えば電気炉内で、ゾル収容体を単純に燃焼や焼成により除去する方法が利用できる。得られた乾燥ゲルは焼成により焼結させシリカガラスとすることが可能であるため、焼成により除去する方法が簡易である。尚、焼成温度が、シリカのガラス転移温度（約１０００℃）より低温の場合は、シリカガラスには成らない。 Subsequently, in the second removal step, the sol container is removed from the dried gel (second intermediate product) to obtain a massive inorganic porous body. The space after removal of the sol container becomes the remaining holes. For the second removal step, for example, a method of removing the sol container simply by combustion or baking in an electric furnace can be used. Since the obtained dried gel can be sintered into a silica glass by firing, a method of removing it by firing is simple. In addition, when a calcination temperature is lower than the glass transition temperature (about 1000 degreeC) of a silica, it does not become a silica glass.

　また、第２除去工程は、第１除去工程と同時或いは第１除去工程前に実行することも可能である。例えば、第１除去工程より前にゾル収容体を除去する場合、有機ポリマー繊維を酸やアルカリで加水分解反応させて溶媒中に溶解させ除去する方法が利用できる。更に、ゲル化工程またはゲル化後工程後に、湿潤ゲルをそのまま焼成することで、第１及び第２除去工程を同時に行うことも可能である。 Also, the second removal step can be performed simultaneously with the first removal step or before the first removal step. For example, when removing the sol container prior to the first removal step, a method in which the organic polymer fiber is hydrolyzed with an acid or alkali and dissolved in a solvent to be removed can be used. Furthermore, the first and second removal steps can be performed simultaneously by baking the wet gel as it is after the gelation step or the post-gelation step.

　破砕工程は、上述のゾル調製工程、ゲル化工程、及び、除去工程を経て得られた塊状の無機多孔体を破砕して粒状化する工程である。塊状の無機多孔体には、除去されたゾル収容体の骨格構造と同じ３次元連続網目状の残存孔を有するため、当該残存孔を有しない塊状の無機多孔体と比べて極めて脆い構造である。更に、上述のゲル化工程において加水分解反応と重縮合反応に伴うゲルの収縮が生じるため、ゾル収容体は当該ゲルの収縮によってゲル側から圧縮される。しかし、ゾル収容体はゲルと同等には収縮できないため、ゾル収容体の骨格構造の屈曲部分等の界面近傍において、ゲルに対して応力集中が生じ易くなる。この結果、塊状の無機多孔体の骨格体の表面には、例えば、残存孔の屈曲部分等の表面において微小なヒビ等が生じている可能性がある。従って、３次元連続網目状の残存孔を有する塊状の無機多孔体は、容易に破砕することができる。また、破砕後の粒状化した無機多孔体から残存孔は消失している。尚、破砕工程は、人手によって行っても良く、乳鉢等を用いても良く、また、ボールミル等の破砕装置を使用しても良い。 The crushing step is a step of crushing and granulating the massive inorganic porous material obtained through the above-described sol preparation step, gelation step, and removal step. Since the massive inorganic porous body has the same three-dimensional continuous network-like residual pores as the skeleton structure of the removed sol container, it has a very brittle structure compared to the massive inorganic porous body that does not have the residual pores. . Further, since the gel shrinkage occurs in the above-described gelation step due to the hydrolysis reaction and the polycondensation reaction, the sol container is compressed from the gel side by the gel shrinkage. However, since the sol container cannot contract as much as the gel, stress concentration easily occurs on the gel in the vicinity of the interface such as the bent portion of the skeleton structure of the sol container. As a result, on the surface of the massive inorganic porous body, for example, there is a possibility that minute cracks or the like are generated on the surface of the bent portion of the remaining hole. Therefore, a massive inorganic porous body having three-dimensional continuous network-like residual pores can be easily crushed. Further, residual pores disappear from the granulated inorganic porous material after crushing. The crushing step may be performed manually, a mortar or the like may be used, and a crushing device such as a ball mill may be used.

　破砕後の粒状化された無機多孔体は、篩掛けして分級することで、所望の粒径範囲の粒状の無機多孔体を精度良く且つ高効率に回収できる。 The granular inorganic porous material after crushing is sieved and classified, whereby the granular inorganic porous material having a desired particle size range can be recovered with high accuracy and high efficiency.

