JP5904814B2 - Granule processing apparatus and granule processing method using the same - Google Patents
Granule processing apparatus and granule processing method using the same Download PDFInfo
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Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Catalysts (AREA)
Description
本発明は、静止している触媒等の粒状体の相対位置を変更する処理を必要とする反応器等の装置の技術に関する。 The present invention relates to the technology of an apparatus such as a reactor that requires a process for changing the relative position of a granular material such as a stationary catalyst.
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て、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、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 processing apparatus that statically accommodates a granular material in a container having an inlet / outlet (an inlet / outlet) and passes the fluid through a gap between the granular materials to process the fluid or the granular material, Widely applied to fixed bed reactors, heat exchangers, filters, etc. 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、流体が粒状触媒表面で反応を生じる反応器においては、粒状体（触媒）の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、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少なくとも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 catalyst, a region that easily contacts fresh fluid on the surface of the granular material (gap where the fluid flows at a large flow rate) due to the difference in the layout of the granular material (catalyst) gap. Distribution of a region that is difficult to be formed (a gap in which the flow stagnates or a surface where the granular materials are in contact) 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 granular material so that at least a part of the granular material surface that has been in contact with the previously stagnant fluid can be in contact with fresh fluid, the granular layout can be obtained. It can be expected that weight loss and deterioration on the body surface will be made uniform, 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、特許文献１（特開２０１０−７７２１９号公報）においては、水素・二酸化炭素・水蒸気・タール含有ガスを、固定床触媒反応装置において、ニッケル・セリウム・アルミニウムを含む触媒に接触させてタールガスの改質を行う技術が開示されており、この技術においては、改質中に触媒表面に固体炭素が析出し、これを除去するために水蒸気または空気を前記炭素に接触させる再生処理の必要なことが記載されている。 For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-77219), hydrogen, carbon dioxide, water vapor, and a tar-containing gas are brought into contact with a catalyst containing nickel, cerium, and aluminum in a fixed bed catalytic reaction apparatus. A technique for reforming is disclosed. In this technique, solid carbon is deposited on the surface of the catalyst during the reforming, and in order to remove it, it is necessary to perform a regeneration treatment in which water vapor or air is brought into contact with the carbon. Is described.
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。例えば、特許文献１には、移動床形式および流動床形式の触媒反応容器の使用も例示されている。これらの方式では触媒表面に析出した炭素を反応作業中に除去しうる。しかし、このような反応容器は、固定床触媒反応容器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容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. For example, Patent Literature 1 also exemplifies the use of moving bed type and fluidized bed type catalytic reaction vessels. In these systems, carbon deposited on the catalyst surface can be removed during the reaction operation. However, such a reaction vessel is more complicated than the fixed bed catalyst reaction vessel, and in the case of a fluidized bed type, the operation tends to become unstable. It is not common as a reaction vessel for processing a fluid.
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１２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１２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. 12, in which the catalyst 2 is accommodated in the catalyst reaction vessel 1, and the catalyst is held by a punching metal plate or a net 3. In FIG. 12, 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.
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。本発明の目的は、容器内に静的に収納された触媒などの粒状体間の相対位置を効率的に変更するのを可能にする粒状体処理装置と、これを用いて容器内の粒状体を処理する粒状体処理方法を提供することである。 Thus, in the prior art, there is no means for efficiently changing the relative position between the granular materials statically stored in the container. An object of the present invention is to provide a granular material processing apparatus that makes it possible to efficiently change a relative position between granular materials such as a catalyst statically stored in a container, and a granular material in a container using the same. It is providing the granule processing method which processes.
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）供給流体の流入路及び流出流体の流出路と、
流入路及び流出路に接続された粒状体処理容器であり、その内壁に接して粒状体層を鉛直方向に充填する粒状体処理容器と、
粒状体層を保持し、かつ、流体の通過が可能な粒状体保持器と、
を有する粒状体処理装置であって、前記粒状体処理容器は、その鉛直方向における少なくとも前記粒状体層が存在する部分において、幅が一定で、且つ、厚み方向に広がり角０．５°〜２０°の範囲で上方に向かうにつれ増大する矩形の水平断面積を有すること、そして当該装置は、前記粒状体保持器を昇降させることにより粒状体層全体を昇降させて、前記粒状体と前記内壁との摩擦を生じさせると共に前記粒状体層の充填率を変動させるための駆動機構を具備するとともに、
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、前記供給流体がガスであり、前記流出流体が当該反応容器での触媒反応生成物のガスであり、その触媒反応では副生物の固体が触媒上に析出して、前記触媒層中に堆積することを特徴とする、粒状体処理装置。
(1) a supply fluid inflow path and an outflow fluid outflow path;
A granular material processing container connected to the inflow path and the outflow path, and in contact with the inner wall of the granular material processing container to fill the granular material layer in the vertical direction;
A granular material holder that retains the granular material layer and allows passage of fluid;
The granular material processing container has a constant width at least in a portion where the granular material layer is present in the vertical direction , and a spread angle of 0.5 ° to 20 ° in the thickness direction . A rectangular horizontal cross-sectional area that increases upward in the range of °, and the apparatus raises and lowers the entire granular material layer by raising and lowering the granular material holder, and the granular material and the inner wall And a drive mechanism for changing the filling rate of the granular layer,
The granular material processing container is a continuous fixed bed catalyst reactor that stores a granular catalyst as the granular material, the supply fluid is a gas, and the outflow fluid is a gas of a catalytic reaction product in the reaction container. In the catalytic reaction, a by-product solid is deposited on the catalyst and deposited in the catalyst layer.
（２）前記保持器が、前記粒状体を略平行に配置された複数のピンの先端部で保持し、且つ、前記複数のピンにおける隣り合うピンの間隔が前記粒状体の大きさよりも小さいように配置され、前記供給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（１）に記載の粒状体処理装置。 (2) The retainer holds the granular body at the tip portions of a plurality of pins arranged substantially in parallel, and the interval between adjacent pins in the plurality of pins is smaller than the size of the granular body. The granular material processing apparatus according to (1) above, wherein the granular material processing apparatus has a structure in which the supply fluid can flow through a space between the pins.
（３）前記保持器が、粒状体が隙間を落下しないように間隔をあけて配列した２以上の棒で粒状体を保持し、棒の中心軸の水平面投影成分は互いに平行とし、隣り合う棒の中心軸の鉛直面投影成分またはその延長線は互いに交差する構造を有することを特徴とする、上記（１）に記載の粒状体処理装置。 (3) The cage holds the granule with two or more bars arranged at intervals so that the granule does not fall through the gap, the horizontal projection components of the central axis of the rods are parallel to each other, and the adjacent bars The granular material processing apparatus according to (1) above, wherein the vertical plane projection component of the central axis of the center or the extension line thereof intersect each other.
（４）前記粒状体処理容器が、角型ダクト状であり、
前記粒状体層の鉛直方向の高さが、前記粒状体処理容器の最小厚みの３倍以下であり、かつ、粒状体の３層分以上であることを特徴とする、請求項１から３のいずれか１項に記載の粒状体処理装置。
(4) The granular material processing container has a rectangular duct shape,
The vertical height of the granular material layer is not more than three times the minimum thickness of the granular material processing container, and is not less than three layers of the granular material, The granule processing apparatus of any one of Claims.
（５）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）から（４）のいずれか１つに記載の粒状体処理装置。 (5) The granular material processing apparatus according to any one of (1) to (4), wherein a speed when the drive mechanism is lowered is faster than a speed when the drive mechanism is raised.
（６）前記供給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と固体の炭化水素または固体のカーボンとであることを特徴とする、上記（５）に記載の粒状体処理装置。 ( 6 ) The granular material as described in ( 5 ) above, wherein the supply fluid is a gas containing hydrocarbon, and the product of the catalytic reaction is a gas and solid hydrocarbon or solid carbon. Processing equipment.
（７）前記炭化水素を含有するガスがタールを含有することを特徴とする、上記（６）に記載の粒状体処理装置。 ( 7 ) The granular material processing apparatus according to ( 6 ) above, wherein the hydrocarbon-containing gas contains tar.
（８）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（１）〜（７）のいずれか１つに記載の粒状体処理装置。 ( 8 ) The catalyst is a composite oxide containing nickel, magnesium, cerium, and aluminum, and is made of a composite oxide not containing alumina, and the composite oxide is NiMgO, MgAl 2 O 4 , CeO. It consists of two crystal phases, The granular material processing apparatus as described in any one of said (1)-(7) characterized by the above-mentioned.
（９）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（１）〜（７）のいずれか１つに記載の粒状体処理装置。 (9) wherein the catalyst is a catalyst comprising a composite oxide containing nickel, magnesium, cerium, zirconium, aluminum, the complex oxide, NiMgO, MgAl 2 O 4, Ce X Zr 1-X O 2 (0 <X <1) The granular material processing apparatus as described in any one of (1) to (7) above, which includes a crystal phase.
（１０）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（１）〜（７）のいずれか１つに記載の粒状体処理。
( 10 ) The catalyst is
A tar-containing gas reforming catalyst 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 , 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. Is,
The granular material treatment according to any one of (1) to (7) above, wherein
（１１）前記粒状体層とそれを保持する粒状体保持器とを複数有し、隣接する粒状体保持器どうしが連結して一体化されていることを特徴とする、上記（１）から（１０）のいずれか１つに記載の粒状体処理装置。
（１２）前記広がり角が２．５°〜４°の範囲であり、前記触媒層のアスペクト比である、触媒層高さ／触媒層下端厚が、３以下であることを特徴とする、上記（４）から（１１）のいずれか１つに記載の粒状体処理装置。
( 11 ) From the above (1), characterized in that it has a plurality of the granular material layers and the granular material holders that hold the granular material layers, and adjacent granular material holders are connected and integrated. 10 ) The granular material processing apparatus as described in any one of 10 ).
(12) The divergence angle is in the range of 2.5 ° to 4 °, and the catalyst layer height / catalyst layer lower end thickness, which is the aspect ratio of the catalyst layer, is 3 or less, The granular material processing apparatus according to any one of (4) to (11).
（１３）上記（１）から（１２）のいずれか１つに記載の粒状体処理装置を使用し、前記粒状体層を昇降させることで前記粒状体の処理を行い、前記粒状体層中に堆積する固体堆積物を除去することを特徴とする、粒状体処理方法。 (13) using the granulate processing apparatus according to any one of the above (1) to (12), it has row processing of the granulate by lifting the granular layer, the granular layer in the A method for treating a granular material, comprising removing solid deposits deposited on the surface.
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。なお、以下では、「粒状体」を「触媒（粒）」を例とし、「粒状体処置装置」を「触媒反応装置」を例として説明する。 Here, the background of the inventor's arrival at the present invention will be described as follows. In the following, a "granulate" as an example a "catalyst (grain)", that describes the "granulate treatment device" as an example "catalytic reactor".
