JP2008238012A - Tar decomposition catalyst - Google Patents
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- JP2008238012A JP2008238012A JP2007080372A JP2007080372A JP2008238012A JP 2008238012 A JP2008238012 A JP 2008238012A JP 2007080372 A JP2007080372 A JP 2007080372A JP 2007080372 A JP2007080372 A JP 2007080372A JP 2008238012 A JP2008238012 A JP 2008238012A
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- 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
Abstract
Description
本発明は、タール分解触媒に関し、より具体的にはバイオマスを熱分解してガス化する際に発生し、そのガス化ガス中に含まれるタール分を分解、除去するためのタール分解触媒に関する。 The present invention relates to a tar cracking catalyst, and more specifically to a tar cracking catalyst that is generated when pyrolyzing biomass to gasify and decomposes and removes a tar content contained in the gasified gas.
バイオマスのガス化は、通常無触媒で、ガス化温度を１０００℃以上の高温にして行われる。その条件は含水率等の如何により異なるが、そのうち低含水率のバイオマスのガス化の場合には、基本的には比較的低圧（常圧〜１.５気圧）、高温（８００〜１０００℃）で行われる。また、そのガス化に際してドロマイト〔ＣａＭｇ（ＣＯ3）2〕、アルミナあるいはゼオライト（ＺＳＭ−５）を用いた触媒を使用する場合もあるが、この場合の触媒機能はガス化で発生したタールの除去が中心である。 Biomass gasification is usually carried out without a catalyst and at a gasification temperature of 1000 ° C. or higher. The conditions vary depending on the moisture content, etc., but in the case of gasification of biomass with a low moisture content, basically, a relatively low pressure (normal pressure to 1.5 atm) and a high temperature (800 to 1000 ° C.) Done in In some cases, a catalyst using dolomite [CaMg (CO 3 ) 2 ], alumina or zeolite (ZSM-5) is used for the gasification. In this case, the catalytic function is removal of tar generated by gasification. Is the center.
このほか、低温でのガス化効率を上げるために低温化が指向されており、このため触媒を用いたガス化も開発されている。例えば、特開２００３−２４６９９０号公報（以下「９９０号公報」と言う）には、バイオマスのガス化方法に関し、Ｒｈ/ＣｅＯ2/Ｍ（Ｍは、ＳｉＯ2、Ａｌ2Ｏ3またはＺｒＯ2である）で表される触媒が収容された流動床反応器を、８００℃未満に加熱する工程と、前記流動床反応器の上部からバイオマス粒子を導入する工程と、前記流動床反応器の下部から空気および水蒸気を導入する工程と、前記バイオマス粒子を前記Ｒｈ/ＣｅＯ2/Ｍ触媒表面と反応させることにより、水素および合成ガスを製造する工程とを具備するものである。 In addition, in order to increase the gasification efficiency at low temperature, low temperature is directed and gasification using a catalyst has also been developed. For example, Japanese Patent Application Laid-Open No. 2003-246990 (hereinafter referred to as “990 Publication”) relates to a biomass gasification method, wherein Rh / CeO 2 / M (M is SiO 2 , Al 2 O 3 or ZrO 2) . A fluidized bed reactor containing the catalyst represented by (A) is heated to less than 800 ° C., a step of introducing biomass particles from the upper part of the fluidized bed reactor, and a lower part of the fluidized bed reactor. A step of introducing air and water vapor, and a step of producing hydrogen and synthesis gas by reacting the biomass particles with the surface of the Rh / CeO 2 / M catalyst.
そして、９９０号公報の技術における触媒：Ｒｈ/ＣｅＯ2/Ｍは、バイオマスガス化用触媒であり、バイオマスのガス化に寄与し、通常では実現できないガス化率１００％を得ることが可能になったとされている。 The catalyst: Rh / CeO 2 / M in the technology of No. 990 is a biomass gasification catalyst, which contributes to the gasification of biomass and can achieve a gasification rate of 100% that cannot be realized normally. It is said that
しかし、触媒を用いるそれらの技術においては、バイオマスをガス化する際に発生するタールを分解、除去することができるが、触媒表面上への炭素析出による触媒活性の失活などの問題がある。また、Ｒｈ/ＣｅＯ2/ＭではＣｅＯ2の効果により比較的、耐炭素析出性に優れているものの、バイオマスのガス化ガス中のような還元雰囲気ではＣｅＯ2の酸素が全て抜けてしまった時点で、その効果は消滅してしまう。そのため、従来の技術では実用に足る充分な耐久性能が得られていない。 However, these techniques using a catalyst can decompose and remove tar generated when gasifying biomass, but there are problems such as deactivation of catalytic activity due to carbon deposition on the catalyst surface. Point addition, relatively the Rh / CeO 2 / M In CeO 2 effects, although excellent in耐炭containing deposition properties, the oxygen of CeO 2 has gone missing all in a reducing atmosphere such as in the biomass gasification gas And the effect disappears. Therefore, sufficient durability performance sufficient for practical use cannot be obtained with the conventional technology.
本発明者らは、上記観点、すなわちバイオマスのガス化ガス中のような還元雰囲気で、タール分解性能、耐炭素析出性能の両性能ともに満たす触媒について各種実験、検討したところ、（ａ）ペロブスカイト型複合酸化物からなる物質、また（ｂ）ペロブスカイト型複合酸化物に触媒金属を担持した物質が、それらの性能を満たす触媒として有効であることを見い出した。 The inventors of the present invention conducted various experiments and studies on a catalyst that satisfies both the tar decomposition performance and the carbon deposition resistance performance in a reducing atmosphere such as in a gasification gas of biomass. (A) Perovskite type It has been found that a substance comprising a composite oxide and (b) a substance in which a catalytic metal is supported on a perovskite type composite oxide are effective as a catalyst satisfying these performances.
