JP2007252988A - Catalyst for carbon monoxide methanation and methanation method of carbon monoxide using the catalyst - Google Patents
Catalyst for carbon monoxide methanation and methanation method of carbon monoxide using the catalyst Download PDFInfo
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Abstract
Description
本発明は、水素含有ガス中の一酸化炭素除去用触媒および該触媒を用いた一酸化炭素の除去方法に関する。さらに詳しくは、低温でも高活性で選択的に一酸化炭素をメタン化(メタネーション)できる一酸化炭素除去用触媒および該触媒を用いた一酸化炭素の除去方法に関する。 The present invention relates to a catalyst for removing carbon monoxide in a hydrogen-containing gas and a method for removing carbon monoxide using the catalyst. More particularly, the present invention relates to a carbon monoxide removal catalyst that can selectively methanate carbon monoxide with high activity even at low temperatures, and a carbon monoxide removal method using the catalyst.
近年、燃料電池による発電は、低公害でエネルギーロスが少なことから、注目を集めており、実用化に向けた研究開発が進められている。
燃料電池には、燃料や電解質の種類あるいは作動温度等によって種々のタイプのものが知られているが、中でも水素を還元剤(活物質)とし、酸素あるいは空気等を酸化剤とする水素−酸素燃料電池(低温作動型の燃料電池)の開発が最も進んでいる。
In recent years, power generation using fuel cells has been attracting attention because of its low pollution and low energy loss, and research and development for practical use is being promoted.
Various types of fuel cells are known, depending on the type of fuel and electrolyte, operating temperature, etc. Among them, hydrogen-oxygen using hydrogen as a reducing agent (active material) and oxygen or air or the like as an oxidizing agent. The development of fuel cells (low temperature operation type fuel cells) is the most advanced.
水素−酸素燃料電池には電解質の種類や電極等の種類によって種々のタイプのものがあり、その代表的なものとして、例えば、リン酸型燃料電池、固体高分子型燃料電池などがある。このような燃料電池には、多くの場合、電極に白金触媒が使用されている。ところが、電極に用いている白金は一酸化炭素(以下、COともいう。)によって被毒されやすいので、燃料中にCOがあるレベル以上含まれていると発電性能が低下したり、濃度によっては全く発電ができなくなってしまうという重大な問題点がある。 There are various types of hydrogen-oxygen fuel cells depending on the type of electrolyte, the type of electrodes, and the like, and typical examples include phosphoric acid fuel cells and solid polymer fuel cells. In such fuel cells, platinum catalysts are often used for electrodes. However, platinum used in the electrode is easily poisoned by carbon monoxide (hereinafter also referred to as CO). Therefore, if the fuel contains more than a certain level of CO, the power generation performance may be reduced or depending on the concentration. There is a serious problem that power generation becomes impossible.
このCO被毒による触媒の活性劣化は、特に低温ほど著しいので、この問題は、低温作動型の燃料電池の場合に特に深刻となる。
したがって、こうした白金系電極触媒を用いる燃料電池の燃料としては純粋な水素が好ましいが、実用的な点からは安価で貯蔵性等に優れたあるいは既に公共的な供給システムが完備されている各種の燃料、例えば、メタン、天然ガス(LNG )、プロパン、ブタ
ン等の石油ガス(LPG )、ナフサ、ガソリン、灯油、軽油等の各種の炭化水素系燃料
あるいはメタノール等のアルコール系燃料、あるいは都市ガス、その他の水素製造用燃料等の水蒸気改質等によって得られる水素含有ガスを用いることが一般的になっており、このような改質設備を組み込んだ燃料電池発電システムの普及が進められている。しかしながら、こうした改質ガス中には、一般に、水素の他にかなりの濃度のCOが含まれているので、このCOを白金系電極触媒に無害なものに転化し、燃料中のCO濃度を減少させる技術の開発が強く望まれている。例えば、固体高分子型燃料電池ではCO濃度を、通常100容量ppm以下、好ましくは50容量ppm以下、更に好ましくは10容量ppm以下という低濃度にまで低減することが望ましいとされている。
The deterioration of the activity of the catalyst due to CO poisoning is particularly remarkable at low temperatures, and this problem becomes particularly serious in the case of a low temperature operation type fuel cell.
