JP5924969B2 - Granule processing equipment - Google Patents
Granule processing equipment Download PDFInfo
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- JP5924969B2 JP5924969B2 JP2012029866A JP2012029866A JP5924969B2 JP 5924969 B2 JP5924969 B2 JP 5924969B2 JP 2012029866 A JP2012029866 A JP 2012029866A JP 2012029866 A JP2012029866 A JP 2012029866A JP 5924969 B2 JP5924969 B2 JP 5924969B2
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- catalyst
- cage
- processing apparatus
- reaction vessel
- lifting
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 78
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Description
本発明は、触媒等の粒状体を加熱炉内の高温下で処理する反応器等の流体または粒状体処理装置の技術に関する。 The present invention relates to a technology of a fluid or granular material processing apparatus such as a reactor for processing granular materials such as a catalyst at a high temperature in a heating furnace.
入口・出口（流入口・流出口）を有する容器の中に粒状体を静的に収容し、これを加熱して高温下に維持し、粒状体間の隙間に流体を通過させて流体または粒状体を処理する粒状体処理装置は、固定床反応器、熱交換器、高温フィルタ等に広く適用されている。このような粒状体処理装置においては、作業中の特定のタイミングで粒状体の相対位置を微小に変更したい状況がしばしば発生する。 A granular material is statically accommodated in a container having an inlet / outlet (inlet / outlet), and is heated and maintained at a high temperature, and a fluid is passed through a gap between the granular materials to form a fluid or a granular material. BACKGROUND ART A granular material processing apparatus for processing a body is widely applied to a fixed bed reactor, a heat exchanger, a high temperature filter and the like. In such a granular material processing apparatus, there often occurs a situation where it is desired to slightly change the relative position of the granular material at a specific timing during work.
例えば、流体が粒状体表面で反応を生じる反応器においては、粒状体隙間のレイアウトの差によって、粒状体表面で新鮮な流体と接触しやすい領域（大流量で隙間を流体が流れる隙間）としにくい領域（流れの澱む隙間や粒状体同士が接触している表面）の分布を生じる。長時間作業を続ければ、新鮮な流体と接触しやすい領域の粒状体表面では表面の減量や汚損・劣化が促進される場合がある。このようなとき、もし、粒状体の相対位置を変更することによって、それまで澱んだ流体と接触していた粒状体表面の一部を新鮮な流体と接触しやすい隙間レイアウトにすることができれば、粒状体表面での減量や劣化の均一化をはかることが期待でき、より長い時間、安定して作業できると考えられる。 For example, in a reactor in which a fluid reacts on the surface of a granular material, due to the difference in the layout of the granular material gap, it is difficult to make a region that easily contacts fresh fluid on the surface of the granular material (a gap through which the fluid flows at a large flow rate). The distribution of the region (the gap where the flow stagnates or the surface where the granular materials are in contact with each other) occurs. If the work is continued for a long time, surface reduction, fouling and deterioration may be promoted on the surface of the granular material in an area where it is easy to come into contact with fresh fluid. In such a case, if it is possible to change the relative position of the granule to make a gap layout that allows easy contact with fresh fluid, a part of the granule surface that has been in contact with the stagnant fluid until then, It can be expected that weight reduction and uniform deterioration will be achieved on the surface of the granular material, and it will be possible to work stably for a longer time.
あるいは、粒状体間の隙間には作業中に異物が堆積する場合があり、通気性や反応性の低下を生じる場合がある。例えば、触媒（粒状体）を充填した固定床触媒反応容器（粒状体処理装置）を用いた流体の化学反応において、触媒反応によって固体等の析出物を生成する場合には、しばしば、触媒間の空間にこの固体析出物が堆積して触媒層を閉塞させ、通気できなくなる問題が発生する。 Alternatively, foreign matters may accumulate in the gaps between the granular materials during the work, and air permeability and reactivity may be reduced. For example, in a fluid chemical reaction using a fixed bed catalytic reaction vessel (granular material processing device) filled with a catalyst (granular material), a precipitate such as a solid is often produced by the catalytic reaction. This solid deposit accumulates in the space, clogs the catalyst layer, and there is a problem that the air cannot be vented.
例えば、触媒を充填した固定床触媒反応装置を用いた流体の化学反応においては、しばしば固体の生成物を生じて触媒反応装置を局部的に閉塞させる問題がある。 For example, in a fluid chemical reaction using a fixed bed catalytic reactor filled with a catalyst, there is often a problem that a solid product is generated and the catalytic reactor is locally blocked.
移動床や流動床を用いれば、粒状体間を相対運動させることは容易である。しかし、移動床や流動床式の反応装置は、固定床触媒反応装置に比べて装置が複雑化することや、流動床形式の場合には操業も不安定になりやすいので、特に、高温・高圧・高腐食性流体を処理するための反応器としては一般的ではない。 If a moving bed or a fluidized bed is used, it is easy to make relative movement between the granular bodies. However, moving bed and fluidized bed type reactors are more complicated than fixed bed catalytic reactors, and in the case of fluidized bed type, the operation tends to be unstable. It is not common as a reactor for treating highly corrosive fluids.
一方、移動床形式および流動床形式の触媒反応容器における上記のような問題がない固定床反応容器では、通常、触媒層を挟んだ両側に空間を設け、一方の空間から他方に流体を流通させて反応させる。触媒層の両側に空間を形成するためには、触媒の保持機構が必要であり、触媒保持機構の代表例は特許文献２（特開２０１１−６２８９号公報）に記載されているが、触媒径よりも小さな孔径を有するパンチングメタル板や網を用いて触媒の保持と通気を確保している。図１にその例を示すが、触媒反応容器１の内部に触媒２が収容されており、触媒の保持はパンチングメタル板や網３によって行われている。図１において、原料ガス４は流入口５から流入し、流出口６から改質ガス７として流出する。 On the other hand, in a fixed bed reaction vessel that does not have the above-mentioned problems in moving bed type and fluidized bed type catalyst reaction vessels, spaces are usually provided on both sides of the catalyst layer, and fluid is circulated from one space to the other. To react. In order to form a space on both sides of the catalyst layer, a catalyst holding mechanism is necessary. A typical example of the catalyst holding mechanism is described in Patent Document 2 (Japanese Patent Laid-Open No. 2011-6289). The catalyst is held and ventilated by using a punching metal plate or net having a smaller hole diameter. An example is shown in FIG. 1, in which a catalyst 2 is accommodated in a catalyst reaction vessel 1, and the catalyst is held by a punching metal plate or a net 3. In FIG. 1, the raw material gas 4 flows in from the inlet 5 and flows out as the reformed gas 7 from the outlet 6.
反応中の固体析出物の堆積による触媒層の閉塞を防止する手段として、例えば特許文献２には、２つの触媒層の間をガスが通気する自由空間において、第１の触媒層から流出したガス中の粉塵を補足することによって第２の触媒層での閉塞を防ぐ技術が記載されている。しかしこの場合には、触媒層内部で生成し、触媒間の空間で触媒に付着・堆積する粉塵による触媒層の閉塞を防止することはできない。 As a means for preventing clogging of the catalyst layer due to the deposition of solid precipitates during the reaction, for example, Patent Document 2 discloses a gas flowing out from the first catalyst layer in a free space in which a gas passes between the two catalyst layers. A technique for preventing clogging in the second catalyst layer by supplementing the dust inside is described. However, in this case, it is impossible to prevent clogging of the catalyst layer due to dust that is generated inside the catalyst layer and adheres to and accumulates on the catalyst in the space between the catalysts.
特許文献３（特開２００９−４８７９７号公報）には、燃料電池用のセル内の触媒層に超音波を照射することによって、触媒上で発生した水を流出・除去する技術が記載されている。超音波は、自由空間中や粒体層・粉体層中での減衰が大きいので、照射源近傍にしか作用できない。このため、燃料電池用セル内の触媒層のように比較的小型のものには有効であるが、大量の流体を処理する大型の触媒層では、超音波によって触媒層全体を振動させることは困難である。 Patent Document 3 (Japanese Patent Application Laid-Open No. 2009-48797) describes a technique for flowing out and removing water generated on a catalyst by irradiating the catalyst layer in the cell for the fuel cell with ultrasonic waves. . Ultrasonic waves can act only in the vicinity of the irradiation source because they are greatly attenuated in free space and in the granular layer and powder layer. For this reason, it is effective for a relatively small catalyst layer such as a catalyst layer in a fuel cell, but it is difficult to vibrate the entire catalyst layer by ultrasonic waves in a large catalyst layer that processes a large amount of fluid. It is.
特許文献４（特開２００８−１２０６０４号公報）には、炭化水素の水蒸気改質を低温で実施することによりコーキングを抑制する技術が記載されている。しかし、触媒反応には触媒耐久性および反応速度上の観点から最適な反応温度条件が存在し、コーキングによる触媒層の閉塞は、この最適条件において発生している。そのため、触媒反応温度を低下させてしまうと、反応の最適条件ではなくなるので、触媒性能が低下する問題がある。 Patent Document 4 (Japanese Patent Laid-Open No. 2008-120604) describes a technique for suppressing coking by performing steam reforming of hydrocarbons at a low temperature. However, there are optimum reaction temperature conditions for the catalytic reaction from the viewpoint of catalyst durability and reaction rate, and clogging of the catalyst layer due to coking occurs under these optimum conditions. For this reason, if the catalyst reaction temperature is lowered, the optimum conditions for the reaction are lost, and there is a problem that the catalyst performance is lowered.
特許文献５（特開平８−２４６２２号公報）には、従来技術として、移動床触媒反応容器における堆積ダストによる触媒層の部分閉塞を槌打装置やバイブレータによって除去することが記載されている。この場合には、槌打やバイブレーションによって、触媒の充填率が上昇して触媒間の空間が狭まり、触媒の流動性がかえって悪化する問題がある。 Patent Document 5 (Japanese Patent Laid-Open No. 8-24622) describes, as a conventional technique, removing a partial blockage of a catalyst layer due to accumulated dust in a moving bed catalyst reaction vessel with a striking device or a vibrator. In this case, there is a problem that the packing ratio of the catalyst increases due to beating or vibration, the space between the catalysts is narrowed, and the fluidity of the catalyst is deteriorated.
非特許文献１には、特殊な固定床触媒反応容器として、平行流式、モノリス式、管壁式等が記載されている。これらはいずれも、触媒反応容器内に触媒層と、触媒層に囲まれた専用の気流路を設けることによって、触媒反応容器内の通気抵抗の低減を図っている。簡単に言うと、平行流式では、網などで両端を保持した通常の触媒層を平行に複数並べ、触媒層間の空間を専用気流路とする。モノリス式では、ハニカム構造等の構造物の表面に触媒を担持し、ハニカム構造の孔を専用気流路とする。管壁式では、管路内を専用気流路とし、管内面に触媒を担持する。 Non-Patent Document 1 describes a parallel flow type, a monolith type, a tube wall type, and the like as special fixed bed catalyst reaction vessels. In any of these, a catalyst layer and a dedicated air flow passage surrounded by the catalyst layer are provided in the catalyst reaction vessel, thereby reducing the ventilation resistance in the catalyst reaction vessel. In brief, in the parallel flow type, a plurality of ordinary catalyst layers holding both ends with a mesh or the like are arranged in parallel, and the space between the catalyst layers is used as a dedicated air flow path. In the monolith type, a catalyst is supported on the surface of a structure such as a honeycomb structure, and the holes in the honeycomb structure are used as dedicated air flow paths. In the tube wall type, the inside of the pipe line is a dedicated air flow path, and the catalyst is supported on the inner surface of the pipe.
専用の気流路を設けた場合、触媒反応によって固体生成物が生じると、専用気流路を構成する触媒表面に固体生成物が堆積して専用気流路の流路幅が狭まり、閉塞を生じることがある。あるいは、気流路の閉塞を生じない場合でも、専用気流路を構成する触媒表面に堆積した固体生成物によって専用気流路と触媒層間の流体の交換が阻まれるので、原料ガスが活性を保持した触媒と接触することなく流出して触媒反応効率が著しく減少してしまうという「吹き抜け」現象を生じる。あるいは、モノリス式のように反応容器内に専用気流路が複数存在し、各専用気流路が互いに孤立（即ち、隣接する気流路間での物質交換およびこれに伴う熱交換の抑制された状態）しており、反応容器の奥深い部位での専用気流路内では外部から熱供給を行えない気流路を設けた反応容器において、触媒反応が強い吸熱反応の場合には、上流側の反応によって下流では流体温度が大きく低下して反応可能温度以下となり、反応効率が極端に低下してしまう。逆に触媒反応が強い発熱反応の場合には、反応容器の奥深い部位では発生した熱量を反応容器を通じて外部に放出できないので、下流では流体温度が過度に上昇して触媒を失活させたり、触媒反応容器を焼損することがある。 In the case where a dedicated air flow path is provided, if a solid product is generated by a catalytic reaction, the solid product may accumulate on the surface of the catalyst constituting the dedicated air flow path and the flow width of the dedicated air flow path may be narrowed, resulting in blockage. is there. Alternatively, even if the air flow path is not blocked, the exchange of fluid between the dedicated air flow path and the catalyst layer is hindered by the solid product deposited on the catalyst surface constituting the dedicated air flow path. This causes a “blown-out” phenomenon in which the catalyst reaction efficiency is remarkably reduced without coming into contact with the catalyst. Alternatively, there are a plurality of dedicated air flow paths in the reaction vessel as in the monolith type, and each dedicated air flow path is isolated from each other (that is, a state in which material exchange between adjacent air flow paths and heat exchange associated therewith is suppressed). In the reaction vessel provided with an air channel that cannot supply heat from outside in the dedicated gas channel in the deep part of the reaction vessel, in the case of endothermic reaction with strong catalytic reaction, The fluid temperature is greatly reduced to be below the reaction possible temperature, and the reaction efficiency is extremely lowered. On the other hand, in the case of an exothermic reaction with a strong catalytic reaction, the amount of heat generated in the deep part of the reaction vessel cannot be released to the outside through the reaction vessel, so that the fluid temperature rises excessively downstream and deactivates the catalyst. The reaction vessel may be burned out.
さらに、モノリス式の場合、一般に複雑な形状で大型となるモノリス全体を、触媒を担持するための担体、または、触媒自身の単一構造物として成形する必要があるため、触媒製造技術上、適用できる触媒設計（構造）が比較的単純なもの（例えば、単一化学成分種の触媒を担体表面に均一塗布する等）に限られるという問題がある。このため、例えば、タール改質触媒のように、表面が複数の異なる化学種成分の区画に微細に分割されて各化学種成分が互いに協調して触媒効果を発揮するような複雑な設計（構造）の触媒にモノリス式を適用することは、著しく困難であり、可能だとしても極めて高価なものになる。 Furthermore, in the case of the monolith type, it is necessary to form the entire monolith having a large shape with a complicated shape as a carrier for supporting the catalyst or a single structure of the catalyst itself. There is a problem that the catalyst design (structure) that can be produced is limited to a relatively simple one (for example, a catalyst of a single chemical component species is uniformly applied to the support surface). For this reason, for example, such as a tar reforming catalyst, a complicated design (structure) in which the surface is finely divided into a plurality of different chemical species component compartments, and each chemical species component cooperates with each other to exert a catalytic effect. It is extremely difficult to apply the monolithic type to the catalyst of), and it is extremely expensive if possible.
このように従来技術では容器内に静的に収納された粒状体間の相対位置を効率的に変更する手段が存在しなかった。 Thus, in the prior art, there is no means for efficiently changing the relative position between the granular materials statically stored in the container.
また、処理装置容器内で何かを昇降させるための昇降機構に関して、処理装置容器内温度が低い場合（例：７０℃以下）には比較的容易に実現できる。例えば、周囲をフッ素樹脂製の市販のジャバラで保護した市販の油圧シリンダを処理装置容器の下部に設置し、油圧シリンダのロッド先端を被昇降物下面に接合すればよい。 Moreover, regarding the raising / lowering mechanism for raising and lowering something in the processing apparatus container, when the temperature in the processing apparatus container is low (eg, 70 ° C. or less), it can be realized relatively easily. For example, a commercially available hydraulic cylinder whose periphery is protected by a commercially available bellows made of fluororesin may be installed at the lower part of the processing apparatus container, and the rod tip of the hydraulic cylinder may be joined to the lower surface of the object to be lifted.
しかし、処理装置容器内温度が加熱炉内に設置され、容器内部および周辺が高温である場合（例：６００℃以上）、内部の物を昇降させるためには、特別製（例：耐熱合金製構造体＋ファインセラミックス製シール材等）の耐熱ガスシリンダを用いる等、高価な手段しかなく、簡易な装置が提案されていなかった。 However, when the temperature inside the processing equipment container is set in a heating furnace and the inside and surroundings of the container are hot (eg, 600 ° C. or higher), a special product (eg, made of heat-resistant alloy) can be used to raise and lower the inside. There is only an expensive means such as using a heat-resistant gas cylinder of structure + fine ceramic sealing material, etc., and no simple device has been proposed.
上記課題を解決するために、本発明者の研究の結果、以下の解決方法を発明するに至った。 In order to solve the above-mentioned problems, the following solutions have been invented as a result of the inventor's research.
（１） Ａ）加熱炉と、
Ｂ）加熱炉内に設置された、略重力方向に中心軸を持つ筒状である粒状体容器と、
Ｃ）粒状体容器内に粒状体を下方から保持する保持器と、
Ｄ）粒状体容器内に保持された粒状体に流体を通過させるための、粒状体容器の一端近傍に設けた流体の流入口及び他端近傍に設けた流体の流出口と、
Ｅ）粒状体撹拌手段とを具備する処理装置であって、
前記粒状体攪拌手段は、保持器を含んで保持器とともに昇降する昇降部と、保持器に接して昇降部に昇降のための駆動力を伝える水平移動部とから構成され、
前記水平移動部は、
−加熱炉内に設けられ、昇降部に接して水平方向に往復動して前記昇降部を昇降させる爪部と、
−加熱炉外に設けられ、前記爪部を水平方向に往復動させる駆動装置と
−加熱炉の壁を貫通して前記駆動装置と前記爪部を連結する連結軸と、
−前記連結軸周囲を囲って粒状体容器を加熱炉雰囲気から遮断するシ−ル手段とから構成され、
前記爪部は、前記駆動装置に向かう方向に上昇する上向き斜面と、前記駆動装置から遠ざかる方向に下降する下向き斜面とを有し、
前記昇降部は、前記昇降部に生じうるスラスト力を前記粒状体容器で受けるものであるとともに、前記爪部の上向き斜面と接触する位置、及び、前記爪部の下向き斜面と接触する位置を有し、
前記駆動装置が前記爪部を押出すと、前記爪部の前記上向き斜面が、前記爪部の上向き斜面と接触する位置で前記昇降部と接触しつつ、前記爪部の上向き斜面と接触する位置の前記昇降部を前記上向き斜面に沿ってスライドして、前記昇降部に上昇力を与えて、前記昇降部が前記粒状体容器の内壁に沿って上昇し、
前記駆動装置が前記爪部を引戻すと、前記爪部の前記下向き斜面が、前記爪部の下向き斜面と接触する位置で前記昇降部と接触しつつ、前記爪部の下向き斜面と接触する位置の前記昇降部を前記下向き斜面に沿ってスライドして、それに接する前記昇降部に下降力を与えて、前記昇降部が前記粒状体容器の内壁に沿って下降するとともに、
前記粒状体処理容器が前記粒状体として粒状の触媒を収納する連続式固定床触媒反応器であり、供給流体がガスであり、前記触媒を用いた流体の触媒反応による生成物が生成ガスと触媒上に析出する固体を含み、
前記析出する固体が前記触媒層中に堆積して前記触媒層が閉塞することを防止するための処理装置。
（２） 前記粒状体容器内に前記粒状体が積層されて粒状体層をなし、前記粒状体が前記粒状体容器の内壁に接するように昇降することを特徴とする上記（１）に記載の処理装置。
（３） 前記保持器が、粒状体を複数のピンの先端部で保持し、且つ、前記複数のピンの間の隙間間隔が粒子状触媒の大きさより小さく設定され、前記流体が当該ピンの間の空間を流通できる構造を有することを特徴とする上記（２）に記載の処理装置。
（４） 前記粒状の触媒を収納する形態は、
前記触媒を内部に貫通孔を有する形状とした触媒と、
前記内部に貫通孔を有する形状の触媒の複数を、前記貫通孔を通して個々の前記触媒を中心棒で貫いて一列に整列させた触媒連と、
複数の前記触媒連を間隔をあけて配列し、保持板に固定して形成した触媒柵と、を備え、
前記保持板が、前記保持器に固定されていることを特徴とする上記（１）に記載の処理装置。
（５） 前記昇降部は保持器の下方に固定ピンを有し、昇降部の降下時に前記爪部の下向き斜面が接する昇降部の位置は、前記昇降部の固定ピンであることを特徴とする上記（１）〜（４）のいずれか１項に記載の処理装置。
（６） 前記昇降部は保持器の下方に固定ピンを有し、昇降部の上昇時に前記爪部の上向き斜面が接する昇降部の位置は、前記昇降部の固定ピンであることを特徴とする上記（１）〜（５）のいずれか１項に記載の処理装置。
（７） 前記昇降部は保持器の下方に、前記爪部の上向き斜面と対向して前記駆動装置に向かう方向に上昇する下向き斜面を有し、昇降部の上昇時に前記爪部の上向き斜面が接する昇降部の位置は、前記昇降部の下向き斜面であることを特徴とする上記（１）〜（５）のいずれか１項に記載の処理装置。
（８） 前記シール手段がシール管であって、外部から非反応性ガスを供給する非反応性ガス供給管が接続されていることを特徴とする上記（１）〜（７）のいずれか１項に記載の処理装置。
（９） 前記爪部は、昇降部の非昇降時には、昇降部から離脱してシール手段内に引き戻されることを特徴とする上記（１）〜（８）のいずれか１項に記載の処理装置。
（１０） 前記駆動機構の下降時の速度が上昇時の速度よりも速いことを特徴とする上記（１）〜（９）のいずれか１項に記載の処理装置。
（１１） 前記触媒反応用の流体が炭化水素を含有するガスであり、前記触媒反応による生成物が固体の炭化水素または固体のカーボンを含むことを特徴とする、上記（１）から（１０）のいずれか１項に記載の処理装置。
（１２） 前記炭化水素を含有するガスがタールを含有するガスであることを特徴とする、上記（１１）に記載の処理装置。
（１３） 前記触媒が、ニッケル、マグネシウム、セリウム、アルミニウムを含む複合酸化物であって、アルミナを含まない複合酸化物からなる触媒であり、前記複合酸化物が、NiMgO、MgAl2O4、CeO2の結晶相からなることを特徴とする、上記（１２）に記載の処理装置。
（１４） 前記触媒が、ニッケル、マグネシウム、セリウム、ジルコニウム、アルミニウムを含む複合酸化物からなる触媒であり、前記複合酸化物が、NiMgO、MgAl2O4、CexZr1-xO2（0<x<1）の結晶相を含むことを特徴とする上記（１２）に記載の処理装置。
（１５） 前記触媒が、ａＭ・ｂＮｉ・ｃＭｇ・ｄＯで表わされる複合酸化物であるタール含有ガスの改質用触媒であって、
ａ、ｂ、及び、ｃは、ａ＋ｂ＋ｃ＝１、０．０２≦ａ≦０．９８、０．０１≦ｂ≦０．９７、かつ、０．０１≦ｃ≦０．９７を満たし、
ｄは、酸素と陽性元素が電気的に中立となる値であり、
Ｍは、Ｔｉ，Ｚｒ，Ｃａ，Ｗ，Ｍｎ，Ｚｎ，Ｓｒ，Ｂａ，Ｔａ，Ｃｏ，Ｍｏ，Ｒｅ，白金、ルニウム、パラジウム、ロジウム、Ｌｉ，Ｎａ，Ｋ，Ｆｅ，Ｃｕ，Ｃｒ，Ｌａ，Ｐｒ，Ｎｄから選ばれる少なくとも１種類の元素であり、
前記複合酸化物に、シリカ、アルミナ、ゼオライトから選ばれる少なくとも１種類の酸化物を加え、シリカ、アルミナ、ゼオライトから選ばれる前記酸化物の含有量が、前記複合酸化物に対し１〜９０％質量％である、ことを特徴とする、上記（１２）に記載の処理装置。
(1) A) a heating furnace;
B) A granular container that is installed in a heating furnace and has a cylindrical shape with a central axis in a substantially gravitational direction;
C) a cage for holding the granular material in the granular material container from below;
D) a fluid inlet provided near one end of the granular container and a fluid outlet provided near the other end for allowing the fluid to pass through the granular body held in the granular container;
E) a processing apparatus comprising granular material stirring means,
The granular material stirring means includes a lifting unit that includes a cage and moves up and down with the cage, and a horizontal moving unit that contacts the cage and transmits a driving force for lifting to the lifting unit,
The horizontal moving part is
-A claw portion provided in the heating furnace, reciprocating in the horizontal direction in contact with the elevating unit and elevating the elevating unit;
A driving device that is provided outside the heating furnace and reciprocates the claw portion in the horizontal direction; and a connecting shaft that connects the driving device and the claw portion through a wall of the heating furnace;
-Sealing means surrounding the connecting shaft and shielding the granular container from the heating furnace atmosphere;
The claw portion has an upward slope that rises in a direction toward the drive device, and a downward slope that descends in a direction away from the drive device,
The elevating part receives the thrust force that can be generated in the elevating part by the granular material container, and has a position in contact with the upward slope of the claw part and a position in contact with the downward slope of the claw part. And
When the driving device pushes out the claw portion, the upward slope of the claw portion is in contact with the up-and-down portion at a position in contact with the upward slope of the claw portion, and is in contact with the upward slope of the claw portion. The elevating part is slid along the upward slope to give an elevating force to the elevating part, and the elevating part rises along the inner wall of the granular container,
When the driving device pulls back the claw portion, the downward slope of the claw portion is in contact with the downward slope of the claw portion while being in contact with the elevating portion at a position of contact with the downward slope of the claw portion. The elevating part is slid along the downward slope, giving a lowering force to the elevating part in contact with the elevating part, and the elevating part descends along the inner wall of the granular container,
The granular material processing container is a continuous fixed bed catalytic reactor in which a granular catalyst is accommodated as the granular material, a supply fluid is a gas, and a product by a catalytic reaction of the fluid using the catalyst is a product gas and a catalyst. Containing solids that precipitate on top,
A processing apparatus for preventing the deposited solid from being deposited in the catalyst layer and blocking the catalyst layer.
(2) The granule is laminated in the granule container to form a granule layer, and the granule is moved up and down so as to contact the inner wall of the granule container. Processing equipment.