　破砕後の粒状化された無機多孔体の粒径は、ゾル収容体の連続空孔内に形成された塊状の無機多孔体の骨格体の太さと同じであるため、粒状の無機多孔体の粒径分布は、ゾル収容体の連続空孔の孔径分布を調整することで制御できる。例えば、連続空孔の孔径分布の平均孔径が所定の範囲内にあるゾル収容体を準備して、当該ゾル収容体をゲル化工程で用いることで、最終的に得られる粒状の無機多孔体の粒径を当該所定の範囲内に高精度で制御できる。尚、連続空孔の平均孔径は、水銀圧入法等によって測定可能であり、また、ゾル収容体の電子顕微鏡写真像から任意の直線上の例えば２０乃至３０箇所の空孔の孔径を計量して、それらの平均値を算出する手法も採用できる。 The particle size of the granulated inorganic porous material after crushing is the same as the thickness of the skeleton body of the massive inorganic porous material formed in the continuous pores of the sol container. The diameter distribution can be controlled by adjusting the hole diameter distribution of the continuous pores of the sol container. For example, by preparing a sol container in which the average pore diameter of the pore size distribution of the continuous pores is within a predetermined range, and using the sol container in the gelation step, the granular inorganic porous body finally obtained The particle size can be controlled within the predetermined range with high accuracy. The average pore diameter of the continuous pores can be measured by mercury porosimetry or the like, and the pore diameters of, for example, 20 to 30 holes on an arbitrary straight line are measured from the electron micrograph image of the sol container. A method for calculating the average value of these can also be employed.

　従って、予め連続空孔の孔径分布が分かっているゾル収容体を用いて、上述の本発明方法のゾル調製工程、ゲル化工程、除去工程、及び、破砕工程を順次実行することで、当該孔径分布に合致した範囲内の粒径の粒状の無機多孔体を精度良く且つ高効率に作製することができる。 Therefore, by using the sol container in which the pore size distribution of the continuous pores is known in advance, the pore size is determined by sequentially executing the sol preparation step, the gelation step, the removal step, and the crushing step of the above-described method of the present invention. A granular inorganic porous body having a particle size within a range matching the distribution can be produced with high accuracy and high efficiency.

　また、粒状の無機多孔体の粒径範囲に適した孔径分布のゾル収容体が無い場合は、当該粒径範囲に適した孔径分布のゾル収容体を作製すれば良い。ゾル収容体の連続空孔の孔径分布の調整方法として、ゾル収容体の材質がポリウレタンの場合、例えば、国際公開公報ＷＯ２０１３／０１５２４５Ａ１に開示されているように、造泡用気体（窒素ガス）の体積割合と整泡剤の種類や添加量により孔径分布を制御することができる。 If there is no sol container having a pore size distribution suitable for the particle size range of the granular inorganic porous material, a sol container having a pore size distribution suitable for the particle size range may be prepared. As a method for adjusting the pore size distribution of the continuous pores of the sol container, when the material of the sol container is polyurethane, for example, as disclosed in International Publication No. WO2013 / 015245A1, the foaming gas (nitrogen gas) The pore size distribution can be controlled by the volume ratio and the type and amount of foam stabilizer.

　以上説明した本発明方法で作製される破砕工程前の塊状の無機多孔体は、残存孔、貫通孔及び細孔の３段階の階層的多孔構造を有する。そして、破砕工程後の粒状の無機多孔体は、貫通孔及び細孔の２段階の階層的多孔構造を有する。階層的多孔構造の各孔の孔径は、小さい順に、細孔、貫通孔、残存孔となる。ここで、貫通孔の孔径は、ゾル収容体の連続空孔の孔径に対して５分の１程度以上に大きいと、連続空孔内に形成される骨格体の繋がりが悪くなり、塊状の無機多孔体を破砕すると、残存孔だけではなく、貫通孔も破壊され、貫通孔を有しない微細な粒子が多く発生し、粉砕後の粒径が不揃いになる可能性が高くなる。従って、破砕工程前の塊状の無機多孔体が貫通孔を有する場合は、当該貫通孔の平均孔径は、ゾル収容体の連続空孔の平均孔径の５分の１未満であることが好ましく、更には、１０分の１未満であることが望ましい。一方、破砕工程では、破砕工程前の塊状の無機多孔体が貫通孔を有する場合は、貫通孔を維持した状態で、残存孔が破壊されるように破砕するので、当然に、残存孔の方が、貫通孔より孔径が大きく、特に、２倍以上の大きいことが望ましい。尚、上述のゲル化工程で想定される貫通孔径は、０．１μｍ～１００μｍで、細孔径は、２ｎｍ～２００ｎｍで、貫通孔径より小さい。 The massive inorganic porous body before the crushing step produced by the method of the present invention described above has a three-stage hierarchical porous structure of residual pores, through-holes and pores. And the granular inorganic porous body after a crushing process has a two-stage hierarchical porous structure of a through-hole and a pore. The pore diameter of each hole in the hierarchical porous structure is a pore, a through-hole, and a remaining pore in ascending order. Here, when the hole diameter of the through-hole is larger than about one-fifth of the hole diameter of the continuous pore of the sol container, the connection of the skeleton formed in the continuous hole becomes poor, and the lump-like inorganic When the porous body is crushed, not only the remaining holes but also the through-holes are destroyed, and many fine particles having no through-holes are generated, and there is a high possibility that the particle sizes after pulverization are uneven. Therefore, when the massive inorganic porous body before the crushing step has through holes, the average pore diameter of the through holes is preferably less than one fifth of the average pore diameter of the continuous pores of the sol container. Is preferably less than 1/10. On the other hand, in the crushing process, when the massive inorganic porous body before the crushing process has through holes, the remaining holes are naturally broken while maintaining the through holes. However, the hole diameter is larger than that of the through-hole, and it is particularly desirable that it is twice or more larger. The through-hole diameter assumed in the above-mentioned gelation step is 0.1 to 100 μm, and the pore diameter is 2 to 200 nm, which is smaller than the through-hole diameter.

