JP5780271B2 - Catalyst for reforming tar-containing gas, method for producing the same, and method for reforming tar-containing gas - Google Patents
Catalyst for reforming tar-containing gas, method for producing the same, and method for reforming tar-containing gas Download PDFInfo
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- JP5780271B2 JP5780271B2 JP2013152132A JP2013152132A JP5780271B2 JP 5780271 B2 JP5780271 B2 JP 5780271B2 JP 2013152132 A JP2013152132 A JP 2013152132A JP 2013152132 A JP2013152132 A JP 2013152132A JP 5780271 B2 JP5780271 B2 JP 5780271B2
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- Prior art keywords
- tar
- catalyst
- containing gas
- reforming
- gas
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- 238000002407 reforming Methods 0.000 title claims description 129
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明は、炭素質原料を熱分解した際に発生するタール含有ガスを改質する触媒、この触媒を用いたタール含有ガスの改質方法であって、水素、一酸化炭素、メタンを中心とするガスへ変換するタール含有ガスの改質方法と、そこで用いられるタール含有ガスの改質用触媒の製造方法、及びタール含有ガスの改質用触媒が劣化した際の再生方法に関するものである。 The present invention is a catalyst for reforming a tar-containing gas generated when a carbonaceous raw material is pyrolyzed, and a reforming method of the tar-containing gas using this catalyst, mainly hydrogen, carbon monoxide, and methane. The present invention relates to a method for reforming a tar-containing gas to be converted into a gas, a method for producing a reforming catalyst for the tar-containing gas used therein, and a regeneration method when the reforming catalyst for the tar-containing gas is deteriorated.
鉄鋼業は、我が国の総エネルギー消費量の約１割を占めるエネルギー多消費産業であるが、高炉法一貫製鉄プロセスのうち、約４割が未利用廃熱である。そのうち、回収しやすいが従来は利用されていない熱源として、コークス炉から発生する高温の未精製ＣＯＧ（コークス炉ガス、以下、粗ＣＯＧ）の顕熱がある。 The steel industry is an energy-intensive industry that accounts for about 10% of Japan's total energy consumption, but about 40% of the blast furnace integrated steelmaking process is unused waste heat. Among them, as a heat source that is easy to recover but has not been conventionally used, there is sensible heat of high-temperature unrefined COG (coke oven gas, hereinafter, crude COG) generated from a coke oven.
粗ＣＯＧの顕熱の回収技術として、従来から間接熱回収を主体とする方法が特許文献１及び２に提案され、コークス炉上昇管内部、又は、上昇管部と集気管部の間に伝熱管を設け、この伝熱管内部に熱媒体を循環流通させて顕熱を回収する方法が開示されている。
As a technique for recovering sensible heat of crude COG, methods mainly using indirect heat recovery have been proposed in
しかし、これらの方法では、伝熱管外表面への発生ＣＯＧに随伴するタール、軽油等の付着、炭化・凝集による緻密化が進行し、経時伝熱効率の低下・熱交換効率低下という問題が不可避である。 However, in these methods, tar, light oil, etc. accompanying the COG generated on the outer surface of the heat transfer tube, and densification due to carbonization / aggregation proceed, and the problem of deterioration in heat transfer efficiency over time and heat exchange efficiency is inevitable. is there.
これら問題点を解決する技術として、伝熱管外表面に、結晶性アルミノシリケート、結晶性シリカ等の触媒を塗布し、タール等の付着物を触媒を介して低分子量の炭化水素に分解し、伝熱効率を安定維持する方法が、特許文献３に開示されている。
As a technique for solving these problems, a catalyst such as crystalline aluminosilicate or crystalline silica is applied to the outer surface of the heat transfer tube, and deposits such as tar are decomposed into low molecular weight hydrocarbons via the catalyst, and transferred.
しかし、この方法も、粗ＣＯＧ顕熱の間接熱回収技術の域を出ず、また、タール等の重質炭化水素の分解生成物がガス燃料等として利用しやすい軽質炭化水素になるかどうか等、全く考慮されていない。さらには、粗ＣＯＧ中に含有する高濃度の硫化水素等の触媒被毒性硫黄化合物成分による分解活性の経時劣化の影響についても検討されていない。 However, this method also does not go out of the indirect heat recovery technology of crude COG sensible heat, and whether the decomposition products of heavy hydrocarbons such as tar become light hydrocarbons that can be easily used as gas fuel, etc. , Not considered at all. Furthermore, the influence of the deterioration over time of the decomposition activity due to the catalytically toxic sulfur compound components such as high-concentration hydrogen sulfide contained in the crude COG has not been studied.
高温で生成する反応性ガスにその顕熱を利用して、触媒存在下、直接化学反応を導入して化学エネルギーに転換する技術はほとんどない。従来、高温ガスの顕熱は間接的に回収されて、又は全く利用されず、冷却されたガスを種々処理して利用するケースがほとんどである。 There are few technologies that use sensible heat for reactive gases generated at high temperatures to directly convert chemical energy into chemical energy in the presence of a catalyst. Conventionally, the sensible heat of a hot gas is indirectly recovered or not used at all, and in most cases, the cooled gas is used after various treatments.
しかし、粗ＣＯＧは顕熱を有しているものの、硫黄化合物の含有量が２０００ｐｐｍを越えるので、タール等の重質炭化水素の分解反応に関する触媒反応設計の観点から、顕熱の利用は極めて実現が困難と考えられる。 However, although crude COG has sensible heat, the sulfur compound content exceeds 2000 ppm, so the use of sensible heat is extremely realized from the viewpoint of catalytic reaction design for the decomposition reaction of heavy hydrocarbons such as tar. Is considered difficult.
この検討は、特許文献６に記載されているように、従来も行われていたが、改質活性は必ずしも十分とは言えなかった。また、エネルギー変換触媒は、硫黄被毒や炭素析出を受けやすいため、上記の高濃度硫黄化合物を含んだ雰囲気下で、炭素析出を起こしやすい縮合多環芳香族主体のタールの分解反応に適する触媒を製造することが困難であった。 As described in Patent Document 6, this examination has been performed conventionally, but the reforming activity is not always sufficient. Moreover, since the energy conversion catalyst is susceptible to sulfur poisoning and carbon deposition, it is a catalyst suitable for the decomposition reaction of tars mainly composed of condensed polycyclic aromatic compounds that easily cause carbon deposition in an atmosphere containing the above-mentioned high concentration sulfur compound. It was difficult to manufacture.
また、一旦反応を進行させて性能が劣化した後、再生のため空気燃焼することにより、担持金属粒子のシンタリング（粗大化）が起こりやすく、再生による活性の再現を実現することも困難であった。 In addition, once the reaction has progressed and the performance has deteriorated, air combustion for regeneration can easily cause sintering of the supported metal particles, which makes it difficult to reproduce the activity by regeneration. It was.
粗ＣＯＧ中に含まれる不純物（Ｈ2Ｓ、ＣＯＳ、芳香族炭化水素、タール、ダスト等）を常法による精製（例えば、特許文献７）をしたもの（以下精製ＣＯＧ）は、都市ガス等の燃料や、化学合成用の原料として使用されてきている。 Impurities (H 2 S, COS, aromatic hydrocarbons, tar, dust, etc.) contained in the crude COG are purified by conventional methods (eg, Patent Document 7) (hereinafter referred to as purified COG) It has been used as a raw material for fuel and chemical synthesis.
コークス炉ガスを用いてメタノール合成プラントを建設する際には、常法による精製ガスには、低級炭化水素や芳香族炭化水素が低濃度だが残留しており、それらが改質装置の触媒の被毒を起こすおそれがある。それを避けるために、市販の触媒を用いたプレリフォーミングを行った後、改質装置で合成ガスを製造する製造システムが開示されている（例えば、特許文献８）。 When constructing a methanol synthesis plant using coke oven gas, low-grade hydrocarbons and aromatic hydrocarbons remain at a low concentration in conventional refined gas. May cause poison. In order to avoid this, a production system is disclosed in which synthesis gas is produced by a reformer after pre-reforming using a commercially available catalyst (for example, Patent Document 8).
しかし、後段の合成ガスを製造する改質装置に用いる触媒については言及されていない等、粗ＣＯＧや精製ＣＯＧの改質触媒に関しては検討されていない。 However, the catalyst used in the reformer for producing the subsequent synthesis gas is not mentioned, and the reforming catalyst for crude COG and purified COG has not been studied.
一方、炭化水素の改質用原料として一般に用いられるメタンの改質用触媒としては、古くから数多くの研究がなされている。 On the other hand, many studies have been made on methane reforming catalysts generally used as hydrocarbon reforming raw materials.
例えば、メタンの部分酸化触媒としては、非特許文献１のように、ニッケル、マグネシウム、アルミニウムの溶液から沈殿物を経由して製造される触媒、メタンの水蒸気又は二酸化炭素による改質用触媒としては、特許文献９のように、マグネシア、アルミナ等の担体にニッケル、及び、ペロブスカイト化合物を担持した触媒が検討されている。 For example, as a partial oxidation catalyst for methane, as in Non-Patent Document 1, as a catalyst produced from a solution of nickel, magnesium, and aluminum via a precipitate, a catalyst for reforming with methane steam or carbon dioxide, As in Patent Document 9, a catalyst in which nickel and a perovskite compound are supported on a carrier such as magnesia or alumina has been studied.
さらに、特許文献１０のように、ニッケル、マグネシウム、カルシウムで構成される酸化物に第３Ｂ族元素、第４Ａ族元素、第６Ｂ族元素、第７Ｂ族元素、第１Ａ族元素及びランタノイド元素の少なくとも一種を混合した触媒が検討されている。 Furthermore, as in Patent Document 10, at least one of Group 3B elements, Group 4A elements, Group 6B elements, Group 7B elements, Group 1A elements, and lanthanoid elements is included in an oxide composed of nickel, magnesium, and calcium. One kind of mixed catalyst has been studied.
また、メタンを主成分とする低級炭化水素との水蒸気改質触媒としては、特許文献１１のように、マグネシウム、アルミニウム、ニッケルを構成元素とし、かつ、アルカリ金属、アルカリ土類金属、Ｚｎ、Ｃｏ、Ｃｅ、Ｃｒ、Ｆｅ、Ｌａから選ばれる一種又は二種以上の元素を含有する触媒が検討されている。 In addition, as a steam reforming catalyst with lower hydrocarbons mainly composed of methane, as disclosed in Patent Document 11, magnesium, aluminum, nickel are used as constituent elements, and alkali metals, alkaline earth metals, Zn, Co Catalysts containing one or more elements selected from, Ce, Cr, Fe, and La have been studied.
特許文献１２では、メタンや天然ガス、都市ガスの水蒸気改質用触媒として、ニッケル、ランタンを含んだペロブスカイト型酸化物が検討されている。 In Patent Document 12, a perovskite oxide containing nickel and lanthanum is studied as a steam reforming catalyst for methane, natural gas, and city gas.
特許文献１３では、低級飽和炭化水素の酸化反応による合成ガス製造用触媒として、アルカリ土類金属とチタンからなるペロブスカイト酸化物にニッケルを担持した化合物が検討されている。 In Patent Document 13, a compound in which nickel is supported on a perovskite oxide composed of an alkaline earth metal and titanium is examined as a catalyst for producing synthesis gas by oxidation reaction of lower saturated hydrocarbons.
特許文献１４では、ペロブスカイト酸化物中の金属元素の析出−固溶現象を利用して、自動車排ガス浄化用触媒として白金族元素を含んだ化合物が検討されている。 In Patent Document 14, a compound containing a platinum group element is studied as a catalyst for automobile exhaust gas purification by utilizing the precipitation-solid solution phenomenon of metal elements in perovskite oxide.
また、非特許文献２のように、メタンの二酸化炭素、スチーム及び酸素によるトリリフォーミング反応用としてセリア、ジルコニア、及びセリアジルコニア化合物へのＮｉ担持触媒と共に、セリアジルコニア化合物へのマグネシア及びＮｉ担持触媒が検討されている。
Further, as in Non-Patent
一方、都市ガス、イソオクタン、灯油、プロパン等の、原料中に硫黄分を含みかつ比較的低級の炭化水素から燃料電池用水素を発生する触媒としては、特許文献１５のように、アルミニウムとマグネシウムからなる多孔質担体に、珪素、ジルコニウム、セリウム、チタン、アルミニウム、イットリウム、スカンジウム、第１Ａ族元素、第２Ａ族元素から選ばれる少なくとも１種類以上の元素の酸化物が検討されている。 On the other hand, as a catalyst for generating hydrogen for fuel cells from relatively low hydrocarbons containing sulfur in the raw materials such as city gas, isooctane, kerosene, propane, etc., as disclosed in Patent Document 15, from aluminum and magnesium. As the porous support, an oxide of at least one element selected from silicon, zirconium, cerium, titanium, aluminum, yttrium, scandium, a group 1A element, and a group 2A element has been studied.
さらに、特許文献１６では、プロパン、ブタン、都市ガス等の低級炭化水素からの水素製造触媒として、マグネシウム、アルミニウム、ニッケルを構成元素とし、かつ、珪素を含有する触媒等が提案、開示されており、特許文献１７では、Ｃｏ含有ペロブスカイト酸化物触媒等が提案、開示されている。 Further, Patent Document 16 proposes and discloses a catalyst for producing hydrogen from lower hydrocarbons such as propane, butane, city gas, etc., containing magnesium, aluminum and nickel as constituent elements and containing silicon. Patent Document 17 proposes and discloses a Co-containing perovskite oxide catalyst and the like.
しかし、これらの触媒の対象となる炭化水素は、いずれも低級かつ鎖式炭化水素で分解しやすく、かつ、原料中に含まれる触媒毒となり得る硫黄分は、特許文献１５に示されているような、高々５０ｐｐｍ以下のものに限られている。 However, the hydrocarbons that are the targets of these catalysts are all low-chain hydrocarbons that are easily decomposed, and the sulfur content that can be a catalyst poison contained in the raw material is shown in Patent Document 15. However, it is limited to those of 50 ppm or less.
一方、非特許文献３では、硫黄分が含まれるジェット燃料用ケロシンの改質用触媒として、ＬａＦｅＯ3を基にＬａ0.6Ｃｅ0.4Ｆｅ0.8ＭｅＮｉ0.2Ｏ3（Ｍｅ＝Ｋ、Ｒｕ等）が開示されているが、ケロシンとして実験に用いたのはデカン、ドデカンが主体の鎖式飽和炭化水素であり、かつ、Ｈ2Ｓが５０ｐｐｍ以上ではＭｅが存在しないと大きく活性が低下する等、耐硫黄被毒性に大きな課題があった。
On the other hand, Non-Patent
したがって、炭素質原料を乾留した際に発生するベンゼン環が縮合した多環芳香族主体のタール等重質炭化水素を高濃度の硫化水素存在下で高効率に改質することへの検討は、全く行われていなかった。 Therefore, the study on reforming heavy hydrocarbons such as tars mainly composed of polycyclic aromatics with condensed benzene rings generated when carbonaceous raw materials are carbonized in the presence of high concentration hydrogen sulfide It was not done at all.
さらに、近年の地球温暖化問題により、二酸化炭素排出量削減の有効手段として、炭素質原料の一つであるバイオマス利用が注目されており、バイオマスの高効率エネルギー転換に関する研究が行われている。また、昨今のエネルギー資源確保の観点から、過去精力的に行われてきた石炭の有効活用に関する研究も、実用化に向けて見直されてきている。 Furthermore, due to the recent global warming problem, the use of biomass, which is one of carbonaceous raw materials, has attracted attention as an effective means for reducing carbon dioxide emissions, and research on high-efficiency energy conversion of biomass is being conducted. In addition, from the viewpoint of securing energy resources in recent years, research on effective use of coal, which has been vigorously conducted in the past, has been reviewed for practical use.
その中で、バイオマスの乾留で生成するタールをガス化して、粗ガス（未精製ガス）を生成し、その顕熱を利用する方法については、特に、触媒を用いたタールの触媒改質を中心に、特許文献１８、１９等を始めとして種々検討されているが、貴金属を使用していて高価であったり、触媒寿命が短いという課題を有していた。 Among these, the method of gasifying tar generated by dry distillation of biomass to generate crude gas (unrefined gas) and utilizing its sensible heat is particularly focused on catalytic reforming of tar using a catalyst. In addition, various studies have been made including Patent Documents 18 and 19 and the like, but noble metals are used, which is expensive and has a problem that the catalyst life is short.
こうした中、特許文献２０では、バイオマスの熱分解によるガス化ガス中のタール分解触媒として、ＡＢＯ3（ＡはＬａ、Ｂａ、Ｓｒ、Ｃａであり、ＢはＴｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ａｌ、Ｚｒ、Ｎｂ、Ｓｎ又はＣｅである）のペロブスカイト型酸化物を用いる提案がなされている。しかしながら、本文献では、触媒として機能する活性種がどの元素であるのか、ペロブスカイト型構造を有した場合、どういう効果を発揮してタール分が分解するかについて、全く記載されていない。 Under these circumstances, in Patent Document 20, as a tar decomposition catalyst in a gasification gas by thermal decomposition of biomass, ABO 3 (A is La, Ba, Sr, Ca, B is Ti, Cr, Mn, Fe, Co, There have been proposals to use perovskite oxides of Ni, Al, Zr, Nb, Sn or Ce. However, this document does not describe at all what element the active species that functions as a catalyst is, and what effect the tar component decomposes when it has a perovskite structure.
また、ペロブスカイト型酸化物のＢサイトにＦｅやＣｏ等が存在しても分解率が高いとしているが、Ｎｉが存在する場合についての触媒活性は何ら触れられていない。また、実施例では、バイオマスガス化ガス中のタールとしてトルエンを用い、Ｈ2Ｓが２０００ｐｐｍの高濃度雰囲気下で５〜１０時間試験を行った結果が示されているが、具体的にバイオマスを使用した試験は行われていない。さらに、長期安定性を含めた記載がなく、実タールで試験を行った際の触媒活性の安定性等は調べられていないという課題を有していた。 Further, although the decomposition rate is said to be high even if Fe, Co or the like is present at the B site of the perovskite type oxide, no catalytic activity is described in the case where Ni is present. In the embodiment, using toluene as tar biomass gasification gas, although H 2 results S are subjected to 5-10 hour test under high concentration atmosphere of 2000ppm are shown, the specific biomass The test used has not been performed. Furthermore, there was no description including long-term stability, and there was a problem that the stability of the catalytic activity when tested with actual tar was not investigated.