すなわち、本発明は、バイオマスをガス化したガス中のタール分の分解、除去用として優れた触媒活性を有し且つ優れた耐久性を備えたタール分解触媒を提供することを目的とするものである。 That is, the present invention aims to provide a tar cracking catalyst having excellent catalytic activity and excellent durability for the decomposition and removal of tar content in gas obtained by gasifying biomass. is there.
本発明は、（１）バイオマスを熱分解する際に発生するガス中のタールを分解するための触媒である。そして、当該触媒が式：ＡＢＯ3（式中、ＡはＬａ、Ｂａ、Ｓｒ、Ｃａであり、ＢはＴｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ａｌ、Ｚｒ、Ｎｂ、Ａｌ、ＳｎまたはＣｅである）で表されるペロブスカイト型複合酸化物からなることを特徴とする。 The present invention is (1) a catalyst for decomposing tar in gas generated when pyrolyzing biomass. The catalyst is represented by the formula: ABO 3 (wherein A is La, Ba, Sr, Ca, and B is Ti, Cr, Mn, Fe, Co, Ni, Al, Zr, Nb, Al, Sn, or Ce). It is characterized by comprising a perovskite complex oxide represented by
本発明は、（２）バイオマスを熱分解する際に発生するガス中のタールを分解するための触媒である。そして、当該触媒が式：Ｍ／ＡＢＯ3（式中、ＡはＬａ、Ｂａ、Ｓｒ、Ｃａであり、ＢはＴｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ａｌ、Ｚｒ、Ｎｂ、Ａｌ、ＳｎまたはＣｅであり、ＭはＯｓ、Ｉｒ、Ｐｔ、Ｒｕ、Ｒｈ、Ｐｄ、Ｆｅ、ＮｉまたはＣｏの１種または２種以上の金属である）で表されるペロブスカイト型複合酸化物に触媒金属を担持してなることを特徴とする。 The present invention is (2) a catalyst for decomposing tar in gas generated when pyrolyzing biomass. The catalyst is represented by the formula: M / ABO 3 (wherein A is La, Ba, Sr, Ca, and B is Ti, Cr, Mn, Fe, Co, Ni, Al, Zr, Nb, Al, Sn). Or a catalyst metal supported on a perovskite-type composite oxide represented by Os, Ir, Pt, Ru, Rh, Pd, Fe, Ni, or Co) It is characterized by.
本発明は、バイオマスを熱分解する際に発生するガス中のタールを分解するための触媒である。そして、タール分解触媒が（ａ）式：ＡＢＯ3（式中、ＡはＬａ、Ｃａ、Ｓｒ、Ｂａであり、ＢはＴｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ａｌ、Ｚｒ、Ｎｂ、Ａｌ、ＳｎまたはＣｅである）で表されるペロブスカイト型複合酸化物からなるタール分解触媒、及び、（ｂ）式：Ｍ／ＡＢＯ3（式中、ＡはＬａ、Ｃａ、Ｓｒ、Ｂａであり、ＢはＴｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ａｌ、Ｚｒ、Ｎｂ、Ａｌ、ＳｎまたはＣｅであり、ＭはＯｓ、Ｉｒ、Ｐｔ、Ｒｕ、Ｒｈ、Ｐｄ、Ｆｅ、ＮｉまたはＣｏの１種または２種以上の触媒金属である）で表されるペロブスカイト型複合酸化物に触媒金属を担持してなるタール分解触媒である。 The present invention is a catalyst for decomposing tar in gas generated when pyrolyzing biomass. The tar decomposition catalyst is represented by the formula (a): ABO 3 (wherein A is La, Ca, Sr, Ba, and B is Ti, Cr, Mn, Fe, Co, Ni, Al, Zr, Nb, Al) And a tar decomposition catalyst composed of a perovskite complex oxide represented by the formula: M / ABO 3 (wherein A is La, Ca, Sr, Ba, B Is Ti, Cr, Mn, Fe, Co, Ni, Al, Zr, Nb, Al, Sn or Ce, and M is one of Os, Ir, Pt, Ru, Rh, Pd, Fe, Ni or Co or A tar decomposition catalyst obtained by supporting a catalyst metal on a perovskite complex oxide represented by (2 or more kinds of catalyst metals).
バイオマスのガス化ガス中にはタール分が含まれている。その主成分はトルエン、ナフタレン、フェナントレンその他の芳香族化合物であるが、本発明のタール分解触媒によりそれら何れのタール成分も炭素の析出無しに乃至炭素の析出をより少なくして分解することができる。 The biomass gasification gas contains tar content. The main components are toluene, naphthalene, phenanthrene and other aromatic compounds, but the tar decomposition catalyst of the present invention can decompose any of these tar components without carbon deposition or with less carbon deposition. .
本発明に係るタール分解触媒を構成するペロブスカイト型複合酸化物は、例えば共沈法などにより製造される。本発明のペロブスカイト型複合酸化物からなるタール分解触媒は、それ自体タール分解触媒として有効であるが、金属触媒を担持することによりその性能をさらに向上させることができる。 The perovskite type complex oxide constituting the tar decomposition catalyst according to the present invention is produced, for example, by a coprecipitation method or the like. The tar decomposition catalyst comprising the perovskite complex oxide of the present invention is effective as a tar decomposition catalyst by itself, but its performance can be further improved by supporting a metal catalyst.
ペロブスカイト型複合酸化物に担持する金属触媒としてはＯｓ、Ｉｒ、Ｐｔ、Ｒｕ、Ｒｈ、Ｐｄ、Ｆｅ、ＮｉまたはＣｏが用いられ、それらの金属から選ばれた１種または２種以上の金属をペロブスカイト型複合酸化物に担持することによりタール分解触媒とする。その担持には例えば含浸法などが適用できる。 As the metal catalyst supported on the perovskite complex oxide, Os, Ir, Pt, Ru, Rh, Pd, Fe, Ni, or Co is used, and one or more metals selected from these metals are perovskite. A tar decomposition catalyst is supported by supporting the composite oxide. For example, an impregnation method can be applied to the support.
