JPH08215562A - Production of silica molded article for catalyst and production of catalyst carried on silica - Google Patents
Production of silica molded article for catalyst and production of catalyst carried on silicaInfo
- Publication number
- JPH08215562A JPH08215562A JP7026919A JP2691995A JPH08215562A JP H08215562 A JPH08215562 A JP H08215562A JP 7026919 A JP7026919 A JP 7026919A JP 2691995 A JP2691995 A JP 2691995A JP H08215562 A JPH08215562 A JP H08215562A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- catalyst
- weight
- sol
- molded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000010304 firing Methods 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- -1 ruthenium halide Chemical class 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000004481 post-translational protein modification Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical compound O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、強度の優れた触媒用シ
リカ成形品の製法ならびにシリカ担持触媒の製法に関す
る。本発明の実施により得られた触媒用シリカ成形品
は、ナフサのクラッキング触媒、エポキシ化合物、リモ
ネンなどの異性化や脱水、塩素化、脱塩素、アミン化用
触媒として有用である。又、シリカ担持触媒は、エステ
ル変換反応触媒、ブタジエンから無水マレイン酸を流動
床を用いて製造するに用いる触媒、１，４−ブタンジオ
ールからγ−ブチロラクトンを製造する際に用いる触媒
等として有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molded silica article for a catalyst having excellent strength and a method for producing a silica-supported catalyst. The silica molded article for catalyst obtained by carrying out the present invention is useful as a catalyst for naphtha cracking catalyst, isomerization of epoxy compounds, limonene and the like, dehydration, chlorination, dechlorination and amination. Further, the silica-supported catalyst is useful as an ester conversion reaction catalyst, a catalyst used for producing maleic anhydride from butadiene using a fluidized bed, a catalyst used for producing γ-butyrolactone from 1,4-butanediol, and the like. is there.
【０００２】[0002]
【従来の技術】シリカ粉末は各種反応用の触媒及び触媒
担体として広く使用されている。これらが触媒として利
用されるには、数ｍｍ程度の粒径に成形されていること
が必要となる。しかし、シリカ粉末を凝集させて成形
し、工業的な使用に耐える十分な強度を持つ成形体を得
る適当な方法がなかった。そこで、シリカを主成分とす
る成形された触媒は通常、シリカゲル担体に他の金属成
分等を含浸法等により担持させることにより得られてい
る。例えば特開平２−２７３６３５号公報にはシリカに
ハロゲン化ルテニウムを担持させた触媒を用い、カルボ
ニル化合物を水素化する方法が記載されている。しかし
ながら、このような方法では、その他の触媒成分をシリ
カ中に均一に分散させることが困難であり、十分な触媒
性能が得られない欠点がある。Silica powder is widely used as a catalyst and a catalyst carrier for various reactions. In order to use these as catalysts, it is necessary to mold them to a particle size of several mm. However, there is no suitable method for forming a compact having sufficient strength to withstand industrial use by aggregating and molding silica powder. Therefore, a molded catalyst containing silica as a main component is usually obtained by supporting another metal component or the like on a silica gel carrier by an impregnation method or the like. For example, JP-A-2-273635 discloses a method of hydrogenating a carbonyl compound using a catalyst in which ruthenium halide is supported on silica. However, such a method has a drawback that it is difficult to uniformly disperse other catalyst components in silica and sufficient catalyst performance cannot be obtained.
【０００３】[0003]
【発明が解決しようとする課題】本発明は強度が優れ、
シリカが主成分の触媒成形品の提供を目的とする。The present invention has excellent strength,
It is intended to provide a catalyst molded product containing silica as a main component.
【０００４】[0004]
【課題を解決するための手段】本発明は、平均粒径が１
００μｍ以下のシリカ粉末１００重量部に、シリカゾル
をシリカゾル中のＳｉＯ2 固型分量が１〜１００重量部
となる割合で配合した組成物を成形し、次いで得られた
成形品を４００〜１０００℃の温度で焼成することを特
徴とする触媒用シリカ成形品の製造方法を提供するもの
である。The present invention has an average particle size of 1
A composition in which 100 parts by weight of silica powder having a particle size of 00 μm or less is mixed with silica sol at a ratio of 1 to 100 parts by weight of SiO 2 solid content in the silica sol is molded, and the obtained molded product is then molded at 400 to 1000 ° C. It is intended to provide a method for producing a silica molded article for a catalyst, which is characterized by firing at a temperature.