本発明は、前記の事情を踏まえて成されたものであって、石炭やバイオマス等の炭素質原料を熱分解した時に発生し、重質鎖式炭化水素や縮合多環芳香族炭化水素等からなるタールを含むとともに、硫化水素を高濃度で含む粗ガス、又は精製ガス等のタール含有ガスを、触媒存在下で、高性能かつ安定的に一酸化炭素、水素等の軽質化学物質に転換するタール含有ガスの改質用触媒及びその製造方法、並びにタール含有ガスの改質方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is generated when a carbonaceous raw material such as coal or biomass is pyrolyzed, and is derived from heavy chain hydrocarbons, condensed polycyclic aromatic hydrocarbons, and the like. The tar-containing gas such as crude gas or refined gas containing hydrogen sulfide at a high concentration is converted into light chemicals such as carbon monoxide and hydrogen stably in the presence of a catalyst. It is an object of the present invention to provide a reforming catalyst for tar-containing gas, a method for producing the same, and a reforming method for tar-containing gas.
本発明者らは、石炭やバイオマスを熱分解した際に発生する、硫化水素を高濃度で含むタール含有ガスについて、硫化水素を高濃度で含む粗ガスや精製ガスを触媒と接触させて、タール又はガス中の炭化水素成分を、一酸化炭素、水素等の軽質化学物質に転換する方法について鋭意検討した。 For the tar-containing gas containing hydrogen sulfide at a high concentration, which is generated when coal or biomass is pyrolyzed, the present inventors contact a crude gas or purified gas containing hydrogen sulfide at a high concentration with the catalyst, Alternatively, the inventors studied diligently about a method for converting hydrocarbon components in gas into light chemical substances such as carbon monoxide and hydrogen.
その結果、触媒として、ＡＮｉxＢ1-xＯ3（Ａは、Ｌａ、Ｃｅ、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも１種類の金属元素、Ｂは、Ｃｏ、Ｆｅ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｒｅ、Ｗから選ばれる少なくとも１種類の金属元素、０．１≦Ｘ≦１）で表される、化合物の単位格子がペロブスカイト型構造である複合酸化物を用いることにより、硫化水素を高濃度で含み、かつ、縮合多環芳香族炭化水素等からなるタールを多く含む粗ガスや精製ガスを改質しても、触媒に硫黄被毒による活性低下や炭素析出が生じにくく、一酸化炭素や水素等の軽質化学物質へ安定的に変換できることを見出した。 As a result, as a catalyst, ANi x B 1-x O 3 (A is at least one metal element selected La, Ce, Ca, Sr, from Ba, B is Co, Fe, Ti, Zr, V, A compound oxide represented by at least one metal element selected from Nb, Ta, Cr, Mo, Re, and W, 0.1 ≦ X ≦ 1), wherein the unit cell of the compound has a perovskite structure Therefore, even if a crude gas or a refined gas containing a high concentration of hydrogen sulfide and containing a large amount of tar consisting of condensed polycyclic aromatic hydrocarbons or the like is reformed, the catalyst may be reduced in activity due to sulfur poisoning or carbon deposition. It has been found that it is less likely to occur and can be stably converted into light chemicals such as carbon monoxide and hydrogen.
本発明者らは、これは、上記ペロブスカイト型酸化物のＢサイトをＮｉが占有した場合、還元雰囲気中でマトリクス（ＡＮｉxＢ1-xＯ3）からＮｉが微細な金属粒子として析出しやすいために、高い触媒活性を発揮することを見出して、本発明を成すに至った。 The present inventors, this is the case of B site Ni perovskite oxide is occupied, Ni from the matrix (ANi x B 1-x O 3) in a reducing atmosphere tends to precipitate as fine metal particles For this reason, the inventors have found that the present invention exhibits high catalytic activity, and have reached the present invention.
また、本発明者らがさらに検討した結果、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た複合酸化物を用いることによっても、硫化水素を高濃度で含み、かつ、縮合多環芳香族炭化水素等からなるタールを多く含む粗ガスや精製ガスを改質しても、触媒に硫黄被毒による活性低下や炭素析出が生じにくく、一酸化炭素や水素等の軽質化学物質へ安定的に変換できることを見出した。 Further, as a result of further studies by the present inventors, hydrogen sulfide can be added at a high concentration by using a composite oxide obtained by adding at least one oxide selected from silica, alumina, and zeolite to the composite oxide. Even if reforming crude gas or refined gas containing a large amount of tar containing a condensed polycyclic aromatic hydrocarbon or the like, it is difficult for the catalyst to decrease the activity due to sulfur poisoning and to cause carbon deposition. It was found that it can be stably converted into light chemical substances such as
また、本発明者らは、さらに鋭意検討した結果、ニッケル化合物、及び、ニッケルを含んだペロブスカイト型構造の金属化合物の混合溶液に、沈殿剤を添加して、ニッケルと他の金属元素を共沈させて沈殿物を生成し、共沈時又は前記沈殿物の生成後に、アルミニウム成分を加えて少なくとも乾燥及び焼成することにより、ペロブスカイト型酸化物中に固溶している活性種金属のＮｉの微細析出が可能で高速反応が可能であり、析出した活性金属がマトリクス（母相）と強固に結合するので、シンタリング（粗大化）しにくく、活性低下を抑制可能であり、さらに、析出した活性種金属を焼成によりマトリクスへ再度吸蔵でき、再生が可能である等の種々の特徴を有する固相晶析法に着眼した。 In addition, as a result of further intensive studies, the present inventors added a precipitant to a mixed solution of a nickel compound and a metal compound having a perovskite structure containing nickel to coprecipitate nickel and other metal elements. To form a precipitate, and at the time of coprecipitation or after the formation of the precipitate, the aluminum component is added and at least dried and fired, so that the active species metal Ni finely dissolved in the perovskite oxide is dissolved. Precipitation is possible, high-speed reaction is possible, and since the precipitated active metal is firmly bonded to the matrix (matrix), it is difficult to sinter (coarse), can suppress the decrease in activity, and the precipitated activity The inventors focused on solid-phase crystallization methods having various characteristics such that the seed metal can be occluded again into the matrix by firing and can be regenerated.
また、本発明者らは、あらかじめ、活性種であるニッケル元素を、ペロブスカイト型構造を有しマトリクスとなる金属酸化物と化合物化し、さらに、アルミニウム成分を共存させ、タール含有ガス中の還元性ガス、又は、反応前の還元性ガスに接触させることで、ペロブスカイト型酸化物マトリクスから、ニッケル金属が酸化物表面にクラスター状に微細析出するのを利用するとり、硫黄被毒となり得る硫黄成分の高濃度の雰囲気下、又は、タール等の重質炭化水素等の炭素析出を起こしやすい成分を多量に含んだ過酷な状況の下でも、活性金属の表面積が大きく、かつ、硫黄被毒を受けても新たに活性金属が析出可能なため、重質炭化水素を高い効率で軽質炭化水素へ変換できることを見出して、本発明を成すに至った。 In addition, the present inventors previously compounded nickel element, which is an active species, with a metal oxide that has a perovskite structure and serves as a matrix, and further coexists with an aluminum component to reduce the reducing gas in the tar-containing gas. Alternatively, by making contact with reducing gas before the reaction, nickel metal is finely deposited in a cluster form on the oxide surface from the perovskite type oxide matrix. Even under harsh conditions where the active metal has a large surface area and is poisoned by sulfur, even under harsh conditions that contain a large amount of components that easily cause carbon deposition such as heavy hydrocarbons such as tar Since the active metal can be newly deposited, it has been found that heavy hydrocarbons can be converted into light hydrocarbons with high efficiency, and the present invention has been achieved.
本発明者らが、さらに鋭意検討した結果、ニッケル化合物、及び、ニッケルを含んだペロブスカイト型構造の金属化合物を含む混合溶液から、共沈により沈殿物を生成した後、該沈殿物を乾燥及び焼成して、ニッケルと他の金属元素を含むペロブスカイト型酸化物を生成し、その後、該酸化物に、ケイ素又はアルミニウム成分を加えて混合物を生成し、次いで、該混合物を、少なくとも乾燥及び焼成して製造された触媒は、タール含有ガスの改質活性が高く、かつ、長時間改質することができ、また、炭素析出や硫黄被毒により触媒性能が劣化しても、水蒸気又は空気の少なくともいずれかを接触させることで、再生することができ、さらに、再生した触媒は、ほぼ劣化前の性能を保持していることを見出し、より長期に安定した運転が可能となるタール含有ガスの改質方法を成すに至った。 As a result of further intensive studies by the present inventors, a precipitate was formed by coprecipitation from a mixed solution containing a nickel compound and a metal compound having a perovskite structure containing nickel, and then the precipitate was dried and calcined. Forming a perovskite oxide containing nickel and other metal elements, and then adding a silicon or aluminum component to the oxide to form a mixture; then, the mixture is at least dried and calcined; The produced catalyst has a high reforming activity of the tar-containing gas and can be reformed for a long time. Even if the catalyst performance deteriorates due to carbon deposition or sulfur poisoning, at least one of water vapor and air is required. It can be regenerated by contacting the catalyst, and the regenerated catalyst has been found to maintain almost the same performance as before. It made leading to the completion of the modification method of the tar-containing gas.
本発明者らは、さらに鋭意検討した結果、ニッケル化合物、及び、ニッケルを含んだペロブスカイト型構造の金属化合物を含む混合溶液から共沈により沈殿物を生成した後、該沈殿物に、シリカ粉末と水、又は、シリカゾル、又は、アルミナ粉末と水、又は、アルミナゾル、又は、ゼオライト粉末と水を加えて混合物を生成し、その後、該混合物を少なくとも乾燥及び焼成して製造された触媒は、タール含有ガスの改質活性が高く、かつ、長時間改質することができ、また、炭素析出や硫黄被毒により触媒性能が劣化しても、水蒸気又は空気の少なくともいずれかを接触させることで、再生することができ、さらに、再生した触媒は、ほぼ劣化前の性能を保持していることを見出して、より長期に安定した運転が可能となるタール含有ガスの改質方法に係る発明を成すに至った。 As a result of further intensive studies, the inventors of the present invention generated a precipitate by coprecipitation from a mixed solution containing a nickel compound and a metal compound having a perovskite structure containing nickel, and then the silica powder and A catalyst produced by adding water, silica sol, or alumina powder and water, or alumina sol or zeolite powder and water, and then drying and calcining the mixture at least contains a tar. It has high gas reforming activity and can be reformed for a long time. Even if the catalyst performance deteriorates due to carbon deposition or sulfur poisoning, it can be regenerated by bringing it into contact with water vapor or air. Furthermore, it is found that the regenerated catalyst retains almost the same performance as before, and the tar-containing gas that enables stable operation over a longer period of time is found. Leading to the completion of the invention according to the quality way.
本発明者らは、さらに鋭意検討した結果、ニッケル化合物、ニッケルを含んだペロブスカイト型構造の金属化合物、及び、ケイ素化合物又はアルミニウム化合物の混合溶液に沈殿剤を添加して、ニッケル、金属元素、及び、ケイ素又はアルミニウムを共沈させて沈殿物を生成した後、該沈殿物を、少なくとも乾燥及び焼成して製造された触媒は、タール含有ガスの改質活性が高く、かつ、長時間改質することができ、また、炭素析出や硫黄被毒により触媒性能が劣化しても、水蒸気又は空気の少なくともいずれかを接触させることで、再生することができ、さらに、再生した触媒は、ほぼ劣化前の性能を保持していることを見出して、より長期に安定した運転が可能となるタール含有ガスの改質方法に係る発明を成すに至った。 As a result of further intensive studies, the inventors added a precipitant to a mixed solution of a nickel compound, a metal compound having a perovskite structure containing nickel, and a silicon compound or an aluminum compound, and the nickel, metal element, and The catalyst produced by coprecipitation of silicon or aluminum to produce a precipitate, and at least drying and calcining the precipitate has a high reforming activity of the tar-containing gas and reforms for a long time. In addition, even if the catalyst performance deteriorates due to carbon deposition or sulfur poisoning, it can be regenerated by bringing it into contact with at least one of water vapor and air. As a result, the inventors have made an invention relating to a method for reforming a tar-containing gas that enables stable operation over a longer period of time.
本発明者らは、さらに鋭意検討した結果、シリカ又はアルミナを担体として、ニッケル化合物、ニッケルを含んだペロブスカイト型構造の金属化合物の各溶液を、外部より上記担体に付着した後、乾燥及び焼成、又は、乾燥、解砕、焼成して製造された触媒は、タール含有ガスの改質活性が高く、かつ、長時間改質することができ、また、炭素析出や硫黄被毒により触媒性能が劣化しても、水蒸気又は空気の少なくともいずれかを接触させることで、再生することができ、さらに、再生した触媒は、ほぼ劣化前の性能を保持していることを見出して、より長期に安定した運転が可能となるタール含有ガスの改質方法に係る発明を成すに至った。 As a result of further intensive studies, the inventors of the present invention, using silica or alumina as a carrier, a nickel compound, each solution of a metal compound having a perovskite structure containing nickel, is attached to the carrier from the outside, and then dried and fired. Alternatively, the catalyst produced by drying, crushing, and calcination has high reforming activity of the tar-containing gas and can be reformed for a long time, and the catalyst performance deteriorates due to carbon deposition and sulfur poisoning. However, it can be regenerated by bringing it into contact with at least one of water vapor and air, and the regenerated catalyst has been found to maintain almost the same performance as before, and has been stabilized for a longer period of time. An invention relating to a method for reforming a tar-containing gas that can be operated has been made.
本発明者らは、さらに鋭意検討した結果、前記触媒は、タール含有ガスの改質の改質を長時間実施して、炭素析出や硫黄被毒により触媒性能が劣化しても、水蒸気又は空気の少なくともいずれかを接触させることで、再生することができ、再生した触媒は、ほぼ劣化前の性能を保持していることを見出して、より長期に安定した運転が可能となるタール含有ガスの改質方法に係る発明を成すに至った。 As a result of further intensive studies, the present inventors have conducted reforming of a tar-containing gas for a long time, and even if the catalyst performance deteriorates due to carbon deposition or sulfur poisoning, It is possible to regenerate by contacting at least one of the above, and it is found that the regenerated catalyst retains almost the performance before deterioration, and the tar-containing gas that enables stable operation for a longer period of time is found. It came to make the invention which concerns on the modification | reformation method.
本発明の要旨は、以下のとおりである。 The gist of the present invention is as follows.
（１）ＡＮｉxＢ1-xＯ3
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は、Ｌａ、Ｃｅ、Ｃａ、Ｓｒ、Ｂａの少なくとも１種から選ばれる金属元素であり、
Ｂは、Ｃｏ、Ｆｅ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｒｅ、Ｗの少なくとも
１種から選ばれる金属元素であり（但し、ＬａＮｉxＦｅ1-xＯ3を除く）、
ｘは、０．１≦ｘ≦１を満たし、
複合酸化物の単位格子は、ペロブスカイト型構造である
ことを特徴とするタール含有ガスの改質用触媒。
(1) ANi x B 1- x
A catalyst for reforming a tar-containing gas that is a composite oxide represented by:
A is a metal element selected from at least one of La, Ce, Ca, Sr, and Ba,
B (except where the LaNi x Fe 1-x O 3 ) Co, Fe, Ti, Zr, V, Nb, Ta, Cr, Mo, Re, a metal element selected from at least one of W,
x satisfies 0.1 ≦ x ≦ 1,
A catalyst for reforming a tar-containing gas, wherein the unit cell of the composite oxide has a perovskite structure.
（２）前記（１）に記載のタール含有ガスの改質用触媒を用いることを特徴とするタール含有ガスの改質方法。 (2) A tar-containing gas reforming method using the tar-containing gas reforming catalyst according to (1).
（３）前記タール含有ガス改質用触媒の存在下又は還元後の前記触媒の存在下において、炭素質原料を熱分解した際に発生するタール含有ガス中の水素、二酸化炭素、及び、水蒸気を接触させて、前記タール含有ガス中のタールを改質してガス化することを特徴とする前記（２）に記載のタール含有ガスの改質方法。 (3) Hydrogen, carbon dioxide, and water vapor in the tar-containing gas generated when the carbonaceous raw material is pyrolyzed in the presence of the tar-containing gas reforming catalyst or in the presence of the catalyst after reduction. The method for reforming a tar-containing gas as described in (2) above, wherein the tar-containing gas is reformed and gasified by contacting.
（４）前記タール含有ガス改質用触媒の存在下又は還元後の前記触媒の存在下において、炭素質原料を熱分解した際に発生するタール含有ガスに、外部から水素、二酸化炭素、水蒸気の少なくともいずれかを接触させて、前記タール含有ガスを改質してガス化することを特徴とする前記（２）又は（３）に記載のタール含有ガスの改質方法。 (4) In the presence of the tar-containing gas reforming catalyst or in the presence of the catalyst after reduction, the tar-containing gas generated when the carbonaceous raw material is thermally decomposed is externally supplied with hydrogen, carbon dioxide, and steam. The method for reforming a tar-containing gas according to (2) or (3), wherein at least one of them is brought into contact to reform and gasify the tar-containing gas.
（５）前記水素、二酸化炭素、水蒸気の少なくともいずれかに、さらに酸素含有ガスを加えて、タール含有ガスに接触させることを特徴とする前記（３）又は（４）のいずれかに記載のタール含有ガスの改質方法。 (5) The tar according to any one of (3) and (4) above, wherein an oxygen-containing gas is further added to at least one of the hydrogen, carbon dioxide, and water vapor, and is brought into contact with the tar-containing gas. Method for reforming contained gas .
（６）前記タール含有ガスが、硫化水素を含むタール含有ガスであることを特徴とする前記（２）〜（５）のいずれかに記載のタール含有ガスの改質方法。 (6) The method for reforming a tar-containing gas according to any one of (2) to (5), wherein the tar-containing gas is a tar-containing gas containing hydrogen sulfide .
（７）前記タール含有ガスが、石炭を乾留したときに発生する乾留ガスであることを特徴とする前記（２）〜（６）のいずれかに記載のタール含有ガスの改質方法。 (7) The method for reforming a tar-containing gas according to any one of (2) to (6), wherein the tar-containing gas is a carbonization gas generated when coal is carbonized.
（８）前記タール含有ガスが、コークス炉から排出されるコークス炉ガスであることを特徴とする前記（２）〜（７）のいずれかに記載のタール含有ガスの改質方法。 (8) The method for reforming a tar-containing gas according to any one of (2) to (7), wherein the tar-containing gas is a coke oven gas discharged from a coke oven.