ペロブスカイト型構造を持つ複合酸化物は、例えば特開平１０−１９７７０３号公報のように、低級炭化水素（特にメタン）と二酸化炭素と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によるペロブスカイト構造を有する複合酸化物を用いるものや、例えば特開２００６−３５１５３公報のように、排ガス浄化用触媒などの酸化雰囲気で使用されることが一般的であり、例外はあるが（特開２００５−２５４０７６号公報）、バイオマスのガス化ガス中のような還元雰囲気では殆ど使用されていない。 A composite oxide having a perovskite structure is composed of an alkaline earth metal and titanium as a catalyst for producing synthesis gas by an oxidation reaction of lower hydrocarbons (particularly methane) and carbon dioxide, as disclosed in, for example, JP-A-10-197703. It is common to use a complex oxide having a perovskite structure or an oxidizing atmosphere such as a catalyst for exhaust gas purification as disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-35153, with exceptions (Japanese Patent Application Laid-Open No. 2005-2005). No. 254076), it is hardly used in a reducing atmosphere such as in the gasification gas of biomass.
これに対して、本発明のペロブスカイト型複合酸化物からなるタール分解触媒、及びペロブスカイト型複合酸化物に触媒金属を担持してなるタール分解触媒は、バイオマスのガス化ガスという還元雰囲気中で当該ガス中のタール分を分解することができる。 In contrast, the tar cracking catalyst comprising the perovskite complex oxide of the present invention and the tar cracking catalyst having a catalyst metal supported on the perovskite complex oxide are produced in a reducing atmosphere called biomass gasification gas. The tar content can be decomposed.
本発明のタール分解触媒の使用形態としては粉末状、粒状、顆粒状（含：球状）、ペレット状、タブレット状（＝錠剤状）、或いはハニカム体（＝モノリス体）等適宜の形状として使用することができる。なお、このタール分解触媒には、これらにバイオマスのガス化ガスを通す必要があるため、粉末状の場合には、これを充填した触媒層から逸散しないように所定粒度範囲に整粒するか又は造粒し、或いは加圧成形や押出成形により成形して用いるのが望ましい。このうち押出成形の場合には適宜所定長さに切断してペレット化して使用される。 The tar decomposition catalyst of the present invention is used in an appropriate shape such as powder, granule, granule (including sphere), pellet, tablet (= tablet), or honeycomb (= monolith). be able to. In addition, since it is necessary to pass the gasification gas of biomass through these tar decomposition catalysts, in the case of a powder form, is it sized within a predetermined particle size range so as not to dissipate from the catalyst layer filled with this? Alternatively, it is desirable to granulate, or to use by molding by pressure molding or extrusion molding. Among these, in the case of extrusion molding, it is cut into a predetermined length and pelletized.
ハニカム体の場合には、ハニカム構造の基材にタール分解触媒を担持する。その担持は、例えばウォッシュコート法によりタール分解触媒の粉末状スラリーをハニカム基材に担持し、常法により乾燥し、焼成する。ハニカム構造の基材としてはセラミック製又はメタル製のものを使用することができる。セラミックの好ましい例としてはコージェライトが挙げられ、メタルの好ましい例としてはステンレス鋼や鉄−アルミニウム−クロム系合金などが挙げられる。 In the case of a honeycomb body, a tar decomposition catalyst is supported on a substrate having a honeycomb structure. For example, the powdery slurry of the tar decomposition catalyst is supported on the honeycomb substrate by, for example, a wash coat method, dried by a conventional method, and fired. As the substrate having a honeycomb structure, a ceramic or metal substrate can be used. A preferred example of the ceramic is cordierite, and a preferred example of the metal is stainless steel or iron-aluminum-chromium alloy.
本発明のタール分解触媒は、バイオマスのガス化ガス、すなわち動植物や動植物を起源とする廃棄物の熱分解によるガス化により得られるガス化ガス中に含まれるタール分を分解する触媒として使用される。この場合、そのガス化ガス自体、１種の合成ガスであり、またタール分の主成分は、芳香族化合物つまり炭化水素であるので、その分解によりガス化することで合成ガスの成分として除去される。 The tar decomposition catalyst of the present invention is used as a catalyst for decomposing a tar content contained in a gasification gas of biomass, that is, a gasification gas obtained by thermal decomposition of wastes originating from animals and plants or animals and plants. . In this case, the gasification gas itself is a kind of synthesis gas, and the main component of the tar is an aromatic compound, that is, a hydrocarbon, so that it is removed as a component of the synthesis gas by gasification by the decomposition. The
また、本発明のタール分解触媒は、バイオマスのガス化ガス中に硫化水素などの硫黄化合物が含まれていても耐性を有している。このため、例えば下水汚泥その他、各種水処理設備で生成する汚泥のガス化ガスのように、硫化水素などの硫黄化合物を含むガス化ガス中のタール分解用としても有効である。触媒は硫黄化合物により被毒する場合が多いが、本発明のタール分解触媒は、硫黄化合物による被毒が無いので、特異な特性と言える。 In addition, the tar decomposition catalyst of the present invention has resistance even when a sulfur compound such as hydrogen sulfide is contained in the biomass gasification gas. For this reason, it is also effective for tar decomposition in gasification gas containing sulfur compounds such as hydrogen sulfide, such as sewage sludge and other gasification gas of sludge generated in various water treatment facilities. The catalyst is often poisoned by a sulfur compound, but the tar decomposition catalyst of the present invention is unique because it is not poisoned by the sulfur compound.