　破砕工程前の塊状の無機多孔体は、残存孔と、貫通孔及び細孔の何れか一方の２段階の階層的多孔構造とすることもできる。その場合、破砕工程後の粒状の無機多孔体は、貫通孔及び細孔の何れか一方のみの１段階の多孔構造となる。斯かる場合も、塊状の無機多孔体が残存孔を有するので、容易に破砕することができる。 The massive inorganic porous body before the crushing step can have a two-stage hierarchical porous structure of any one of the remaining holes and the through holes and pores. In that case, the granular inorganic porous material after the crushing step has a one-stage porous structure including only one of the through holes and the fine pores. Also in such a case, since the massive inorganic porous body has residual pores, it can be easily crushed.

　塊状の無機多孔体が残存孔と貫通孔の２段階の階層的多孔構造とする方法として、ゾル調製工程で貫通孔と細孔の２段階の階層的多孔構造が発現する前駆体ゾルを調整しておき、２ｎｍ程度の超微細な細孔を形成した上で、常圧下で乾燥及び焼結して、毛管凝集力により当該細孔を塞ぐか、或いは、焼結を１０００℃以上で行い、細孔部分を焼結して塞いでしまい、残存孔と貫通孔のみとする。また、塊状の無機多孔体が残存孔と細孔の２段階の階層的多孔構造とする方法として、ゾル調製工程で貫通孔が発現しない前駆体ゾルを調整して、ゲル化工程において、細孔だけを発現させることができる。 As a method of forming a porous inorganic porous body with a two-stage hierarchical porous structure of residual pores and through-holes, a precursor sol that expresses a two-stage hierarchical porous structure of through-holes and pores is prepared in the sol preparation process. In addition, after forming ultrafine pores of about 2 nm, drying and sintering under normal pressure, the pores are blocked by capillary cohesive force, or sintering is performed at 1000 ° C. or higher to make fine pores. The hole portion is sintered and plugged, leaving only the remaining holes and the through holes. In addition, as a method in which the massive inorganic porous body has a two-stage hierarchical porous structure of residual pores and pores, a precursor sol that does not exhibit through-holes in the sol preparation step is prepared, Only can be expressed.

　次に、本発明方法の具体的な実施例について、比較例と対照して説明する。以下において、７種類の実施例１～７と２種類の比較例１～２の各製造条件を説明する。 Next, specific examples of the method of the present invention will be described in contrast to comparative examples. In the following, manufacturing conditions of seven types of Examples 1 to 7 and two types of Comparative Examples 1 and 2 will be described.

　〈実施例１〉
　０．０１Ｍ（体積モル濃度）の酢酸水溶液１０ｍＬ（ミリリットル）中に、共存物質であるポリエチレングリコール（分子量１００００）０．８ｇと尿素０．２ｇを溶解させ、オルトケイ酸テトラメチル（テトラメトキシシラン、シリカ前駆体）５ｍＬを添加し、氷冷下にて３０分攪拌して均一溶液とし、前駆体ゾルを得た（ゾル調製工程）。ゾル収容体として、メラミンスポンジ（ＢＡＳＦ社製、３×３×５ｃｍ角ブロック状）を準備し、得られた前駆体ゾルを当該メラミンスポンジに吸収させ、当該メラミンスポンジをポリエチレン製のポリ袋に収容して密閉し、４０℃に設定した湯浴に浸して加温しゲル化させた（ゲル化工程）。得られた湿潤ゲルを密閉容器に入れ１００℃で１８時間加熱処理した（ゲル化後工程）。その後、湿潤ゲルを水１Ｌに浸漬し洗浄し、洗浄した湿潤ゲルを自然乾燥させ（第１除去工程）、得られた乾燥ゲルを６５０℃にて５時間焼結し、メラミンスポンジを除去して塊状の無機多孔体を得た（第２除去工程）。塊状の無機多孔体を、乳鉢を用いて軽く破砕した（破砕工程）。得られた粒状の無機多孔体の貫通孔及び細孔の平均孔径は、１．５μｍと１０ｎｍであった。貫通孔の平均孔径は、ＳＥＭ（走査型電子顕微鏡）写真像から求め、細孔の平均孔径は、窒素吸着測定によるＢＪＨ法により求めた（実施例２～７、比較例１～２において同じ）。 <Example 1>
In 10 mL (milliliter) of acetic acid aqueous solution of 0.01 M (volume molar concentration), 0.8 g of polyethylene glycol (molecular weight 10,000) and 0.2 g of urea, which are coexisting substances, are dissolved, and tetramethyl orthosilicate (tetramethoxysilane, silica (Precursor) 5 mL was added and stirred for 30 minutes under ice cooling to obtain a uniform solution to obtain a precursor sol (sol preparation step). A melamine sponge (manufactured by BASF, 3 × 3 × 5 cm square block shape) is prepared as a sol container, the obtained precursor sol is absorbed into the melamine sponge, and the melamine sponge is stored in a polyethylene plastic bag. Then, it was sealed and immersed in a hot water bath set at 40 ° C. to heat and gel (gelation step). The obtained wet gel was put in an airtight container and heat-treated at 100 ° C. for 18 hours (post-gelation step). Thereafter, the wet gel is immersed in 1 L of water and washed, the washed wet gel is naturally dried (first removal step), and the obtained dried gel is sintered at 650 ° C. for 5 hours to remove the melamine sponge. A massive inorganic porous body was obtained (second removal step). The massive inorganic porous material was lightly crushed using a mortar (crushing step). The average pore sizes of the through-holes and pores of the obtained granular inorganic porous material were 1.5 μm and 10 nm. The average pore diameter of the through holes was determined from a SEM (scanning electron microscope) photographic image, and the average pore diameter was determined by the BJH method based on nitrogen adsorption measurement (the same applies to Examples 2 to 7 and Comparative Examples 1 and 2). .