（９）前記タール含有ガスが、木質系バイオマス、食品廃棄物系バイオマスの少なくともいずれかを乾留したときに発生する乾留ガスであることを特徴とする前記（２）〜（５）のいずれかに記載のタール含有ガスの改質方法。 (9) In any one of the above (2) to (5), the tar-containing gas is a dry distillation gas generated when dry distillation of at least one of a woody biomass and a food waste biomass. The method for reforming a tar-containing gas as described.
（１０）前記（１）に記載のタール含有ガス改質用触媒の製造方法であって、
ニッケル化合物と前記（１）に記載のタール含有ガス改質用触媒を構成するニッケル以外の金属の化合物とを含む混合溶液に、沈殿剤を添加して、ニッケルと該ニッケル以外の金属を共沈させて沈殿物を生成し、該沈殿物を乾燥及び焼成して、ニッケルと該ニッケル以外の金属を含むペロブスカイト型酸化物からなる触媒を製造することを特徴とするタール含有ガスの改質に用いられる触媒の製造方法。
(10) The method for producing the tar-containing gas reforming catalyst according to (1),
A precipitant is added to a mixed solution containing a nickel compound and a compound of a metal other than nickel that constitutes the tar-containing gas reforming catalyst described in (1), so that nickel and a metal other than the nickel are coprecipitated. And producing a catalyst comprising a perovskite-type oxide containing nickel and a metal other than the nickel to produce a precipitate, and drying and calcining the precipitate. A method for producing a catalyst.
（１１）前記（２）〜（９）のいずれかに記載のタール含有ガスの改質方法を実施した後、炭素析出、硫黄被毒の少なくともいずれかにより性能劣化した前記触媒に、水蒸気又は空気の少なくともいずれかを接触させて、前記触媒を再生し、再び前記タール改質用触媒として用いることを特徴とするタール含有ガスの改質方法。 (11) After carrying out the reforming method of the tar-containing gas according to any one of (2) to (9), steam or air is added to the catalyst whose performance is deteriorated by at least one of carbon deposition and sulfur poisoning. A method for reforming a tar-containing gas, wherein the catalyst is regenerated by contacting at least one of the above and used again as the tar reforming catalyst.
本発明によれば、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。 According to the present invention, 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.
例えば、硫化水素を数十ｐｐｍ〜２０００ｐｐｍ程度含有する粗ＣＯＧ、精製ＣＯＧやバイオマス乾留ガス等のタール含有ガスに対しても、本発明の触媒により高効率でかつ安定に、改質反応によって軽質化学物質へと転換、及び改質用触媒の製造をすることができる。 For example, even for crude COG containing about several tens of ppm to 2000 ppm of hydrogen sulfide, tar-containing gas such as purified COG or biomass dry distillation gas, the catalyst of the present invention enables high-efficiency and stable light chemicals through a reforming reaction. Conversion to a substance and production of a reforming catalyst can be performed.
また、本発明の一形態によれば、タール含有ガスの改質後、水蒸気又は空気の少なくともいずれかを反応後の触媒に接触させることにより、触媒を再生させて、この再生触媒を再度タール含有ガスの改質に使用することができ、触媒性能の劣化を抑えながら、長期に安定した運転が可能となる。 Further, according to one aspect of the present invention, after reforming the tar-containing gas, the catalyst is regenerated by bringing at least one of water vapor and air into contact with the catalyst after the reaction, and the regenerated catalyst is again tar-containing. It can be used for gas reforming, and stable operation is possible for a long time while suppressing deterioration of catalyst performance.
以下、具体例を示して、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to specific examples.
本発明のタール含有ガスの改質方法で用いるタール含有ガス改質用触媒は、ＡＮｉxＢ1-xＯ3（Ａは、Ｌａ、Ｃｅ、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも１種類の金属元素、Ｂは、Ｃｏ、Ｆｅ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｒｅ、Ｗから選ばれる少なくとも１種類の金属元素、０．１≦Ｘ≦１）で表される、化合物の単位格子がペロブスカイト型構造である複合酸化物である。また、さらに上記複合酸化物に、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た酸化物である。 The tar-containing gas reforming catalyst used in the method for reforming a tar-containing gas according to the present invention is an Anix x B 1-x O 3 (A is at least one metal selected from La, Ce, Ca, Sr, Ba) Element, B is a compound represented by at least one metal element selected from Co, Fe, Ti, Zr, V, Nb, Ta, Cr, Mo, Re, and W, 0.1 ≦ X ≦ 1) Is a complex oxide having a perovskite structure. Further, it is an oxide obtained by adding at least one oxide selected from silica, alumina, and zeolite to the composite oxide.
ＡＢＯ3の組成式をもつ多くの化合物が、ペロブスカイト型構造をつくり、立方単位格子の中心をＡ原子が、隅をＢ原子が、稜の中心をＯ原子が占めた構造を有する。しかしながら、Ｂで表される占有位置（Ｂサイト）を、Ｎｉが一部又は全部占有した場合には、Ｎｉイオンの大きさや電荷との違いから、Ｂサイトとして上述した元素でのみ本構造を形成することができる。また、この場合には、Ａサイトとして、上述のような限定した元素でのみ本構造を形成することができる。さらに、還元雰囲気になっても安定して存在することが必須なため、Ａ、Ｂは上記の元素群に限定される。 Many compounds having the composition formula of ABO 3 form a perovskite structure, and have a structure in which A atom is centered in the cubic unit cell, B atom is in the corner, and O atom is in the center of the ridge. However, when Ni occupies part or all of the occupied position (B site) represented by B, this structure is formed only by the elements described above as the B site due to the difference in the size and charge of Ni ions. can do. In this case, this structure can be formed only with the limited elements as described above as the A site. Furthermore, A and B are limited to the above element group because it is essential that they exist stably even in a reducing atmosphere.
ニッケルは、重質炭化水素を、ガス中に存在又は外部より導入される水蒸気、水素、若しくは二酸化炭素との間で改質反応を進行させる主活性成分として機能する。タール含有ガス中に高濃度の硫化水素が共存する場合でも、上記ニッケル金属が触媒表面上でクラスター上に微細分散して表面積が大きく、かつ、還元雰囲気下では反応中に活性金属粒子が被毒を受けても新たな活性金属粒子がマトリクス（ペロブスカイト型酸化物）から微細析出するので、硫黄被毒による活性低下の影響を受けにくいと考えられる。 Nickel functions as a main active component that causes heavy hydrocarbons to proceed with the reforming reaction with water vapor, hydrogen, or carbon dioxide present in the gas or introduced from the outside. Even when high-concentration hydrogen sulfide coexists in the tar-containing gas, the nickel metal is finely dispersed on the catalyst surface on the cluster to increase the surface area, and in a reducing atmosphere, active metal particles are poisoned during the reaction. New active metal particles are finely precipitated from the matrix (perovskite type oxide) even if it is applied, so it is considered that the active metal particles are hardly affected by the decrease in activity due to sulfur poisoning.
このマトリクスの化合物から、還元雰囲気下で、活性金属粒子を微細クラスター状に析出させることができる。また、縮合多環芳香族主体のタールも、乾留直後の高温状態で反応性に富む状態であり、かつ、微細分散して高比表面積をもった高活性なニッケル金属と接触することにより、高効率に軽質炭化水素へ変換・分解するものと考えられる。また、析出したニッケルがマトリクスの化合物と強固に結合しているために、ニッケル粒子間での凝集（シンタリング）を抑制し、長時間の反応中でも触媒活性が低下しにくい効果があると考えられる。 From this matrix compound, active metal particles can be precipitated in a fine cluster under a reducing atmosphere. In addition, the condensed polycyclic aromatic-based tar is also highly reactive at a high temperature immediately after dry distillation, and is highly dispersed by contact with highly active nickel metal having a finely dispersed and high specific surface area. It is thought that it is efficiently converted to light hydrocarbons and decomposed. In addition, since the precipitated nickel is firmly bonded to the matrix compound, it is considered that the aggregation (sintering) between the nickel particles is suppressed, and the catalytic activity is hardly lowered even during a long-time reaction. .
シリカ、アルミナ、又は、ゼオライトは、反応場としての担体の役割を果たすだけでなく、ペロブスカイト型酸化物と一部反応して、ペロブスカイト型酸化物結晶相を細かく分断すること等の役割を果たす。その結果、各結晶相から表面に析出する活性種のニッケルが高度な分散状態になり、特に、炭素析出の起点となりやすいニッケルの偏在部分等が形成されにくく、高い耐炭素析出性を発揮するような機能も果たすものと推察される。また、シリカについても同様の役割を果たす。 Silica, alumina, or zeolite not only serves as a carrier as a reaction field, but also serves to partly react with the perovskite oxide to finely divide the perovskite oxide crystal phase. As a result, the active species nickel precipitated on the surface from each crystal phase is in a highly dispersed state, and in particular, the unevenly-distributed portion of nickel that tends to be the starting point of carbon deposition is not easily formed, so that high carbon precipitation resistance is exhibited. It is presumed that these functions are also performed. Silica also plays a similar role.
本発明でいう炭素質原料とは、熱分解してタールを生成する炭素を含む原料のことであり、石炭及びバイオマスやプラスチックの容器包装類等の、構成元素に炭素を含む広範囲なものを指す。バイオマスとは、林地残材、間伐材、未利用樹、製材残材、建設廃材、稲わら等の木質系廃棄物、又は、それらを原料とした木質チップ、ペレット等の二次製品や、再生紙として再利用できなくなった古紙等の製紙系廃棄物、農業残渣、厨芥類等の食品廃棄物、活性汚泥等を指す。 The carbonaceous raw material referred to in the present invention is a raw material containing carbon that is pyrolyzed to produce tar, and refers to a wide range of materials containing carbon as a constituent element, such as coal and biomass and plastic containers and packaging. . Biomass refers to forest land residues, thinned wood, unused trees, lumber residue, construction waste, woody waste such as rice straw, or secondary products such as wood chips and pellets, and recycled This refers to papermaking waste such as waste paper that can no longer be reused as paper, food residues such as agricultural residues and potatoes, and activated sludge.
炭素質原料を熱分解した際に発生するタールとは、熱分解される原料により性状が異なるが、炭素が５個以上含まれた常温で液体の有機化合物であって、鎖式炭化水素や芳香族炭化水素等からなる混合物を指す。石炭の熱分解であれば、例えば、ナフタレン、フェナンスレン、ピレン、アントラセン等の縮合多環芳香族等が主成分であり、木質系廃棄物の熱分解であれば、例えば、ベンゼン、トルエン、ナフタレン、インデン、アントラセン、フェノール等が主成分であり、食品廃棄物の熱分解であれば、例えば、上記以外にインドール、ピロール等の六員環又は五員環に窒素等の異種元素を含むヘテロ化合物も含まれるが、特にそれらに限定されるものではない。熱分解タールは、熱分解直後の高温状態ではガス状で存在する。また、ほぼ室温に冷却された精製ＣＯＧ中では、ミスト状で存在する。 Tar generated when pyrolyzing a carbonaceous raw material differs in properties depending on the raw material to be pyrolyzed, but is an organic compound that is liquid at room temperature and contains 5 or more carbons. It refers to a mixture of group hydrocarbons. If it is pyrolysis of coal, for example, condensed polycyclic aromatics such as naphthalene, phenanthrene, pyrene, anthracene, etc. are the main components, and if pyrolysis of wood waste, for example, benzene, toluene, naphthalene, Indene, anthracene, phenol, etc. are the main components, and if it is the thermal decomposition of food waste, for example, in addition to the above, hetero compounds containing different elements such as nitrogen in 6-membered rings or 5-membered rings such as indole, pyrrole, etc. Although it is included, it is not limited to them in particular. Pyrolysis tar exists in a gaseous state at a high temperature immediately after pyrolysis. In purified COG cooled to approximately room temperature, it exists in the form of a mist.
炭素質原料の熱分解には、石炭を原料とする場合には一般にコークス炉が用いられ、バイオマスを原料とする場合には外熱式ロータリーキルンや移動床炉、流動床炉等を用いることができるが、特にこれらに限定するものではない。 For pyrolysis of carbonaceous raw materials, a coke oven is generally used when coal is used as a raw material, and an external heating rotary kiln, moving bed furnace, fluidized bed furnace, etc. can be used when biomass is used as a raw material. However, it is not particularly limited to these.
タール含有ガスを接触分解してガス化するタール含有ガスの改質反応は、重質炭化水素であるタールからメタン、一酸化炭素、水素等の軽質化学物質へ変換する反応である。反応経路が複雑で必ずしも明らかではないが、タール含有ガス中の又は外部より導入する水素や水蒸気、二酸化炭素、若しくは酸素等との間で起こり得る水素化反応やスチームリフォーミング反応、ドライリフォーミング反応等が考えられる。 The reforming reaction of a tar-containing gas that gasifies by catalytic cracking of the tar-containing gas is a reaction that converts tar, which is a heavy hydrocarbon, into light chemical substances such as methane, carbon monoxide, and hydrogen. Although the reaction route is complicated and not always clear, hydrogenation reaction, steam reforming reaction, dry reforming reaction that may occur in tar-containing gas or between hydrogen, water vapor, carbon dioxide, or oxygen introduced from outside Etc. are considered.
これら一連の反応は吸熱反応なので、実機に適用した場合、反応器に入る高温の顕熱を有するガスが触媒層内で改質されて出口では温度が低下する。より高効率にタール等の重質炭化水素成分を改質する場合には、必要に応じて、空気又は酸素を触媒層内に導入することで、一部水素や炭化水素成分を燃焼させた燃焼熱で、触媒層の温度をある程度保ちながら、さらに改質反応を進めることも可能である。 Since these series of reactions are endothermic reactions, when applied to an actual machine, the gas having high sensible heat entering the reactor is reformed in the catalyst layer and the temperature is lowered at the outlet. When reforming heavy hydrocarbon components such as tar with higher efficiency, combustion that partially burns hydrogen or hydrocarbon components by introducing air or oxygen into the catalyst layer as necessary It is possible to further advance the reforming reaction while maintaining the temperature of the catalyst layer to some extent with heat.
次に、本発明のタール含有ガス改質用触媒の製造方法について説明する。 Next, a method for producing the tar-containing gas reforming catalyst of the present invention will be described.
本発明のタール含有ガスの改質用触媒は、ＡＮｉxＢ1-xＯ3（Ａは、Ｌａ、Ｃｅ、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも１種類の金属元素、Ｂは、Ｃｏ、Ｆｅ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｒｅ、Ｗから選ばれる少なくとも１種類の金属元素、０．１≦Ｘ≦１）を構成する、ニッケルと他の金属化合物との混合溶液から共沈により沈殿物を生成し、該沈殿物を、少なくとも乾燥及び焼成して、ペロブスカイト型酸化物を生成することにより製造することができる。 Reforming catalyst of tar-containing gas of the present invention, ANi x B 1-x O 3 (A is, La, Ce, Ca, Sr , at least one metal element selected from Ba, B is, Co, Fe , Ti, Zr, V, Nb, Ta, Cr, Mo, Re, W, mixed solution of nickel and other metal compounds constituting at least one metal element, 0.1 ≦ X ≦ 1) Can be produced by coprecipitation, and the precipitate is at least dried and calcined to produce a perovskite oxide.
本発明のタール含有ガスの改質用触媒は、前記複合酸化物に、さらに、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た酸化物とすることもできる。上記酸化物は、ニッケル化合物と、ペロブスカイト型酸化物を構成するニッケル以外の金属の化合物との混合溶液に沈殿剤を添加して、ニッケルとニッケル以外の金属を共沈させて沈殿物を生成し、共沈時、又は、該沈殿物の生成後に、さらにケイ素又はアルミニウム成分を加えて、ニッケル、他の金属元素、及び、ケイ素又はアルミニウムを含有した混合物とし、該混合物を少なくとも乾燥及び焼成して製造することができる。 The reforming catalyst for tar-containing gas of the present invention may be an oxide obtained by adding at least one oxide selected from silica, alumina and zeolite to the composite oxide. The above oxide forms a precipitate by adding a precipitant to a mixed solution of a nickel compound and a compound of a metal other than nickel constituting the perovskite oxide, and coprecipitating nickel and a metal other than nickel. At the time of coprecipitation or after the formation of the precipitate, a silicon or aluminum component is further added to form a mixture containing nickel, other metal elements, and silicon or aluminum, and the mixture is at least dried and calcined. Can be manufactured.
他の方法として、ニッケル化合物と、ペロブスカイト型酸化物を構成するニッケル以外の金属の化合物との混合溶液に沈殿剤を添加して、マグネシウム化合物、及び金属化合物との混合溶液に沈殿剤を添加して、ニッケルとニッケル以外の金属を共沈させて沈殿物を生成した後、該沈殿物を乾燥及びか焼して、ニッケルとニッケル以外の金属を含むペロブスカイト型酸化物を生成し、その後、該酸化物に、シリカ粉末と水、又は、シリカゾル、又は、アルミナ粉末と水、又は、アルミナゾル、又は、ゼオライト粉末と水を加えて混合して混合物を生成し、その混合物を少なくとも乾燥及び焼成して製造することができる。この方法の中で混合物を乾燥、粉砕した後に焼成する、又は、乾燥、か焼、粉砕、成型した後に焼成することもできる。 As another method, a precipitant is added to a mixed solution of a nickel compound and a metal compound other than nickel constituting the perovskite oxide, and a precipitant is added to a mixed solution of the magnesium compound and the metal compound. The nickel and a metal other than nickel are co-precipitated to produce a precipitate, and then the precipitate is dried and calcined to produce a perovskite oxide containing a metal other than nickel and nickel. Silica powder and water, or silica sol, or alumina powder and water, or alumina sol, or zeolite powder and water are mixed with the oxide to form a mixture, and the mixture is at least dried and calcined. Can be manufactured. In this method, the mixture can be baked after being dried and pulverized, or baked after being dried, calcined, pulverized and molded.
