JP2003230839A - Rapid preparation method for many kinds of solid catalysts and device used therefor - Google Patents
Rapid preparation method for many kinds of solid catalysts and device used thereforInfo
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- JP2003230839A JP2003230839A JP2002031689A JP2002031689A JP2003230839A JP 2003230839 A JP2003230839 A JP 2003230839A JP 2002031689 A JP2002031689 A JP 2002031689A JP 2002031689 A JP2002031689 A JP 2002031689A JP 2003230839 A JP2003230839 A JP 2003230839A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、固体触媒の有効性
の簡便な探索法として極めて有用な、多種の固体触媒の
迅速調製方法及びそのための装置、並びに固体触媒の有
効性を簡便に探索する方法及びそのための装置に関す
る。TECHNICAL FIELD The present invention relates to a method for rapidly preparing various solid catalysts, which is extremely useful as a simple method for searching the effectiveness of solid catalysts, an apparatus therefor, and simply searching for the effectiveness of solid catalysts. A method and a device therefor.
【０００２】[0002]
【従来の技術】従来より、各種の化学品の合成、燃料の
合成および各種排気ガスの浄化等で非常に多くの触媒が
使用されているが、近年、環境問題やエネルギー問題か
らの要請により、触媒の特性や効率を更に上げるために
新たな高性能触媒の迅速な開発が望まれている。この触
媒探索の迅速化はエネルギー・環境問題の改善に貢献で
きる極めて重要な技術となっている。特に多元系の固体
触媒では各成分の組み合わせの数も膨大になり、例え
ば、５成分系の触媒で互いに異なる１０種ずつの成分を
組み合わせたとすると、単なる組み合わせの数だけでも
１０万種近くの触媒があることになり、さらには濃度等
の組み合わせを含めると更に膨大な数となるため触媒探
索の迅速化がどうしても必要となる。2. Description of the Related Art Conventionally, a great number of catalysts have been used for synthesizing various chemicals, synthesizing fuels, purifying various exhaust gases, etc., but in recent years, due to demands from environmental and energy problems, Rapid development of new high-performance catalysts is desired in order to further improve the characteristics and efficiency of the catalysts. This rapid catalyst search is an extremely important technology that can contribute to the improvement of energy and environmental problems. Especially in the case of multi-component solid catalysts, the number of combinations of each component becomes enormous. For example, if 10 different components are combined in a five-component catalyst, the number of combinations is close to 100,000. In addition, the number of catalysts will be enormous if the combination of concentrations and the like is included. Therefore, it is absolutely necessary to accelerate the catalyst search.
【０００３】これら多元系の固体触媒の探索にはこれま
でのところ効果的な迅速化方法がないため、触媒の探索
は過去に蓄積したデータや知識から推定して探索範囲を
一部に絞り込んで行われており、範囲を絞らない全面的
な探索は経費や時間の面から困難と考えられている。一
方、近年、コンビナトリアルケミストリーとして医薬品
等を並列的に多数作る方法が行われている。しかし、多
元系固体触媒の場合には、各触媒成分の担持は一段で行
われることが通常であり、多段で行う場合は成分の担持
は反応でなく乾燥であることもあり、後段の操作により
前段で処理した成分の移動等が起こりやすく目的とする
ものを得にくい。また、固体触媒では、固体そのもの又
は固体に担持した成分から特に特定の化合物を作りそれ
を直接利用する訳ではなく、それが持つ触媒特性を利用
するという特徴を持つため、通常のコンビナトリアルケ
ミストリーで採用されているような、固相上に固定した
基に対し反応を選択的に繰り返し、固相ごとに分離して
最後に生成物を切り出すという、手数が非常に節約でき
且つスマートな方法である”いわゆる固相合成法”を適
用することは困難である。更に、固体触媒の分野におい
ては、確かな結果を得るためには、調製した触媒につい
て簡単なモデル反応ではなく、実際に目的とする反応で
の反応性能評価を行う必要があり、目的とする性能の優
劣を示す有効なデータを得るためにはこの部分にも非常
に経費と時間がかかるため、並列合成により大量の試料
が作れた場合も、大量の試料の試験が簡単に行える状況
ではない。特に経費に糸目を付けない場合をのぞき、大
量の試料で通常行えるのは必ずしも目的とする反応と同
じ傾向を示すとは言えないごく単純な反応による予備評
価に過ぎない。実際、固体触媒の調製自体を考えても、
先に示したように多元系では組み合わせの数が極めて多
く、調製すべき試料の数も膨大になり、通常の方法によ
り一つづつを並行して独立に作る方法では莫大な経費が
かかるため広範な探索は非常に難しい。さりとて何らか
の方法で一時に混合物として調製されたものでは各粒子
に標識をつけ分離することも困難であり、通常では各粒
子ごとに成分分析をする以外に区別方法が無いため、簡
単にはその分離ができずその結果として特殊な例を除き
種類別の性能評価は困難である。Since there has been no effective method for expediting the search for these multi-component solid catalysts, the search for catalysts is limited to a part by presuming from the data and knowledge accumulated in the past. Since it is conducted, it is considered difficult to conduct a full-scale search without limiting the scope in terms of cost and time. On the other hand, in recent years, as a combinatorial chemistry, a method of making a large number of drugs in parallel has been performed. However, in the case of a multi-component solid catalyst, the loading of each catalyst component is usually carried out in one step, and in the case of carrying out in multiple steps, the loading of the components may be dry rather than reaction, so that the operation of the subsequent step It is difficult to obtain the intended product because the components processed in the previous stage are likely to move. In addition, solid catalysts have the characteristic that they do not directly use a specific compound made from the solid itself or the components supported on the solid, but utilize the catalytic properties that it has, so it is used in ordinary combinatorial chemistry. As described above, the reaction is selectively repeated on the groups immobilized on the solid phase, the solid phase is separated, and the product is finally cut out, which is a very labor-saving and smart method. ” It is difficult to apply the so-called solid phase synthesis method. Furthermore, in the field of solid catalysts, in order to obtain reliable results, it is necessary to evaluate the reaction performance of the prepared catalyst, not by a simple model reaction, but by the reaction actually intended. Even in the case where a large amount of sample is produced by parallel synthesis, it is not easy to test a large amount of sample, because this part also requires much cost and time to obtain effective data indicating the superiority or inferiority of. Except when the cost is not particularly marked, what can usually be done with a large amount of sample is only preliminary evaluation by a very simple reaction that does not necessarily show the same tendency as the desired reaction. In fact, even considering the preparation of the solid catalyst itself,
As shown above, the number of combinations is extremely large in the multi-component system, the number of samples to be prepared also becomes enormous, and the method of making one by one in parallel by the usual method requires a huge cost, and therefore it has a wide range. Search is very difficult. It is difficult to label each particle with a mixture that is prepared as a mixture at one time by some method, and there is usually no method other than the component analysis for each particle. As a result, it is difficult to evaluate the performance by type except for special cases.
【０００４】このような触媒探索において最も問題とな
るのは探索範囲内に有効な触媒が在るか否かが判らない
と言うことである。もし有効な触媒がその範囲に無いと
膨大な数の個別の触媒の調製と評価に多大の時間と経費
を無駄に費やすことになる。広範な触媒探索では、具体
的にどの組み合わせのどんな組成の触媒が有効かが明ら
かになる前に、この探索範囲には有効な触媒が存在する
か否かを大略知ることが最も効率的である。現在の技術
では、有効な触媒が特定のグループの中に存在すること
が明らかになればそこから個々の触媒を絞り込み最適化
することは比較的容易である。従って、多くの種類の多
元系固体触媒をごく簡単に作れる方法とそこで調製され
た大量の触媒試料に関して少ない回数の反応試験を行う
ことによりある範囲の成分の組み合わせから成る有効な
触媒の存在を明らかにできる方法を見いだし、更に、そ
れを簡便に行うための装置を工夫できれば、高価な特別
に新しい分析法や機器を考案したり、多大の費用をかけ
て大がかりな装置を導入しなくとも既存の方法を工夫す
ることにより経済的に有効な触媒の探索の迅速化が可能
となる。しかしながら、現時点では、そのような効率的
な多くの触媒を創り出す簡便な装置や方法やそこで調製
した触媒の中に有効な触媒が在るか否かを少ない手数で
短時間に知る方法がないのが現状である。The most problematic point in such a catalyst search is that it is not known whether or not there is an effective catalyst within the search range. If there are no effective catalysts in that range, a great deal of time and money will be wasted preparing and evaluating a large number of individual catalysts. In a broad catalyst search, it is most efficient to roughly know whether or not there is an effective catalyst in this search range before it becomes clear which combination and composition of catalyst are effective. . With current technology, it is relatively easy to narrow down and optimize individual catalysts once it becomes clear that the effective catalysts are present in a particular group. Therefore, it was revealed that an effective catalyst consisting of a range of component combinations was obtained by conducting a few times of reaction tests on a large number of catalyst samples prepared therein, by making it possible to easily prepare many kinds of multi-component solid catalysts. If we can find a method that can be done and further devise a device for performing it easily, we will be able to devise an expensive new special analytical method and equipment, and without introducing a large-scale device at a large cost By devising a method, it becomes possible to speed up the search for an economically effective catalyst. However, at the present time, there is no simple device or method for creating such an efficient many catalysts, or a method for knowing whether or not there is an effective catalyst among the catalysts prepared there in a short time with a small number of steps. Is the current situation.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記した問
題を解決するためになされたものであって、その第１の
目的は、触媒の迅速探索に適した多種の固体触媒の効率
的な簡便調製法とそのための装置を提供することであ
り、第２の目的は、そこで調製した触媒に関して少ない
数の反応性能評価から探索範囲内での有効な触媒の存在
の有無と、有効な触媒構成成分を明らかにできる固体触
媒の探索方法並びにそのための装置を提供することにあ
る。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and a first object thereof is to efficiently use various solid catalysts suitable for rapid catalyst search. The second purpose is to provide a simple preparation method and an apparatus therefor, and the second purpose is the presence or absence of an effective catalyst within the search range from the evaluation of a small number of reaction performances of the prepared catalyst, and the effective catalyst composition. It is intended to provide a method for searching for a solid catalyst whose components can be clarified and an apparatus therefor.
【０００６】[0006]
【問題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討した結果、個々の担体粒子ごと
に所定の触媒成分を段階的・並行的に直接、即ち含浸容
器を用いることなく供給・担持することにより、多種類
の多元系固体触媒が個別的に簡便に調製できることを知
見し、更に、これら個々の触媒から予め設定した成分を
持つ多種の触媒混合物を得、該触媒混合物と同時に調製
される基準となる触媒混合物との触媒作用を比較・評価
することにより、極めて少ない評価回数で有効成分の有
無の判定と、更にはそこに含まれる個々の触媒について
評価を行うことで有効な個々の触媒を知ることができ、
このようにすることにより触媒探索で大幅に触媒調製及
び評価の手数が省かれることを見いだし、本発明を完成
するに至った。Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a predetermined catalyst component is directly and stepwisely used for each carrier particle, that is, an impregnation container is used. It was discovered that various kinds of multi-component solid catalysts can be individually and simply prepared by supplying and supporting them without using the catalysts. Furthermore, various catalyst mixtures having preset components were obtained from these individual catalysts. By comparing and evaluating the catalytic action with a reference catalyst mixture that is prepared at the same time as the mixture, it is possible to judge the presence or absence of the active ingredient with an extremely small number of evaluations, and further evaluate the individual catalysts contained therein. To know the effective individual catalyst
By doing so, it was found that the catalyst search and the catalyst preparation and evaluation steps were greatly saved, and the present invention was completed.