本発明者らの調査の結果、固定床触媒反応器の閉塞除去を例に説明すれば、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。
（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。
（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。
（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。
（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。
（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。
（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）。
（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）。
As a result of the investigation by the present inventors, it was found that the mechanism for depositing the generated solid carbon between the catalysts in the fixed bed catalyst layer was as follows, taking clogging removal of the fixed bed catalyst reactor as an example. .
(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 from the gap on the upstream side of the mainstream, and from the gap on the downstream side of the mainstream The reformed gas (a part of the remaining raw material gas) flows out as the reformed gas.
(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) When the raw material gas supplied to the inter-catalyst space is reformed by a catalytic reaction, the solid carbon fine particles generated on the catalyst surface and separated from the catalyst surface by the air flow are solid carbon particles already attached to the catalyst surface. A carbon sphere having a diameter of several tens μm to about 1 mm grows on the catalyst surface.
(4) The above-mentioned carbon spheres are sometimes detached from the catalyst surface and reattached on other carbon spheres already present, so that the thickness composed of multi-layer carbon spheres on the catalyst surface is several millimeters. A deposited layer of solid carbon is formed.
(5) Since this solid carbon deposition layer is substantially porous, a large pressure loss occurs when high-speed gas flows.
(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) 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 and a “clogged state” occurs (in the catalyst reaction vessel, the raw material gas is supplied at a given flow rate). No matter which catalyst space is vented at this given gas flow rate, the pressure loss can be prevented from exceeding the allowable value of the reactor (determined by gas transfer capacity, vessel strength, etc.). In the absence, 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。 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、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 catalytic reaction byproduct, 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いので、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 a large number of 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.
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。 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「最密重点化」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、堆積していたカーボンは、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 catalyst is in a state of close packing or close to that by vibration (for the sake of simplicity, this will be referred to as “closest emphasis” hereinafter). 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]
Thus, the deposited carbon 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.
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、次のことがわかった。すなわち、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。 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, the following was found. That is, 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 is necessary to secure.
図１に、従来の代表的な反応容器形状である、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構成の装置において、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／触媒層下端厚は、以下において触媒層の「アスペクト比」とも呼ぶ指標である。触媒層下端厚は、触媒層下端における反応容器厚方向の触媒層の長さに相当する。反応容器厚は、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。 In FIG. 1, 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, which is a typical conventional reaction vessel shape, and a cage is provided below the catalyst layer. In the apparatus configured to hold the catalyst layer, by raising the cage by 27 mm, the catalyst layer upper end height in a 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 The upper height of the catalyst layer expressed as a displacement of the height is shown. 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 / catalyst layer lower end thickness on the horizontal axis is an index also referred to as “aspect ratio” of the catalyst layer below. The catalyst layer lower end thickness corresponds to the length of the catalyst layer in the reaction vessel thickness direction at the catalyst layer lower end. The reaction vessel thickness corresponds to, for example, the length of the short side when the horizontal cross section of the reaction vessel is rectangular, and the diameter when the reaction vessel is circular.
図１から、触媒層のアスペクト比（触媒層高さ／触媒層下端厚）＞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. 1, when the aspect ratio of the catalyst layer (catalyst layer height / catalyst layer lower end 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 amount of increase in () is much smaller than the amount of increase in the cage (27 mm) and the 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、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, the catalyst layer moves up and down while the catalyst is in contact with the inner wall of the reaction vessel. The effect of generating can be demonstrated. 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.
しかしながら、好適な触媒層の高さには以下のように上限が存在する。
触媒層アスペクト比（触媒層高さ／触媒層下端厚）に対して、特定の条件において触媒層を押し上げる際の触媒層下端の押し上げストロークを基準として規格化した触媒層上端高さの変位の測定結果をプロットした図２を参照して説明すると、従来の反応容器形状である、垂直断面の形状・寸法が一定で水平断面積が均一の反応容器（広がり角０°）の場合、触媒層全体で触媒を相対運動させるためには、触媒層のアスペクト比は２以下であることが必要である。これは、先に図１を参照してした説明と一致する。即ち、触媒層撹拌の観点から、触媒層は、高さ方向に薄く設定しなければならない。
However, there is an upper limit to the preferred catalyst layer height as follows.
Measurement of displacement of catalyst layer upper end height normalized with respect to catalyst layer aspect ratio (catalyst layer height / catalyst layer lower end thickness) with reference to the pushing stroke of the catalyst layer lower end when pushing up the catalyst layer under specific conditions Referring to FIG. 2 in which the results are plotted, in the case of a conventional reaction vessel shape having a uniform vertical cross-sectional shape and size and a uniform horizontal cross-sectional area (a spread angle of 0 °), the entire catalyst layer In order to make the catalyst relatively move, the aspect ratio of the catalyst layer needs to be 2 or less. This is consistent with the description given above with reference to FIG. That is, from the viewpoint of stirring the catalyst layer, the catalyst layer must be set thin in the height direction.
図３は、触媒が破壊しないものとして離散要素法（ＤＥＭ）で数値計算した結果であり、この図から明らかなように、触媒層の高さが増大するにつれて、触媒層を上昇させるのに必要な力は加速度的に増大し、これに伴って触媒に付与される荷重も急増する。従って、一般的な触媒（例：圧壊強度１００Ｎ）を破壊しないレベルに触媒に負荷される荷重を維持するように触媒層への上昇力を制限するためには、従来の反応容器形状である広がり角０°の触媒反応器を前提とした場合、アスペクト比が２程度以下であるのが好ましい。即ち、触媒層押し上げ荷重の観点から、触媒層は、高さ方向に薄く設定しなければならない。 FIG. 3 shows the result of numerical calculation by the discrete element method (DEM) assuming that the catalyst does not break. As is clear from this figure, it is necessary to raise the catalyst layer as the height of the catalyst layer increases. As the force increases at an accelerated rate, the load applied to the catalyst increases rapidly. Therefore, in order to limit the ascending force to the catalyst layer so as to maintain the load applied to the catalyst at a level that does not destroy a general catalyst (eg, crushing strength 100 N), the conventional reaction vessel shape spread Assuming a catalyst reactor having an angle of 0 °, the aspect ratio is preferably about 2 or less. That is, from the viewpoint of the catalyst layer push-up load, the catalyst layer must be set thin in the height direction.
しかし、高さ方向に薄い触媒層にはいくつかの問題点が存在する。
第１の問題は、吹き抜け現象の発生に関するものである。吹き抜け現象とは、触媒層に流入する原料ガスが触媒層中の局所を集中的に流通し、かつ、ほとんど改質されることなく触媒層から流出する状態のことをいう。吹き抜け現象は、触媒層中の特定の部位において触媒活性が何らかの原因で低く、かつ、そこでの通気抵抗が低い場合に生じ易い。コーキングを生じる触媒改質反応の場合、触媒活性の低い領域ではコーキングによる局所での圧損上昇を生じにくいので触媒活性の低い領域を集中的に原料ガスが通気しやすい。このため、この様な触媒層では吹き抜け現象が生じる可能性がある。但し、このような触媒の低活性領域は一般に局所的なものであり、高さ方向（即ち、原料ガスの通気方向）に連続して存在することは稀なので、触媒層が高さ方向に十分に厚ければ吹き抜け現象は容易には生じない。しかし、高さ方向に触媒層が極端に薄い場合、例えば、上記局所的に発生しうる触媒低活性領域長さと同程度の触媒層厚みしかない場合、一旦、触媒低活性領域が発生すると、そこを集中的に原料ガスが通気することになり、吹き抜け現象を生じてしまう。従って、吹き抜け防止の観点から、高さ方向に触媒層を可能な限り厚く設定することが好ましい。
However, there are some problems with the catalyst layer that is thin in the height direction.
The first problem relates to the occurrence of a blow-through phenomenon. The blow-through phenomenon refers to a state in which the raw material gas flowing into the catalyst layer circulates locally in the catalyst layer and flows out of the catalyst layer with almost no modification. The blow-through phenomenon is likely to occur when the catalytic activity is low for a certain reason in a specific part of the catalyst layer and the ventilation resistance is low there. In the case of a catalytic reforming reaction that causes coking, it is difficult for local pressure loss to increase due to coking in a region where the catalytic activity is low. For this reason, a blow-through phenomenon may occur in such a catalyst layer. However, since the low activity region of such a catalyst is generally local and rarely exists continuously in the height direction (that is, the flow direction of the raw material gas), the catalyst layer is sufficient in the height direction. If it is too thick, the blow-through phenomenon does not easily occur. However, if the catalyst layer is extremely thin in the height direction, for example, if there is only a catalyst layer thickness comparable to the locally generated catalyst low active region length, once the catalyst low active region is generated, As a result, the source gas is intensively ventilated, resulting in a blow-through phenomenon. Therefore, from the viewpoint of preventing blow-through, it is preferable to set the catalyst layer as thick as possible in the height direction.
第２の問題は、反応容器の等方性に関するものである。触媒層高さと同様に、触媒層厚にも上限が存在する。これは、改質反応に必要な熱の授受を反応容器外部から反応容器外壁面を通じて行う場合には、反応容器の厚方向中心部においても十分に伝熱がなされるように、極端に厚い反応容器を避けなければならないからである。反応容器に充填される触媒層には触媒反応装置の所要改質性能から規定される所要体積が存在するため、上述のように触媒層高さおよび厚みに上限が存在する場合に大量の触媒を充填する触媒反応器を実現しようとすれば、反応容器幅を大きく設定せざるをえない。その結果、反応容器の形状が著しく細長い（幅方向に長い）ものとなりうるので、設計上の大きな制約となる。なぜならば、一般に反応容器の寸法の等方性が低いほど、比表面積が上昇するので、所要触媒体積に対して容器製作のためにより多量の材料を必要とするとともに、大きな据え付け面積を必要とする等の不利を生じるからである。この観点からも、高さ方向の触媒層を可能な限り厚く設定することが好ましい。 The second problem relates to the isotropy of the reaction vessel. Similar to the catalyst layer height, there is an upper limit to the catalyst layer thickness. This is because when the heat necessary for the reforming reaction is transferred from the outside of the reaction vessel through the outer wall surface of the reaction vessel, an extremely thick reaction is performed so that sufficient heat transfer is performed even in the central portion in the thickness direction of the reaction vessel. This is because the container must be avoided. Since the catalyst layer filled in the reaction vessel has a required volume defined by the required reforming performance of the catalyst reactor, a large amount of catalyst is added when there is an upper limit in the catalyst layer height and thickness as described above. If a catalytic reactor to be filled is to be realized, the reaction vessel width must be set large. As a result, the shape of the reaction vessel can be extremely long (long in the width direction), which is a great design limitation. This is because, in general, the lower the isotropic dimension of the reaction vessel, the higher the specific surface area. Therefore, a larger amount of material is required for manufacturing the vessel with respect to the required catalyst volume, and a larger installation area is required. This is because of disadvantages such as. From this viewpoint, it is preferable to set the catalyst layer in the height direction as thick as possible.