Therefore, pure hydrogen is preferable as a fuel for a fuel cell using such a platinum-based electrode catalyst. However, from a practical point of view, it is inexpensive and has excellent storage properties or is already equipped with a public supply system. Fuel, for example, methane, natural gas (LNG), petroleum gas (LPG) such as propane, butane, various hydrocarbon fuels such as naphtha, gasoline, kerosene, light oil, alcohol fuel such as methanol, city gas, It has become common to use hydrogen-containing gas obtained by steam reforming of other fuels for hydrogen production or the like, and fuel cell power generation systems incorporating such reforming equipment are being promoted. However, since these reformed gases generally contain a considerable concentration of CO in addition to hydrogen, this CO is converted into a harmless to the platinum-based electrode catalyst, and the CO concentration in the fuel is reduced. There is a strong demand for the development of technologies that can be used. For example, in a polymer electrolyte fuel cell, it is desirable to reduce the CO concentration to a low concentration of usually 100 ppm by volume or less, preferably 50 ppm by volume or less, more preferably 10 ppm by volume or less.
上記の問題を解決するために、燃料ガス(改質ガス中の水素含有ガス)中のCOの濃度を低減させる手段の一つとして、下記の式(1)で表されるシフト反応(水性ガスシフト反応)を利用する技術が提案されている。
CO + H2O = CO2 + H2 (1)
しかしながら、このシフト反応のみによる反応では、化学平衡上の制約からCO濃度の低減には限界があり、一般に、CO濃度を1%以下にするのは困難である。
In order to solve the above problem, as one of means for reducing the concentration of CO in the fuel gas (hydrogen-containing gas in the reformed gas), a shift reaction represented by the following formula (1) (water gas shift) A technique using reaction) has been proposed.
CO + H 2 O = CO 2 + H 2 (1)
However, in the reaction using only this shift reaction, there is a limit to the reduction of the CO concentration due to restrictions on chemical equilibrium, and it is generally difficult to reduce the CO concentration to 1% or less.
そこで、CO濃度をより低濃度まで低減する手段として、改質ガス中に酸素または酸素含有ガス(空気等)を導入し、COをCO2に変換する方法が提案されている。しかしな
がら、この場合改質ガス中には水素が多量存在しているため、COを酸化しようとすると水素も酸化されてしまい、水素がロスするとともにCOの除去が不充分となることがあっ
た。
Therefore, as a means for reducing the CO concentration to a lower concentration, a method has been proposed in which oxygen or an oxygen-containing gas (air or the like) is introduced into the reformed gas and CO is converted to CO 2 . However, in this case, since a large amount of hydrogen is present in the reformed gas, hydrogen is also oxidized when attempting to oxidize CO, resulting in loss of hydrogen and insufficient removal of CO.
ところで、最近COを水素でメタネーション(以下、メタン化ともいう。)することによりメタンに変換する方法も見直されている。例えば、特開平3−93602号公報(特許文献1)、特開平11−86892号公報(特許文献2)には、γ−アルミナ担体にRuを担持した触媒(Ru/γ−アルミナ触媒)と、COを含有する水素ガスを接触させる方法が開示されている。しかし、水素ガスに二酸化炭素(CO2)が含まれている場合、
副反応である二酸化炭素のメタン化反応も起こり、それだけ水素が消費され望ましくないことがあった。このため、主反応であるCOのメタン化反応の活性が高く、選択率の高い(二酸化炭素のメタン化反応の少ない)触媒の開発が望まれている。
Recently, a method of converting CO to methane by methanation with hydrogen (hereinafter also referred to as methanation) has been reviewed. For example, in JP-A-3-93602 (Patent Document 1) and JP-A-11-86892 (Patent Document 2), a catalyst (Ru / γ-alumina catalyst) in which Ru is supported on a γ-alumina carrier, A method of contacting hydrogen gas containing CO is disclosed. However, if the hydrogen gas contains carbon dioxide (CO 2 ),
There was also a methanation reaction of carbon dioxide, which was a side reaction. For this reason, the development of a catalyst having high activity of CO methanation reaction, which is the main reaction, and high selectivity (low carbon dioxide methanation reaction) is desired.