【０００７】すなわち、本発明によれば、以下の発明が
提供される。
１．多種の固体触媒を迅速に調製する方法であって、担
体１粒子ごとに各触媒成分を混合することなく個別的に
逐次、担持させることを特徴とする多種の固体触媒の迅
速調製方法。
２．触媒成分の担持を、各触媒成分が重複しないように
して、複数並行して段階的に行うことを特徴とする上記
１に記載の多種の固体触媒の迅速調製方法。
３．触媒成分の担持を、各段での触媒成分からそれぞれ
１つを選ぶ論理的な組み合わせにより行うことを特徴と
する上記１又は２に記載の多種の固体触媒の迅速調製方
法。
４．触媒成分の担持を、担体各１粒子に対して各触媒成
分溶液を直接供給することにより行うことを特徴する上
記１乃至３何れかに記載の多種の固体触媒の迅速調製方
法。
５．以下の多段工程を含むことを特徴とする上記１乃至
４何れかに記載の多種の固体触媒の迅速調製方法。
（１）担体粒子を貯留する工程
（２）貯留された担体粒子を第１触媒成分群担持帯域に
分配する工程
（３）この帯域に第１触媒成分群に含まれる各触媒成分
溶液を直接供給し、各担体粒子に第１触媒成分のそれぞ
れが担持された第１触媒成分担持粒子を得る工程
（４）上記で得た各第１触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第２触媒成分
群担持帯域に分配する工程
（５）この帯域に第２触媒成分群に含まれる各触媒成分
溶液を直接供給し、各触媒粒子に第２触媒成分のそれぞ
れが更に担持された第２触媒成分担持粒子を得る工程
（６）上記で得た各第２触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第３触媒成分
群担持帯域に分配する工程
（７）この帯域に第３触媒成分群に含まれる各触媒成分
溶液を直接供給し、各触媒粒子に第３触媒成分のそれぞ
れが更に担持された第３触媒成分担持粒子を得る工程
（８）以下最後の触媒成分群が担持されるまで上記と同
様な操作を行い所定の固体触媒を調製する工程
（９）上記（１）〜（８）の工程を必要な数だけ繰り返
し行い、各段から次の段への同種の触媒粒子の供給数は
次の段の触媒成分数またはその倍数として、次の段では
各粒子にすべての成分をそれぞれ担持することにより、
各段階での触媒成分群から各々１つずつを選ぶ組み合わ
せにおいて論理的に可能な触媒成分の組み合わせの全て
を持つ固体触媒を調製する工程
６．すべての段の触媒成分担持帯域に無処理帯域を設
け、無処理帯域も含めたすべての第１触媒成分担持帯域
へ担体粒子を供給し、その後の処理は無処理帯域も担持
帯域と同様にして扱うことを特徴とする上記５に記載の
多種の固体触媒の迅速調製方法。
７．担体が多孔体球状粒子であることを特徴とする上記
１乃至６何れかに記載の多種の固体触媒の迅速調製方
法。
８．担体粒子又は触媒担持粒子への触媒成分の担持が、
担体各粒子又は触媒担持各粒子に対して触媒成分溶液を
直接吸収させることにより行われることを特徴とする上
記１乃至７何れかに記載の多種の固体触媒の迅速調製方
法。
９．触媒成分がポンプにより担体粒子又は触媒担持粒子
に直接送られることを特徴とする上記８に記載の多種の
固体触媒の迅速調製方法。
１０．触媒成分がサイホンにより担体粒子又は触媒担持
粒子に直接送られることを特徴とする上記８に記載の多
種の固体触媒の迅速調製方法。
１１．担体粒子又は触媒担持粒子に供給される触媒成分
溶液の量の調節を触媒担体の吸収能により自律的に行わ
せることを特徴とする上記１０に記載の多種の固体触媒
の迅速調製方法。
１２．上記１乃至１１何れかに記載の調製方法で得られ
た各触媒担持粒子を所定の複数の触媒群とし、当該触媒
群に含まれる固体触媒の有効性を該触媒群を構成する個
々の固体触媒に分離することなく判別することを特徴と
する固体触媒の迅速探索評価方法。
１３．多種の固体触媒を迅速に調製する装置であって、
担体各１粒子に対し各触媒成分を混合することなく個別
的に逐次、担持させる手段を備えたことを特徴とする多
種の固体触媒の迅速調製装置。
１４．触媒成分の担持を、各触媒成分が重複しないよう
にして、複数並行して段階的に行う手段を備えたことを
特徴とする上記１３に記載の多種の固体触媒の迅速調製
装置。
１５．触媒成分の担持を、各段での触媒成分からそれぞ
れ１つを選ぶ論理的な組み合わせにより行う手段を備え
たことを特徴とする上記１３又は１４に記載の多種の固
体触媒の迅速調製装置。
１６．触媒成分の担持を、担体各１粒子に対して各触媒
成分溶液を直接供給することにより行う手段を備えたこ
とを特徴する上記１３乃至１５何れかに記載の多種の固
体触媒の迅速調製方法。
１７．以下の手段を備えたことを特徴とする上記１３乃
至１６何れかに記載の多種の固体触媒の迅速調製装置。
（１）担体粒子を貯留する手段
（２）貯留された担体粒子を第１触媒成分群担持帯域に
分配する手段
（３）この帯域に第１触媒成分群に含まれる各触媒成分
溶液を直接供給し、各担体粒子に第１触媒成分のそれぞ
れが担持された第１触媒成分担持粒子を得る手段
（４）上記で得た各第１触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第２触媒成分
群担持帯域に分配する手段
（５）この帯域に第２触媒成分群に含まれる各触媒成分
溶液を直接供給し、各触媒粒子に第２触媒成分のそれぞ
れが更に担持された第２触媒成分担持粒子を得る手段
（６）上記で得た各第２触媒成分担持粒子を必要により
乾燥及び／又はは焼成、還元した後、所定の第３触媒成
分群担持帯域に分配する手段
（７）この帯域に第３触媒成分群に含まれる各触媒成分
溶液を直接供給し、各触媒粒子に第３触媒成分のそれぞ
れが更に担持された第３触媒成分担持粒子を得る手段
（８）以下最後の触媒成分群が担持されるまで上記と同
様な操作を行い所定の固体触媒を調製する手段
（９）上記（１）〜（８）の手段を必要な数だけ繰り返
し行い、各段から次の段への同種の触媒粒子の供給数は
次の段の触媒成分数またはその倍数として、次の段では
各粒子にすべての成分をそれぞれ担持することより、各
段階での触媒成分群から各々１つずつを選ぶ組み合わせ
において論理的に可能な触媒成分の組み合わせの全てを
持つ固体触媒を調製する手段
１８．すべての段の触媒成分担持帯域に無処理帯域を設
け、無処理帯域も含めたすべての第１触媒成分担持帯域
へ担体粒子を供給し、その後の処理は無処理帯域も担持
帯域と同様にして扱うことを特徴とする上記１７に記載
の多種の固体触媒の迅速調製方法。
１９．担体粒子が多孔体球状粒子であることを特徴とす
る上記１３乃至１８何れかに記載の多種の固体触媒の迅
速調製装置。
２０．貯留された各担体粒子を第１触媒成分群担持帯域
に分配する手段が自重で行われることを特徴とする上記
１７乃至１９に記載の多種の固体触媒の迅速調製装置。
２１．各触媒担持粒子を各触媒成分群担持帯域に分配す
る手段が自重を利用したものであることを特徴とする上
記１７乃至２０何れかに記載の多種の固体触媒の迅速調
製装置。
２２．担体粒子又は触媒担持粒子への触媒成分の担持
が、担体各粒子又は触媒担持各粒子に対して触媒成分溶
液を直接吸収させる手段により行われることを特徴とす
る上記１７乃至２１何れかに記載の多種の固体触媒の迅
速調製装置。
２３．触媒成分がポンプにより担体粒子又は触媒担持粒
子に直接送られることを特徴とする上記２２に記載の多
種の固体触媒の迅速調製装置。
２４．触媒成分がサイホンにより担体粒子又は触媒担持
粒子に直接送られることを特徴とする上記２２に記載の
多種の固体触媒の迅速調製装置。
２５．上記１３乃至２４何れかに記載の多種の固体触媒
調製装置と該調製装置で得られた各担持触媒粒子を所定
の複数の触媒群とする分配混合装置と、該触媒群に含ま
れる固体触媒の有効性を該触媒群を構成する個々の固体
触媒に分離することなく判別する装置を備えたことを特
徴とする固体触媒の迅速探索評価装置。That is, according to the present invention, the following inventions are provided. 1. What is claimed is: 1. A method for rapidly preparing various kinds of solid catalysts, which comprises sequentially and individually supporting each catalyst component without mixing each catalyst component for each particle of a carrier. 2. 2. The rapid preparation method for various kinds of solid catalysts according to the above 1, characterized in that a plurality of solid catalysts are loaded in parallel and stepwise so that the catalyst components do not overlap. 3. 3. The rapid preparation method for various kinds of solid catalysts described in 1 or 2 above, wherein the catalyst components are loaded by a logical combination in which one catalyst component is selected from each stage. 4. 4. The rapid preparation method for various kinds of solid catalysts described in any one of 1 to 3 above, wherein the catalyst component is supported by directly supplying each catalyst component solution to each particle of the carrier. 5. 5. The rapid preparation method for various kinds of solid catalysts described in any one of 1 to 4 above, which comprises the following multi-steps. (1) Step of storing carrier particles (2) Step of distributing stored carrier particles to the first catalyst component group carrying zone (3) Direct supply of each catalyst component solution contained in the first catalyst component group to this zone Then, the step (4) of obtaining the first catalyst component-supporting particles in which the first catalyst component is supported on the respective carrier particles (4) Each of the first catalyst component-supporting particles obtained above is dried and / or calcined and reduced if necessary. After that, a step (5) of distributing to a predetermined second catalyst component group-supporting zone, each catalyst component solution contained in the second catalyst component group is directly supplied to this zone, and each catalyst particle further contains the second catalyst component. Step (6) of Obtaining Supported Second Catalyst Component-Supporting Particles Each of the second catalyst component-supporting particles obtained above is dried and / or calcined and reduced if necessary, and then distributed to a predetermined third catalyst component group-supporting zone. Step (7) included in the third catalyst component group in this zone Step (8), in which each catalyst component solution is directly supplied to obtain third catalyst component-supporting particles in which each catalyst particle further supports each third catalyst component. Step (9) of performing a similar operation to prepare a predetermined solid catalyst The above steps (1) to (8) are repeated as many times as necessary, and the number of the same type of catalyst particles supplied from each stage to the next stage is As the number of catalyst components in the next stage or a multiple thereof, by loading all the components on each particle in the next stage,
5. A step of preparing a solid catalyst having all logically possible combinations of catalyst components in a combination in which one catalyst component group is selected at each stage. An untreated zone is provided in the catalyst component carrying zone of all stages, carrier particles are supplied to all the first catalyst component carrying zones including the untreated zone, and the subsequent treatment is carried out in the untreated zone in the same manner as the carrying zone. 6. A rapid method for preparing various solid catalysts as described in 5 above, which is characterized by handling. 7. 7. The rapid preparation method for various kinds of solid catalysts according to any one of 1 to 6 above, wherein the carrier is spherical particles of a porous body. 8. Supporting the catalyst component on the carrier particles or the catalyst-supported particles,
8. The rapid preparation method for various kinds of solid catalysts described in any one of 1 to 7 above, which is carried out by directly absorbing the catalyst component solution to each carrier particle or each catalyst supporting particle. 9. 9. The method for rapid preparation of various solid catalysts according to the above 8, wherein the catalyst component is directly sent to the carrier particles or the catalyst-supported particles by a pump. 10. 9. The rapid preparation method for various kinds of solid catalysts according to the above 8, wherein the catalyst component is directly sent to the carrier particles or the catalyst-supported particles by siphon. 11. 11. The rapid preparation method for various kinds of solid catalysts described in 10 above, wherein the amount of the catalyst component solution supplied to the carrier particles or the catalyst-supported particles is adjusted autonomously by the absorption capacity of the catalyst carrier. 12. Each of the catalyst-supported particles obtained by the preparation method according to any one of 1 to 11 above is used as a predetermined plurality of catalyst groups, and the effectiveness of the solid catalysts contained in the catalyst group is determined by the individual solid catalysts constituting the catalyst group. A rapid search and evaluation method for a solid catalyst, which is characterized in that it is distinguished without being separated. 13. A device for rapidly preparing various kinds of solid catalysts,
A rapid preparation apparatus for various kinds of solid catalysts, which is provided with a means for individually and sequentially supporting one catalyst on each particle of a carrier without mixing each catalyst component. 14. 14. The rapid preparation apparatus for various types of solid catalysts described in 13 above, further comprising a means for carrying out stepwise loading of catalyst components in parallel so that the catalyst components do not overlap. 15. 15. The rapid preparation apparatus for various kinds of solid catalysts described in 13 or 14 above, which is provided with means for carrying a catalyst component by a logical combination of selecting one catalyst component from each stage. 16. 16. The rapid preparation method for various kinds of solid catalysts described in any one of 13 to 15 above, which comprises means for carrying the catalyst component by directly supplying each catalyst component solution to each particle of the carrier. 17. 17. The rapid preparation apparatus for various kinds of solid catalysts described in any one of 13 to 16 above, which is provided with the following means. (1) Means for storing carrier particles (2) Means for distributing stored carrier particles to the first catalyst component group carrying zone (3) Direct supply of each catalyst component solution contained in the first catalyst component group to this zone Then, means for obtaining first catalyst component-supporting particles in which the first catalyst component is supported on each carrier particle (4) Each of the first catalyst component-supporting particles obtained above is dried and / or calcined and reduced if necessary. After that, means (5) for distributing to a predetermined second catalyst component group supporting zone, each catalyst component solution contained in the second catalyst component group is directly supplied to this zone, and each catalyst particle further contains the second catalyst component. Means for Obtaining Supported Second Catalyst Component-Supporting Particles (6) Each of the second catalyst component-supporting particles obtained above is dried and / or calcined and reduced if necessary, and then placed in a predetermined third catalyst component group-supporting zone. Distributing means (7) Included in the third catalyst component group in this zone Means for directly supplying each catalyst component solution to obtain third catalyst component-supporting particles in which each catalyst particle further supports each of the third catalyst components (8) and the following steps until the last catalyst component group is supported. Means for preparing a predetermined solid catalyst by performing the same operation (9) The above-mentioned means (1) to (8) are repeated as many times as necessary, and the number of the same kind of catalyst particles supplied from each stage to the next stage is As the number of catalyst components in the next stage or a multiple thereof, it is logically possible in a combination in which all the components are supported on each particle in the next stage, and one is selected from the catalyst component group in each stage. Means for preparing a solid catalyst having all combinations of catalyst components 18. An untreated zone is provided in the catalyst component carrying zone of all stages, carrier particles are supplied to all the first catalyst component carrying zones including the untreated zone, and the subsequent treatment is carried out in the untreated zone in the same manner as the carrying zone. 18. A rapid method for preparing various kinds of solid catalysts according to the above 17, characterized by being handled. 19. 19. The rapid preparation apparatus for various types of solid catalysts described in any one of 13 to 18 above, wherein the carrier particles are porous spherical particles. 20. 20. The rapid preparation apparatus for various kinds of solid catalysts described in the above 17 to 19, wherein the means for distributing each of the stored carrier particles to the first catalyst component group carrying zone is performed by its own weight. 21. 21. The rapid preparation apparatus for various types of solid catalysts described in any of 17 to 20 above, wherein the means for distributing each catalyst-supporting particle to each catalyst component group-supporting zone utilizes its own weight. 22. The catalyst component is loaded on the carrier particles or the catalyst-supporting particles by a means for directly absorbing the catalyst component solution to each carrier particle or each catalyst-supporting particle. Rapid preparation equipment for various solid catalysts. 23. 23. The rapid preparation apparatus for various kinds of solid catalysts described in the above 22, wherein the catalyst component is directly sent to the carrier particles or the catalyst-supported particles by a pump. 24. 23. The rapid preparation apparatus for various kinds of solid catalysts according to the above 22, wherein the catalyst component is directly sent to the carrier particles or the catalyst-supported particles by siphon. 25. 25. A variety of solid catalyst preparation devices described in any one of 13 to 24, a distribution / mixing device in which each supported catalyst particle obtained by the preparation device is a predetermined plurality of catalyst groups, and a solid catalyst contained in the catalyst group. A rapid search and evaluation device for a solid catalyst, comprising a device for discriminating the effectiveness without separating the individual solid catalysts constituting the catalyst group.
【０００８】[0008]
【発明の実施の形態】以下、本発明を更に詳細に説明す
る。本発明の多種の固体触媒の迅速調製方法は、担体各
１粒子に対し各触媒成分を混合することなく個別的に逐
次、担持させることを特徴としている。担体粒子に対す
る触媒成分の担持は、各触媒成分が重複しないようにし
て、複数並行して段階的に行なうことが好ましい。この
場合、触媒成分の担持を、各段での触媒成分からそれぞ
れ１つを選ぶ論理的な組み合わせにより行うことが好ま
しく、更に、触媒成分の担持を、担体各１粒子に対して
各触媒成分溶液を直接供給することにより行うことが最
も好ましい。The present invention will be described in more detail below. The rapid preparation method for various kinds of solid catalysts of the present invention is characterized in that each catalyst component is sequentially and individually supported on each carrier particle without being mixed. It is preferable that the catalyst components are carried on the carrier particles stepwise in parallel so that the catalyst components do not overlap. In this case, it is preferable that the catalyst components are loaded by a logical combination in which one catalyst component is selected from each catalyst component in each stage. Further, the catalyst component is loaded on each carrier particle for each catalyst component solution. Is most preferably carried out by directly supplying
【０００９】本発明の触媒成分の担持法は、特に制限さ
れないが、含浸容器などを用いず１つずつの担体粒子に
直接、触媒成分溶液を供給することにより触媒担持粒子
が調製できる方法が好ましい。担体としては、通常、最
初の出発物質にシリカゲル、各種の構造規則性物質やア
ルミナ、ジルコニア等などの多孔性担体球状粒子を用い
るのが最も単純で良好であるが、その他、各種の酸化物
系担体の使用も可能である。また、はじめに用いる担体
の代わりに触媒成分を担持した粒子や各種塩類の加水分
解等により調製した共沈物の粒子等を用いることも可能
である。さらに担体粒子は１種である必要はなく、規則
的に変えて担体の異なるものを同時に作ることもでき
る。なお用いる粒子の形状としては球状のものが最も良
い結果を与える。担体の粒子径は、含浸担持及びその分
配が問題なくできれば特に制限はないが、当然のことな
がらあまり粒子が大きい場合は含浸に時間がかかり不均
一になりやすく全体の量が増え現実的でない。あまり小
さいとその後の各種の処理が困難になる。実際には含浸
や移動の容易さも含め、直径０．５ー３ｍｍの粒子が適
当である。また、粒子の形状としては球状が自重で動く
際に必要であるが、動力により移動させるのであれば破
砕状等特に制限はない。The method for supporting the catalyst component of the present invention is not particularly limited, but a method in which the catalyst-supported particles can be prepared by directly supplying the catalyst component solution to each carrier particle without using an impregnation container or the like is preferable. . As the carrier, usually, the first starting material is silica gel, various structurally ordered substances or alumina, porous carrier spherical particles such as zirconia are the simplest and the best, but other various oxide-based The use of carriers is also possible. Further, instead of the carrier used first, it is also possible to use particles carrying a catalyst component or particles of a coprecipitate prepared by hydrolysis of various salts. Furthermore, the carrier particles do not have to be of one kind, and it is possible to make different carriers at the same time by regularly changing them. It should be noted that the shape of the particles used is spherical and gives the best result. The particle size of the carrier is not particularly limited as long as it can be impregnated and supported and its distribution can be carried out without problems, but naturally, when the particles are too large, impregnation takes time and tends to be non-uniform, and the total amount increases, which is not practical. If it is too small, various subsequent processes become difficult. In practice, particles having a diameter of 0.5 to 3 mm are suitable, including the ease of impregnation and transfer. The shape of the particles is required to be spherical when moving by its own weight, but there is no particular limitation such as a crushed shape if it is moved by power.
【００１０】これらの担体粒子に、各種の触媒成分溶液
を吸収担持する方法は、液を一定量ポンプで送る方法、
液を吹き付ける方法、液をサイフォンを通して自分で吸
収させる方法などがあり、特に制限はない。粒径のそろ
った粒子で定量性をあげたい場合は装置コストが高くな
るがポンプを用いる方法が優れている。通常は含浸法に
よりサイフォンを通し担体への吸着量を自律的に制御さ
せる方法が最も簡便であり好ましい。A method for absorbing and supporting various catalyst component solutions on these carrier particles is to pump a fixed amount of liquid,
There is no particular limitation, such as a method of spraying the liquid or a method of absorbing the liquid by a siphon by yourself. When it is desired to improve the quantitativeness of particles having a uniform particle size, the cost of the device increases, but the method using a pump is superior. Usually, the method of controlling the amount of adsorption to the carrier autonomously through a siphon by the impregnation method is the simplest and preferable.