【０００５】本発明は又、触媒活性成分を０．１〜５０
重量％含有する平均粒径が１００μｍ以下のシリカ粉末
１００重量部に、バインダー０〜６０重量部と、シリカ
ゾルをシリカゾル中のＳｉＯ2 固型分量が１〜１００重
量部となる割合で配合した組成物を成形し、次いで得ら
れた成形品を４００〜１０００℃の温度で焼成すること
を特徴とするシリカ担持触媒の製造方法を提供するもの
である。The present invention also comprises 0.1 to 50 catalytically active components.
A composition in which 100 parts by weight of silica powder having an average particle size of 100 μm or less, which is contained in an amount of 100% by weight, is mixed with 0 to 60 parts by weight of a binder and silica sol in a ratio such that the amount of SiO 2 solid content in the silica sol is 1 to 100 parts by weight. The present invention provides a method for producing a silica-supported catalyst, which comprises: molding, and then calcining the obtained molded product at a temperature of 400 to 1000 ° C.
【０００６】[0006]
【作用】シリカゾルを粉末シリカに混合することによ
り、焼成後も成形品が十分な強度を保持する。 （発明の具体的な説明）シリカ粉末 シリカ粉末は粒径が１００μｍ以下、好ましくは１ナノ
メーターから１μｍのもので、石英、無定形シリカの粉
砕品、アルコキシシランを加水分解して得たゾルを乾燥
・粉砕して得られたもの（ゾル・ゲル法）等が挙げられ
る。中でも最後に記載したゾル・ゲル法で得たものが好
ましい。アルコキシシランとしては、テトラメトキシシ
ラン、テトラエトキシシラン、テトラプロポキシシラ
ン、テトラブトキシシラン、トリメトキシ・水素シラ
ン、ジメトキシ・ジヒドロキシシラン、等が挙げられ
る。By mixing silica sol with powdered silica, the molded product retains sufficient strength even after firing. (Detailed Description of the Invention) Silica Powder Silica powder having a particle size of 100 μm or less, preferably 1 nanometer to 1 μm, is a quartz, a crushed product of amorphous silica, or a sol obtained by hydrolyzing an alkoxysilane. Examples thereof include those obtained by drying and crushing (sol-gel method). Among them, those obtained by the last-mentioned sol-gel method are preferable. Examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, trimethoxy.hydrogensilane, dimethoxy.dihydroxysilane and the like.
【０００７】また、本発明で対象とするシリカ粉末は触
媒活性成分を含んでいてもよい。この成分としては例え
ばＳｎ、Ａｌ、Ｆｅ、Ｚｒ、Ｉｎ、Ｇａ、Ｈｆ、Ｔａ、
Ｃｅ、Ｒｈ、Ｖ、Ｗ等の金属及びそれらの酸化物等が考
えられる。これらの活性成分はシリカ粉末と混合しても
よいが、上記ゾル−ゲル法によりシリカ粉末を製造する
場合は、その製造過程で添加するのが好ましい。乾燥
は、常温〜１００℃で行われる。粉砕は、粒径が１００
μｍ以下、好ましくは１μｍ以下となるように行なう。
触媒成分は用途により異なるが、シリカ粉末と触媒成分
の和中の０．１〜５０重量％である。The silica powder of the present invention may contain a catalytically active component. Examples of this component include Sn, Al, Fe, Zr, In, Ga, Hf, Ta,
Metals such as Ce, Rh, V, W and oxides thereof are considered. These active ingredients may be mixed with the silica powder, but when the silica powder is produced by the sol-gel method, it is preferable to add it in the production process. Drying is performed at room temperature to 100 ° C. Grinding has a particle size of 100
It is performed so as to be not more than μm, preferably not more than 1 μm.
Although the catalyst component varies depending on the use, it is 0.1 to 50% by weight in the sum of the silica powder and the catalyst component.
【０００８】シリカゾル シリカゾルとしては、粒径が５〜１００ｎｍのＳｉＯ2
濃度が１０〜５０重量％のものが市場より容易に入手で
きる。例えば、触媒化成工業（株）よりカタロイド−Ｓ
の商品名で入手できる。シリカゾルは、シリカ粉末１０
０重量部に対し、ゾル中のＳｉＯ2 の固型分量が１〜１
００重量部、好ましくは１０〜５０重量部となる割合で
使用される。シリカゾルの添加量が少ないと触媒成形品
の強度が十分でない。シリカゾルの添加量が多すぎる
と、触媒性能が低下する。また、押出機等の成形品の成
形が水分が多くて困難となる。 Silica sol As silica sol, SiO 2 having a particle size of 5 to 100 nm
Those having a concentration of 10 to 50% by weight are easily available from the market. For example, Cataloid-S from Catalysts & Chemicals Co., Ltd.