(3) The cage holds the granular material at the tip portions of the plurality of pins, the gap interval between the plurality of pins is set smaller than the size of the particulate catalyst, and the fluid is between the pins. The processing apparatus according to (2) above, wherein the processing apparatus has a structure capable of flowing through the space.
( 4 ) The form which accommodates the said granular catalyst is
A catalyst having a shape having a through-hole in the catalyst;
A plurality of catalysts having through holes in the interior, and a catalyst chain in which the individual catalysts are passed through the through holes with a central rod and aligned in a line;
A plurality of catalyst trains arranged at intervals, and a catalyst fence formed by being fixed to a holding plate,
The processing apparatus according to (1), wherein the holding plate is fixed to the cage.
( 5 ) The elevating part has a fixed pin below the cage, and the position of the elevating part that the downward sloping surface of the claw part contacts when the elevating part descends is the fixed pin of the elevating part. The processing apparatus according to any one of (1) to ( 4 ) above.
( 6 ) The elevating part has a fixing pin below the cage, and the position of the elevating part where the upward slope of the claw part contacts when the elevating part is raised is the fixing pin of the elevating part. The processing apparatus according to any one of (1) to ( 5 ) above.
( 7 ) The elevating part has a downward slope that rises in a direction toward the driving device, facing the upward slope of the claw part, below the cage, and the upward slope of the claw part is raised when the lift part is raised. The position of the raising / lowering part which touches is a downward slope of the said raising / lowering part, The processing apparatus of any one of said (1)-( 5 ) characterized by the above-mentioned.
( 8 ) Any one of the above (1) to ( 7 ), wherein the sealing means is a seal pipe, and a non-reactive gas supply pipe for supplying a non-reactive gas from the outside is connected. The processing apparatus according to item.
( 9 ) The processing apparatus according to any one of (1) to ( 8 ), wherein the claw part is separated from the lifting part and pulled back into the sealing means when the lifting part is not lifted. .
(10) The processing apparatus according to any one of (1) to (9), wherein a speed when the drive mechanism is lowered is faster than a speed when the drive mechanism is raised.
(11) The above (1) to (10), wherein the catalytic reaction fluid is a gas containing hydrocarbon, and the product of the catalytic reaction contains solid hydrocarbon or solid carbon. The processing apparatus of any one of.
(12) The processing apparatus according to (11), wherein the hydrocarbon-containing gas is a tar-containing gas.
(13) The catalyst is a composite oxide including nickel, magnesium, cerium, and aluminum, and includes a composite oxide not including alumina. The composite oxide includes NiMgO, MgAl 2 O 4 , and CeO. The processing apparatus according to (12) above, comprising two crystal phases.
(14) The catalyst is a catalyst made of a composite oxide containing nickel, magnesium, cerium, zirconium, and aluminum, and the composite oxide contains NiMgO, MgAl 2 O 4 , Ce x Zr 1-x O 2 (0 <x <1) The processing apparatus according to (12) above, which contains a crystal phase.
(15) The catalyst is a reforming catalyst for a tar-containing gas that is a composite oxide represented by aM · bNi · cMg · dO,
a, b, and c satisfy a + b + c = 1, 0.02 ≦ a ≦ 0.98, 0.01 ≦ b ≦ 0.97, and 0.01 ≦ c ≦ 0.97,
d is a value at which oxygen and positive elements are electrically neutral;
M is Ti, Zr, Ca, W, Mn, Zn, Sr, Ba, Ta, Co, Mo, Re, platinum, runium, palladium, rhodium, Li, Na, K, Fe, Cu, Cr, La, Pr. , Nd, and at least one element selected from Nd,
At least one oxide selected from silica, alumina, and zeolite is added to the composite oxide, and the content of the oxide selected from silica, alumina, and zeolite is 1 to 90% by mass with respect to the composite oxide. %, The processing apparatus according to (12) above.
以下、「粒状体」を「触媒（粒）」、「流体または粒状体処置装置」を「触媒反応器」を例として説明する。 Hereinafter, that describes a "granulate" and "catalyst (grain)", "fluid or particulate material treating apparatus" as an example "catalytic reactor".
ここで、本発明者が本発明に到達した経緯を説明すると、次のとおりである。 Here, the background of the inventor's arrival at the present invention will be described as follows.
固定床触媒層中の触媒間に生成固体カーボンの堆積する機構
本発明者らの調査の結果、固定床触媒層中の触媒間に生成固体カーボンの堆積する機構は次のとおりであることがわかった。
Mechanism of deposition of generated solid carbon between the catalysts in the fixed bed catalyst layer As a result of our investigation, it was found that the mechanism of deposition of the generated solid carbon between the catalysts in the fixed bed catalyst layer was as follows. It was.
１）固定床触媒層中の隣り合う複数の触媒で形成される触媒間空間において、主流の上流側の隙間から原料ガス（一部改質済み）が流入し、主流の下流側の隙間から改質されたガス（一部は残留した原料ガス）が改質ガスとして流出する。 1) In the inter-catalyst space formed by a plurality of adjacent catalysts in the fixed bed catalyst layer, the raw material gas (partially reformed) flows in from the gap on the upstream side of the mainstream, and is reformed from the gap on the downstream side of the mainstream. The refined gas (a part of the remaining raw material gas) flows out as the reformed gas.
２）触媒間空間に供給された原料ガスが触媒反応によって改質される際、触媒表面で生成した固体カーボンの一部が触媒表面に付着する。 2) When the raw material gas supplied to the inter-catalyst space is reformed by a catalytic reaction, a part of the solid carbon generated on the catalyst surface adheres to the catalyst surface.
３）触媒間空間に供給された原料ガスが触媒反応によって改質される際、触媒表面で生成し、気流によって触媒表面から離脱した固体カーボン微粒子は、上記の既に触媒表面に付着した固体カーボン上に付着して、触媒表面で直径数十μｍから約１ｍｍのカーボン球が成長する。 3) When the raw material gas supplied to the inter-catalyst space is reformed by the catalytic reaction, the solid carbon fine particles generated on the catalyst surface and separated from the catalyst surface by the air flow are on the solid carbon already attached to the catalyst surface. A carbon sphere having a diameter of several tens of μm to about 1 mm grows on the catalyst surface.
４）上記のカーボン球は、時に触媒表面から離脱し、既に存在する他のカーボン球の上に再付着するなどして、触媒表面に多層のカーボン球から構成される厚みが数ｍｍにもおよぶ固体カーボンの堆積層が形成される。 4) The above-mentioned carbon spheres are sometimes detached from the catalyst surface and reattached onto other carbon spheres already present, resulting in a thickness of several millimeters composed of multi-layer carbon spheres on the catalyst surface. A deposited layer of solid carbon is formed.
５）この固体カーボン堆積層は実質的に多孔質であるので、高速のガスが通気する際には大きな圧力損失を生じる。 5) Since this solid carbon deposition layer is substantially porous, a large pressure loss occurs when high-speed gas is vented.
６）特定の触媒間空間での通気抵抗が過大となれば、主流は、他のより通気抵抗の低い触媒間空間を優先的に通気するようになる。但し、固体カーボン堆積層が多孔質であるため、固体カーボンの堆積によって通気抵抗が過大になった空間においても、触媒間空間へのガスの流れが完全に遮断されるわけではなく、触媒表面には低流量で原料ガスが供給され続ける。この結果、触媒表面でのガス改質による固体カーボンの成長は常に進行し続ける（但し、触媒表面での露出面積は減少するので、改質速度は初期に比べて大幅に低下する）。 6) If the ventilation resistance in a specific inter-catalyst space becomes excessive, the mainstream preferentially ventilates other inter-catalyst spaces having lower ventilation resistance. However, since the solid carbon deposition layer is porous, the gas flow to the inter-catalyst space is not completely blocked even in a space where the ventilation resistance is excessive due to the deposition of the solid carbon. The material gas continues to be supplied at a low flow rate. As a result, the growth of solid carbon by gas reforming on the catalyst surface always proceeds (however, since the exposed area on the catalyst surface decreases, the reforming rate is greatly reduced compared to the initial stage).
７）触媒層中の大半の触媒間空間において固体カーボンの堆積が進むと触媒層全体としての圧力損失が過大となり、「閉塞状態」が生じる（触媒反応容器では所与の流量で原料ガスを処理しなければならず、この所与のガス流量時にいずれの触媒間空間を通気しても圧力損失が反応装置の許容値（ガス搬送能力や容器の強度等によって定まる）を超えることが避けられない状態で触媒層は実質的な「閉塞」となる）。 7) When solid carbon deposits in most of the inter-catalyst space in the catalyst layer, the pressure loss of the entire catalyst layer becomes excessive, resulting in a “clogged state” (the raw material gas is processed at a given flow rate in the catalyst reaction vessel). It is inevitable that the pressure loss will exceed the allowable value of the reactor (determined by the gas carrying capacity, container strength, etc.) even if any space between the catalysts is vented at this given gas flow rate. In this state, the catalyst layer is substantially “clogged”).
水素・二酸化炭素・水蒸気・タール含有ガスの改質反応を行い、閉塞を生じた固定床触媒反応容器の触媒表面から固体カーボン堆積層を単独で取り出し、容器の中に入れて軽くシェイクする様な機械的外力を加えると、構成単位であるカーボン球の境界で容易に分離し、粉化した。このような固体カーボンの堆積により閉塞を生じた触媒層から固体カーボンを除去するために、本発明者らは、種々の対策を試みた。 A reforming reaction of hydrogen, carbon dioxide, water vapor, and tar-containing gas is performed, and the solid carbon deposit layer is taken out from the catalyst surface of the fixed bed catalytic reactor that has become clogged, and it is placed in the container and shaken lightly. When mechanical external force was applied, it was easily separated and pulverized at the boundaries of the carbon spheres as the constituent units. In order to remove the solid carbon from the catalyst layer clogged by such solid carbon deposition, the present inventors have tried various measures.
第１の対策（触媒層の逆洗）
第１の対策として、触媒層外部からのブローによる触媒層の逆洗を試みた。詳しく言えば、反応容器内に触媒層の下流側に窒素ガス供給配管を設け、触媒層に対して高速窒素流を噴射して、触媒層の逆洗を試みた。逆洗は、粉塵除去用のフィルタの閉塞時の対策として一般に用いられる手法である。
First countermeasure (backwashing of the catalyst layer)
As a first countermeasure, an attempt was made to backwash the catalyst layer by blowing from the outside of the catalyst layer. More specifically, a nitrogen gas supply pipe was provided in the reaction vessel on the downstream side of the catalyst layer, and a high-speed nitrogen flow was jetted onto the catalyst layer to attempt backwashing of the catalyst layer. Backwashing is a technique that is generally used as a countermeasure when a filter for removing dust is blocked.
結果として、一部の固体カーボンは除去されたが、触媒層の圧力損失の変化は軽微であり、閉塞を解消する効果はなかった。その理由としては、次のことが考えられる。 As a result, a part of the solid carbon was removed, but the change in the pressure loss of the catalyst layer was slight, and there was no effect of eliminating the blockage. The reason is considered as follows.
１）フィルタの場合、上流からフィルタ内に流入した粉塵粒のうち、フィルタの目開きよりも大きいものをその場で捕集する。フィルタは、通常、上流ほど目開きが大きい。従って、フィルタの閉塞部に対して主流の下流側から高速流を供給して逆洗を行う場合、捕集された粉塵粒のうちフィルタの目から離脱したものは、高速気流に搬送されて主流の上流側に進行する際、より大きな目開きを通過するので、メッシュに再捕集されることは少なく、フィルタ外に排出できる。 1) In the case of a filter, dust particles larger than the opening of the filter among dust particles flowing into the filter from upstream are collected on the spot. The filter usually has a larger opening toward the upstream. Accordingly, when backwashing is performed by supplying a high-speed flow from the downstream side of the main flow to the filter block, the collected dust particles separated from the filter eyes are transferred to the high-speed air flow and flowed into the main flow. When traveling to the upstream side of the filter, it passes through a larger mesh, so it is less likely to be collected again by the mesh and can be discharged out of the filter.
一方、本発明が対象とする触媒反応副生物である固体カーボンなどの堆積層は、主流の上流から流入するのではなく、触媒間空間中で、ガスを原料として生成する。このため、堆積カーボンの大きさが触媒間空間の流出入の隙間よりも小さいとは限らないので、そのままでは触媒間空間から流出できない堆積カーボンが多量に存在する。 On the other hand, a deposited layer of solid carbon or the like, which is a by-product of the catalytic reaction of the present invention, does not flow from the upstream of the main stream, but generates gas as a raw material in the space between the catalysts. For this reason, the size of the deposited carbon is not necessarily smaller than the gap between the inflow and the outflow of the intercatalyst space, and there is a large amount of the deposited carbon that cannot flow out from the intercatalyst space as it is.
カーボン堆積層を破壊して微粉化すれば触媒間空間から流出できる可能性がある。しかし、気流が堆積カーボンに与える応力は一般に小さいので（触媒層全体に大きい気圧差を与えても、触媒層中で触媒は、通常多数の層で積載されているので、個々の触媒間空間の入側−出側気圧差は微小となり、大きな応力を堆積カーボンに与えることはできない）、堆積カーボン層を破壊することはできない。 If the carbon deposit layer is destroyed and pulverized, there is a possibility that it can flow out from the space between the catalysts. However, since the stress exerted on the deposited carbon by the airflow is generally small (even if a large pressure difference is given to the entire catalyst layer, the catalyst is usually loaded in many layers in the catalyst layer. The difference between the pressure on the inlet side and the outlet side becomes very small and a large stress cannot be applied to the deposited carbon), and the deposited carbon layer cannot be destroyed.
２）一部のカーボンを除去した時点で、カーボン除去の結果として通気抵抗の小さくなった少数の触媒間空間を連ねた狭い流路が触媒層の中に新たに形成され、主流の大半はこの流路に集中して流れる。この際、新たに形成された流路以外の触媒間空間には気流はほとんど通過しないので、これ以上カーボンが除去されることはない。このため、主流が通過する狭い流路で流速が上昇して大きな圧力損失が生じるので、閉塞状態はあまり改善されない。このように形成された新たな流路も、流路内で新たなカーボンが生成・堆積することよって急速に再閉塞していくので、逆洗の効果は短時間とならざるをえない。その一方、早期に失活を生じた触媒によって構成される（囲まれる）触媒間空間ではこのような触媒間空間の再閉塞を生じない。しかし、そもそも、主流が失活した触媒のみと接触して触媒層を通過するのであれば、ガスの改質を行えないので、触媒反応容器としての性能を発揮できない。 2) When a part of the carbon is removed, a narrow channel that connects a small number of inter-catalyst spaces with reduced ventilation resistance as a result of carbon removal is newly formed in the catalyst layer. Concentrates in the flow path. At this time, since the air flow hardly passes through the space between the catalyst other than the newly formed flow path, no more carbon is removed. For this reason, since the flow velocity increases in a narrow flow path through which the main flow passes and a large pressure loss occurs, the closed state is not improved so much. Since the new flow path formed in this way is re-closed rapidly as new carbon is generated and deposited in the flow path, the effect of backwashing must be short. On the other hand, such inter-catalyst space re-occlusion does not occur in the inter-catalyst space constituted (enclosed) by the catalyst that has deactivated early. However, in the first place, if the main stream comes into contact with only the deactivated catalyst and passes through the catalyst layer, the gas cannot be reformed, so that the performance as a catalyst reaction vessel cannot be exhibited.
これらから、次のように結論することができる。
すなわち、一般に、閉塞を生じた触媒層においては、
［個々の堆積カーボンの大きさ］＞［当該触媒間空間の隙間］
の状態となっており、
［個々の堆積カーボンの大きさ］＜［当該触媒間空間の隙間］
としない限り、触媒層からカーボンを大量に除去することはできず、触媒層外部からのブローによる触媒層の逆洗はこれに有効ではない。
From these, we can conclude as follows.
That is, in general, in a catalyst layer that has clogged,
[Size of individual deposited carbon]> [Gap in the space between the catalysts]
It is in the state of
[Size of individual deposited carbon] <[Gap in the space between the catalysts]
Unless this is true, a large amount of carbon cannot be removed from the catalyst layer, and backwashing of the catalyst layer by blowing from the outside of the catalyst layer is not effective for this.
第２の対策（反応容器外面を槌打）
そこで次に、第２の対策として、反応容器外面を槌打して、堆積カーボン層の破壊、または触媒間空間の拡大を試みた。
Second countermeasure (strike the outer surface of the reaction vessel)
Therefore, as a second countermeasure, the outer surface of the reaction vessel was beaten to try to destroy the deposited carbon layer or expand the space between the catalysts.
結果として、最初の閉塞発生後に槌打（第１回目の槌打）すると、一部の堆積カーボンを除去でき、圧力損失も半分程度に減少し、一定の効果が見られた。この後、再閉塞発生後に再び槌打（第２回目の槌打）すると、堆積カーボンの除去は微小であり、圧力損失の変化はなく、閉塞を回避することはできなかった。すなわち、反応容器外面の槌打は、２回目以降は堆積カーボンの除去に有効でないことがわかった。その理由としては、次のことが考えられる。 As a result, when striking after the first occurrence of clogging (the first striking), a part of the deposited carbon could be removed, the pressure loss was reduced to about half, and a certain effect was seen. Thereafter, when striking again after the occurrence of re-occlusion (second striking), removal of the deposited carbon was minute, there was no change in pressure loss, and clogging could not be avoided. That is, it was found that the strike on the outer surface of the reaction vessel was not effective for removing the deposited carbon after the second time. The reason is considered as follows.
１）通常、触媒を反応容器内に積層する際には上部から単純に落下させるので、触媒層における触媒は最密充填状態にはない。ここに、第１回目の槌打を加えると、振動によって触媒が最密充填あるいはそれに近い状態になる（簡単にするために、以下ではこれを「最密充填化」と称することにする）。最密充填化の過程で触媒間の相対位置は、合計で触媒代表長さの３０％程度の大きさで移動する。この相対位置の移動（即ち、触媒間相対運動）時に、一部の堆積カーボンが触媒との接触応力によって破壊されて小型化するとともに、触媒間の間隔が一時的に広がる瞬間を生じるので、
［個々の堆積カーボンの大きさ］＜［当該触媒間空間の隙間］
の関係が実現されて触媒層中を落下し、遂には触媒層から除去された。
1) Normally, when the catalyst is stacked in the reaction vessel, it is simply dropped from the top, so that the catalyst in the catalyst layer is not in the closest packing state. When the first strike is added here, the vibration causes the catalyst to be close packed or close to it (for the sake of simplicity, this will be referred to as “close packed” below). In the process of close-packing, the relative position between the catalysts moves by a total of about 30% of the catalyst representative length. At the time of this relative position movement (ie, relative movement between the catalysts), a part of the deposited carbon is destroyed by contact stress with the catalyst and becomes smaller, and the interval between the catalysts temporarily increases.
[Size of individual deposited carbon] <[Gap in the space between the catalysts]
The above relationship was realized, and it dropped in the catalyst layer and was finally removed from the catalyst layer.
２）一方、第１回の槌打終了後に触媒層は最密充填化されているので、第２回目以降の槌打を行っても触媒間の相対位置はほとんど変化せず、堆積カーボンの破壊や触媒間の間隔の広がりは生じない。このため、第２回目以降の槌打では堆積カーボンの除去の効果が認められなかった。 2) On the other hand, since the catalyst layer is closely packed after the first strike, the relative position between the catalysts hardly changes even after the second and subsequent strikes, and the deposited carbon is destroyed. Further, there is no widening of the interval between the catalysts. For this reason, the effect of removing the deposited carbon was not recognized in the second and subsequent strikes.
これらから、次のように結論することができる。
すなわち、１回限りの閉塞解消効果では、多くの場合、触媒反応容器における所要処理継続時間を満足できないので、反応容器外面の槌打は堆積カーボンの継続的な除去のためには不十分である。触媒層から堆積カーボンを継続的に除去するためには、
［個々の堆積カーボンの大きさ］＜［当該触媒間空間の隙間］
とした後に、触媒層の最密充填状態を解消する手段が必要である。
From these, we can conclude as follows.
That is, in many cases, the one-time clogging relieving effect cannot satisfy the required processing duration in the catalytic reaction vessel, so that the strike on the outer surface of the reaction vessel is insufficient for the continuous removal of the deposited carbon. . In order to continuously remove deposited carbon from the catalyst layer,
[Size of individual deposited carbon] <[Gap in the space between the catalysts]
After that, a means for eliminating the closest packing state of the catalyst layer is required.
第３の対策（反応容器内での触媒層自体の移動）
前述の結論を踏まえ、第３の対策として、反応容器内での触媒層自体の移動を試みた。より詳しく言えば、静止反応容器の中で触媒が反応容器内壁に接した状態で、触媒層の底に設けた保持器を昇降することによって触媒層全体を昇降させることを試みた。その結果、数回の昇降操作の後、触媒層の昇降運動は安定状態（昇降操作の１サイクルの後、触媒層が当該サイクルの始点の状態に平均的に戻る）に到達する。この安定状態において、保持器の上昇時には触媒層下端の上昇量に対して触媒層上端での上昇量の方が一般に小さく、保持器の下降後には触媒層上下端とも始点の位置に戻る。従って、保持器昇降のサイクル内では、触媒層の平均充填率の変動を生じており（触媒層平均充填率は、保持器上昇時に増大し、保持器下降時には減少する）、触媒層内において少なくとも上下方向での触媒間相対運動が発生する。この保持器昇降時の触媒層の上端と下端の上昇量の差は、触媒層高さ（触媒層上端と下端間の距離）が大きいほど増大し、遂には触媒層上端がほとんど上昇しない状態に至る。この触媒層上端の移動しない状態では、触媒層上端近傍の触媒はそもそも保持器昇降によって移動しないので、触媒間相対運動が生じない。この結果、この領域では触媒間の堆積カーボンを保持器昇降によって除去することはできない。従って、触媒層全体で保持器昇降によって触媒間の堆積カーボンを除去するためには、保持器昇降によって、単に触媒層の平均充填率を変動させるだけでなく、触媒層上端でも十分な昇降ストロークを確保することが必要であることがわかった。
Third measure (movement of the catalyst layer itself in the reaction vessel)
Based on the above conclusion, as a third countermeasure, an attempt was made to move the catalyst layer itself in the reaction vessel. More specifically, an attempt was made to raise and lower the entire catalyst layer by raising and lowering a cage provided at the bottom of the catalyst layer while the catalyst was in contact with the inner wall of the reaction vessel in a stationary reaction vessel. As a result, after several raising / lowering operations, the raising / lowering movement of the catalyst layer reaches a stable state (after one cycle of the raising / lowering operation, the catalyst layer returns to the state of the starting point of the cycle on average). In this stable state, when the cage is raised, the amount of rise at the upper end of the catalyst layer is generally smaller than the amount of rise at the lower end of the catalyst layer, and after the cage is lowered, both the upper and lower ends of the catalyst layer return to the starting position. Therefore, the average packing rate of the catalyst layer fluctuates within the cage ascending / descending cycle (the catalyst layer average packing rate increases when the cage rises and decreases when the cage descends), and at least within the catalyst layer. Relative motion between the catalysts in the vertical direction occurs. The difference between the rising amounts of the upper and lower ends of the catalyst layer when the cage is raised and lowered increases as the catalyst layer height (distance between the upper and lower ends of the catalyst layer) increases, and finally the upper end of the catalyst layer hardly rises. It reaches. In the state where the upper end of the catalyst layer does not move, the catalyst in the vicinity of the upper end of the catalyst layer does not move by raising and lowering the cage in the first place, so that no relative movement between the catalysts occurs. As a result, in this region, the deposited carbon between the catalysts cannot be removed by raising and lowering the cage. Therefore, in order to remove the carbon deposited between the catalysts by raising and lowering the cage in the entire catalyst layer, not only simply changing the average filling rate of the catalyst layer by raising and lowering the cage, but also a sufficient raising and lowering stroke at the upper end of the catalyst layer. It turns out that it is necessary to secure.
図２に、断面積の一定な矩形断面のダクト状反応容器内に触媒を充填して触媒層を形成し、触媒層の下方に保持器を設けて触媒層を保持する機構の装置において、保持器を２７ｍｍ上昇させることにより、静止反応容器内の触媒層を触媒が反応容器内壁に接した状態で５回昇降後の安定状態における、触媒層上端高さの変位として表した触媒層上端高さを示す。縦軸が触媒層上端高さであり、基準となる０ｍｍは、保持器上昇前の触媒層上端の垂直方向の位置に対応している。横軸の触媒層高さ／反応容器厚は、以下において触媒層の「アスペクト比」とも呼ぶ指標であり、反応容器厚は、水平平面における反応容器の代表長さのうちの最短の長さに相当し、例えば、反応容器の水平断面が長方形の場合はその短辺の長さ、円形の場合はその直径に相当する。 Fig. 2 shows a mechanism in which a catalyst layer is formed by filling a catalyst in a duct-shaped reaction vessel having a rectangular cross section with a constant cross-sectional area, and a retainer is provided below the catalyst layer to hold the catalyst layer. The catalyst layer upper end height expressed as a displacement of the catalyst layer upper end height in the stable state after raising and lowering the catalyst layer in the stationary reaction vessel 5 times while the catalyst is in contact with the inner wall of the reaction vessel by raising the vessel by 27 mm Indicates. The vertical axis represents the catalyst layer upper end height, and 0 mm serving as a reference corresponds to the vertical position of the catalyst layer upper end before the cage rises. The catalyst layer height / reaction vessel thickness on the horizontal axis is an index also referred to as “aspect ratio” of the catalyst layer in the following, and the reaction vessel thickness is the shortest of the representative lengths of the reaction vessel in the horizontal plane. For example, when the horizontal cross section of the reaction vessel is rectangular, it corresponds to the length of its short side, and when it is circular, it corresponds to its diameter.
図２から、触媒層のアスペクト比（触媒層高さ／反応容器厚）＞２のとき、触媒層の上昇量（５回の昇降動作後に最終的に認められた昇降開始前の高さからの上昇量）は保持器上昇量（２７ｍｍ）や触媒外寸(直径)１５ｍｍに比べてはるかに小さいことがわかる。これは、保持器上昇時（触媒層上昇時）には触媒充填率が大きくなり、保持器下降時（触媒層下降時）には充填率が小さくなることを意味している。ここで、保持器上昇・下降時とも、下方の触媒ほど移動速度が大きいので、触媒層高さ方向の各触媒の移動速度が異なることから、少なくとも上下方向の触媒間相対運動を生じる。この条件（アスペクト比＞２）では、触媒層上端部の上昇の振幅が小さいので、この部分での触媒間の相対運動は比較的小さく、触媒間の堆積カーボンの排出能力は低い。 From FIG. 2, when the aspect ratio of the catalyst layer (catalyst layer height / reaction vessel thickness)> 2, the amount of rise of the catalyst layer (from the height before the start of raising / lowering finally recognized after five raising / lowering operations) It can be seen that the increase amount is much smaller than the increase amount of the cage (27 mm) and the catalyst outer dimension (diameter) of 15 mm. This means that the catalyst filling rate increases when the cage rises (when the catalyst layer rises) and decreases when the cage descends (when the catalyst layer descends). Here, even when the cage is raised and lowered, the lower the catalyst, the higher the moving speed. Therefore, the moving speed of each catalyst in the catalyst layer height direction is different. Under this condition (aspect ratio> 2), the rising amplitude of the upper end portion of the catalyst layer is small, so the relative motion between the catalysts in this portion is relatively small, and the ability to discharge deposited carbon between the catalysts is low.