【００１１】含浸に使用する溶媒は水が最も使いやすい
が、使用する塩類が溶解するものであればアルコールな
ど特に制限は無い。触媒成分として使用する塩類は、使
用する溶媒に溶解するものであれば、通常の塩類の他、
複塩、錯化合物、有機金属化合物、及びそれらの混合物
等特に制限はない。担持する触媒成分の濃度は溶液にで
き担体に担持できる範囲では特に制限はない。Water is the easiest solvent to use for impregnation, but there is no particular limitation such as alcohol as long as the salt used is soluble. Salts used as a catalyst component, as long as it is soluble in the solvent used, other than usual salts,
There are no particular restrictions on double salts, complex compounds, organometallic compounds, and mixtures thereof. The concentration of the catalyst component to be supported is not particularly limited as long as it can be made into a solution and supported on a carrier.
【００１２】ところで、先に記したように、例えば、４
種づつの４つのグループからなる１６種類の異なる成分
のうち、それぞれのグループから一つずつ成分を選ぶ４
成分系の触媒を調製する場合、通常の並列合成であれば
１成分および２成分のものも含め６２４種の触媒を通常
の方法により６２４種の含浸溶液を作って１種ずつ作り
評価しなくてはならない。 また、４成分触媒系で成分
を固定し、その組成の影響を見る場合、濃度を各々４種
類変える場合は、２５６種の溶液を作り含浸して評価し
なくてはならない。更に、上の両者を併せて成分と濃度
を同時に変える場合は８万種程度の含浸溶液が必要とな
り、並列合成としても大変な仕事となる。By the way, as described above, for example, 4
Of the 16 different components consisting of 4 groups of species, one component is selected from each group 4
In the case of preparing a component-type catalyst, in the case of ordinary parallel synthesis, 624 kinds of catalysts including one-component and two-component catalysts are prepared by the usual method to make 624 kinds of impregnating solutions, one by one without evaluation. Don't Further, when the components are fixed with a four-component catalyst system and the effect of the composition is to be observed, when changing the concentration by four types, respectively, 256 types of solutions must be prepared and impregnated for evaluation. Furthermore, in the case of changing the composition and the concentration at the same time for both of the above, about 80,000 kinds of impregnating solutions are required, which is a difficult task for parallel synthesis.
【００１３】これに対して、本発明方法によれば、４種
４グループからなる４成分系では、４段階で担持しその
操作を５列並列して行う４段５列の並列の含浸装置を用
い、わずか１６種の触媒成分溶液を用意するだけで先に
述べた６２４種の触媒が簡単に調製でき、それを自動的
に、最後に担持した成分別に集めるようにすると、調製
した触媒は最終段が無処理のものも含め各々１２５個の
触媒を含む５つの触媒混合物として得ることができる。
そして、たとえば、この５個の触媒混合物の５回の反応
性能評価の比較から有効な触媒の有無と最終段の成分の
効果が分かり、調製法を変更して効果的な触媒が含まれ
る部分についてのみ調製し更に絞り込むか、または予め
取り分けておいた個別の触媒の性能を調べれば有効成分
を探索することができ、触媒調製と評価の手間を大幅に
低減することが可能となる。On the other hand, according to the method of the present invention, in a four-component system consisting of four groups of four types, a parallel impregnating device of four rows and five rows is carried out in four steps and the operation is performed in five rows in parallel. It is possible to easily prepare the above-mentioned 624 catalysts by preparing a solution of only 16 catalyst components, and to collect them automatically by the last loaded component. It can be obtained as a mixture of 5 catalysts, each containing 125 catalysts, including those with no treatment.
Then, for example, by comparing the reaction performance evaluations of these five catalyst mixtures five times, the presence or absence of an effective catalyst and the effect of the final stage component can be understood. It is possible to search for the active ingredient by only preparing and further narrowing down, or examining the performance of individual catalysts that have been set aside beforehand, and it is possible to greatly reduce the time and effort for catalyst preparation and evaluation.
【００１４】同様なことは先に示した組成の影響を見る
実験でも同様であり、本発明方法によれば、４つの濃度
の異なる１６種の触媒成分溶液があれば２５６種の触媒
が簡単に調製でき触媒の最適化に利用できる。さらに、
濃度と成分を同時に変える場合は通常の方法であれば８
万種に近い触媒溶液の調製を必要とするが、本発明で
は、わずか６４種の触媒溶液を用意すれば良いことにな
る。The same is true in the above-mentioned experiment for examining the influence of the composition. According to the method of the present invention, 256 kinds of catalysts can be easily obtained if there are 16 kinds of catalyst component solutions having different concentrations. It can be prepared and used to optimize the catalyst. further,
When changing the concentration and the component at the same time, it is 8 if the usual method
Although it is necessary to prepare almost all kinds of catalyst solutions, in the present invention, it is sufficient to prepare only 64 kinds of catalyst solutions.
【００１５】即ち、従来の多元系固体触媒の調製法で
は、触媒を構成する各成分を一度で担持するには目的と
する触媒の種類だけの数の溶液を作る必要があるが、本
発明方法では、調製時必要とされる触媒成分溶液は、濃
度の異なる成分も独立した成分として、組み合わせに用
いる触媒成分の数だけでよく、極めて簡単に予め設定さ
れた論理的に可能な触媒成分溶液の全ての組み合わせを
持つ多種の触媒粒子を調製することができるのである。That is, in the conventional method for preparing a multi-component solid catalyst, in order to support each component constituting the catalyst at one time, it is necessary to prepare as many solutions as the kind of the target catalyst. In the above, the catalyst component solution required at the time of preparation needs only the number of catalyst components to be used in combination as components having different concentrations as independent components, and it is extremely easy to set a preset theoretically possible catalyst component solution. It is possible to prepare a wide variety of catalyst particles with all combinations.
【００１６】また、成分溶液の含浸は、通常は触媒粒子
の集まりを用いて、容器を用いこの容器内に収容した触
媒溶液を担体に加えたり、逆に、担体を容器内の触媒溶
液に加えることにより行われている。この方法での担体
を容器から出し入れする操作は処理が煩雑であり、更に
は他成分による汚染を回避するには非常に面倒な操作を
必要とする。更に、このような処理においては殆どの場
合が粉体と同様の扱いになり容器への付着等がおこり、
特に少量の場合正確な自動的な取り扱いは非常に難しく
完全な自動化は困難である。これに対し、本発明方法に
よれば、担体の取り扱いは一粒ずつ個別に行いしかも触
媒成分溶液の担持は容器を用いずに球状粒子に直接吸収
させる方式で十分であり、しかも粒子の移動及び供給は
例えばその自重により行うことができるため、移動や供
給のための動力機構や含浸容器の使用が省かれ、全ての
取り扱いが非常に簡素化でき完全自動化も容易となる。Further, the impregnation of the component solution is usually carried out by using a collection of catalyst particles, and the catalyst solution contained in the container is added to the carrier, or conversely, the carrier is added to the catalyst solution in the container. It is done by. The operation of putting the carrier in and out of the container by this method is complicated in processing, and furthermore, a very troublesome operation is required to avoid contamination with other components. Furthermore, in such a treatment, in almost all cases, it is treated in the same manner as powder and adheres to the container,
Precise automatic handling is very difficult, especially for small amounts, and complete automation is difficult. On the other hand, according to the method of the present invention, it is sufficient to carry out the handling of the carrier individually one by one and to carry the catalyst component solution directly into the spherical particles without using a container. Since the supply can be performed by its own weight, for example, the use of a power mechanism or an impregnation container for movement and supply is omitted, and all handling is greatly simplified and complete automation is facilitated.
【００１７】更にまた、本発明方法では、担体粒子の取
り扱いが一粒ずつで済むため担体（例えばシリカゲル粒
子は直径1.0-1.4mm で１０００個で１ｇ程度）や触媒溶
液も非常に少ない量で調製でき大量の探索ではコスト、
時間、保存などで多くの利点があり、小型にできるうえ
非常に簡便に低コストで自動化による広範な探索ができ
る。このためこれまでにコンビナトリアルケミストリー
として各種企業で開発された高価な並列合成装置とは異
なり、現在ごく普通に用いられているガスクロと同程度
の簡便安価な装置として個人レベルでの利用が可能であ
る。因みに、本発明方法の能力を試算すると、たとえ
ば、４段５列の処理系を持つ小型の装置１台で４成分を
主体とする多成分系触媒を調製する場合、１列で１分間
に１個処理ができる場合、同じ種類のものを５個ずつ作
るとすると、処理量は１分間に１種で、乾燥や、焼成・
還元などの処理に伴うタイムラグや溶液の交換や担体粒
子の交換などを別として、一日に１２時間稼働させると
１日７２０種、年間２５０日とすれば年間１８万種とな
り、１種１個では９０万種となり、本発明方法の能力の
高さを示している。固体触媒を扱う分野ではこのような
莫大な量を検討した例はなく、このように簡便な方法で
５成分系などこれまでは広範な検討が困難なもので大量
の調製・探索が自動化できることは触媒開発にとって画
期的なものということができる。Furthermore, in the method of the present invention, since the carrier particles can be handled one by one, the carrier (for example, silica gel particles having a diameter of 1.0-1.4 mm and 1000 particles of about 1 g) and the catalyst solution are prepared in a very small amount. Can cost a lot of exploration,
It has many advantages in terms of time, storage, etc., it can be made compact, and it is very easy and inexpensive to perform a wide range of searches by automation. Therefore, unlike expensive parallel synthesizers developed by various companies as combinatorial chemistry up to now, it can be used at the individual level as a simple and inexpensive device similar to the gas chromatography that is commonly used today. . Incidentally, when the capacity of the method of the present invention is calculated, for example, in the case of preparing a multi-component catalyst mainly composed of four components in one small apparatus having a treatment system of four stages and five rows, one catalyst is prepared for one minute in one row. If you can process 5 pieces of the same kind, if you can make 5 pieces of the same kind, the processing amount is 1 kind per minute, and drying, baking,
Aside from the time lag associated with treatment such as reduction, solution exchange, carrier particle exchange, etc., operating for 12 hours a day results in 720 types per day, and 250 days per year gives 180,000 types per year, 1 type per 1 Shows 900,000, which shows the high capability of the method of the present invention. In the field dealing with solid catalysts, there is no example of studying such an enormous amount, and it has been difficult to conduct a wide range of studies such as a five-component system with such a simple method, and it is impossible to automate a large amount of preparation / search. It can be said that it is a breakthrough for catalyst development.
【００１８】つぎに、本発明で好ましく採られる機械的
で簡便な多種の固体触媒の第１の迅速調製方法について
説明する。この迅速調製方法は、以下の工程を含むこと
を特徴としている。
（１）担体粒子を貯留する工程
（２）貯留された担体粒子を第１触媒成分群担持帯域に
分配する工程
（３）この帯域に第１触媒成分群に含まれる各触媒成分
溶液を直接供給し、各担体粒子に第１触媒成分のそれぞ
れが担持された第１触媒成分担持粒子を得る工程
（４）上記で得た各第１触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第２触媒成分
群担持帯域に分配する工程
（５）この帯域に第２触媒成分群に含まれる各触媒成分
溶液を直接供給し、各触媒粒子に第２触媒成分のそれぞ
れが更に担持された第２触媒成分担持粒子を得る工程
（６）上記で得た各第２触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第３触媒成分
群担持帯域に分配する工程
（７）この帯域に第３触媒成分群に含まれる各触媒成分
溶液を直接供給し、各触媒粒子に第３触媒成分のそれぞ
れが更に担持された第３触媒成分担持粒子を得る工程
（８）以下最後の触媒成分群が担持されるまで上記と同
様な操作を行い所定の固体触媒を調製する工程
（９）上記（１）〜（８）の工程を必要な数だけ繰り返
し行い、各段から次の段への同種の触媒粒子の供給数は
次の段の触媒成分数またはその倍数として、次の段では
各粒子にすべての成分をそれぞれ担持する事により、各
段階での触媒成分群から各々１つずつを選ぶ組み合わせ
において論理的に可能な触媒成分の組み合わせの全てを
持つ固体触媒を調製する工程Next, the first rapid preparation method of various mechanical and convenient solid catalysts preferably used in the present invention will be described. This rapid preparation method is characterized by including the following steps. (1) Step of storing carrier particles (2) Step of distributing stored carrier particles to the first catalyst component group carrying zone (3) Direct supply of each catalyst component solution contained in the first catalyst component group to this zone Then, the step (4) of obtaining the first catalyst component-supporting particles in which the first catalyst component is supported on the respective carrier particles (4) Each of the first catalyst component-supporting particles obtained above is dried and / or calcined and reduced if necessary. After that, a step (5) of distributing to a predetermined second catalyst component group-supporting zone, each catalyst component solution contained in the second catalyst component group is directly supplied to this zone, and each catalyst particle further contains the second catalyst component. Step (6) of Obtaining Supported Second Catalyst Component-Supporting Particles Each of the second catalyst component-supporting particles obtained above is dried and / or calcined and reduced if necessary, and then distributed to a predetermined third catalyst component group-supporting zone. Step (7) included in the third catalyst component group in this zone Step (8), in which each catalyst component solution is directly supplied to obtain third catalyst component-supporting particles in which each catalyst particle further supports each third catalyst component. Step (9) of performing a similar operation to prepare a predetermined solid catalyst The above steps (1) to (8) are repeated as many times as necessary, and the number of the same type of catalyst particles supplied from each stage to the next stage is As the number of catalyst components in the next stage or a multiple thereof, by carrying all the components in each particle in the next stage, it is logically possible in a combination in which one is selected from the catalyst component group at each stage. The process of preparing a solid catalyst with all combinations of catalyst components
【００１９】つぎに、上記（１）〜（９）工程について
順次説明する。Next, the steps (1) to (9) will be sequentially described.
【００２０】［（１）の工程について］担体粒子を準備
する工程であり１つまたは複数の貯留槽を持ち、例えば
後記する図１の貯留槽では、少なくとも、調製する触媒
成分群の数×各触媒成分群に含まれる触媒成分数の担体
粒子が貯留される[Regarding Step (1)] This is a step of preparing carrier particles and has one or more storage tanks. For example, in the storage tank of FIG. 1 described later, at least the number of catalyst component groups to be prepared × each Carrier particles of the number of catalyst components contained in the catalyst component group are stored
【００２１】［（２）の工程について］貯留された担体
粒子を最初に触媒成分を担持させる第１触媒成分群担持
帯域に分配する工程である。この分配工程では、担体自
体の自重を利用する方法を採ることが好ましい。また、
第１触媒成分群担持帯域には、少なくとも第１触媒成分
群に含まれる触媒成分の数の帯域が設けられることが好
ましく、通常、粒子は全ての帯域に等しく供給される。
帯域数が少ない場合は同じ帯域で異なる成分を複数担持
できるようにする必要が生じ装置は複雑になり、並列的
な処理の部分が減るため調製効率は落ちる。また、誤り
無く各触媒成分を自動的に所定の帯域に供給する上で、
その担持帯域をたとえば１列、２列・・の如く指定して
おくことが好ましい。[Regarding Step (2)] This is a step in which the stored carrier particles are first distributed to the first catalyst component group carrying zone in which the catalyst components are carried. In this distribution step, it is preferable to adopt a method of utilizing the own weight of the carrier itself. Also,
It is preferable that at least the number of zones of the catalyst components included in the first catalyst component group is provided in the first catalyst component group supporting zone, and normally, the particles are supplied to all zones equally.
When the number of zones is small, it becomes necessary to carry a plurality of different components in the same zone, the apparatus becomes complicated, and the number of parallel processing parts is reduced, so that the preparation efficiency decreases. Moreover, in order to automatically supply each catalyst component to a predetermined zone without error,
It is preferable to designate the carrying zone as one row, two rows, ...