　〈実施例２〉
　ゾル収容体として、ポリウレタンスポンジ（住友３Ｍ社製、３×３×５ｃｍ角ブロック状）を使用した以外は、実施例１と全く同じである。粒状の無機多孔体の貫通孔及び細孔の平均孔径は、実施例１と同じく、１．５μｍと１０ｎｍであった。 <Example 2>
Example 1 is the same as Example 1 except that polyurethane sponge (manufactured by Sumitomo 3M, 3 × 3 × 5 cm square block shape) is used as the sol container. The average pore diameter of the through-holes and pores of the granular inorganic porous material was 1.5 μm and 10 nm as in Example 1.

　〈実施例３〉
　ゾル調製工程における、０．０１Ｍの酢酸水溶液１０ｍＬ中に溶解させる、ポリエチレングリコールの分量を０．９５ｇ、尿素の分量を０．９ｇに増量した以外は、実施例１と全く同じである。粒状の無機多孔体の貫通孔及び細孔の平均孔径は、０．１μｍと１０ｎｍであった。 <Example 3>
In the sol preparation step, exactly the same as Example 1, except that the amount of polyethylene glycol dissolved in 10 mL of 0.01 M acetic acid aqueous solution was increased to 0.95 g and the amount of urea was increased to 0.9 g. The average pore sizes of the through-holes and pores of the granular inorganic porous material were 0.1 μm and 10 nm.

　〈実施例４〉
　ゲル化後工程において、ゲル化後の湿潤ゲルを密閉容器にいれ０．１Ｍアンモニア水に浸し、１２０℃で１８時間加熱処理した以外は、実施例１と全く同じである。粒状の無機多孔体は貫通孔及び細孔の平均孔径は、１．５μｍと３０ｎｍであった。 <Example 4>
In the post-gelation step, the same procedure as in Example 1 was performed except that the wet gel after gelation was placed in a sealed container and immersed in 0.1 M ammonia water and heat-treated at 120 ° C. for 18 hours. In the granular inorganic porous material, the average pore sizes of the through-holes and pores were 1.5 μm and 30 nm.

　〈実施例５〉
　第２除去工程の焼結温度を１０００℃とした以外は、実施例１と全く同じである。焼結温度が１０００℃と高くなったので、細孔が焼結した貫通孔のみの粒状の無機多孔体が得られた。貫通孔の平均孔径は１．０μｍであった。 <Example 5>
Except for the sintering temperature of the second removal step being 1000 ° C., it is exactly the same as Example 1. Since the sintering temperature was as high as 1000 ° C., a granular inorganic porous body having only through-holes with sintered pores was obtained. The average hole diameter of the through holes was 1.0 μm.

　〈実施例６〉
　ゾル調製工程における、０．０１Ｍの酢酸水溶液１０ｍＬ中に溶解させる、ポリエチレングリコールの分量を０．９５ｇ、尿素の分量を０．９ｇに増量した点（実施例３と同様）と、ゲル化後工程での熱処理を行わなかった点以外は、実施例１と全く同じである。この結果、細孔の無い貫通孔のみの粒状の無機多孔体が得られた。貫通孔の平均孔径は０．１μｍであった。 <Example 6>
In the sol preparation step, the amount of polyethylene glycol dissolved in 10 mL of 0.01 M acetic acid aqueous solution was increased to 0.95 g, the amount of urea was increased to 0.9 g (same as in Example 3), and post-gelation step Except that the heat treatment in was not performed, it is the same as Example 1. As a result, a granular inorganic porous material having only through holes without pores was obtained. The average hole diameter of the through holes was 0.1 μm.