それに対し、触媒層のアスペクト比≦２（アスペクト比＝１．８）のときは、触媒層上端の上昇量は保持器上昇量に比べてやや小さい（保持器上昇量２７ｍｍに対し、２０ｍｍの上昇）ことがわかる。即ち、この条件では、触媒層上端でも保持器と同レベルの昇降ストロークを満足し、かつ、保持器昇降による触媒層充填率の変動も確保するという、前記の触媒層全域での触媒間相対運動を実現でき、触媒間の堆積カーボンの排出能力が高い。 On the other hand, when the aspect ratio of the catalyst layer ≦ 2 (aspect ratio = 1.8), the rising amount of the upper end of the catalyst layer is slightly smaller than the rising amount of the cage (an increase of 20 mm with respect to the raising amount of the cage of 27 mm). ) That is, under this condition, the relative movement between the catalysts in the entire catalyst layer is such that the upper and lower strokes of the catalyst layer satisfy the same lifting stroke as that of the cage, and also ensure the fluctuation of the catalyst layer filling rate due to the raising and lowering of the cage. And the ability to discharge deposited carbon between the catalysts is high.
また、このような上下方向の触媒間相対運動の効果に加えて、本発明では、触媒が反応容器内壁に接触した状態で触媒層が昇降することによって、触媒層の厚方向および幅方向にも触媒間相対運動を発生させる効果を発揮できる。即ち、触媒層の昇降に伴う充填率変化の際の触媒間相対位置の変化を考察すると、触媒層厚み方向（反応容器厚み方向に同じ）の各触媒の移動に対する拘束状態が異なる。これは、壁面との摩擦によって、壁面に近い触媒ほど、拘束が大きく、初期の上昇・下降速度が小さいことに起因している。その結果、触媒層厚み方向の各触媒の移動速度が異なるので、触媒間の相対運動を生じる。 In addition to the effect of the relative movement between the catalysts in the vertical direction, in the present invention, the catalyst layer moves up and down while the catalyst is in contact with the inner wall of the reaction vessel, so that the catalyst layer also moves in the thickness direction and the width direction. The effect of generating relative movement between the catalysts can be exhibited. That is, when the change in the relative position between the catalysts during the change in the packing rate accompanying the raising and lowering of the catalyst layer is considered, the restraint state with respect to the movement of each catalyst in the catalyst layer thickness direction (the same in the reaction vessel thickness direction) is different. This is due to the fact that the closer the catalyst is to the wall surface due to friction with the wall surface, the greater the restraint and the lower the initial ascent / descent speed. As a result, the movement speed of each catalyst in the catalyst layer thickness direction is different, so that relative movement between the catalysts occurs.
こうして、反応容器内で触媒を容器内壁に接触させて触媒層自体を昇降させた場合、触媒層の昇降に伴う充填率変化の際の触媒間相対位置の変化は大きくなり、例えば、保持器の昇降ストロークが３０ｍｍの場合、昇降の度に触媒代表長さ（例えば１５ｍｍ）の３０％程度になる。 Thus, when the catalyst layer is brought into contact with the inner wall of the vessel in the reaction vessel and the catalyst layer itself is raised and lowered, the change in the relative position between the catalysts when the filling rate changes accompanying the raising and lowering of the catalyst layer becomes large. When the lifting stroke is 30 mm, it is about 30% of the catalyst representative length (for example, 15 mm) every time the lifting stroke is performed.
前述のように反応容器内で触媒を容器内壁に接触させて触媒層自体を昇降させることにより個々の触媒間の相対位置を移動させ、触媒層全体を撹拌すると、触媒層全域において触媒間に堆積した固体、例えばタール分を含むガスの改質反応の際に堆積するカーボンなどを、効率的に触媒間から落下させて触媒層から除去できることがわかった。 As described above, the catalyst is brought into contact with the inner wall of the reaction vessel in the reaction vessel, and the catalyst layer itself is moved up and down to move the relative position between the individual catalysts. It was found that the solids such as carbon deposited during the reforming reaction of the gas containing tar content can be efficiently dropped from the catalyst and removed from the catalyst layer.
特に、下降時に保持器を触媒層下部の自由落下速度よりも速く、より好ましくは触媒層下端の触媒の自由落下速度よりも速く、下降させると、触媒層下端は保持器から離脱し、保持器下端位置で先に停止した保持器上に触媒が次々と振り積もるので、最密化されていた触媒層であっても、触媒の再配列によって、低充填化することができる。それと同時に、触媒の落下中に触媒間の隙間が極端に大きくなる瞬間を生じ得るので、触媒間に堆積した固体を効率的に除去できる。 In particular, when the cage is lowered when descending, it is faster than the free fall speed of the lower part of the catalyst layer, more preferably faster than the free fall rate of the catalyst at the lower end of the catalyst layer. Since the catalyst is piled up one after another on the cage previously stopped at the lower end position, even if the catalyst layer is close-packed, it can be reduced by reordering the catalyst. At the same time, a moment in which the gap between the catalysts becomes extremely large during the fall of the catalyst can occur, so that the solid deposited between the catalysts can be efficiently removed.
それに対して、保持器と反応容器を同一速度で昇降した場合、触媒層全体は保持器・反応容器と同一速度で昇降するので、触媒間の相対移動は生じない。そのため、触媒表面の固体カーボンなどの除去効果は低い（反応容器外部からの槌打なみ）。また、触媒全体をかご等に入れてかごと触媒層を同時に昇降する場合も同様である。 On the other hand, when the cage and the reaction vessel are moved up and down at the same speed, the entire catalyst layer is moved up and down at the same speed as the cage and the reaction vessel, so that relative movement between the catalysts does not occur. For this reason, the effect of removing solid carbon or the like on the catalyst surface is low (similar to strike from outside the reaction vessel). The same applies to the case where the entire catalyst is put in a car or the like and the car and the catalyst layer are moved up and down simultaneously.
以上から、固定床触媒層内で触媒上に生成・堆積する固体堆積物を除去するためには、触媒層をその保持器とともに、反応容器に対して相対移動させることが必要であることがわかった。そこで、本発明は、粒状体を収容した反応容器内で粒状体を反応容器に対して相対移動させること、すなわち、攪拌する装置を提供するものであり、本発明の処理装置は、その適用範囲は触媒反応装置に限定されないが、触媒層全体の撹拌（個々の触媒間の相対位置を移動させること）を、固体カーボン等の固体生成物が発生する触媒反応に短時間適用することによって、触媒層全域において触媒間に堆積した固体生成物を効率的に触媒間から落下させて触媒層から除去できるという顕著な効果を得ることができるものである。触媒層から除去された固体生成物は、保持器の開口部を通して落下させることができ、落下して下方に溜まった固体生成物は、例えば触媒の交換時などに系外へ排出することができる。 From the above, it was found that in order to remove solid deposits generated and deposited on the catalyst in the fixed bed catalyst layer, it is necessary to move the catalyst layer together with its retainer relative to the reaction vessel. It was. Therefore, the present invention provides a device for moving the granular material relative to the reaction vessel in the reaction vessel containing the granular material, that is, an agitation device. Is not limited to catalytic reactors, but by applying agitation of the entire catalyst layer (moving the relative position between the individual catalysts) to catalytic reactions in which solid products such as solid carbon are generated, It is possible to obtain a remarkable effect that the solid product deposited between the catalysts in the entire layer can be efficiently dropped from between the catalysts and removed from the catalyst layer. The solid product removed from the catalyst layer can be dropped through the opening of the cage, and the solid product that has fallen and accumulated below can be discharged out of the system, for example, when the catalyst is replaced. .
第３の対策、その２（保持器の昇降機構）
本発明では、もう１つの特徴として、粒状体保持器の昇降を行うための駆動機構として、保持器を昇降させる昇降部と、水平方向の往復移動をこの昇降移動に変換する水平移動部とを用いることによって、簡易に保持器を昇降できる機構（請求項に記載した機構）を創作し、採用する。
Third countermeasure, part 2 (lifting mechanism of cage)
In the present invention, as another feature, as a drive mechanism for raising and lowering the granular material holder, an elevation part for raising and lowering the cage and a horizontal movement part for converting horizontal reciprocation into this elevation movement By using it, a mechanism (mechanism described in claims) that can easily raise and lower the cage is created and adopted.
（本発明の昇降機構の利点）
本発明の上記の昇降機構が簡易である理由を以下に説明する。
１）鉛直方向に直接、駆動装置を設ける場合には、処理装置容器の下方に設ける必要があり、以下の配慮が必要になる不利がある。
(Advantages of the lifting mechanism of the present invention)
The reason why the above lifting mechanism of the present invention is simple will be described below.
1) When the drive device is provided directly in the vertical direction, it is necessary to provide it below the processing device container, and there is a disadvantage that the following considerations are required.
一般に重量物である処理装置容器の下方に空間を設けて駆動装置を配置するためには特別な設計上の配慮が必要であり、たとえば、粒状体容器を支える炉体基礎に開渠を設けて、その中に駆動装置を埋め込む等の配慮が必要であり、装置も高価になる。 In general, special design considerations are required to provide a space below the processing equipment container, which is a heavy object, and to arrange the driving device. For example, an open base is provided on the furnace body base that supports the granular container. Therefore, it is necessary to consider such as embedding a driving device in the device, and the device becomes expensive.
また、粒状体層を昇降すると、堆積物等が下方に落下するので、駆動装置に防塵対策が必要であり、特に、粒状体処理装置がカーボン等の生成物を粒状体層中に生成する触媒反応器の場合にその対策が必要である。 Further, when the granular material layer is moved up and down, the deposits and the like fall downward, so the drive device needs to be protected against dust, and in particular, the catalyst that the granular material processing device generates a product such as carbon in the granular material layer. In the case of reactors, countermeasures are necessary.
２）水平方向駆動の場合、駆動軸は、粒状体処理装置炉体のいずれかの側壁を貫通させることによって駆動装置を容易に炉外に配置することができるので、駆動装置に安価な汎用品を用いることができる。 2) In the case of horizontal driving, the drive shaft can be easily placed outside the furnace by penetrating one of the side walls of the granular material processing apparatus furnace body. Can be used.
すなわち、駆動軸は一般に細くてよいので、駆動装置が直接、炉内に開放される場合等に比べて貫通口は比較的小さな大きさでよく、断熱性・シール性の観点から有利であることができる。 That is, since the drive shaft may be generally thin, the through-hole may be relatively small compared to the case where the drive device is directly opened in the furnace, which is advantageous from the viewpoint of heat insulation and sealing properties. Can do.
３）水平移動部の上向き斜面および下向き斜面が昇降部の一部と接触しながら移動することによって、前進時の上昇時に保持器に上昇力を与えるのみでなく、後退時の下降時にも保持器に下降力を与えることができる。 3) The upward slope and the downward slope of the horizontal moving part move while in contact with a part of the lifting part, so that not only the raising force is given to the cage when ascending but also the cage when descending when retreating. Can be given a downward force.
すなわち、保持器上昇時に保持器が粒状体層に噛みこんで、自由落下しなくなることがあるが、重力以上の下向きの力を保持器に付与すれば、このような状態を解消できる。 In other words, when the cage is raised, the cage may bite into the granular layer and may not fall freely, but such a state can be eliminated by applying a downward force more than gravity to the cage.
４）水平移動部の上向き斜面と下向き斜面間に昇降ピンの通過できる切り欠きをもうければ、水平移動部の後退限において昇降部と水平移動部の接触のない状態を実現できる。この後退限で水平移動部がシール管内に収まるように配置すれば、昇降動作を行わない、大部分の時間において、水平移動部を炉内の高温・腐食性の雰囲気・生成物の付着等から保護することができる。また、昇降部を分解することなく、水平移動部のみをシール管を通して処理装置容器内から取り出すことができるので、先端部のみを交換することができる。 4) If there is a notch through which the elevating pin can pass between the upward slope and the downward slope of the horizontal moving part, it is possible to realize a state where the elevating part and the horizontal moving part are not in contact in the retreat limit of the horizontal moving part. If the horizontal moving part is placed in the seal tube at the retreat limit, it does not move up and down, and the horizontal moving part is removed from the high temperature / corrosive atmosphere in the furnace, adhesion of products, etc. for most of the time. Can be protected. Moreover, since only the horizontal moving part can be taken out from the processing apparatus container through the seal tube without disassembling the elevating part, only the tip part can be exchanged.
一方、本発明の方法以外に、以下の方法でも水平移動を昇降運動に変換できるが、それぞれ問題がある。 On the other hand, in addition to the method of the present invention, the horizontal movement can be converted into the vertical movement by the following methods, but each has a problem.
＜比較１：くさびの抜き差しのみによる昇降機構の場合＞
くさびの挿入時には保持器に上昇力を与えられるが、くさびを抜いた場合には、保持器には重力しか付与されない。保持器は、接触する触媒および壁面間との摩擦力によっていわゆる噛み込み現象を生じて、昇降動作の上昇端に保持されて自由落下できなくなる場合があり、この昇降機構の場合、下降時には保持器に接触的な下降力を与えないため、保持器を下降できない問題を生じる。
<Comparison 1: In case of lifting mechanism only by inserting / removing wedge>
When the wedge is inserted, a lifting force is applied to the cage, but when the wedge is removed, only the gravity is applied to the cage. The cage may cause a so-called biting phenomenon due to the friction force between the contacting catalyst and the wall surface, and may be held at the rising end of the lifting operation and cannot be freely dropped. Since the contact lowering force is not applied to the cage, the cage cannot be lowered.
＜比較２：昇降機構としてリンク機構を採用し、水平駆動装置の先端をピン等でリンクに固定することによって、水平移動を昇降に変換する機構＞
水平駆動装置はリンクに固定されているので、水平移動部のみを昇降部から切り離して退避させることはできない問題がある。
<Comparison 2: A mechanism that converts a horizontal movement into a lift by adopting a link mechanism as a lift mechanism and fixing the tip of a horizontal drive device to the link with a pin or the like>
Since the horizontal driving device is fixed to the link, there is a problem that only the horizontal moving unit cannot be separated from the lifting unit and retracted.
＜比較３：ラックアンドピニオン機構による昇降機構＞
この方式の場合、構造が複雑なので、水平移動部のみを昇降部から切り離して退避させることは、困難である。また、水平移動を昇降運動に変換する接触部位の面積が一般に小さく、面圧が高い。高温炉内では、このような部位は、容易に損傷してしまう問題がある。
<Comparison 3: Lifting mechanism by rack and pinion mechanism>
In the case of this method, since the structure is complicated, it is difficult to separate and retract only the horizontal moving unit from the lifting unit. In addition, the area of the contact part that converts the horizontal movement into the up-and-down movement is generally small and the surface pressure is high. In a high temperature furnace, there is a problem that such a part is easily damaged.
タール改質触媒における効果
本発明は、固定床触媒層内で触媒上に生成・堆積する固体生成物の除去に好適に適用することができる。例えば、ニッケル、マグネシウム、セリウム、ジルコニウム、アルミニウムを含む複合金属酸化物触媒によるタール含有ガスの改質反応では、他の反応に比べて触媒表面への固体カーボンの堆積量が多く、それを除去するニーズがより高い。本発明は、このように他の反応に比べ触媒表面への固体カーボンの堆積量が多いタール含有ガス改質反応用の触媒を用いる場合においても、触媒上に生成・堆積する固体生成物の効率的な除去を可能にする。
Effect in Tar Reforming Catalyst The present invention can be suitably applied to the removal of a solid product produced and deposited on a catalyst in a fixed bed catalyst layer. For example, in a reforming reaction of a tar-containing gas with a composite metal oxide catalyst containing nickel, magnesium, cerium, zirconium, and aluminum, the amount of solid carbon deposited on the catalyst surface is larger than other reactions, and it is removed. Needs are higher. In the present invention, the efficiency of the solid product produced / deposited on the catalyst is obtained even when the tar-containing gas reforming catalyst having a large amount of solid carbon deposited on the catalyst surface as compared with other reactions is used. Allows for efficient removal.
移動床との違い
本発明の対象である触媒固定床と異なり、移動床は、原則として反応中に絶えず触媒を移動（および撹拌）させる。それに対し、本発明では、反応容器内での触媒層の移動を間欠的に、短時間実施すればよいので、反応中に触媒撹拌を行う必要はない。さらに、移動床では、反応中に一定量の触媒を系外に排出するとともに同量の触媒を系外から供給する。それに対し、本発明では、反応中に触媒の入れ替えは行わない（触媒層が固定床であるから）。
Difference from moving bed Unlike the fixed catalyst bed which is the subject of the present invention, the moving bed in principle moves the catalyst continuously (and agitates) during the reaction. On the other hand, in the present invention, it is only necessary to intermittently move the catalyst layer in the reaction vessel for a short time, so that it is not necessary to stir the catalyst during the reaction. Further, in the moving bed, a certain amount of catalyst is discharged out of the system during the reaction and the same amount of catalyst is supplied from outside the system. In contrast, in the present invention, the catalyst is not replaced during the reaction (because the catalyst layer is a fixed bed).
本発明によって、容器内に静的に収納された粒状体間の相対位置を効率的に変更する手段が提供される。また、処理装置容器内温度が加熱炉内に設置され、容器内部および周辺が高温である場合（例：６００℃以上）でも、高価なシーリング手段を用いる必要なく、簡易に実施できる上記の装置が提供される。 The present invention provides a means for efficiently changing the relative position between the granules statically stored in the container. In addition, even when the temperature inside the processing apparatus container is set in the heating furnace and the inside and surroundings of the container are high temperature (eg, 600 ° C. or higher), the above apparatus that can be easily implemented without using expensive sealing means is provided. Provided.
以下に添付図面を参照しながら、本発明の好適な実施の形態について詳細に説明する。
なお、本明細書及び図面において、実質的に同一の機能構成を有する構成要素については、同一の符号を付することにより重複説明を省略する。
また、以下では、粒子処理装置として触媒反応器を想定して説明する。したがって、以下の記載において、粒状触媒は粒状体に置き換えて考えることができるものであるが、本発明は触媒反応器に限定されるものではないので、触媒反応器において好適なものとして記載した要件や条件は、本発明においても好適な要件や条件であることができるが、必ずしも本発明あるいは本発明の好適な態様を一般的に限定するものではないことに留意されるべきである。
Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.
In the following description, a catalytic reactor is assumed as the particle processing apparatus. Accordingly, in the following description, the granular catalyst can be considered as a granular material, but the present invention is not limited to the catalytic reactor, and therefore the requirements described as being suitable for the catalytic reactor. It should be noted that the conditions and conditions may be suitable requirements and conditions in the present invention, but do not necessarily limit the present invention or preferred aspects of the present invention in general.
[第１の実施形態]
（全体構造）
図４、５に、本発明の第１の実施形態の連続式固定床触媒反応装置１０を示す。これらの図の（ａ）は平面図、（ｂ）は正面図、（ｃ）は側面図である。図４は触媒保持器が下降したとき、図５は触媒保持器が上昇したときを表わしている。本発明の触媒反応装置１０は、反応容器１１を含み、その内部には、下部を保持器１２によって支持された粒状触媒が堆積された触媒層１３が収容され、触媒層１３中の触媒のうち反応容器内壁に隣接する触媒（図示せず）は反応容器内壁に接触している。本発明では、触媒を反応容器内壁に接触させて触媒層を昇降させるので、昇降作業時の触媒の移動の妨げとならないように、反応容器１１の内面は平滑であることが好ましい。
[First embodiment]
(Overall structure)
4 and 5 show a continuous fixed bed catalytic reactor 10 according to a first embodiment of the present invention. In these drawings, (a) is a plan view, (b) is a front view, and (c) is a side view. FIG. 4 shows a case where the catalyst holder is lowered, and FIG. 5 shows a case where the catalyst holder is raised. The catalytic reaction apparatus 10 of the present invention includes a reaction vessel 11, in which a catalyst layer 13 on which a granular catalyst supported by a cage 12 is deposited is accommodated, and among the catalysts in the catalyst layer 13. A catalyst (not shown) adjacent to the inner wall of the reaction vessel is in contact with the inner wall of the reaction vessel. In the present invention, since the catalyst layer is moved up and down by bringing the catalyst into contact with the inner wall of the reaction vessel, the inner surface of the reaction vessel 11 is preferably smooth so as not to hinder the movement of the catalyst during the lifting operation.
反応容器１１には、下方から原料ガス１４が供給されて触媒層１３で反応し、触媒層１３からの改質ガス１５は反応容器１１の上方から排出される。原料ガス１４の例は、炭化水素を含有するガス、炭化水素とともにタールを含有するガスなどでよい。改質ガス１５の例は、炭化水素を含有するガスを改質して得られる改質ガスなどでよい。触媒の例を挙げると、炭化水素改質用の塊状触媒などでよく、その表面には触媒反応の副生物として固形物、例えば固体カーボンなどが堆積する。触媒反応が吸熱反応の場合、反応に必要な温度と熱を、触媒反応容器１１を例えば加熱炉（図示せず）中に配置することにより、与えてもよい。触媒反応が発熱反応の場合は、反応熱を、触媒反応容器の外部に設けた冷媒流路（図示せず）に冷媒を流すなどにより除去してもよい。場合により、反応容器１１への原料ガスは、図４，５とは逆に、触媒層１３の上方から下方へ流れるように供給することも可能である。 A raw material gas 14 is supplied to the reaction vessel 11 from below and reacts in the catalyst layer 13, and the reformed gas 15 from the catalyst layer 13 is discharged from above the reaction vessel 11. An example of the source gas 14 may be a gas containing hydrocarbons, a gas containing tar together with hydrocarbons, or the like. An example of the reformed gas 15 may be a reformed gas obtained by reforming a gas containing hydrocarbon. As an example of the catalyst, a bulk catalyst for hydrocarbon reforming may be used, and a solid substance such as solid carbon is deposited on the surface as a by-product of the catalytic reaction. When the catalytic reaction is an endothermic reaction, the temperature and heat necessary for the reaction may be provided by placing the catalytic reaction vessel 11 in, for example, a heating furnace (not shown). When the catalytic reaction is an exothermic reaction, the reaction heat may be removed by flowing a refrigerant through a refrigerant flow path (not shown) provided outside the catalytic reaction vessel. In some cases, the raw material gas to the reaction vessel 11 can be supplied so as to flow downward from above the catalyst layer 13, contrary to FIGS.
保持器１２は昇降部１６の一部を構成しており、昇降部１６は水平移動部１９と合わせて保持器の昇降機構（粒状触媒攪拌手段）を構成している。昇降機構（粒状触媒攪拌手段）の水平移動部１９は、爪部２０、駆動装置２１、駆動軸２２、シール管２３からなり、駆動装置２１が駆動軸２１を介して爪部２０を押出し及び引戻すと、爪部２０に設けられた斜面と接する固定ピン１７に上昇力及び下降力が与えられて、触媒保持器１２及び触媒層１３を含む昇降部１６が昇降して、触媒層の粒状触媒を攪拌するものである。 The cage 12 constitutes a part of the lifting / lowering unit 16, and the lifting / lowering unit 16 together with the horizontal moving unit 19 constitutes a lifting / lowering mechanism (granular catalyst stirring means) of the cage. The horizontal moving part 19 of the elevating mechanism (granular catalyst stirring means) includes a claw part 20, a drive device 21, a drive shaft 22, and a seal tube 23. The drive device 21 pushes and pulls the claw part 20 through the drive shaft 21. When returned, the ascending force and the descending force are applied to the fixing pin 17 in contact with the inclined surface provided in the claw portion 20, and the ascending / descending portion 16 including the catalyst holder 12 and the catalyst layer 13 is moved up and down, and the granular catalyst of the catalyst layer Is agitated.
（触媒層の攪拌機構）
本発明では、保持器１２を昇降させることによってその上の触媒層１３を反応容器１１内で昇降させることで、粒状触媒を攪拌することを特徴とする。そのために、本発明の反応容器１１には触媒保持器１２を昇降させる駆動機構が装備される。本発明の触媒層の昇降機構（攪拌手段）は、触媒保持器１２を含む昇降部１６と、水平移動部１９からなる。
(Catalyst layer stirring mechanism)
The present invention is characterized in that the granular catalyst is stirred by raising and lowering the cage 12 to raise and lower the catalyst layer 13 in the reaction vessel 11. For this purpose, the reaction vessel 11 of the present invention is equipped with a drive mechanism for raising and lowering the catalyst holder 12. The catalyst layer elevating mechanism (stirring means) of the present invention includes an elevating unit 16 including a catalyst holder 12 and a horizontal moving unit 19.
昇降部１６は、触媒保持器１２の下方延長部１８に略水平の固定ピン１７を有する。 The elevating part 16 has a substantially horizontal fixing pin 17 in the downward extension 18 of the catalyst holder 12.
一方、水平移動部１９は、固定ピン１７と係合する爪部２０と、駆動軸２２を介して爪部２０を水平移動させる駆動装置２１からなる。駆動装置２１が駆動軸２２を介して爪部２０を押出し及び引き戻すと、爪部２０に設けられた斜面２４、２５が固定ピン１７に上昇力及び下降力を与えて、昇降部１６を上昇及び下降させる。爪部２０の斜面と接する昇降部１６の位置は必ずしも固定ピン１７である必要はなく、爪部２０の斜面と面接触する斜面（保持器側）であってもよい。爪部２０の斜面と接する昇降部１６側の位置（部材）が固定ピン１７でないときは、爪部２０側の斜面も図４、５の斜面と異なることができる。 On the other hand, the horizontal movement part 19 includes a claw part 20 that engages with the fixing pin 17 and a drive device 21 that horizontally moves the claw part 20 via a drive shaft 22. When the driving device 21 pushes and pulls back the claw portion 20 via the drive shaft 22, the slopes 24 and 25 provided on the claw portion 20 apply a rising force and a lowering force to the fixing pin 17, and lift and lower the lifting portion 16. Lower. The position of the elevating / lowering portion 16 in contact with the inclined surface of the claw portion 20 does not necessarily need to be the fixing pin 17 and may be an inclined surface (on the cage side) in surface contact with the inclined surface of the claw portion 20. When the position (member) on the elevating part 16 side that contacts the slope of the claw part 20 is not the fixing pin 17, the slope on the claw part 20 side can also be different from the slopes of FIGS.