【００２２】［（３）の工程について］第１触媒成分群
担持帯域に分配された担体粒子に第１触媒成分群に含ま
れる触媒成分溶液を直接供給し、各担体粒子のそれぞれ
に第１の触媒成分のそれぞれが担持された第１触媒成分
担持粒子を得る工程であり、並列的に処理が行われる。
第１触媒成分は例えば図１に示される触媒成分溶液貯留
溜に保持され、任意の手段例えばサイフォンやポンプに
より第１触媒成分群担持帯域に供給され、該帯域に分配
されている担体粒子に直接吸収含浸される。[Regarding Step (3)] The catalyst component solution contained in the first catalyst component group is directly supplied to the carrier particles distributed in the first catalyst component group carrying zone, and the first catalyst component is supplied to each carrier particle. This is a step of obtaining first catalyst component-supporting particles on which respective catalyst components are supported, and the treatments are carried out in parallel.
The first catalyst component is held in, for example, the catalyst component solution reservoir shown in FIG. 1, is supplied to the first catalyst component group carrying zone by any means such as a siphon or a pump, and is directly attached to the carrier particles distributed in the zone. Absorbed and impregnated.
【００２３】［（４）の工程について］上記で得た各第
１触媒成分担持粒子を必要により乾燥及び／又は焼成、
更には還元処理した後、第２触媒成分群担持帯域のそれ
ぞれに分配する工程である。通常は乾燥のみで行うこと
が各成分の混合をよくするために好ましいが、別の効果
をねらう場合は焼成・還元も有効である。この分配工程
では、触媒担持粒子の自重を利用する手段を採ることが
好ましい。また、第２触媒成分群担持帯域には、少なく
とも第２触媒成分群に含まれる触媒成分の数の帯域が設
けられる。また、誤り無く各触媒成分を自動的に所定の
帯域に供給する上で、その担持帯域をたとえば１列、２
列・・の如く指定しておくことが好ましい。[Regarding Step (4)] Each of the first catalyst component-supported particles obtained above may be dried and / or calcined, if necessary.
Further, it is a step of performing reduction treatment and then distributing to each of the second catalyst component group carrying zones. Usually, it is preferable to carry out only drying in order to improve the mixing of each component, but if another effect is aimed at, calcination / reduction is also effective. In this distribution step, it is preferable to employ a means that utilizes the own weight of the catalyst-supported particles. The second catalyst component group supporting zone is provided with at least zones corresponding to the number of catalyst components included in the second catalyst component group. In addition, in order to automatically supply each catalyst component to a predetermined zone without error, the carrying zone is set to, for example, one row or two.
It is preferable to specify in a row.
【００２４】［（５）の工程について］第２触媒成分群
担持帯域に分配された第１触媒成分担持粒子に第２触媒
成分群に含まれる触媒成分溶液を直接供給し、各担持粒
子のそれぞれに第２触媒成分のそれぞれがさらに担持さ
れた第２触媒成分担持粒子を得る工程である。第２触媒
成分は例えば図１に示される触媒成分溶液貯留溜に保持
され、任意の手段例えばサイフォンやポンプにより第２
触媒成分群担持帯域に供給され、該帯域に分配されてい
る担体粒子に直接含浸吸収される。なお、第２触媒成分
溶液の該帯域への供給は簡単に全ての組み合わせができ
るように、その供給先が重複することなく、全てに均等
となるようにしておくが好ましい。[Regarding Step (5)] The catalyst component solution contained in the second catalyst component group is directly supplied to the first catalyst component-supporting particles distributed in the second catalyst component group-supporting zone, and the respective support particles are respectively supplied. Is a step of obtaining second catalyst component-supporting particles further supporting each of the second catalyst components. The second catalyst component is held in, for example, the catalyst component solution reservoir shown in FIG. 1, and the second catalyst component is retained by any means such as a siphon or a pump.
The catalyst particles are supplied to the catalyst component supporting zone and directly impregnated and absorbed by the carrier particles distributed in the zone. In addition, it is preferable that the supply of the second catalyst component solution to the zone be made uniform so that the supply destinations do not overlap so that all combinations can be easily performed.
【００２５】［（６）の工程について］上記で得た各第
２触媒成分担持粒子を必要により乾燥及び又は焼成及び
又は還元処理した後、第３触媒成分群担持帯域のそれぞ
れに分配する工程である。この分配工程では、触媒担持
粒子の自重を利用する手段を採ることが好ましい。ま
た、第３触媒成分群担持帯域には、少なくとも第３触媒
成分群に含まれる触媒成分の数の帯域が設けられる。ま
た、誤り無く各触媒成分を自動的に所定の帯域に供給す
る上で、その担持帯域をたとえば１列、２列・・の如く
指定しておくことが好ましい。[Regarding Step (6)] In the step of distributing the second catalyst component-supporting particles obtained above to the respective third catalyst component group-supporting zones after drying and / or calcination and / or reduction treatment if necessary. is there. In this distribution step, it is preferable to employ a means that utilizes the own weight of the catalyst-supported particles. Further, at least the number of zones of the catalyst components included in the third catalyst component group is provided in the third catalyst component group supporting zone. Further, in order to automatically supply each catalyst component to a predetermined zone without error, it is preferable to designate the supporting zone as, for example, one row, two rows.
【００２６】［（７）の工程について］第３触媒成分群
担持帯域に分配された第２触媒成分担持粒子に第３触媒
成分群に含まれる触媒成分溶液を直接供給し、各担持粒
子のそれぞれに第３触媒成分のそれぞれがさらに担持さ
れた第３触媒成分担持粒子を得る工程である。第３触媒
成分は例えば図１に示される触媒成分溶液貯留溜に保持
され、任意の手段例えばサイフォンやポンプにより第３
触媒成分群担持帯域に供給され、該帯域に分配されてい
る担体粒子に直接含浸吸収される。なお、第３触媒成分
溶液の該帯域への供給は簡単に全ての組み合わせができ
るように、その供給先が重複することなく、全てに均等
となるようにしておくが好ましい。[Regarding Step (7)] The catalyst component solution contained in the third catalyst component group is directly supplied to the second catalyst component-supporting particles distributed in the third catalyst component group-supporting zone, and the respective support particles are respectively supplied. Is a step of obtaining third catalyst component-supporting particles further supporting each of the third catalyst components. The third catalyst component is held in, for example, the catalyst component solution reservoir shown in FIG. 1, and the third catalyst component is retained by any means such as a siphon or a pump.
The catalyst particles are supplied to the catalyst component supporting zone and directly impregnated and absorbed by the carrier particles distributed in the zone. In addition, it is preferable that the third catalyst component solution is supplied to the zone so that all the combinations can be easily performed, and that the supply destinations of the third catalyst component solution are equal to each other without overlapping.
【００２７】［（８）の工程について］上記のような工
程を最後の触媒成分群が担持され乾燥必要に応じ焼成・
還元されるまで行い、最初の各担体粒子に各段の触媒成
分群から各々１つずつ選ばれた触媒成分が逐次、段階的
に担持された所定の固体触媒を調製する工程である。[Regarding Step (8)] The above steps are carried out after the last catalyst component group is supported and dried as necessary.
This is a step of preparing a predetermined solid catalyst in which the catalyst components selected from the catalyst component group of each stage are successively and stepwise carried on the respective carrier particles at the beginning until the reduction.
【００２８】［（９）の工程について］（９）上記
（１）〜（８）の工程を必要な数だけ繰り返し行い、各
段から次の段への同種の触媒粒子の供給数は次の段の触
媒成分数またはその倍数として、次の段では各粒子にす
べての成分をそれぞれ担持する事により、各段階での触
媒成分群から各々１つずつを選ぶ組み合わせにおいて論
理的に可能な触媒成分の組み合わせの全てを持つ固体触
媒を調製する工程である。[Regarding Step (9)] (9) The above steps (1) to (8) are repeated as many times as necessary, and the number of the same kind of catalyst particles supplied from each stage to the next stage is as follows. As the number of catalyst components of a stage or a multiple thereof, in the next stage, by supporting all the components on each particle, a catalyst component logically possible in a combination in which one is selected from the catalyst component group at each stage Is a step of preparing a solid catalyst having all the combinations of.
【００２９】また、本発明に於いて、簡単な手順で触媒
成分の組み合わせとして考え得る限りの多種の触媒の混
合物を効率よく創り得る第二の機械的で簡便な多種の固
体触媒の迅速調製方法は、前記第一の方法において、す
べての段の触媒成分担持帯域に無処理帯域を設け、
（２）の工程の貯留槽からの担体粒子の分配で、無処理
帯域も含めたすべての第１触媒成分担持帯域へ担体粒子
を供給し、各段の触媒成分担持帯域から次の段へ供給す
る同種の触媒粒子の数を次の段で担持する成分数＋１又
はその和の倍数とし、それらに対し、無処理も含め次の
段でのすべての成分の担持等の処理を均等に行なう方法
である。この方法は、たとえば１つだけある貯留槽から
供給する最初の触媒担体粒子を、第１段階で担持する触
媒成分数＋１として、これらを１つの未処理帯域を備え
た成分数に等しい担持帯域を持つ第１段階の触媒成分担
持帯域に均等に供給することで、第１段階の各触媒成分
が各々が担持された担持触媒粒子と第１段階の触媒が担
持されていない未処理担体が得られ、その後、各段の各
成分担持帯域からの次の段への触媒担持粒子の供給を同
種のものについて次の段の触媒成分数＋１とし、同様の
操作を必要な段数繰り返すと最も機械的・効率的に無担
持のものから、１成分、２成分、３成分・・から多成分
まで考えられる組み合わせの種類を持つ触媒を調製する
ことができる。なお、これらの方法では同じ触媒成分群
のものが共含浸された触媒はできないのでそのようなも
のを調製したい場合は、他の触媒成分群にその成分を入
れるか、又は、触媒成分群を作り直して再度調らべれば
よい。なお、ここで用いる触媒成分は全てが異なってい
る必要はなく、目的とする成分組成により任意に選べば
よい。Further, in the present invention, the second mechanical and simple rapid preparation method of various solid catalysts capable of efficiently producing a mixture of various catalysts which can be considered as a combination of catalyst components by a simple procedure In the first method, the non-treatment zone is provided in the catalyst component carrying zone of all stages,
By distributing the carrier particles from the storage tank in the step (2), the carrier particles are supplied to all the first catalyst component supporting zones including the untreated zone, and then supplied from the catalyst component supporting zone of each stage to the next stage. The number of the same kind of catalyst particles to be carried in the next stage is set to the number of components to be carried in the next stage +1 or a multiple of the sum, and the treatment such as carrying all the components in the next stage, including no treatment, is uniformly performed on them. Is. In this method, for example, the first catalyst carrier particles supplied from only one storage tank is defined as the number of catalyst components to be supported in the first stage + 1, and these are subjected to a supporting zone equal to the number of components having one untreated zone. By uniformly supplying to the first stage catalyst component supporting zone, supported catalyst particles on which each first stage catalyst component is supported and untreated carrier on which the first stage catalyst is not supported are obtained. After that, the catalyst-supporting particles are fed from each component-supporting zone of each stage to the next stage with the number of catalyst components of the next stage being +1 for the same type, and the same operation is repeated the required number of stages to achieve the most mechanical. It is possible to efficiently prepare a catalyst having a combination of various types from unsupported ones, two-components, three-components ... Note that these methods cannot produce a catalyst that is co-impregnated with the same catalyst component group, so if you want to prepare such a catalyst component, put it in another catalyst component group or recreate the catalyst component group. And try again. The catalyst components used here do not have to be all different, and may be arbitrarily selected according to the target component composition.
【００３０】上の操作で各段間での担持触媒粒子の再配
分の方法は、コンピュータによる制御を考えると各種可
能であるが、全ての組み合わせができる方法であれば特
に制限はない。There are various methods of redistributing the supported catalyst particles between the stages in the above operation, considering the control by the computer, but there is no particular limitation as long as all the methods can be combined.
【００３１】各段の成分数が異なるときは配分方法が複
雑になるため、ここではまず、手順が比較的簡明な各段
の成分数が等しい場合について表１に基づいて説明する
が、、実際に行う場合もできるだけ各段の担持帯域数を
等しくして極く簡便な機械的分配方法で行うことが効率
化のため好ましい。When the number of components in each stage is different, the allocation method becomes complicated. Therefore, first, the case where the number of components in each stage is the same, which is relatively simple, will be described with reference to Table 1. Also in the case of the above, it is preferable for the efficiency to carry out by a very simple mechanical distribution method by equalizing the number of supporting zones in each stage as much as possible.
【００３２】[0032]
【表１】 [Table 1]
【００３３】表１において、Ｓは担体粒子、第１段の１
列〜５列は第１触媒成分群担持帯域、Ａ１〜Ａ５は第１
触媒成分群に含まれる各触媒成分、第２段の１列〜５列
は第２触媒成分群担持帯域、Ｂ１〜Ｂ５は第２触媒成分
群に含まれる各触媒成分、第３段の１列〜５列は第３触
媒成分群担持帯域、Ｃ１〜Ｃ５は第３触媒成分群に含ま
れる触媒成分、第４段の１列〜５列は第４触媒成分群担
持帯域、Ｄ１〜Ｄ５は第４触媒成分群に含まれる触媒成
分を表す。なお、この表１において、各段の５列目を無
処理帯域とし、Ａ５、Ｂ５、Ｃ５、Ｄ５をそれぞれ空成
分とすれば上記第二の方法となる。In Table 1, S is carrier particles, 1 in the first stage
Rows 5 to 5 are the first catalyst component group carrying zone, and A1 to A5 are the first zone.
Each catalyst component included in the catalyst component group, the second row from the first row to the fifth row is a second catalyst component group carrying zone, B1 to B5 are each catalyst component included in the second catalyst component group, the third row from the first row Rows 5 to 5 are third catalyst component group supporting zones, C1 to C5 are catalyst components contained in the third catalyst component group, rows 1 to 5 of the fourth stage are fourth catalyst component group supporting zones, and D1 to D5 are the first zone. 4 represents a catalyst component included in the 4 catalyst component group. In Table 1, if the fifth column of each stage is a non-processed band and A5, B5, C5, and D5 are empty components, the second method is performed.
【００３４】表１において、第１段目に供給された第１
巡の担体粒子Ｓは、第１段の各列から第２、３、４段の
同じ列へ配分される、その結果、第１巡の担体粒子Ｓの
それぞれは各列でＡ１Ｂ１Ｃ１Ｄ１、Ａ２Ｂ２Ｃ２Ｄ
２、−−−−、Ａ５Ｂ５Ｃ５Ｄ５の触媒担持粒子を与え
る（以下第１巡目という）
第２巡の粒子は第１段では第１巡の粒子と同じように第
一段の各列に供給されるが、第１段から第２段の配布先
を第一段と同じ列から１列ずつ左（又は右）の列に変
え、２段目から３段目、３段目から４段目のの配布は第
１巡目の粒子については同じ列に行う。その結果第２巡
の粒子はそれぞれＡ５Ｂ１Ｃ１Ｄ１，Ａ１Ｂ２Ｃ２Ｄ
２，−−−−、Ａ４Ｂ５Ｃ５Ｄの触媒担持粒子を与える
（以下、第２巡目という）。１巡ごとに第２段の配布先
を左に変えてまた配布先が元に戻るまで行う。次に２段
目から３段目への配布先を全ての列において１つ左に移
し上の操作を繰り返す。この操作を１段目から２段目へ
の配布先が１回りするたびに行い、２段目から３段目へ
の配布先が元に戻るまで続け、戻ったところで３段目か
ら４段目への配布先を一つ左へずらし、このような操作
を最下段への配布が１回りするまで続ける。In Table 1, the first supplied to the first stage
The carrier particles S of the round are distributed from each row of the first stage to the same row of the second, third, and fourth rows, so that each of the carrier particles S of the first round is A1B1C1D1, A2B2C2D in each row.
2, ---, giving catalyst-supported particles of A5B5C5D5 (hereinafter referred to as the first round) The particles of the second round are supplied to each row of the first stage in the same manner as the particles of the first round in the first stage. However, the distribution destination of the 1st to 2nd tiers is changed from the same column as the 1st tier to the left (or right) column one by one, and the 2nd to 3rd tiers and the 3rd to 4th tiers are distributed. For the first round particles in the same column. As a result, particles in the second round are A5B1C1D1, A1B2C2D
2, ---, A4B5C5D catalyst-supported particles are provided (hereinafter referred to as the second cycle). The distribution destination of the second stage is changed to the left for each cycle, and the distribution destination is restored again. Next, the distribution destinations from the second row to the third row are moved to the left by one in all columns, and the above operation is repeated. Repeat this operation every time the distribution destination from the 1st stage to the 2nd stage makes one turn, and continue until the distribution destination from the 2nd stage to the 3rd stage returns to the original state, and then return to the 3rd to 4th stage Move the distribution destination to the left one, and continue such operations until the distribution to the bottom reaches once.