そこで、本発明では、触媒反応容器の水平断面積を上部ほど大きくした形状の触媒反応器（以下「上広型触媒反応容器」と呼ぶことにする）を用い、それによって平均的な触媒層厚の上限の範囲内で、触媒層高さを極力大きく設定できるようにしている。 Therefore, in the present invention, a catalyst reactor having a shape in which the horizontal cross-sectional area of the catalyst reaction vessel is increased toward the top is used (hereinafter referred to as an “upper-wide catalyst reaction vessel”), whereby the average catalyst layer thickness is increased. Within the upper limit range, the catalyst layer height can be set as large as possible.
本発明によれば、例えば図２に示したように、触媒層アスペクト比が３の場合、触媒上端変位（触媒層上端高さ/昇降機ストローク）は、従来形状の広がり角０°では高々、０．１程度しか期待できないのに対し、本発明形状である広がり角を２．５°に設定した場合には、約０.３以上の値を示しており、本発明形状では触媒層昇降に対して触媒層全体がより追従し易くなっていることがわかる。つまり、広がり角２．５°の上広型触媒反応容器とすることによって、触媒層アスペクト比が約３であっても触媒層全体で触媒を大きく相対運動させることができ、高い粒子撹拌効果を得ることができる（「広がり角」の定義は後記のとおり）。 According to the present invention, as shown in FIG. 2, for example, when the catalyst layer aspect ratio is 3, the catalyst upper end displacement (catalyst layer upper end height / elevator stroke) is at most 0 when the spread angle of the conventional shape is 0 °. Whereas it can only be expected to be about 1, when the divergence angle of the present invention is set to 2.5 °, a value of about 0.3 or more is shown. It can be seen that the entire catalyst layer is easier to follow. In other words, by using a wide catalyst reaction vessel with a widening angle of 2.5 °, the catalyst can be greatly moved relative to the entire catalyst layer even if the catalyst layer aspect ratio is about 3, and a high particle stirring effect can be obtained. (The definition of “divergence angle” is as described below.)
図２に例示した上広型触媒反応容器の広がり角２．５°は、小さな角度に過ぎない。例えば、触媒層下端厚さが１２０ｍｍ、触媒層アスペクト比（触媒層高さ／触媒層下端厚）が３（触媒層高さ３６０ｍｍ）の場合、触媒層上端厚さは、高々１３５ｍｍである。仮に、触媒層全体で上広型時の最大厚１３５ｍｍ（広がり角０°）としても、広がり角０°において効率的な撹拌の可能な触媒層高さの限界（アスペクト比２）は、２７０ｍｍに過ぎない。これに対して、上広型では３６０ｍｍまで、効率的な撹拌が可能である。このとおり、本発明による上広型触媒反応容器には、単に上部で触媒層厚を大きくした以上の、特別な効果がある。 The spread angle of 2.5 ° of the upper wide catalytic reaction vessel illustrated in FIG. 2 is only a small angle. For example, when the catalyst layer lower end thickness is 120 mm and the catalyst layer aspect ratio (catalyst layer height / catalyst layer lower end thickness) is 3 (catalyst layer height 360 mm), the catalyst layer upper end thickness is at most 135 mm. Even if the entire catalyst layer has a maximum thickness of 135 mm (expansion angle 0 °) when the upper catalyst is wide, the limit of the catalyst layer height (aspect ratio 2) that allows efficient stirring at an expansion angle of 0 ° is 270 mm. Not too much. On the other hand, in the upper wide type, efficient stirring is possible up to 360 mm. As described above, the wide catalytic reaction vessel according to the present invention has a special effect that is more than simply increasing the thickness of the catalyst layer at the top.
また、容器を上広型にすることによって、触媒層押し上げ時の推力も大幅に減少させることができ、触媒や容器の変形や破損を減少させることができる。例えば、アスペクト比５（触媒層下端厚１２０ｍｍ、触媒層高さ６００ｍｍ）の条件で、広がり角４°の容器での触媒層押し上げ時のピーク荷重は、図３に示したように、広がり角０°の容器の場合の約１／４に低下する。この触媒層押し上げ時のピーク荷重の減少効果は、主に容器形状を上広型に設定したことによるものである。なぜならば、広がり角４°の場合には触媒層上部で容器厚さが増大して実質的なアスペクト比が減少することによる押し上げ荷重減少効果も考えられるが、この効果は小さいからである。広がり角４°の条件において触媒層上端部での容器厚さは１６０ｍｍである。仮に、全高さにわたって厚さ１６０ｍｍとした広がり角０°の容器の場合（触媒層高さは６００ｍｍのまま）、アスペクト比は、３.７５となる。図３における触媒層高さとピーク荷重の関係から推定される、このときの押し上げ荷重ピーク値は、高々、アスペクト比５の場合のおよそ半分に減少するに過ぎない。 Further, by making the container wider, the thrust when the catalyst layer is pushed up can be greatly reduced, and the deformation and breakage of the catalyst and the container can be reduced. For example, when the aspect ratio is 5 (catalyst layer lower end thickness: 120 mm, catalyst layer height: 600 mm), the peak load when the catalyst layer is pushed up in a container having a spread angle of 4 ° is 0 as shown in FIG. It drops to about 1/4 of the case of a container of °. The effect of reducing the peak load at the time of pushing up the catalyst layer is mainly due to the fact that the container shape is set to the upper wide type. This is because, when the spread angle is 4 °, the effect of reducing the push-up load due to the increase of the container thickness at the upper part of the catalyst layer and the reduction of the substantial aspect ratio can be considered, but this effect is small. Under the condition of a spread angle of 4 °, the container thickness at the upper end of the catalyst layer is 160 mm. Temporarily, in the case of a container having a spread angle of 0 ° with a thickness of 160 mm over the entire height (the catalyst layer height remains at 600 mm), the aspect ratio is 3.75. The push-up load peak value at this time estimated from the relationship between the catalyst layer height and the peak load in FIG. 3 is only reduced to about half that in the case of the aspect ratio of 5.
以上のように、触媒撹拌および触媒層押し上げ荷重の観点から、本発明における上広型反応容器は、従来型反応容器に対して、高さ方向に触媒層をより厚くすることが可能であり、広がり角の設定次第で少なくとも３程度の触媒層アスペクト比を実現することができる。尚、広がり角を十分大きく設定することによってより大きなアスペクト比でも好適に昇降作業できる可能性がある。しかし、広がり角度とアスペクト比が同時に増大するにつれて、上広型触媒反応容器に対応する従来型反応容器での触媒層上端厚（上記の例では、触媒層下端厚１２０ｍｍ・広がり角４°・アスペクト比５の上広型反応器に対応する従来型反応器での触媒層上端厚は、１６０ｍｍ）が急増するため、上広型反応器の効果を従来型反応容器と比較し難くなる。また、上記の実例のように、広がり角が微小角である範囲（即ち、反応容器側壁間を略平行とみなせる範囲）でのみ、触媒層のアスペクト比の定義は、高い妥当性を有する。例えば、広がり角が鈍角の場合、触媒層下端幅を用いて定義した上記のアスペクト比には物理的に妥当な意味が存在しない。また、広がり角が、鈍角のように極端に大きい場合、触媒撹拌の実効性も悪化する。なぜならば、この様な形状の反応容器内で触媒層の底部を上昇させたとしても、触媒層の厚方向中心部近傍の触媒しか上昇運動に追従せず、壁面近傍の触媒を撹拌することができないからである。従って、広がり角の増大によってアスペクト比３を大きく超える作業は、好適に行うことが困難であるか、あるいは、妥当には定義できない。尚、上記の例から、少なくとも広がり角が２．５°〜４°の範囲では本発明の顕著な効果を発揮できる。 As described above, from the viewpoint of catalyst stirring and catalyst layer push-up load, the broad reaction vessel in the present invention can make the catalyst layer thicker in the height direction than the conventional reaction vessel, Depending on the setting of the divergence angle, a catalyst layer aspect ratio of at least about 3 can be realized. Note that by setting the spread angle sufficiently large, there is a possibility that the lifting operation can be suitably performed even with a larger aspect ratio. However, as the spread angle and aspect ratio increase at the same time, the catalyst layer upper end thickness in the conventional reaction vessel corresponding to the upper catalyst reaction vessel (in the above example, the catalyst layer lower end thickness is 120 mm, the spread angle is 4 °, the aspect ratio). The catalyst layer upper end thickness in the conventional reactor corresponding to the upper reactor with a ratio of 5 increases rapidly (160 mm), making it difficult to compare the effect of the upper reactor with that of the conventional reactor. Further, as in the above-described example, the definition of the aspect ratio of the catalyst layer has high validity only in a range where the spread angle is a minute angle (that is, a range in which the reaction vessel side walls can be regarded as substantially parallel). For example, when the divergence angle is an obtuse angle, the above aspect ratio defined using the bottom width of the catalyst layer does not have a physically reasonable meaning. Moreover, when the divergence angle is extremely large, such as an obtuse angle, the effectiveness of catalyst agitation also deteriorates. This is because even if the bottom of the catalyst layer is raised in the reaction vessel having such a shape, only the catalyst near the center in the thickness direction of the catalyst layer can follow the upward movement, and the catalyst near the wall surface can be stirred. It is not possible. Therefore, an operation that greatly exceeds an aspect ratio of 3 due to an increase in the spread angle is difficult to perform suitably or cannot be defined properly. From the above example, the remarkable effect of the present invention can be exhibited at least in the range of the divergence angle of 2.5 ° to 4 °.
（上広型触媒反応容器での効果発揮の原理）
図４（従来技術、触媒反応容器の広がり角＝０）と、図５（本発明、触媒反応容器の広がり角＞０）を用いて説明する。前提として、第一に、粒子層（触媒層）の移動に対して反応容器壁の影響の大きい粒子層（図３でアスペクト比が大きい状態に相当）を想定する。第二に、初期条件を粒子の最密充填状態とする。従来技術では、粒子層の槌打（容器を外部から打撃等）等を行う場合があり、そうすると粒子層の充填率は徐々に高まり、最密充填状態に向かうので、ここでは粒子の代表的状態として最密充填状態を採用した。図４、５において、（ａ）は、初期条件で粒子層の下部から荷重を加えて粒子層が動き出す直前の状態（粒子−粒子間および粒子−反応容器内壁間は、静止摩擦）を示し、（ｂ）は、（ａ）の状態から粒子層が上方に動いている最中の状態を示す。
(Principle of effect in superior wide catalytic reactor)
This will be described with reference to FIG. 4 (prior art, spread angle of catalyst reaction vessel = 0) and FIG. 5 (present invention, spread angle of catalyst reaction vessel> 0). As a premise, first, a particle layer (corresponding to a state having a large aspect ratio in FIG. 3) having a large influence of the reaction vessel wall on the movement of the particle layer (catalyst layer) is assumed. Second, the initial condition is the closest packed state of particles. In the prior art, there is a case where the particle layer is hit (for example, the container is hit from the outside), and the filling rate of the particle layer is gradually increased and the state is close packed. The close-packed state was adopted. 4 and 5, (a) shows a state immediately before the particle layer starts moving by applying a load from the lower part of the particle layer in the initial condition (static friction between the particles and the particles and between the particles and the inner wall of the reaction vessel), (B) shows a state in which the particle layer is moving upward from the state of (a).