他の方法として、ニッケル化合物とペロブスカイト型酸化物を構成するニッケル以外の金属の化合物との混合溶液に沈殿剤を添加して、ニッケルとニッケル以外の金属を共沈させて沈殿物を生成した後、該沈殿物に、シリカ粉末と水、又は、シリカゾル、又は、アルミナ粉末と水、又は、アルミナゾル、又は、ゼオライト粉末と水を加えて混合して混合物を生成し、その混合物を少なくとも乾燥及び焼成した後、さらにシリカ粉末と水、又は、シリカゾル、又は、アルミナ粉末と水、又は、アルミナゾル、又は、ゼオライト粉末と水を混合して第２の混合物を生成、その第２の混合物を、少なくとも乾燥及び焼成して製造することができる。この方法の中で混合物を乾燥、粉砕した後に焼成する、又は、乾燥、か焼、粉砕、成型した後に焼成することもできる。 As another method, after adding a precipitating agent to a mixed solution of a nickel compound and a metal compound other than nickel constituting the perovskite oxide, coprecipitates nickel and a metal other than nickel to generate a precipitate. The silica powder and water, or the silica sol, or the alumina powder and water, or the alumina sol, or the zeolite powder and water are mixed with the precipitate to form a mixture, and the mixture is at least dried and calcined. Thereafter, silica powder and water, or silica sol, or alumina powder and water, or alumina sol, or zeolite powder and water are mixed to form a second mixture, and the second mixture is at least dried. And can be produced by firing. In this method, the mixture can be baked after being dried and pulverized, or baked after being dried, calcined, pulverized and molded.
他の方法として、ニッケル化合物、ニッケル以外の金属化合物、及び、ケイ素又はアルミニウム化合物の混合溶液に沈殿剤を添加して、ニッケル、マグネシウム、金属元素、及び、ケイ素又はアルミニウムを共沈させて沈殿物を生成し、その混合物を少なくとも乾燥及び焼成して製造することができる。この方法の中で沈殿物を乾燥、粉砕した後に焼成する、又は、乾燥、か焼、粉砕、成型した後に焼成することもできる。 As another method, a precipitant is added to a mixed solution of a nickel compound, a metal compound other than nickel, and a silicon or aluminum compound, and nickel, magnesium, a metal element, and silicon or aluminum are coprecipitated to be a precipitate. And the mixture can be produced by at least drying and baking. In this method, the precipitate can be baked after being dried and pulverized, or baked after being dried, calcined, pulverized and molded.
各製法における沈殿物の乾燥は、特に温度や乾燥方法を問わず、一般的な乾燥方法でよい。乾燥後の共沈殿物は、必要に応じて粗粉砕を行った後、焼成すればよい。流動層等の乾燥により乾燥後の沈殿物が粉状を保っている場合は、粗粉砕は不要である。 The drying of the precipitate in each production method may be a general drying method regardless of the temperature or the drying method. The co-precipitate after drying may be baked after roughly pulverizing as necessary. When the precipitate after drying is kept in a powder form by drying the fluidized bed or the like, coarse pulverization is unnecessary.
沈殿物の乾燥の前には、ろ過をしておくことが、乾燥の手間を少なくすることができ、好ましい。さらに、ろ過後の沈殿物は、純水等で洗浄しておくことが、不純物量を低減できることからより好ましい。 Filtration prior to drying of the precipitate is preferable because it can reduce the labor of drying. Furthermore, it is more preferable to wash the precipitate after filtration with pure water or the like because the amount of impurities can be reduced.
上記混合物の焼成は、空気中で行うことができ、温度は７００〜１３００℃の範囲であればよい。焼成温度が高いと混合物の焼結が進行し、強度は上昇するが、比表面積が小さくなり、触媒活性は低下するので、そのバランスを考慮して決定するのが望ましい。 Firing of the mixture can be performed in air, and the temperature may be in the range of 700 to 1300 ° C. When the calcination temperature is high, sintering of the mixture proceeds and the strength increases, but the specific surface area decreases and the catalytic activity decreases. Therefore, it is desirable to determine the balance in consideration.
乾燥と焼成の間に、か焼や成型工程も加えることができ、その場合、か焼は空気中で４００〜８００℃程度で行えば良く、成型は、プレス成型等で行えばよい。焼成後は、そのまま触媒として使用することもできるし、プレス成型等で成型して成型物して使用することもできる。 A calcination or molding step can be added between the drying and the calcination. In that case, the calcination may be performed in air at about 400 to 800 ° C., and the molding may be performed by press molding or the like. After calcination, it can be used as it is as a catalyst, or it can be molded by press molding or the like and used as a molded product.
他の方法として、ニッケル化合物とペロブスカイト型酸化物を構成する他の金属の酸化物を含んだ溶液を、粉末、粒、成型したシリカ、又は、アルミナ担体上に担持して製造することができる。その過程において、担体表面に各化合物をインシピエントウエットネス法、蒸発乾固法等の通常の含浸法により調製できる。また、各元素を担持する方法は、すべての元素を含んだ溶液を一度に担持する同時含浸法であってもよいし、各化合物の一部を含んだ溶液を一旦含浸した後に、それ以外の化合物を含んだ溶液を１回又は複数回に分けて含浸する逐次含浸法であってもよい。 As another method, a solution containing a nickel compound and an oxide of another metal constituting the perovskite oxide can be produced by supporting it on powder, granules, molded silica, or an alumina support. In the process, each compound can be prepared on the surface of the carrier by a conventional impregnation method such as an incipient wetness method or an evaporation to dryness method. The method for supporting each element may be a simultaneous impregnation method in which a solution containing all the elements is supported at once, or after impregnating a solution containing a part of each compound, A sequential impregnation method in which a solution containing a compound is impregnated once or plural times may be used.
このようにして調製した触媒前駆体を、５０〜１５０℃において乾燥し、水又は有機溶媒を除去する。その際、有機溶媒を用いた場合には、経済性の面から有機溶媒を回収し、再使用することが望ましい。次いで、得られた触媒前駆体乾燥品を焼成することにより調製することができる。なお、最終的な焼成温度は各化合物の熱分解温度及びその速度、比表面積、並びに成型体の強度等を総合的に考慮して適宜決めることが望ましい。 The catalyst precursor thus prepared is dried at 50 to 150 ° C. to remove water or the organic solvent. At that time, when an organic solvent is used, it is desirable to recover and reuse the organic solvent from the economical aspect. Subsequently, it can prepare by baking the obtained catalyst precursor dried product. The final calcination temperature is preferably appropriately determined in consideration of the thermal decomposition temperature and speed of each compound, the specific surface area, the strength of the molded body, and the like.
このような製造方法で製造される触媒を用いることにより、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、炭素析出を起こしやすい縮合多環芳香族主体のタール含有ガスであっても、随伴するタール等の重質炭化水素を高効率に改質して、水素、一酸化炭素を主体とする軽質炭化水素に変換することが可能となる。 By using a catalyst produced by such a production method, it is a tar-containing gas mainly composed of a condensed polycyclic aromatic that contains a large amount of hydrogen sulfide generated when the carbonaceous raw material is thermally decomposed and is liable to cause carbon deposition. However, the accompanying heavy hydrocarbon such as tar can be reformed with high efficiency and converted into light hydrocarbons mainly composed of hydrogen and carbon monoxide.
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ることができ、長期間安定した運転が可能になる。 In addition, when the catalyst performance deteriorates, by contacting at least one of water vapor or air with the catalyst at a high temperature, the deposited carbon and adsorbed sulfur on the catalyst can be removed to recover the catalyst performance, Stable operation is possible.
この製造方法で製造されたタール含有ガスの改質用触媒は、担持法では担体表層部、その他の方法では材料全体にわたり、ニッケル、ペロブスカイト型酸化物を構成する他の金属元素、及び、シリカ又はアルミニウム成分が、ニッケル含有ペロブスカイト型酸化物との間で高度に均質な混合物を形成する。そのため、その混合物を乾燥及び焼成、又は乾燥、か焼、粉砕、成型及び焼成することで、ニッケル、他の金属元素、及び、シリカ又はアルミニウムが均質に分布した焼結体を形成し、ニッケル含有ペロブスカイト型酸化物相がより一層微細化され、そこから析出するＮｉ粒が高度に微細分散することから、高活性で炭素析出量の少ない成型物を得ることができると予想される。 The reforming catalyst for the tar-containing gas produced by this production method is nickel, other metal elements constituting the perovskite oxide, and silica or The aluminum component forms a highly homogeneous mixture with the nickel-containing perovskite oxide. Therefore, the mixture is dried and fired, or dried, calcined, pulverized, molded and fired to form a sintered body in which nickel, other metal elements, and silica or aluminum are homogeneously distributed. Since the perovskite type oxide phase is further refined and Ni grains precipitated therefrom are highly finely dispersed, it is expected that a molded product having a high activity and a small amount of carbon deposition can be obtained.
これら製造法の中で、ニッケル、ペロブスカイト酸化物を構成する他の金属、及び、必要に応じて加えられるケイ素又はアルミニウム化合物の溶液を作成する際には、水に対して溶解度の高い各金属化合物を用いることが適当である。例えば、硝酸塩、炭酸塩、硫酸塩、塩化物等の無機塩のみならず、酢酸塩等の有機塩も好適に用いられる。特に好ましいのは、焼成後に触媒被毒になり得る不純物が残りにくいと考えられる硝酸塩、炭酸塩又は酢酸塩である。 Among these manufacturing methods, when preparing solutions of nickel, other metals constituting perovskite oxide, and silicon or aluminum compounds added as necessary, each metal compound having high solubility in water It is appropriate to use For example, not only inorganic salts such as nitrates, carbonates, sulfates and chlorides, but also organic salts such as acetates are suitably used. Particularly preferred are nitrates, carbonates or acetates, which are thought to be less likely to retain impurities that can become catalyst poisons after calcination.
それらの溶液から沈殿物を形成する場合に用いる沈殿剤は、上記溶液のｐＨを、ニッケル、ペロブスカイト酸化物を構成する他の金属、及び、必要により添加されるケイ素又はアルミニウムが主に水酸化物として沈殿する中性〜塩基性へ変化させるものであれば、何でも用いることができる。例えば、炭酸カリウム水溶液や炭酸ナトリウム水溶液、水酸化カリウム水溶液や水酸化ナトリウム水溶液、アンモニア水溶液や尿素溶液等が好適に用いられる。 The precipitant used in the case of forming a precipitate from these solutions is a hydroxide mainly composed of nickel, other metals constituting the perovskite oxide, and silicon or aluminum added as necessary. Anything can be used as long as it changes from neutral to basic. For example, a potassium carbonate aqueous solution, a sodium carbonate aqueous solution, a potassium hydroxide aqueous solution, a sodium hydroxide aqueous solution, an ammonia aqueous solution, a urea solution, or the like is preferably used.
上記の方法で製造されたタール含有ガス改質用触媒を用いることにより、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、炭素析出を起こしやすい縮合多環芳香族主体のタール含有ガスであっても、高い耐炭素析出性を示し、随伴するタール等の重質炭化水素を高効率に改質して、一酸化炭素、水素を主体とする軽質化学物質に、経時劣化が少なく安定に変換することができる。 By using the tar-containing gas reforming catalyst produced by the above method, it contains a large amount of hydrogen sulfide generated when the carbonaceous raw material is pyrolyzed, and is a condensed polycyclic aromatic-based tar that easily causes carbon precipitation. Even in the case of contained gas, it shows high carbon precipitation resistance, and the accompanying heavy hydrocarbons such as tar are reformed with high efficiency, so that light chemical substances mainly composed of carbon monoxide and hydrogen will deteriorate over time. Less stable conversion.
本発明のタール含有ガス改質方法は、硫化水素含有雰囲気下でも安定して改質反応が進行するが、ガス中の硫化水素濃度は低ければ低いほど被毒されないため好ましい。ガス中の硫化水素濃度は、４０００ｐｐｍ以下が好ましく、３０００ｐｐｍ以下がより好ましい。 In the tar-containing gas reforming method of the present invention, the reforming reaction proceeds stably even in a hydrogen sulfide-containing atmosphere. However, the lower the hydrogen sulfide concentration in the gas, the better the poisoning. The hydrogen sulfide concentration in the gas is preferably 4000 ppm or less, and more preferably 3000 ppm or less.
さらに、本発明のタール含有ガス改質方法で用いるタール含有ガス改質用触媒は、ペロブスカイト構造のＢサイトを占めるニッケル及び金属元素Ｂの中で、主活性成分であるニッケルが占める割合が１０〜１００原子量％である。ニッケルが占める割合が１０原子量％未満では、ニッケルの改質性能が十分発揮されないため、好ましくない。 Furthermore, in the tar-containing gas reforming catalyst used in the tar-containing gas reforming method of the present invention, the proportion of nickel as the main active component in the nickel and metal element B occupying the B site of the perovskite structure is 10 to 10. 100 atomic weight%. When the proportion of nickel is less than 10 atomic weight%, the modification performance of nickel is not sufficiently exhibited, which is not preferable.
ニッケルが占める割合は、１００％であってもよい。すなわち、本発明のタール含有改質用触媒は、Ｃｏ、Ｆｅ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｒｅ、Ｗから選ばれる少なくとも１種類の金属元素は必須ではなく、ＡＮｉＯ3（Ａは、Ｌａ、Ｃｅ、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも１種類の金属元素）で表されるペロブスカイト型酸化物であってもよい。 The proportion of nickel may be 100%. That is, in the tar-containing reforming catalyst of the present invention, at least one metal element selected from Co, Fe, Ti, Zr, V, Nb, Ta, Cr, Mo, Re, and W is not essential, and ANiO 3 A perovskite oxide represented by (A is at least one metal element selected from La, Ce, Ca, Sr, and Ba) may be used.
また、上記ペロブスカイト型酸化物と混合するシリカ又はアルミナの含有量は、２０〜８０質量％であることが好ましい。シリカ又はアルミナの含有量が２０質量％未満では、ニッケル含有ペロブスカイト型酸化物主体のセラミックスとなり、成型した際、強度が著しく低くなる傾向がある。シリカ又はアルミナの含有量が８０質量％を超えると、主活性成分であるニッケルの割合が低くなるので、触媒の改質活性を十分発揮できなくなるおそれがある。 The content of silica or alumina mixed with the perovskite oxide is preferably 20 to 80% by mass. When the content of silica or alumina is less than 20% by mass, the ceramic is mainly composed of a nickel-containing perovskite oxide, and the strength tends to be remarkably lowered when molded. When the content of silica or alumina exceeds 80% by mass, the ratio of nickel as the main active component is lowered, and there is a possibility that the catalyst's reforming activity cannot be sufficiently exhibited.
また、ケイ素又はアルミナを担体として用いる場合は、表面積と強度との兼ね合いで細孔容積、細孔径を、また、特に成型体であれば、形状等を適宜調整することが好ましい。 Further, when silicon or alumina is used as the carrier, it is preferable to appropriately adjust the pore volume and the pore diameter in consideration of the surface area and the strength, and particularly the shape or the like in the case of a molded body.
本発明の改質触媒は、ニッケル含有量が１０〜８０原子量％となるように製造することが、さらに好ましい。 The reforming catalyst of the present invention is more preferably produced so that the nickel content is 10 to 80 atomic%.
本発明の改質触媒は、粉体、粒体又は成型体のいずれの形態としてもよく、成型体の場合には、球状、シリンダー状、リング状、ホイール状、粒状等、さらに、金属又はセラミックスのハニカム状基材へ触媒成分をコーティングしたもの等、いずれでもよい。 The reforming catalyst of the present invention may be in any form of powder, granule, or molded body. In the case of a molded body, spherical, cylindrical, ring-shaped, wheel-shaped, granular, etc., and metal or ceramics Any of those obtained by coating the honeycomb substrate with a catalyst component may be used.
各金属種の含有量を上記範囲になるように調製するためには、各出発原料をあらかじめ計算の上準備しておくことが好ましい。一度触媒が狙いの成分組成となれば、それ以降はその時の配合で調製すればよい。 In order to prepare the content of each metal species so as to be in the above range, it is preferable to prepare each starting material in advance by calculation. Once the catalyst has the target component composition, it can be prepared by blending at that time.
上記の元素以外に、本発明の特性を損なわない範囲で、触媒製造工程等で混入する不可避的不純物や触媒性能が変わらない他成分を含んでも構わないが、できるだけ不純物が混入しないようにするのが望ましい。 In addition to the above elements, inevitable impurities mixed in the catalyst manufacturing process or the like may be included within the range not impairing the characteristics of the present invention, and other components that do not change the catalyst performance may be included. Is desirable.
上記の改質触媒を構成する各金属種の含有量の測定方法は、走査型高周波誘導結合プラズマ法（ＩＣＰ）を用いた。具体的には、試料を粉砕後、アルカリ融解剤（例えば、炭酸ナトリウム、ホウ酸ナトリウム等）を加えて白金坩堝内で加熱融解し、冷却後に塩酸溶液に加温下で全量溶解させる。その溶液をＩＣＰ分析装置へインジェクションすると、装置内の高温プラズマ状態の中で試料溶液が原子化・熱励起し、これが基底状態に戻る際に元素固有の波長の発光スペクトルを生じるので、その発光波長及び強度から含有元素種、量を定性・定量することができる。 A scanning high frequency inductively coupled plasma method (ICP) was used as a method for measuring the content of each metal species constituting the reforming catalyst. Specifically, after pulverizing the sample, an alkali melting agent (for example, sodium carbonate, sodium borate, etc.) is added and heated and melted in a platinum crucible. After cooling, the whole amount is dissolved in a hydrochloric acid solution under heating. When the solution is injected into the ICP analyzer, the sample solution is atomized and thermally excited in the high-temperature plasma state in the device, and when this returns to the ground state, an emission spectrum with a wavelength unique to the element is generated. In addition, the element type and amount can be qualitatively and quantitatively determined from the strength.
調製した酸化物がペロブスカイト型構造を形成しているかどうかを確認するためには、例えば、以下のとおり、触媒の広角Ｘ線回折により評価する。 In order to confirm whether or not the prepared oxide forms a perovskite type structure, for example, it is evaluated by wide-angle X-ray diffraction of the catalyst as follows.
まず、材料を粉末試料用ホルダーにセットした後、Ｒｉｇａｋｕ製ＲＩＮＴ１５００を用い、４０ｋＶ、１５０ｍＡの出力でＣｕＫα線を発生させる。モノクロメーターを黒鉛とし、発散スリット及び散乱スリットを１°、受光スリットを０．１５ｍｍ、モノクロ受光スリットを０．８ｍｍとして、サンプリング幅を０．０１ｄｅｇ、スキャン速度を２ｄｅｇ／ｍｉｎの条件で測定し、ピーク位置、強度より結晶構造を評価する。 First, the material is set in a powder sample holder, and then a CuKα ray is generated at an output of 40 kV and 150 mA using a RINT 1500 manufactured by Rigaku. The monochromator is graphite, the divergence slit and the scattering slit are 1 °, the light receiving slit is 0.15 mm, the monochrome light receiving slit is 0.8 mm, the sampling width is 0.01 deg, and the scanning speed is 2 deg / min. The crystal structure is evaluated from the peak position and intensity.