下水汚泥などの汚泥を熱分解（通常、無触媒熱分解）する際の熱分解炉出口のガス化ガス温度は９００℃以上である。そのガス化ガス中のタール分を分解するには、図１に示すように、そのガス化ガスをパイプにより導出し、タール分解装置すなわちタール分解触媒充填装置に通して処理することになる。このため、タール分解装置での処理温度は、熱分解炉出口温度：９００℃より低下しているので、タール分解触媒はそのように低下した温度で有効である必要があるが、本発明のタール分解触媒は９００〜７００℃、特に８５０〜７５０℃という温度で高いタール分解性能、耐炭素析出性能を有する。 The gasification gas temperature at the outlet of the pyrolysis furnace when pyrolyzing sludge such as sewage sludge (usually non-catalytic pyrolysis) is 900 ° C. or higher. In order to decompose the tar content in the gasified gas, as shown in FIG. 1, the gasified gas is led out through a pipe and processed through a tar decomposition apparatus, that is, a tar decomposition catalyst filling apparatus. For this reason, since the treatment temperature in the tar decomposition apparatus is lower than the pyrolysis furnace outlet temperature: 900 ° C., the tar decomposition catalyst needs to be effective at such a reduced temperature. The cracking catalyst has high tar decomposition performance and carbon deposition resistance at a temperature of 900 to 700 ° C, particularly 850 to 750 ° C.
なお、図１中、１はガス化炉（バイオマスの無触媒熱分解炉）、２、４はガス化ガス導出用パイプ、３は集塵機、５はタール分解装置、６はタール分解装置５に充填したタール分解触媒である。集塵機３は必要に応じて配置される。
In FIG. 1, 1 is a gasification furnace (biocatalytic non-catalytic pyrolysis furnace), 2, 4 is a gasification gas outlet pipe, 3 is a dust collector, 5 is a tar decomposition apparatus, and 6 is filled in a
以下、実施例に基づき本発明をさらに詳しく説明するが、本発明が実施例に限定されないことはもちろんである。本実施例では、各供試触媒を下記のとおりに調製し、各供試触媒に対する性能試験を実施した。 EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, it cannot be overemphasized that this invention is not limited to an Example. In this example, each test catalyst was prepared as follows, and a performance test was performed on each test catalyst.
〈触媒の調製１〉
（１）ペロブスカイト型複合酸化物：ＬａＡｌＯ3の調製
（ａ）原料として硝酸ランタン：Ｌａ（ＮＯ3）3・６Ｈ2Ｏと硝酸アルミニウム：Ａｌ（ＮＯ3）3・９Ｈ2Ｏを用いた。両原料をＬａ（ＮＯ3）3：Ａｌ（ＮＯ3）3のモル比＝１となるように秤量、混合し、５０℃の温水に溶解した。
（ｂ） （ａ）で得た水溶液を、８０℃に加温し、ロータリーエバポレータにより、５０〜２０ｍｍＨｇの減圧下、蒸発、乾燥した。
（ｃ） （ｂ）で得た乾燥物を乾燥器中、１０５℃で２時間、次いで４００℃で５時間、さらに３００℃で１５時間乾燥した。
（ｄ） （ｃ）で得た乾燥物を電気炉中で焼成してペロブスカイト型複合酸化物：ＬａＡｌＯ3を得た。焼成条件は、５℃/ｍｉｎの速度で昇温し、２７０℃に３時間保持した後、１℃/ｍｉｎの速度で昇温し、４００℃に３時間保持した後、さらに１℃/ｍｉｎの速度で昇温し、８５０℃に１０時間保持した後、自然冷却により冷却した。
<Preparation of
(1) Preparation of perovskite complex oxide: LaAlO 3 (a) Lanthanum nitrate: La (NO 3 ) 3 .6H 2 O and aluminum nitrate: Al (NO 3 ) 3 .9H 2 O were used as raw materials. Both raw materials were weighed and mixed so that the molar ratio of La (NO 3 ) 3 : Al (NO 3 ) 3 = 1 and dissolved in hot water at 50 ° C.
(B) The aqueous solution obtained in (a) was heated to 80 ° C., and evaporated and dried by a rotary evaporator under a reduced pressure of 50 to 20 mmHg.
(C) The dried product obtained in (b) was dried in a dryer at 105 ° C. for 2 hours, then at 400 ° C. for 5 hours, and further at 300 ° C. for 15 hours.
(D) The dried product obtained in (c) was baked in an electric furnace to obtain a perovskite complex oxide: LaAlO 3 . The firing conditions were as follows: the temperature was raised at a rate of 5 ° C./min, held at 270 ° C. for 3 hours, then heated at a rate of 1 ° C./min, held at 400 ° C. for 3 hours, and further at 1 ° C./min. The temperature was increased at a rate and maintained at 850 ° C. for 10 hours, and then cooled by natural cooling.
（２）ペロブスカイト型複合酸化物：ＬａＦｅＯ3の調製
上記（１）のＬａＡｌＯ3の調製における原料のうち硝酸アルミニウムを硝酸鉄：Ｆｅ（ＮＯ3）3・９Ｈ2Ｏに替えた以外は、上記（１）と同様にして、ペロブスカイト型複合酸化物：ＬａＦｅＯ3を得た。
(2) Preparation of perovskite complex oxide: LaFeO 3 Above (1) except that aluminum nitrate is replaced with iron nitrate: Fe (NO 3 ) 3 · 9H 2 O in the raw material for the preparation of LaAlO 3 In the same manner as in 1), a perovskite complex oxide: LaFeO 3 was obtained.