爪部２０に設ける斜面は、駆動装置２１から引戻される方向に向かって下降する下向きの斜面（爪側）２４と、駆動装置２１から押出される方向に向かって下降する上向きの斜面（爪側）２５を有する。爪部２０の下向きの斜面（爪側）２４が固定ピン１７と接していて、爪部２０が駆動装置２１から引戻される方向に水平移動すると、爪部２０の下向きの斜面（爪側）２４が固定ピン１７を押下げて昇降部１６に下降力を付与する（図４）。同様に、上向きの斜面（爪側）２５が固定ピン１７と接していて、爪部２０が駆動装置２１から押出される方向に水平移動すると、上向きの斜面（爪側）２５が固定ピン１７を押上げて昇降部１６に上昇力を付与する（図５）。 The inclined surface provided in the claw portion 20 includes a downward inclined surface (claw side) 24 that descends in the direction pulled back from the driving device 21 and an upward inclined surface (claw side) that descends in the direction pushed out from the driving device 21. ) 25. When the downward sloping surface (claw side) 24 of the claw portion 20 is in contact with the fixing pin 17 and the claw portion 20 is horizontally moved in a direction to be pulled back from the driving device 21, the downward sloping surface (claw side) 24 of the claw portion 20 is obtained. Pushes down the fixing pin 17 and applies a downward force to the elevating part 16 (FIG. 4). Similarly, when the upward inclined surface (claw side) 25 is in contact with the fixing pin 17 and the claw portion 20 is horizontally moved in the direction in which it is pushed out from the driving device 21, the upward inclined surface (claw side) 25 causes the fixing pin 17 to move. The lifting force is applied to the elevating part 16 by pushing up (FIG. 5).
爪部２０と駆動装置２１を結ぶ駆動軸２２は、シール管２３によって覆われて、駆動軸２２を加熱炉雰囲気から遮断されている。たとえば、シール管２３内に接続された非反応性ガス供給管２６に非反応性ガス２７を供給して駆動軸２２を加熱炉雰囲気から遮断することができる。 A drive shaft 22 that connects the claw portion 20 and the drive device 21 is covered with a seal tube 23 to isolate the drive shaft 22 from the heating furnace atmosphere. For example, the non-reactive gas 27 can be supplied to the non-reactive gas supply pipe 26 connected in the seal pipe 23 to shut off the drive shaft 22 from the heating furnace atmosphere.
本発明では、触媒反応容器１１は加熱炉（図示せず）内にあるが、駆動装置２１と駆動軸２２の少なくとも一部は加熱炉の外部に設置する。 In the present invention, the catalytic reaction vessel 11 is in a heating furnace (not shown), but at least a part of the driving device 21 and the driving shaft 22 is installed outside the heating furnace.
（昇降部）
昇降部の材質は、耐熱ステンレス鋼や耐熱ニッケル合金等の耐熱金属、黒鉛・窒化ケイ素・炭化ケイ素等のセラミックス、または、石英ガラス等を用いることができる。また、本体を金属製として、爪部の斜面と係合する斜面のみに前記セラミックスや窒化硼素等を取り付け、または、溶射等によって表面処理する等して、耐久性向上や摩擦力低減を図ってもよい。昇降部には保持器が付帯しているが、斜面を形成する部品を保持器の裏面に溶接する等して、保持器と一体構造としてよい。あるいは、独立に昇降可能な昇降部本体を製作して、その上に独立の保持器をネジ等の締結によって装着して全体として昇降部としてもよい。昇降時に昇降部には、爪部が水平移動することによって、正味のスラスト力が負荷される。このため、反応容器内のどこかでこのスラスト力を受ける機構が必要である。本実施形態では、昇降部前後面に設けられたスラスト台車が反応容器内面に押し付けられながら昇降部が昇降する構造となっており、スラスト力は、反応容器内壁面で担う。
固定ピン１７は、構造上、比較的小さな断面積で保持器の上昇力・下降力を担わなければならいので、高温用の高強度・高靭性材料を用いるべきである。耐熱ステンレス鋼や耐熱ニッケル合金等をこれに適用できる。また、表面のみ、昇降部斜面で述べた硬化・高潤滑化するための表面処理を併用してもよい。固定ピン１７の形状は、丸棒が好ましい。少なくとも断面に接触面の移動の妨げとなりうる角部を有しないことが必要である。加工上の便宜から、丸棒を楕円断面や六角形以上の多角形としてもよい。固定ピン１７は昇降部の一部として昇降部本体に溶接することができる。固定ピン１７の軸方向長さは、爪部２０の幅よりも広いことが好ましい。また、固定ピン１７の軸方向長さを昇降部の幅よりも小さくすることができる。図４に示すように、固定ピン１７は昇降部との接続構造によって、昇降物構造物系内に爪部先端の一部が進入可能な空間を構成する。この空間の大きさが大きいほど、爪部の設計許容度が拡大するものの、この空間が過大な場合には、周辺の反応容器をより大きく設定しなければならない。
これらの材料を用いて昇降部を製造する方法には、金属の場合には、例えば、溶接によって、機械加工された部品を接合すればよい。またセラミックスの場合には、最終形状となる型を製作して、型の中でセラミックスを焼成してもよい。
(Elevating part)
As the material of the elevating part, heat-resistant metals such as heat-resistant stainless steel and heat-resistant nickel alloy, ceramics such as graphite, silicon nitride, and silicon carbide, or quartz glass can be used. In addition, the body is made of metal, and ceramics, boron nitride, etc. are attached only to the slope that engages the slope of the claw part, or surface treatment is performed by thermal spraying, etc. to improve durability and reduce frictional force. Also good. A cage is attached to the elevating / lowering portion, but a structure that forms an inclined surface may be integrated with the cage by, for example, welding a part forming a slope to the back surface of the cage. Alternatively, it is also possible to manufacture an elevating part main body that can be moved up and down independently, and attach an independent cage thereon by fastening screws or the like to form an elevating part as a whole. A net thrust force is applied to the elevating unit when the elevating unit moves up and down as the claw portion moves horizontally. For this reason, a mechanism for receiving this thrust force somewhere in the reaction vessel is necessary. In this embodiment, the elevating part moves up and down while thrust carts provided on the front and rear surfaces of the elevating part are pressed against the inner surface of the reaction vessel, and the thrust force is borne by the inner wall surface of the reaction vessel.
Since the fixing pin 17 must bear the ascending / descending force of the cage with a relatively small cross-sectional area, a high-strength and high-toughness material for high temperature should be used. Heat resistant stainless steel, heat resistant nickel alloy, etc. can be applied to this. Further, only the surface may be used in combination with the surface treatment for hardening and high lubrication described in the slope of the elevating part. The shape of the fixing pin 17 is preferably a round bar. It is necessary that at least the cross section does not have corners that may hinder the movement of the contact surface. For convenience of processing, the round bar may be an elliptical cross section or a polygon more than a hexagon. The fixing pin 17 can be welded to the lifting part main body as a part of the lifting part. The axial length of the fixing pin 17 is preferably wider than the width of the claw portion 20. Further, the axial length of the fixing pin 17 can be made smaller than the width of the elevating part. As shown in FIG. 4, the fixing pin 17 constitutes a space in which a part of the tip of the claw part can enter into the lifted object structure system by a connection structure with the lift part. As the size of this space increases, the design tolerance of the claw portion increases. However, if this space is excessive, the surrounding reaction vessel must be set larger.
In the method of manufacturing the lifting part using these materials, in the case of metal, for example, a machined part may be joined by welding. In the case of ceramics, a mold having a final shape may be manufactured and the ceramics may be fired in the mold.
（爪部）
爪部２０の構造は、図４に示すものが典型的なものであり、先端に開口を有する貫通溝を備え、下面は水平で反応容器または流入管の底面上をスライド移動でき、上面には傾斜面が設けられている構造である。貫通溝は水平面に対して傾斜を有しており、この溝の表面が昇降部の固定ピン１７と係合しつつスライド移動できる。爪部の傾斜は、このように１つ以上の上向き傾斜面（図４では、貫通溝の下側の面）と１つ以上の下向き傾斜面（図４では、貫通溝の上側の面）を備える。尚、本実施例では、爪部の上面は必ずしも傾斜面である必要はない。
昇降部の斜面と係合する斜面の傾斜については、傾斜の小さいほど、より小さな駆動軸推力で所要とされる保持器昇降推力を満足できる。但し、この傾斜が小さいほど、駆動軸の所要ストロークを長く設定する必要があり設備が大型化する。従って、この傾斜については、所要保持器推力、所要保持器ストローク、駆動軸の許容推力、駆動軸の許容ストローク、並びに、適用される材料強度等を考慮して、エンジニアリング的に決定すべきである。例えば、この斜面の勾配を２°以上１５°以下とすることができる。この斜面は平面、かつ、平滑であることが好ましい。但し、昇降部との衝突時の衝撃を低減するために、微小な曲率の凸面としてもよい。斜面の表面に窒化硼素ベースのペースト等の固体潤滑剤等の潤滑剤を付与して摩擦低減を図ってもよい。固定ピンの傾斜を抑制するため、また、強度を確保する点から、爪の幅は大きいことが好ましい。しかし、過大な爪の幅を設定した場合、昇降部と固定ピンで形成される爪進入用の孔の所要寸法が大型化して装置の巨大化を招くので、避けるべきである。また、爪部２０の上面と貫通溝の上側の面に挟まれた部位には片持ち荷重が負荷されるので、強度確保のために十分な断面積を確保すべきである。例えば、１００ｍｍ２以上の断面積とすることが好ましい。但し、過大な断面積とした場合には、昇降部とピンで構成される爪部先端の進入空間で必要とされる区間寸法も増大して設備が巨大化する問題があるので避けるべきである。貫通溝の溝幅は、固定ピン１７が容易に通過できる寸法とすべきである。温度差による熱膨張差等の影響も考慮して、貫通溝の溝幅は、固定ピンの直径よりも１ｍｍ程度以上大きくすることができる。貫通溝の長さは、駆動軸のストロークよりも長く設定すべきである。前記傾斜面は、平坦、かつ、平滑であることが好ましいが、昇降部との衝突による衝撃を低減するために、微小な曲率の凸面としてもよい。爪部２０の材質には昇降部に記載したものと同様の材料を用いることができる。製造方法にも昇降部と同様の方法を適用することができる。
(Nail part)
The structure of the claw portion 20 is a typical structure shown in FIG. 4. The claw portion 20 has a through groove having an opening at the tip, and the bottom surface is horizontal and can slide on the bottom surface of the reaction vessel or the inflow pipe. In this structure, an inclined surface is provided. The through groove has an inclination with respect to the horizontal plane, and the surface of the groove can slide while engaging with the fixing pin 17 of the elevating part. In this way, the inclination of the claw portion includes one or more upward inclined surfaces (the lower surface of the through groove in FIG. 4) and one or more downward inclined surfaces (the upper surface of the through groove in FIG. 4). Prepare. In the present embodiment, the upper surface of the claw portion is not necessarily an inclined surface.
As for the inclination of the inclined surface engaged with the inclined surface of the lifting / lowering unit, the smaller the inclination, the more the cage lifting / lowering thrust required with a smaller driving shaft thrust can be satisfied. However, the smaller this inclination, the longer the required stroke of the drive shaft, and the larger the equipment. Therefore, this inclination should be determined engineeringly in consideration of the required cage thrust, the required cage stroke, the allowable thrust of the drive shaft, the allowable stroke of the drive shaft, the applied material strength, etc. . For example, the slope of the slope can be 2 ° or more and 15 ° or less. This slope is preferably flat and smooth. However, in order to reduce the impact at the time of collision with the elevating part, it may be a convex surface with a minute curvature. Friction reduction may be achieved by applying a lubricant such as a solid lubricant such as a boron nitride-based paste to the surface of the slope. In order to suppress the inclination of the fixing pin and to ensure the strength, it is preferable that the width of the nail is large. However, if an excessive claw width is set, the required size of the claw entry hole formed by the elevating part and the fixing pin is increased, resulting in an enlargement of the apparatus, and should be avoided. Further, since a cantilever load is applied to a portion sandwiched between the upper surface of the claw portion 20 and the upper surface of the through groove, a sufficient cross-sectional area should be ensured to ensure strength. For example, the cross-sectional area is preferably 100 mm 2 or more. However, if the cross-sectional area is too large, there is a problem that the size of the section required in the entry space at the tip of the claw part composed of the lifting part and the pin is increased and there is a problem that the equipment becomes enormous and should be avoided. . The groove width of the through groove should be a dimension that allows the fixing pin 17 to pass easily. Considering the influence of the difference in thermal expansion due to the temperature difference, the groove width of the through groove can be made about 1 mm or more larger than the diameter of the fixing pin. The length of the through groove should be set longer than the stroke of the drive shaft. The inclined surface is preferably flat and smooth, but may be a convex surface having a minute curvature in order to reduce an impact caused by a collision with the elevating part. The material of the claw part 20 can be the same material as that described in the elevating part. A method similar to that of the lifting unit can also be applied to the manufacturing method.
（駆動装置）
駆動装置２１は常温である加熱炉外に設置されるので、駆動装置には繰り返し往復運動可能な市販の各種装置を適用することができる。例えば、複動式のものを前提として、エアシリンダ、油圧シリンダ、電動や油圧ジャッキ、あるいは、ネジ式のリニアガイド、リニアモータ等を用いることができる。駆動装置２１のストロークは、昇降部の所要昇降ストロークと爪部の斜面の勾配によって決定する。例えば、１０〜５００ｍｍのストロークとすることができる。駆動装置２１作動時の移動速度は、昇降部の所要昇降速度と爪部の斜面の勾配によって決定する。駆動装置２１の押し出し時（昇降部の上昇時）には低速で、駆動装置２１の引き抜き時（昇降部の下降時）には高速で移動することができる。速度の調整のためには、市販のスピードコントローラ等を用いればよい。例えば、駆動速度を１〜１００ｍｍ／ｓとすることができる。駆動装置の操作は、手動操作、または、自動制御によって行うことができる。
(Driver)
Since the drive device 21 is installed outside the heating furnace at room temperature, various commercially available devices capable of reciprocating motion can be applied to the drive device. For example, on the premise of a double acting type, an air cylinder, a hydraulic cylinder, an electric or hydraulic jack, a screw type linear guide, a linear motor, or the like can be used. The stroke of the drive device 21 is determined by the required lifting stroke of the lifting part and the slope of the claw slope. For example, the stroke can be 10 to 500 mm. The moving speed when the driving device 21 operates is determined by the required lifting speed of the lifting part and the slope of the claw part. It can move at a low speed when the drive device 21 is pushed out (when the elevating part is raised) and at a high speed when the drive device 21 is pulled out (when the elevating part is lowered). In order to adjust the speed, a commercially available speed controller or the like may be used. For example, the driving speed can be set to 1 to 100 mm / s. The driving device can be operated manually or by automatic control.
（駆動軸）
駆動軸２２は、棒状であるべきであり、シール性を考慮して丸棒であることが好ましい。駆動軸２２は、加熱炉を貫通して設置されるので、高温に耐えるとともに、炉内外の温度差に対しても耐久性を有することが必要であり、駆動時には衝撃力も生じうるので、強度・靭性も必要である。耐熱ステンレス鋼や耐熱ニッケル合金を用いることができる。
(Drive shaft)
The drive shaft 22 should be rod-shaped and is preferably a round bar in consideration of sealing performance. Since the drive shaft 22 is installed through the heating furnace, it needs to withstand high temperatures and have durability against temperature differences between the inside and outside of the furnace. Toughness is also necessary. Heat resistant stainless steel or heat resistant nickel alloy can be used.
（シール部）
シール部は、加熱炉を貫通して内部で駆動軸の往復運動が可能であり、かつ、反応容器内ガスの外部への漏出、若しくは、外気の反応容器内への進入を防止できるものであればどのような構造のものでも適用できる。加熱炉を貫通する円管等を用いることができる。図４の例では、円管の両端は、加熱炉内の反応装置の流入管および加熱炉外の駆動装置とそれぞれフランジ接続されている。シール部は、加熱炉内の部分では加熱・保温されて高温に維持され、加熱炉外の部分では配管はむき出しに放冷されて少なくとも駆動装置２１との接続部においては常温となっている。フランジ部のシールは、市販のシール剤を塗布した市販の高温用ガスケットを用いることで、ほぼ完全な封止を実現できる。また、必須機能ではないが、タールを含む原料ガスがシール部の低温部に進入するとシール部内面や駆動軸表面に多量のタールが凝縮して駆動の妨げとなりうるので、シール部には外部から非反応性ガス２７（アルゴン等）を、小流量（例えば、０.００１ｍ３／ｍｉｎ以上、かつ、原料ガス流量の５％以下の流量）で供給するガス供給管をシール部に接続して、シール部内を非反応性ガスで満たしてもよい。外部からシール部に供給された非反応性ガスは反応容器内に放出されるが、原料ガスの流入量に比べて、非反応性ガス流量を十分に小さく設定することで作業上の問題を回避できる。
(Seal part)
The seal portion should be capable of reciprocating the drive shaft inside through the heating furnace and preventing leakage of gas in the reaction vessel to the outside or entry of outside air into the reaction vessel. Any structure can be applied. A circular pipe or the like penetrating the heating furnace can be used. In the example of FIG. 4, both ends of the circular pipe are flange-connected to the inflow pipe of the reaction apparatus in the heating furnace and the driving apparatus outside the heating furnace, respectively. The seal part is heated and kept warm at the part inside the heating furnace and kept at a high temperature, and the pipe is barely cooled at the part outside the heating furnace, and is at room temperature at least at the connection part with the driving device 21. The flange part can be sealed almost completely by using a commercially available high temperature gasket coated with a commercially available sealing agent. In addition, although it is not an essential function, if a raw material gas containing tar enters the low temperature part of the seal part, a large amount of tar may condense on the inner surface of the seal part or the surface of the drive shaft, which may hinder driving. A gas supply pipe for supplying the non-reactive gas 27 (such as argon) at a small flow rate (for example, a flow rate of 0.001 m 3 / min or more and 5% or less of the raw material gas flow rate) is connected to the seal portion; The seal portion may be filled with a non-reactive gas. Non-reactive gas supplied from the outside to the seal is released into the reaction vessel, but avoiding operational problems by setting the non-reactive gas flow rate sufficiently small compared to the inflow of raw material gas it can.
（反応容器の形状）
反応容器１１は、両端に開口を有し、これらの開口間に触媒を収納できるものであればどのような形状でもよい。一方の端部の開口は、触媒反応用流体（原料ガス）の流入路を構成する供給管（流入管）２８に通じており、触媒反応用の原料ガスの反応容器１１への流入口に当たるものである。他端の開口は、反応容器１１の改質ガスの流出路を構成する排出管２９に通じており、改質ガスの反応容器１１からの流出口に当たるものである。反応容器１１は、例えば、円筒状、角型ダクト状などの形状であることができる。以下では、角型ダクト状の反応容器を例に説明する。
(Reaction vessel shape)
The reaction vessel 11 may have any shape as long as it has openings at both ends and can accommodate a catalyst between these openings. The opening at one end communicates with a supply pipe (inflow pipe) 28 that constitutes an inflow path for the catalytic reaction fluid (raw material gas), and corresponds to the inlet of the catalytic reaction raw material gas to the reaction vessel 11. It is. The opening at the other end leads to a discharge pipe 29 that constitutes an outflow path for the reformed gas in the reaction vessel 11 and corresponds to an outlet of the reformed gas from the reaction vessel 11. For example, the reaction vessel 11 may have a cylindrical shape, a rectangular duct shape, or the like. Hereinafter, a rectangular duct-shaped reaction vessel will be described as an example.
以下の説明において、「容器の中心軸」とは、容器の水平断面の図心を鉛直方向に連ねたものと定義する。「反応容器厚」は、水平断面における反応容器の代表長さのうちの最小の長さに相当し、「反応容器幅」は、水平平面における反応容器の代表長さのうちの最大の長さに相当する。容器が円筒の場合には、容器の「幅」および「厚」を「直径」と置き換えればよい。 In the following description, the “center axis of the container” is defined as a centroid of a horizontal section of the container connected in the vertical direction. “Reaction vessel thickness” corresponds to the minimum length of the representative length of the reaction vessel in the horizontal section, and “Reaction vessel width” is the maximum length of the representative length of the reaction vessel in the horizontal plane. It corresponds to. When the container is a cylinder, the “width” and “thickness” of the container may be replaced with “diameter”.
（反応容器の材質）
反応容器１１の材質は、触媒を保持する強度、触媒反応に関与する流体への耐熱・耐食性、反応生成物への耐汚染性を有する材料であれば、どのようなものでも使用できる。例えば、炭素鋼、ステンレス鋼、ニッケル合金、銅、銅合金、アルミニウム、アルミニウム合金、チタン、チタン合金等の金属材料、シリカ、アルミナ、窒化ケイ素、炭化ケイ素等のセラミックス材料（煉瓦に加工されたものを含む）、ソーダガラス、溶融石英等のガラス材料を使用することができる。
(Reaction vessel material)
Any material can be used as the material of the reaction vessel 11 as long as it has strength to hold the catalyst, heat resistance / corrosion resistance to the fluid involved in the catalyst reaction, and contamination resistance to the reaction product. For example, carbon steel, stainless steel, nickel alloy, copper, copper alloy, aluminum, aluminum alloy, titanium, titanium alloy and other metal materials, silica, alumina, silicon nitride, silicon carbide and other ceramic materials (those processed into bricks) Glass materials such as soda glass and fused silica can be used.
（反応容器の寸法）
反応容器の厚みは、下限が塊状触媒の代表寸法（例：直径）以上でなければならない（例えば、１０ｍｍ）。一般に触媒反応では発熱または吸熱があり、かつ、反応容器の表面を通じてこれらの熱を外部と授受するため、触媒反応容器内部まで伝熱を確保するために、厚みには上限が存在する。上限の値は、反応熱・流量・伝熱特性等によってエンジニアリング的に定めればよい（例えば、２００ｍｍあるいは５００ｍｍ）。
(Reaction vessel dimensions)
The lower limit of the thickness of the reaction vessel must be equal to or larger than the representative dimension (eg, diameter) of the bulk catalyst (for example, 10 mm). In general, in the catalytic reaction, heat is generated or absorbed, and the heat is transferred to the outside through the surface of the reaction vessel. Therefore, there is an upper limit on the thickness in order to ensure heat transfer to the inside of the catalytic reaction vessel. The upper limit value may be determined in terms of engineering by reaction heat, flow rate, heat transfer characteristics, etc. (for example, 200 mm or 500 mm).
反応容器の幅には、機能上、特段の制約はない。保持すべき触媒層体積、反応容器厚を基に、構造上・強度上の制約を考慮してエンジニアリング的に定めればよい（例えば、５０００ｍｍ）。 There is no particular limitation on the width of the reaction vessel in terms of function. Based on the volume of the catalyst layer to be retained and the thickness of the reaction vessel, it may be determined from an engineering viewpoint (for example, 5000 mm) in consideration of structural and strength constraints.
反応容器の高さは、触媒層の高さよりも大きくなければならない。一方、反応容器高さの上限については、機能上の制約はなく、構造上・強度上の制約を考慮してエンジニアリング的に定めればよい（例えば、５０００ｍｍ）。 The height of the reaction vessel must be greater than the height of the catalyst layer. On the other hand, the upper limit of the reaction vessel height is not limited in terms of function, and may be determined in terms of engineering in consideration of structural and strength limitations (for example, 5000 mm).
（触媒層の保持器）
触媒層１３を支持する保持器１２には、網、パンチングメタル、複数の棒を用いて棒の間に空間を生じるように水平方向に各棒を互いに平行に並べて棒の両端を固定したもの等を用いることができる。
(Catalyst layer cage)
The cage 12 that supports the catalyst layer 13 includes a net, punching metal, a plurality of rods, the rods arranged in parallel to each other in a horizontal direction so as to create a space between the rods, and the like. Can be used.
（触媒層の好適な保持）
粒子状触媒を複数のピンの先端部で保持し、触媒反応用流体が当該ピンの間の空間を流通できる構造を有する触媒保持手段が好ましい。図５に、複数のピン１２ａの一端を底板１２ｂで固定して作製したもので、ピン１２ａの先端で粒状触媒を保持する好適な保持器の例を示す。
(Suitable retention of catalyst layer)
A catalyst holding means having a structure in which the particulate catalyst is held at the tip portions of a plurality of pins and the catalyst reaction fluid can flow through the space between the pins is preferable. FIG. 5 shows an example of a suitable cage that is produced by fixing one end of a plurality of pins 12a with a bottom plate 12b and holds the granular catalyst at the tip of the pin 12a.
保持器においてピンの間の隙間間隔を粒子状触媒の大きさより小さく設定することで、これらのピンの先端部で粒子状触媒を保持することが可能であり、ピン間の隙間が原料流体の流入口または改質流体の流出口として機能する。 By setting the gap interval between the pins smaller than the size of the particulate catalyst in the cage, it is possible to hold the particulate catalyst at the tip of these pins, and the gap between the pins causes the flow of the raw material fluid to flow. It functions as an inlet or outlet for reforming fluid.
この触媒保持器では、ピンは同じ形状であるが、必ずしも同じ形状である必要はない。塊状触媒をピンの先端部で保持し、ピンの間の間隙を流体が流通できればよく、ピンの大きさも長さも角度も同じでなくてよいし、ピンは直線状に限定されるものでもない。
この触媒保持器では、ピンの先端は同一平面を形成しているが、ピンの先端が形成する面が曲面状であったり、例外的に一部のピンが先端を形成する面から突き出ていてもよい。
In this catalyst holder, the pins have the same shape, but need not necessarily have the same shape. It is only necessary to hold the massive catalyst at the tip of the pin and allow fluid to flow through the gap between the pins, and the size, length, and angle of the pins need not be the same, and the pins are not limited to a straight line.
In this catalyst holder, the tip of the pin forms the same plane, but the surface formed by the tip of the pin is a curved surface, or exceptionally, some pins protrude from the surface forming the tip. Also good.
このような触媒保持器によれば、高い開口率と閉塞の防止が実現される。 According to such a catalyst holder, a high opening ratio and prevention of clogging are realized.