本発明の触媒を用いたタール含有ガス改質方法は、上述したタール含有ガス改質触媒の存在下、又は、還元後の触媒の存在下で、炭素質原料を熱分解した際に発生するタール含有ガス中の水素、二酸化炭素、及び水蒸気を接触させて、タール含有ガスを改質してガス化するものである。 The tar-containing gas reforming method using the catalyst of the present invention is a tar generated when a carbonaceous raw material is pyrolyzed in the presence of the above-mentioned tar-containing gas reforming catalyst or in the presence of a catalyst after reduction. Hydrogen, carbon dioxide, and water vapor in the contained gas are brought into contact with each other to reform and gasify the tar-containing gas.
また、タール含有ガス改質触媒の存在下、又は、還元後の触媒の存在下で、炭素質原料を熱分解した際に発生するタール含有ガスに、前記水素、二酸化炭素、水蒸気の少なくともいずれかを加えて、タール含有ガスを改質してガス化するものである。 Further, the tar-containing gas generated when the carbonaceous raw material is thermally decomposed in the presence of the tar-containing gas reforming catalyst or in the presence of the catalyst after the reduction, at least one of the hydrogen, carbon dioxide, and water vapor. Is added to reform and gasify the tar-containing gas.
タール含有ガス中のタールを接触改質してガス化するタールガス化反応は、反応経路が複雑で必ずしも明らかではないが、タール含有ガス中又は外部より導入する水素との間では、例えば、式１で表されるようなタール中縮合多環芳香族の水素化分解によるメタンを始めとする軽質炭化水素への転化反応が進行すると考えられる（式１ではメタンのみが生成される場合を記す）。 A tar gasification reaction in which tar in a tar-containing gas is gasified by catalytic reforming has a complicated reaction route and is not necessarily clear. However, for example, the formula 1 It is considered that the conversion reaction to light hydrocarbons such as methane proceeds by hydrogenolysis of the condensed polycyclic aromatic in tar as represented by (Formula 1 describes the case where only methane is produced).
ＣmＨn＋（２ｍ−ｎ／２）Ｈ2 → ｍＣＨ4 （式１）
C m H n + (2m- n / 2)
タール含有ガス中又は外部より導入する二酸化炭素との間では、式２で表されるようなタール中縮合多環芳香族の二酸化炭素によるドライリフォーミングによる水素と一酸化炭素への転化反応が進行する。
Conversion reaction to hydrogen and carbon monoxide by dry reforming of condensed polycyclic aromatics in tar as represented by
ＣmＨn＋ｍ／２ＣＯ2 → ｍＣＯ＋ｎ／２Ｈ2 （式２） C m H n + m / 2CO 2 → mCO + n / 2H 2 (Formula 2)
タール含有ガス中又は外部より導入する水蒸気との間では、式３で表されるようなスチームリフォーミング及び水性ガスシフト反応が進行する。また、タール含有ガス中タール以外の炭化水素成分についても、同様にして反応が進行する。
Steam reforming and a water gas shift reaction as represented by
ＣmＨn＋２ｍＨ2Ｏ → ｍＣＯ2＋（ｍ＋ｎ／２）Ｈ2 （式３）
C m H n + 2mH 2 O →
したがって、メタン等の高カロリーガスを製造する場合には、外部から水素を加えることが望ましい。また、水素や一酸化炭素を製造する場合には、外部から二酸化炭素を加えることが望ましい。さらに、水素をより多く製造する場合には、外部から水蒸気を加えることが望ましい。タール以外の炭化水素成分も、上記の式１〜３に従って、反応が進行する。 Therefore, when producing a high calorie gas such as methane, it is desirable to add hydrogen from the outside. Further, when producing hydrogen or carbon monoxide, it is desirable to add carbon dioxide from the outside. Furthermore, when producing more hydrogen, it is desirable to add water vapor from the outside. For hydrocarbon components other than tar, the reaction proceeds according to the above formulas 1 to 3.
タール含有ガス改質用触媒は、還元することが好ましいが、反応中に還元が進行するため、還元しなくてもよい。特に、タール含有ガス改質触媒が反応前に還元処理を必要とする場合、本発明の触媒から活性金属であるニッケル粒子が微細クラスター状に析出するので、還元条件は、比較的高温でかつ還元性雰囲気にするのであれば特に制限されるものではない。 The tar-containing gas reforming catalyst is preferably reduced, but it does not need to be reduced because the reduction proceeds during the reaction. In particular, when the tar-containing gas reforming catalyst requires a reduction treatment before the reaction, since the active metal nickel particles are precipitated in the form of fine clusters from the catalyst of the present invention, the reduction condition is relatively high temperature and reduction. If it is a sex atmosphere, there is no particular limitation.
例えば、水素、一酸化炭素、メタンの少なくともいずれかを含むガス雰囲気下、又は、それら還元性ガスに水蒸気を混合したガス雰囲気下、又は、それらのガスに窒素などの不活性ガスを混合した雰囲気下であってもよい。還元温度は、例えば、５００℃〜１０００℃が好適である。還元時間は充填する触媒量にも依存し、例えば、３０分〜４時間が好適であるが、充填した触媒全体が還元するのに必要な時間であればよく、特にこの条件に制限されるものではない。 For example, in a gas atmosphere containing at least one of hydrogen, carbon monoxide, and methane, or a gas atmosphere in which water vapor is mixed with these reducing gases, or an atmosphere in which an inert gas such as nitrogen is mixed with those gases. It may be below. The reduction temperature is preferably 500 ° C. to 1000 ° C., for example. The reduction time depends on the amount of catalyst to be charged, and is preferably, for example, 30 minutes to 4 hours. However, the time required for reducing the entire packed catalyst may be any time and is particularly limited to this condition. is not.
触媒反応器としては、触媒が粉末の場合には流動床形式や移動床形式等が、触媒が成型体の場合には固定床形式や移動床形式等が好適に用いられる。触媒層の入口温度は、５００〜１０００℃であることが好ましく、５５０〜１０００℃であることがより好ましい。触媒層の入口温度が５００℃未満の場合は、タール及び炭化水素が水素、一酸化炭素を主体とする軽質炭化水素へ改質する際の触媒活性がほとんど発揮されないため、好ましくない。触媒層の入口温度が１０００℃を超える場合は、耐熱構造化が必要になる等、改質装置が高価になるので、経済的に不利となる。炭素質原料が石炭の場合には比較的高温で、バイオマスの場合には比較的低温で反応を進めることも可能である。 As the catalyst reactor, a fluidized bed format or moving bed format is suitably used when the catalyst is powder, and a fixed bed format or moving bed format is suitably used when the catalyst is a molded body. The inlet temperature of the catalyst layer is preferably 500 to 1000 ° C, and more preferably 550 to 1000 ° C. When the inlet temperature of the catalyst layer is less than 500 ° C., the catalytic activity at the time of reforming tar and hydrocarbon to light hydrocarbons mainly composed of hydrogen and carbon monoxide is hardly exhibited, which is not preferable. When the inlet temperature of the catalyst layer exceeds 1000 ° C., a reforming apparatus becomes expensive, for example, a heat resistant structure is required, which is economically disadvantageous. It is possible to proceed the reaction at a relatively high temperature when the carbonaceous raw material is coal and at a relatively low temperature when it is biomass.
炭素質原料を熱分解、又は部分酸化して生成されるタール含有ガスが、コークス炉から排出される粗ＣＯＧのような硫化水素濃度が非常に高いタール含有ガスであっても、本発明によりガス中のタールや炭化水素を改質してガス化することができる。熱分解又は部分酸化とは、具体的には、乾留、又は炭素質原料をガス化のために一部のみ酸化させてタール含有ガスを製造することを言う。 Even if the tar-containing gas generated by pyrolyzing or partially oxidizing the carbonaceous raw material is a tar-containing gas having a very high hydrogen sulfide concentration such as crude COG discharged from the coke oven, The tar and hydrocarbons inside can be reformed and gasified. Pyrolysis or partial oxidation specifically refers to dry distillation, or producing a tar-containing gas by oxidizing only a part of a carbonaceous raw material for gasification.
現在のコークス炉では、炉内に原料の石炭を充填後、加熱・乾留してコークスを製造する。図１に示すように、付随して発生するコークス炉ガスは、炉頂部の上昇管１から安水２（アンモニア水）を噴霧して冷却後、集気管であるドライメーン４に集められる。ガス成分は、コークス炉３の上昇管１で８００℃程度の顕熱を有しているにもかかわらず、安水２噴霧後には１００℃以下まで急冷されてしまい、その顕熱を有効に利用できていない。
In the current coke oven, coke is produced by filling the furnace with raw coal and then heating and dry distillation. As shown in FIG. 1, coke oven gas generated concomitantly is collected in a dry main 4 that is an air collecting tube after spraying cold water 2 (ammonia water) from an ascending pipe 1 at the top of the furnace and cooling it. Despite having a sensible heat of about 800 ° C. in the riser 1 of the
このガス顕熱を有効に利用し、かつ、タール含有ガスを水素、一酸化炭素等軽質炭化水素等の燃料成分に転換できれば、エネルギー増幅に繋がる。さらに、そこで生成される還元性ガス体積が大幅に増幅されることにより、例えば、鉄鉱石に適用して還元鉄を製造するプロセスが可能となれば、現在鉄鉱石をコークスにより還元する高炉プロセスで発生する二酸化炭素排出量を大幅に削減できる可能性がある。 If this gas sensible heat can be used effectively and the tar-containing gas can be converted into fuel components such as light hydrocarbons such as hydrogen and carbon monoxide, it will lead to energy amplification. Furthermore, if the reducing gas volume produced there is greatly amplified, for example, if a process for producing reduced iron by applying it to iron ore becomes possible, the current blast furnace process for reducing iron ore by coke will be possible. There is a possibility that the generated carbon dioxide emissions can be greatly reduced.
また、それを従来の燃料用途のみに用いるのでなく、有用物に変換可能であり、また、鉄鉱石の直接還元にも適する合成ガスに転換することにより、より高度なエネルギー利用に繋がる可能性がある。 In addition, it can be converted into a useful gas, not just used for conventional fuel applications, and it can lead to higher energy use by converting it to synthesis gas suitable for direct reduction of iron ore. is there.
粗ＣＯＧ中に含まれるタールは、コークス炉装炭から窯出しまでの間で経時的に変化し、おおよそ０．１〜１５０ｇ／Ｎｍ3の範囲で変動する。上記粗ＣＯＧをコークス炉の上昇管で安水２を噴霧して冷却し、ドライメーン４で集められた後、常法で精製した精製ＣＯＧは、プライマリークーラー、タール抽出器、電気集塵機等の処理を行って精製したとはいえ、おおよそ０．０１〜０．０２ｇ／Ｎｍ3程度のタールが存在する。その後のファイナルクーラーで精製してもナフタレンを約０．２〜０．４ｇ／Ｎｍ3、スクラバー処理をした後でも軽油分を５〜１０ｇ／Ｎｍ3程度含んでいる。
The tar contained in the crude COG changes with time from the coke oven charging to the start of the kiln and varies in the range of approximately 0.1 to 150 g / Nm 3 . The above-mentioned crude COG is cooled by spraying
そのタール含有ガスである精製ＣＯＧを、水素、一酸化炭素等軽質炭化水素等の燃料成分に転換できれば、粗ＣＯＧの転換と同様、二酸化炭素排出量の削減や、燃料以外の有用物への変換等の可能性が期待できる。 If the purified COG, which is the tar-containing gas, can be converted into fuel components such as light hydrocarbons such as hydrogen and carbon monoxide, as with the conversion of crude COG, reduction of carbon dioxide emissions and conversion to useful materials other than fuel Etc. can be expected.
触媒反応器に内蔵されるタール含有ガス改質触媒は、タール及び炭化水素成分から、水素、一酸化炭素を主体とする軽質化学物質への転換時に、触媒表面上に析出する炭素、又は熱分解工程で得られた熱分解ガス中に含まれる硫黄成分が触媒に吸着することで、触媒が性能劣化する。劣化した触媒は、触媒反応器へ水蒸気を導入し、水蒸気と炭素の反応により触媒表面の炭素を除去、又は、水蒸気と硫黄の反応により触媒に吸着した硫黄を硫化水素の形で除去することで、再生することが可能である。 The tar-containing gas reforming catalyst incorporated in the catalytic reactor is carbon deposited on the catalyst surface during thermal conversion from tar and hydrocarbon components to light chemicals mainly composed of hydrogen and carbon monoxide, or thermal decomposition. When the sulfur component contained in the pyrolysis gas obtained in the process is adsorbed on the catalyst, the performance of the catalyst deteriorates. The deteriorated catalyst can be obtained by introducing water vapor into the catalytic reactor and removing the carbon on the catalyst surface by the reaction of water vapor and carbon, or removing sulfur adsorbed on the catalyst in the form of hydrogen sulfide by the reaction of water vapor and sulfur. It is possible to play.
また、水蒸気の一部又は全部を空気に変えて導入することで、空気中の酸素と炭素の燃焼反応により触媒表面の炭素を除去、又は酸素と硫黄の反応により触媒に吸着した硫黄を除去することで、触媒を再生することも可能である。再生した触媒は、全量再使用することも可能であるし、また、一部を新触媒に置き換えて使用することも可能である。 Also, by introducing some or all of the water vapor into air, the carbon on the catalyst surface is removed by the combustion reaction of oxygen and carbon in the air, or the sulfur adsorbed on the catalyst is removed by the reaction of oxygen and sulfur. Thus, the catalyst can be regenerated. The entire amount of the regenerated catalyst can be reused, or a part of the regenerated catalyst can be replaced with a new catalyst.
（実施例）
以下、実施例を用いて、本発明をさらに詳細に説明する。
(Example)
Hereinafter, the present invention will be described in more detail with reference to examples.
（実施例１）
ニッケル、及び、表１に示す第一金属元素、第二金属元素の原子量比が、３：１０：７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、ニッケルとマグネシウムと金属元素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。
Example 1
Nickel and the first metal element and the second metal element shown in Table 1 were precisely weighed so that the atomic weight ratio of 3: 10: 7, and a mixed aqueous solution was prepared by heating at 60 ° C. A potassium carbonate aqueous solution heated to 60 ° C. was added to coprecipitate nickel, magnesium, and metal elements 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.
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、ＡＮｉ0.3Ｂ0.7Ｏ3からなる触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＡＮｉ0.3Ｂ0.7Ｏ3がペロブスカイト型構造を形成していることが確認できた。 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 catalyst molded body made of ANi 0.3 B 0.7 O 3 . As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that ANi 0.3 B 0.7 O 3 formed a perovskite structure.
この触媒を６０ｃｍ3用い、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。 The catalyst was fixed at 60 cm 3 with quartz wool so as to be located at the center of the SUS reaction tube, a thermocouple was inserted at the center 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）の模擬ガスとして水素：窒素＝１：１、Ｈ2Ｓ＝２０００ｐｐｍ、トータルで１２５ｍＬ／ｍｉｎになるよう各ガスを調整して導入し、常圧下、８００℃で８時間反応を行い、触媒性能を評価した。 Before starting the reforming reaction, the reactor was heated to 800 ° C. under a nitrogen atmosphere, and then reduced for 30 minutes while flowing hydrogen gas at 100 mL / min. After that, as a simulated gas for coke oven gas (crude gas), hydrogen: nitrogen = 1: 1, H 2 S = 2000 ppm, each gas was adjusted and introduced so that the total was 125 mL / min. The reaction was carried out for 8 hours to evaluate the catalyst performance.
また、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用い、精密ポンプで０．０２５ｇ／ｍｉｎの流量で反応管へ導入した。 Moreover, as a simulated substance for tar generated during coal dry distillation, 1-methylnaphthalene, which is a liquid substance that is actually contained in tar and has a low viscosity at room temperature, is used as a representative substance, and a flow rate of 0.025 g / min with a precision pump. Into the reaction tube.
また、Ｓ／Ｃ＝３となるよう、純水を精密ポンプで０．１ｇ／ｍｉｎの流量で反応管へ導入した。出口から排出された生成ガスを室温トラップ、氷温トラップを経由させて、各々ナフタレン、水分を除去した後、ガスクロマトグラフィー（ヒューレットパッカード製ＨＰ６８９０）に注入してＴＣＤ、ＦＩＤ分析を行った。 Further, pure water was introduced into the reaction tube at a flow rate of 0.1 g / min with a precision pump so that S / C = 3. The product gas discharged from the outlet was passed through a room temperature trap and an ice temperature trap to remove naphthalene and moisture, respectively, and then injected into gas chromatography (HP 6890 manufactured by Hewlett-Packard) to perform TCD and FID analysis.
改質反応の反応度合（メチルナフタレンの分解率）は、メタン選択率、ＣＯ選択率、ＣＯ2選択率、触媒上に堆積した炭素析出率で判断した。それらは出口ガス中の各成分濃度より、以下の式で算出した。 The degree of reaction of the reforming reaction (decomposition rate of methylnaphthalene) was judged by methane selectivity, CO selectivity, CO 2 selectivity, and carbon deposition rate deposited on the catalyst. They were calculated by the following formula from the concentration of each component in the outlet gas.
メタン選択率（％）＝（ＣＨ4の体積量）／（供給された１−メチルナフタレンのＣ供給量）×１００ Methane selectivity (%) = (volume amount of CH 4 ) / (C supply amount of supplied 1-methylnaphthalene) × 100
ＣＯ選択率（％） ＝（ＣＯの体積量）／（供給された１−メチルナフタレンのＣ供給量）×１００ CO selectivity (%) = (CO volume) / (C supply of supplied 1-methylnaphthalene) × 100
ＣＯ2選択率（％）＝（ＣＯ2の体積量）／（供給された１−メチルナフタレンのＣ供給量）×１００ CO 2 selectivity (%) = (volume amount of CO 2 ) / (C supply amount of supplied 1-methylnaphthalene) × 100
炭素析出率（％） ＝（析出炭素重量）／（供給された１−メチルナフタレンのＣ供給量）×１００ Carbon deposition rate (%) = (weight of precipitated carbon) / (C supply amount of supplied 1-methylnaphthalene) × 100
また、入口水素ガス体積に対する出口水素ガス体積の比（水素増幅率）も併記した。 Further, the ratio of the hydrogen gas volume at the outlet to the hydrogen gas volume at the inlet (hydrogen amplification factor) is also shown.