It is available under the brand name. Silica sol is silica powder 10
The solid content of SiO 2 in the sol is 1 to 1 with respect to 0 part by weight.
It is used in an amount of 00 parts by weight, preferably 10 to 50 parts by weight. When the amount of silica sol added is small, the strength of the catalyst molded product is insufficient. If the amount of silica sol added is too large, the catalytic performance will be reduced. In addition, molding of a molded product such as an extruder is difficult due to the large amount of water.
【０００９】バインダー バインダーとしては、通常固体触媒などの粉末成形の助
剤として使用しているもの、例えばポリビニルアルコー
ル、結晶セルロース、メチルエチルセルロース、ポリビ
ニルピロリドン、ポリアクリル酸ソーダ、ワックス、ポ
リ酢酸ビニル、酢酸ビニル・アクリル酸アルキルエステ
ル共重合体等が利用できる。これらは、水溶液として、
又はエマルジョンの形態で利用される。バインダーは固
型分量でシリカ粉末１００重量部に対し、０〜６０重量
部、好ましくは５〜３０重量部配合される。より好まし
くは、シリカ粉末とシリカゾル中のＳｉＯ2 の和１００
重量部に対し、５〜２５重量部の割合で用いられる。 Binder The binder is usually used as an auxiliary agent for powder molding such as solid catalyst, for example, polyvinyl alcohol, crystalline cellulose, methylethyl cellulose, polyvinylpyrrolidone, sodium polyacrylate, wax, polyvinyl acetate, acetic acid. A vinyl / acrylic acid alkyl ester copolymer or the like can be used. These are aqueous solutions
Alternatively, it is used in the form of an emulsion. The solid content of the binder is 0 to 60 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of silica powder. More preferably, the sum of silica powder and SiO 2 in silica sol is 100.
It is used in a proportion of 5 to 25 parts by weight with respect to parts by weight.
【００１０】成形 粉末シリカ、又は他の金属成分を加えた粉末シリカにシ
リカゾル、必要によりバインダーを双腕型のニーダ、ス
ーパーミキサー等の混合機を用いて混合して得た粉粒状
またはペースト状の混合物を次のような成形法で円筒
状、円柱状、円板状、球状等に形造る。 混練−押出成形 攪拌造粒 流動層造粒 転動造粒 打錠成形 触媒成形品の大きさは、長手方向で０．５〜２０ｍｍ、
好ましくは５〜１５ｍｍであり、短辺の直径または一辺
の長さは０．５〜１０ｍｍである。 Molded powdered silica or powdered silica added with other metal components is mixed with silica sol and, if necessary, a binder using a mixer such as a twin-arm kneader or a super mixer to obtain a powdery or paste-like powder. The mixture is formed into a cylindrical shape, a cylindrical shape, a disk shape, a spherical shape or the like by the following molding method. Kneading-extrusion molding Stirring granulation Fluidized bed granulation Rolling granulation Tablet molding The size of the catalyst molded product is 0.5 to 20 mm in the longitudinal direction,
It is preferably 5 to 15 mm, and the diameter of the short side or the length of one side is 0.5 to 10 mm.
【００１１】焼成 成形品の焼成条件は触媒の種類、用途等に依存する。通
常、焼成後の触媒強度をある程度以上得るためには、シ
リカゾルのシラノール脱水が起こる４００℃〜１０００
℃の温度で１時間〜２０時間、焼成を行う。このように
して得られた焼成触媒成形品の圧壊強度は、５Ｎ／個
（０．５ｋｇｆ／個）以上、好ましくは１０〜１００Ｎ
個（１〜１０ｋｇｆ／個）である。圧壊強度の測定は、
オートグラフもしくは木屋式硬度計を用いて、以下の条
件で行われる。 ・圧壊方法：圧子による一軸荷重 ・圧子降下速度：１ｍｍ／分〜５０ｍｍ／分The firing conditions for the fired molded article depend on the type and use of the catalyst. Usually, in order to obtain a certain level of catalyst strength after calcination, silanol dehydration of silica sol occurs at 400 ° C to 1000 ° C.