　〈実施例７〉
　ゾル調製工程における、０．０１Ｍの酢酸水溶液１０ｍＬ中に溶解させる、ポリエチレングリコールの添加を止めて、尿素の分量を０．９ｇに増量した以外は、実施例１と全く同じである。この結果、貫通孔の無い細孔のみの粒状の無機多孔体が得られた。細孔の平均孔径は３０ｎｍであった。 <Example 7>
Except for the addition of polyethylene glycol dissolved in 10 mL of 0.01 M acetic acid aqueous solution in the sol preparation step, the amount of urea was increased to 0.9 g. As a result, a granular inorganic porous material having only fine pores without through-holes was obtained. The average pore diameter of the pores was 30 nm.

　〈比較例１，２〉
　ゲル化工程において、メラミンスポンジ（実施例１）やポリウレタンスポンジ（実施例２）等のゾル収容体を用いずに、湿潤ゲルを得た点以外は、実施例１及び２と全く同じである。従って、比較例１，２は、実施例１～７と異なり、破砕工程に供する塊状の無機多孔体は、残存孔を有さず、貫通孔と細孔のみの２段階の階層的多孔構造を有する。尚、比較例１と比較例２は、後述する破砕工程後の分級処理に使用する篩の目開きが異なる。 <Comparative Examples 1 and 2>
In the gelation step, it is exactly the same as in Examples 1 and 2 except that a wet gel was obtained without using a sol container such as melamine sponge (Example 1) or polyurethane sponge (Example 2). Accordingly, Comparative Examples 1 and 2 are different from Examples 1 to 7 in that the massive inorganic porous material used in the crushing process has no residual pores and has a two-stage hierarchical porous structure consisting of only through-holes and fine pores. Have. In addition, the comparative example 1 and the comparative example 2 differ in the opening of the sieve used for the classification process after the crushing process mentioned later.

　上記要領で得られた実施例１，３～７と比較例１の粒状の無機多孔体に対して、目開きが１００μｍと２５０μｍの篩で篩掛けして分級し、粒径範囲が１００～２５０μｍの粒状の無機多孔体を選別した。実施例１，３～７の収率は何れも８５％またはそれ以上で、比較例１の収率は１５％であった。また、上記要領で得られた実施例２と比較例２の粒状の無機多孔体に対して、目開きが２５０μｍと７５０μｍの篩で篩掛けして分級し、粒径範囲が２５０～７５０μｍの粒状の無機多孔体を選別した。実施例２の収率は９５％以上で、比較例２の収率は４０％であった。 The granular inorganic porous materials of Examples 1, 3 to 7 and Comparative Example 1 obtained as described above are classified by sieving with a sieve having openings of 100 μm and 250 μm, and the particle size range is 100 to 250 μm. The granular inorganic porous material was selected. The yields of Examples 1 and 3 to 7 were all 85% or higher, and the yield of Comparative Example 1 was 15%. Further, the granular inorganic porous materials of Example 2 and Comparative Example 2 obtained in the above manner were classified by sieving with a sieve having openings of 250 μm and 750 μm, and a particle size range of 250 to 750 μm. The inorganic porous material was selected. The yield of Example 2 was 95% or more, and the yield of Comparative Example 2 was 40%.

　図１に、実施例１～７、比較例１，２の平均粒径、粒径範囲、収率、貫通孔及び細孔の平均孔径を夫々、一覧表示する。図２に、実施例１，２及び比較例１のレーザ散乱法で求めた粒度分布の測定結果を示す。図３に、実施例１と実施例４の粒状の無機多孔体の窒素吸着測定によるＢＪＨ法により求めた微分細孔径分布の測定結果を示す。尚、図３の縦軸が微分細孔径（ｄＶｐ／ｄｌｏｇ（ｄｐ），単位：ｃｍ^３／ｇ）で、横軸が、細孔径（直径）（単位：ｎｍ）である。 FIG. 1 shows a list of average particle diameters, particle diameter ranges, yields, average pore diameters of through holes and pores of Examples 1 to 7 and Comparative Examples 1 and 2, respectively. In FIG. 2, the measurement result of the particle size distribution calculated | required with the laser scattering method of Examples 1, 2 and Comparative Example 1 is shown. In FIG. 3, the measurement result of the differential pore diameter distribution calculated | required by BJH method by the nitrogen adsorption measurement of the granular inorganic porous body of Example 1 and Example 4 is shown. In addition, the vertical axis | shaft of FIG. 3 is a differential pore diameter (dVp / dlog (dp), unit: cm < ³ > / g), and a horizontal axis | shaft is a pore diameter (diameter) (unit: nm).

　また、図４に、実施例１，３～７でゾル収容体として使用したメラミンスポンジのＳＥＭ写真を、図５に、実施例２でゾル収容体として使用したポリウレタンスポンジのＳＥＭ写真を、夫々示す。 FIG. 4 shows an SEM photograph of the melamine sponge used as the sol container in Examples 1 and 3 to 7, and FIG. 5 shows an SEM photograph of the polyurethane sponge used as the sol container in Example 2. .