表１の結果から、Ｈ2Ｓ濃度が２０００ｐｐｍという高濃度に含まれる雰囲気下でも、模擬タールである１−メチルナフタレンの分解反応が進んでおり、ニッケル、及び、表１の各第一金属元素、第二金属元素からなるペロブスカイト型複合酸化物の触媒は耐硫黄被毒性に強く、耐炭素析出性が高く、模擬タールの分解活性に優れていることが分かる。 From the results shown in Table 1, the decomposition reaction of 1-methylnaphthalene, which is a simulated tar, has progressed even in an atmosphere containing H 2 S at a high concentration of 2000 ppm. Nickel and each first metal element in Table 1 It can be seen that the catalyst of the perovskite type complex oxide composed of the second metal element is strong in sulfur poisoning resistance, high in carbon precipitation resistance, and excellent in the decomposition activity of the simulated tar.
（実施例２）
硝酸ランタン、硝酸ニッケル、硝酸鉄を各金属元素のモル比が１０：３：７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、ランタン、ニッケル、及び、鉄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。
(Example 2)
A lanthanum nitrate, nickel nitrate, and iron nitrate were precisely weighed so that the molar ratio of each metal element was 10: 3: 7, and a mixed aqueous solution was prepared by heating at 60 ° C., and then heated to 60 ° C. Aqueous potassium carbonate was added to coprecipitate lanthanum, nickel, and iron 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.
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。 The precipitate obtained after washing was dried at 120 ° C. and coarsely pulverized, then baked (calcinated) at 600 ° C. in the air, crushed, put in a beaker, added with alumina sol, and a mixer equipped with stirring blades The mixture that had been sufficiently mixed in was transferred to a flask made of eggplant, attached to a rotary evaporator, and sucked with stirring to evaporate water.
なすフラスコ壁面に付着したランタン、ニッケル、鉄、及び、アルミナの化合物を蒸発皿に移して、１２０℃で乾燥した後、６００℃でか焼し、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、ＬａＮｉ0.3Ｆｅ0.7Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＬａＮｉ0.3Ｆｅ0.7Ｏ3がペロブスカイト型構造を形成していることが確認できた。 The compound of lanthanum, nickel, iron, and alumina adhering to the flask wall is transferred to an evaporating dish, dried at 120 ° C., calcined at 600 ° C., and then the powder is compressed to 3 mmφ using a compression molding machine. Press-molded into a tablet shape to obtain a tablet-molded body. The molded body was fired at 950 ° C. in air to prepare a catalyst molded body in which 50% by mass of alumina was mixed with LaNi 0.3 Fe 0.7 O 3 . As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that LaNi 0.3 Fe 0.7 O 3 formed a perovskite structure.
この触媒６０ｃｍ3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、反応管を所定の位置にセットした。 The catalyst 60 cm 3 was fixed with quartz wool so as to be located at the center of the SUS reaction tube, a thermocouple was inserted at the center of the catalyst layer, and the reaction tube was set at a predetermined position.
改質反応を始める前に、反応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）の模擬ガスとして、水素：窒素＝１：１、Ｈ2Ｓを表２に示す濃度で、トータルで１２５ｍＬ／ｍｉｎになるよう各ガスを調整して導入し、常圧下、表１に示す各温度で８時間反応を行って触媒活性を評価した。それ以外はすべて実施例１と同様に行った。 Before starting the reforming reaction, the reactor was heated to 800 ° C. under a nitrogen atmosphere, and then reduced for 30 minutes while flowing hydrogen gas at 100 mL / min. Then, as a simulated gas for coke oven gas (crude gas), hydrogen: nitrogen = 1: 1, H 2 S at the concentrations shown in Table 2, each gas was adjusted and introduced so that the total was 125 mL / min. Under normal pressure, the reaction was carried out at each temperature shown in Table 1 for 8 hours to evaluate the catalyst activity. The rest was performed in the same manner as in Example 1.
表２のＮｏ．９〜１３の結果から、Ｈ2Ｓ濃度が２０００ｐｐｍという高濃度に含まれる雰囲気下でも、模擬タールである１−メチルナフタレンの分解反応が進んでおり、本製造方法で作成した触媒は耐硫黄被毒性に強いことが分かる。また、特に反応温度の上昇に伴い分解率（メタン選択率＋ＣＯ選択率＋ＣＯ2選択率＋炭素析出率）が高く、耐硫黄被毒性が高く、炭素析出性の高い過酷な状況下であっても，１−メチルナフタレンの分解反応が進行していることが分かる。 No. in Table 2 From the results of 9 to 13, the decomposition reaction of 1-methylnaphthalene, which is a simulated tar, has progressed even in an atmosphere containing H 2 S at a high concentration of 2000 ppm. It turns out to be strong in toxicity. In particular, as the reaction temperature rises, the decomposition rate (methane selectivity + CO selectivity + CO 2 selectivity + carbon deposition rate) is high, the sulfur poisoning resistance is high, and the carbon deposition property is high. It can be seen that the decomposition reaction of 1-methylnaphthalene proceeds.
また、Ｎｏ．１１、１４、１５の結果から、Ｈ2Ｓ濃度が低くなるに従い、硫黄被毒の影響が少なくなり、より分解率が向上したことが分かる。さらに、模擬タールの分解率の上昇に伴い、水素増幅率も上昇したことから、１−メチルナフタレンを構成する炭素と結合した水素が、触媒による分解に伴って水素分子に変換されたと考えられる。 No. From the results of 11, 14, and 15, it can be seen that as the H 2 S concentration is lowered, the influence of sulfur poisoning is reduced and the decomposition rate is further improved. Furthermore, since the hydrogen amplification factor also increased with an increase in the decomposition rate of the simulated tar, it is considered that hydrogen combined with carbon constituting 1-methylnaphthalene was converted into hydrogen molecules along with the decomposition by the catalyst.
また、炭素析出率は、比較的低い数値であり、温度が上昇するほど低くなる。全体の改質反応は、８００℃以上の高温領域で改質反応がほぼ全量分解していることが判明した。 Further, the carbon deposition rate is a relatively low value, and becomes lower as the temperature rises. It was found that the entire reforming reaction decomposed almost entirely in a high temperature region of 800 ° C. or higher.
（実施例３）
硝酸カルシウム、タングステン酸アンモニウム、硝酸ニッケルを各金属元素のモル比が２：１：１になるようにする他は実施例２と同様にして、共沈及び熟成を行った後、吸引ろ過を行い、８０℃の純粋で十分に洗浄を行った。
(Example 3)
Coprecipitation and aging were carried out in the same manner as in Example 2 except that calcium nitrate, ammonium tungstate, and nickel nitrate were made to have a molar ratio of each metal element of 2: 1: 1, followed by suction filtration. 80 ° C. pure and thoroughly washed.
その後、この沈殿物にアルミナゾルがアルミナとして５０質量％になるように加えて攪拌羽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。 Then, add the precipitate to the precipitate so that the alumina sol is 50% by mass as alumina and mix well with a mixer equipped with stirring blades. Transfer the mixture to a flask and place it on a rotary evaporator. The water was evaporated.
なすフラスコ壁面に付着したカルシウム、タングステン、ニッケルとアルミナの化合物を蒸発皿に移して１２０℃で乾燥、乳鉢で粉砕後、６００℃でか焼した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、ＣａＷ0.5Ｎｉ0.5Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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、広角ＸＲＤ解析の結果、ＣａＷ0.5Ｎｉ0.5Ｏ3がペロブスカイト型構造を形成していることが確認できた。 Calcium, tungsten, nickel and alumina compounds adhering to the flask wall are transferred to an evaporating dish, dried at 120 ° C, pulverized in a mortar, and calcined at 600 ° C into a 3mmφ tablet using a compression molding machine. Press molding was performed to obtain a tablet molding. The molded body was fired at 950 ° C. in air to prepare a catalyst molded body in which 50% by mass of alumina was mixed with CaW 0.5 Ni 0.5 O 3 . As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that CaW 0.5 Ni 0.5 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．５％、炭素析出率は３．２％、水素増幅率は２．６倍を発現し、安定して非常に高い改質活性を有し、かつ、炭素析出率が低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of performing the reforming experiment for 8 hours under the condition of 11, the decomposition rate of the simulated tar was 90.5%, the carbon deposition rate was 3.2%, the hydrogen amplification rate was 2.6 times, and stable It has been confirmed that it has a very high reforming activity and has a low carbon deposition rate.
（実施例４）
ランタン、ストロンチウム、クロム、ニッケル、及び、アルミニウムを含んだ水溶液から沈殿剤により沈殿物を作成、焼成する製法で調製した。すなわち、硝酸ランタン、硝酸ストロンチウム、硝酸クロム、及び、硝酸ニッケルを、ランタン、ストロンチウム、クロム、ニッケルの金属元素のモル比が、８：２：９：１になるようにし、アルミナとして５０質量％になるように計算して精秤し、６０℃の純粋に混合した混合溶液を調製したものに、実施例１と同様、６０℃に加温した炭酸カリウム水溶液を加え、スターラーで十分に攪拌した。
Example 4
A precipitate was prepared from an aqueous solution containing lanthanum, strontium, chromium, nickel, and aluminum with a precipitating agent, and prepared by a baking method. That is, lanthanum nitrate, strontium nitrate, chromium nitrate, and nickel nitrate were made so that the molar ratio of metal elements of lanthanum, strontium, chromium, and nickel was 8: 2: 9: 1, and 50% by mass as alumina. In the same manner as in Example 1, an aqueous potassium carbonate solution heated to 60 ° C. was added to a solution prepared by mixing and precisely weighing and preparing a purely mixed solution at 60 ° C., and 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した。 Thereafter, with the temperature kept at 60 ° C., the mixture was aged for a certain period of time, and then subjected to suction filtration and sufficiently washed with pure water at 80 ° C.
その後、この沈殿物を蒸発皿に移して、１２０℃で乾燥、乳鉢で粉砕後、６００℃でか焼した粉末を圧縮成型器を用いて、実施例１と同様にプレス成型し、錠剤成型体を得た。その成型体を空気中９５０℃で焼成を行って、Ｌａ0.8Ｓｒ0.2Ｃｒ0.9Ｎｉ0.1Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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、広角ＸＲＤ解析の結果、Ｌａ0.8Ｓｒ0.2Ｃｒ0.9Ｎｉ0.1Ｏ3がペロブスカイト型構造を形成していることが確認できた。 Thereafter, the precipitate is transferred to an evaporating dish, dried at 120 ° C., pulverized in a mortar, and calcined at 600 ° C., and then press-molded in the same manner as in Example 1 using a compression molding machine. Got. 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 La 0.8 Sr 0.2 Cr 0.9 Ni 0.1 O 3 . As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that La 0.8 Sr 0.2 Cr 0.9 Ni 0.1 O 3 formed a perovskite structure.
この触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．８％、炭素析出率は３．５％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was repeated, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.8%, the carbon deposition rate was 3.5%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例５）
１２００℃で３時間かけて予備焼成したアルミナ（表面積：１４３ｍ2／ｇ）に、硝酸ランタン、塩化チタン、硝酸ニッケルの混合水溶液を、ランタン、チタン、ニッケルの金属元素のモル比が、実施例１と同じ、１０：８：２になるようにし、アルミナとして８０質量％になるように含浸後、１１０℃で１２時間かけて乾燥させ、その後５００℃で３時間かけて焼成を行って、ＬａＴｉ0.8Ｎｉ0.2Ｏ3にアルミナを８０質量％混合した触媒成型体を調整した。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、広角ＸＲＤ解析の結果、ＬａＴｉ0.8Ｎｉ0.2Ｏ3がペロブスカイト型構造を形成していることが確認できた。
(Example 5)
Example 1 shows a mixed aqueous solution of lanthanum nitrate, titanium chloride and nickel nitrate in alumina preliminarily calcined at 1200 ° C. for 3 hours (surface area: 143 m 2 / g). same, 10: 8: 2 to become so, after impregnation to be 80 mass% of alumina, dried over 12 hours at 110 ° C., and fired over the next 3 hours at 500 ° C., LATi 0.8 A catalyst molded body in which 80% by mass of alumina was mixed with Ni 0.2 O 3 was prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that LaTi 0.8 Ni 0.2 O 3 formed a perovskite structure.
この触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．２％、炭素析出率は３．６％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を保有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was repeated, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.2%, the carbon deposition rate was 3.6%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it has been confirmed that it has stable and very high reforming activity and exhibits a low carbon deposition rate.
（実施例６）
硝酸バリウム、硝酸コバルト、硝酸ニッケルを、各金属元素のモル比が２：１：１になるようにする他は実施例２と同様に調製して、ＢａＣｏ0.5Ｎｉ0.5Ｏ3にアルミナを５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＢａＣｏ0.5Ｎｉ0.5Ｏ3がペロブスカイト型構造を形成していることを確認した。
(Example 6)
Barium nitrate, cobalt nitrate, and nickel nitrate were prepared in the same manner as in Example 2 except that the molar ratio of each metal element was 2: 1: 1, and 50 masses of alumina in BaCo 0.5 Ni 0.5 O 3. % Of the catalyst molded body was prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that BaCo 0.5 Ni 0.5 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．４％、炭素析出率は３．８％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.4%, the carbon deposition rate was 3.8%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例７）
ストロンチウム、ニオブ、ニッケルを各金属元素のモル比が３：２：１になるようにする他は実施例２と同様に調製して、ＳｒＮｂ0.67Ｎｉ0.33Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＳｒＮｂ0.67Ｎｉ0.33Ｏ3がペロブスカイト型構造を形成していることを確認した。
(Example 7)
Catalyst prepared by mixing SrNb 0.67 Ni 0.33 O 3 with 50% by mass of alumina except that strontium, niobium and nickel were prepared in the same manner as in Example 2 except that the molar ratio of each metal element was 3: 2: 1. A molded body was prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that SrNb 0.67 Ni 0.33 O 3 formed a perovskite structure.
この触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．０％、炭素析出率は３．７％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was repeated, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.0%, the carbon deposition rate was 3.7%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例８）
ストロンチウム、タンタル、ニッケルを各金属元素のモル比が３：２：１になるようにする他は実施例２と同様に調製して、ＳｒＴａ0.67Ｎｉ0.33Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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できた。また、広角ＸＲＤ解析の結果、ＳｒＴａ0.67Ｎｉ0.33Ｏ3がペロブスカイト型構造を形成していることを確認した。
(Example 8)
Catalyst prepared by mixing SrTa 0.67 Ni 0.33 O 3 with 50% by mass of alumina except that strontium, tantalum and nickel were prepared in the same manner as in Example 2 except that the molar ratio of each metal element was 3: 2: 1. A molded body was prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that SrTa 0.67 Ni 0.33 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．１％、炭素析出率は３．８％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the conditions of No. 11, the decomposition rate of the simulated tar was 90.1%, the carbon deposition rate was 3.8%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例９）
ストロンチウム、モリブデン、ニッケルを各金属元素のモル比が２：１：１になるようにする他は実施例２と同様に調製して、ＳｒＭｏ0.5Ｎｉ0.5Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＳｒＭｏ0.5Ｎｉ0.5Ｏ3がペロブスカイト型構造を形成していることを確認した。
Example 9
A catalyst prepared by mixing SrMo 0.5 Ni 0.5 O 3 with 50% by mass of alumina except that strontium, molybdenum and nickel were prepared in the same manner as in Example 2 except that the molar ratio of each metal element was 2: 1: 1. A molded body was prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that SrMo 0.5 Ni 0.5 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．２％、炭素析出率は３．８％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.2%, the carbon deposition rate was 3.8%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例１０）
バリウム、レニウム、ニッケルを各金属元素のモル比が２：１：１になるようにする他は実施例２と同様に調製して、ＢａＲｅ0.5Ｎｉ0.5Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＢａＲｅ0.5Ｎｉ0.5Ｏ3がペロブスカイト型構造を形成していることを確認した。
(Example 10)
Catalyst prepared by mixing barium, rhenium and nickel in the same manner as in Example 2 except that the molar ratio of each metal element is 2: 1: 1, and a mixture of BaRe 0.5 Ni 0.5 O 3 and 50% by mass of alumina. A molded body was prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that BaRe 0.5 Ni 0.5 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．１％、炭素析出率は３．６％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.1%, the carbon deposition rate was 3.6%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例１１）
ストロンチウム、バナジウム、ニッケルを各金属元素のモル比が３：２：１になるようにする他は実施例２と同様に調製してＳｒＶ0.67Ｎｉ0.33Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＳｒＶ0.67Ｎｉ0.33Ｏ3がペロブスカイト型構造を形成していることを確認した。
(Example 11)
Catalyst molding in which strontium, vanadium and nickel were prepared in the same manner as in Example 2 except that the molar ratio of each metal element was 3: 2: 1, and SrV 0.67 Ni 0.33 O 3 was mixed with 50% by mass of alumina. The body was prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that SrV 0.67 Ni 0.33 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．３％、炭素析出率は３．９％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.3%, the carbon deposition rate was 3.9%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例１２）
ランタン、ジルコニウム、ニッケルを各金属元素のモル比が１０：８：２になるようにする他は、実施例２と同様に調製して、ＬａＺｒ0.8Ｎｉ0.2Ｏ3にアルミナが５０質量％混合した触媒成型体を調製した。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、広角ＸＲＤ解析の結果、ＬａＺｒ0.8Ｎｉ0.2Ｏ3がペロブスカイト型構造を形成していることを確認した。
(Example 12)
It was prepared in the same manner as in Example 2 except that lanthanum, zirconium and nickel had a molar ratio of each metal element of 10: 8: 2, and 50% by mass of alumina was mixed with LaZr 0.8 Ni 0.2 O 3 . A catalyst molded body was prepared. As a result of confirming the component of the molded body by ICP analysis, it was confirmed that it was a desired component, and as a result of wide-angle XRD analysis, it was confirmed that LaZr 0.8 Ni 0.2 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は９０．５％、炭素析出率は４．０％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 90.5%, the carbon deposition rate was 4.0%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例１３）
ランタン、ニッケルを各金属元素のモル比が１：１になるようにする他は実施例２と同様に調製してＬａＮｉＯ3にアルミナが５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＬａＮｉＯ3がペロブスカイト型構造を形成していることを確認した。
(Example 13)
A catalyst molded body prepared by mixing lanthanum and nickel in the same manner as in Example 2 except that the molar ratio of each metal element was 1: 1 was prepared by mixing 50% by mass of alumina with LaNiO 3 . As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that LaNiO 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は８９．７％、炭素析出率は９．７％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 89.7%, the carbon deposition rate was 9.7%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例１４）
アルミナの代わりにシリカを用いる他は実施例２と同様に調製してＬａＮｉ0.3Ｆｅ0.7Ｏ3にシリカが５０質量％混合した触媒成型体を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ＬａＮｉ0.3Ｆｅ0.7Ｏ3がペロブスカイト型構造を形成していることを確認した。
(Example 14)
A catalyst molded body was prepared in the same manner as in Example 2 except that silica was used in place of alumina to mix LaNi 0.3 Fe 0.7 O 3 with 50% by mass of silica. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that LaNi 0.3 Fe 0.7 O 3 formed a perovskite structure.