（３）ペロブスカイト型複合酸化物：ＬａＣｏＯ3の調製
上記（１）のＬａＡｌＯ3の調製における原料のうち硝酸アルミニウムを硝酸コバルト：Ｃｏ（ＮＯ3）3・６Ｈ2Ｏに替えた以外は、上記（１）と同様にして、ペロブスカイト型複合酸化物：ＬａＣｏＯ3を得た。
(3) Preparation of Perovskite Complex Oxide: LaCoO 3 Above (1) except that aluminum nitrate was replaced with cobalt nitrate: Co (NO 3 ) 3 · 6H 2 O among the raw materials in the preparation of LaAlO 3 In the same manner as in 1), a perovskite complex oxide: LaCoO 3 was obtained.
以上（１）−（３）で得たペロブスカイト型複合酸化物：ＬａＡｌＯ3、ＬａＦｅＯ3、ＬａＣｏＯ3は、後述のとおり、いずれもそれ自体でタール分解触媒として有効であるのに加え、金属触媒の担体としても有効である。 The perovskite complex oxides obtained in the above (1) to (3): LaAlO 3 , LaFeO 3 , and LaCoO 3 are all effective as a tar decomposition catalyst by themselves as described later. It is also effective as a carrier.
〈触媒の調製２：金属触媒担持−含浸法−〉
（ａ）原料金属硝酸塩Ｒｈ（ＮＯ3）3、Ｎｉ（ＮＯ3）2を、それぞれ５０℃の温水に溶解し、各金属塩の水溶液を得た。
（ｂ）Ｒｈ（ＮＯ3）3、Ｎｉ（ＮＯ3）2の各金属塩水溶液にそれぞれ〈触媒の調製１〉と同様にして調製した各担体を混合し、１．５時間攪拌した。
（ｃ）５０℃、５０〜３０ｍｍＨｇの減圧下、ロータリーエバポレータにより、蒸発、乾燥した。
（ｄ） （ｃ）で得た乾燥物を乾燥器中、１０５℃で１.５時間、次いで１７５℃で６時間、さらに２７５℃で１２時間乾燥した。
（ｅ） （ｄ）で得た乾燥物を電気炉中で焼成した。焼成条件は、５℃/ｍｉｎの速度で昇温し、２７０℃に３時間保持した後、１℃/ｍｉｎの速度で昇温し、８５０℃に５時間保持した後、自然冷却により冷却した。
（ｆ） （ｅ）で得た焼成物、すなわち触媒粉末を打錠成型器で成型し（圧力５００ｋｇ/ｃｍ2）、３５５〜７１０μｍに整粒（分粒）した。
<Catalyst Preparation 2: Metal Catalyst Support-Impregnation Method->
(A) Raw material metal nitrates Rh (NO 3 ) 3 and Ni (NO 3 ) 2 were each dissolved in hot water at 50 ° C. to obtain an aqueous solution of each metal salt.
(B) Each support prepared in the same manner as in <
(C) It evaporated and dried with the rotary evaporator under the reduced pressure of 50 degreeC and 50-30 mmHg.
(D) The dried product obtained in (c) was dried in a dryer at 105 ° C. for 1.5 hours, then at 175 ° C. for 6 hours, and further at 275 ° C. for 12 hours.
(E) The dried product obtained in (d) was fired in an electric furnace. As firing conditions, the temperature was raised at a rate of 5 ° C./min, held at 270 ° C. for 3 hours, then raised at a rate of 1 ° C./min, held at 850 ° C. for 5 hours, and then cooled by natural cooling.
(F) The fired product obtained in (e), that is, the catalyst powder, was molded with a tableting machine (pressure 500 kg / cm 2 ) and sized (sized) to 355 to 710 μm.
〈触媒の調製３：各種触媒の調製〉
以上のほか、Ｎｉ/Ａｌ2Ｏ3（Ｎｉ：１ｗｔ％）、Ｎｉ/Ａｌ2Ｏ3−ＣｅＯ2（Ｎｉ：１ｗｔ％）、Ｒｈ/Ａｌ2Ｏ3（Ｒｈ：０．１ｗｔ％）、Ｒｈ/ＳｉＯ2/ＣｅＯ2（Ｒｈ：０．１ｗｔ％）を調製した。このうちＮｉ/Ａｌ2Ｏ3（Ｎｉ：１ｗｔ％）、Ｎｉ/Ａｌ2Ｏ3−ＣｅＯ2（Ｎｉ：１ｗｔ％）はそれぞれ、担体としてのＡｌ2Ｏ3（アルミナ）及びＡｌ2Ｏ3−ＣｅＯ2（アルミナ−セリア）に含浸法によりＮｉを担持することで調製し、Ｒｈ/Ａｌ2Ｏ3はＡｌ2Ｏ3（アルミナ）に含浸法によりＲｈを担持することで調製した。括弧内の数値は各担体に対する担持量である。また、Ｒｈ/ＳｉＯ2/ＣｅＯ2は、前述９９０号公報の００１４段落に記載の方法に準じて調製した。
<Catalyst preparation 3: Preparation of various catalysts>
In addition to the above, Ni / Al 2 O 3 (Ni: 1 wt%), Ni / Al 2 O 3 —CeO 2 (Ni: 1 wt%), Rh / Al 2 O 3 (Rh: 0.1 wt%), Rh / SiO 2 / CeO 2 (Rh: 0.1 wt%) was prepared. Of these, Ni / Al 2 O 3 (Ni: 1 wt%) and Ni / Al 2 O 3 —CeO 2 (Ni: 1 wt%) are Al 2 O 3 (alumina) and Al 2 O 3 —CeO as supports, respectively. 2 (alumina-ceria) was prepared by supporting Ni by an impregnation method, and Rh / Al 2 O 3 was prepared by supporting Rh on Al 2 O 3 (alumina) by an impregnation method. The numerical value in the parenthesis is the loading amount for each carrier. Rh / SiO 2 / CeO 2 was prepared according to the method described in paragraph 0014 of the aforementioned 990 publication.