粒子層を押し上げる所要推力の発生機構は次のとおりである。
粒子層を移動させるための推力（粒子層下端での押し力）５０は、全ての粒子５１についての壁面摩擦力の積算値によって支配される。壁面摩擦力５２は、全粒子５１のうち壁面に接触する特定の粒子５９が反応容器壁面５８から受ける反力５３に比例する。粒子５９が壁面から受ける反力５３は、推力５０が粒子間を伝わる際の粒子間力５４の水平成分である。一般に、上方の粒子５１ほど、粒子に働く力は等方化する。従って、粒子間力５４が大きいほど、粒子が壁面から受ける反力５３も上昇し、その結果、粒子の壁面摩擦力が増大する。粒子の壁面摩擦力は全て下向きの力であるので、上下方向の力の釣り合いから、特定高さに位置する粒子全体に与えられる粒子間力５４の合計は、粒子の下面側（正味で上向きの力）の方が上面側（正味で下向きの力）よりも常に大きい。その結果、粒子層の下方ほど粒子間力５４は急速に増大する。このように、粒子層の上昇時に、粒子層の最下端における推力は、全ての粒子の壁面摩擦力と同等以上の力が必要なので、粒子層高さが増大すると（アスペクト比が増大すると）急激に所要推力が増大する。
The generation mechanism of the required thrust to push up the particle layer is as follows.
The thrust (pushing force at the lower end of the particle layer) 50 for moving the particle layer is governed by the integrated value of the wall friction force for all the particles 51. The wall frictional force 52 is proportional to the reaction force 53 received from the reaction vessel wall surface 58 by specific particles 59 in contact with the wall surface among all particles 51. The reaction force 53 received by the particle 59 from the wall surface is a horizontal component of the interparticle force 54 when the thrust 50 is transmitted between the particles. In general, the force acting on the particles becomes isotropic as the particles 51 are on the upper side. Therefore, the greater the interparticle force 54, the higher the reaction force 53 that the particle receives from the wall surface, and as a result, the wall frictional force of the particle increases. Since the wall frictional force of the particles is all downward force, the total interparticle force 54 applied to the whole particle located at a specific height from the balance of the force in the vertical direction is the lower surface side of the particle (net upward force) (Force) is always greater than the top side (net and downward force). As a result, the interparticle force 54 rapidly increases as the particle layer is located below. In this way, when the particle layer rises, the thrust at the lowermost end of the particle layer needs to be equal to or greater than the wall friction force of all the particles, so when the particle layer height increases (when the aspect ratio increases) The required thrust increases.
図４の従来技術の場合、粒子層は最密状態であるので、上昇中も粒子間の相対位置は変化しない。従って、粒子−粒子間摩擦は静摩擦のままである。粒子−壁面間摩擦は、動摩擦であるが、一般に動摩擦係数≒静摩擦係数なので、粒子間力５４および壁面摩擦力５２は初期状態からほとんど変化しない。 In the case of the prior art of FIG. 4, since the particle layer is in a close-packed state, the relative position between the particles does not change even during ascent. Therefore, the particle-particle friction remains static. The friction between the particles and the wall surface is kinetic friction, but since generally the kinetic friction coefficient≈the static friction coefficient, the interparticle force 54 and the wall surface friction force 52 hardly change from the initial state.
一方、図５の本発明の場合も初期条件では、粒子層は最密状態であり、粒子に働く力の関係も図４と同様である。しかし、粒子層が上昇し始めると、反応容器が上方に向かって広がる形状（広がり角＞０）の効果により、各粒子５１は、平均的に水平方向に互いに広がる運動を生じる。この結果、粒子間の相対位置が変化して最密充填状態が解消され、粒子５１の相対移動はより容易になる。また、粒子間が水平方向に互いに広がる方向に移動する効果によって、少なくとも水平方向の粒子間力成分が減少するので、粒子の壁面摩擦力５２が減少する。その結果、粒子層上昇に必要な推力５０が減少する効果を生じる。 On the other hand, in the case of the present invention shown in FIG. 5, the particle layer is in a close-packed state under the initial conditions, and the relationship between the forces acting on the particles is the same as in FIG. However, when the particle layer starts to rise, the particles 51 averagely move in the horizontal direction due to the effect of the shape in which the reaction vessel expands upward (expansion angle> 0). As a result, the relative position between the particles changes, the close-packed state is eliminated, and the relative movement of the particles 51 becomes easier. Further, since the interparticle force component in the horizontal direction is reduced by the effect that the particles move in the direction in which the particles are spread in the horizontal direction, the wall frictional force 52 of the particles is reduced. As a result, there is an effect that the thrust 50 necessary for raising the particle layer is reduced.
粒子層に対する壁面摩擦の影響を減少させることは、前述のように粒子層のアスペクト比（粒子層高さ／触媒層下端厚）を低下させることでも実現できる。しかし、図５のような最密充填状態で反応容器厚を少々増大させても、粒子層の上昇中に粒子間での相対運動を生じるわけではないので、粒子層高さが同一であれば、所要推力を減少させる効果はかなり限定的である。 Reducing the influence of wall friction on the particle layer can also be realized by reducing the aspect ratio of the particle layer (particle layer height / catalyst layer lower end thickness) as described above. However, even if the reaction vessel thickness is slightly increased in the close-packed state as shown in FIG. 5, there is no relative movement between the particles during the rise of the particle layer. The effect of reducing the required thrust is quite limited.
一方、本発明では仮に初期条件が、所要推力が一般に大きい最密充填状態であったとしても、粒子層上昇開始直後には、最密充填状態が解消されて粒子間の相対移動を容易に実現できるので、比較的僅かな広がり角（即ち、平均容器厚の比較的小さな増大）の条件でも、所要推力を減少させる効果がより大きい。なお、平均容器厚を大きく設定しないことは、容器表面から粒子に熱供給や冷却を行う場合に有利な条件である。このため、反応容器の総合的な性能の観点から平均容器厚を大きくすることには制約が存在する。 On the other hand, in the present invention, even if the initial condition is the close packed state where the required thrust is generally large, the close packed state is canceled and the relative movement between the particles is easily realized immediately after the start of rising of the particle layer. As a result, the effect of reducing the required thrust is greater even under conditions of a relatively small spread angle (ie, a relatively small increase in average vessel thickness). It should be noted that not setting the average container thickness large is an advantageous condition when supplying heat or cooling the particles from the container surface. For this reason, there exists a restriction | limiting in enlarging average container thickness from a viewpoint of the comprehensive performance of reaction container.
また、触媒層を反応容器とともに昇降した場合には、触媒層全体は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並み）。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。 Further, when the catalyst layer is lifted and lowered together with the reaction container, the entire catalyst layer is lifted and lowered at the same speed as the reaction container, so that relative movement between the catalysts does not occur. Therefore, the removal effect of solid carbon and the like on the catalyst surface is low (similar to a 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の除去を目的として触媒間の相対位置を効率的に変更するためには、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。本発明によれば、触媒反応中に触媒層全体の撹拌（個々の触媒間の相対位置の変更）を短時間適用することによって、触媒反応で生じて触媒間に堆積した固体カーボン等の固体生成物を触媒層全域において効率的に触媒間から落下させて触媒層から除去できる。触媒層から除去され、保持器の下部（例えば、下記で詳しく説明する保持器の底板上）や、反応容器の底部など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, in order to efficiently change the relative position between the catalysts for the purpose of removing the solid deposits generated and deposited on the catalyst in the fixed bed catalyst layer, the catalyst layer together with its cage is placed in the reaction vessel. It was found that relative movement was necessary. According to the present invention, by applying agitation of the entire catalyst layer (change of relative position between individual catalysts) for a short time during the catalytic reaction, solid generation such as solid carbon generated by the catalytic reaction and deposited between the catalysts is produced. A thing can be efficiently dropped from between the catalysts in the entire catalyst layer and removed from the catalyst layer. The solid product removed from the catalyst layer and accumulated in the lower part of the cage (for example, on the bottom plate of the cage described in detail below) or the bottom of the reaction vessel is discharged outside the system, for example, when the catalyst is replaced. can do.
本発明は、触媒等の粒状体の相対位置を変更する処理を必要とする反応器等の装置全般に適用することができ、上の説明で例示した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特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を、触媒の相対位置を変更する処理により効率的に除去するのを可能にする。 The present invention can be applied to all devices such as reactors that require a treatment for changing the relative position of a granular material such as a catalyst, and is formed on the catalyst in the fixed bed catalyst layer exemplified in the above description. The present invention can be particularly preferably applied to the removal of the deposited solid product. 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, even when using a tar-containing gas reforming catalyst in which the amount of solid carbon deposited on the catalyst surface is large compared to other reactions, the solid product produced and deposited on the catalyst is It is possible to remove efficiently by the process of changing the relative position of the catalyst.
触媒移動床は、本発明の適用対象の一つである固定触媒床と異なり、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く、反応中に絶えず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）。 Unlike the fixed catalyst bed, which is one of the objects to which the present invention is applied, the catalyst moving bed moves (and agitate) the catalyst continuously during the reaction in principle. On the other hand, in the present invention, the movement of the catalyst layer in the reaction vessel may be carried out intermittently for a short time, and it is not necessary to continuously 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).
本発明によれば、容器内に静的に収納された触媒などの粒状体の相対位置を短時間で効率的に変更することが可能となる。本発明を例えば触媒反応に適用すれば、閉塞した触媒層の回復を反応装置の運転を停止する必要なしに簡単に行うことができる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to change efficiently the relative position of granular materials, such as a catalyst statically accommodated in the container, in a short time. When the present invention is applied to, for example, a catalytic reaction, the clogged catalyst layer can be easily recovered without having to stop the operation of the reaction apparatus.
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。本発明は、粒状体処理装置全般に関するものであるが、以下においてはその代表例としての連続式固定床触媒反応装置を取り上げることにする。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。 Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. The present invention relates generally to a granular material processing apparatus. In the following, a continuous fixed bed catalytic reactor as a representative example will be taken up. 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.
［第１の実施形態］
（全体構造）
図６に、本発明の第１の実施形態の粒状体処理装置である連続式固定床触媒反応装置１０を示す。この図の（ａ）は平面図、（ｂ）は正面図、（ｃ）は側面図である。図１の触媒反応装置１０は、反応容器１１を含み、その内部に触媒保持器１２によって支持された触媒層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。保持器１２の下には、保持器１２を昇降させることにより触媒層１３を上下に移動させるための駆動機構２０が位置し、この駆動機構２０は昇降装置２１と、昇降装置２１を保持器１２につなぐ伝導軸２２で構成されている。
[First Embodiment]
(Overall structure)
FIG. 6 shows a continuous fixed bed catalytic reactor 10 which is a granular material processing apparatus according to the first embodiment of the present invention. In this figure, (a) is a plan view, (b) is a front view, and (c) is a side view. 1 includes a reaction vessel 11, in which a catalyst layer 13 supported by a catalyst holder 12 is accommodated, and among the catalysts in the catalyst layer 13, a catalyst adjacent to the inner wall of the reaction vessel (FIG. 1). (Not shown) 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. A drive mechanism 20 for moving the catalyst layer 13 up and down by moving the retainer 12 up and down is located under the retainer 12. The drive mechanism 20 includes the lift device 21 and the lift device 21. It is comprised with the conduction shaft 22 connected to.