触媒成型体の調製方法以外はすべて実施例２と同様にして、表２のＮｏ．１１の条件で８時間の改質実験を行った結果、模擬タールの分解率は８９．６％、炭素析出率は９．９％、水素増幅率は２．６倍を発現し、実施例２と同様、安定して非常に高い改質活性を有し、かつ、炭素析出率の低い性能を示すことを確認できた。 Except for the method for preparing the catalyst molded body, the same procedure as in Example 2 was performed, and the No. in Table 2 was obtained. As a result of the reforming experiment for 8 hours under the condition of No. 11, the decomposition rate of the simulated tar was 89.6%, the carbon deposition rate was 9.9%, and the hydrogen amplification rate was 2.6 times. In the same manner as above, it was confirmed that it had a stable and very high reforming activity and had a low carbon deposition rate.
（実施例１５）
ランタン、セリウム、鉄、ニッケル、及び、アルミニウムの酸化物のうち、各金属元素の原子量％、及び、アルミナの質量％が表３になるように調製する他は、実施例２と同様に触媒を調製した。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が確認できた。また、広角ＸＲＤ解析の結果、ペロブスカイト型構造を形成していることを確認した。
(Example 15)
A catalyst was prepared in the same manner as in Example 2, except that the oxides of lanthanum, cerium, iron, nickel, and aluminum were prepared so that the atomic weight% of each metal element and the mass% of alumina were as shown in Table 3. Prepared. As a result of confirming the components of the molded body by ICP analysis, it was confirmed that they were the desired components. As a result of wide-angle XRD analysis, it was confirmed that a perovskite structure was formed.
実験条件としては、表２のＮｏ．１１の条件で評価した。その結果を表３に示す。 As the experimental conditions, No. Evaluation was performed under 11 conditions. The results are shown in Table 3.
表３の結果から分かるように、主活性成分であるＮｉ原子量％が小さいものほど１−メチルナフタレンの分解率は低く、水素増幅率も低くなり、Ｎｉ原子量％が１０％を下回るＮｏ．１６の場合には、分解率、水素増幅率共に低い結果となった。一方、Ｎｉ原子量が大きくなるほど分解率、水素増幅率も高くなった。Ｎｉ質量が１００原子量％のＮｏ．２４の場合には、炭素析出量が多い結果となった。 As can be seen from the results in Table 3, the smaller the Ni atomic weight% as the main active component, the lower the decomposition rate of 1-methylnaphthalene, the lower the hydrogen amplification rate, and the Ni atomic weight% lower than 10%. In the case of 16, both the decomposition rate and the hydrogen amplification rate were low. On the other hand, the decomposition rate and the hydrogen amplification rate increased as the Ni atomic weight increased. No. having a Ni mass of 100 atomic weight%. In the case of 24, the result was a large amount of carbon deposition.
また、Ｎｏ．１９とＮｏ．２２を比較すると、ほぼ同等のＮｉ質量であってもアルミナ質量の違いにより、アルミナ成分が少ない方が触媒活性は高かった。 No. 19 and No. When 22 was compared, even if the Ni mass was almost the same, the catalyst activity was higher when the alumina component was smaller due to the difference in the alumina mass.
（実施例１６）
反応温度８００℃、Ｈ2Ｓ濃度２０００ｐｐｍ、反応時にＨ2Ｏ、ＣＯ2及びＯ2を表４に示した各条件になるように導入した他は、実施例２と同様に触媒調製、評価を行った。その結果を表４に示す。なお、ここでＨ2Ｏ／Ｃ、ＣＯ2／Ｃ及びＯ2／ＣのＣは供給された１−メチルナフタレンのＣ供給量を示す。
(Example 16)
The catalyst was prepared and evaluated in the same manner as in Example 2 except that the reaction temperature was 800 ° C., the H 2 S concentration was 2000 ppm, and H 2 O, CO 2, and O 2 were introduced so as to satisfy the conditions shown in Table 4. went. The results are shown in Table 4. Here, C in H 2 O / C, CO 2 / C, and O 2 / C indicates the C supply amount of supplied 1-methylnaphthalene.
表４の結果、外部からＨ2ＯやＣＯ2やＯ2を導入することにより、表２のＮｏ．１１の結果と比較すると、改質反応が進むことが確認された。なお、Ｏ2を導入する場合、Ｈ2ＯによるスチームリフォーミングやＣＯ2によるドライリフォーミングの吸熱を燃焼熱で熱補償できるため、実際の反応器を想定した場合、非常に有効な手法である。また、Ｏ2を導入することにより、炭素析出率がさらに低下した。 As a result of Table 4, by introducing H 2 O, CO 2 or O 2 from the outside, No. 1 in Table 2 was obtained. Compared with the result of 11, it was confirmed that the reforming reaction proceeds. When introducing O 2 , the heat absorption of steam reforming due to H 2 O and dry reforming due to CO 2 can be compensated with combustion heat, so this is a very effective technique when an actual reactor is assumed. . Moreover, the carbon deposition rate further decreased by introducing O 2 .
（実施例１７）
コークス炉をシミュレートできるバッチ炉に、実際のコークス炉で使用している装入炭を８０ｋｇ充填し、実コークス炉に合わせて昇温して、実コークス炉ガス及び随伴する実タールを発生させた。そのガスを吸引ポンプで捕集し、実験に用いた。
(Example 17)
A batch furnace capable of simulating a coke oven is charged with 80 kg of charging coal used in an actual coke oven and heated to match the actual coke oven to generate actual coke oven gas and accompanying actual tar. It was. The gas was collected with a suction pump and used in the experiment.
反応温度が８００℃になるよう昇温した電気炉内部に反応管を配置して、その中央部に実施例２と同様にして、ＬａＮｉ0.3Ｆｅ0.7Ｏ3にアルミナが５０質量％混合した触媒成型体を調製し、リング状に成型した。 A reaction tube is placed inside an electric furnace heated to a reaction temperature of 800 ° C., and the catalyst is molded in the same way as in Example 2 by mixing 50% by mass of alumina with LaNi 0.3 Fe 0.7 O 3. A body was prepared and molded into a ring.
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、広角ＸＲＤ解析の結果、ペロブスカイト型構造を形成していることを確認した。 As a result of confirming the component of the molded body by ICP analysis, it was confirmed that it was a desired component, and as a result of wide-angle XRD analysis, it was confirmed that a perovskite structure was formed.
触媒成型体を、反応管の所定の位置に設置し、水素を１０ＮＬ／ｍｉｎ流通して２時間還元後、バッチ炉から捕集したガスを触媒層へ流すことにより、実コークス炉ガス及び随伴実タールの触媒分解活性を５時間継続して評価した。 The catalyst molded body is installed at a predetermined position of the reaction tube, hydrogen is circulated at 10 NL / min and reduced for 2 hours, and then the gas collected from the batch furnace is caused to flow to the catalyst layer, so that the actual coke oven gas and the accompanying actual The catalytic cracking activity of tar was evaluated continuously for 5 hours.
入口ガス流量は１０ＮＬ／ｍｉｎで、触媒充填量は約１Ｌであった。なお、入口ガス組成は、実コークス炉ガスとほぼ同じ組成であることをガスクロマトグラフィーで確認した。また、そのガス中には硫化水素が２４００〜２５００ｐｐｍ含まれていることを確認した。 The inlet gas flow rate was 10 NL / min, and the catalyst filling amount was about 1 L. The inlet gas composition was confirmed by gas chromatography to be almost the same as the actual coke oven gas. Further, it was confirmed that 2400 to 2500 ppm of hydrogen sulfide was contained in the gas.
タール分解率は、触媒層の入口と出口からガスをサンプリングし、秤量することにより評価した。その結果、タール分解率は平均８９％、水素増幅率は平均で２．６倍まで到達した。タール分解率は、触媒層入口ガス中のタール質量に対する、触媒層出口ガス中のタール質量の割合である。 The tar decomposition rate was evaluated by sampling and weighing gas from the inlet and outlet of the catalyst layer. As a result, the tar decomposition rate reached 89% on average and the hydrogen amplification rate reached 2.6 times on average. The tar decomposition rate is the ratio of the tar mass in the catalyst layer outlet gas to the tar mass in the catalyst layer inlet gas.
（実施例１８）
表２のＮｏ．１１の条件で８時間継続して反応を進行させた後、原料の投入を停止し、キャリアガスとしてＮ2６０ｍＬ／ｍｉｎ、Ｈ2Ｏをガス換算で６０ｍＬ／ｍｉｎを供給し、触媒層温度を８００℃で５時間保持して、触媒上に堆積した炭素や硫黄を除去した。その後、新たに実施例２と同じ条件で原料の投入を開始したところ、再生前の９割以上の活性を示すことが確認された。また、本試験における改質後のガス中の水素濃度も高く、水素、一酸化炭素、メタンが主成分のガスに変換されたことが確認された。
(Example 18)
No. in Table 2 After continuing the reaction for 8 hours under the conditions of 11, the input of the raw material was stopped, N 2 60 mL / min as a carrier gas, and H 2 O as a gas equivalent of 60 mL / min were supplied. The carbon and sulfur deposited on the catalyst were removed by holding at 800 ° C. for 5 hours. After that, when the starting of the raw material was newly started under the same conditions as in Example 2, it was confirmed that 90% or more of the activity before regeneration was exhibited. In addition, the hydrogen concentration in the reformed gas in this test was high, and it was confirmed that hydrogen, carbon monoxide, and methane were converted to the main gas.
（実施例１９）
実施例１８と同様、表２のＮｏ．６の条件で８時間継続して反応を進行させた後、原料の投入を停止し、キャリアガスとしてＮ2６０ｍＬ／ｍｉｎ、空気６０ｍＬ／ｍｉｎを供給し、触媒層温度を８００℃で２時間保持して、触媒上に堆積した炭素や硫黄を除去した。その後、新たに実施例２と同じ条件で原料の投入を開始したところ、再生前の９割以上の活性を示すことが確認された。また、本試験における改質後のガス中の水素濃度も高く、水素、一酸化炭素、メタンが主成分のガスに変換されたことが確認された。
(Example 19)
As in Example 18, No. 2 in Table 2 was used. The reaction was allowed to proceed for 8 hours under the conditions of 6, after which the starting material was stopped, N 2 60 mL / min and air 60 mL / min were supplied as carrier gases, and the catalyst layer temperature was maintained at 800 ° C. for 2 hours. Thus, carbon and sulfur deposited on the catalyst were removed. After that, when the starting of the raw material was newly started under the same conditions as in Example 2, it was confirmed that 90% or more of the activity before regeneration was exhibited. In addition, the hydrogen concentration in the reformed gas in this test was high, and it was confirmed that hydrogen, carbon monoxide, and methane were converted to the main gas.
（実施例２０）
実施例５と同様にして調製した触媒１ｇを用いて、固定床反応器で、バイオマスとして杉の粉（約０．２ｍｍ、Ｃ：５１．１％、Ｈ：５．９％、Ｏ：４２．５％、Ｎ：０．１％、灰分：０．３％）のガス化を行った。
(Example 20)
Using 1 g of the catalyst prepared in the same manner as in Example 5, cedar flour (about 0.2 mm, C: 51.1%, H: 5.9%, O: 42. 5%, N: 0.1%, ash content: 0.3%).
杉の粉は、固定床反応器の上部よりＮ2をキャリアガスとして、連続的に供給を行った。反応温度は、反応器外壁に取り付けた熱電対により制御した。生成ガスの流量は、石鹸膜流量計により測定し、ガス組成の分析は、ガスクロマトグラフを用いて行った。使用したガスクロマトグラフは、Ｓｈｉｍａｄｚｕ ＣＧ−１４ＢでＨ2をＴＣＤ（モレキュラーシーブ１３Ｘ）、それ以外の生成物はＦＩＤ（ガスクロパック５４）を用いて分析し、その記録はインテグレーター（Ｓｈｉｍａｄｚｕ クロマトパックＣＲ−５Ａ）で行った。 Cedar flour was continuously supplied from the top of the fixed bed reactor using N 2 as a carrier gas. The reaction temperature was controlled by a thermocouple attached to the reactor outer wall. The flow rate of the product gas was measured with a soap film flow meter, and the gas composition was analyzed using a gas chromatograph. The gas chromatograph used was Shimadzu CG-14B, and H 2 was analyzed using TCD (Molecular Sieve 13X), and the other products were analyzed using FID (Gascropack 54). )
反応器には、改質用触媒とチャー（析出した固体状の炭素成分）が別々に貯留されるデュアルベッド式を使用した。デュアルベッド式の利点として、バイオマスのガス化時に発生するチャーや灰分を直接触媒と接触させないため、触媒寿命の長期化が図れることがあげられる。また、燃焼しても殆どＣＯ2にしかならないチャーをガス化しないことによって、生成ガスの組成をより有用なものとすることができる。反応器の下流には、蒸気及びタールをトラップするために、氷を入れたデュワー瓶を設置した。 The reactor used was a dual bed system in which the reforming catalyst and char (deposited solid carbon component) were stored separately. As an advantage of the dual bed system, the char life and ash generated during the gasification of biomass are not brought into direct contact with the catalyst, so that the catalyst life can be extended. Moreover, the composition of the product gas can be made more useful by not gasifying the char that only becomes CO 2 even if it is burned. A dewar with ice was installed downstream of the reactor to trap steam and tar.
試験条件は以下のとおりである。 The test conditions are as follows.
改質用触媒量：１ｇ、
杉の粉供給速度：６０ｍｇ／ｍｉｎ（Ｃ：２１９１μｍｏｌ／ｍｉｎ、Ｈ：３５４３μｍｏｌ／ｍｉｎ、Ｏ：１４７５μｍｏｌ／ｍｉｎ、）、キャリアガスＮ2：６０ｍＬ／ｍｉｎ、Ｈ2Ｏ／Ｃ＝０．５（Ｈ2Ｏ：１１１０μｍｏｌ／ｍｉｎ）、
反応時間：１５分、
水素還元：５００℃、３０分間。
Reforming catalyst amount: 1 g
Cedar powder supply rate: 60 mg / min (C: 2191 μmol / min, H: 3543 μmol / min, O: 1475 μmol / min), carrier gas N 2 : 60 mL / min, H 2 O / C = 0.5 (H 2 O: 1110 μmol / min),
Reaction time: 15 minutes,
Hydrogen reduction: 500 ° C., 30 minutes.
改質用触媒の性能は、タール分解率（Ｔａｒ−ｃｏｎｖ．％）、出口ガスのＨ2生成速度、出口ガス中の水素組成で判断し、それらは以下の式で算出した。なお、本試験条件で発生したバイオマスガス化ガスの生成速度並びにガス組成及び入口タール（Ｔａｒ）量は表５に示すとおりであり、そのガス中に含まれる硫化水素濃度は約２０ｐｐｍであった。 The performance of the reforming catalyst was judged by the tar decomposition rate (Tar-conv.%), The H 2 production rate of the outlet gas, and the hydrogen composition in the outlet gas, and these were calculated by the following formula. The production rate, gas composition, and inlet tar (Tar) amount of the biomass gasification gas generated under the test conditions are as shown in Table 5, and the concentration of hydrogen sulfide contained in the gas was about 20 ppm.
ｃｏｋｅ％ ＝（コーク中のＣ原子量）／（供給されたバイオマスの総Ｃ原子量）
×１００
coke% = (C atomic weight in coke) / (total C atomic weight of supplied biomass)
× 100
ｃｈａｒ％ ＝ （チャー中のＣ原子量）／（供給されたバイオマスの総Ｃ原子量）
×１００
char% = (C atomic weight in char) / (Total C atomic weight of supplied biomass)
× 100
ｔａｒ％ ＝ （１００−（Ｃ−ｃｏｎｖ．％）−（ｃｈａｒ％）−（ｃｏｋｅ％）） tar% = (100- (C-conv.%)-(char%)-(coke%))
入口Ｔａｒ量（ｍｇ・ｍｉｎ-1） ＝ 入口ｔａｒ％×（供給されたバイオマスの
総Ｃ供給速度）
Inlet Tar amount (mg · min −1 ) = Inlet tar% × (of supplied biomass
Total C supply speed)
出口Ｔａｒ量（ｍｇ・ｍｉｎ-1） ＝ 出口ｔａｒ％×（供給されたバイオマスの
総Ｃ供給速度）
Outlet Tar amount (mg · min −1 ) = Outlet tar% × (of supplied biomass
Total C supply speed)
Ｔａｒ−ｃｏｎｖ．％ ＝ （１−（出口Ｔａｒ量ｍｇ・ｍｉｎ-1）
／（入口Ｔａｒ量ｍｇ・ｍｉｎ-1）×１００
Tar-conv. % = (1- (Exit Tar amount mg · min −1 ))
/ (Inlet Tar amount mg · min −1 ) × 100
コーク（ｃｏｋｅ）とは、改質用触媒表面に堆積した炭素のことであり、チャーとは、バイオマスの熱分解により生成され、ガス化されずに残った固定炭素分のことである。 The coke is carbon deposited on the surface of the reforming catalyst, and the char is a fixed carbon component generated by pyrolysis of biomass and remaining without being gasified.
コーク中のＣ原子量、及び、チャー中のＣ原子量の測定方法は、以下のとおりである。 The measuring method of C atomic weight in coke and C atomic weight in char is as follows.
（コーク中Ｃ原子量）
(1) １５分間の改質試験後、バイオマスの供給を停止し、反応器にＮ2を添加することで、反応器内のガスを追い払う。
(2) Ｏ2を反応器１の上部より添加し、改質用触媒に発生したチャーの燃焼時に発生するＣＯ、ＣＯ2の発生量をガスクロマトグラフで測定する。
(3) ＣＯ、ＣＯ2発生量からチャー中のＣ原子量を算出する。
(C atomic weight in coke)
(1) After the reforming test for 15 minutes, the supply of biomass is stopped, and N 2 is added to the reactor to drive off the gas in the reactor.
(2) Add O 2 from the upper part of the reactor 1 and measure the amount of CO and CO 2 generated during combustion of char generated in the reforming catalyst with a gas chromatograph.
(3) Calculate the amount of C atoms in the char from the amount of CO and CO 2 generated.