Baking is performed at a temperature of ° C for 1 to 20 hours. The crushing strength of the calcined catalyst molded product thus obtained is 5 N / piece (0.5 kgf / piece) or more, preferably 10 to 100 N
The number is 1 to 10 kgf / unit. The measurement of crush strength is
It is carried out under the following conditions using an autograph or Kiya type hardness tester.・ Crushing method: Uniaxial load by indenter ・ Indenter descending speed: 1 mm / min to 50 mm / min
【００１２】[0012]
【実施例】実施例１（ＳｉＯ2 触媒） 三菱化学（株）製テトラメトキシシラン「三菱化学ＭＳ
−５１（商品名）」２，００２．８ｇにエタノール３０
リットルと水１，５００ミリリットルを加えて攪拌した
のち、２８％濃度のアンモニウム水溶液１２００ミリリ
ットルを加えて、テトラメトキシシランの加水分解を行
い、シリカを析出させ、ゾルを得た。その後、濾過、自
然乾燥することにより、粒径が１〜１００ｎｍの粉末シ
リカ１０００ｇを得た。[Example] Example 1 (SiO 2 catalyst) Tetramethoxysilane manufactured by Mitsubishi Chemical Corporation "Mitsubishi Chemical MS"
-51 (trade name) "
After adding 1 liter of water and 1,500 ml of water and stirring, 1200 ml of a 28% aqueous solution of ammonium was added to hydrolyze tetramethoxysilane to precipitate silica to obtain a sol. Then, by filtration and natural drying, 1000 g of powder silica having a particle size of 1 to 100 nm was obtained.
【００１３】上記粉末シリカ８００ｇに、触媒化成工業
（株）のシリカゾル「カタロイドＳ−２０Ｌ（商品
名）」（シリカ分が２０重量％）１，０００ｇ、日本合
成化学工業（株）のポリビニルアルコール「ゴーセノー
ルＥＧ−０５（商品名）」２０ｇおよび旭化成工業
（株）のアビセル「ＴＧ−１０１（商品名）」１００ｇ
を加えて、双腕型ニーダーにより混練後、押出成形を行
い、直径１．７ｍｍφの棒状の成形品を得た。押出成形
時の温度は２０℃で圧力は３０〜４０ｃｍＨｇに減圧し
て行った。得た成形品を乾燥後、へし折り、篩分により
５〜８ｍｍの長の製品に整粒した。この棒状の製品を８
００℃で３時間加熱して焼成を行った。このようにして
粉末シリカとシリカゾルのＳｉＯ2 分が重量比で８０：
２０の触媒成形品を得た。この触媒の圧壊強度を島津製
作所（株）製オートグラフＡＧＳ−５００Ｂにて測定し
たところ、６０Ｎ／個であった。To 800 g of the above powdered silica, 1,000 g of silica sol "Cataloid S-20L (trade name)" (silica content is 20% by weight) manufactured by Catalysts & Chemicals Industries, Ltd., polyvinyl alcohol manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 20 g of Gohsenol EG-05 (trade name) and 100 g of Avicel "TG-101 (trade name)" from Asahi Kasei Corporation.
Was added, and the mixture was kneaded with a double-arm kneader and extrusion-molded to obtain a rod-shaped molded product having a diameter of 1.7 mmφ. The temperature at the time of extrusion molding was 20 ° C. and the pressure was reduced to 30 to 40 cmHg. The obtained molded product was dried, fold-folded, and sieved to form a product having a length of 5 to 8 mm. This stick product is 8
Firing was performed by heating at 00 ° C. for 3 hours. In this way, the powder silica and the SiO 2 content of the silica sol are in a weight ratio of 80:
20 catalyst moldings were obtained. When the crushing strength of this catalyst was measured by Autograph AGS-500B manufactured by Shimadzu Corporation, it was 60 N / piece.
【００１４】実施例２（Ｓｎ／ＳｉＯ2 触媒） 三菱化学（株）製テトラメトキシシラン；“三菱化学Ｍ
Ｓ５１”（商品名）２００２．８ｇに、エタノール３０
リットルと塩化スズ（ＳｎＣｌ2 ・２Ｈ2 Ｏ）２０４．
９ｇ及び水１，５００ミリリットルを加えて攪拌した
後、２８％濃度のアンモニウム水溶液１，２００ミリリ
ットルを加えてテトラメトキシシランの加水分解を行
い、シリカを析出させ、ゾルを得る。その後、濾過、自
然乾燥することにより、５モル％のＳｎを含む粒径が１
〜１００ｎｍの粉末シリカ１，１００ｇを得た。Example 2 (Sn / SiO 2 catalyst) Tetramethoxysilane manufactured by Mitsubishi Chemical Corporation; “Mitsubishi Chemical M”
S51 "(trade name) 2002.8 g, ethanol 30
Liter and tin chloride (SnCl 2 .2H 2 O) 204.