【００３５】このようにすると表１で担体粒子Ｓは第１
列から第５列まで順次配分され、１巡目の粒子は直下に
配分され各列でＡ１Ｂ１Ｃ１Ｄ１、Ａ２Ｂ２Ｃ２Ｄ２、
−−−−、Ａ５Ｂ５Ｃ５Ｄ５を生成する。２巡目の粒子
はそれぞれＡ５Ｂ１Ｃ１Ｄ１，Ａ１Ｂ２Ｃ２Ｄ２，−−
−−、Ａ４Ｂ５Ｃ５Ｄ５を与え、これを４段目の配布先
が一回りするまで続けることにより各段の成分を１つず
つ含む全ての組み合わせの触媒がそれぞれ１つずつ得ら
れる。これらの配分方法を上の例とは逆に、先ず３段目
から４段目への配布先を一回り変えることから始めて上
の段を変えていくようにしても結果としては同じことに
なる。In this way, in Table 1, the carrier particles S are
The particles from the first row to the fifth row are sequentially distributed, and the particles in the first round are distributed immediately below, and A1B1C1D1, A2B2C2D2,
---, generate A5B5C5D5. The particles in the second round are A5B1C1D1, A1B2C2D2, ---
---, A4B5C5D5 is given, and this is continued until the distribution destination of the fourth stage makes one round, so that one catalyst each of all combinations containing one component of each stage is obtained. Contrary to the above example, the distribution method will be the same even if the distribution destination from the third stage to the fourth stage is changed once and then the upper stage is changed. .
【００３６】次に、各触媒成分群に含まれる触媒成分数
が異なる場合の本発明の触媒の調製方法の１つの例を表
２に示す。Next, Table 2 shows one example of the method for preparing the catalyst of the present invention when the number of catalyst components contained in each catalyst component group is different.
【００３７】[0037]
【表２】 [Table 2]
【００３８】表２において、Ｓは担体粒子、第１段の１
列〜５列は第１触媒成分群担持帯域、Ａ１〜Ａ５は第１
触媒成分群に含まれる各触媒成分、第２段の１列〜３列
は第２触媒成分群担持帯域、Ｂ１〜Ｂ３は第２触媒成分
群に含まれる各触媒成分、第３段の１列〜４列は第３触
媒成分群担持帯域、Ｃ１〜Ｃ４は第３触媒成分群に含ま
れる触媒成分を表す。なお、この表２において、一段の
５列目、２段の３列目、３段の４列目を無処理帯域と
し、Ａ５、Ｂ３、Ｃ４をそれぞれ空成分とすれば上記第
二の方法となる。In Table 2, S is carrier particles, 1 in the first stage
Rows 5 to 5 are the first catalyst component group carrying zone, and A1 to A5 are the first zone.
Each catalyst component included in the catalyst component group, the first row to third row of the second stage is the second catalyst component group carrying zone, B1 to B3 are each catalyst component included in the second catalyst component group, the first row of the third stage The fourth to fourth columns represent the third catalyst component group carrying zone, and C1 to C4 represent the catalyst components contained in the third catalyst component group. In Table 2, if the fifth column of the first row, the third column of the second row, and the fourth row of the third row are unprocessed bands, and A5, B3, and C4 are empty components, respectively, the second method is obtained. Become.
【００３９】先ず第１段の各列の第１触媒担持帯域に１
つずつの担体粒子Ｓが配布される。このうちＡ１、Ａ
２、Ａ３ではそれぞれの成分が担持されて直下のＢ１，
Ｂ２，Ｂ３に配布されそれぞれの成分を担持される。Ｂ
１，Ｂ２，Ｂ３にある粒子はそれぞれ直下のＣ１，Ｃ
２，Ｃ３に配布されそれぞれの成分が担持され、ここで
Ａ１Ｂ１Ｃ１、Ａ２Ｂ２Ｃ２、Ａ３Ｂ３Ｃ３なる成分を
持つ触媒担持粒子が生成する。一方Ａ４，Ａ５はそれぞ
れの成分を担持された後Ｂ１，Ｂ２に配布されそれぞれ
の成分を担持した後直下のＣ１，Ｃ２に配布され更にそ
れぞれの成分を担持し、ここでＡ４Ｂ１Ｃ１、Ａ５Ｂ２
Ｃ２なる成分を持つ触媒担持粒子が生成する。ここまで
が１巡目の粒子である。２巡目の粒子のうちＡ１，Ａ
２，Ａ３はそれぞれ直下のＢ１，Ｂ２，Ｂ３に配布され
Ｂ１，Ｂ２，Ｂ３からは配布先を１つ左に移してＣ２，
Ｃ３，Ｃ４に配布されそれぞれＡ１Ｂ１Ｃ２、Ａ２Ｂ２
Ｃ３、Ａ３Ｂ３Ｃ４ なる成分を持つ触媒担持粒子を生
成する。一方、Ａ４，Ａ５はそれぞれＢ１，Ｂ２に配布
された後そこから配布先を１つ左に移し、Ｃ２，Ｃ３に
配布されＣ４Ｂ１Ｃ２、Ａ５Ｂ２Ｃ３ なる成分を含む
触媒担持粒子を生成する。このようにして３段目の配布
先を一回り変え終わったら２段目の配布先を一回り変え
ることで各段から次の段へ同種の触媒担持粒子を各帯域
に均等に供給でき各段の触媒成分からそれぞれ１つを選
ぶ組み合わせのすべてが作られることになる。First, 1 is set in the first catalyst carrying zone of each row of the first stage.
Each carrier particle S is distributed. Of these, A1 and A
In A and A3, the respective components are carried and B1 directly below
It is distributed to B2 and B3 and each component is carried. B
Particles at 1, B2 and B3 are C1 and C just below
2, C3 are distributed to support the respective components, and catalyst-supported particles having the components A1B1C1, A2B2C2, and A3B3C3 are generated here. On the other hand, A4 and A5 are loaded with their respective components and then distributed to B1 and B2. After bearing their respective components, they are further distributed to C1 and C2 immediately below and further loaded with their respective components, where A4B1C1 and A5B2
Catalyst-supported particles having a component of C2 are produced. The particles up to this point are the particles in the first round. Of the particles in the second round, A1 and A
2 and A3 are distributed to B1, B2 and B3 directly below, respectively, and from B1, B2 and B3, the distribution destination is moved to the left by C2.
It is distributed to C3 and C4 and is A1B1C2 and A2B2 respectively.
Catalyst-supported particles having components C3 and A3B3C4 are produced. On the other hand, A4 and A5 are distributed to B1 and B2, respectively, and after that, the distribution destination is moved one place to the left, and distributed to C2 and C3 to generate catalyst-supported particles containing components C4B1C2 and A5B2C3. In this way, once the distribution destination of the third stage has been changed once, the distribution destination of the second stage is changed once so that the same type of catalyst-supported particles can be uniformly supplied to each zone from each stage to the next stage. All of the combinations will be made, selecting one from each of the catalyst components.
【００４０】表１と表２の比較からわかるように表２の
方法はあまり効率的でなく、可能な場合は少ない段の同
じ成分の帯域数を倍にするなどしてなるべく各段の数を
等しくすることが望ましいなお、同じ種類の触媒粒子を
複数作るには、配布先を変えた後、更に配布先を変える
ことなく１段目への配布を必要なだけ巡回させればよ
い。このようにすることで調製時には組み合わせる成分
溶液を成分数だけ用意することで多種の多元触媒を簡単
に得ることができる。また、調製の迅速化のためには操
作の待ち時間をできるだけ少なくするように、これらの
粒子の移動は各列で全ての粒子がほぼ均等に動くように
適当な時間差を持って同期して行うことが望ましい。As can be seen from the comparison of Tables 1 and 2, the method of Table 2 is not very efficient, and if possible, the number of bands of the same component of a small number of stages is doubled to reduce the number of stages as much as possible. It is desirable to make them equal. In order to make a plurality of catalyst particles of the same type, after changing the distribution destination, the distribution to the first stage may be repeated as necessary without changing the distribution destination. By doing so, it is possible to easily obtain various multi-way catalysts by preparing the component solutions to be combined in the number of components at the time of preparation. Also, in order to minimize the waiting time of the operation in order to speed up the preparation, the movement of these particles is synchronized with an appropriate time difference so that all the particles move almost uniformly in each row. Is desirable.
【００４１】本発明に係る多種の固体触媒の迅速調製方
法によれば、各成分の担持が制御されて行われているた
め、最終段から出る粒子ごとに触媒の組成は決まってお
り、装置の最終段においては調製された触媒をその後の
評価に合わせて個別、または混合物として集めることが
できる。According to the rapid preparation method for various kinds of solid catalysts according to the present invention, since the loading of each component is controlled, the composition of the catalyst is determined for each particle from the final stage, and the catalyst composition of the apparatus is In the final stage, the prepared catalysts can be collected individually or as a mixture for subsequent evaluation.
【００４２】調製が終わった触媒について、探索範囲に
有効な触媒があるか否かを知る簡単な評価法は、実際に
は有効な触媒ができそうな系が触媒成分の組み合わせな
どで変わるため、各人の各種知見に基づく適当なグルー
プ分けをするなど各種考えられる。しかし、最も汎用性
の高い自動的、機械的に行う方法は、調製した粒子を最
終段の成分別（列別）に集めその混合物を評価にかける
方法である。With respect to the prepared catalyst, a simple evaluation method for knowing whether or not there is an effective catalyst in the search range is because the system in which an effective catalyst is likely to be formed varies depending on the combination of catalyst components. There are various possibilities such as appropriate grouping based on various knowledge of each person. However, the most versatile automatic and mechanical method is to collect the prepared particles by component (row) in the final stage and evaluate the mixture.
【００４３】成分を４つずつ持つ４つのグループから１
成分ずつを選ぶ４成分系の触媒を表１の例に従って作る
場合について説明すると、１列、２列、３列、４列では
触媒成分を担持し、５列は無処理とし、１段目でＡ成分
群、２段目でＢ成分群、３段目はＣ成分群、４段目は最
終段でＤ成分群を担持する。最後に、最終段の担持成分
ごとに生成触媒粒子を分けると、実際には列ごとに生成
物を集めればよいが、各々のグループはそれぞれ１２５
種の触媒粒子を含む５つのグループに分けられる。1 out of 4 groups with 4 components each
Explaining the case of making a four-component catalyst which selects each component according to the example of Table 1, the catalyst components are loaded in the first row, the second row, the third row, and the fourth row, and the fifth row is untreated, The A component group carries the B component group in the second stage, the C component group in the third stage, and the D component group in the final stage in the fourth stage. Finally, if the catalyst particles produced are divided for each of the final stage supported components, the products may actually be collected for each row, but each group has 125
It is divided into five groups containing seed catalyst particles.
【００４４】ここで、見方を変え各グループの違いを見
直すと、各グループは無処理のＤ５列のメンバーである
各触媒成分にそれぞれＤ１，Ｄ２，Ｄ３，Ｄ４を更に加
えたものとなっており、Ｄ５列とその他のグループの差
は最終段の担持成分となり、各々の効果を比べることが
できる。即ち、各グループの混合触媒を用いて５回の反
応評価を行い、このうち最終段で無処理の混合物（即ち
Ｄ５列のグループ）による反応結果と、その他のグルー
プを用いての結果を比較することにより、最終段の成分
の効果の比較ができ、どの成分で処理したものの中に活
性の高い触媒が存在するかが推定でき、各成分が有効か
あるいは負に働くかが分かる。Here, if the viewpoints are changed and the differences between the groups are reexamined, each group is obtained by further adding D1, D2, D3, D4 to each catalyst component which is a member of the untreated D5 row. , D5 row and the difference between the other groups are the loaded components in the final stage, and the respective effects can be compared. That is, the reaction evaluation was performed 5 times using the mixed catalysts of each group, and the reaction result of the untreated mixture (that is, the group of D5 row) in the final stage is compared with the result of the other groups. This makes it possible to compare the effects of the components in the final stage, to estimate which component treated with a highly active catalyst, and to know whether each component is effective or negative.
【００４５】更に、それぞれの混合物の活性の大きさか
らそのグループに有効な触媒が存在するか否かも分か
る。有効な触媒の存在が推定された場合には、実際には
１グループが１２５種も触媒を含むため、更なる触媒の
絞り込みが必要である。例えば、Ｄ１のグループに有効
触媒の存在が推定される場合は、表１で第１段を全てＤ
１とし２段目への配布は全て直下のみに行い、２段目を
Ａ成分群、３段をＢ成分群、最終段をＣ成分群とし、列
ごとに集めると、Ｃ成分別に分類された２５種の触媒か
らなる５つのグループが得られ、これを用いまた５回反
応評価する事によりＣ成分の比較と有効成分の絞り込み
ができることになる。その結果これらの中でＣ２が有効
となれば更に絞り込みをするため１段目は全てＤ１とし
更に２段目は全てＣ２として３段目Ａ成分群、最終段Ｂ
成分群とし調製を行い各列ごとに５個ずつグループを
得、５回の評価を行うと有効なＢ成分が分かる。最後は
このグループの個々の触媒の５つについて反応評価をす
れば有効なＡ成分と、有効な触媒が明らかになることに
なり、有効触媒の決定が全部で僅か２５回の反応評価で
できることになる。実際は１グループ２５種ぐらいに絞
れた段階でどこかのグループに確かに有効触媒がありそ
うだとなったら更に絞り込みを行わなくとも、後は個々
の触媒について反応評価を行ったとしても２５回であ
り、これまでの５回を２回と合わせ３５回の反応評価で
６２５種の触媒から有効触媒が見いだせることになる。Furthermore, the magnitude of the activity of each mixture also indicates whether there is an effective catalyst in that group. When the existence of an effective catalyst is estimated, since one group actually includes as many as 125 kinds of catalysts, further narrowing down of the catalyst is necessary. For example, if the presence of effective catalysts in the D1 group is estimated, all D
All distributions to the second stage were made just underneath, and the second stage was the A component group, the third stage was the B component group, and the last stage was the C component group. Five groups of 25 kinds of catalysts are obtained, and by using this and performing reaction evaluation 5 times, it becomes possible to compare the C components and narrow down the effective components. As a result, if C2 is effective among these, further narrowing down is performed, so that the first stage is all D1 and the second stage is all C2, the third stage A component group, and the final stage B.
Preparation is performed as a component group, and five groups are obtained for each row. When the evaluation is performed 5 times, the effective B component is found. Finally, the reaction evaluation of 5 individual catalysts in this group reveals the effective A component and the effective catalyst, and the effective catalyst can be determined by only 25 reaction evaluations in total. Become. Actually, if there seems to be an effective catalyst in some group at the stage of narrowing down to about 25 kinds in one group, even if it is not further narrowed down, even if the reaction evaluation is performed for each catalyst, it is 25 times, The effective catalyst can be found from 625 kinds of catalysts by the reaction evaluation of 35 times including the above 5 times and 2 times.