（チャー中のＣ原子量）
(1) コーク中のＣ量の測定完了後、反応器の上部からのＯ2の添加を停止し、反応器の下部からのＯ2を添加する。
(2) コーク中Ｃ量測定と同様に、チャーの燃焼時に発生するＣＯ、ＣＯ2の発生量をガスクロマトグラフで測定する。
(3) ＣＯ、ＣＯ2発生量からチャー中のＣ原子量を算出する。
(C atomic weight in char)
(1) After the measurement of the amount of C in the coke is completed, the addition of O 2 from the top of the reactor is stopped, and O 2 from the bottom of the reactor is added.
(2) Similarly to the measurement of C content in coke, the amount of CO and CO 2 generated during char combustion is measured with a gas chromatograph.
(3) Calculate the amount of C atoms in the char from the amount of CO and CO 2 generated.
以上のような固定床反応器において、反応温度を表６に示すように５５０、６００、６５０℃の各温度で１５分間の改質試験を行ったところ、表６に示すような改質ガスの生成速度並びにガス組成及び出口Ｔａｒ量・分解率の結果が得られ、表５と比較すると、いずれの反応温度でも、タール分解率（Ｔａｒ−ｃｏｎｖ．）が高く、かつ水素が大きく増幅され（水素ガス生成速度又は水素ガス組成）、高活性な性能を発揮することが確認された。 In the fixed bed reactor as described above, the reforming test was conducted for 15 minutes at 550, 600, and 650 ° C. as shown in Table 6. The results of the production rate, gas composition and outlet Tar amount / decomposition rate are obtained. Compared with Table 5, the tar decomposition rate (Tar-conv.) Is high and hydrogen is greatly amplified at any reaction temperature (hydrogen It was confirmed that gas production rate or hydrogen gas composition) and highly active performance were exhibited.
（実施例２１）
精製ＣＯＧを用いた改質装置としては、通常の水素製造プラントの規模を縮小した以外は全く同一の試験プラントで、改質ガス流量が約４００Ｎｍ3／ｈ規模の設備を用いた。
(Example 21)
As the reformer using the purified COG, equipment having a reformed gas flow rate of about 400 Nm 3 / h was used in the same test plant except that the scale of a normal hydrogen production plant was reduced.
触媒充填反応管は、改質炉の中に約８０ｍｍφ、約１０ｍのものを４本設置し、そこへ改質触媒として、実施例１７で用いたのと同じリング状に成型した触媒をそれぞれ約２５ｋｇ、合計で約１００ｋｇを充填した。 Four catalyst-packed reaction tubes of about 80 mmφ and about 10 m were installed in the reforming furnace, and the catalysts formed in the same ring shape as used in Example 17 were used as reforming catalysts there. 25 kg, a total of about 100 kg was filled.
その改質炉の天井に設置したバーナーを点火して、火炎が下方へ向かうダウンファイヤード形式により炉内を加熱し、その輻射熱で反応管を加熱する方式で所定の温度になるように昇温した。また、その高温の排ガスを熱交換器を通して、原料ガスである精製ＣＯＧを加熱した。また、改質剤には水蒸気を用い、純水をボイラーで加熱した後、上記改質炉の排ガスとの熱交換で加熱蒸気にして精製ＣＯＧと共に反応管上部から導入した。 A burner installed on the ceiling of the reforming furnace is ignited, the inside of the furnace is heated by a downfire method in which the flame is directed downward, and the reaction tube is heated by the radiant heat to raise the temperature to a predetermined temperature. did. The high-temperature exhaust gas was passed through a heat exchanger to heat purified COG as a raw material gas. Further, steam was used as a modifier, and pure water was heated by a boiler, and then heated steam by heat exchange with the exhaust gas from the reforming furnace and introduced from the upper part of the reaction tube together with purified COG.
反応に先立ち、窒素ガスで約９００℃、常圧の条件に設定した後、還元処理を行うべく、窒素から水素に水蒸気を混合したガス（水蒸気のモル比／水素のモル比＝７）に切り替えて、約２００Ｎｍ3／ｈで３時間保持した。得られた改質ガスは、反応管出口に設置した冷却器で冷却し、水分離器で水分を除去した後、ガスクロマトグラフィーでガス組成を分析した。 Prior to the reaction, after setting the condition of nitrogen gas to about 900 ° C. and normal pressure, switch to a gas in which water vapor is mixed from nitrogen to hydrogen (water vapor molar ratio / hydrogen molar ratio = 7) for reduction treatment. And held at about 200 Nm 3 / h for 3 hours. The obtained reformed gas was cooled with a cooler installed at the outlet of the reaction tube, and after removing water with a water separator, the gas composition was analyzed by gas chromatography.
ここで用いた原料ガスは、常法で精製した精製ＣＯＧの後段に、酸化鉄（Ｆｅ2Ｏ3）系市販触媒（ズードケミー製、Ｎ−ＩＤＳ）を充填した脱硫装置により、硫化水素の濃度を約０．５ｐｐｍまで脱硫したものを用いた。 The raw material gas used here was subjected to the concentration of hydrogen sulfide by a desulfurization unit filled with an iron oxide (Fe 2 O 3 ) -based commercial catalyst (manufactured by Zude Chemie, N-IDS) after the purified COG purified by a conventional method. What was desulfurized to about 0.5 ppm was used.
そのようにして脱硫した原料ガス、及び、改質剤としての水蒸気は、水蒸気のモル数と原料ガス中の炭化水素成分の炭素モル数との比（Ｓ／Ｃ）が１となるよう、各々約２６０Ｎｍ3／ｈ、約８０Ｎｍ3／ｈ（約６０ｋｇ／ｈ相当）を反応管に導入した。また、反応温度、圧力は、反応管の出口温度、圧力として約９００℃、常圧となるように調整して約１０００時間の運転を行った。その結果、改質後のガスとして、約４００Ｎｍ3／ｈの合成ガスを安定して得ることができた。 The raw material gas thus desulfurized and the water vapor as the modifier are each set so that the ratio (S / C) of the number of moles of water vapor to the number of carbon moles of the hydrocarbon component in the raw material gas is 1. About 260 Nm 3 / h and about 80 Nm 3 / h (equivalent to about 60 kg / h) were introduced into the reaction tube. The reaction temperature and pressure were adjusted so that the outlet temperature and pressure of the reaction tube were about 900 ° C. and normal pressure, and the operation was performed for about 1000 hours. As a result, a synthesis gas of about 400 Nm 3 / h could be stably obtained as the reformed gas.
［比較例１］
実施例２と同じ実験手法で、表２のＮｏ．１１の条件で、触媒として工業触媒の一つであるズードケミー製ナフサ一次リフォーミング触媒（ＳＣ１１ＮＫ；Ｎｉ−２０質量％担持）を用いて改質試験を行ったところ、メタン選択率が２．５％、ＣＯ選択率が４．２％、ＣＯ2選択率が５．９％、炭素析出率が３２．８％、分解率４５．４％、水素増幅率が１．３となった。
[Comparative Example 1]
In the same experimental method as Example 2, No. When a reforming test was carried out using a naphtha primary reforming catalyst (SC11NK; Ni-20% by mass supported) made by Sued Chemie, which is one of industrial catalysts, as a catalyst under the conditions of No. 11, the methane selectivity was 2.5%. The CO selectivity was 4.2%, the CO 2 selectivity was 5.9%, the carbon deposition rate was 32.8%, the decomposition rate was 45.4%, and the hydrogen amplification rate was 1.3.
したがって、工業触媒は、１−メチルナフタレンのガス成分への変換率が低い（１２．６％）一方、炭素析出率が非常に高い結果となった。工業触媒は、炭素析出率が非常に高いため、触媒寿命が短いおそれがある。反応後に再生処理を行ったとしても、高温又は長期間酸化処理を行う必要があるために、その際の大きな燃焼熱により触媒活性粒子がシンタリングを引き起こして、再生後の性能がさらに低くなると予想される。 Therefore, the industrial catalyst had a low conversion rate of 1-methylnaphthalene to a gas component (12.6%), but a very high carbon deposition rate. An industrial catalyst has a very high carbon deposition rate, and thus there is a possibility that the catalyst life is short. Even if the regeneration process is performed after the reaction, it is necessary to perform the oxidation process for a high temperature or for a long period of time. Is done.
［比較例２］
実施例１７と同じ試験設備を用い、実施例１７と同じ条件で、比較例１で用いた工業触媒（ＳＣ１１ＮＫ）を反応管に設置して、評価を行った。その結果、タール分解率は２２％にとどまり、水素増幅率も約１．５となり、工業触媒は、実コークス炉ガス、実タール下での評価でも、タール分解率が低いことが判明した。
[Comparative Example 2]
Using the same test equipment as in Example 17, the same conditions as in Example 17 were used, and the industrial catalyst (SC11NK) used in Comparative Example 1 was installed in the reaction tube for evaluation. As a result, the tar decomposition rate was only 22%, the hydrogen amplification rate was about 1.5, and it was found that the industrial catalyst had a low tar decomposition rate even when evaluated under actual coke oven gas and actual tar.
［比較例３］
実施例１と同様にして、ニッケルとマグネシウムの沈殿物を調製した後、ろ過、洗浄、乾燥した後、空気中９５０℃で焼成を行い、ニッケルとマグネシアの化合物を得た。その後、アルミナ粉末を５０質量％になるように秤量し、両者を乳鉢を用いて物理的に混合した。その混合物を実施例１と同じ実験手法で成型、焼成した後、表２のＮｏ．１１と同じ条件で活性評価を行った。その結果、触媒活性は、１−メチルナフタレンの分解率が６６．７％程度、水素増幅率は１．６と中程度の触媒活性であった。
[Comparative Example 3]
In the same manner as in Example 1, a nickel and magnesium precipitate was prepared, filtered, washed and dried, and then fired at 950 ° C. in air to obtain a nickel and magnesia compound. Thereafter, the alumina powder was weighed to 50% by mass, and both were physically mixed using a mortar. After the mixture was molded and fired by the same experimental method as in Example 1, No. 2 in Table 2 was obtained. The activity was evaluated under the same conditions as in No. 11. As a result, the catalytic activity was such that the decomposition rate of 1-methylnaphthalene was about 66.7%, and the hydrogen amplification rate was 1.6, which was an intermediate level.
［比較例４］
非特許文献１や特許文献８等で開示されている要領で、ニッケル、マグネシウム、及び、アルミナを含んだ水溶液から、沈殿剤により沈殿物を作成、焼成する製法で調製した。すなわち、硝酸ニッケル、硝酸マグネシウム、及び、硝酸アルミニウムを、ニッケルとマグネシウムの金属元素のモル比が、実施例１と同じく、１：９になるようにし、アルミナとして５０質量％になるように計算して精秤した後、６０℃の純水に混合して、混合溶液を調製したものに、実施例１と同様に、６０℃に加温した炭酸カリウム水溶液を加え、スターラーで十分に攪拌した。
[Comparative Example 4]
In the manner disclosed in Non-Patent Document 1, Patent Document 8 and the like, a precipitate was prepared from an aqueous solution containing nickel, magnesium, and alumina using a precipitating agent, and prepared by a method of firing. That is, nickel nitrate, magnesium nitrate, and aluminum nitrate were calculated so that the molar ratio of the metal element of nickel and magnesium was 1: 9 as in Example 1, and 50% by mass as alumina. After precisely weighing, the mixture was mixed with pure water at 60 ° C. to prepare a mixed solution. As in Example 1, an aqueous potassium carbonate solution heated to 60 ° C. was added, 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した。次いで、この沈殿物を蒸発皿に移して、１２０℃で乾燥、乳鉢で粉砕後、粉末を圧縮製計器を用いて、実施例１と同様に、プレス成型し、錠剤成型体を得た。その成型体を空気中９５０℃で焼成を行って触媒成型体を調製した。 Thereafter, with the temperature kept at 60 ° C., the mixture was aged for a certain period of time, and then subjected to suction filtration and sufficiently washed with pure water at 80 ° C. Next, the precipitate was transferred to an evaporating dish, dried at 120 ° C., pulverized in a mortar, and the powder was press-molded in the same manner as in Example 1 using a compression meter to obtain a tablet molded body. The molded body was fired in air at 950 ° C. to prepare a catalyst molded body.
調製した触媒成型体を用いて、表２のＮｏ．１１と同じ条件で活性評価を行った。その結果、触媒活性はメチルナフタレンの分解率が６２．６％程度（うち、炭素析出率が１９．９％）、水素増幅率は１．６と中程度の触媒活性しか示さず、炭素析出量が非常に多いことが判明した。 Using the prepared catalyst molded body, no. The activity was evaluated under the same conditions as in No. 11. As a result, the catalytic activity was about 62.6% of the decomposition rate of methylnaphthalene (of which the carbon deposition rate was 19.9%), and the hydrogen amplification rate was only 1.6 with a moderate catalytic activity. It turns out that there are very many.
［比較例５］
特許文献２０で開示されている方法で、ＬａＦｅＯ3、ＬａＣｏＯ3、Ｒｈ／ＬａＡｌＯ3、Ｎｉ／ＬａＦｅＯ3を調製した。これを用いて、表２のＮｏ．１１と同じ条件で活性評価を行った。その結果を、表７に各々Ｎｏ．２９、Ｎｏ．３０、Ｎｏ．３１、Ｎｏ．３２で示す。
[Comparative Example 5]
LaFeO 3 , LaCoO 3 , Rh / LaAlO 3 , and Ni / LaFeO 3 were prepared by the method disclosed in Patent Document 20. Using this, no. The activity was evaluated under the same conditions as in No. 11. The results are shown in Table 7. 29, no. 30, no. 31, no. 32.
表７のＮｏ．２９、３０に示すように、Ｎｉを含まず、単にペロブスカイト型構造を有する酸化物を触媒に用いるだけでは、タール分解がほとんど起こらないことが分かる。また、メタン等の低級炭化水素に対する水蒸気改質活性を有するＲｈを担持したＮｉを含まないペロブスカイト型酸化物のＮｏ．３１では、ごくわずかに分解しているにとどまった。 No. in Table 7 29 and 30, it can be seen that tar decomposition hardly occurs when an oxide that does not contain Ni and has a perovskite structure is used as a catalyst. In addition, perovskite oxide No. 1 containing Ni containing Rh and having steam reforming activity for lower hydrocarbons such as methane. At 31 it was only slightly disassembled.
同様に水蒸気改質活性を示すＮｉを担持したＮｉを含まないペロブスカイト型酸化物のＮｏ．３２では、Ｎｉを担持した後８５０℃で焼成しているため、一部ＬａＦｅＯ3のペロブスカイト型構造に固溶すると予想され、タール分解活性も中程度発現した。しかし、担持したＮｉすべてがペロブスカイト型構造に固溶していないため、触媒表面に形成するＮｉ粒のほとんどが担持Ｎｉから形成されるために粗大なものが多くなってしまう。その結果、タール分解活性に劣り、かつ、炭素析出量も非常に多くなった。 Similarly, perovskite oxide No. 1 containing Ni and supporting steam-reforming activity and not containing Ni. In No. 32, since Ni was supported and baked at 850 ° C., it was expected to partially dissolve in the perovskite structure of LaFeO 3 , and tar decomposition activity was also moderately expressed. However, since all of the supported Ni is not dissolved in the perovskite structure, most of the Ni particles formed on the catalyst surface are formed from the supported Ni, so that coarse particles increase. As a result, the tar decomposition activity was inferior, and the amount of carbon deposition was very large.
本発明によれば、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。さらに、タール含有ガスの改質後、水蒸気又は空気の少なくともいずれかを反応後の触媒に接触させることにより、触媒を再生させて、この再生触媒を再度タール含有ガスの改質に使用することができ、触媒性能の劣化を抑えながら、長期に安定した運転が可能となる。したがって、特に鉄鋼業において従来は利用されていなかった熱源が利用できるようになり、産業上の利用可能性は大きい。 According to the present invention, tar-containing gas generated when coal or biomass is pyrolyzed can be stably converted into light chemical substances such as carbon monoxide and hydrogen. Furthermore, after reforming the tar-containing gas, it is possible to regenerate the catalyst by contacting at least one of water vapor or air with the catalyst after the reaction, and use the regenerated catalyst again for reforming the tar-containing gas. This enables stable operation over a long period of time while suppressing deterioration of catalyst performance. Therefore, heat sources that have not been used in the steel industry in particular can be used, and industrial applicability is great.
１ 上昇管
２ 安水（アンモニア水）
３ コークス炉
４ ドライメーン
1 Ascending
3 Coke oven 4 Dry main
Claims (11)
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は、Ｌａ、Ｃｅ、Ｃａ、Ｓｒ、Ｂａの少なくとも１種から選ばれる金属元素であり、
Ｂは、Ｃｏ、Ｆｅ、Ｔｉ、Ｚｒ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｒｅ、Ｗの少なくとも１種から選ばれる金属元素であり（但し、ＬａＮｉxＦｅ1-xＯ3を除く）、
ｘは、０．１≦ｘ≦１を満たし、
複合酸化物の単位格子は、ペロブスカイト型構造である
ことを特徴とするタール含有ガスの改質用触媒。 Anix x B 1-x O 3
A catalyst for reforming a tar-containing gas that is a composite oxide represented by:
A is a metal element selected from at least one of La, Ce, Ca, Sr, and Ba,
B (except where the LaNi x Fe 1-x O 3 ) Co, Fe, Ti, Zr, V, Nb, Ta, Cr, Mo, Re, a metal element selected from at least one of W,
x satisfies 0.1 ≦ x ≦ 1,
A catalyst for reforming a tar-containing gas, wherein the unit cell of the composite oxide has a perovskite structure.
ニッケル化合物と請求項１に記載のタール含有ガス改質用触媒を構成するニッケル以外の金属の化合物とを含む混合溶液に、沈殿剤を添加して、ニッケルと該ニッケル以外の金属を共沈させて沈殿物を生成し、該沈殿物を乾燥及び焼成して、ニッケルと該ニッケル以外の金属を含むペロブスカイト型酸化物からなる触媒を製造することを特徴とするタール含有ガスの改質に用いられる触媒の製造方法。 A method for producing a tar-containing gas reforming catalyst according to claim 1,
A precipitating agent is added to a mixed solution containing a nickel compound and a compound of a metal other than nickel constituting the tar-containing gas reforming catalyst according to claim 1 to coprecipitate nickel and a metal other than the nickel. To produce a precipitate, and drying and calcining the precipitate to produce a catalyst comprising nickel and a perovskite oxide containing a metal other than nickel. A method for producing a catalyst.
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