After 9 g and 1,500 ml of water were added and stirred, 1,200 ml of a 28% aqueous solution of ammonium was added to hydrolyze tetramethoxysilane to precipitate silica to obtain a sol. After that, by filtration and natural drying, the particle size containing 5 mol% of Sn is reduced to 1
1,100 g of powdered silica of -100 nm was obtained.
【００１５】上記粉末シリカ８００ｇに、触媒化成工業
（株）のシリカゾル“カタロイドＳ−２０Ｌ”（商品
名、ＳｉＯ2 が２０重量％）１，０００ｇ、日本合成化
学工業（株）のポリビニルアルコール“ゴーセノールＥ
Ｇ−０５”（商品名）２０ｇおよび旭化成工業（株）の
アビセル“ＴＧ−１０１”（商品名）１００ｇを加え
て、双腕型ニーダーにより混練後、押出成形を行い、直
径１．７ｍｍφの棒状の成形品を得た。押出成形時の温
度は２０℃で圧力は３０〜４０ｃｍＨｇに減圧して行っ
た。得た成形品を乾燥後、へし折り、篩分により５〜８
ｍｍの長さの製品に整粒した。この棒状の製品を８００
℃で３時間加熱して焼成を行った。このようにして粉末
シリカとシリカゾルのＳｉＯ2 分が重量比で８０：２０
の触媒成形品を得た。この触媒の圧壊強度を島津製作所
（株）製オートグラフＡＧＳ−５００Ｂにて測定したと
ころ、５９Ｎ／個であった。[0015] The above powdered silica 800 g, silica sol "Cataloid S-20L" of Catalysts & Chemicals Industries Co. (trade name, SiO 2 is 20 wt%) 1,000 g, polyvinyl alcohol manufactured by Nippon Synthetic Chemical Industry Co., "Gohsenol E
20 g of G-05 "(trade name) and 100 g of Avicel" TG-101 "(trade name) of Asahi Kasei Kogyo Co., Ltd. were kneaded by a double-arm kneader and then extrusion-molded to give a rod shape with a diameter of 1.7 mmφ. The molded product was obtained by extrusion molding at a temperature of 20 ° C. and a pressure of 30 to 40 cmHg, and the molded product was dried, then folded and sieved to 5 to 8 cm.
The product was sized to a product having a length of mm. 800 this stick product
Firing was performed by heating at 0 ° C. for 3 hours. Thus, the powder silica and the SiO 2 content of the silica sol are in a weight ratio of 80:20.
A catalyst molded product of was obtained. The crushing strength of this catalyst was measured by Autograph AGS-500B manufactured by Shimadzu Corporation, and it was 59 N / piece.
【００１６】実施例３ 成形時の粉末シリカとシリカゲルの重量をそれぞれ９０
０ｇと５００ｇにしたこと以外は実施例２と同様にして
ＳｉＯ2 粉末とシリカゲルのＳｉＯ2 分が重量比で９
０：１０の触媒を得た。この触媒の圧壊強度は１６Ｎ／
個であった。Example 3 The weight of powdered silica and that of silica gel at the time of molding were 90% respectively.
In the same manner as in Example 2 except that the amounts were 0 g and 500 g, the SiO 2 powder and the silica 2 had a SiO 2 content of 9 by weight.
A catalyst of 0:10 was obtained. The crushing strength of this catalyst is 16 N /
It was an individual.
【００１７】比較例１ 成形時にシリカゾルを加えないこと以外は実施例２と同
様にして触媒を得た。触媒は非常に脆いものであり、強
度の測定は不能であった。以上の実施例、比較例で得た
触媒の物性、強度を表１に示す。Comparative Example 1 A catalyst was obtained in the same manner as in Example 2 except that silica sol was not added during molding. The catalyst was very brittle and its strength could not be measured. Table 1 shows the physical properties and strengths of the catalysts obtained in the above Examples and Comparative Examples.