反応容器１１には、下方から原料ガス１５が供給されて触媒層１３で改質反応し、触媒層１３からの改質ガス１６は反応容器１１の上方から排出される。原料ガス１５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１６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、炭化水素改質用の粒状触媒などでよく、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１５は、図１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 15 is supplied to the reaction vessel 11 from below and undergoes a reforming reaction in the catalyst layer 13, and the reformed gas 16 from the catalyst layer 13 is discharged from above the reaction vessel 11. Examples of the raw material gas 15 may be a gas containing hydrocarbons, a gas containing tar together with hydrocarbons, or the like. An example of the reformed gas 16 may be a reformed gas obtained by reforming a gas containing hydrocarbon. As an example of the catalyst, a granular 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 15 to the reaction vessel 11 can be supplied so as to flow downward from above the catalyst layer 13, contrary to FIG. 1.
（反応容器の形状）
反応容器１１は、上方に向けて水平断面積が増大する「上広型」であって、両端に開口１７ａ、１８ａ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。例えば、円筒状、角型ダクト状などの任意の形状であることができる。反応容器１１の開口１７ａは、触媒反応用流体（原料ガス）の流入路１７を構成する供給管に通じており、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。開口１８ａは、反応容器１１からの改質ガスの流出路１８を構成する排出管に通じており、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。
(Reaction vessel shape)
The reaction vessel 11 is an “upper wide type” whose horizontal cross-sectional area increases upward, has openings 17a and 18a at both ends, and can accommodate any catalyst between these openings. Shape may be sufficient. For example, it can be any shape such as a cylindrical shape or a rectangular duct shape. The opening 17a of the reaction vessel 11 communicates with a supply pipe constituting the inflow passage 17 for the catalytic reaction fluid (raw material gas), and corresponds to the inlet of the raw material gas for catalytic reaction to the reaction vessel 11. The opening 18 a leads to a discharge pipe constituting the reformed gas outflow passage 18 from the reaction vessel 11 and corresponds to an outlet of the reformed gas from the reaction vessel 11.
本発明の特徴として、反応容器１１は、上方に向けて水平断面積が増大する「上広型」である。水平断面における断面積の増大は、特定方向のみ（例えば、幅方向のみ）であってもよいし、全ての方向（例えば、形状が相似に拡大する）であってもよい。図６の反応容器１１は、厚方向の水平断面積のみが増大している。 As a feature of the present invention, the reaction vessel 11 is an “upper wide type” in which the horizontal sectional area increases upward. The increase in cross-sectional area in the horizontal cross section may be only in a specific direction (for example, only in the width direction), or may be in all directions (for example, the shape expands similarly). In the reaction vessel 11 of FIG. 6, only the horizontal cross-sectional area in the thickness direction is increased.
水平断面積を増大させるために、図６の反応容器１１は、厚方向に広がり角αを有する。ここで言う「広がり角」は、水平断面積の上方への増大率を、仮に二次元的に生じたものとして換算した場合に、対向する反応容器壁面が互いになす角と定義する。 In order to increase the horizontal cross-sectional area, the reaction vessel 11 of FIG. 6 has a spread angle α in the thickness direction. The “spread angle” here is defined as an angle formed by the opposing reaction vessel wall surfaces when the upward increase rate of the horizontal cross-sectional area is converted as if it occurred two-dimensionally.
広がり角αは、大きいほど粒状体層（触媒層）を昇降させる所要推力低下の効果が高い。但し、粒状体層下端では上向きの変位のみが起こり、上端では上向きの変位とともに水平方向にも変位が生じ、すなわち次の関係、
粒状体層下端の断面積×下端での変位量（上昇量）
＝粒状体層上端の断面積×上端での変位量（上昇量および水平移動量）
があるため、広がり角αが大きすぎると、粒状体層（触媒層）上端での面積が過大となり、下端を上昇させても、上方での粒状体（触媒）移動量は微小となってしまう問題を生じる。所要推力を低減することと同時に、粒状体層全体の変位量を十分に大きく確保することが、本発明の目的である粒状体間の相対位置の変更にとって重要である。この観点から、本発明においては、所要推力削減効果と粒状体層全体の変位量確保を両立させるために、広がり角αは０．５°以上２０°以下が好ましい。広がり角は、より好ましくは１°以上１０°以下、さらに好ましくは２．５°以上４°以下である。
The larger the spread angle α, the higher the effect of lowering the required thrust that raises and lowers the granular material layer (catalyst layer). However, only the upward displacement occurs at the lower end of the granular material layer, and the displacement occurs in the horizontal direction together with the upward displacement at the upper end, that is, the following relationship:
Cross-sectional area at the bottom of the granular material layer x displacement at the bottom (rise)
= Cross-sectional area at the top of the granular material layer x Displacement at the top (amount of rise and horizontal movement)
Therefore, if the spread angle α is too large, the area at the upper end of the granular material layer (catalyst layer) becomes excessive, and even if the lower end is raised, the amount of movement of the granular material (catalyst) above becomes small. Cause problems. It is important for the change of the relative position between the granular materials, which is the object of the present invention, to reduce the required thrust and to ensure a sufficiently large displacement amount of the entire granular material layer. From this viewpoint, in the present invention, in order to achieve both the required thrust reduction effect and securing the amount of displacement of the entire granular material layer, the spread angle α is preferably 0.5 ° or more and 20 ° or less. The divergence angle is more preferably 1 ° or more and 10 ° or less, and further preferably 2.5 ° or more and 4 ° or less.
図６の反応容器１１では、水平断面積は上方に向けて一様に増大しているが、反応容器の一部分だけで水平断面積が増大するようにしてもよい。例えば、昇降分を含めて容器１１内に位置する触媒層１３の範囲だけを、水平断面積が上方に向け増大するようにしてもよい。 In the reaction vessel 11 of FIG. 6, the horizontal cross-sectional area increases uniformly upward, but the horizontal cross-sectional area may be increased only by a part of the reaction vessel. For example, the horizontal cross-sectional area may be increased upward only in the range of the catalyst layer 13 located in the container 11 including the lift.
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１１の厚みは、下限が粒状触媒の代表寸法（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１１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）。
(Reaction vessel dimensions)
The lower limit of the thickness of the reaction vessel 11 must be greater than or equal to the representative dimension (eg, diameter) of the granular catalyst (for example, 10 mm). In general, a catalytic reaction generates heat or absorbs heat, and since the heat is transferred to the outside through the surface of the reaction vessel 11, 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).
反応容器１１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 restriction on the width of the reaction vessel 11 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１１の高さは、駆動機構２０により保持器１２ととともに触媒層１３を上下動させたときに、少なくとも触媒層１３の下端から上端までが反応容器内に収まる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 11 must be larger than the height at which at least the lower end to the upper end of the catalyst layer 13 can be accommodated in the reaction vessel when the drive mechanism 20 moves the catalyst layer 13 together with the cage 12. . 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).
（触媒保持器）
通常の反応容器における触媒保持器の例としては、網やパンチングメタルなどを挙げることができる。このタイプの保持器は、触媒を保持するとともに、網の目明きやパンチングメタルの開口を流路として利用することができる。
(Catalyst cage)
Examples of the catalyst cage in a normal reaction vessel include a net and punching metal. This type of retainer retains the catalyst and can use a mesh opening or a punching metal opening as a flow path.
保持器として網やパンチングメタルを用いる場合、強度上の制約があるので、開口率を大きく設定することができない。単に触媒の落下を防止する目的であれば、開口率は７０％程度まで許容できるが、本発明のように保持器によって触媒を押し上げるための強い推力に耐えるためには、開口率は２０％程度が最大であり、場合によって開口部で閉塞を生じる可能性がある。 When a net or punching metal is used as the cage, the aperture ratio cannot be set large due to strength restrictions. For the purpose of simply preventing the catalyst from falling, the aperture ratio can be allowed up to about 70%. However, in order to withstand strong thrust for pushing up the catalyst by the cage as in the present invention, the aperture ratio is about 20%. Is maximum, and in some cases, the opening may be blocked.
本発明では、図６に示したような反応容器の幅方向に配置した複数の棒３１を利用した保持器１２を用いることによって、網やパンチングメタルを保持器として用いる場合の前述の問題を解消することができる。図７に、保持器１２を詳細に示す。この図の（ａ）は平面図、（ｂ）は側面図である。この保持器１２においては、十分に太い複数の棒３１を触媒が隙間を落下しない間隔をあけて略平行に配置して、両端の固定具３２により全体を固定するようにしている。このような保持器１２では、反応容器１１の内寸の範囲内で自由に棒を太くできるので、所要推力に耐える十分な強度を得ることができる。また、保持器１２の開口率は、［棒間の隙間幅］／［棒の水平間隔］であるので、棒間の隙間幅と棒の太さを調整することで、ある程度大きな開口率を実現できる。さらに、同じ開口率であっても、この方式で実現される開口は棒間ごとに単一であり、比較的大きな開口単体面積をもつので、網やパンチングメタルよりも閉塞しにくい（網やパンチングメタルでは、高々、触媒並みの寸法の小面積の開口を多数設けて開口率をかせぐ方式なので、個々の開口では開口周囲から付着・成長した固体生成物等によって閉塞しやすい）。 In the present invention, by using the cage 12 using a plurality of rods 31 arranged in the width direction of the reaction vessel as shown in FIG. 6, the above-mentioned problems when using a net or punching metal as the cage are eliminated. can do. FIG. 7 shows the cage 12 in detail. In this figure, (a) is a plan view and (b) is a side view. In this cage 12, a plurality of sufficiently thick rods 31 are arranged substantially in parallel with an interval at which the catalyst does not fall through the gap, and the whole is fixed by fixtures 32 at both ends. In such a cage 12, since the rod can be thickened freely within the range of the inner dimension of the reaction vessel 11, a sufficient strength to withstand the required thrust can be obtained. Further, since the opening ratio of the cage 12 is [gap width between bars] / [horizontal spacing between bars], a certain degree of opening ratio is realized by adjusting the gap width between the bars and the thickness of the bars. it can. Furthermore, even if the aperture ratio is the same, the opening realized by this method is single for each bar and has a relatively large opening area, so it is less likely to close than a net or punching metal (net or punching). Metal is a system that increases the aperture ratio by providing a large number of small-area openings that are at the same size as the catalyst, and each opening is likely to be clogged with solid products that adhere and grow from the periphery of the opening).