　更に、図６に、実施例１の破砕工程前の塊状の無機多孔体のＳＥＭ写真を、図７及び図８に、実施例１の破砕工程後の粒状の無機多孔体の倍率の異なる２点のＳＥＭ写真を、夫々示す。図９に、実施例２の破砕工程後の粒状の無機多孔体のＳＥＭ写真を示す。 Furthermore, in FIG. 6, the SEM photograph of the massive inorganic porous body before the crushing process of Example 1 is shown, and FIG. 7 and FIG. 8 are two points where the magnification of the granular inorganic porous body after the crushing process of Example 1 is different. Each SEM photograph is shown. In FIG. 9, the SEM photograph of the granular inorganic porous body after the crushing process of Example 2 is shown.

　図４のＳＥＭ写真より、実施例１で使用したゾル収容体の連続空孔の孔径が、概ね１００μｍ以上２５０μｍ以下の範囲に分布していることが分かる。一方、図５のＳＥＭ写真より、実施例２で使用したゾル収容体の連続空孔の孔径が、概ね２５０μｍ以上７５０μｍ以下の範囲に分布していることが分かる。従って、実施例１の１００～２５０μｍ粒径範囲の収率が８５％であることと、実施例１で使用したゾル収容体の連続空孔の孔径分布が、概ね良好に一致していることが分かる。同様に、実施例２の２５０～７５０μｍ粒径範囲の収率が９５％であることと、実施例２で使用したゾル収容体の連続空孔の孔径分布が、概ね良好に一致していることが分かる。この点は、図２に示す実施例１，２の粒度分布と対応している。 4 shows that the pore diameters of the continuous pores of the sol container used in Example 1 are distributed in a range of approximately 100 μm to 250 μm. On the other hand, it can be seen from the SEM photograph in FIG. 5 that the pore diameters of the continuous holes of the sol container used in Example 2 are distributed in a range of approximately 250 μm to 750 μm. Therefore, the yield in the 100 to 250 μm particle size range of Example 1 is 85%, and the pore size distribution of the continuous pores of the sol container used in Example 1 is generally in good agreement. I understand. Similarly, the yield in the 250 to 750 μm particle size range of Example 2 is 95%, and the pore size distribution of the continuous pores of the sol container used in Example 2 is generally in good agreement. I understand. This point corresponds to the particle size distribution of Examples 1 and 2 shown in FIG.

　一方、比較例１，２は夫々同じ製造条件で破砕工程まで進み、粒状の無機多孔体を得ているが、比較例１の１００～２５０μｍ粒径範囲の収率が１５％で、比較例２の２５０～７５０μｍ粒径範囲の収率が４０％であることを考慮すると、比較例１，２全体では、粒度分布が、１００～７５０μｍ粒径範囲に概ね５５％、上記範囲外に４５％存在することが分かり、粒度分布が実施例１，２と比較して、非常に広範囲にばらついていることが分かる。 On the other hand, Comparative Examples 1 and 2 proceeded to the crushing step under the same production conditions to obtain a granular inorganic porous material, but the yield in the 100 to 250 μm particle size range of Comparative Example 1 was 15%. In consideration of the fact that the yield in the 250 to 750 μm particle size range is 40%, in Comparative Examples 1 and 2 as a whole, the particle size distribution is approximately 55% in the 100 to 750 μm particle size range and 45% outside the above range. It can be seen that the particle size distribution varies in a very wide range as compared with Examples 1 and 2.

　実施例１と比較例１の分級後の粒度分布を比較すると、何れも同様の分布を示しているが、収率が８５％と１５％と、比較例１の方が大幅に低くなっている。実施例１～７では、予め所望の粒度分布と一致した孔径分布の連続空孔を有するゾル収容体を用いて、当該連続空孔内に前駆体ゾルを充填してゲル化を行っているため、破砕工程において、粒度分布が一定範囲内に制御された粒状の無機多孔体を、高い収率で得ることができる。 Comparing the particle size distribution after classification of Example 1 and Comparative Example 1, both show the same distribution, but the yields are 85% and 15%, and Comparative Example 1 is significantly lower. . In Examples 1 to 7, a sol container having continuous pores having a pore size distribution that coincides with a desired particle size distribution is used, and the precursor sol is filled into the continuous pores to perform gelation. In the crushing step, a granular inorganic porous body whose particle size distribution is controlled within a certain range can be obtained with high yield.