（触媒保持器のピン配置）
触媒保持器のピンの配置をピンの先端側から見た図（ピンの軸に垂直な平面）において、ピンの軸に垂直な平面上でのピンの中心を頂点とし、隣り合う３本のピンの中心で構成される三角形が、全て合同な二等辺三角形、特に正三角形であることが好ましい。それによって保持すべき触媒の所要断面積に対して最小のピン数で触媒保持構造を実現できる。
(Catalyst cage pin arrangement)
In the figure showing the arrangement of the pins of the catalyst cage as seen from the tip end side (plane perpendicular to the pin axis), three adjacent pins with the center of the pin on the plane perpendicular to the pin axis as the apex It is preferable that all the triangles formed by the centers of is an isosceles triangle, particularly a regular triangle. As a result, a catalyst holding structure can be realized with a minimum number of pins for the required cross-sectional area of the catalyst to be held.
全てのピンは、ピンの中心軸が互いに平行に配置されることが好ましい。ピン側面での開口が均一になり、より、閉塞しにくくなるからである。ピン軸間が極端に近接する部位ではピン側面間で閉塞を生じやすい。ピンが平行な部分の長さはピン間の間隙が閉塞しないで原料流体や改質流体が自由に流通できる空間を形成するように決められる。 All the pins are preferably arranged so that the central axes of the pins are parallel to each other. This is because the opening on the side surface of the pin becomes uniform and becomes more difficult to close. In a region where the pin shafts are extremely close to each other, blockage between the pin side surfaces is likely to occur. The length of the portion where the pins are parallel is determined so as to form a space in which the raw material fluid and the reformed fluid can freely flow without closing the gap between the pins.
設計上の便宜等がある場合には、触媒方向に向けて中心軸間の距離が徐々に広がる、または、狭まる等のように設定して、必ずしも平行でなくてもよい。同様に、ピンの中心軸は平行であるが、ピン間の間隔は徐々に広がる、または、狭まる等のように設定してもよい。
ピンが略平行な部分の長さはピン間の間隙が閉塞しないで反応流体が自由に流通できる空間を形成するように決められる。
When there is a design convenience, the distance between the central axes gradually increases or decreases toward the catalyst direction and does not necessarily have to be parallel. Similarly, although the central axes of the pins are parallel, the interval between the pins may be set so as to gradually widen or narrow.
The length of the portion where the pins are substantially parallel is determined so as to form a space in which the reaction fluid can freely flow without closing the gap between the pins.
（保持器におけるピン間の間隔）
ピン間の間隔は下記不等式を満たすことが望ましい。
［ピンの軸間距離］−［ピンの外径寸法］＜[触媒の通過しうる最小のメッシュ目開き寸法]
［ピンの外径寸法］： ピンの外径寸法は、２つのピンの軸間における半径（ピンの軸から外径までの距離）の合計、好ましい円筒ピンの配列ではピンの直径になる。
「メッシュ」： 篩の目のこと。
「目開き寸法」： 正方形の開口を前提とした、ＪＩＳ等の一般的な定義に基づくが、本発明においては、単一の触媒塊外形の代表寸法（直径、高さ等）のうち、最小のものに相当する。
(Distance between pins in cage)
The spacing between pins preferably satisfies the following inequality.
[Pin-axis distance]-[Pin outer diameter] <[Minimum mesh opening size through which catalyst can pass]
[Outer Diameter of Pin]: The outer diameter of the pin is the sum of the radii between the axes of the two pins (distance from the axis of the pin to the outer diameter), which is the diameter of the pin in the preferred cylindrical pin arrangement.
"Mesh": A sieve eye.
“Aperture size”: Based on the general definition of JIS, etc., assuming a square opening, but in the present invention, the smallest of the representative dimensions (diameter, height, etc.) of a single catalyst mass outer shape Corresponds to
すなわち、全てのピンの直径（外径寸法）を除いた軸間距離が、特に触媒保持器の頂部（ピン先端部）において、触媒の通過しうる最小のメッシュ目開き寸法より小さければ、触媒塊子はピンの間を落下することはなく、これらのピンで支持されることができる。触媒の破損により生じた触媒の小片のように、例外的に一部の触媒寸法がピンの直径を除いた軸間距離より小さくて、ピンの間を落下することがありうるが、触媒保持器１８の下部および下方に十分な落下物の貯留空間を設けることによって、少なくとも触媒反応容器閉塞の観点からは特に問題ではない。
通気性および保持器の耐閉塞性の観点から、通気の主流方向垂直断面での開口率（１−［ピン断面積の合計］／［流路の見かけ断面積］）は、９０％以上であることが好ましい。開口率の上限は、ピンの耐座屈性等から定まる個々のピンの断面積から制約される。
That is, if the distance between the shafts excluding the diameters (outer diameters) of all the pins is smaller than the minimum mesh opening size through which the catalyst can pass, particularly at the top part (pin tip part) of the catalyst cage, the catalyst mass The child does not fall between the pins and can be supported by these pins. Some catalyst dimensions are exceptionally smaller than the distance between the axes excluding the pin diameter, such as a small piece of catalyst caused by catalyst failure, but may fall between the pins. By providing sufficient storage space for falling objects below and below 18, there is no particular problem at least from the viewpoint of clogging the catalytic reaction vessel.
From the viewpoint of air permeability and resistance to blockage of the cage, the opening ratio (1- [total pin cross-sectional area] / [apparent cross-sectional area of the channel]) in the vertical cross section in the main flow direction of the air flow is 90% or more. It is preferable. The upper limit of the aperture ratio is restricted by the cross-sectional area of each pin determined from the buckling resistance of the pin.
保持器１２の開口率が小さくなると、通気性や固体カーボンなどの通過性が悪化する。高開口率では、保持器で触媒を保持する部位が少なくなるで、保持器の強度が不足する。上記いずれかの形式の保持器の場合、保持器１２の開口率は３０〜７０％程度が好ましい。 When the opening ratio of the cage 12 becomes small, the air permeability and the permeability of solid carbon and the like deteriorate. When the aperture ratio is high, the number of parts for holding the catalyst in the cage decreases, and the strength of the cage is insufficient. In the case of any of the above types of cages, the aperture ratio of the cage 12 is preferably about 30 to 70%.
保持器１２の材質は、耐熱・耐腐食性・強度を備えた金属材料が好ましい。そのような金属材料の例として、ステンレス鋼、ハステロイ（登録商標）やインコネル（登録商標）等のＮｉ合金、チタン、チタン合金等を挙げることができる。 The material of the cage 12 is preferably a metal material having heat resistance, corrosion resistance, and strength. Examples of such metal materials include stainless steel, Ni alloys such as Hastelloy (registered trademark) and Inconel (registered trademark), titanium, titanium alloys, and the like.
（保持器の昇降ストローク）
触媒間の相対運動を十分行うためには、保持器１２の昇降ストロークは大きいことが好ましい。例えば、触媒外面の代表寸法（例：直径）の０．１倍程度の昇降ストロークであっても加振の効果は存在するので、触媒表面の固体カーボンなどの堆積物の除去効果は一定程度は得られる。とは言え、十分な堆積物除去効果を挙げるためには、保持器１２の昇降ストロークは触媒外面代表寸法の０．５倍以上であることが好ましく、１倍以上であることがより好ましい。
(Climbing stroke of cage)
In order to sufficiently perform the relative movement between the catalysts, it is preferable that the raising / lowering stroke of the cage 12 is large. For example, even with a lifting stroke of about 0.1 times the representative dimension (eg, diameter) of the outer surface of the catalyst, there is an effect of vibration, so that the removal effect of deposits such as solid carbon on the catalyst surface is to a certain extent. can get. However, in order to obtain a sufficient deposit removal effect, the raising / lowering stroke of the cage 12 is preferably 0.5 times or more, more preferably 1 time or more, of the catalyst outer surface representative dimension.
一方、昇降ストロークが極端に大きい場合には、反応容器１１および駆動機構２２が大型化するので効率的ではない。また、小さいストローク（但し、１倍以上）の昇降を繰り返し行うことで、より大きな昇降ストロークと同様の効果が得られる。よって、昇降ストロークは、触媒外面の代表寸法の１０倍以下であることが好ましい。 On the other hand, when the lift stroke is extremely large, the reaction vessel 11 and the drive mechanism 22 are increased in size, which is not efficient. Moreover, the effect similar to a bigger raising / lowering stroke is acquired by repeatedly raising / lowering a small stroke (however, 1 times or more). Therefore, the lifting stroke is preferably 10 times or less of the representative dimension of the catalyst outer surface.
（昇降速度）
保持器１２とともに触媒層１３を上昇させるのに要する所要上昇力は、上昇速度が小さいほど小さい。限定するものではないが、本発明者らの調査の結果、粒子状触媒を用いる特にタールガスを改質する連続式固定床式触媒反応装置において、１０ｍｍ／ｓで保持器とともに触媒層を上昇させるときの所要上昇力は、１ｍｍ／ｓで上昇させる場合の２倍が必要であることがわかった。また、大きな上昇速度では、触媒が破壊しやすくなる。従って、上昇速度は小さいことが好ましい。但し、１ｍｍ／ｓで上昇させる場合と０．５ｍｍ／ｓで上昇させる場合の所要上昇力の差は小さいので、１ｍｍ／ｓよりも遅くする必要は必ずしもない。また、１０ｍｍ／ｓの上昇速度であっても、触媒が破壊しないのであれば、適用してよい。
(Lifting speed)
The required ascending force required to raise the catalyst layer 13 together with the cage 12 is smaller as the ascent rate is smaller. Although it is not limited, as a result of investigation by the present inventors, in a continuous fixed bed type catalytic reactor using a particulate catalyst, particularly for reforming tar gas, when raising the catalyst layer together with the cage at 10 mm / s It has been found that the required ascending force of 2 is required to be double that when raising at 1 mm / s. Further, at a high rising speed, the catalyst is easily destroyed. Therefore, it is preferable that the rising speed is small. However, the difference in required ascending force between the case of raising at 1 mm / s and the case of raising at 0.5 mm / s is small, so it is not always necessary to make it slower than 1 mm / s. Further, even if the rising speed is 10 mm / s, it may be applied as long as the catalyst is not destroyed.
前述のように、保持器の下降速度は大きいことが好ましい。特に、最下端での触媒の自由落下速度よりも大きい速度（例：１００ｍｍ／ｓ）で保持器を下降すれば、触媒は保持器から離脱して触媒間の拘束が小さくなり、触媒間の相対運動を大きくとれるので好ましい。但し、触媒の自由落下速度よりも極端に大きな速度で保持器を下降させても得られる効果に差はない。 As described above, the descending speed of the cage is preferably large. In particular, if the cage is lowered at a speed (for example, 100 mm / s) larger than the free fall speed of the catalyst at the lowermost end, the catalyst is detached from the cage and the restriction between the catalysts is reduced, and the relative relationship between the catalysts is reduced. It is preferable because a large amount of exercise can be taken. However, there is no difference in the effect obtained even if the cage is lowered at a speed extremely higher than the free fall speed of the catalyst.
（触媒）
本発明の粒状体は触媒に限定されないが、本発明の好ましい実施例として、連続式固定床式触媒反応、特にタールガスを改質する連続式固定床式触媒反応に用いる粒状触媒について述べる。
(catalyst)
The granular material of the present invention is not limited to a catalyst, but as a preferred embodiment of the present invention, a granular catalyst used in a continuous fixed bed catalytic reaction, particularly a continuous fixed bed catalytic reaction for reforming tar gas will be described.
（触媒の大きさ）
一般に触媒作用を有する物質を多孔質の単体に担持して構成される触媒は、保持器１２の上に位置する触媒層１３にとどまる必要がある。そのため、触媒は、保持器１２の開口を通過しない大きさである必要がある。
(Catalyst size)
In general, a catalyst configured by supporting a substance having a catalytic action on a porous simple substance needs to remain in the catalyst layer 13 located on the cage 12. Therefore, the catalyst needs to have a size that does not pass through the opening of the cage 12.
（触媒の形状）
前述のように、特定の保持器で触媒を保持する際、同一触媒外面の代表寸法のうち最小のものに下限値が存在する。触媒層１３の容積が一定の場合、一般に触媒の数が多いほど、触媒の総表面積は増大し、反応容器１１の反応速度を向上できる。従って、球や球に近い形状の触媒は、一定の体積の中で触媒の数を増やしやすいので好ましい。触媒の外周で囲まれる体積が同一でも、表面積のより大きい形状、例えば、円筒やリング状の形状も好ましい。一方、棒状あるいは円盤状の形状は、保持しにくいので、好ましくない。
(Catalyst shape)
As described above, when a catalyst is held by a specific cage, a minimum value exists in the smallest representative dimension of the same catalyst outer surface. When the volume of the catalyst layer 13 is constant, generally, the greater the number of catalysts, the greater the total surface area of the catalyst, and the reaction rate of the reaction vessel 11 can be improved. Therefore, a sphere or a catalyst having a shape close to a sphere is preferable because the number of catalysts can be easily increased in a certain volume. Even if the volume surrounded by the outer periphery of the catalyst is the same, a shape having a larger surface area, for example, a cylindrical shape or a ring shape is also preferable. On the other hand, a rod-like or disk-like shape is not preferable because it is difficult to hold.
（触媒層の高さ）
触媒層１３の上昇時に、触媒層中では上にいくほど触媒間に働く力が等方化し、触媒層１３を押し上げるための上下方向の力と同程度の力がこれ以外の方向にも生じ、この力に比例した摩擦力が触媒間で生じる。この摩擦力の下向き成分が触媒層押し上げの抵抗力として働く。触媒層１３を下端から押し上げる際には触媒層の下側ほど触媒間の反力および触媒−反応容器内壁間で働く力が大きい。上昇中の触媒層内での上下方向の力は、その位置より上方の抵抗力の上下方向成分の合計以上でなければならないので、触媒層の下側ほど、押し上げに必要な力は急速に上昇する。触媒層の下端では最大の押し力となり、この力が過大であれば、触媒や反応容器の破壊を招き得る。
(Catalyst layer height)
When the catalyst layer 13 rises, the force acting between the catalysts becomes more isotropic in the catalyst layer, and a force equivalent to the vertical force for pushing up the catalyst layer 13 is generated in the other directions, A frictional force proportional to this force is generated between the catalysts. The downward component of this frictional force acts as a resistance force for pushing up the catalyst layer. When the catalyst layer 13 is pushed up from the lower end, the reaction force between the catalysts and the force acting between the catalyst and the inner wall of the reaction vessel are larger toward the lower side of the catalyst layer. Since the vertical force in the rising catalyst layer must be greater than or equal to the sum of the vertical components of the resistance force above that position, the force required to push up rapidly increases at the lower side of the catalyst layer. To do. The maximum pressing force is at the lower end of the catalyst layer, and if this force is excessive, the catalyst and the reaction vessel may be destroyed.
この観点から、触媒層の高さは低いほどよい。圧壊強度１００Ｎ、安息角３５°の一般的な触媒（円筒状）を、次に説明する第２の実施形態のピン式保持器で保持して昇降する試験を行った。その結果を図３に示す。この図の横軸は触媒層高さ／反応容器厚比（触媒層のアスペクト比）であり、縦軸は特定の条件において触媒層を押し上げる際の押し上げピーク荷重を基準として規格化した触媒層押し上げのピーク荷重である。この図から、触媒層のアスペクト比（触媒層高さ／反応容器厚比）が２を超えると押し上げ荷重が急激に上昇することがわかる。そして、触媒層のアスペクト比（触媒層高さ／反応容器厚比）が２以下であれば、触媒はほとんど破壊しないことを見出した。また、前述のように、触媒層全体で触媒を相対運動させるためにもアスペクト比が２以下であることが好ましい。 From this point of view, the lower the catalyst layer, the better. A test was conducted in which a general catalyst (cylindrical shape) having a crushing strength of 100 N and an angle of repose of 35 ° was held and moved up and down by the pin type cage of the second embodiment described below. The result is shown in FIG. The horizontal axis of this figure is the catalyst layer height / reaction vessel thickness ratio (catalyst layer aspect ratio), and the vertical axis is the catalyst layer push-up normalized based on the push-up peak load when pushing up the catalyst layer under specific conditions. The peak load. From this figure, it can be seen that when the aspect ratio of the catalyst layer (catalyst layer height / reaction vessel thickness ratio) exceeds 2, the push-up load increases rapidly. It was found that the catalyst hardly breaks if the aspect ratio of the catalyst layer (catalyst layer height / reaction vessel thickness ratio) is 2 or less. Further, as described above, the aspect ratio is preferably 2 or less in order to cause the catalyst to move relative to the entire catalyst layer.
一方、触媒層高さが極端に低い場合には、反応容器内壁と触媒の相対運動による触媒間の相対運動は、反応容器厚方向の反応容器内壁面近傍に限定され、反応容器厚方向の中央部では触媒間の相対運動が生じなくなるので好ましくない。特に、触媒高さが平均的に触媒の２層分の高さ（触媒を垂直方向に２つ積み重ねた最大高さ）以下である場合、上層の触媒の拘束が小さいので、触媒は容易に最密充填化し、低充填化できなくなるので相対運動をいっそう阻む効果を生じる。従って、触媒層高さは触媒の３層分以上の高さ（触媒を垂直方向に３つ積み重ねた最大高さ）、すなわち、触媒外面代表長さの最大値の３倍以上であることが好ましい。 On the other hand, when the catalyst layer height is extremely low, the relative movement between the catalyst due to the relative movement of the inner wall of the reaction vessel and the catalyst is limited to the vicinity of the inner wall surface of the reaction vessel in the thickness direction of the reaction vessel, and the center in the thickness direction of the reaction vessel. This is not preferable because the relative movement between the catalysts does not occur in the portion. In particular, when the catalyst height is equal to or less than the height of two layers of catalyst (the maximum height in which two catalysts are stacked vertically), the upper layer catalyst is less constrained, so the catalyst is easily Since it becomes densely packed and cannot be lowly filled, the relative movement is further prevented. Therefore, the catalyst layer height is preferably at least three times the height of the catalyst (the maximum height obtained by stacking three catalysts in the vertical direction), that is, at least three times the maximum value of the catalyst outer surface representative length. .
（触媒の流動性）
反応容器１１内において保持器１２とともに上昇させた触媒は、反応容器内で棚吊り（触媒層１３を保持器１２で上昇させた後、保持器１２を下降させても触媒同士のセルフロックを生じて触媒が下降しない現象）を起こすことがある。反応容器１１内での触媒の棚吊り防止の観点から、触媒層１３における粒体群としての触媒の流動性は、低いことが好ましく、安息角が５０°未満であることが好ましい。
(Catalyst fluidity)
The catalyst raised together with the cage 12 in the reaction vessel 11 is suspended in the reaction vessel (the catalyst layer 13 is lifted by the cage 12 and then the cage 12 is lowered to cause self-locking between the catalysts. Cause the catalyst not to descend). From the viewpoint of preventing the catalyst from hanging in the reaction vessel 11, the fluidity of the catalyst as the particle group in the catalyst layer 13 is preferably low, and the angle of repose is preferably less than 50 °.
一方、保持器１２の上昇時に保持器から触媒層１３に与える力の触媒層内での非等方性（上向きの力が卓越）を触媒層１３のより高い位置まで保持するためには、触媒の流動性が極端に低くないことが好ましく、安息角は１０°以上が好ましい。触媒層内での力の非等方性の高い領域が広いほど、より小さい推力で保持器１２を上昇させることができ、触媒が破壊しにくくなるからである。 On the other hand, in order to maintain the anisotropy (upward force is superior) in the catalyst layer of the force applied from the cage to the catalyst layer 13 when the cage 12 is raised, to a higher position of the catalyst layer 13, the catalyst It is preferable that the fluidity is not extremely low, and the angle of repose is preferably 10 ° or more. This is because the cage 12 can be raised with a smaller thrust, and the catalyst is less likely to be broken, as the region with higher force anisotropy in the catalyst layer is wider.
（触媒の材質・作用）
本発明の触媒反応装置を適用できる触媒の材質や触媒作用は、流体、特にガスを原料とする触媒反応に用いられる触媒であれば、特に制限はない。流体がガスであり、触媒反応による生成物がガスと固体または液体とである触媒反応、中でも、触媒反応用流体が炭化水素を含有するガスであり、触媒反応による生成物がガスおよび固体または液体である触媒反応、特に、触媒反応用流体がタールを含有するガスであり、触媒反応による生成物が固体の炭化水素または固体のカーボンを含む触媒反応に用いられる触媒に好適に使用できる。
(Catalyst material and action)
The material and catalytic action of the catalyst to which the catalytic reaction apparatus of the present invention can be applied are not particularly limited as long as it is a catalyst used for a catalytic reaction using a fluid, particularly a gas as a raw material. Catalytic reaction in which the fluid is a gas, and the product of the catalytic reaction is a gas and a solid or liquid. In particular, the catalytic reaction fluid is a gas containing hydrocarbons, and the product of the catalytic reaction is a gas and a solid or liquid. In particular, the catalyst reaction fluid is a gas containing tar, and the product of the catalyst reaction can be suitably used for a catalyst used in a catalytic reaction containing solid hydrocarbon or solid carbon.
一般的には、上記のような触媒反応に用いられる酸化物触媒に広く使用でき、特に触媒反応用流体がタールを含有するガスであり、触媒反応による生成物が固体の炭化水素または固体のカーボンを含む触媒反応に用いられる酸化物触媒に好適に適用できる。 In general, it can be widely used for oxide catalysts used in the catalytic reaction as described above. In particular, the catalytic reaction fluid is a gas containing tar, and the product of the catalytic reaction is solid hydrocarbon or solid carbon. It can apply suitably for the oxide catalyst used for the catalytic reaction containing.
本発明の触媒反応装置に好適に使用できる触媒の具体的な例としては、たとえば、ニッケル、マグネシウム、セリウム、アルミニウムを含む酸化物であって、少なくとも１種の複合酸化物を含み、単独化合物としてアルミナを含まないタール含有ガスの改質用触媒を挙げることができる（ＷＯ２０１０／１３４３２６）。この複合酸化物の好適な例は、ＮｉＭｇＯ、ＭｇＡｌ2Ｏ4、ＣｅＯ2の結晶相からなり、さらには、各結晶相の内、Ｘ線回折測定により求めたＮｉＭｇＯ結晶相の（２００）面の結晶子の大きさが１ｎｍ〜５０ｎｍ、ＭｇＡｌ2Ｏ4結晶相の（３１１）面の結晶子の大きさが１ｎｍ〜５０ｎｍ、ＣｅＯ2結晶相の（１１１）面の結晶子の大きさが１ｎｍ〜５０ｎｍである。この触媒は、炭素質原料を熱分解した際に発生する多量の硫化水素を含み、炭素析出を起こし易い縮合多環芳香族主体のタール含有ガスであっても、随伴するタール等重質炭化水素を高効率に改質して、水素、一酸化炭素、メタンを主体とする軽質炭化水素に変換すること、また、触媒性能が劣化した際、水蒸気又は空気の少なくともいずれかを高温下で触媒に接触させることにより、触媒上の析出炭素や吸着硫黄を除去して触媒性能を回復させ長期間安定した運転が可能になるという特徴を有する。 Specific examples of the catalyst that can be suitably used in the catalytic reactor of the present invention include, for example, oxides containing nickel, magnesium, cerium, and aluminum, including at least one complex oxide, and as a single compound Mention may be made of catalysts for reforming tar-containing gases not containing alumina (WO 2010/134326). A preferred example of this composite oxide is a crystal phase of NiMgO, MgAl 2 O 4 , and CeO 2 , and among the crystal phases, the (200) plane of the NiMgO crystal phase determined by X-ray diffraction measurement is used. The crystallite size is 1 nm to 50 nm, the crystallite size of the (311) plane of the MgAl 2 O 4 crystal phase is 1 nm to 50 nm, and the crystallite size of the (111) plane of the CeO 2 crystal phase is 1 nm to 50 nm. This catalyst contains a large amount of hydrogen sulfide generated when a carbonaceous raw material is thermally decomposed, and even if it is a condensed polycyclic aromatic-based tar-containing gas that easily causes carbon deposition, the accompanying heavy hydrocarbon such as tar Is converted to light hydrocarbons mainly composed of hydrogen, carbon monoxide, and methane, and when the catalyst performance deteriorates, at least one of water vapor and air is converted to the catalyst at a high temperature. By contacting, the carbon is removed from the catalyst and adsorbed sulfur, and the catalyst performance is restored to enable stable operation over a long period of time.
また、ニッケル、マグネシウム、セリウム、ジルコニウム、アルミニウムを含む複合酸化物からなることを特徴とするタール含有ガスの改質用触媒を挙げることができる（特願２０１０−０８２５７６）。この複合酸化物の好適な例は、ＮｉＭｇＯ、ＭｇＡｌ2Ｏ4、ＣｅxＺｒ1-xＯ2（０＜ｘ＜１）の結晶相を含み、さらには、各結晶相の内、Ｘ線回折測定により求めたＮｉＭｇＯ結晶相の（２２０）面の結晶子サイズが１ｎｍ〜５０ｎｍ、ＭｇＡｌ2Ｏ4結晶相の（３１１）面の結晶子サイズが１ｎｍ〜５０ｎｍ、ＣｅxＺｒ1-xＯ2結晶相の（１１１）面の結晶子サイズが１ｎｍ〜５０ｎｍであることが好ましい。この触媒によれば、石炭やバイオマスを熱分解した際に発生するタール含有ガスを、安定的に一酸化炭素、水素等の軽質化学物質へ転換することができる。特に、タール含有ガス中に、硫化水素を高濃度で含むタール含有ガスであっても、脱硫処理せずにそのまま触媒と接触させて、粗ガス中のタールを改質して、又は、精製ガス中の炭化水素成分を改質して、タール含有ガスを一酸化炭素、水素等の軽質化学物質へ安定的に転換することができる。 Further, a reforming catalyst for tar-containing gas, which is composed of a composite oxide containing nickel, magnesium, cerium, zirconium and aluminum, can be mentioned (Japanese Patent Application No. 2010-082576). Suitable examples of the composite oxide, NiMgO, include MgAl 2 O 4, Ce x Zr 1-x O 2 (0 <x <1) crystal phase, and further, among the crystalline phase, X-rays diffraction the crystallite size of (220) plane of NiMgO crystalline phase determined by measurement 1 nm to 50 nm, a crystallite size of (311) plane of the MgAl 2 O 4 crystalline phase 1nm~50nm, Ce x Zr 1-x O 2 crystals The crystallite size of the (111) plane of the phase is preferably 1 nm to 50 nm. According to this catalyst, the tar-containing gas generated when coal or biomass is pyrolyzed can be stably converted into light chemical substances such as carbon monoxide and hydrogen. In particular, even if the tar-containing gas contains a high concentration of hydrogen sulfide in the tar-containing gas, it is brought into contact with the catalyst without desulfurization to reform the tar in the crude gas, or a refined gas The tar-containing gas can be stably converted into light chemical substances such as carbon monoxide and hydrogen by reforming the hydrocarbon component therein.