図８（ａ）（側面図）、８（ｂ）（（ａ）のＢ−Ｂ断面図）に示したように棒３１を単純に平行に並べる（保持器を水平方向から見て棒の中心軸が交差しない）方式で棒を完全に平行に配置した場合（特に、触媒３５の代表寸法よりも棒３１が太い場合）には、棒と棒の間で触媒３５が整列する効果が現れ、棒間の隙間を触媒が広くふさいでしまう現象の発生することを本発明者らは発見した（特に触媒が円柱形状の場合に顕著）。 As shown in FIGS. 8 (a) (side view) and 8 (b) (BB sectional view of (a)), the bars 31 are simply arranged in parallel (the center of the bars when the cage is viewed from the horizontal direction). When the bars are arranged in a completely parallel manner (particularly when the bar 31 is thicker than the representative dimension of the catalyst 35), the effect of the catalyst 35 being aligned between the bars appears. The present inventors have discovered that a phenomenon occurs in which the catalyst clogs the gaps between the rods widely (particularly when the catalyst is cylindrical).
この問題は、図８（ｃ）（側面図）、８（ｄ）（（ｃ）のＤ−Ｄ断面図）に示したように、棒３１を配置する際に棒の中心軸の水平面投影成分は互いに平行とし、隣り合う棒の中心軸の鉛直面投影成分またはその延長線は互いに交差する構造とすることにより、解決されることがわかった。こうすることで、円柱状の触媒であっても棒間で整列することはなく、棒間に常に開口を生じるようにすることができる。 As shown in FIGS. 8 (c) (side view) and 8 (d) (DD sectional view of (c)), this problem is caused by the horizontal plane projection component of the central axis of the rod when the rod 31 is arranged. It has been found that this can be solved by making them parallel to each other and the vertical plane projection components of the central axes of adjacent bars or their extension lines intersecting each other. By doing so, even a columnar catalyst is not aligned between the rods, and it is possible to always create an opening between the rods.
（保持器における棒の配置）
本発明による棒を用いた保持器１２では、図６に示したように、棒３１の中心軸を反応容器１１の幅方向とすることができる。あるいはまた、棒３１の中心軸を反応容器１１の厚方向とすることもできる。
(Arrangement of rods in cage)
In the cage 12 using the rod according to the present invention, as shown in FIG. 6, the central axis of the rod 31 can be the width direction of the reaction vessel 11. Alternatively, the central axis of the rod 31 can be the thickness direction of the reaction vessel 11.
（保持器における棒の形状）
棒３１は、中心軸が直線であることが好ましいが、設計上の便宜等の理由で曲がり棒としてもよい。断面形状は円形が好ましいが、楕円、多角形等であってもよい。
(Shape of cage in cage)
The rod 31 preferably has a straight central axis, but may be a bent rod for reasons of design convenience. The cross-sectional shape is preferably a circle, but may be an ellipse, a polygon, or the like.
（保持器における棒の太さ）
棒３１は、保持器１２の推力に耐えうる太さ以上である必要がある。直径３ｍｍ以上が好ましい。反応容器１１に収まり、かつ、周囲に通気のための空間を設ける必要があるので、反応容器厚の５０％未満（棒中心軸が反応容器幅方向の場合）、または、反応容器幅の５０％未満（棒中心軸が反応容器厚方向の場合）である必要がある。
(Thickness of rod in cage)
The rod 31 needs to have a thickness that can withstand the thrust of the cage 12. A diameter of 3 mm or more is preferable. Since it is necessary to provide a space for ventilation around the reaction vessel 11, the reaction vessel thickness is less than 50% (when the central axis of the rod is in the reaction vessel width direction) or 50% of the reaction vessel width. Must be less than (when the center axis of the rod is in the thickness direction of the reaction vessel).
（保持器における棒の材質）
保持器１２の棒３１は、触媒層１３を押し上げるために大きな強度と靭性が必要なので、金属材料が好ましい。金属材料の一例として、ステンレス鋼、ハステロイ（登録商標）等のＮｉ合金、アルミニウム、アルミニウム合金、銅合金、チタン、チタン合金等を挙げることができる。
(Material of rod in cage)
The rod 31 of the cage 12 is preferably made of a metal material because it requires high strength and toughness to push up the catalyst layer 13. Examples of the metal material include Ni alloys such as stainless steel and Hastelloy (registered trademark), aluminum, aluminum alloys, copper alloys, titanium, and titanium alloys.
（保持器における棒の固定方法）
棒３１の両端に板等の固定具３２を配置し、棒を共通の固定具３２に溶接して固定することができる。場合によっては、複数組の固定具を用いることも可能であり、この場合には保持器は固定具の組数に分割されることになる。固定具３２は、棒３１と同様の材料により製作することができる。
(How to fix the rod in the cage)
A fixing tool 32 such as a plate is disposed at both ends of the bar 31, and the bar can be fixed to the common fixing tool 32 by welding. In some cases, it is possible to use a plurality of sets of fixtures. In this case, the cage is divided into the number of sets of fixtures. The fixture 32 can be made of the same material as the rod 31.
（触媒層の駆動機構）
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。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２０が装備される。駆動機構２０には、エアシリンダ、ラックピニオン等の歯車を利用した昇降装置２１などの、一般的な駆動機構を用いることができる。保持器１２は、伝導軸２２を用いて昇降装置２１に結合される。昇降装置２１を作動させると、保持器１２の全体が反応容器１１の軸線に沿って移動して、触媒層１３の全体をやはり反応容器１１の軸線に沿って上下に移動させる。
(Catalyst layer drive mechanism)
In the present invention, the cage 12 is moved up and down 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 20 for raising and lowering the catalyst holder 12. As the drive mechanism 20, a general drive mechanism such as an elevating device 21 using a gear such as an air cylinder or a rack and pinion can be used. The cage 12 is coupled to the lifting device 21 using the conduction shaft 22. When the elevating device 21 is operated, the entire cage 12 moves along the axis of the reaction vessel 11, and the entire catalyst layer 13 is also moved up and down along the axis of the reaction vessel 11.
少なくとも伝導軸２２の保持器１２側の一部は反応容器１１、または、反応容器１１の下方に存在しうる原料ガス流入路１６や改質ガス流出路１７の内側に存在する必要がある。昇降装置２１は、反応容器１１の外部に設けることができる。反応容器１１を例えば加熱炉などの加熱装置（図示せず）内に配置する場合には、昇降装置２１を加熱装置外に設けることもできる。この場合、市販の昇降装置を使える一方で、伝導軸２２が反応容器１１を貫通する部分を高温用パッキン等で封止する必要がある。 At least a part of the conduction shaft 22 on the side of the cage 12 needs to be present inside the reaction vessel 11 or the raw material gas inflow passage 16 or the reformed gas outflow passage 17 that may exist below the reaction vessel 11. The elevating device 21 can be provided outside the reaction vessel 11. In the case where the reaction vessel 11 is arranged in a heating device (not shown) such as a heating furnace, the elevating device 21 can be provided outside the heating device. In this case, while a commercially available lifting device can be used, it is necessary to seal the portion where the conductive shaft 22 penetrates the reaction vessel 11 with high-temperature packing or the like.
駆動機構２０全体を、図６に示したように反応容器１１内に設ける場合には、昇降装置２１を、例えば反応容器１１内の高温や腐食性物質から保護するために、耐熱・耐食性のものとする必要がある。これは、一例として、駆動機構２０のエアシリンダ全体をハステロイ（登録商標）等の耐熱合金製とすることによって実現できる。この場合、エアシリンダへの供給エア配管（図示せず）は反応容器１１を貫通するが、この部分は非可動部なので、配管を全周溶接するなどして封止を図ればよい。 In the case where the entire drive mechanism 20 is provided in the reaction vessel 11 as shown in FIG. 6, in order to protect the elevating device 21 from, for example, high temperature and corrosive substances in the reaction vessel 11, it is heat and corrosion resistant. It is necessary to. As an example, this can be realized by making the entire air cylinder of the drive mechanism 20 made of a heat-resistant alloy such as Hastelloy (registered trademark). In this case, a supply air pipe (not shown) to the air cylinder passes through the reaction vessel 11, but since this part is a non-movable part, the pipe may be welded around the circumference and the like may be sealed.
保持器上昇時に、保持器１２の一部が触媒層１３に食い込む場合があるので（特に、次に説明する第２の実施形態で用いるピン式保持器の場合）、保持器１２は上昇時だけでなく下降時も駆動することが好ましい。 When the cage is raised, a part of the cage 12 may bite into the catalyst layer 13 (particularly in the case of the pin type cage used in the second embodiment described below), so that the cage 12 is only raised. It is preferable to drive even when the vehicle is lowered.
（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２０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 20 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。本発明者らの調査の結果、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. As a result of the investigation by the present inventors, it has been found that the required ascending force when raising the catalyst layer together with the cage at 10 mm / s needs 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。本発明では、先に図２を参照して説明したように、上広型触媒反応容器を用いることにより、約３以下の触媒層アスペクト比（触媒層高さ／触媒層下端厚）において、触媒層全体で触媒を大きく相対運動させることができ、高い粒子撹拌効果を得ることができる。 From this point of view, the lower the catalyst layer, the better. In the present invention, as described above with reference to FIG. 2, the catalyst layer aspect ratio (catalyst layer height / catalyst layer lower end thickness) can be reduced to about 3 or less by using an upper wide catalyst reaction vessel. The catalyst can be relatively moved relative to the entire layer, and a high particle stirring effect can be obtained.
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。
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。
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。
(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) 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) 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］
（全体構造）
本発明の粒状体処理装置は、図９のような触媒反応装置であってもよい。この図の（ａ）は平面図であり、（ｂ）は正面図、（ｃ）は側面図である。図９の触媒反応装置１０は、後に詳しく説明するように複数のピンを底板に立設した触媒保持器１２’を用いていることと、それに関連した触媒に関する要件を除いて、図６を参照して説明した第１の実施形態のものと同様である。
[Second Embodiment]
(Overall structure)
The granular material processing apparatus of the present invention may be a catalytic reaction apparatus as shown in FIG. (A) of this figure is a plan view, (b) is a front view, and (c) is a side view. The catalyst reaction apparatus 10 in FIG. 9 uses FIG. 6 except that a catalyst holder 12 ′ having a plurality of pins erected on the bottom plate and the related requirements for the catalyst are used, as will be described in detail later. This is the same as that of the first embodiment described above.