【００４６】このように焼成した触媒を自動的に適当な
混合物として集め、それを反応評価することにより、非
常に少ない回数で触媒の探索が可能となる。これらの評
価において１グループに含まれる触媒の種類が多いと高
活性と低活性で活性の差があまりない場合は有効触媒の
推定が難しくなる。活性の大きさと、分析精度等を考え
その数を選ぶ必要があり、それを最終段での自動的な収
集に反映させる必要がある。収集はコンピュータ等で自
由に制御できるため、列ごとでも、列をいくつかに分け
ても、更に異なる収集形態で収集しても特に問題はな
い。しかし、触媒性能の最適化の場合のようにあまり大
きくない活性の大小を比較したい場合は上記の方法は必
ずしも適していない。その場合、最終段で触媒粒子を種
類別に集め個々に反応テストを行う方法によれば有効な
触媒は確実に見いだせる。ただしその場合、反応テスト
の数は当然多くなる。そこで通常の触媒探索では本発明
で示したように触媒調製自体は簡単に行えるため、収集
法を変える等して範囲をしぼり、有効な触媒が推定され
た点で個々の触媒の評価を行うように、この両者を組合
わせることが最も効果的である。なお、目的によって
は、例えば迅速探索を目的としないのであれば、調製し
た触媒を適当な種ごとに混合したり全く混合しないで評
価するなどその方法に特に制限はない。例えば、反応性
能のライブラリーを作るのであれば、本装置を用い個々
の触媒を分けて集めそれを評価する事で大量データの取
得が可能である。By thus automatically collecting the calcined catalysts as an appropriate mixture and evaluating the reaction thereof, it becomes possible to search for the catalyst with a very small number of times. In these evaluations, if there are many types of catalysts included in one group, it will be difficult to estimate the effective catalyst if there is not much difference in activity between high activity and low activity. It is necessary to select the number in consideration of the size of activity and analysis accuracy, and it is necessary to reflect it in the automatic collection at the final stage. Since the collection can be freely controlled by a computer or the like, there is no particular problem even if the collection is performed for each column, the column is divided into several columns, or different collection modes are used. However, the above method is not necessarily suitable for comparing the activity sizes that are not so large as in the case of optimizing the catalyst performance. In that case, an effective catalyst can be surely found by the method of collecting the catalyst particles by type in the final stage and conducting a reaction test individually. However, in that case, the number of reaction tests naturally increases. Therefore, in the ordinary catalyst search, the catalyst preparation itself can be easily performed as shown in the present invention, so that the range of the catalyst can be narrowed down by changing the collection method, etc. Moreover, it is most effective to combine these two. Depending on the purpose, for example, if the purpose is not to conduct a quick search, there is no particular limitation on the method, such as mixing the prepared catalysts with suitable species or evaluating without mixing at all. For example, if a library of reaction performance is created, it is possible to collect a large amount of data by separately collecting individual catalysts using this device and evaluating them.
【００４７】評価する反応としては固体触媒の評価装置
で評価できる反応であれば特に制限は無い。触媒性能の
評価に際しては、その方法に特に制限はない。しかし、
その目的とするところにより、評価用の触媒混合物に含
まれる触媒の種類の数を選ぶことが望ましい。活性の確
認が容易な特異的な反応では多くの種類をその中に含ま
せることができ、分析可能な範囲で有ればその数に特に
制限はない。なお、活性があまり変わらない触媒の組み
合わせでは、その数を多くすると活性の高いものを確認
することが難しくなるので、直接個別の触媒について評
価をする方が効果的である。The reaction to be evaluated is not particularly limited as long as it can be evaluated by a solid catalyst evaluation apparatus. The method for evaluating the catalyst performance is not particularly limited. But,
Depending on its purpose, it is desirable to select the number of types of catalysts contained in the catalyst mixture for evaluation. Many kinds can be included in a specific reaction whose activity can be easily confirmed, and the number thereof is not particularly limited as long as it can be analyzed. In addition, in the case of a combination of catalysts whose activity does not change so much, it becomes more difficult to confirm the one having high activity when the number is large, so it is more effective to directly evaluate individual catalysts.
【００４８】本発明方法において、触媒混合物の活性評
価をどのような手順で行うかは省力化に大きな影響があ
る。最も簡単な方法は、最終段での担持の後、無処理の
部分も含め全てを混合しこれを評価に用いる方法であ
り、一度で考えられる全ての組み合わせの触媒の評価が
できる。この方法は活性の有無だけを見ることになり、
通常は起こり難い、即ち通常は活性のあるものが殆どな
い反応に特異的に有効な触媒を探索する場合には適して
おり、大略ではあるが１回の評価で広い範囲の探索がで
きる。In the method of the present invention, the procedure for evaluating the activity of the catalyst mixture has a great influence on labor saving. The simplest method is a method in which after the loading in the final stage, all the untreated parts are mixed and used for evaluation, and all combinations of catalysts that can be considered at one time can be evaluated. This method only looks for activity,
It is usually suitable for searching for a catalyst that is difficult to occur normally, that is, a catalyst that is specifically effective for a reaction that usually has few active substances, and a broad range of search can be performed with a single evaluation, although it is roughly the same.
【００４９】通常、最も効果的な方法は、最終段階で生
成した触媒を列ごとにそのまま混合し、得た混合物を評
価し、どれかのグループで高い活性が認められ有効な触
媒の存在が推定された時点で、そのグループのみを再調
製して更に細分化するか、またはそのグループの個々の
触媒を改めて調製を行い個々の触媒の評価を行う、また
は予め取り分けておいた個々の触媒で反応評価を行う方
法であり、こうすると有効な触媒が明らかにできる。な
お、生成する触媒の数が少ない場合は、生成した触媒の
一部を予め取り分けて保存し再評価に使用することも良
いが、生成する数が多い場合はその保存管理に労力を要
するため、ライブラリーの形成を目的とせず単に探索の
みであれば本発明に関わる装置で再調整する方が容易で
ある。Usually, the most effective method is to mix the catalysts produced in the final stage as they are in each row and evaluate the resulting mixture to estimate the existence of effective catalysts with high activity in any group. At that time, only the group is re-prepared and further subdivided, or the individual catalysts of the group are newly prepared for evaluation of the individual catalysts, or the individual catalysts previously prepared are reacted. This is a method of evaluation, which makes it possible to identify effective catalysts. If the number of catalysts to be produced is small, it is also possible to save a part of the catalysts produced in advance and store it for re-evaluation. It is easier to readjust with the apparatus according to the present invention if only searching is performed without the purpose of forming a library.
【００５０】なお、本発明における混合物を用いての評
価での重要な知見は以下の通りである。第一は、通常、
担持型固体触媒の混合物では、各々の触媒粒子はある程
度の大きさを持つ粒子内がほぼ均一の組成の触媒であ
り、これは粒子内で成分が混合した触媒とは異なり、各
粒子においては互いに独立してその粒子特有の反応が起
こり触媒の混合の影響が大きくでることは少ないという
点である。第二は、混合の影響がでる例は、反応生成物
の二次反応が非常に速く、その反応に有効な触媒が混合
物の中に含まれる場合にみられるが、この場合でも主反
応は進行しているため有効触媒の探索上では大きな障害
とならないということである。第三は、まれに水素の活
性化等が関連する反応で、水素の活性化能力を持つもの
が別に存在し単独では見いだせない活性を示すことがあ
るが、この場合も本来の反応が同時に起こるため、この
様な混合物で新規な反応が起これば更に新たな発見とな
るだけで、ここでの触媒探索を特に妨げるものとはなら
ないということである。The important findings in the evaluation using the mixture of the present invention are as follows. The first is usually
In a supported solid catalyst mixture, each catalyst particle has a certain size and has a substantially uniform composition within the particle.This is different from the catalyst in which the components are mixed in the particle, and in each particle, This is because the reaction peculiar to the particles independently occurs and the influence of the mixing of the catalyst is not large. Secondly, the case where the effect of mixing appears is seen when the secondary reaction of the reaction product is very fast and a catalyst effective for the reaction is contained in the mixture, but even in this case, the main reaction proceeds. Therefore, it is not a major obstacle in the search for effective catalysts. The third is rarely a reaction related to activation of hydrogen, etc. There is another one with hydrogen activation ability and it may show an activity that can not be found alone, but in this case also the original reaction occurs simultaneously Therefore, if a new reaction occurs in such a mixture, it will be a new discovery and will not particularly hinder the catalyst search here.
【００５１】次に、本発明方法で好ましく採用される機
械的で簡便な多種の固体触媒の迅速調製装置について説
明する。The mechanical and simple rapid preparation apparatus for various solid catalysts preferably employed in the method of the present invention will be described below.
【００５２】本発明の簡便な多種の固体触媒の迅速調製
装置は、担体１粒子ごとに各触媒成分を混合することな
く個別的に逐次、直接供給して担持させる手段を備えた
ことを特徴としている。このような装置においては、更
に触媒成分の担持を、各触媒成分が重複しないようにし
て、複数並行して段階的に行う手段を備えていることが
好ましく、更には、触媒成分の担持を、各段での触媒成
分からそれぞれ１つを選ぶ論理的な組み合わせ方法に従
って行う手段を備えているものが好ましい。The simple and rapid preparation apparatus for various kinds of solid catalysts of the present invention is characterized in that it is provided with means for directly supplying and supporting the catalyst components individually and successively without mixing them for each particle of the carrier. There is. In such an apparatus, it is preferable to further include a means for carrying the catalyst components so that the respective catalyst components do not overlap with each other, and carrying out a stepwise process in parallel. It is preferable to provide a means for carrying out according to a logical combination method of selecting one from the catalyst components in each stage.
【００５３】また、本発明の簡便な多種の固体触媒の迅
速探索評価装置は上記のごとき調製装置で得られた各担
持触媒粒子を所定の複数の触媒群とする分配混合装置
と、該触媒群に含まれる固体触媒の有効性を該触媒群を
構成する個々の固体触媒に分離することなく判別する装
置を備えたことを特徴としている。Further, the simple and quick search and evaluation apparatus for various solid catalysts of the present invention is a distribution and mixing apparatus in which each supported catalyst particle obtained by the above-mentioned preparation apparatus is a predetermined plurality of catalyst groups, and the catalyst group. It is characterized in that it is provided with a device for discriminating the effectiveness of the solid catalyst contained in the above (3) without separating it into individual solid catalysts constituting the catalyst group.
【００５４】本発明の代表的な固体触媒迅速調製装置の
概要を図１のブロック図で説明する。この固体触媒迅速
調製装置は大きく２つの部分からなる。１つは前記工程
（１）を行う担体粒子貯留部であり、もう一つは工程
（２）から（９）を行う触媒成分担持部（ここでは４
段）である。この触媒成分担持部は、粒子分配部と触媒
成分供給部、触媒成分担持帯域部と乾燥部から構成され
る。この場合、全ての触媒成分の担持を終了した触媒担
持粒子の焼成還元を行う焼成・還元部を必要により設け
ておくことが好ましい。An outline of a typical solid catalyst rapid preparation apparatus of the present invention will be described with reference to the block diagram of FIG. This rapid solid catalyst preparation system consists of two parts. One is a carrier particle storage part for performing the step (1), and the other is a catalyst component supporting part (here, 4) for performing the steps (2) to (9).
Dan). The catalyst component supporting part is composed of a particle distributing part, a catalyst component supplying part, a catalyst component supporting zone part and a drying part. In this case, it is preferable to provide a calcination / reduction unit for calcination and reduction of the catalyst-supported particles after supporting all the catalyst components.
【００５５】本発明の代表的な固体触媒迅速探索評価装
置の概要を図２のブロック図で説明する。この固体触媒
迅速探索評価装置は図１に示される調製装置に、該調製
装置で得られた各担持触媒粒子を所定の複数の触媒群と
する分配混合部と、該触媒群に含まれる固体触媒の有効
性を該触媒群を構成する個々の固体触媒に分離すること
なく判別する評価する触媒評価部とからなる。この触媒
評価部においては、反応に適した触媒粒子のグループ化
を行う。また、最適な固体触媒の調製、探索評価が効率
よく行えるように、この触媒評価部には触媒調製装置と
反応評価部の両者を適宜コントールできる、制御部を設
けておくことが望ましい。An outline of a typical solid catalyst rapid search and evaluation apparatus of the present invention will be described with reference to the block diagram of FIG. This solid catalyst rapid search and evaluation apparatus is the same as the preparation apparatus shown in FIG. 1, except that a distribution / mixing section in which each supported catalyst particle obtained by the preparation apparatus is used as a predetermined plurality of catalyst groups, and a solid catalyst contained in the catalyst group. And a catalyst evaluation section for evaluating the effectiveness of the solid state catalyst without separating it into individual solid catalysts constituting the catalyst group. In this catalyst evaluation unit, catalyst particles suitable for the reaction are grouped. Further, in order to efficiently perform the optimum solid catalyst preparation and search evaluation, it is desirable to provide a control unit in the catalyst evaluation unit, which can appropriately control both the catalyst preparation device and the reaction evaluation unit.
【００５６】次に、本発明の具体的な固体触媒迅速調製
装置の１例を図３に示す。この装置は傾斜した台の上に
設置されている構造を有する。１は担体粒子貯留部、２
は担体貯留部１から粒子分配部３に分配される担体粒子
を制御するゲート部、３は粒子分配部、４は触媒成分供
給部、５は触媒成分担持帯域部、６は次段の乾燥部７に
分配される触媒担持粒子を制御するゲート部、７は触媒
担持粒子を乾燥する乾燥部、８は触媒担持粒子の焼成
部、９は触媒担持粒子の還元部である。担体粒子貯留部
１に貯留された担体粒子はゲート部２により適宜調製さ
れて粒子分配部３に分配され、分配された各担体粒子は
触媒成分担持帯域部５に供給される。ここで各担体粒子
には、触媒成分供給部４から供給された第１の触媒成分
群に含まれる触媒成分溶液が含浸される。第１の触媒成
分溶液がそれぞれ含浸された粒子はついでゲート６によ
り乾燥部７に送られ乾燥される。乾燥された第１触媒担
持粒子は次の段の粒子分配部、第２触媒成分担持帯域部
に移送され、ここで第２触媒成分溶液が含浸され、つい
で乾燥部７で第１段と同様にして乾燥され、第１触媒成
分と第２触媒成分の両方が担持された触媒担持粒子が得
られる。同様にして全ての群の触媒成分（図３の場合、
第１触媒成分群〜第４触媒成分群）が含浸された触媒担
持粒子は焼成部８、必要に応じ還元部９に導かれ、この
部分の先にある分配混合部１０で各種触媒が混合した触
媒群として得ることができる。なお、図３に示される装
置においては、その斜面の傾きは１０〜２０度がよく直
径１mm程度の球状粒子を用いる場合は１５度程度が最も
好ましい。Next, one example of a concrete solid catalyst rapid preparation apparatus of the present invention is shown in FIG. This device has a structure installed on a tilted table. 1 is a carrier particle reservoir, 2
Is a gate unit for controlling carrier particles distributed from the carrier storage unit 1 to the particle distribution unit 3, 3 is a particle distribution unit, 4 is a catalyst component supply unit, 5 is a catalyst component carrying zone unit, and 6 is a drying unit of the next stage. A gate section for controlling the catalyst-supporting particles distributed to 7, a drying section for drying the catalyst-supporting particles, a calcination section for the catalyst-supporting particles, and a reducing section for the catalyst-supporting particles. The carrier particles stored in the carrier particle storage unit 1 are appropriately prepared by the gate unit 2 and distributed to the particle distribution unit 3, and the distributed carrier particles are supplied to the catalyst component supporting zone unit 5. Here, each carrier particle is impregnated with the catalyst component solution contained in the first catalyst component group supplied from the catalyst component supply unit 4. The particles impregnated with the first catalyst component solution are then sent to the drying section 7 through the gate 6 and dried. The dried first catalyst-supported particles are transferred to the particle distribution section of the next stage, the second catalyst component-supporting zone, where the second catalyst component solution is impregnated, and then in the drying section 7 in the same manner as in the first stage. And dried to obtain catalyst-supported particles on which both the first catalyst component and the second catalyst component are supported. Similarly, catalyst components of all groups (in the case of FIG. 3,
The catalyst-supported particles impregnated with the first catalyst component group to the fourth catalyst component group) are guided to the calcination section 8 and, if necessary, the reduction section 9, and various catalysts are mixed in the distribution mixing section 10 at the tip of this section. It can be obtained as a catalyst group. In the apparatus shown in FIG. 3, the inclination of the slope is preferably 10 to 20 degrees, and most preferably about 15 degrees when spherical particles having a diameter of about 1 mm are used.