【００１８】[0018]
【表１】 [Table 1]
【００１９】応用例１ 実施例３で得た圧壊強度１６Ｎ／個のＳｎ／ＳｉＯ2 焼
成触媒を用いて、ポリオキシメチレングリコール（ＰＴ
ＭＧ）の酢酸ジエステルの製造を行った。即ち、ＳＵＳ
製反応器に実施例２で得た触媒を２８０ｇ充填し、それ
に無水酢酸とテトラヒドロフラン（ＴＨＦ）を「無水酢
酸／ＴＨＦ（モル比）＝０．０３９」の比率で混合した
液を１時間当り１００ミリリットルの割合で流通させ、
５０℃で７００時間反応を行った。Application Example 1 Using the Sn / SiO 2 calcining catalyst having a crushing strength of 16 N / piece obtained in Example 3, polyoxymethylene glycol (PT
The production of the acetic acid diester of MG) was carried out. That is, SUS
280 g of the catalyst obtained in Example 2 was charged in a reactor made by the method, and acetic anhydride and tetrahydrofuran (THF) were mixed at a ratio of “acetic anhydride / THF (molar ratio) = 0.039” at a ratio of 100 per hour. Distribute at a rate of milliliters,
The reaction was carried out at 50 ° C. for 700 hours.
【００２０】その結果、供給したＴＨＦに対するＰＴＭ
Ｇの酢酸ジエステルの収率が４０重量％の割合でポリオ
キシメチレングリコールの酢酸ジエステルを得た。ま
た、使用後の触媒を取り出したところ、損傷がなく、圧
壊強度は１６Ｎ／個であり、使用前と同様のものであっ
た。As a result, PTM for the supplied THF
An acetic acid diester of polyoxymethylene glycol was obtained at a yield of the acetic acid diester of G of 40% by weight. When the catalyst after use was taken out, there was no damage and the crush strength was 16 N / piece, which was the same as before use.
【００２１】[0021]
【発明の効果】本発明の実施により得られる焼成シリカ
触媒もしくは触媒担持ＳｉＯ2 は高強度の成形体であ
る。The calcined silica catalyst or the catalyst-supporting SiO 2 obtained by the practice of the present invention is a high-strength compact.
Claims (3)
１００重量部に、シリカゾルをシリカゾル中のＳｉＯ2
固型分量が１〜１００重量部となる割合で配合した組成
物を成形し、次いで得られた成形品を４００〜１０００
℃の温度で焼成することを特徴とする触媒用シリカ成形
品の製造方法。1. A silica sol is added to 100 parts by weight of silica powder having an average particle diameter of 100 μm or less, and SiO 2 in the silica sol is added.
A composition blended in a proportion such that the solid content is 1 to 100 parts by weight is molded, and the obtained molded product is then molded to 400 to 1000.
A method for producing a silica molded article for a catalyst, which comprises firing at a temperature of ° C.
する平均粒径が１００μｍ以下のシリカ粉末１００重量
部に、バインダー０〜６０重量部と、シリカゾルをシリ
カゾル中のＳｉＯ2 固型分量が１〜１００重量部となる
割合で配合した組成物を成形し、次いで得られた成形品
を４００〜１０００℃の温度で焼成することを特徴とす
るシリカ担持触媒の製造方法。2. 100 parts by weight of silica powder containing 0.1 to 50% by weight of a catalytically active component and having an average particle size of 100 μm or less, 0 to 60 parts by weight of a binder, and a silica sol containing SiO 2 solid content in the silica sol. Is molded in a ratio of 1 to 100 parts by weight, and the molded product obtained is then calcined at a temperature of 400 to 1000 ° C., which is a method for producing a silica-supported catalyst.
分解して得たゾルを乾燥、粉砕することにより得られた
ものである請求項１または請求項２の製造方法。3. The production method according to claim 1 or 2, wherein the silica powder is obtained by drying and pulverizing a sol obtained by hydrolyzing an alkoxysilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7026919A JPH08215562A (en) | 1995-02-15 | 1995-02-15 | Production of silica molded article for catalyst and production of catalyst carried on silica |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7026919A JPH08215562A (en) | 1995-02-15 | 1995-02-15 | Production of silica molded article for catalyst and production of catalyst carried on silica |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08215562A true JPH08215562A (en) | 1996-08-27 |
Family
ID=12206608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7026919A Pending JPH08215562A (en) | 1995-02-15 | 1995-02-15 | Production of silica molded article for catalyst and production of catalyst carried on silica |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08215562A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009523606A (en) * | 2006-01-17 | 2009-06-25 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Method for producing silica molded body |
-
1995
- 1995-02-15 JP JP7026919A patent/JPH08215562A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009523606A (en) * | 2006-01-17 | 2009-06-25 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | Method for producing silica molded body |
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