上記問題点を解決するために無機酸化物担体にRu化合物とアルカリ金属化合物および/またはアルカリ土類金属化合物を担持した触媒が提案されている。(特許文献3:特開2002−68707号公報)
しかしながら、上記従来の触媒、特に低温作動型の燃料電池用電極触媒では、活性が不充分であったり、時に反応温度が急激に上昇するなどの問題があった。
すなわち、反応温度が低い場合であっても、主反応である一酸化炭素のメタネーション反応の選択率および活性が高く、水素含有ガス中の一酸化炭素を効率的に除去できる触媒および除去方法を提供することが望まれていた。
However, the above-described conventional catalysts, particularly low temperature operation type fuel cell electrode catalysts, have problems such as insufficient activity and sometimes a rapid increase in reaction temperature.
That is, even when the reaction temperature is low, a catalyst and a removal method that can efficiently remove carbon monoxide in a hydrogen-containing gas with high selectivity and activity of the methanation reaction of carbon monoxide, which is the main reaction. It was desired to provide.
このような情況のもと、本発明者等は前記課題を解決すべく鋭意検討した結果、金属酸化物担体に活性成分として、RuとともにRu以外の金属が担持されてなる触媒は反応温度が低い場合であってもCOのメタン化反応において高い活性および選択性を発現し、加えて前記したシフト反応が併起し、CO除去効果が向上することを見出して本発明を完成するに至った。 Under these circumstances, the present inventors diligently studied to solve the above problems, and as a result, the reaction temperature of the catalyst in which a metal other than Ru is supported together with Ru as an active component on the metal oxide support is low. Even in this case, high activity and selectivity were exhibited in the methanation reaction of CO, and in addition, the shift reaction described above was accompanied and the CO removal effect was improved, and the present invention was completed.
すなわち、本発明の構成は以下の通りである。
[1]RuとRu以外の金属が金属酸化物担体に担持されてなり、
RuとRu以外の金属の担持量が触媒中に0.5〜15重量%の範囲にあることを特徴とする一酸化炭素メタネーション用触媒。
[2]前記Ru以外の金属が4B族、6A族、7A族および8族から選ばれる1種以上の金属であることを特徴とする[1]の一酸化炭素メタネーション用触媒。
[3]前記Ru以外の金属が、Sn、Mo、W、Re、Pt、Pd、Rh、NiおよびCoからなる群から選ばれる少なくとも1種であることを特徴とする[1]または[2]の一酸化炭素
メタネーション用触媒。
[4]前記RuとRu以外の金属の合計を100重量%としたときに、Ruの割合が20〜90重量%の範囲にある[1]〜[3]の一酸化炭素メタネーション用触媒。
[5]前記金属酸化物担体がNiO、CoO(Co3O4を含む)、CeO2、ZrO2、Al2O3、TiO2、SiO2から選ばれる1種以上の酸化物、またはこれらの複合酸化物であ
る[1]〜[4]の一酸化炭素メタネーション用触媒。
[6]CO吸着量が3〜20cm3/g-Catの範囲にある[1]〜[5]の一酸化炭素メタネーショ
ン用触媒。
[7]CO吸着から求めた前記RuとRu以外の金属の平均粒子径が0.5〜5nmの範囲に
ある[1]〜[6]の一酸化炭素メタネーション用触媒。
[8][1]〜[5]のメタネーション用触媒と一酸化炭素ガス含有水素ガスと接触させることを
特徴とする一酸化炭素のメタネーション方法。
[9]前記、接触させる際の温度(反応温度)が120〜200℃の範囲にある[8]の一酸化炭素のメタネーション方法。
That is, the configuration of the present invention is as follows.
[1] A metal other than Ru and Ru is supported on a metal oxide support,
A catalyst for carbon monoxide methanation, wherein the supported amount of metal other than Ru and Ru is in the range of 0.5 to 15% by weight in the catalyst.
[2] The catalyst for carbon monoxide methanation according to [1], wherein the metal other than Ru is one or more metals selected from Group 4B, Group 6A, Group 7A and Group 8.