【００５７】本発明の固体触媒迅速調製装置において
は、多種の固体触媒の調製に際して、たとえば担体とし
て球状の多孔体粒子を用い先ず担持したい触媒成分溶液
を成分数だけパイプ等で供給し、好ましくは並行する斜
面上のＶ字型の溝を自重で移動した粒子の一粒ずつに容
器を用いず直接吸収させることで行われる。これによ
り、装置が非常に簡略化できる。また、第１段階として
の第１触媒成分群に含まれる触媒成分溶液の吸収担持
後、この担持粒子は例えば自重で乾燥部に移り、加熱下
不活性ガス中を所定の時間をかけて移動することにより
短時間で乾燥され、第２段階としての第２触媒成分群に
含まれる触媒成分の担持が可能となる。In the solid catalyst rapid preparation apparatus of the present invention, when preparing various kinds of solid catalysts, for example, spherical porous particles are used as a carrier, and the catalyst component solution to be supported is first supplied by the number of components, preferably, by a pipe or the like. It is carried out by directly absorbing each particle moved by its own weight in the V-shaped grooves on the parallel slopes without using a container. This greatly simplifies the device. In addition, after the catalyst component solution contained in the first catalyst component group is absorbed and supported as the first step, the supported particles are moved to the drying section by their own weight, for example, and are moved in the inert gas under heating for a predetermined time. As a result, the catalyst components contained in the second catalyst component group can be supported as the second stage by drying in a short time.
【００５８】この場合、各段における触媒担持帯域のそ
れぞれに無処理帯域を設ける手段を付加すると、各列か
ら出た乾燥した粒子は全ての組み合わせを作る設定に従
い第２触媒成分群に含まれる触媒成分担持帯域と無処理
帯域の列に振り分けられ、１段目と同様に１列は無処理
とし、残りの列では第２の触媒成分がそれぞれ担持され
乾燥される。以下同様にして４元系であれば成分溶液は
４回担持される。このように担持を多段で行い、且つ、
各段ごとに列の間で粒子を規則的に再配分する事で操作
が非常に簡単になり、先にも示した４種４グループから
１種ずつを選ぶ４成分系では、用いる成分溶液は担持す
る成分溶液数のみ（ここでは１６種）でよく、それで理
論上あり得る組み合わせの全てを持つ触媒がこの簡便な
調製装置でほぼ自動的に得られることになる。なお、各
段における成分数はそれぞれ異なっていても全く問題は
ない。In this case, if means for providing an untreated zone is added to each of the catalyst-supporting zones in each stage, the dried particles discharged from each row are catalysts included in the second catalyst component group according to the setting to make all combinations. The column is divided into the component-supporting zone and the non-treatment zone, and one row is untreated as in the first stage, and the second row is loaded with the second catalyst component and dried. Similarly, in the case of a quaternary system, the component solution is loaded four times. In this way, loading is performed in multiple stages, and
Regularly redistributing the particles among the columns in each row makes the operation very simple. In the four-component system shown above, in which one type is selected from each of the four types and four groups, the component solution used is Only the number of component solutions to be supported (here, 16 kinds) is required, so that a catalyst having all theoretically possible combinations can be obtained almost automatically by this simple preparation apparatus. There is no problem even if the number of components in each stage is different.
【００５９】また、本発明の探索範囲に有効な触媒があ
るか否かを知る簡単な探索評価装置によれば、上記調製
装置により調製した粒子を最終段の成分別（列別）に集
めその混合物と、例えば最終段で無処理の混合物と比較
することにより、最終段での成分が有効か否かが分か
り、またそれぞれの混合物の活性の大きさから有効な触
媒の有無が分かり、非常に少ない反応評価で触媒の探索
評価が可能となる。Further, according to the simple search and evaluation apparatus for knowing whether or not there is an effective catalyst in the search range of the present invention, the particles prepared by the above preparation apparatus are collected in the final stage of each component (each column) and By comparing the mixture with, for example, a mixture that has not been treated in the final stage, it can be seen whether the components in the final stage are effective, and the magnitude of the activity of each mixture can determine the presence or absence of an effective catalyst. It is possible to search and evaluate the catalyst with a few reaction evaluations.
【００６０】[0060]
【実施例】次に本発明を概要を以下の例によって説明す
るが、本発明はもちろんこれらの例に限定されるもので
はない。EXAMPLES The present invention will next be described by way of the following examples, but the present invention is not limited to these examples.
【００６１】例１
本実験例に関わる装置では担体粒子及び触担持媒粒子の
移動を重力で行うために各種の部品は図３に示すように
斜面上に設置されている。装置最上部の担体貯留部１に
は原料となる直径1.0-1.4mmの担体粒子が貯留されてお
り、これの下部からＶ字溝がのび、溝の中に担体粒子を
１粒ずつ取り出すための、短い間隔で縦に並んだ２本の
下から突き出したピンからなるゲート２がそのすぐ下流
に設置されている。更にその下流にはゲート２から送り
出された担体粒子をその下流にある触媒成分供給部４の
５列の触媒成分担持帯域部５に分配するための粒子分配
部３が設けられている。この部分は平面上に刻まれたＶ
字溝を下にあるリニア移動機構で左右に動かすことで上
の段の各列からでた粒子を下の目的とする列に送ること
ができる。Example 1 In the apparatus according to this experimental example, various parts are installed on the slope as shown in FIG. 3 in order to move the carrier particles and the contact carrier medium particles by gravity. Carrier particles with a diameter of 1.0-1.4 mm, which is the raw material, are stored in the carrier storage part 1 at the top of the device, and V-shaped grooves extend from the bottom of this to extract the carrier particles one by one into the grooves. A gate 2 consisting of two pins vertically protruding at a short interval and protruding from the bottom is installed immediately downstream of the gate 2. Further downstream thereof, there is provided a particle distribution unit 3 for distributing the carrier particles sent out from the gate 2 to the catalyst component carrying zone 5 in the five rows of the catalyst component supply unit 4 located downstream thereof. This part is V carved on the plane
By moving the groove from side to side with the linear moving mechanism below, the particles emitted from each row in the upper stage can be sent to the target row below.
【００６２】各触媒群に含まれる触媒成分溶液は必要量
が触媒成分液供給部４の溶液溜に入れられ液がサイホン
で移動し易いように含浸する位置よりもやや高い位置に
保持されている。触媒成分担持帯域部５では上から送ら
れてきた担持粒子が決まった位置で、下からでたピンの
ゲートで止められそこに担持する触媒成分の溶液溜に繋
がった先端のごく細いパイプがスリットを通して上から
下がり、担体粒子と接触し、毛細管引力とサイフォンの
原理により、担体粒子に自然に吸収される。吸収は通常
３０秒以内に終わる。The required amount of the catalyst component solution contained in each catalyst group is put in the solution reservoir of the catalyst component liquid supply unit 4 and is held at a position slightly higher than the position where it is impregnated so that the liquid can be easily siphoned. . In the catalyst component supporting zone 5, the carrier particles sent from above are fixed at a predetermined position, and a very thin pipe at the tip connected to the solution reservoir of the catalyst component supported there is stopped by the gate of the pin coming out from below. It goes down from above and comes into contact with the carrier particles, and is naturally absorbed by the carrier particles due to the capillary attraction and the siphon principle. Absorption usually ends within 30 seconds.
【００６３】次にパイプを上げこの触媒担持粒子をパイ
プから離した後、ゲート６を開いてこの触媒担持粒子を
下に送る。この部分は例えばフッ素樹脂で作られてお
り、溶液および粒子は通路に付着することなく移送する
ことができる。触媒成分含浸帯域部５から出た触媒担持
粒子は乾燥のために乾燥部７に送られる。乾燥部７（例
えばフッ素樹脂上に刻まれたＶ字型の溝の上面に発熱板
を設けたもの）は、たとえば１２０℃に加熱されてお
り、その中を窒素ガスが流れている。粒子を一定時間こ
こに留めるため2.5mmの間隔で２５本が２組の５０本の
ピンが溝の中で交互に上下する構造を持ち通常は２５分
間かかってここを通過し、次の担持のために乾燥され
る。Next, after the pipe is raised to separate the catalyst-supporting particles from the pipe, the gate 6 is opened to send the catalyst-supporting particles downward. This part is made of, for example, a fluororesin, and the solution and particles can be transferred without adhering to the passage. The catalyst-supported particles that have come out of the catalyst component impregnated zone section 5 are sent to the drying section 7 for drying. The drying section 7 (for example, a heating plate provided on the upper surface of a V-shaped groove carved on a fluororesin) is heated to, for example, 120 ° C., and nitrogen gas flows therein. In order to hold the particles here for a certain period of time, 25 pins at 2.5 mm intervals have a structure in which two sets of 50 pins are alternately moved up and down in the groove, and it usually takes 25 minutes to pass through here, and the next loading To be dried.
【００６４】ここで乾燥した触媒担持粒子は、所定の時
間間隔で乾燥部下部から送り出され、次の成分を担持す
るための成分担持ユニットに粒子分配部を通して送られ
る。触媒成分溶液の全ての組み合わせを作る場合は規則
的に粒子の移送先を変えて２つ目の成分が担持される。
全ての成分を担持するためにこの操作を４段にわたり繰
り返すことにより全ての組み合わせを作ることができ
る。通常の簡便機械的分配方法では前述したような表１
の操作法が採られる。このようにして調製時には組み合
わせる１６の成分数だけの成分溶液を用意することで６
２４種の多元触媒を簡単に得ることができる。The dried catalyst-carrying particles are sent out from the lower part of the drying section at a predetermined time interval and sent to the component carrying unit for carrying the next component through the particle distributing section. When all combinations of catalyst component solutions are prepared, the transfer destination of particles is regularly changed to support the second component.
All combinations can be made by repeating this procedure over 4 steps to load all components. In the usual simple mechanical distribution method, as shown in Table 1 above.
The operation method of is adopted. In this way, by preparing component solutions with the number of 16 components to be combined at the time of preparation, 6
24 kinds of multi-way catalysts can be easily obtained.
【００６５】第１触媒群から始まって第４触媒群に含ま
れる触媒成分の全てが担持された触媒担持粒子は、必要
により例えば石英ガラスからなる焼成部８、還元部９と
移送される。焼成部８は、例えば先の乾燥部７と同様に
上面に発熱板を持つ構造からなり、触媒担持粒子は乾燥
空気が流れる中で所定の温度に加熱され、左右に傾くジ
グザグの通路を左右に動きながら所定の時間でこの中を
下に移動して焼成される。ついで、所望により、焼成部
８と同様な構造を持つ還元部９で水素気流中でその還元
が行われる。このようにして多種の多元触媒担持粒子は
最終的に還元部から送り出され、すぐ後ろにある分配混
合部１０で予め設定したように各列ごとに分けて収集さ
れ、その後の触媒反応評価に供される。The catalyst-supported particles supporting all of the catalyst components contained in the fourth catalyst group starting from the first catalyst group are transferred to the firing section 8 and the reduction section 9 made of, for example, quartz glass, if necessary. The calcination unit 8 has, for example, a structure having a heating plate on the upper surface similarly to the drying unit 7, and the catalyst-supported particles are heated to a predetermined temperature in the flow of dry air, and the zigzag passages inclined to the left and right are moved to the left and right. While moving, it moves down inside for a predetermined time and is baked. Then, if desired, the reduction is performed in a hydrogen stream in a reducing section 9 having the same structure as the firing section 8. In this way, various kinds of multi-component catalyst-supported particles are finally sent out from the reducing section, collected in each row as preset in the distribution mixing section 10 immediately behind, and used for subsequent catalytic reaction evaluation. To be done.
【００６６】[0066]
【発明の効果】本発明方法によれば、多種の多元系固体
触媒を容器を用いず直接１粒ずつの粒子に成分溶液を並
列して段階的に含浸担持する装置を用い、個々の触媒又
はそれらの固体触媒粒子の集まりからなる所定の触媒混
合物をごく簡便に自動的に調製でき、ついで該触媒混合
物に含まれる触媒粒子の有効性を該触媒混合物を用いた
反応により判別する事により、有効な多元系固体触媒の
有無が迅速に探索でき、更にその中の触媒に関して個々
に評価する事により有効な触媒を明らかにできる。従っ
て、個々に多元系固体触媒を調製し、その都度その触媒
の有効性を判定する従来法に比べ、極めて簡便に多種の
多元系触媒を調製できると共に、極めて少ない回数の反
応性能評価から探索範囲内での有効な触媒の存在の有無
を知り、有効な触媒構成成分を低コストで飛躍的に迅速
に探索することができる。EFFECTS OF THE INVENTION According to the method of the present invention, various multi-component solid catalysts are directly used in a stepwise impregnating and supporting manner for individual catalysts in parallel with each other without using a container. A predetermined catalyst mixture consisting of a collection of these solid catalyst particles can be prepared very simply and automatically, and then the effectiveness of the catalyst particles contained in the catalyst mixture can be determined by a reaction using the catalyst mixture. The existence of such multi-component solid catalysts can be rapidly searched, and the effective catalysts can be clarified by individually evaluating the catalysts therein. Therefore, compared with the conventional method in which multi-component solid catalysts are individually prepared and the effectiveness of the catalyst is judged each time, various multi-component catalysts can be prepared very easily and the search range is evaluated from the reaction performance evaluation of extremely few times. By knowing whether or not there is an effective catalyst inside, it is possible to rapidly and rapidly search for an effective catalyst component at low cost.
【図１】本発明に係る代表的な多種の固体触媒調製装置
の説明図である。FIG. 1 is an explanatory diagram of various types of typical solid catalyst preparation devices according to the present invention.
【図２】本発明に係る代表的な多種の固体触媒探索評価
装置の説明図である。FIG. 2 is an explanatory diagram of various types of typical solid catalyst search and evaluation devices according to the present invention.
【図３】本発明の具体的な多種の固体触媒迅速調製装置
の１例の説明図である。FIG. 3 is an explanatory view of an example of various specific solid catalyst rapid preparation apparatuses of the present invention.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA08 AA20 EA02X EA02Y EA04X EA04Y EB18Y FA02 FB14 FB18 FB19 FB78 FB79 4G075 AA22 AA39 AA61 BB04 BB10 BD16 CA57 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4G069 AA08 AA20 EA02X EA02Y EA04X EA04Y EB18Y FA02 FB14 FB18 FB19 FB78 FB79 4G075 AA22 AA39 AA61 BB04 BB10 BD16 CA57
Claims (25)
あって、担体各１粒子に対し各触媒成分を混合すること
なく個別的に逐次、担持させることを特徴とする多種の
固体触媒の迅速調製方法。1. A method for rapidly preparing various kinds of solid catalysts, characterized in that one particle of each carrier is sequentially and individually supported without mixing each catalyst component. Rapid preparation method.
ないようにして、複数並行して段階的に行うことを特徴
とする請求項１に記載の多種の固体触媒の迅速調製方
法。2. The rapid preparation method for various kinds of solid catalysts according to claim 1, wherein a plurality of solid catalysts are loaded in parallel and stepwise so that the respective catalyst components do not overlap.
らそれぞれ１つを選ぶ論理的な組み合わせ方法に従って
行うことを特徴とする請求項１又は２に記載の多種の固
体触媒の迅速調製方法。3. The rapid preparation of various solid catalysts according to claim 1 or 2, wherein the catalyst components are loaded according to a logical combination method in which one catalyst component is selected from each catalyst component in each stage. Method.
て各触媒成分溶液を直接供給することにより行うことを
特徴する請求項１乃至３何れかに記載の多種の固体触媒
の迅速調製方法。4. The rapid preparation of various kinds of solid catalysts according to claim 1, wherein the catalyst component is supported by directly supplying each catalyst component solution to each particle of the carrier. Method.