　実施例１と実施例３～７を比較すると、何れも１００～２５０μｍ粒径範囲の収率が８５％以上であり、収率に差が無い。つまり、同じゾル収容体を用いていることで、各工程の製造条件の違い、例えば、前駆体ゾルの成分の違い（各成分の分量、共存物質の有無、等の違い：実施例３，６，７）、ゲル化後工程の違い（実施例４）、第２除去工程の焼結温度の違い（実施例５）の影響や、その結果としての貫通孔、細孔の有無や孔径の違いの影響を受けずに、粒度分布が一定範囲内に制御された粒状の無機多孔体を、高い収率で得られることが分かる。 When comparing Example 1 and Examples 3 to 7, the yield in the particle size range of 100 to 250 μm is 85% or more, and there is no difference in yield. That is, by using the same sol container, differences in manufacturing conditions in each step, for example, differences in the components of the precursor sol (difference in the amount of each component, presence of coexisting substances, etc .: Examples 3 and 6 7), the difference in post-gelation process (Example 4), the influence of the sintering temperature difference in the second removal process (Example 5), and the resulting through-holes, the presence or absence of pores, and the difference in pore diameter It can be seen that a granular inorganic porous body whose particle size distribution is controlled within a certain range can be obtained in high yield without being affected by the above.

　以下に、本発明方法の別実施形態につき説明する。 Hereinafter, another embodiment of the method of the present invention will be described.

　上記実施形態では、３次元連続網目状構造のシリカゲルまたはシリカガラスからなる粒状の無機多孔体を作製する場合について説明したが、無機多孔体は、シリカゲルまたはシリカガラスに限定されるものではない。例えば、Ａｌ_２Ｏ_３、ＺｒＯ_２、ＴｉＯ_２等の高融点酸化物の無機多孔体、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛等の遷移金属元素を含む無機多孔体やその酸化物多孔体、或いは、当該高融点酸化物を含むシリカゲルやシリカガラス等の多成分系の無機多孔体であっても、本発明方法を適用することで、微細粉の発生が少なく粒径分布範囲の狭い粒状の無機多孔体を高い収率で製造することができる。 In the above-described embodiment, the case where a granular inorganic porous body made of silica gel or silica glass having a three-dimensional continuous network structure has been described, but the inorganic porous body is not limited to silica gel or silica glass. For example, inorganic porous bodies of high melting point oxides such as Al ₂ O ₃ , ZrO ₂ , TiO ₂ , inorganic porous bodies containing transition metal elements such as chromium, manganese, iron, cobalt, nickel, copper, zinc, and oxides thereof Even in the case of a porous material or a multi-component inorganic porous material such as silica gel or silica glass containing the high melting point oxide, by applying the method of the present invention, the generation of fine powder is reduced and the particle size distribution range is reduced. A narrow granular inorganic porous material can be produced with high yield.

　また、上記実施形態では、具体的な数値（分量、温度、時間、寸法等）を明示した実施例を説明したが、本発明方法は、当該実施例で例示された数値条件に限定されるものではない。また、最終的に作製される粒状の無機多孔体の形状、サイズ、用途等に応じて、詳細な条件は適宜変更される。 Further, in the above-described embodiment, an example in which specific numerical values (amount, temperature, time, dimensions, etc.) are clearly described has been described. However, the method of the present invention is limited to the numerical conditions exemplified in the example. is not. Further, the detailed conditions are appropriately changed according to the shape, size, use and the like of the granular inorganic porous material finally produced.

　本発明に係る粒状無機多孔体の製造方法は、粒径分布範囲の狭い粒状の無機多孔体を高い収率で製造するのに利用可能であり、また、製造された粒状の無機多孔体は、吸着材・クロマトカラム材料・触媒や合成担体といった用途、その他広範な用途に利用できる。 The method for producing a granular inorganic porous material according to the present invention can be used to produce a granular inorganic porous material having a narrow particle size distribution range in a high yield, and the produced granular inorganic porous material is It can be used for a wide variety of applications such as adsorbents, chromatographic column materials, catalysts and synthetic carriers.