（触媒保持器）
この実施形態の触媒保持器１２’は、図１０に示されるような多数のピン２５を底板２６で保持した構造物であり、ピン２５の先端部で粒状の触媒（図示せず）を保持する触媒保持手段である。隣り合うピン２５の間隔を粒状触媒の大きさより小さく設定することで、ピン２５の先端部で粒状の触媒を保持することが可能であり、ピン間の隙間が触媒反応用流体の触媒層１３への流入口または流出口として機能する。
(Catalyst cage)
The catalyst holder 12 ′ of this embodiment is a structure in which a large number of pins 25 as shown in FIG. 10 are held by a bottom plate 26, and a granular catalyst (not shown) is held at the tip of the pins 25. It is a catalyst holding means. By setting the interval between adjacent pins 25 to be smaller than the size of the granular catalyst, it is possible to hold the granular catalyst at the tip of the pin 25, and the gap between the pins leads to the catalyst layer 13 of the catalytic reaction fluid. Functions as an inlet or outlet.
図１０の触媒保持器１２’では、ピン２５は、例えば丸棒などで製作することができる。ピン２５は、同一形状が一般的であるが、必ずしも同じ形状である必要はない。粒状触媒をピン２５の先端部で保持し、ピン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。また、図１０の触媒保持器１２’では、ピン２５の先端は同一平面を形成しているが、ピン２５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。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。 In the catalyst holder 12 ′ of FIG. 10, the pin 25 can be made of, for example, a round bar. The pins 25 are generally the same shape, but are not necessarily the same shape. It is only necessary to hold the granular catalyst at the tip of the pin 25 and to allow fluid to flow through the gap between the pins. The pin may not have the same size, length, and angle, and the pin is not limited to a straight line. Further, in the catalyst holder 12 ′ of FIG. 10, the tip of the pin 25 forms the same plane, but the surface formed by the tip of the pin 25 is a curved surface, or exceptionally, some pins are at the tip. You may protrude from the surface which forms. According to such a catalyst holder, a high opening ratio and prevention of clogging are realized.
触媒保持器１２’におけるピン２５の配置は、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。 The arrangement of the pins 25 in the catalyst holder 12 ′ is an isosceles triangle in which all the triangles formed by the centers of three adjacent pins with the center of the pin on the plane perpendicular to the axis of the pin as a vertex are congruent. In particular, an equilateral triangle is preferable. 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２５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 25 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、ピン２５の軸線は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。 If there is a design convenience, the distance between the central axes gradually increases or decreases toward the catalyst direction, and the axis of the pin 25 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.
ピン間の間隔は、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（篩の目明き寸法）より小さければよい。こうすれば、触媒粒はピンの間を落下することはなく、これらのピンで支持することができる。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１２’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。 The distance between the pins is such that the distance between the shafts excluding the diameters (outer diameters) of all the pins is the smallest mesh opening size (sieving sieve) through which the catalyst can pass, particularly at the top (pin tip) of the catalyst holder. Smaller than the apparent dimension). In this way, the catalyst particles do 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 a sufficient storage space for fallen objects below and below 12 ', 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.
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明き寸法]
［ピンの径］： 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。
「目明き寸法」： 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、単一の触媒粒外形の代表寸法（直径、高さ等）のうち、最小のものに相当する。
The spacing between pins preferably satisfies the following inequality.
[Pin-axis distance]-[Pin outer diameter] <[Minimum mesh size that can pass through the catalyst]
[Pin Diameter]: The pin outer diameter is the sum of the radii between the two pin axes (the distance from the pin axis to the outer diameter), which is the pin diameter in the preferred cylindrical pin array.
"Mesh": A sieve eye.
“Meticulous dimension”: Based on the general definition of JIS, etc., assuming a square opening, but in the present invention, it is the smallest of the representative dimensions (diameter, height, etc.) of a single catalyst particle outer shape. It corresponds to a thing.
ピンの長さは、［ガス流入口（流出口）での流体の流通見かけ断面積］≧［触媒層における流体の流通見かけ断面積］とするのが好ましい。触媒反応容器の厚さと幅（直径）が所与のとき、ピンの高さを変更して、流入口（流出口）での流体の流通見かけ断面積を調整できる。但し、触媒層における流体の流通見かけ断面積が極端に大きい場合（反応容器が主流方向に扁平等）には、この限りではない。ここで、「流体の流通見かけ断面積」とは、原料流体や改質流体の主流に垂直な平面上で触媒反応容器側壁で囲また領域の面積である。 The length of the pin is preferably [apparent cross-sectional area of fluid flow at the gas inlet (outlet)] ≧ [apparent cross-sectional area of fluid in the catalyst layer]. When the thickness and width (diameter) of the catalytic reaction vessel are given, the height of the pin can be changed to adjust the apparent flow sectional area of the fluid at the inlet (outlet). However, this is not the case when the apparent cross-sectional area of the fluid in the catalyst layer is extremely large (the reaction vessel is flat in the main flow direction, etc.). Here, the “fluid apparent sectional area” is an area of a region surrounded by the side wall of the catalyst reaction vessel on a plane perpendicular to the main flow of the raw material fluid and the reforming fluid.
ピンのアスペクト比（長さ／直径比）は、座屈防止の観点から１００以下の値が好ましく、２０以下がより好ましい。但し、ピンに加わる最大荷重が十分に小さい場合には、これ以上の値であってもよい。また、流入口（流出口）での流体の流通見かけ断面積を十分大きく設定するために、ピンのアスペクト比は、１以上が好ましく、５以上がより好ましい。 The aspect ratio (length / diameter ratio) of the pin is preferably a value of 100 or less, more preferably 20 or less, from the viewpoint of preventing buckling. However, when the maximum load applied to the pin is sufficiently small, a value larger than this may be used. Further, in order to set the apparent flow sectional area of the fluid at the inlet (outlet) sufficiently large, the pin aspect ratio is preferably 1 or more, and more preferably 5 or more.
ピン２５の材質は、触媒を保持する強度、接触する流体への耐熱・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。たとえば、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、ソーダガラス、溶融石英等のガラス材料、を使用できる。タール改質用の触媒反応容器では、通常、８００℃以上の高温で操作されるので、ステンレス鋼やハステロイ（登録商標）、インコネル（登録商標）等のニッケル合金が特に好ましい。 As the material of the pin 25, any material can be used as long as it has strength to hold the catalyst, heat resistance / corrosion resistance to the fluid in contact, 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, soda glass, fused quartz, etc. Glass material, can be used. Since the catalytic reactor for tar reforming is usually operated at a high temperature of 800 ° C. or higher, nickel alloys such as stainless steel, Hastelloy (registered trademark), and Inconel (registered trademark) are particularly preferable.
同様に、底板２６の材質も、例えばステンレス鋼、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。 Similarly, examples of the material of the bottom plate 26 include stainless steel, Ni alloys such as Hastelloy (registered trademark) and Inconel (registered trademark), titanium, titanium alloys, and the like.
ピン２５の底板２６への固定方法は、特に限定されず、例えば、全てのピンを溶接で底板へ固定することができる。 The method for fixing the pins 25 to the bottom plate 26 is not particularly limited. For example, all the pins can be fixed to the bottom plate by welding.
このような触媒保持器１２’を用いることにより、パンチングメタルや網の場合と違い開口率を大きくしても強度を維持することができるので、実質的な開口率（ピン列の触媒への接触部においてピン軸に垂直な面内での空間の比率）を９０％以上という、パンチングメタルや網では従来実現できなかった高い値とすることができる。９５％以上も可能である。 By using such a catalyst retainer 12 ', the strength can be maintained even when the aperture ratio is increased unlike the case of punching metal or net, so that the substantial aperture ratio (contact of the pin array to the catalyst) can be maintained. The ratio of the space in the plane perpendicular to the pin axis in the part) can be set to a high value of 90% or more, which could not be realized by punching metal or a net. More than 95% is possible.
また、触媒保持器１２’の各ピン２５は、ピン中心軸垂直断面内で全て孤立し、ピン列の間に広がる空間が互いに連結しているので、仮にピン表面にカーボン等の固体が析出したとしても、隣り合うピン間でこの固体が架橋して開口を閉塞させることは容易には生じない。 In addition, each pin 25 of the catalyst retainer 12 ′ is isolated in the vertical cross section of the pin central axis, and the spaces extending between the pin rows are connected to each other, so that a solid such as carbon is temporarily deposited on the surface of the pin. Even so, it is not easy for this solid to bridge between adjacent pins to close the opening.
（触媒の大きさ）
触媒が保持器１２’の上に位置する触媒層１３にとどまる必要から、この実施形態の反応容器１１の触媒層１３中の粒状触媒は、前記ピンにおける寸法制約を満足できなければならない。例えば、次の例１の触媒を用いることができる。
（例１）直径１０ｍｍの球形触媒粒を見かけ断面が直径１００ｍｍの円筒触媒反応容器に収めた場合、ピン高さは、１００ｍｍあれば十分である。一方、ピン直径を５ｍｍにできるので、このときのピンのアスペクト比は２０程度であり、実現可能である。
(Catalyst size)
Since the catalyst needs to remain in the catalyst layer 13 located on the cage 12 ', the granular catalyst in the catalyst layer 13 of the reaction vessel 11 of this embodiment must be able to satisfy the dimensional constraints at the pin. For example, the catalyst of the following Example 1 can be used.
(Example 1) When spherical catalyst particles having a diameter of 10 mm are accommodated in a cylindrical catalyst reaction vessel having an apparent cross section of 100 mm in diameter, a pin height of 100 mm is sufficient. On the other hand, since the pin diameter can be 5 mm, the pin aspect ratio at this time is about 20, which is feasible.
一方、前記ピンにおける寸法制約を満足できないので、次の例２の触媒は、採用できない。
（例２）直径０．１ｍｍの球形触媒粒を見かけ断面が直径１００ｍｍの円筒触媒反応容器に納めた場合、ピン高さは、少なくとも数十ｍｍ必要である。一方、ピン直径は触媒粒直径よりも小さくなければならない。従って、ピンのアスペクト比は１００を超えるので、実現不可能である。
On the other hand, since the dimensional constraints on the pin cannot be satisfied, the catalyst of Example 2 below cannot be used.
(Example 2) When a spherical catalyst particle having a diameter of 0.1 mm is accommodated in a cylindrical catalyst reaction vessel having an apparent cross section of 100 mm, the pin height needs to be at least several tens of mm. On the other hand, the pin diameter must be smaller than the catalyst particle diameter. Therefore, the pin aspect ratio exceeds 100, which is not feasible.
触媒の寸法は、触媒反応の効率から決定され、一概ではない。触媒の寸法を考慮して触媒保持器のピン間の間隔を決めればよいが、必要に応じて、触媒の寸法を触媒保持器のピン間の間隔を考慮して決めることができる。例えば、触媒粒の外寸は、触媒保持器での保持のしやすさと、反応性のための高い比表面積確保の観点から、５〜５０ｍｍ程度であることが好ましい。 The size of the catalyst is determined from the efficiency of the catalytic reaction and is not general. The distance between the pins of the catalyst holder may be determined in consideration of the size of the catalyst. However, if necessary, the dimension of the catalyst can be determined in consideration of the distance between the pins of the catalyst holder. For example, the outer size of the catalyst particles is preferably about 5 to 50 mm from the viewpoint of easy retention in the catalyst cage and securing a high specific surface area for reactivity.