[3] The metal other than Ru is at least one selected from the group consisting of Sn, Mo, W, Re, Pt, Pd, Rh, Ni and Co [1] or [2] Catalyst for carbon monoxide methanation.
[4] The catalyst for carbon monoxide methanation [1] to [3], wherein the ratio of Ru is in the range of 20 to 90% by weight when the total of the metals other than Ru and Ru is 100% by weight.
[5] The metal oxide support is one or more oxides selected from NiO, CoO (including Co 3 O 4 ), CeO 2 , ZrO 2 , Al 2 O 3 , TiO 2 , SiO 2 , or these A catalyst for carbon monoxide methanation [1] to [4], which is a composite oxide.
[6] The catalyst for carbon monoxide methanation having a CO adsorption amount in the range of 3 to 20 cm 3 / g-Cat [1] to [5].
[7] The catalyst for carbon monoxide methanation [1] to [6], wherein the average particle diameter of the metal other than Ru and Ru determined from CO adsorption is in the range of 0.5 to 5 nm.
[8] A carbon monoxide methanation method comprising contacting the methanation catalyst of [1] to [5] with a carbon monoxide gas-containing hydrogen gas.
[9] The method for methanation of carbon monoxide, wherein the temperature (reaction temperature) at the time of contact is in the range of 120 to 200 ° C.
本発明によれば、無機酸化物担体に、RuとともにRu以外の金属が所定量担持されているために反応温度が低い場合であっても、主反応である一酸化炭素のメタネーション反応の選択率および活性が高く、水素含有ガス中の一酸化炭素を効果的に除去できる触媒および除去方法を提供することができる。 According to the present invention, the carbon monoxide methanation reaction, which is the main reaction, is selected even when the reaction temperature is low because a predetermined amount of metal other than Ru is supported together with Ru on the inorganic oxide support. It is possible to provide a catalyst and a removal method that have a high rate and activity and can effectively remove carbon monoxide in a hydrogen-containing gas.
以下、本発明を実施するための形態について説明する。
本発明に係る一酸化炭素メタネーション用触媒は、RuとRu以外の金属が金属酸化物担体に担持されている。Ru以外の金属としては4B族、6A族、7A族および8族から選
ばれる1種または2種以上の金属であることが好ましい。
なかでも、4B族の金属としてはSn、6A族の金属としてはMo、W、7A族の金属としてはRe、8族の金属としてはPt、Pd、Rh、NiおよびCoからなる群から選ばれる1種以上の金属が好適に用いられる。
Hereinafter, modes for carrying out the present invention will be described.
In the carbon monoxide methanation catalyst according to the present invention, Ru and a metal other than Ru are supported on a metal oxide support. The metal other than Ru is preferably one or more metals selected from Group 4B, Group 6A, Group 7A and Group 8.
Among them, the group 4B metal is selected from the group consisting of Sn, the group 6A metal is Mo, W, the group 7A metal is Re, and the group 8 metal is Pt, Pd, Rh, Ni and Co. One or more metals are preferably used.
上記した各金属の好ましい理由については必ずしも明らかではないが、Snの場合、Ruに吸着した炭素種の脱離を促進することにより活性を向上させることが考えられる。
Mo、Wの場合、H2の解離吸着による活性水素が生成して水素化を促進することによ
り活性を向上させていることが考えられる。Reの場合、Ruへの炭素種の吸着および脱離を促進することにより活性を向上させていることが考えられる。Pt、Pd、RhおよびNi、Coの場合、COおよびH2を解離吸着することにより活性を向上させているこ
とが考えられる。
The reason why each of the above metals is preferable is not clear, but in the case of Sn, it is conceivable to improve the activity by promoting the elimination of the carbon species adsorbed on Ru.
In the case of Mo and W, it is considered that active hydrogen is generated by dissociative adsorption of H 2 and promotes hydrogenation to improve the activity. In the case of Re, it is considered that the activity is improved by promoting the adsorption and desorption of the carbon species to Ru. In the case of Pt, Pd, Rh, Ni, and Co, it is considered that the activity is improved by dissociating and adsorbing CO and H 2 .