Claims

　前駆体ゾルを調製するゾル調製工程と、
　３次元網目状に連続した空孔を有する高分子化合物からなるゾル収容体の前記空孔内に、前記前駆体ゾルを充填し、前記空孔内の前記前駆体ゾルに対して、ゾルゲル転移と相分離を並行して発現させ、前記空孔内に、ヒドロゲル相と溶媒相の共連続構造体を形成するゲル化工程と、
　前記共連続構造体と前記ゾル収容体からなる第１中間生成物から前記溶媒相と前記ゾル収容体を個別或いは同時に除去し、塊状の無機多孔体を得る除去工程と、
　前記塊状の無機多孔体を破砕して粒状の無機多孔体を得る破砕工程と、を有し、
　前記塊状の無機多孔体は、前記ゾル収容体を除去した後の空隙に形成された残存孔、及び、前記残存孔に囲まれた３次元網目状の骨格体に形成された、前記骨格体内を貫通する３次元網目状に連続した貫通孔と前記骨格体の表面から内部に向けて延伸する細孔の少なくとも何れか一方を備えて構成される３次元網目状の階層的多孔構造を有し、
　前記粒状の無機多孔体は、破砕され粒状化した前記骨格体からなる多孔体であることを特徴とする粒状無機多孔体の製造方法。 A sol preparation step of preparing a precursor sol;
The precursor sol is filled in the pores of a sol container made of a polymer compound having pores continuous in a three-dimensional network, and the sol-gel transition is performed on the precursor sol in the pores. A gelling step of developing phase separation in parallel and forming a co-continuous structure of a hydrogel phase and a solvent phase in the pores;
Removing the solvent phase and the sol container separately or simultaneously from the first intermediate product comprising the co-continuous structure and the sol container, to obtain a massive inorganic porous body;
A crushing step of crushing the massive inorganic porous material to obtain a granular inorganic porous material,
The massive inorganic porous body includes a residual hole formed in a void after removing the sol container, and a three-dimensional network-shaped skeleton body surrounded by the residual hole. Having a three-dimensional network-like hierarchical porous structure comprising at least one of through-holes continuous in a three-dimensional network that penetrates and pores extending from the surface of the skeleton to the inside;
The method for producing a granular inorganic porous material, wherein the granular inorganic porous material is a porous material composed of the crushed and granulated skeleton.
　前記粒状の無機多孔体の粒径を所定の範囲内に制御するために、前記空孔の孔径分布の平均孔径が前記所定の範囲内にある前記ゾル収容体を準備する工程を更に有することを特徴とする請求項１に記載の粒状無機多孔体の製造方法。 In order to control the particle diameter of the granular inorganic porous body within a predetermined range, the method further includes a step of preparing the sol container having an average pore diameter of the pore diameter distribution of the pores within the predetermined range. The manufacturing method of the granular inorganic porous body of Claim 1 characterized by the above-mentioned.
　前記ゾル収容体が、前記空孔に囲まれた３次元網目状の骨格構造を有することを特徴とする請求項１または２に記載の粒状無機多孔体の製造方法。 The method for producing a granular inorganic porous material according to claim 1 or 2, wherein the sol container has a three-dimensional network skeleton structure surrounded by the pores.
　前記除去工程が、前記第１中間生成物から前記溶媒相を除去して第２中間生成物を得る第１除去工程と、前記第２中間生成物から前記ゾル収容体を除去する第２除去工程を有することを特徴とする請求項１～３の何れか１項に記載の粒状無機多孔体の製造方法。 The removal step includes a first removal step of removing the solvent phase from the first intermediate product to obtain a second intermediate product, and a second removal step of removing the sol container from the second intermediate product. The method for producing a granular inorganic porous material according to any one of claims 1 to 3, wherein:
　前記第１除去工程は、前記第１中間生成物中のゲルを、洗浄する工程、乾燥する工程、または、洗浄して乾燥する工程であることを特徴とする請求項４に記載の粒状無機多孔体の製造方法。 The granular inorganic porous material according to claim 4, wherein the first removing step is a step of washing, drying, or washing and drying the gel in the first intermediate product. Body manufacturing method.
　前記第２除去工程において、第２中間生成物中のゲルを焼結するとともに、前記ゾル収容体を燃焼して消失させることを特徴とする請求項４または５に記載の粒状無機多孔体の製造方法。 6. The production of a granular inorganic porous material according to claim 4, wherein, in the second removal step, the gel in the second intermediate product is sintered and the sol container is burned and disappeared. Method.
　前記除去工程において、前記第１中間生成物中のゲルを焼結するとともに、焼結時の加熱により、前記第１中間生成物中の前記溶媒相を除去し、前記ゾル収容体を燃焼して消失させることを特徴とする請求項１～３の何れか１項に記載の粒状無機多孔体の製造方法。 In the removing step, the gel in the first intermediate product is sintered, the solvent phase in the first intermediate product is removed by heating during sintering, and the sol container is burned. The method for producing a granular inorganic porous material according to any one of claims 1 to 3, wherein the porous inorganic material is eliminated.
　前記塊状の無機多孔体の前記骨格体に前記貫通孔が形成され、前記粒状の無機多孔体が、前記貫通孔と前記細孔によって構成される３次元網目状の階層的多孔構造を有することを特徴とする請求項１～７の何れか１項に記載の粒状無機多孔体の製造方法。 The through-holes are formed in the skeleton body of the massive inorganic porous body, and the granular inorganic porous body has a three-dimensional network hierarchical porous structure constituted by the through-holes and the pores. The method for producing a granular inorganic porous material according to any one of claims 1 to 7, characterized in that:
　前記塊状の無機多孔体の前記骨格体に前記貫通孔が形成される場合、前記塊状の無機多孔体の前記貫通孔の平均孔径が、前記ゾル収容体の前記空孔の平均孔径の５分の１未満であり、且つ、前記塊状の無機多孔体に形成された前記残存孔の平均孔径より小さいことを特徴とする請求項１～８の何れか１項に記載の粒状無機多孔体の製造方法。 When the through-hole is formed in the skeleton body of the massive inorganic porous body, the average pore diameter of the through-hole of the massive inorganic porous body is 5 minutes of the average pore diameter of the pores of the sol container. The method for producing a granular inorganic porous material according to any one of claims 1 to 8, wherein the method is less than 1 and smaller than an average pore diameter of the remaining pores formed in the massive inorganic porous material. .