（触媒の形状）
前述のように、特定の触媒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、反応容器の反応速度を向上できる。従って、球や球に近い形状のものは、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。また、触媒の外周で囲まれる体積が同一でも、触媒粒の表面積の大きい形状、例えば、円筒やリング状の形状も好ましい。
(Catalyst shape)
As described above, when a catalyst is held by a specific catalyst holder, 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 can be improved. Accordingly, a sphere or a shape close to a sphere is preferable because the number of catalysts can be easily increased in a certain volume. Moreover, even if the volume enclosed by the outer periphery of a catalyst is the same, the shape with a large surface area of a catalyst particle, for example, a cylindrical shape or a ring shape, is also preferable.
一方、円盤のように、一方向の代表長さのみが極端に小さい形状のものは、この実施形態で使用するピン式の保持器では保持しにくいので、概して好ましくない（比較： 従来より一般に用いられている網やパンチングメタルでは、メッシュ寸法よりも若干大きな円盤が、触媒の数を最も増やしうる形状であった）。また、棒状の形状は、従来技術と同様に保持しにくいので、好ましくない。 On the other hand, a shape such as a disk that has an extremely small representative length only in one direction is generally not preferred because it is difficult to hold with the pin type retainer used in this embodiment (comparison: generally used than before). In the nets and punched metal used, a disk slightly larger than the mesh size was the shape that could increase the number of catalysts most). Further, the rod-like shape is not preferable because it is difficult to hold as in the prior art.
（本発明の他の適用例）
本発明は、第１及び第２の実施形態を例に説明したような触媒反応器に限らず、粒状体充填層の乾燥器、熱交換器、高温フィルタ等にも適用することができる。
(Other application examples of the present invention)
The present invention can be applied not only to the catalytic reactor described with reference to the first and second embodiments, but also to a granular packed bed dryer, a heat exchanger, a high-temperature filter, and the like.
上で説明したいずれの実施形態でも、触媒層（粒状体層）は１つであったが、本発明の粒状体処理装置における粒状体層は複数であっても差し支えない。この場合、各粒状体層ごとに保持器を設け、隣接する粒状体保持器どうしを連結して一体化することにより、全ての粒状体層を同時に昇降させて、各層における粒状体間の相対位置を効率的に変更することができる。 In any of the embodiments described above, there is one catalyst layer (granular material layer), but there may be a plurality of granular material layers in the granular material processing apparatus of the present invention. In this case, a cage is provided for each granular material layer, and by connecting and integrating adjacent granular material cages, all the granular material layers can be moved up and down at the same time, and the relative position between the granular materials in each layer. Can be changed efficiently.
以下の実施例により本発明をさらに説明する。しかし、本発明はこれらの実施例に限定されるものではない。 The following examples further illustrate the present invention. However, the present invention is not limited to these examples.
［実施例］
図９に示した触媒反応装置で試験した。
[Example]
The test was conducted using the catalytic reactor shown in FIG.
（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。
(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.
（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.
（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： 矩形水平断面の上広型ダクト状
・反応容器材質： ステンレス鋼
・反応容器厚： １２０ｍｍ（容器下部にて）
・反応容器幅： ３００ｍｍ
・反応容器広がり角： ２．５°
・触媒層高さ： ３５０ｍｍ
・触媒層アスペクト比： ２．９
・触媒保持器： スレンレス丸棒製のピン式
・ピン： 直径５．１ｍｍ、長さ９０ｍｍ、頂部平坦、コーナ部１ｍｍを面取り
・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
・ピン開口率： ９２％
・使用触媒量： ７ｋｇ
・駆動装置昇降ストローク： １５ｍｍ
・駆動装置上昇速度： ２ｍｍ／秒
・駆動装置下降速度： １０ｍｍ／秒
(Catalytic reactor)
The catalytic reactor used was as follows.
・ Reaction vessel shape: Wide and wide duct shape with rectangular horizontal cross section ・ Reaction vessel material: Stainless steel ・ Reaction vessel thickness: 120mm (at bottom of vessel)
・ Reaction vessel width: 300 mm
-Reaction container spread angle: 2.5 °
・ Catalyst layer height: 350mm
Catalyst layer aspect ratio: 2.9
・ Catalyst cage: Pin type made of stainless steel round bar ・ Pin: Diameter 5.1mm, Length 90mm, Flat top, Chamfered corner 1mm ・ Pin arrangement: Bottom 16mm (reaction vessel width direction), Height 13. 5mm (reaction vessel thickness direction) isosceles triangle, all welded to catalyst retainer bottom plate ・ Pin opening ratio: 92%
・ Amount of catalyst used: 7kg
・ Driver lifting stroke: 15mm
・ Drive device ascent speed: 2 mm / sec ・ Drive device ascent speed: 10 mm / sec
上記の触媒を図９の触媒反応装置の反応容器に収容し、各触媒層中央位置に熱電対を挿入した。
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、反応させた。
駆動装置の操作タイミングは、石炭乾留ガスの通気を開始してから３時間４０分後及び５時間１５分後に、それぞれ第１回及び第２回の昇降を、各２往復実施した。
Said catalyst was accommodated in the reaction container of the catalyst reaction apparatus of FIG. 9, and the thermocouple was inserted in each catalyst layer center position.
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 reacted under normal pressure.
As for the operation timing of the driving device, the first and second ascending and descending operations were performed two reciprocations each 3 hours 40 minutes and 5 hours 15 minutes after the start of aeration of the coal dry distillation gas.
（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℃
・電気加熱炉温度： 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１５分
(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 15 minutes
（結果）
通気性（圧力損失）についての試験結果を図１１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。
また、改質特性に関しては、水素増幅率（改質ガス中水素流量／原料ガス中水素流量）の連続測定値を用いて評価した。試験を通じて水素増幅率は、約２以上の良好な状態を維持した。
(result)
FIG. 11 shows the test results for air permeability (pressure loss). 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.
Further, the reforming characteristics were evaluated using continuously measured values of the hydrogen amplification rate (hydrogen flow rate in reformed gas / hydrogen flow rate in raw material gas). Throughout the test, the hydrogen amplification rate maintained a good state of about 2 or more.
試験終了後に、装置を分解して内部を調査した結果、保持器底板上に１２０ｇ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及び棒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 the test, the device was disassembled and the inside was examined. As a result, 120 g of solid carbon was deposited on the cage bottom plate, but only a thin solid carbon film was formed on the cage surface. There was no adhesion of solid carbon to the pins and rods, and the ventilation resistance of the cage was the same as at the time of installation.
［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、触媒間の相対位置を変更するわずかな撹拌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、実施例の装置を用いれば、触媒層保持部での生成物の付着・閉塞を大幅に回避できると考えられる。 Therefore, when this catalyst was used, it turned out that most of the solid carbon deposited between the catalysts passes between the catalysts and falls with slight stirring that changes the relative position between the catalysts. From this result, it is considered that, in the reforming reaction using the present catalyst, if the apparatus of the example is used, the adhesion / clogging of the product in the catalyst layer holding part 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 vibrations and dropped through the sieve mesh.
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、触媒間の相対位置を変更するわずかな撹拌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、実施例の装置を用いれば、触媒層保持部での生成物の付着・閉塞を大幅に回避できると考えられる。 Therefore, when this catalyst was used, it turned out that most of the solid carbon deposited between the catalysts passes between the catalysts and falls with slight stirring that changes the relative position between the catalysts. From this result, it is considered that, in the reforming reaction using the present catalyst, if the apparatus of the example is used, the adhesion / clogging of the product in the catalyst layer holding part can be largely avoided.
１０ 連続式固定床触媒反応装置
１１ 反応容器
１２、１２’ 触媒保持器
１３ 触媒層
１５ 原料ガス
１６ 改質ガス
１７ 原料ガス流入路
１８ 改質ガス流出路
２０ 駆動機構
２１ 昇降装置
２２ 伝導軸
２５ ピン
２６ 底板
３１ 棒
３２ 固定具
３５ 触媒
DESCRIPTION OF SYMBOLS 10 Continuous type fixed bed catalyst reactor 11 Reaction container 12, 12 'Catalyst holder 13 Catalyst layer 15 Raw material gas 16 Reformed gas 17 Raw material gas inflow path 18 Reformed gas outflow path 20 Drive mechanism 21 Lifting device 22 Conduction shaft 25 Pin 26 Bottom plate 31 Bar 32 Fixing tool 35 Catalyst
Claims (13)
流入路及び流出路に接続された粒状体処理容器であり、その内壁に接して粒状体層を鉛直方向に充填する粒状体処理容器と、
粒状体層を保持し、かつ、流体の通過が可能な粒状体保持器と、
を有する粒状体処理装置であって、前記粒状体処理容器は、その鉛直方向における少なくとも前記粒状体層が存在する部分において、幅が一定で、且つ、厚み方向に広がり角０．５°〜２０°の範囲で上方に向かうにつれ増大する矩形の水平断面積を有すること、そして当該装置は、前記粒状体保持器を昇降させることにより粒状体層全体を昇降させて、前記粒状体と前記内壁との摩擦を生じさせると共に前記粒状体層の充填率を変動させるための駆動機構を具備するとともに、
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、前記供給流体がガスであり、前記流出流体が当該反応容器での触媒反応生成物のガスであり、その触媒反応では副生物の固体が触媒上に析出して、前記触媒層中に堆積することを特徴とする、粒状体処理装置。 A supply fluid inflow path and an outflow fluid outflow path;
A granular material processing container connected to the inflow path and the outflow path, and in contact with the inner wall of the granular material processing container to fill the granular material layer in the vertical direction;
A granular material holder that retains the granular material layer and allows passage of fluid;
The granular material processing container has a constant width at least in a portion where the granular material layer is present in the vertical direction , and a spread angle of 0.5 ° to 20 ° in the thickness direction . A rectangular horizontal cross-sectional area that increases upward in the range of °, and the apparatus raises and lowers the entire granular material layer by raising and lowering the granular material holder, and the granular material and the inner wall And a drive mechanism for changing the filling rate of the granular layer,
The granular material processing container is a continuous fixed bed catalyst reactor that stores a granular catalyst as the granular material, the supply fluid is a gas, and the outflow fluid is a gas of a catalytic reaction product in the reaction container. In the catalytic reaction, a by-product solid is deposited on the catalyst and deposited in the catalyst layer.
前記粒状体層の鉛直方向の高さが、前記粒状体処理容器の最小厚みの３倍以下であり、かつ、粒状体の３層分以上であることを特徴とする、請求項１から３のいずれか１項に記載の粒状体処理装置。 The granular material processing container has a rectangular duct shape,
The vertical height of the granular material layer is not more than three times the minimum thickness of the granular material processing container, and is not less than three layers of the granular material, The granule processing apparatus of any one of Claims.
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、請求項１〜７のいずれか１項に記載の粒状体処理装置。 The catalyst is
A tar-containing gas reforming catalyst 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 , 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. Is,
The granular material processing apparatus of any one of Claims 1-7 characterized by the above-mentioned.
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