このようにこれらの金属をRuとともに担持することで、従来にはなかった優れた効果が発現される。
このような、RuとRu以外の金属の担持量は、合計量が、触媒重量中に0.5〜15重量%、さらには1.0〜10重量%の範囲にあることが好ましい。
In this way, by supporting these metals together with Ru, an excellent effect that has not existed in the past is exhibited.
The amount of the metal supported other than Ru and Ru is preferably in the range of 0.5 to 15% by weight, more preferably 1.0 to 10% by weight, based on the catalyst weight.
RuとRu以外の金属の担持量が前記範囲の下限よりも小さい場合は、活性が不充分となる。RuとRu以外の金属の担持量が前記範囲を越えて大きい場合、活性は高いもののCO2のメタネーション反応が起こり、選択性が低下し、結果としてCOの除去効果が不充分
となる。
When the loading amount of metals other than Ru and Ru is smaller than the lower limit of the above range, the activity is insufficient. When the loading amount of the metal other than Ru and Ru exceeds the above range, CO 2 methanation occurs although the activity is high, the selectivity is lowered, and as a result, the effect of removing CO becomes insufficient.
RuとRu以外の金属中、合計を100重量%としたときにRuの割合は20〜90重量%
、さらには25〜60重量%の範囲にあることが好ましい。
RuとRu以外の金属中のRuの割合が前記範囲にあれば炭素種の吸着および脱離、H2
の解離吸着、COの解離吸着が調和を持って促進され、反応温度が低くても高い活性を有し、副反応を抑制することができるために高い選択性を有する触媒が得られる。
Of metals other than Ru and Ru, the ratio of Ru is 20 to 90% by weight when the total is 100% by weight.
Furthermore, it is preferable that it exists in the range of 25 to 60 weight%.
If the ratio of Ru in the metal other than Ru and Ru is within the above range, adsorption and desorption of carbon species, H 2
The dissociative adsorption of CO and the dissociative adsorption of CO are promoted in a coordinated manner, have high activity even when the reaction temperature is low, and can suppress side reactions, so that a highly selective catalyst can be obtained.
なお、RuとRu以外の金属中のRuの割合が前記範囲にある本発明の一酸化炭素メタネーション用触媒は上記特性に加えて反応温度が低い場合にCO2の増加が認められ、シフ
ト反応が併起しており、このことによっても高いCO除去効果が得られる。
In addition to the above characteristics, the catalyst for carbon monoxide methanation according to the present invention in which the ratio of Ru in the metal other than Ru and Ru falls within the above range shows an increase in CO 2 when the reaction temperature is low. This also causes a high CO removal effect.
つぎに、本発明に用いる金属酸化物担体としては、NiO、CoO(Co3O4等を含む
)、CeO2、ZrO2、Al2O3から選ばれる1種または2種以上の酸化物、特に複合酸化物であることが好ましい。
具体的にはZrO2-CoO、ZrO2-NiO、ZrO2-CeO2、ZrO2-CoO-NiO、NiO-CoO、CoO-CeO2、NiO-CoO-CeO2、ZrO2-NiO-CoO-CeO2、Al2O3−Co3O4、Al2O3−CeO2−CoO、Al2O3−NiO、
TiO2−CoO、TiO2−NiO、TiO2−SiO2−Co3O 4 等が挙げられる。
Next, as the metal oxide support used in the present invention, one or more oxides selected from NiO, CoO (including Co 3 O 4 etc.), CeO 2 , ZrO 2 and Al 2 O 3 , A composite oxide is particularly preferable.
Specifically, ZrO 2 —CoO, ZrO 2 —NiO, ZrO 2 —CeO 2 , ZrO 2 —CoO—NiO, NiO—CoO, CoO—CeO 2 , NiO—CoO—CeO 2 , ZrO 2 —NiO—CoO— CeO 2, Al 2 O 3 -Co 3 O 4, Al 2 O 3 -CeO 2 -CoO, Al 2 O 3 -NiO,
Examples thereof include TiO 2 —CoO, TiO 2 —NiO, and TiO 2 —SiO 2 —Co 3 O 4 .