さらに、ａＭ・ｂＮｉ・ｃＭｇ・ｄＯで表される複合酸化物であるタール含有ガスの改質用触媒であって、ａ、ｂ、及びｃは、ａ＋ｂ＋ｃ＝１、０．０２≦ａ≦０．９８、０．０１≦ｂ≦０．９７、かつ、０．０１≦ｃ≦０．９７を満たし、ｄは、酸素と陽性元素が電気的に中性となる値であり、Ｍは、Ｌｉ、Ｎａ、Ｋから選ばれる少なくとも１種類の元素であるタール含有ガスの改質用触媒を挙げることができる（特願２０１０−０８１８６７、特願２０１０−０８１９７、特願２０１０−０８３５２７）。この複合酸化物の好適な例は、シリカ、アルミナ、ゼオライトから選ばれる少なくとも１種類の酸化物を加えてなり、さらには、シリカ、アルミナ、ゼオライトから選ばれる少なくとも１種類の酸化物の含有量が、複合酸化物全体に対し１〜９０質量％であることが好ましい。この触媒によれば、石炭やバイオマスを熱分解した際に発生するタール含有ガスを、安定的に一酸化炭素、水素等の軽質化学物質へ転換することができる。特に、タール含有ガス中に、硫化水素を高濃度で含むタール含有ガスであっても、脱硫処理せずにそのまま触媒と接触させて、粗ガス中のタールを改質して、又は精製ガス中の炭化水素成分を改質して、タール含有ガスを一酸化炭素、水素等の軽質化学物質へ安定的に転換することができる。 Furthermore, a catalyst for reforming a tar-containing gas that is a composite oxide represented by aM · bNi · cMg · dO, wherein a, b, and c are a + b + c = 1, 0.02 ≦ a ≦ 0. 98, 0.01 ≦ b ≦ 0.97 and 0.01 ≦ c ≦ 0.97 are satisfied, d is a value at which oxygen and a positive element are electrically neutral, M is Li, Mention may be made of a catalyst for reforming a tar-containing gas which is at least one element selected from Na and K (Japanese Patent Application Nos. 2010-081867, 2010-08197, and 2010-083527). A suitable example of this composite oxide is formed by adding at least one oxide selected from silica, alumina, and zeolite, and further contains at least one oxide selected from silica, alumina, and zeolite. It is preferable that it is 1-90 mass% with respect to the whole complex oxide. According to this catalyst, the tar-containing gas generated when coal or biomass is pyrolyzed can be stably converted into light chemical substances such as carbon monoxide and hydrogen. In particular, even if the tar-containing gas contains a high concentration of hydrogen sulfide in the tar-containing gas, it is brought into contact with the catalyst as it is without desulfurization treatment to reform the tar in the crude gas or in the purified gas. Thus, the tar-containing gas can be stably converted to light chemical substances such as carbon monoxide and hydrogen.
（その他の適用可能な例）
本発明は、上記に例示した触媒反応装置及び触媒のほか、コーキング等を生じる、下記の触媒反応装置にも好適に使用できる。
(Other applicable examples)
The present invention can be suitably used for the following catalytic reaction apparatus that causes coking, in addition to the catalytic reaction apparatus and catalyst exemplified above.
１）メタン改質触媒反応装置： 特開２００６−３５１７２号公報の「比較例」には、炭化水素であるメタンガスを原料ガスとして大量のコーキング（炭素析出）が発生することが記載されている。 1) Methane reforming catalytic reactor: “Comparative Example” of Japanese Patent Application Laid-Open No. 2006-35172 describes that a large amount of coking (carbon deposition) occurs using methane gas as a raw material gas.
２）都市ガス改質触媒反応装置： 特許文献２にコーキングの事例が記載されている。
３）その他、ＬＰＧ等の各種石油精製ガスや天然ガスの改質のための触媒反応装置、水素を含有するガスと酸化剤ガスを作用させて発電し、水を副生する、燃料電池用の触媒反応装置（例：特開２００９−４８７９７号公報）等に適用できる。
2) City gas reforming catalytic reactor: Patent Document 2 describes a case of coking.
3) In addition, catalytic reactors for reforming various petroleum refining gases such as LPG and natural gas, and fuel cells that generate hydrogen by generating gas by acting hydrogen-containing gas and oxidant gas. The present invention can be applied to a catalytic reactor (eg, JP 2009-48797 A).
[第２の実施形態]
図７，８を参照すると、第１の実施態様と異なるところは、昇降部１６が爪部２０と係合する部材として、固定ピン１７のほかに、触媒保持器の下部に爪部の上向き斜面（爪側）と対向する下向き斜面（保持器側）３１を有する部材３０を有することである。この昇降部１６の下向き斜面（保持器側）３１が爪部２０の上向き斜面（爪側）３２と接して係合しているので、駆動装置２２によって爪部２０が押出されたとき、爪部２０の上向き斜面（爪側）３２が昇降部１６の下向き斜面（保持器側）３１を上昇させるように力が作用し、昇降部１６が上昇する。保持器１２の下側に設けた部材３０の下向き斜面（保持器側）３１は、固定ピン１７と比べて、爪部の上向き斜面（爪側）３２と接する面積が大きいので、上昇力の伝達の効率が高く、また機構及び部材の安定性及び耐久性にも優れる。
[Second Embodiment]
7 and 8, the difference from the first embodiment is that the elevating part 16 is a member that engages with the claw part 20, and in addition to the fixed pin 17, the claw part has an upward slope on the lower part of the catalyst holder. It has the member 30 which has the downward slope (cage side) 31 which opposes (nail | claw side). Since the downward slope (retainer side) 31 of the elevating part 16 is in contact with and engaged with the upward slope (nail side) 32 of the claw part 20, when the claw part 20 is pushed out by the driving device 22, A force acts so that the upward slope (claw side) 20 of the 20 raises the downward slope (cage side) 31 of the lift part 16, and the lift part 16 rises. The downward slope (retainer side) 31 of the member 30 provided on the lower side of the cage 12 has a larger area in contact with the upward slope (nail side) 32 of the claw portion than the fixing pin 17, so that the upward force is transmitted. And the stability and durability of the mechanism and members are also excellent.
一方、昇降部１６に爪部２０の下向き斜面（爪側）と対向する上向き斜面（保持器側）を有する部材を設けることで、駆動装置２１によって爪部２０が引戻されるときに、爪部の下向き斜面（爪側）が昇降部の上向き斜面（保持器側）を下降させるように力が作用させて昇降部を下降させることも可能であるが、この実施態様では、この下降力は固定ピン１７によって行う。下降する力は、触媒保持器を含む昇降部と触媒層の重力が加算されるので、接触面積が小さい固定ピンでも十分に安定に下降力を付与することができる。接触面積が大きい斜面どうしと比べて、斜面とピンとの係合は動きが滑らかであることが可能である。 On the other hand, when the elevating part 16 is provided with a member having an upward slope (cage side) facing the downward slope (claw side) of the claw part 20, when the claw part 20 is pulled back by the driving device 21, the claw part It is possible to lower the lifting part by applying a force so that the downward slope (claw side) lowers the upward slope (cage side) of the lifting part. In this embodiment, this downward force is fixed. This is done with pins 17. Since the descending force is added to the gravity of the elevating part including the catalyst holder and the catalyst layer, the descending force can be applied sufficiently stably even with a fixed pin having a small contact area. Compared with slopes having a large contact area, the engagement between the slope and the pin can be smooth.
触媒保持器１２の下部に爪部２０の上向き斜面３１と対向する下向き斜面３２を有する部材３０は、たとえば、所定の下向き斜面を有していればよく、保持器１２と一体に製造しても、保持器１２に後付で溶接等の方法で固定してもよい。傾斜角度及び長さ等は爪部の上向き斜面に対応すればよい。材質は、耐熱性、強度等のため、保持器と同様の材料から選択することが好ましい。 The member 30 having the downward slope 32 facing the upward slope 31 of the claw 20 at the lower part of the catalyst holder 12 may have a predetermined downward slope, for example, and may be manufactured integrally with the cage 12. The cage 12 may be fixed later by welding or the like. The inclination angle, length, and the like may correspond to the upward slope of the claw portion. The material is preferably selected from the same materials as the cage for heat resistance, strength, and the like.
（昇降部）
爪部の斜面と係合する斜面の傾斜については、傾斜の小さいほど、より小さな駆動軸推力で所要とされる保持器昇降推力を満足できる。但し、この傾斜が小さいほど、駆動軸の所要ストロークを長く設定する必要があり設備が大型化する。従って、この傾斜については、所要保持器推力、所要保持器ストローク、駆動軸の許容推力、駆動軸の許容ストローク、並びに、適用される材料強度等を考慮して、エンジニアリング的に決定すべきである。例えば、この斜面の勾配を２°以上１５°以下とすることができる。昇降時に保持器の姿勢を安定させて円滑に昇降を実施するためには、この斜面の長さおよび幅は、係合する爪部の斜面との接触長および接触幅を十分に長く設定する必要がある。傾斜面は、保持器の重心直下に存在することが好ましいが、そうではない場合には、より長い接触長を確保する必要がある。この接触長は、少なくとも５０ｍｍ以上設けることが好ましく、接触幅は、少なくとも１０ｍｍ以上設けることが好ましい。強度上の理由で面圧を低値としなければならない場合には、より広い接触幅を用いることができる。また、設備が巨大化するので、保持器長さを大きく超える斜面長や保持器幅を大きく超える斜面幅は、好ましくない。この斜面は平面、かつ、平滑であることが好ましい。但し、爪部との衝突時の衝撃を低減するために、微小な曲率の凸面としてもよい。斜面の表面に窒化硼素ベースのペースト等の固体潤滑剤等の潤滑剤を付与して摩擦低減を図ってもよい。昇降部本体を金属製として、爪部の斜面と係合する斜面のみに前記セラミックスや窒化硼素等を取り付け、または、溶射等によって表面処理する等して、耐久性向上や摩擦力低減を図ってもよい。昇降時のスラスト力は、本実施形態においては、保持器の側面を経由して反応容器内面で担う。
（爪部）
爪部２０の構造は、図４に示すものと同様である。爪部の傾斜は、このように１つ以上の上向き傾斜面（図４では、爪上面と貫通溝の下側の面）と１つ以上の下向き傾斜面（図４では、貫通溝の上側の面）を備える。昇降部・固定ピンとの接触部は、この２つの上向き斜面のどちらか一方若しくは両方を用いることができる。貫通溝の勾配と爪部上面の勾配は一致させてもよいし、微小に異ならせてもよい。爪部２０の傾斜面の勾配および昇降部との接触面の寸法に関しては、昇降部での記載と同様である。前記傾斜面は、平坦、かつ、平滑であることが好ましいが、昇降部や固定ピンとの衝突による衝撃を低減するために、微小な曲率の凸面としてもよい。
この第２の実施態様における、上記以外の、反応容器の形状、反応容器の材質、反応容器の寸法、触媒層の保持器、昇降ストローク、昇降速度、触媒粒の各種条件（大きさ、形状、流動性）、触媒層の高さ、触媒の材質・作用、その他の適用可能事例等については、第１の実施態様で説明したと同様であることができる。
(Elevating part)
As for the inclination of the inclined surface engaged with the inclined surface of the claw portion, the smaller the inclination, the more the cage lifting thrust required with a smaller driving shaft thrust can be satisfied. However, the smaller this inclination, the longer the required stroke of the drive shaft, and the larger the equipment. Therefore, this inclination should be determined engineeringly in consideration of the required cage thrust, the required cage stroke, the allowable thrust of the drive shaft, the allowable stroke of the drive shaft, the applied material strength, etc. . For example, the slope of the slope can be 2 ° or more and 15 ° or less. In order to stabilize the posture of the cage during raising and lowering and smoothly raise and lower it, the length and width of this slope must be set sufficiently long so that the contact length and contact width with the slope of the engaging claw part are sufficiently long. There is. The inclined surface is preferably present immediately below the center of gravity of the cage, but if this is not the case, it is necessary to ensure a longer contact length. The contact length is preferably provided at least 50 mm, and the contact width is preferably provided at least 10 mm. A wider contact width can be used when the surface pressure must be low for strength reasons. In addition, since the equipment becomes enormous, a slope length greatly exceeding the cage length or a slope width greatly exceeding the cage width is not preferable. This slope is preferably flat and smooth. However, in order to reduce the impact at the time of collision with the claw portion, a convex surface with a minute curvature may be used. Friction reduction may be achieved by applying a lubricant such as a solid lubricant such as a boron nitride-based paste to the surface of the slope. The lifting / lowering body is made of metal, and the ceramics, boron nitride, etc. are attached only to the slope that engages the slope of the claw part, or surface treatment is performed by thermal spraying, etc., to improve durability and reduce frictional force. Also good. In this embodiment, the thrust force at the time of raising and lowering is borne by the reaction vessel inner surface via the side surface of the cage.
(Nail part)
The structure of the nail | claw part 20 is the same as that shown in FIG. In this way, the inclination of the claw portion includes one or more upward inclined surfaces (in FIG. 4, the upper surface of the nail and the lower side of the through groove) and one or more downward inclined surfaces (in FIG. 4, the upper side of the through groove). Surface). Either one or both of these two upward slopes can be used for the contact portion with the elevating part / fixing pin. The gradient of the through groove and the gradient of the upper surface of the claw portion may be matched or may be slightly different. The gradient of the inclined surface of the claw part 20 and the dimension of the contact surface with the lifting part are the same as described in the lifting part. The inclined surface is preferably flat and smooth, but may be a convex surface having a minute curvature in order to reduce an impact caused by a collision with the elevating part or the fixing pin.
In this second embodiment, other than the above, the shape of the reaction vessel, the material of the reaction vessel, the dimensions of the reaction vessel, the retainer of the catalyst layer, the elevating stroke, the elevating speed, various conditions (size, shape, The fluidity), the height of the catalyst layer, the material and action of the catalyst, and other applicable cases can be the same as described in the first embodiment.
[第３の実施形態]
図９，１０のような触媒反応器であってもよい。
[Third embodiment]
A catalytic reactor as shown in FIGS.
（全体構造）
図９、１０に、第３の実施形態の連続式固定床触媒反応装置の触媒反応容器の部分を示す。図９，１０の（ａ）は平面図、（ｂ）は正面図、（ｃ）は側面図であり、図７，８に対応する。図９，１０は反応容器と触媒保持器と触媒の部分が図７，８と異なるが、その他の部分は図７，８と同様である。第３の実施態様は、反応容器と触媒保持器と触媒の部分以外は第１及び第２の実施形態さらには第４の実施形態その他の形態と同様であることができる。触媒反応容器１１は、その内部に、保持板４１によって保持された触媒連４２の集合体である触媒柵４３が収容されている。
(Overall structure)
9 and 10 show a portion of the catalytic reaction vessel of the continuous fixed bed catalytic reactor of the third embodiment. FIGS. 9 and 10 are (a) a plan view, (b) a front view, and (c) a side view, which correspond to FIGS. 9 and 10 are different from FIGS. 7 and 8 in the reaction vessel, the catalyst holder, and the catalyst, but the other parts are the same as those in FIGS. The third embodiment can be the same as the first and second embodiments, the fourth embodiment, and other forms except for the reaction vessel, catalyst holder, and catalyst. The catalyst reaction vessel 11 accommodates therein a catalyst fence 43 that is an assembly of the catalyst series 42 held by the holding plate 41.
このように、触媒連４２とその集合体である触媒柵４３を用いることがこの実施形態の特徴である。触媒連４２は、複数の触媒４４と、それらの可動性を損なわずに貫通して触媒連を形成する中心棒４５とにより形成される。触媒柵４３は、図１０，１１に示したように、複数の触媒連４２と、その中心棒４５を立設する、すなわち立てた状態で固定する、保持板４１により形成される。保持板４１と触媒連４２との間には、カラー（図示せず）を配置してもよい。 Thus, the feature of this embodiment is to use the catalyst train 42 and the catalyst fence 43 that is an assembly thereof. The catalyst series 42 is formed by a plurality of catalysts 44 and a center bar 45 that penetrates and forms a catalyst series without impairing their mobility. As shown in FIGS. 10 and 11, the catalyst fence 43 is formed by a holding plate 41 that erects a plurality of catalyst stations 42 and a center rod 45 thereof, that is, fixes them in an upright state. A collar (not shown) may be disposed between the holding plate 41 and the catalyst train 42.
この実施形態においても、保持板４１の下に、保持板を昇降させることにより触媒柵を一斉に上下方向に往復運動させるための駆動機構が存在するが、図示及び説明は省略する。 Also in this embodiment, there is a drive mechanism for reciprocating the catalyst fences in the vertical direction all at once by raising and lowering the holding plate under the holding plate 41, but illustration and description thereof are omitted.
反応容器１１には、下方から原料ガスが供給されて、その主流が触媒連４２と平行に触媒柵４３を通過する際に反応し、触媒層１４からの改質ガスは反応容器１１の上方から排出される。触媒反応が発熱反応の場合は、反応熱を、触媒反応容器の外部に設けた冷媒流路（図示せず）に冷媒を流すなどにより除去してもよい。場合により、反応容器１１への原料ガスは、図９，１０とは逆に、触媒柵４３の上方から下方へ流れるように供給することも可能である。 A raw material gas is supplied to the reaction vessel 11 from below and reacts when the main flow passes through the catalyst fence 43 in parallel with the catalyst train 42, and the reformed gas from the catalyst layer 14 is sent from above the reaction vessel 11. Discharged. When the catalytic reaction is an exothermic reaction, the reaction heat may be removed by flowing a refrigerant through a refrigerant flow path (not shown) provided outside the catalytic reaction vessel. In some cases, the raw material gas to the reaction vessel 11 can be supplied so as to flow from the upper side to the lower side of the catalyst fence 43, contrary to FIGS.
（触媒保持器の利点） (Advantages of catalyst cage)
内部に貫通孔を有する複数の触媒を用いて個々の触媒を中心棒で貫いて一列に整列させたものとして定義する「触媒連」を用い、複数の触媒連を間隔をあけて配列して形成したものとして定義する「触媒柵」を触媒反応容器内に配置して、各触媒連間の空間を専用気流路とし、触媒反応容装置の運転を開始してから一定時間経過後に短時間往復運動させることを試みた。その結果、次のことがわかった。 Formed by arranging multiple catalyst series at intervals, using "catalyst series" that defines multiple catalysts with through-holes inside and arranged in a row by passing each catalyst through a central rod. A “catalyst fence” that is defined as the one that has been defined is placed in the catalyst reaction vessel, and the space between each catalyst station is used as a dedicated air flow path. I tried to make it. As a result, the following was found.
ａ）反応の初期状態から反応固体生成物の触媒表面への堆積が所定量進むまでの期間では、
［個々の堆積カーボンの大きさ］＜［当該触媒間空間の隙間（専用気流路の幅）］
を実現できている。従って、固体生成物が触媒上に所定量堆積するまでの間に触媒柵を往復運動させることによって堆積物を触媒表面から離脱させることができる。さらに、離脱させた固体生成物を、専用気流路を通じて落下または気流搬送することによって、触媒反応容器外に排出することができる。このようにして、触媒表面の生成物を除去することによって、触媒表面での生成物堆積状態を反応の初期状態と同様の状態に戻すことができるので、この往復運動操作を生成物の堆積が進行するたびに繰り返すことによって、反応容器の通気性を常に良好に保つことができる。
a) In the period from the initial state of the reaction until the deposition of the reaction solid product on the catalyst surface proceeds by a predetermined amount,
[Size of individual carbon deposits] <[Gap between the catalyst space (width of dedicated air flow path)]
Has been realized. Therefore, the deposit can be separated from the catalyst surface by reciprocating the catalyst fence until a predetermined amount of the solid product is deposited on the catalyst. Furthermore, the separated solid product can be discharged out of the catalytic reaction vessel by dropping or air-flowing through the dedicated air flow path. In this way, by removing the product on the catalyst surface, the product deposition state on the catalyst surface can be returned to the same state as the initial state of the reaction. By repeating each time it proceeds, the air permeability of the reaction vessel can always be kept good.
ここで、従来の単純な積層構造の触媒層と同一レベルの触媒充填率を維持しつつ、各専用気流路の断面を広大なもの（例えば、主流方向に反応容器高さのレベル、かつ、主流垂直方向に触媒断面積と同等レベル）にできる。このため、気流路内での少々の生成物堆積量では反応容器の通気性が阻害されることはないので、上記の往復動作の所要頻度を、少なくすることができきる（例えば、１回／時間）。これは、従来の単純な積層構造の触媒層では触媒ごとに分散した多数の小空間であった触媒間の隙間を、少数の太い気流路に集約することによって、高い通気性と高い触媒充填率を両立できるからである。一方、従来の単純な積層構造の触媒層では、個々の触媒が互いに支え合って触媒層を形成・保持するという構造であるため、隣接する触媒間で構成される気流路は、触媒ごとに細分化されるとともに狭窄部を生じ易い。このような触媒層では気流路の狭窄部において高々、触媒断面積の１／１０程度の流路断面積しか確保できないため、気流路内での少量の生成物の堆積があっても、反応容器の通気抵抗が急上昇してしまう（気流路の通気抵抗は、一般に狭窄部での断面積に依存する）。しかも、この方式に限らず、従来の触媒層では気流路に一旦、生成物が堆積すると、これを取り除く手段が存在しなかったので、反応によって生成物を生じ易い反応容器では、通気抵抗の上昇による制約によって、連続運転可能な時間は極めて短いものであった。 Here, while maintaining the catalyst filling rate at the same level as that of the conventional catalyst layer having a simple laminated structure, each dedicated air channel has a wide cross section (for example, the level of the reaction vessel in the mainstream direction and the mainstream). The vertical cross-sectional area is equivalent to the catalyst cross-sectional area. For this reason, since the air permeability of the reaction container is not hindered by a small amount of product accumulation in the air flow path, the required frequency of the reciprocating operation can be reduced (for example, once / time). This is because high air permeability and high catalyst filling rate are achieved by consolidating the gaps between the many small spaces dispersed for each catalyst in the conventional catalyst layer with a simple laminated structure into a small number of thick air passages. This is because both can be achieved. On the other hand, in the conventional catalyst layer having a simple laminated structure, each catalyst supports each other to form and hold the catalyst layer, and therefore the air flow path formed between adjacent catalysts is subdivided for each catalyst. And a stenosis is likely to occur. In such a catalyst layer, the flow passage cross-sectional area of about 1/10 of the cross-sectional area of the catalyst can be secured at most in the constricted portion of the air flow path, so that even if a small amount of product is deposited in the air flow path, the reaction vessel The airflow resistance of the air flow path rises rapidly (the airflow resistance of the air flow path generally depends on the cross-sectional area at the narrowed portion). In addition, the present invention is not limited to this method, and there is no means for removing the product once accumulated in the air flow path in the conventional catalyst layer. Due to the restriction of, continuous operation time was extremely short.
ｂ）触媒柵の往復運動時には、各触媒連において、隣あう触媒は互いに結合されていないので、触媒間での相対運動を容易に生じる（例えば、触媒内孔壁と、これに接する中心棒表面間の摩擦力は触媒によって異なるので、中心棒を一定の速度で移動させたとしても、中心棒に駆動される個々の触媒の速度にはばらつきを生じる）。そのため、触媒間での衝突が容易に生じるので衝突時に各触媒で強い表面振動を生じて生成物を触媒表面から離脱させることができる。 b) At the time of reciprocating movement of the catalyst fence, neighboring catalysts are not coupled to each other in each catalyst series, so that relative movement between the catalysts easily occurs (for example, the inner wall of the catalyst and the surface of the center rod in contact with it) Since the frictional force varies depending on the catalyst, even if the center bar is moved at a constant speed, the speed of individual catalysts driven by the center bar varies. For this reason, collision between the catalysts easily occurs, so that strong surface vibration is generated in each catalyst at the time of collision, and the product can be separated from the catalyst surface.
それに対し、例えば、管路内を専用気流路とし、管内面に触媒を担持する、従来技術の管壁式の触媒反応容器の場合は、触媒担体が単一の構造物であるので、往復運動させたとしても担体全体が移動するのみで担体内に相対運動を生じない。このため、触媒の表面振動は限定的となり（例えば、部分的に打撃を与えても打撃点から離れると触媒表面の振動は急激に減衰してしまう。また、管壁全体を均一に打撃しようとしても、構造上、過剰に複雑な機構となるため好ましくない）、生成物を触媒表面から離脱させる効果は小さい。他の専用気流路を設ける形式の反応容器（例えば、モノリス式）でも、触媒構造が単一構造物で構成されているため、管壁式の反応容器と同様の理由で、触媒全体を効率的に振動させることは、困難である。 On the other hand, for example, in the case of a conventional tube wall type catalyst reaction vessel in which the inside of the pipe line is a dedicated air flow path and the catalyst is supported on the inner surface of the pipe, the catalyst carrier is a single structure, Even if it is made to move, the entire carrier only moves and no relative movement occurs in the carrier. For this reason, the surface vibration of the catalyst is limited (for example, even if a partial hit is given, the vibration of the catalyst surface is abruptly attenuated when it is moved away from the hitting point. In addition, trying to hit the entire tube wall uniformly) However, this is not preferable because of an excessively complicated mechanism in terms of structure), and the effect of detaching the product from the catalyst surface is small. Even in a reaction vessel (for example, a monolith type) provided with other dedicated air flow paths, the catalyst structure is composed of a single structure, so that the entire catalyst is efficient for the same reason as the tube wall type reaction vessel. It is difficult to vibrate.
ｃ）触媒柵を定期的に往復運動させることによって触媒表面のバルク状の生成物の堆積が少なくなるので、触媒反応容器内で原料ガスが常に触媒表面に到達できる。このため、触媒反応効率の低下が少ない。 c) By periodically reciprocating the catalyst fence, the accumulation of bulk products on the catalyst surface is reduced, so that the raw material gas can always reach the catalyst surface in the catalyst reaction vessel. For this reason, there is little fall of catalytic reaction efficiency.
ｄ）触媒連間の専用気流路が互いに連結しているので流体の主流垂直方向にガスが拡散（物質交換およびこれに伴う熱交換）しやすい。このため、加熱面（触媒反応が吸熱反応の場合）である触媒反応容器の外壁面から遠く離れた触媒に対しても、ガス拡散によって加熱面から十分に熱を供給することがきでき、吹き抜けを生じにくい。 d) Since the dedicated air flow paths between the catalyst stations are connected to each other, gas easily diffuses (substance exchange and heat exchange associated therewith) in the vertical direction of the main flow of the fluid. Therefore, heat can be sufficiently supplied from the heating surface by gas diffusion to the catalyst far from the outer wall surface of the catalytic reaction vessel which is the heating surface (when the catalytic reaction is endothermic reaction). Hard to occur.