〈タール分解性能評価試験及び炭素析出量分析−その１−〉
〈試験条件〉
固定床流通型反応装置（管型流通式）を用いてタール分解性能を評価し、炭素析出量分析を実施した。図２に試験装置の概略を示している。試験条件は以下のとおりである。
反応温度＝８５０℃、空間速度（ＳＶ）＝３０００ｈ-1（全流量２５０ｍＬ/ｍｉｎ）、触媒体積＝５.０ｃｍ3、触媒重量＝３.０ｇ。
試験ガス＝ＣＯ：８％（ドライベース、容量％、以下同じ）、Ｈ2＝８％、ＣＯ2＝１４％、ＣＨ4＝２．５％、Ｈ2Ｓ＝２０００ｐｐｍ、Ｈ2Ｏ＝２０％、タール（トルエン）＝８０００ｐｐｍ、Ｎ2＝バランス。
<Tar decomposition performance evaluation test and carbon deposition amount analysis-1->
<Test conditions>
Tar decomposition performance was evaluated using a fixed bed flow type reactor (tube type flow type), and a carbon deposition amount analysis was performed. FIG. 2 shows an outline of the test apparatus. The test conditions are as follows.
Reaction temperature = 850 ° C., space velocity (SV) = 3000 h −1 (total flow rate 250 mL / min), catalyst volume = 5.0 cm 3 , catalyst weight = 3.0 g.
Test gas = CO: 8% (dry base, volume%, the same applies hereinafter), H 2 = 8%, CO 2 = 14%, CH 4 = 2.5%, H 2 S = 2000 ppm, H 2 O = 20% , Tar (toluene) = 8000 ppm, N 2 = balance.
〈タール分解性能評価試験の結果〉
図３は本タール分解性能評価試験の結果である。ここで、タール分解除去率（％）は下記式により求めた。式中“排出ガス中のタール濃度”は、試験装置である固定床流通型反応装置（管型流通式）出口のガスをＧＣ分析つまりガスクロマトグラフィー（ＴＣＤ，ＦＩＤ：ヤナコ分析工業社製）により測定したタール濃度である。
<Results of tar decomposition performance evaluation test>
FIG. 3 shows the results of the tar decomposition performance evaluation test. Here, the tar decomposition removal rate (%) was determined by the following formula. In the formula, the “tar concentration in the exhaust gas” is determined by GC analysis, that is, gas chromatography (TCD, FID: manufactured by Yanaco Analytical Industries) of the gas at the outlet of the fixed bed flow type reactor (tube type flow type) as a test device. The measured tar concentration.
図３のとおり、Ｒｈ/ＳｉＯ2/ＣｅＯ2（Ｒｈ：０．１ｗｔ％）のタール分解除去率は、試験開始時から４．５時間経過時までは１００％に近いが、それ以降急激に低下し、５．５時間経過時には７６％にまで落ち込み、それ以降は測定時毎に上下するが、９．５時間経過時には７６％を示すに過ぎない。当該Ｒｈ/ＳｉＯ2/ＣｅＯ2は前述９９０号公報のバイオマスガス化用触媒に相当するが、耐久性に問題があることを示している。 As shown in FIG. 3, the tar decomposition / removal rate of Rh / SiO 2 / CeO 2 (Rh: 0.1 wt%) is close to 100% from the start of the test until 4.5 hours elapses, but rapidly decreases thereafter. Then, it drops to 76% when 5.5 hours have elapsed, and thereafter goes up and down at every measurement, but only shows 76% when 9.5 hours have passed. The Rh / SiO 2 / CeO 2 corresponds to the biomass gasification catalyst described in the aforementioned 990 publication, but has a problem in durability.
これに対して、ＬａＦｅＯ3、ＬａＣｏＯ3、Ｒｈ/ＬａＦｅＯ3（Ｒｈ：０．１ｗｔ％）、Ｒｈ/ＬａＣｏＯ3（Ｒｈ：０．１ｗｔ％）及びＮｉ/ＬａＦｅＯ3（Ｎｉ：１ｗｔ％）では、いずれも試験開始時から良好なタール分解除去率を示し、５時間経過時にタール分解除去率は９５％以上であり、それ以降においても良好なタール分解除去率を示している。 In contrast, in LaFeO 3 , LaCoO 3 , Rh / LaFeO 3 (Rh: 0.1 wt%), Rh / LaCoO 3 (Rh: 0.1 wt%) and Ni / LaFeO 3 (Ni: 1 wt%), whichever Also shows a good tar decomposition and removal rate from the beginning of the test, and the tar decomposition and removal rate is 95% or more after 5 hours, and also shows a good tar decomposition and removal rate after that.
〈炭素析出量の分析、結果〉
炭素析出率の分析には元素分析計（ＣＨＮ計：パーキンエルマージャパン社製）を使用した。表１は本炭素析出量の分析結果である。表１のとおり、Ｎｉ/Ａｌ2Ｏ3（Ｎｉ：１ｗｔ％）、Ｎｉ/Ａｌ2Ｏ3−ＣｅＯ2（Ｎｉ：１ｗｔ％）及びＲｈ/Ａｌ2Ｏ3（Ｒｈ：０．１ｗｔ％）の各炭素析出量は、５時間経過時にそれぞれ３．２１％、１．２７％及び０．４９％であった。
<Analysis of carbon deposition amount, results>
An elemental analyzer (CHN meter: manufactured by PerkinElmer Japan) was used for the analysis of the carbon deposition rate. Table 1 shows the analysis results of the carbon deposition amount. As shown in Table 1, each of Ni / Al 2 O 3 (Ni: 1 wt%), Ni / Al 2 O 3 —CeO 2 (Ni: 1 wt%) and Rh / Al 2 O 3 (Rh: 0.1 wt%) The amount of carbon deposition was 3.21%, 1.27% and 0.49% after 5 hours, respectively.