請求項１乃至４何れかに記載の多種の固体触媒の迅速調
製方法。 （１）担体粒子を貯留する工程 （２）貯留された担体粒子を第１触媒成分群担持帯域に
分配する工程 （３）この帯域に第１触媒成分群に含まれる各触媒成分
溶液を供給し、各担体粒子に第１触媒成分のそれぞれが
担持された第１触媒成分担持粒子を得る工程 （４）上記で得た各第１触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第２触媒成分
群担持帯域に分配する工程 （５）この帯域に第２触媒成分群に含まれる各触媒成分
溶液を供給し、各触媒粒子に第２触媒成分のそれぞれが
更に担持された第２触媒成分担持粒子を得る工程 （６）上記で得た各第２触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第３触媒成分
群担持帯域に分配する工程 （７）この帯域に第３触媒成分群に含まれる各触媒成分
溶液を供給し、各触媒粒子に第３触媒成分のそれぞれが
更に担持された第３触媒成分担持粒子を得る工程 （８）以下最後の触媒成分群が担持されるまで上記と同
様な操作を行い所定の固体触媒を調製する工程 （９）上記（１）〜（８）の工程を必要な数だけ繰り返
し行い、各段から次の段への同種の触媒粒子の供給数は
次の段の触媒成分数またはその倍数として、次の段では
各粒子にすべての成分をそれぞれ担持することにより、
各段階での触媒成分群から各々１つずつを選ぶ組み合わ
せにおいて論理的に可能な触媒成分の組み合わせの全て
を持つ固体触媒を調製する工程5. The rapid preparation method for various kinds of solid catalysts according to claim 1, which comprises the following multi-steps. (1) Step of storing carrier particles (2) Step of distributing stored carrier particles to a first catalyst component group carrying zone (3) Supplying each catalyst component solution contained in the first catalyst component group to this zone Step (4) of obtaining first catalyst component-supporting particles in which each of the carrier particles carries each of the first catalyst component (4) After drying and / or calcining and reducing the first catalyst component-supporting particles obtained above, if necessary And (5) supplying each catalyst component solution contained in the second catalyst component group to the predetermined second catalyst component group supporting zone (5) and further supporting each of the second catalyst components on each catalyst particle. Step (6): Obtaining the second catalyst component-supporting particles, and, after optionally drying and / or calcining and reducing each of the second catalyst component-supporting particles obtained above, a step of distributing the particles to a predetermined third catalyst component group-supporting zone. (7) Each catalyst contained in the third catalyst component group in this zone Step (8) of supplying a component solution to obtain third catalyst component-supporting particles in which each catalyst particle further supports each of the third catalyst components, and the same operation as above until the last catalyst component group is supported. Step (9) of performing a predetermined solid catalyst by repeating the above steps (1) to (8) as many times as necessary, and the number of the same type of catalyst particles supplied from each stage to the next stage is As the number of catalyst components or a multiple thereof, in the next step, by loading all components on each particle,
A process for preparing a solid catalyst having all logically possible combinations of catalyst components in a combination of selecting one from each of the catalyst components at each stage
帯域を設け、無処理帯域も含めたすべての第１触媒成分
担持帯域へ担体粒子を供給し、その後の処理は無処理帯
域も担持帯域と同様にして扱うことを特徴とする請求項
５に記載の多種の固体触媒の迅速調製方法。6. An untreated zone is provided in the catalyst component carrying zone of all stages, carrier particles are supplied to all the first catalyst component carrying zones including the untreated zone, and the subsequent treatment also carries the untreated zone. The method for rapid preparation of various kinds of solid catalysts according to claim 5, which is treated in the same manner as the zone.
とする請求項１乃至６何れかに記載の多種の固体触媒の
迅速調製方法。7. The method for rapid preparation of various kinds of solid catalysts according to claim 1, wherein the carrier is porous spherical particles.
の担持が、担体各粒子又は触媒担持各粒子に対して触媒
成分溶液を個別に直接吸収させることにより行われるこ
とを特徴とする請求項１乃至７何れかに記載の多種の固
体触媒の迅速調製方法。8. A method of supporting a catalyst component on carrier particles or catalyst-supporting particles by directly adsorbing a catalyst component solution to each carrier particle or catalyst-supporting particle. 8. A method for rapidly preparing various kinds of solid catalysts according to any one of 1 to 7.
媒担持粒子に直接送られることを特徴とする請求項８に
記載の多種の固体触媒の迅速調製方法。9. The method for rapid preparation of various kinds of solid catalysts according to claim 8, wherein the catalyst component is directly sent to the carrier particles or the catalyst-supported particles by a pump.
は触媒担持粒子に直接送られることを特徴とする請求項
８に記載の多種の固体触媒の迅速調製方法。10. The method for rapid preparation of various kinds of solid catalysts according to claim 8, wherein the catalyst component is directly transferred by siphon to carrier particles or catalyst-supported particles.
る触媒成分溶液の量の調節を触媒担体の吸収能により自
律的に行わせることを特徴とする請求項１０に記載の多
種の固体触媒の迅速調製方法。11. The various kinds of solid catalysts according to claim 10, wherein the amount of the catalyst component solution supplied to the carrier particles or the catalyst-supported particles is adjusted autonomously by the absorption capacity of the catalyst carrier. Rapid preparation method.
方法で得られた各触媒担持粒子を所定の複数の触媒群と
し、当該触媒群に含まれる固体触媒の有効性を該触媒群
を構成する個々の固体触媒に分離することなく判別する
ことを特徴とする固体触媒の迅速探索評価方法。12. The catalyst-supporting particles obtained by the preparation method according to any one of claims 1 to 11 are defined as a plurality of predetermined catalyst groups, and the effectiveness of the solid catalysts contained in the catalyst groups is determined by the catalyst groups. A rapid search and evaluation method for solid catalysts, characterized in that the solid catalysts are distinguished without being separated.
することなく個別的に逐次、担持させる手段を備えたこ
とを特徴とする多種の固体触媒の迅速調製装置。13. A rapid preparation apparatus for various kinds of solid catalysts, which is provided with means for individually and successively loading the respective catalyst particles on the carrier without mixing the respective catalyst components.
複しないようにして、複数並行して段階的に行う手段を
備えたことを特徴とする請求項１３に記載の多種の固体
触媒の迅速調製装置。14. The rapid solid-state catalyst for various kinds of catalysts according to claim 13, further comprising means for carrying a plurality of catalyst components in parallel and stepwise so that the respective catalyst components do not overlap. Preparation equipment.
からそれぞれ１つを選ぶ論理的な組み合わせ方法に従っ
て行う手段を備えたことを特徴とする請求項１３乃至１
４何れかに記載の多種の固体触媒の迅速調製装置。15. A means for carrying a catalyst component according to a logical combination method of selecting one from the catalyst components at each stage, is provided.
4. A rapid preparation device for various kinds of solid catalysts according to any of 4 above.
して各触媒成分溶液を直接供給することにより行う手段
を備えたことを特徴する請求項１３乃至１５何れかに記
載の多種の固体触媒の迅速調製装置。16. A variety of solids according to claim 13, further comprising means for carrying the catalyst component by directly supplying each catalyst component solution to each particle of the carrier. Rapid catalyst preparation equipment.
請求項１３乃至１６何れかに記載の多種の固体触媒の迅
速調製装置。 （１）担体粒子を貯留する手段 （２）貯留された担体粒子を第１触媒成分群担持帯域に
分配する手段 （３）この帯域に第１触媒成分群に含まれる各触媒成分
溶液を供給し、各担体粒子に第１触媒成分のそれぞれが
担持された第１触媒成分担持粒子を得る手段 （４）上記で得た各第１触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第２触媒成分
群担持帯域に分配する手段 （５）この帯域に第２触媒成分群に含まれる各触媒成分
溶液を供給し、各触媒粒子に第２触媒成分のそれぞれが
更に担持された第２触媒成分担持粒子を得る手段 （６）上記で得た各第２触媒成分担持粒子を必要により
乾燥及び／又は焼成、還元した後、所定の第３触媒成分
群担持帯域に分配する手段 （７）この帯域に第３触媒成分群に含まれる各触媒成分
溶液を供給し、各触媒粒子に第３触媒成分のそれぞれが
更に担持された第３触媒成分担持粒子を得る手段 （８）以下最後の触媒成分群が担持されるまで上記と同
様な操作を行い所定の固体触媒を調製する手段 （９）上記（１）〜（８）の手段を必要な数だけ繰り返
し行い、各段から次の段への同種の触媒粒子の供給数は
次の段の触媒成分数またはその倍数として、次の段では
各粒子にすべての成分をそれぞれ担持することにより、
各段階での触媒成分群から各々１つずつを選ぶ組み合わ
せにおいて論理的に可能な触媒成分の組み合わせの全て
を持つ固体触媒を調製する手段17. The rapid preparation apparatus for various kinds of solid catalysts according to claim 13, characterized by comprising the following means. (1) Means for storing carrier particles (2) Means for distributing stored carrier particles to the first catalyst component group carrying zone (3) Supplying each catalyst component solution contained in the first catalyst component group to this zone Means for obtaining first catalyst component-supporting particles in which each of the carrier particles carries each of the first catalyst component (4) after drying and / or calcining and reducing the respective first catalyst component-supporting particles obtained above, if necessary Means for distributing to a predetermined second catalyst component group supporting zone (5) supplying each catalyst component solution contained in the second catalyst component group to this zone, and further supporting each second catalyst component on each catalyst particle Means for obtaining second catalyst component-supporting particles (6) Means for distributing each second catalyst component-supporting particle obtained above to a predetermined third catalyst component group-supporting zone after drying and / or calcining and reducing if necessary (7) Each catalyst contained in the third catalyst component group in this zone A means for supplying a component solution to obtain third catalyst component-supporting particles in which each catalyst particle further supports each of the third catalyst components (8) and thereafter, the same operation as above is performed until the last catalyst component group is supported. Means for preparing a predetermined solid catalyst (9) The above-mentioned means (1) to (8) are repeated as many times as necessary, and the number of the same type of catalyst particles supplied from each stage to the next stage is the same as that of the next stage. As the number of catalyst components or a multiple thereof, in the next step, by loading all components on each particle,
Means for preparing a solid catalyst having all logically possible combinations of catalyst components in a combination of selecting one from each of the catalyst component groups at each stage
理帯域を設け、無処理帯域も含めたすべての第１触媒成
分担持帯域へ担体粒子を供給し、その後の処理は無処理
帯域も担持帯域と同様にして扱うことを特徴とする請求
項１７に記載の多種の固体触媒の迅速調製装置。18. An untreated zone is provided in the catalyst component carrying zone of all stages, carrier particles are supplied to all the first catalyst component carrying zones including the untreated zone, and the untreated zone is carried in the subsequent treatment. The rapid preparation apparatus for various kinds of solid catalysts according to claim 17, which is treated in the same manner as the zone.
を特徴とする請求項１３乃至１８何れかに記載の多種の
固体触媒の迅速調製装置。19. The rapid preparation apparatus for various kinds of solid catalysts according to claim 13, wherein the carrier particles are porous spherical particles.
群担持帯域に分配する手段が自重で行われることを特徴
とする請求項１７乃至１９に記載の多種の固体触媒の迅
速調製装置。20. The rapid preparation apparatus for various kinds of solid catalysts according to claim 17, wherein the means for distributing each of the stored carrier particles to the first catalyst component group carrying zone is performed by its own weight.
持帯域に分配する手段が自重を利用したものであること
を特徴とする請求項１７乃至２０何れかに記載の多種の
固体触媒の迅速調製装置。21. The rapid production of various solid catalysts according to claim 17, characterized in that the means for distributing each catalyst component-supporting particle to each catalyst component group-supporting zone utilizes its own weight. Preparation equipment.
分の担持が、担体各粒子又は触媒担持各粒子に対して触
媒成分溶液を個別に直接吸収させる手段により行われる
ことを特徴とする請求項１７乃至２１何れかに記載の多
種の固体触媒の迅速調製装置。22. Supporting of the catalyst component on the carrier particles or the catalyst-supporting particles is carried out by a means for directly absorbing the catalyst component solution to each carrier particle or each catalyst-supporting particle. An apparatus for rapid preparation of various solid catalysts according to any one of 17 to 21.
触媒担持粒子に直接送られることを特徴とする請求項２
２に記載の多種の固体触媒の迅速調製装置。23. The catalyst component is directly sent to the carrier particles or the catalyst-supported particles by a pump.
2. A rapid preparation apparatus for various kinds of solid catalysts described in 2.
は触媒担持粒子に直接送られることを特徴とする請求項
２２に記載の多種の固体触媒の迅速調製装置。24. The rapid preparation apparatus for various kinds of solid catalysts according to claim 22, wherein the catalyst component is directly sent to the carrier particles or the catalyst-supported particles by siphon.
種の固体触媒調装置と該調製装置で得られた各担持触媒
粒子を所定の複数の触媒群とする分配混合装置と、該触
媒群に含まれる固体触媒の有効性を該触媒群を構成する
個々の固体触媒に分離することなく判別する装置を備え
たことを特徴とする固体触媒の迅速探索評価装置。25. A variety of solid catalyst preparation apparatus according to any one of claims 13 to 24, a distribution mixing apparatus in which each supported catalyst particle obtained by the preparation apparatus is a predetermined plurality of catalyst groups, and the catalyst group. A rapid search and evaluation device for solid catalysts, comprising a device for determining the effectiveness of the solid catalysts contained in the solid catalysts without separating them into individual solid catalysts constituting the catalyst group.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1057822A (en) * | 1996-08-20 | 1998-03-03 | Fuji Oil Co Ltd | Method and apparatus for preparing catalyst |
| JP2000262907A (en) * | 1999-03-18 | 2000-09-26 | Agency Of Ind Science & Technol | Integrated catalyst and its production |
| WO2000058003A1 (en) * | 1999-03-31 | 2000-10-05 | General Electric Company | Method for preparing and screening catalysts |
| JP2000516856A (en) * | 1997-06-26 | 2000-12-19 | アジプ ペトローリ ソシエタ ペル アチオニ | Process for preparing catalysts based on cobalt and scandium |
| JP2001004615A (en) * | 1999-06-24 | 2001-01-12 | Showa Denko Kk | Screening method |
| JP2001264309A (en) * | 2000-03-15 | 2001-09-26 | Fumiaki Otani | Catalyst searching method |
| JP2002166160A (en) * | 2000-12-01 | 2002-06-11 | Asahi Kasei Corp | System for automatically synthesizing catalyst precursor and system for automatically synthesizing catalyst |
| JP2003033667A (en) * | 2001-07-23 | 2003-02-04 | National Institute Of Advanced Industrial & Technology | Method of rapidly searching multicomponent solid catalyst |
| JP2003135977A (en) * | 2001-10-31 | 2003-05-13 | Asahi Kasei Corp | Method for synthesizing catalyst precursor, automatic synthesizing device and catalyst |
| JP2003516308A (en) * | 1998-12-14 | 2003-05-13 | ドイチェス クレープスフォルシュングスツェントルム シュティフトゥング デス エッフェントリッヒェン レヒツ | Method and apparatus for attaching substances for combinatorial synthesis of molecular libraries, especially monomers, to carriers |
| JP2003164767A (en) * | 2001-09-19 | 2003-06-10 | National Institute Of Advanced Industrial & Technology | Rapid searching method for vapor phase reaction catalyst |
-
2002
- 2002-02-08 JP JP2002031689A patent/JP4139883B2/en not_active Expired - Lifetime
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1057822A (en) * | 1996-08-20 | 1998-03-03 | Fuji Oil Co Ltd | Method and apparatus for preparing catalyst |
| JP2000516856A (en) * | 1997-06-26 | 2000-12-19 | アジプ ペトローリ ソシエタ ペル アチオニ | Process for preparing catalysts based on cobalt and scandium |
| JP2003516308A (en) * | 1998-12-14 | 2003-05-13 | ドイチェス クレープスフォルシュングスツェントルム シュティフトゥング デス エッフェントリッヒェン レヒツ | Method and apparatus for attaching substances for combinatorial synthesis of molecular libraries, especially monomers, to carriers |
| JP2000262907A (en) * | 1999-03-18 | 2000-09-26 | Agency Of Ind Science & Technol | Integrated catalyst and its production |
| WO2000058003A1 (en) * | 1999-03-31 | 2000-10-05 | General Electric Company | Method for preparing and screening catalysts |
| JP2001004615A (en) * | 1999-06-24 | 2001-01-12 | Showa Denko Kk | Screening method |
| JP2001264309A (en) * | 2000-03-15 | 2001-09-26 | Fumiaki Otani | Catalyst searching method |
| JP2002166160A (en) * | 2000-12-01 | 2002-06-11 | Asahi Kasei Corp | System for automatically synthesizing catalyst precursor and system for automatically synthesizing catalyst |
| JP2003033667A (en) * | 2001-07-23 | 2003-02-04 | National Institute Of Advanced Industrial & Technology | Method of rapidly searching multicomponent solid catalyst |
| JP2003164767A (en) * | 2001-09-19 | 2003-06-10 | National Institute Of Advanced Industrial & Technology | Rapid searching method for vapor phase reaction catalyst |
| JP2003135977A (en) * | 2001-10-31 | 2003-05-13 | Asahi Kasei Corp | Method for synthesizing catalyst precursor, automatic synthesizing device and catalyst |
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