ｅ）特に、触媒連の中心棒を高熱伝導性材料とし、中心棒の端部を加熱することによって、壁面から遠く離れた触媒を中心軸を介して加熱して反応による吸熱を補償することによって触媒低温化および触媒低温化に伴う改質効率低下を回避することができるので、吹き抜けを一層生じにくくすることができる。 e) In particular, by making the center rod of the catalyst chain a highly thermally conductive material and heating the end of the center rod, the catalyst far from the wall surface is heated through the center axis to compensate for the endothermic reaction. Since it is possible to avoid a reduction in catalyst efficiency and a reduction in reforming efficiency associated with a reduction in catalyst temperature, it is possible to make it more difficult for blow-through to occur.
こうして、個々の触媒を中心棒で貫いて一列に整列させた触媒連を複数用い、各触媒連間の空間を専用気流路とするとともに、触媒連の集合体である触媒柵を触媒反応容器内で往復運動させることによって、触媒層全域（触媒柵全体）において触媒表面に堆積した固体生成物を効率的に落下させて触媒層（触媒柵）から除去できるという顕著な効果を奏する。 In this way, a plurality of catalyst trains in which individual catalysts are penetrated by a central rod and arranged in a line are used, and the space between each catalyst train is used as a dedicated air flow path, and the catalyst fence that is an assembly of the catalyst trains is placed in the catalyst reaction vessel. By reciprocating, the solid product deposited on the catalyst surface in the entire catalyst layer (entire catalyst fence) can be efficiently dropped and removed from the catalyst layer (catalyst fence).
本発明の触媒反応装置によれば、触媒反応容器内において隣り合う触媒連どうしは一定の間隔をあけて配置されるため、触媒をランダムに充填して構成される触媒層などにおいて生じる触媒間の空間での固体生成物の堆積による閉塞の問題は、本質的に回避される。そのため、従来のように触媒や触媒保持器を洗浄するために運転を停止する必要なしに、反応装置を連続運転することが可能となる。また、その触媒反応装置を用いて、固体カーボンなどの固体生成物を発生する触媒反応を高い効率で行うことができる。 According to the catalyst reaction apparatus of the present invention, the adjacent catalyst groups are arranged at regular intervals in the catalyst reaction vessel. The problem of clogging due to the deposition of solid product in space is essentially avoided. Therefore, it is possible to continuously operate the reaction apparatus without having to stop the operation in order to wash the catalyst and the catalyst retainer as in the prior art. In addition, the catalytic reaction apparatus can be used to perform a catalytic reaction that generates a solid product such as solid carbon with high efficiency.
（反応容器の寸法）
反応容器の厚みが大きいほど、厚み方向に熱が伝わりにくくなる。このため、反応容器の厚み（反応容器断面が円形の場合には直径）は、５００ｍｍ以下であることが好ましい。
(Reaction vessel dimensions)
The greater the thickness of the reaction vessel, the less heat is transmitted in the thickness direction. For this reason, the thickness of the reaction vessel (or the diameter when the reaction vessel cross section is circular) is preferably 500 mm or less.
（触媒連と触媒柵）
図１０、１１に示したように、触媒連４２は、円筒状などの内部に貫通孔を有する触媒４４と、一群の触媒４４を貫く中心棒４５により構成される。触媒柵は、一群の触媒連４３を保持板４１に固定して製作される。
(Catalyst train and catalyst fence)
As shown in FIGS. 10 and 11, the catalyst series 42 includes a catalyst 44 having a through-hole inside a cylindrical shape and the like, and a center rod 45 penetrating the group of catalysts 44. The catalyst fence is manufactured by fixing a group of catalyst trains 43 to the holding plate 41.
触媒柵４３が、図１１に示したように触媒連４２を垂直方向に向けて反応容器１１内に配置される場合には、中心棒４５の下部（触媒連４２と保持板４１とが接合する部分）に、触媒４４の落下防止用のカラーを設けることができる。カラーの直径を触媒孔径よりも大きくすることで、触媒の落下を防止できる。また，この場合には、カラーより下方が流体の流入または流出のための空間、並びに、触媒表面で生成した生成物を落下・堆積させるための空間となる。尚、この実施形態において、保持板４１は、保持器１２と共用される。この保持器は、反応容器内において昇降部の頂部に接続される。 When the catalyst fence 43 is disposed in the reaction vessel 11 with the catalyst series 42 oriented in the vertical direction as shown in FIG. 11, the lower part of the center rod 45 (the catalyst series 42 and the holding plate 41 are joined together). A collar for preventing the catalyst 44 from falling can be provided in the portion). By making the collar diameter larger than the catalyst pore diameter, the catalyst can be prevented from falling. In this case, the space below the collar is a space for inflow or outflow of fluid, and a space for dropping and depositing products generated on the catalyst surface. In this embodiment, the holding plate 41 is shared with the cage 12. This cage is connected to the top of the elevating unit in the reaction vessel.
触媒柵４３が、触媒連４２を水平方向に向けて反応容器１１内に配置される場合には、中心棒４５の両端を保持板４１に接合する。 When the catalyst fence 43 is disposed in the reaction vessel 11 with the catalyst chain 42 oriented in the horizontal direction, both ends of the center bar 45 are joined to the holding plate 41.
（触媒柵の開口率）
触媒柵の開口率は、開口率＝（１−［触媒柵の主流に垂直な断面の断面積］／［触媒反応容器の主流に垂直方向の見かけ断面積］）×１００（％）として定義することができる。「主流」とは、反応容器１１へ供給された流体が、反応容器１１内でその流入口から流出口へと向かう流れ、として定義され、図９，１０の場合には、主流は触媒連３３に平行な方向の流体の流れとなる。触媒柵の開口率が大きいほど、通気抵抗が小さい。一方、開口率が過大だと必要な触媒反応容器体積が増大し、また、通気抵抗が小さいので吹き抜けも生じやすい。従って、開口率は、３０％以上６０％以下の範囲が好ましい。
(Catalyst fence opening ratio)
The opening ratio of the catalyst fence is defined as opening ratio = (1− [cross-sectional area perpendicular to the main flow of the catalyst fence] / [apparent cross-sectional area perpendicular to the main flow of the catalyst reaction vessel) × 100 (%). be able to. The “main flow” is defined as a flow in which the fluid supplied to the reaction vessel 11 is directed from the inlet to the outlet in the reaction vessel 11. In the case of FIGS. The flow of the fluid is parallel to the direction. The larger the opening ratio of the catalyst fence, the smaller the ventilation resistance. On the other hand, if the opening ratio is excessively large, the required volume of the catalytic reaction vessel increases, and the ventilation resistance is small, so that blow-through is likely to occur. Therefore, the aperture ratio is preferably in the range of 30% to 60%.
（触媒連の中心棒）
触媒連の中心棒は、触媒を貫くことでそれを損傷させないように、丸棒が好ましい。但し、加工の便宜等の理由によって、多角形断面の棒であってもよい。
(Catalyst center rod)
The center bar of the catalyst chain is preferably a round bar so as not to damage it by penetrating the catalyst. However, it may be a rod having a polygonal cross section for reasons of processing convenience or the like.
中心棒の直径は、触媒の孔径よりも小さくなければならない。また、触媒の保持や昇降運動に耐えうる強度を保ち、高温時のクリープ等による座屈を避けるために、適度の直径であることが好ましい。例えば、直径１ｍｍ以上、３０ｍｍ以下を適用することができる。 The diameter of the center rod must be smaller than the pore size of the catalyst. Moreover, in order to maintain the strength which can bear the holding | maintenance and raising / lowering movement of a catalyst, and to avoid buckling by the creep at the time of high temperature, it is preferable that it is a moderate diameter. For example, a diameter of 1 mm or more and 30 mm or less can be applied.
中心棒の材質は、強度・剛性・耐熱性等の観点から、また、高熱伝導性材料であるのが好ましいことから、金属、特に、ステンレス鋼、インコネル（登録商標）等のニッケル合金、チタン、チタン合金を用いることができる。また、銅、銅合金、アルミニウム、アルミニウム合金等は、高熱伝導性材料として特に好ましい。 The center rod is made of metal, particularly nickel alloys such as stainless steel and Inconel (registered trademark), titanium, titanium, from the viewpoint of strength, rigidity, heat resistance, and the like, and is preferably a highly heat conductive material. A titanium alloy can be used. Further, copper, copper alloy, aluminum, aluminum alloy and the like are particularly preferable as the high thermal conductivity material.
触媒連の末端には、加熱装置を設けることができる。 A heating device can be provided at the end of the catalyst chain.
（触媒連の保持板）
触媒連を支持する保持板は、中心棒を、溶接やねじ込みなどの方法で取り付けることができる材料で製作される。その材質は、強度・剛性・耐熱性等の観点から、中心棒と同様に、ステンレス鋼、インコネル（登録商標）等のニッケル合金、チタン、チタン合金などでよい。カラーを用いる場合、それも保持板の材料と同様の材料で製作することができる。
(Catalyst plate)
The holding plate that supports the catalyst train is made of a material that allows the center rod to be attached by a method such as welding or screwing. The material may be stainless steel, nickel alloy such as Inconel (registered trademark), titanium, titanium alloy, or the like, from the viewpoint of strength, rigidity, heat resistance, and the like. If a collar is used, it can also be made of a material similar to that of the holding plate.
（保持板の昇降速度）
上昇速度には特段の制約はない。下降速度は、固体堆積物を触媒表面から離脱させるのに十分な触媒間の相対運動を可能にするように設定する必要がある。極端に遅い下降速度では、触媒間で相対運動を生じないので好ましくない。下降速度は、触媒の自由落下速度（例：１００ｍｍ／ｓ）よりも速くすることができる。このようにすることによって、個々の触媒が下降する際に触媒と中心棒との接触状態に応じて下降速度のバラツキを生じ、触媒間で相対運動と衝突を生じさせることができる。
(Lifting speed of holding plate)
There are no particular restrictions on the ascent rate. The rate of descent needs to be set to allow relative movement between the catalysts sufficient to dislodge solid deposits from the catalyst surface. An extremely low descending speed is not preferable because no relative movement occurs between the catalysts. The descending speed can be higher than the free falling speed of the catalyst (for example, 100 mm / s). By doing so, when each catalyst descends, the descending speed varies according to the contact state between the catalyst and the center rod, and relative motion and collision can be caused between the catalysts.
（触媒の形状）
触媒は、触媒連から脱落しないことが必要である。従って、中心棒が貫通することができる孔を有する形状であることが有利である。例えば、リング状、円筒状、ダクト状等の触媒を用いることができる。また、触媒の脱落防止の要件を満たす形状として、中心棒の直径よりも開口幅の小さい馬蹄形としてもよい。
(Catalyst shape)
It is necessary that the catalyst does not fall out of the catalyst chain. Therefore, it is advantageous to have a shape with a hole through which the central bar can penetrate. For example, a ring-shaped, cylindrical, duct-shaped catalyst can be used. Further, as a shape satisfying the requirement for preventing the catalyst from falling off, a horseshoe shape having an opening width smaller than the diameter of the center rod may be used.
触媒の孔寸法は、触媒連の中心棒に対して自由に移動できるように、中心棒の直径よりも十分に大きくなければならない。特に、次に説明する第２の実施形態のように触媒連が水平に配置され、触媒柵の往復動が鉛直方向になされる場合には、個々の触媒の鉛直方向の相対移動（中心棒に対する）距離は、［中心孔径］−［中心棒直径］の範囲に限られるので、この差を十分に大きく設定することが好ましい。例えば、［中心孔径］を［中心棒直径］＋１ｍｍとすることができる。 The pore size of the catalyst must be sufficiently larger than the diameter of the center rod so that it can move freely with respect to the center rod of the catalyst chain. In particular, as in the second embodiment described below, when the catalyst train is arranged horizontally and the reciprocating motion of the catalyst fence is made in the vertical direction, the relative movement of the individual catalysts in the vertical direction (relative to the center rod). ) Since the distance is limited to the range of [center hole diameter] − [center rod diameter], it is preferable to set this difference sufficiently large. For example, the [center hole diameter] can be set to [center rod diameter] +1 mm.
（昇降機構）
昇降機（保持器）へのピンおよび下向き傾斜面の形状・接続方法は、第１及び第２の実施形態と同様でよい。
(Elevating mechanism)
The shape and connection method of the pins and the downward inclined surface to the elevator (retainer) may be the same as those in the first and second embodiments.
（昇降部）
本実施例においては、保持器は、昇降部と一体構造となっており、保持器の裏面に固定ピンおよび傾斜面部品が接続されている。また、保持器端部には触媒柵の保持板が接続されている。
（その他）
触媒保持器及び触媒層の構成以外の部分、すなわち、反応容器の形状、反応容器の材質、反応容器の寸法、昇降ストローク、昇降速度、触媒層の高さ、その他の適用可能事例等については、第１及び第２の実施態様で説明したと同様であるが、触媒層の保持機構の変更に応じて適当に変更してもよい。
(Elevating part)
In the present embodiment, the cage has an integrated structure with the elevating unit, and a fixing pin and an inclined surface component are connected to the back surface of the cage. A retainer plate of the catalyst fence is connected to the end of the retainer.
(Other)
For parts other than the structure of the catalyst holder and the catalyst layer, that is, the shape of the reaction vessel, the material of the reaction vessel, the dimensions of the reaction vessel, the lifting stroke, the lifting speed, the height of the catalyst layer, and other applicable cases, etc. Although it is the same as that of having demonstrated in the 1st and 2nd embodiment, you may change suitably according to the change of the retention mechanism of a catalyst layer.
[第４の実施形態]
図１２に示すように、爪部２０用の退避領域５１を設けてもよい。図１２は、爪部２０用の退避領域５１が設けられている以外は、図４，５の第１の実施態様と同様である。しかし、第２及び第３の実施態様と同様でもよいことは明らかである。
この実施態様では、反応装置は加熱炉（図示せず）の中にあるが、爪部２０の退避位置５１には、外部から供給された非反応性ガス２７を充満させて、爪部２０を反応から保護できる。昇降動作を必要としない、反応中の大半の期間は、爪部２０を退避領域５１に配置して、保護することができる。
[Fourth Embodiment]
As shown in FIG. 12, a retraction area 51 for the claw portion 20 may be provided. FIG. 12 is the same as the first embodiment of FIGS. 4 and 5 except that a retraction area 51 for the claw portion 20 is provided. However, it is obvious that the same may be applied to the second and third embodiments.
In this embodiment, the reactor is in a heating furnace (not shown), but the retraction position 51 of the claw portion 20 is filled with the non-reactive gas 27 supplied from the outside, and the claw portion 20 is Can be protected from reaction. The claw portion 20 can be disposed in the retreat area 51 to protect it during most of the reaction period that does not require the lifting operation.
[実施例１]
（反応系全体の構成）
石炭供給装置（石炭ホッパー定量供給器）から、加熱されたキルンに２０ｋｇ／時の速度で石炭を供給して石炭乾留ガス（石炭中の水分に起因する水蒸気を含む）を連続発生させた。触媒反応装置の流入口は、保温管によってキルンに接続し、触媒反応装置流出口は、保温管によってスクラバ経由で誘引ファンに接続した。石炭乾留ガスは、ガス中のタールが触媒反応容器で改質されて軽質ガス（水素等）を生成し、改質ガスとして誘引ファンによってフレアスタック（改質ガスを燃焼する）経由で大気中に放散させた。触媒反応容器は、炉温が一定温度に制御された電気加熱炉内に収容した。誘引ファンは、流量を調節でき、石炭乾留ガスの発生速度に対応する流量に制御された。
[Example 1]
(Composition of the entire reaction system)
Coal was supplied from a coal supply device (coal hopper quantitative supply device) to a heated kiln at a rate of 20 kg / hr to continuously generate coal dry distillation gas (including water vapor caused by moisture in the coal). The inlet of the catalyst reactor was connected to the kiln by a heat insulating tube, and the outlet of the catalyst reactor was connected to the induction fan via a scrubber by the heat insulating tube. In coal dry distillation gas, tar in the gas is reformed in a catalytic reaction vessel to produce light gas (hydrogen, etc.), which is then introduced into the atmosphere via a flare stack (burning reformed gas) by an induction fan as reformed gas. Dissipated. The catalytic reaction vessel was accommodated in an electric heating furnace in which the furnace temperature was controlled at a constant temperature. The induction fan was able to adjust the flow rate and was controlled to a flow rate corresponding to the generation rate of coal dry distillation gas.
図７，８に示した装置で試験した。反応器は加熱炉内に設置し、加熱炉は電気加熱炉であり、炉内を一定炉温度に制御可能なものである。駆動装置は加熱炉外に設置し、先端部爪は反応容器内に設置し、シール管は加熱炉壁を貫通して設けた。駆動装置軸の軸方向に往復運動可能なように、反応容器側にガイドが設けられている。 Tests were performed with the apparatus shown in FIGS. The reactor is installed in a heating furnace, and the heating furnace is an electric heating furnace, and the inside of the furnace can be controlled to a constant furnace temperature. The driving device was installed outside the heating furnace, the tip claw was installed in the reaction vessel, and the seal tube was provided through the heating furnace wall. A guide is provided on the reaction vessel side so as to reciprocate in the axial direction of the drive unit shaft.
（触媒反応装置）
使用した触媒反応装置は、次のとおりであった。
・反応容器形状： 中心軸垂直断面の形状・寸法が一定な矩形断面となるダクト状
・反応容器材質： ステンレス鋼
・反応容器厚： １２０ｍｍ
・反応容器幅： ３００ｍｍ
・反応容器高さ： ４５０ｍｍ
・触媒層高さ： ２３０ｍｍ
・触媒層アスペクト比： １．９
・触媒保持器： スレンレス丸棒製のピン式（図６に示すもの）
・触媒保持器のピン： 直径５．１ｍｍ、長さ９０ｍｍ、頂部は平坦、コーナ部１ｍｍを面取り
・触媒保持器のピンの配置： 底辺１６ｍｍ（反応容器幅方向）、高さ１３.５ｍｍ（反応容器厚方向）の二等辺三角形、全て触媒保持器底板に溶接
(Catalytic reactor)
The catalytic reactor used was as follows.
・ Reaction vessel shape: Duct shape with a rectangular cross-section with a constant central axis shape ・ Reaction vessel material: Stainless steel ・ Reaction vessel thickness: 120 mm
・ Reaction vessel width: 300 mm
・ Reaction container height: 450mm
・ Catalyst layer height: 230mm
Catalyst aspect ratio: 1.9
・ Catalyst cage: A pin type made of slender rods (shown in Fig. 6)
・ Catalyst cage pin: Diameter 5.1 mm, length 90 mm, flat top, chamfered corner 1 mm ・ Catalyst cage pin arrangement: bottom 16 mm (in the reaction vessel width direction), height 13.5 mm (reaction) Isosceles triangle in the container thickness direction), all welded to the catalyst retainer bottom plate
・触媒保持器のピン開口率： ９２％
・使用触媒量： ７ｋｇ
（昇降機構）
保持器の底板の裏面に、前記裏面との間に隙間を設けるように直径１２ｍｍの固定ピンを保持器に溶接して固定した。
・ Pin opening ratio of catalyst cage: 92%
・ Amount of catalyst used: 7kg
(Elevating mechanism)
A fixing pin having a diameter of 12 mm was welded and fixed to the rear surface of the bottom plate of the cage so as to provide a gap between the rear surface.
駆動装置： 市販の複動式エアシリンダ。推力：２０００Ｎ
駆動措置軸： φ４０ｍｍ丸棒。ハステロイＣ２２製。
シール管： ＪＩＳ ５０ＡのＳＵＳ３１０Ｓ管。
加熱炉外にＪＩＳ １０Ａのパージガス供給管を接続した。
爪： ハステロイＣ２２製。上向き斜面、下向き斜面とも１５／１００の勾配。
爪の隙間１５ｍｍ。
駆動装置ストローク：１００ｍｍ → 昇降装置ストローク：１５ｍｍ
駆動装置上昇速度： ３ｍｍ／秒
駆動装置下降速度： ３０ｍｍ／秒
操作タイミング： 石炭乾留ガス通気開始後、５時間２０分後（第１回昇降）および５時間３０分後（第2回昇降）。各２往復実施。
Drive unit: Commercially available double-acting air cylinder. Thrust: 2000N
Drive measure shaft: φ40mm round bar. Made of Hastelloy C22.
Seal tube: SUS310S tube of JIS 50A.
A JIS 10A purge gas supply pipe was connected to the outside of the heating furnace.
Nail: Made of Hastelloy C22. Slope of 15/100 for both upward and downward slopes.
Nail gap 15mm.
Drive device stroke: 100 mm → Lifting device stroke: 15 mm
Driving device ascent speed: 3 mm / sec Driving device descending speed: 30 mm / sec Operation timing: 5 hours and 20 minutes (first ascending and descending) and 5 hours 30 minutes (second ascending and descending) after the start of coal dry distillation gas aeration. 2 round trips each.
（触媒）
触媒としては、Ｎｉ0.1Ｃｅ0.1Ｍｇ0.8Ｏなる成分系のものを使用した。
硝酸ニッケル、硝酸セリウム、硝酸マグネシウムを各金属元素のモル比が１：１：８になるように精秤して、６０℃の加温で混合水溶液を調製したものに、６０℃に加温した炭酸カリウム水溶液を加えて、ニッケル、マグネシウム、及びセリウムを水酸化物として共沈させ、スターラーで十分に攪拌した。その後、６０℃に保持したまま一定時間攪拌を続けて熟成を行った後、吸引ろ過を行い、８０℃の純水で十分に洗浄を行った。洗浄後に得られた沈殿物を１２０℃で乾燥し粗粉砕した後、空気中６００℃で焼成（か焼）したものを解砕した後にビーカーに入れ、アルミナゾルを加えて攪拌羽根を取り付けた混合器で十分混合したものをなすフラスコに移してロータリーエバポレーターに取り付け、攪拌しながら吸引することで、水分を蒸発させた。なすフラスコ壁面に付着したニッケルとマグネシウムとセリウムとアルミナの化合物を蒸発皿に移して１２０℃で乾燥、６００℃でか焼後、粉末を圧縮成形器を用いて３ｍｍφの錠剤状にプレス成型し、外径１５ｍｍ、内径５ｍｍ、高さ１５ｍｍの円筒状成型体を得た。
(catalyst)
As the catalyst, a component system of Ni 0.1 Ce 0.1 Mg 0.8 O was used.
Nickel nitrate, cerium nitrate, and magnesium nitrate were precisely weighed so that the molar ratio of each metal element was 1: 1: 8, and a mixed aqueous solution was prepared by heating at 60 ° C., and heated to 60 ° C. A potassium carbonate aqueous solution was added to coprecipitate nickel, magnesium, and cerium as hydroxides, and the mixture was sufficiently stirred with a stirrer. Thereafter, the mixture was aged for a certain period of time while being kept at 60 ° C., and then subjected to suction filtration and sufficiently washed with pure water at 80 ° C. The precipitate obtained after washing was dried at 120 ° C. and coarsely pulverized, then baked (calcined) at 600 ° C. in the air, crushed, put into a beaker, added with alumina sol, and a mixer equipped with stirring blades Then, the mixture was transferred to a flask which was mixed well and attached to a rotary evaporator, and the water was evaporated by suction while stirring. The nickel, magnesium, cerium, and alumina compounds attached to the flask wall are transferred to an evaporating dish, dried at 120 ° C., calcined at 600 ° C., and pressed into a 3 mmφ tablet using a compression molding machine. A cylindrical molded body having an outer diameter of 15 mm, an inner diameter of 5 mm, and a height of 15 mm was obtained.
その成型体を空気中９５０℃で焼成を行い、Ｎｉ0.1Ｃｅ0.1Ｍｇ0.8Ｏにアルミナが５０質量％混合した触媒成型体を調製した。その成型体の成分をＩＣＰ分析で確認した結果、所望の成分であることを確認した。また、その成型体を木屋式硬度計で計測したところ、約１００Ｎの強度を保持することがわかった。 The molded body was fired in air at 950 ° C. to prepare a catalyst molded body in which 50% by mass of alumina was mixed with Ni 0.1 Ce 0.1 Mg 0.8 O. As a result of confirming the component of the molded body by ICP analysis, it was confirmed to be a desired component. Moreover, when the molding was measured with the Kiyama-type hardness meter, it turned out that the intensity | strength of about 100N is hold | maintained.
上記の触媒を図７，８に示した触媒反応装置に収容し、触媒層中央位置に熱電対を挿入した。 The above catalyst was accommodated in the catalyst reaction apparatus shown in FIGS. 7 and 8, and a thermocouple was inserted at the center position of the catalyst layer.
改質反応を始める前に、まず反応器を窒素雰囲気下で８００℃まで昇温した後、水素ガスを８０Ｎｌ／ｍｉｎ流しながら３０分間還元処理を行った。その後、コークス炉ガスを調整して導入し、常圧下、反応評価した。 Before starting the reforming reaction, the reactor was first heated to 800 ° C. in a nitrogen atmosphere, and then reduced for 30 minutes while flowing hydrogen gas at 80 Nl / min. Thereafter, coke oven gas was adjusted and introduced, and the reaction was evaluated under normal pressure.
（作業条件）
作業条件は、次のとおりであった。
・石炭乾留キルン温度： ７５０℃
・電気加熱炉温： ８００℃
・石炭乾留ガス流量： 平均１０Ｎｍ3／ｈ
・石炭乾留ガス通気時間： ５時間
（結果）
・通気性（圧力損失）の測定結果を図１３に示す。通気とともに、触媒間でのコーキングによって通気抵抗が徐々に増大したが、第１回、第２回の昇降操作によって、十分に圧力損失を低下させることができた。
(Process conditions)
The working conditions were as follows:
・ Coal dry distillation kiln temperature: 750 ℃
・ Electric heating furnace temperature: 800 ℃
・ Coal dry distillation gas flow rate: 10Nm 3 / h on average
・ Coal carbonization gas ventilation time: 5 hours (result)
-The measurement result of air permeability (pressure loss) is shown in FIG. Along with the aeration, the aeration resistance gradually increased by coking between the catalysts, but the pressure loss could be sufficiently reduced by the first and second elevating operations.
試験終了後に、保持器基板上に１００ｇの固体カーボンが堆積していたが、保持器表面には薄い固体カーボン膜を生じたのみであり、バルク状の固体カーボンのピンへの付着は一切なく、保持器の通気抵抗は、設置時と同一であった。 After completion of the test, 100 g of solid carbon was deposited on the cage substrate, but only a thin solid carbon film was formed on the cage surface, and there was no adhesion of bulk solid carbon to the pins. The airflow resistance of the cage was the same as when installed.