Ｒｈ/ＳｉＯ2/ＣｅＯ2の炭素析出量は、試験開始時から５時間経過時までは０％であるが、１０時間経過時に４．７２％もの炭素析出量を示している。これを、当該Ｒｈ/ＳｉＯ2/ＣｅＯ2のタール分解除去率との関連をみると、前述のとおり、タール分解除去率は、試験開始時から４．５時間経過時までは１００％に近いが、それ以降急激に低下し、９．５時間経過時には７６％を示すに過ぎない。 The carbon deposition amount of Rh / SiO 2 / CeO 2 is 0% from the start of the test until the lapse of 5 hours, but shows a carbon deposition amount of 4.72% after the lapse of 10 hours. Looking at the relationship with the tar decomposition removal rate of the Rh / SiO 2 / CeO 2 , as described above, the tar decomposition removal rate is close to 100% from the start of the test until 4.5 hours have passed. After that, it drops sharply, showing only 76% after 9.5 hours.
このことからすれば、当該Ｒｈ/ＳｉＯ2/ＣｅＯ2のタール分解除去率のタール分解除去率の低下は、Ｒｈ/ＳｉＯ2/ＣｅＯ2への炭素析出量の増加と関連しているようにも思われるが、後述〈タール分解性能評価試験及び炭素析出量分析−その２−〉における結果を併せて考慮すると、その間に明確な相関があるとは必ずしも言えない。当該Ｒｈ/ＳｉＯ2/ＣｅＯ2は、前記９９０号公報のバイオマスガス化用触媒に相当するが、タール分解触媒としては耐久性に問題があることを示している。 From this fact, decrease in the tar decomposition rate of removal of the Rh / SiO 2 / CeO 2 tar decomposition rate of removal, to be associated with increased carbon deposition amount of the Rh / SiO 2 / CeO 2 Although it seems, if the result in <the tar decomposition | disassembly performance evaluation test and carbon deposition amount analysis-part 2-> mentioned later is considered together, it cannot necessarily be said that there is a clear correlation between them. The Rh / SiO 2 / CeO 2 corresponds to the biomass gasification catalyst described in the above-mentioned 990 publication, but shows a problem in durability as a tar decomposition catalyst.
これに対して、ＬａＦｅＯ3、ＬａＣｏＯ3、Ｒｈ/ＬａＦｅＯ3及びＲｈ/ＬａＣｏＯ3の炭素析出量は、試験開始時から５時間経過時までは０％であり、１０時間経過時にも０％である。このように、これに触媒は長時間にわたり炭素析出が無いことを示している。また、Ｎｉ/ＬａＦｅＯ3の炭素析出量は、試験開始時から５時間経過時までは０％であり、炭素析出が無いことを示している。 On the other hand, the amount of carbon deposition of LaFeO 3 , LaCoO 3 , Rh / LaFeO 3 and Rh / LaCoO 3 is 0% from the start of the test until 5 hours have elapsed and 0% after 10 hours have elapsed. . Thus, this indicates that the catalyst has no carbon deposition for a long time. Moreover, the amount of carbon deposition of Ni / LaFeO 3 is 0% from the start of the test until the lapse of 5 hours, indicating that there is no carbon deposition.
各触媒はいずれも４．５時間経過時において９５％以上の分解率を有しているが、この事実だけからはタール分解性能におけるペロブスカイト触媒の優位性ははっきりとは分らない。しかし、Ｒｈ/ＳｉＯ2/ＣｅＯ2のタール分解性能は、５．５時間経過時に７６％に低下し、それ以降上下しているのに対して、ペロブスカイト型酸化物、金属担持のペロブスカイト型酸化物のタール分解性能に変化がなく、９．５時間経過時にもほぼ同様の性能を示している。そして、炭素析出率については、５時間経過後に両者間で大きな違いが見えることから、ペロブスカイト型酸化物、金属担持のペロブスカイト型酸化物はＲｈ/ＳｉＯ2/ＣｅＯ2に比べて総合的に優れているといえる。 Each catalyst has a decomposition rate of 95% or more after 4.5 hours, but this fact alone does not clearly show the superiority of the perovskite catalyst in tar decomposition performance. However, the tar decomposition performance of Rh / SiO 2 / CeO 2 declines to 76% after 5.5 hours, and since then it has fluctuated, while the perovskite oxide and metal-supported perovskite oxide There is no change in the tar decomposition performance, and almost the same performance is exhibited even after 9.5 hours. As for the carbon deposition rate, a large difference can be seen between the two after 5 hours. Therefore, the perovskite oxide and the metal-supported perovskite oxide are generally superior to Rh / SiO 2 / CeO 2. It can be said that.
また、本試験における試験ガスには２０００ｐｐｍのＨ2Ｓが含まれているが、本発明に係るそれらのタール分解触媒は、いずれも硫黄化合物による劣化は無く、硫黄化合物による被毒耐性を有していることを示している。 In addition, the test gas in this test contains 2000 ppm of H 2 S, but these tar decomposition catalysts according to the present invention are not deteriorated by the sulfur compound and have poisoning resistance by the sulfur compound. It shows that.
〈タール分解性能評価試験及び炭素析出量分析−その２−〉
以上は反応温度８５０℃という高温における実験であるが、一例としてＬａＣｏＯ3系のペロブスカイト型複合酸化物について、それより低温度における性能如何についての性能試験、炭素析出量分析を実施した。
<Tar decomposition performance evaluation test and carbon deposition amount analysis-Part 2->
The above is an experiment at a high reaction temperature of 850 ° C. As an example, a LaCoO 3 -based perovskite complex oxide was subjected to a performance test and a carbon deposition amount analysis at a lower temperature.
前記〈触媒の調製１〉〜〈触媒の調製３〉で調製したＲｈ/ＳｉＯ2/ＣｅＯ2（Ｒｈ：０．１ｗｔ％）、Ｒｈ/ＬａＣｏＯ3（Ｒｈ：０．１ｗｔ％）、Ｎｉ/ＬａＣｏＯ3（Ｎｉ：１ｗｔ％）及びＬａＣｏＯ3について、反応温度を７５０℃とした点以外は前記〈タール分解性能評価試験及び炭素析出量分析−その１−〉における〈試験条件〉、〈炭素析出量の分析〉と同様にしてタール分解性能評価試験及び炭素析出量分析を行った。
Rh / SiO 2 / CeO 2 (Rh: 0.1 wt%), Rh / LaCoO 3 (Rh: 0.1 wt%), Ni / LaCoO 3 prepared in the above <Preparation of
〈反応温度７５０℃におけるタール分解性能評価試験の結果〉
図４はそのタール分解性能評価試験の結果である。図４のとおり、Ｒｈ/ＳｉＯ2/ＣｅＯ2のタール分解除去率は、試験開始時以降急激に低下し、試験開始時から約１時間経過時から約５時間経過時までは８２〜８１％程度の除去率を示すが、それ以降急激に低下し、途中上下はするが、１０時間経過時には４６％を示すに過ぎない。
<Results of tar decomposition performance evaluation test at reaction temperature of 750 ° C.>
FIG. 4 shows the results of the tar decomposition performance evaluation test. As shown in FIG. 4, the tar decomposition and removal rate of Rh / SiO 2 / CeO 2 rapidly decreases after the start of the test, and is about 82 to 81% from about 1 hour to about 5 hours after the start of the test. The rate of removal is shown, but after that it drops sharply and goes up and down halfway, but only 46% when 10 hours have passed.
これに対して、Ｒｈ/ＬａＣｏＯ3のタール分解除去率は、試験開始時の９７％から、短時間で１００％となり、以降幾分の変動はあるが、１０時間経過時においても９８％のタール分解除去率を示している。Ｎｉ/ＬａＣｏＯ3のタール分解除去率は、試験開始時の９９％からすぐに１００％となり、以降上下に変動するが、１０時間経過時では７４％のタール分解除去率を示している。ＬａＣｏＯ3のタール分解除去率は、試験開始時以降、途中上下変動しながら下降するが、１０時間経過時では７６％のタール分解除去率を示している。 On the other hand, the tar decomposition and removal rate of Rh / LaCoO 3 was reduced from 97% at the start of the test to 100% in a short time, and after that, there was some fluctuation, but 98% of tar even after 10 hours. The decomposition removal rate is shown. The tar decomposition removal rate of Ni / LaCoO 3 immediately became 100% from 99% at the start of the test, and thereafter fluctuates up and down, but shows a tar decomposition removal rate of 74% after 10 hours. The tar decomposition removal rate of LaCoO 3 decreases while moving up and down halfway from the start of the test, but shows a tar decomposition removal rate of 76% after 10 hours.
〈反応温度７５０℃における炭素析出量の分析結果〉
表２は試験開始から１０時間経過時における炭素析出量の分析結果である。表２のとおり、Ｒｈ/ＳｉＯ2/ＣｅＯ2の炭素析出量は０．７７％、Ｒｈ/ＬａＣｏＯ3の炭素析出量は０．１％、Ｎｉ/ＬａＣｏＯ3の炭素析出量は１．０１％、ＬａＣｏＯ3の炭素析出量は０．７８％であった。
<Analytical result of carbon deposition amount at a reaction temperature of 750 ° C.>
Table 2 shows the analysis result of the carbon deposition amount after 10 hours from the start of the test. As shown in Table 2, the carbon deposition amount of Rh / SiO 2 / CeO 2 is 0.77%, the carbon deposition amount of Rh / LaCoO 3 is 0.1%, the carbon deposition amount of Ni / LaCoO 3 is 1.01%, The amount of deposited carbon of LaCoO 3 was 0.78%.
以上の結果から、ペロブスカイト型複合酸化物は反応温度７５０〜８５０℃において良好なタール分解性能及び耐炭素析出性能を有することがわかった。また、ＬａＣｏＯ3系ペロブスカイト型複合酸化物のタール分解性能はＲｈ/ＬａＣｏＯ3＞Ｎｉ/ＬａＣｏＯ3＞ＬａＣｏＯ3となり、耐炭素析出性はＲｈ/ＬａＣｏＯ3＞ＬａＣｏＯ3＞Ｎｉ/ＬａＣｏＯ3となることから、担持金属としてＲｈを使用することにより、より高い性能を発揮することを示している。 From the above results, it was found that the perovskite complex oxide has good tar decomposition performance and carbon deposition resistance at a reaction temperature of 750 to 850 ° C. Further, the tar decomposition performance of the LaCoO 3 perovskite complex oxide is Rh / LaCoO 3 > Ni / LaCoO 3 > LaCoO 3 , and the carbon precipitation resistance is Rh / LaCoO 3 > LaCoO 3 > Ni / LaCoO 3. It shows that higher performance is exhibited by using Rh as a supported metal.
１ ガス化炉（バイオマスの無触媒熱分解炉）
２、４ ガス化ガス導出用パイプ
３ 集塵機
５ タール分解装置
６ タール分解装置５に充填したタール分解触媒
1 Gasification furnace (non-catalytic pyrolysis furnace for biomass)
2, 4 Pipe for gasification gas extraction 3
Claims (4)
The tar decomposition catalyst according to claim 3, wherein the gasification gas containing a sulfur compound obtained by thermal decomposition of biomass is a gasification gas generated by thermal decomposition of sludge.
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