[実施例２]
（反応系全体の構成）
基本的に実施例１と同様であるが、図９、１０の装置において、触媒柵を図１１のものに置き換えて保持器に接続した装置を用いて、下記の条件で試験した。
[Example 2]
(Composition of the entire reaction system)
The test was basically performed in the same manner as in Example 1 except that the apparatus shown in FIGS. 9 and 10 was replaced with the catalyst fence shown in FIG. 11 and connected to a cage.
（昇降機構）
実施例１と同様の昇降機構及び昇降条件であるが、保持器の底板３０に下向き斜面３１（勾配１５／１００）を形成するともに、直径１２ｍｍの固定ピン１７を溶接した。操作タイミングは、石炭乾留ガス通気開始後、３．５時間後に触媒柵の昇降操作を実施し、各３往復実施した。
(Elevating mechanism)
The lifting mechanism and lifting conditions were the same as in Example 1, but a downward slope 31 (gradient 15/100) was formed on the bottom plate 30 of the cage, and a fixing pin 17 having a diameter of 12 mm was welded. As for the operation timing, the catalyst fence was moved up and down 3.5 hours after the start of aeration of the coal dry distillation gas, and each operation was performed three times.
（触媒反応装置）
反応容器１１は、ステンレス鋼製であり、寸法が８０ｍｍ厚×３００ｍｍ幅×７００ｍｍ高さで、上下に開口を持つダクト形状であった。反応容器１１のダクトの上端に、ＪＩＳ ８０Ａの流出管２９を、ダクトの下端にＪＩＳ １５０Ａの流入管２８を接続して通気するようにした。
(Catalytic reactor)
The reaction vessel 11 was made of stainless steel, had a size of 80 mm thickness × 300 mm width × 700 mm height, and had a duct shape with openings at the top and bottom. The outlet pipe 29 of JIS 80A was connected to the upper end of the duct of the reaction vessel 11, and the inlet pipe 28 of JIS 150A was connected to the lower end of the duct so as to ventilate.
（作業条件）
作業条件は、次のとおりであった。
・石炭乾留キルン温度： ７５０℃
・電気加熱炉温： ８００℃
・石炭乾留ガス流量： 平均１０Ｎｍ3／ｈ
・石炭乾留ガス通気時間： ５時間
改質反応を始める前に、まず反応器を窒素雰囲気下で８００℃まで昇温した後、水素ガスを８０Ｎｌ／ｍｉｎ流しながら３０分間還元処理を行った。その後、コークス炉ガスを調整して導入し、常圧下、反応評価した。
(Process conditions)
The working conditions were as follows:
・ Coal dry distillation kiln temperature: 750 ℃
・ Electric heating furnace temperature: 800 ℃
・ Coal dry distillation gas flow rate: 10Nm 3 / h on average
-Coal dry distillation gas aeration time: 5 hours Before starting the reforming reaction, the reactor was first heated to 800 ° C under a nitrogen atmosphere, and then reduced for 30 minutes while flowing hydrogen gas at 80 Nl / min. Thereafter, coke oven gas was adjusted and introduced, and the reaction was evaluated under normal pressure.
以下の触媒７ｋｇを当該触媒反応装置に収容し、触媒層中央位置に熱電対を挿入した。 7 kg of the following catalyst was accommodated in the catalyst reaction apparatus, and a thermocouple was inserted at the center position of the catalyst layer.
（触媒柵）
直径４ｍｍ、長さ５００ｍｍのステンレス製丸棒を中心棒として使用し、下端から８０ｍｍの位置に直径１０ｍｍの円筒状のカラーを溶接して、触媒の脱落防止とした。触媒連の中心棒を保持器である底板に溶接し、カラーの上の部分に３０個の触媒を貫通させて、触媒柵を製作した。触媒連の配置は、反応容器厚み方向に５列、幅方向に１４または１５列の千鳥配置とした。
(Catalyst fence)
A stainless steel round bar having a diameter of 4 mm and a length of 500 mm was used as a center bar, and a cylindrical collar having a diameter of 10 mm was welded at a position 80 mm from the lower end to prevent the catalyst from falling off. The catalyst bar was manufactured by welding the center rod of the catalyst string to the bottom plate, which is a cage, and passing 30 catalysts through the upper part of the collar. The arrangement of the catalyst trains was a staggered arrangement of 5 rows in the reaction vessel thickness direction and 14 or 15 rows in the width direction.
（保持板の駆動機構）
・駆動装置昇降ストローク： ２０ｍｍ
・駆動装置上昇速度： １０ｍｍ／秒
・駆動装置下降速度： ８０ｍｍ／秒
・操作タイミング： 石炭乾留ガス通気開始後３．５時間で３往復の昇降を行う
（結果）
図１５を使って試験結果を説明する。図１４の横軸は通気時間、左側の縦軸は反応容器での圧力損失、右側の縦軸は増幅水素流量（触媒単位質量当たりの、触媒による改質反応により反応容器内で生成した水素の流量）を表している。試験中に通気抵抗の上昇は特に認められなかった。石炭乾留ガス通気開始後に改質性能は徐々に低下したが、触媒柵の往復運動を実施した直後に、急激に回復した。
(Driving mechanism for holding plate)
・ Driver lifting stroke: 20mm
・ Drive device ascent speed: 10 mm / sec ・ Drive device ascent speed: 80 mm / sec ・ Operation timing: Move up and down three times in 3.5 hours after the start of aeration of coal dry distillation gas (result)
The test results will be described with reference to FIG. The horizontal axis in FIG. 14 is the ventilation time, the left vertical axis is the pressure loss in the reaction vessel, the right vertical axis is the amplified hydrogen flow rate (the amount of hydrogen generated in the reaction vessel by the reforming reaction by the catalyst per unit mass of the catalyst). Flow rate). No particular increase in ventilation resistance was observed during the test. The reforming performance gradually decreased after the start of aeration of coal dry distillation gas, but recovered rapidly immediately after the reciprocation of the catalyst fence.
試験終了後に、反応容器を冷却し、解体して内部を調査した結果、底板上に５０ｇの固体カーボンが堆積していたが、触媒上には顕著なバルク状の生成物は付着していなかった。 After completion of the test, the reaction vessel was cooled, disassembled, and the inside was examined. As a result, 50 g of solid carbon was deposited on the bottom plate, but no noticeable bulk product was deposited on the catalyst. .
[参考例１]
硝酸ニッケル、硝酸セリウム、硝酸酸化ジルコニウム、硝酸マグネシウムを各金属元素のモル比が１：１：１：７になるように精秤して、６０℃の加温で混合水溶液を調製したものに、６０℃に加温した炭酸カリウム水溶液を加えて、ニッケル、セリウム、ジルコニウム、及びマグネシウムを水酸化物として共沈させ、スターラーで十分に攪拌した。
[Reference Example 1]
To the one prepared by precisely weighing nickel nitrate, cerium nitrate, zirconium nitrate oxide and magnesium nitrate so that the molar ratio of each metal element is 1: 1: 1: 7, and preparing a mixed aqueous solution by heating at 60 ° C., A potassium carbonate aqueous solution heated to 60 ° C. was added to coprecipitate nickel, cerium, zirconium, and magnesium as hydroxides, and the mixture was sufficiently stirred with a stirrer.
その後、６０℃に保持したまま一定時間攪拌を続けて熟成を行った後、吸引ろ過を行い、８０℃の純水で十分に洗浄を行った。洗浄後に得られた沈殿物を１２０℃で乾燥し粗粉砕した後、空気中６００℃でか焼したものを解砕した後にビーカーに入れ、アルミナゾルを加えて攪拌羽根を取り付けた混合器で十分混合したものを、なすフラスコに移してロータリーエバポレーターに取り付け、攪拌しながら吸引することで、水分を蒸発させた。なすフラスコ壁面に付着したニッケルとマグネシウムとアルミナの化合物を蒸発皿に移して１２０℃で乾燥、６００℃でか焼後、圧縮成形器を用いて粉末を３ｍｍφの錠剤状にプレス成型し、錠剤成型体を得た。その成型体を空気中９５０℃で焼成を行い、Ｎｉ0.1Ｃｅ0.1Ｚｒ0.1Ｍｇ0.7Ｏにアルミナが５０質量％混合した触媒成型体を調製した。 Thereafter, the mixture was aged for a certain period of time while being kept at 60 ° C., and then subjected to suction filtration and sufficiently washed with pure water at 80 ° C. The precipitate obtained after washing is dried at 120 ° C and coarsely pulverized, then the material calcined at 600 ° C in the air is crushed and then placed in a beaker, mixed with alumina sol and thoroughly mixed in a mixer equipped with stirring blades The product was transferred to a flask made of eggplant, attached to a rotary evaporator, and sucked with stirring to evaporate water. The nickel, magnesium, and alumina compounds attached to the flask wall are transferred to an evaporating dish, dried at 120 ° C, calcined at 600 ° C, and then press-molded into 3mmφ tablets using a compression molding machine. Got the body. The molded body was fired in air at 950 ° C. to prepare a catalyst molded body in which 50% by mass of alumina was mixed with Ni 0.1 Ce 0.1 Zr 0.1 Mg 0.7 O.
その成型体の成分をＩＣＰ分析で確認した結果、所望の成分であることを確認した。また、本調製品をＸＲＤ測定した結果、ＮｉＭｇＯ、ＭｇＡｌ2Ｏ4、ＣｅxＺｒ1-xＯ2相からなることが判明し、各々の結晶子の大きさは、１４ｎｍ、１１ｎｍ、２２ｎｍであった。 As a result of confirming the component of the molded body by ICP analysis, it was confirmed to be a desired component. As a result of this preparation was subjected to XRD measurement, NiMgO, proved to consist of MgAl 2 O 4, Ce x Zr 1-x O 2 phases, the size of each crystallite, 14 nm, 11 nm, 22 nm met It was.
この触媒をＳＵＳ製反応管の中央に位置するよう石英ウールで固定し、触媒層中央位置に熱電対を挿入し、これら固定床反応管を所定の位置にセットした。 This catalyst was fixed with quartz wool so as to be located at the center of the reaction tube made of SUS, a thermocouple was inserted at the center position of the catalyst layer, and these fixed bed reaction tubes were set at predetermined positions.
改質反応を始める前に、まず反応容器を窒素雰囲気下で８００℃まで昇温した後、水素ガスを１００ｍＬ／ｍｉｎ流しながら３０分間還元処理を行った。その後、コークス炉ガス（粗ガス）の模擬ガス（水素：窒素＝１：１、Ｈ2Ｓを２０００ｐｐｍ含有、トータル流量１２５ｍＬ／ｍｉｎ）を調製して反応容器に導入するとともに、石炭乾留時発生タールの模擬物質として、タール中にも実際に含まれ且つ常温で粘度の低い液体物質である１−メチルナフタレンを代表物質として、０．０２５ｇ／ｍｉｎの流量で反応容器へ導入し、常圧下で反応させた。 Before starting the reforming reaction, the reaction vessel was first heated to 800 ° C. in a nitrogen atmosphere, and then reduced for 30 minutes while flowing hydrogen gas at 100 mL / min. Then, a simulated gas (hydrogen: nitrogen = 1: 1, containing 2000 ppm of H 2 S, total flow rate 125 mL / min) of coke oven gas (crude gas) is prepared and introduced into the reaction vessel, and tar generated during coal dry distillation As a representative substance, 1-methylnaphthalene, which is a liquid substance that is actually contained in tar and has a low viscosity at room temperature, is introduced into a reaction vessel at a flow rate of 0.025 g / min as a representative substance, and reacted under normal pressure. I let you.
試験終了後に触媒を回収して観察した結果、触媒間に大量のバルク状カーボンが堆積していた。この触媒および堆積物を篩分けしたところ、触媒表面のバルク状固体カーボンは、数回の軽微な振動で大半が触媒表面から離脱し篩の目を通過して落下した。 As a result of collecting and observing the catalyst after the test was completed, a large amount of bulk carbon was deposited between the catalysts. As a result of sieving the catalyst and the deposit, most of the bulk solid carbon on the catalyst surface was detached from the catalyst surface by several slight vibrations and dropped through the sieve eyes.
従って、本触媒を用いた場合、触媒間に堆積した固体カーボンの大半は、わずかな触媒振動で触媒間を通過して落下することがわかった。この結果から、本触媒を用いた改質反応において、実施例１や２の装置を用いれば、触媒への固体生成物の付着を大幅に回避できると考えられる。 Therefore, it was found that when this catalyst was used, most of the solid carbon deposited between the catalysts fell between the catalysts with slight catalyst vibration. From this result, it is considered that, in the reforming reaction using the present catalyst, if the apparatus of Examples 1 and 2 is used, adhesion of the solid product to the catalyst can be largely avoided.
[参考例２]
ニッケル、マグネシウム、ナトリウムの原子量％がそれぞれ１０％、８０％、１０％になるように精秤して、６０℃の加温で混合水溶液を調製したものに、６０℃に加温した炭酸カリウム水溶液を加えて、ニッケルとマグネシウムとナトリウムを水酸化物として共沈させ、スターラーで十分に攪拌した。その後、６０℃に保持したまま一定時間攪拌を続けて熟成を行った後、吸引ろ過を行い、８０℃の純水で十分に洗浄を行った。
[Reference Example 2]
A potassium carbonate aqueous solution heated to 60 ° C. was prepared by accurately weighing the atomic weight% of nickel, magnesium and sodium to 10%, 80% and 10%, respectively, and preparing a mixed aqueous solution by heating at 60 ° C. Was added, nickel, magnesium and sodium were coprecipitated as hydroxides and stirred well with a stirrer. Thereafter, the mixture was aged for a certain period of time while being kept at 60 ° C., and then subjected to suction filtration and sufficiently washed with pure water at 80 ° C.
洗浄後に得られた沈殿物を１２０℃で乾燥し粗粉砕した後、空気中６００℃で焼成（か焼）したものを解砕し、その後、粉末を圧縮成形器を用いて３ｍｍφの錠剤状にプレス成型し、錠剤成型体を得た。その成型体を空気中９５０℃で焼成を行い、Ｎｉ0.1Ｍ0.1Ｍｇ0.8Ｏの触媒成型体を調製した。 The precipitate obtained after washing is dried at 120 ° C. and coarsely pulverized, and then baked (calcinated) at 600 ° C. in the air, and then pulverized into a 3 mmφ tablet using a compression molding machine. Press molding was performed to obtain a tablet molding. The molded body was fired in air at 950 ° C. to prepare a Ni 0.1 M 0.1 Mg 0.8 O catalyst molded body.
この触媒をＳＵＳ製反応管の中央に位置するよう石英ウールで固定し、触媒層中央位置に熱電対を挿入し、これら固定床反応管を所定の位置にセットした。 This catalyst was fixed with quartz wool so as to be located at the center of the reaction tube made of SUS, a thermocouple was inserted at the center position of the catalyst layer, and these fixed bed reaction tubes were set at predetermined positions.
改質反応を始める前に、反応容器を窒素雰囲気下で８００℃まで昇温した後、水素ガスを１００ｍＬ／ｍｉｎ流しながら３０分間還元処理を行った。その後、コークス炉ガス（粗ガス）の模擬ガス（水素：窒素＝１：１、Ｈ2Ｓを２０００ｐｐｍ含有、トータル流量１２５ｍＬ／ｍｉｎ）を調製して反応容器に導入するとともに、石炭乾留時発生タールの模擬物質として、タール中にも実際に含まれかつ常温で粘度の低い液体物質である１−メチルナフタレンを代表物質として、０．０２５ｇ／ｍｉｎの流量で反応容器へ導入し、常圧下で反応させた。 Before starting the reforming reaction, the temperature of the reaction vessel was raised to 800 ° C. in a nitrogen atmosphere, and then reduction treatment was performed for 30 minutes while flowing hydrogen gas at 100 mL / min. Then, a simulated gas (hydrogen: nitrogen = 1: 1, containing 2000 ppm of H 2 S, total flow rate 125 mL / min) of coke oven gas (crude gas) is prepared and introduced into the reaction vessel, and tar generated during coal dry distillation As a representative substance, 1-methylnaphthalene, which is a liquid substance that is actually contained in tar and has a low viscosity at room temperature, is introduced into a reaction vessel at a flow rate of 0.025 g / min as a representative substance, and the reaction is performed under normal pressure. I let you.
試験終了後に触媒を回収して観察した結果、触媒間に大量のバルク状カーボンが堆積していた。この触媒および生成物を篩分けしたところ、触媒表面のバルク状固体カーボンは、数回の軽微な振動で大半が触媒表面から離脱し篩の目を通過して落下した。 As a result of collecting and observing the catalyst after the test was completed, a large amount of bulk carbon was deposited between the catalysts. As a result of sieving the catalyst and the product, most of the bulk solid carbon on the catalyst surface was detached from the catalyst surface by several slight vibrations and dropped through the mesh of the sieve.
従って、本触媒を用いた場合、触媒間に堆積した固体カーボンの大半は、わずかな触媒振動で触媒間を通過して落下することがわかった。この結果から、本触媒を用いた改質反応において、実施例１や２の装置を用いれば、触媒への固体生成物の付着を大幅に回避できると考えられる。 Therefore, it was found that when this catalyst was used, most of the solid carbon deposited between the catalysts fell between the catalysts with slight catalyst vibration. From this result, it is considered that, in the reforming reaction using the present catalyst, if the apparatus of Examples 1 and 2 is used, adhesion of the solid product to the catalyst can be largely avoided.
１：触媒反応容器、 ２：触媒、 ３：パンチングメタル又は網、 ４：原料ガス、 ６：流出口、 ７：改質ガス、
１０：連続式固定床触媒反応装置、 １１：反応容器、 １２：保持器、 １２ａ：ピン、 １２ｂ：底板、 １３：触媒層、 １４：原料ガス、 １５：改質ガス、 １６：昇降部、 １７：固定ピン、 １８：延長部、 １９：水平移動部、 ２０：爪、 ２１：駆動装置、 ２２：駆動軸、 ２３：シール管、 ２４：下向き斜面（爪側）、 ２５上向き斜面（爪側）、 ２６：非反応性ガス供給管、 ２７：非反応性ガス、 ２８：流入管、 ２９：流出管、
３０：保持器側部材、 ３１：下向き斜面（保持器側）、 ３２：上向き斜面（爪側）、
４１：保持板、 ４２：触媒連、 ４３：触媒柵、 ４４：触媒、 ４５：中心棒、
５１：爪部退避位置
1: catalytic reaction vessel, 2: catalyst, 3: punching metal or net, 4: raw material gas, 6: outlet, 7: reformed gas,
10: Continuous fixed bed catalyst reactor, 11: Reaction vessel, 12: Cage, 12a: Pin, 12b: Bottom plate, 13: Catalyst layer, 14: Raw material gas, 15: Reformed gas, 16: Lifting section, 17 : Fixing pin, 18: Extension part, 19: Horizontal movement part, 20: Claw, 21: Drive device, 22: Drive shaft, 23: Seal pipe, 24: Downward slope (claw side), 25 Upward slope (claw side) 26: non-reactive gas supply pipe, 27: non-reactive gas, 28: inflow pipe, 29: outflow pipe,
30: Cage side member, 31: Down slope (cage side), 32: Up slope (nail side),
41: holding plate, 42: catalyst chain, 43: catalyst fence, 44: catalyst, 45: center rod,
51: Claw retreat position
Claims (15)
Ｂ）加熱炉内に設置された、略重力方向に中心軸を持つ筒状である粒状体容器と、
Ｃ）粒状体容器内に粒状体を下方から保持する保持器と、
Ｄ）粒状体容器内に保持された粒状体に流体を通過させるための、粒状体容器の一端近傍に設けた流体の流入口及び他端近傍に設けた流体の流出口と、
Ｅ）粒状体撹拌手段とを具備する処理装置であって、
前記粒状体攪拌手段は、保持器を含んで保持器とともに昇降する昇降部と、保持器に接して昇降部に昇降のための駆動力を伝える水平移動部とから構成され、
前記水平移動部は、
−加熱炉内に設けられ、昇降部に接して水平方向に往復動して前記昇降部を昇降させる爪部と、
−加熱炉外に設けられ、前記爪部を水平方向に往復動させる駆動装置と
−加熱炉の壁を貫通して前記駆動装置と前記爪部を連結する連結軸と、
−前記連結軸周囲を囲って粒状体容器を加熱炉雰囲気から遮断するシ−ル手段とから構成され、
前記爪部は、前記駆動装置に向かう方向に上昇する上向き斜面と、前記駆動装置から遠ざかる方向に下降する下向き斜面とを有し、
前記昇降部は、前記昇降部に生じうるスラスト力を前記粒状体容器で受けるものであるとともに、前記爪部の上向き斜面と接触する位置、及び、前記爪部の下向き斜面と接触する位置を有し、
前記駆動装置が前記爪部を押出すと、前記爪部の前記上向き斜面が、前記爪部の上向き斜面と接触する位置で前記昇降部と接触しつつ、前記爪部の上向き斜面と接触する位置の前記昇降部を前記上向き斜面に沿ってスライドして、前記昇降部に上昇力を与えて、前記昇降部が前記粒状体容器の内壁に沿って上昇し、
前記駆動装置が前記爪部を引戻すと、前記爪部の前記下向き斜面が、前記爪部の下向き斜面と接触する位置で前記昇降部と接触しつつ、前記爪部の下向き斜面と接触する位置の前記昇降部を前記下向き斜面に沿ってスライドして、それに接する前記昇降部に下降力を与えて、前記昇降部が前記粒状体容器の内壁に沿って下降するとともに、
前記粒状体処理容器が前記粒状体として粒状の触媒を収納する連続式固定床触媒反応器であり、供給流体がガスであり、前記触媒を用いた流体の触媒反応による生成物が生成ガスと触媒上に析出する固体を含み、
前記析出する固体が前記触媒層中に堆積して前記触媒層が閉塞することを防止するための処理装置。 A) a heating furnace;
B) A granular container that is installed in a heating furnace and has a cylindrical shape with a central axis in a substantially gravitational direction;
C) a cage for holding the granular material in the granular material container from below;
D) a fluid inlet provided near one end of the granular container and a fluid outlet provided near the other end for allowing the fluid to pass through the granular body held in the granular container;
E) a processing apparatus comprising granular material stirring means,
The granular material stirring means includes a lifting unit that includes a cage and moves up and down with the cage, and a horizontal moving unit that contacts the cage and transmits a driving force for lifting to the lifting unit,
The horizontal moving part is
-A claw portion provided in the heating furnace, reciprocating in the horizontal direction in contact with the elevating unit and elevating the elevating unit;
A driving device that is provided outside the heating furnace and reciprocates the claw portion in the horizontal direction; and a connecting shaft that connects the driving device and the claw portion through a wall of the heating furnace;
-Sealing means surrounding the connecting shaft and shielding the granular container from the heating furnace atmosphere;
The claw portion has an upward slope that rises in a direction toward the drive device, and a downward slope that descends in a direction away from the drive device,
The elevating part receives the thrust force that can be generated in the elevating part by the granular material container, and has a position in contact with the upward slope of the claw part and a position in contact with the downward slope of the claw part. And
When the driving device pushes out the claw portion, the upward slope of the claw portion is in contact with the up-and-down portion at a position in contact with the upward slope of the claw portion, and is in contact with the upward slope of the claw portion. The elevating part is slid along the upward slope to give an elevating force to the elevating part, and the elevating part rises along the inner wall of the granular container,
When the driving device pulls back the claw portion, the downward slope of the claw portion is in contact with the downward slope of the claw portion while being in contact with the elevating portion at a position of contact with the downward slope of the claw portion. The elevating part is slid along the downward slope, giving a lowering force to the elevating part in contact with the elevating part, and the elevating part descends along the inner wall of the granular container,
The granular material processing container is a continuous fixed bed catalytic reactor in which a granular catalyst is accommodated as the granular material, a supply fluid is a gas, and a product by a catalytic reaction of the fluid using the catalyst is a product gas and a catalyst. Containing solids that precipitate on top,
A processing apparatus for preventing the deposited solid from being deposited in the catalyst layer and blocking the catalyst layer.
前記触媒を内部に貫通孔を有する形状とした触媒と、
前記内部に貫通孔を有する形状の触媒の複数を、前記貫通孔を通して個々の前記触媒を中心棒で貫いて一列に整列させた触媒連と、
複数の前記触媒連を間隔をあけて配列し、保持板に固定して形成した触媒柵と、を備え、
前記保持板が、前記保持器に固定されていることを特徴とする請求項１に記載の処理装置。 The form for storing the granular catalyst is:
A catalyst having a shape having a through-hole in the catalyst;
A plurality of catalysts having through holes in the interior, and a catalyst chain in which the individual catalysts are passed through the through holes with a central rod and aligned in a line;
A plurality of catalyst trains arranged at intervals, and a catalyst fence formed by being fixed to a holding plate,
The processing apparatus according to claim 1, wherein the holding plate is fixed to the cage.
ａ、ｂ、及び、ｃは、ａ＋ｂ＋ｃ＝１、０．０２≦ａ≦０．９８、０．０１≦ｂ≦０．９７、かつ、０．０１≦ｃ≦０．９７を満たし、
ｄは、酸素と陽性元素が電気的に中立となる値であり、
Ｍは、Ｔｉ，Ｚｒ，Ｃａ，Ｗ，Ｍｎ，Ｚｎ，Ｓｒ，Ｂａ，Ｔａ，Ｃｏ，Ｍｏ，Ｒｅ，白金、ルニウム、パラジウム、ロジウム、Ｌｉ，Ｎａ，Ｋ，Ｆｅ，Ｃｕ，Ｃｒ，Ｌａ，Ｐｒ，Ｎｄから選ばれる少なくとも１種類の元素であり、
前記複合酸化物に、シリカ、アルミナ、ゼオライトから選ばれる少なくとも１種類の酸化物を加え、シリカ、アルミナ、ゼオライトから選ばれる前記酸化物の含有量が、前記複合酸化物に対し１〜９０％質量％である、ことを特徴とする、請求項１２に記載の処理装置。 The catalyst is a catalyst for reforming a tar-containing gas, which is a composite oxide represented by aM · bNi · cMg · dO,
a, b, and c satisfy a + b + c = 1, 0.02 ≦ a ≦ 0.98, 0.01 ≦ b ≦ 0.97, and 0.01 ≦ c ≦ 0.97,
d is a value at which oxygen and positive elements are electrically neutral;
M is Ti, Zr, Ca, W, Mn, Zn, Sr, Ba, Ta, Co, Mo, Re, platinum, runium, palladium, rhodium, Li, Na, K, Fe, Cu, Cr, La, Pr. , Nd, and at least one element selected from Nd,
At least one oxide selected from silica, alumina, and zeolite is added to the composite oxide, and the content of the oxide selected from silica, alumina, and zeolite is 1 to 90% by mass with respect to the composite oxide. The processing apparatus according to claim 12, wherein the processing apparatus is%.
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