複合酸化物中にNi、Coの酸化物の少なくともいずれかが概ね10重量%以上、好ましくは30重量%以上含まれていると反応温度が低い場合であっても高い活性を得ることができる。 When the composite oxide contains at least one of Ni and Co oxides in an amount of approximately 10% by weight or more, preferably 30% by weight or more, high activity can be obtained even when the reaction temperature is low.
また、Zr、Al、Ti、Siの酸化物の少なくともいずれかが概ね20重量%以上、好ましくは50重量%以上含まれていると、比表面積が向上し、このため高い活性を得ることができる。 Further, when at least one of the oxides of Zr, Al, Ti, and Si is contained in an amount of approximately 20% by weight or more, preferably 50% by weight or more, the specific surface area is improved, and thus high activity can be obtained. .
また、Ceの酸化物が概ね3.0重量%以上、好ましくは10.0重量%以上含まれていると、選択性に優れるほか、CO2のメタネーションに起因する発熱を伴う暴走反応を
抑制することができる。なかでも、CoO-NiO−ZrO2−CeO2、CoO-NiO−CeO2、ZrO2−CeO2−NiO、TiO2−CeO2−CoO、ZrO2−CeO2−
CoO等のCeO2を含む複合酸化物は、選択性を向上させ発熱を伴う暴走反応を抑制す
る効果が顕著である。
When the Ce oxide is contained in an amount of 3.0% by weight or more, preferably 10.0% by weight or more, the selectivity is excellent and the runaway reaction accompanied by heat generation due to the methanation of CO 2 is suppressed. can do. Among them, CoO—NiO—ZrO 2 —CeO 2 , CoO—NiO—CeO 2 , ZrO 2 —CeO 2 —NiO, TiO 2 —CeO 2 —CoO, ZrO 2 —CeO 2 —
A composite oxide containing CeO 2 such as CoO has a remarkable effect of improving selectivity and suppressing a runaway reaction accompanied by heat generation.
本発明に係る一酸化炭素メタネーション用触媒は、CO吸着量が3〜20cm3/g-Cat、さらには8〜20cm3/g-Catの範囲にあることが好ましい。
CO吸着量が前記範囲の下限未満の場合は、COの吸着と活性化が不充分となるため充分な活性を得ることができない。CO吸着量が前記上限を越えて大きいものは、吸着することは困難であり、吸着したとしても活性が高すぎて発熱を伴う暴走反応を伴うことがある。
The catalyst for carbon monoxide methanation according to the present invention preferably has a CO adsorption amount of 3 to 20 cm 3 / g-Cat, more preferably 8 to 20 cm 3 / g-Cat.
When the amount of CO adsorption is less than the lower limit of the above range, sufficient adsorption cannot be obtained because CO adsorption and activation are insufficient. When the amount of CO adsorption exceeds the above upper limit, it is difficult to adsorb, and even if adsorbed, the activity is too high and a runaway reaction accompanied by heat generation may occur.
なお、本発明におけるCO吸着量は触媒分析装置(日本ベル株式会社製:BEL−CAT)を用い、装置内で触媒を400℃で30分間還元処理を行い、パルス法にてCO吸着を行うことによって測定することができる。 The amount of CO adsorption in the present invention is determined by using a catalyst analyzer (BEL-CAT, manufactured by Nippon Bell Co., Ltd.), reducing the catalyst at 400 ° C. for 30 minutes in the device, and performing CO adsorption by the pulse method. Can be measured.
CO吸着量は、金属粒子径、金属に依存し、小さい金属微粒子が多いほど高くなる。金属粒子径は、還元条件(還元できる温度であれば低温の方が望ましい)、金属の種類、担体の種類、比表面積を制御することによって調整することが可能である。 The amount of CO adsorption depends on the metal particle diameter and metal, and increases as the number of small metal particles increases. The metal particle diameter can be adjusted by controlling the reduction conditions (lower temperature is preferable if the temperature can be reduced), the type of metal, the type of support, and the specific surface area.
また、上記で得たCO吸着量から求められる担持しているRuとRu以外の金属の平均粒子径が0.5〜5nm、さらに0.8〜4nmの範囲にあることが好ましい。金属の平均粒子径が上記範囲の上限を越えると、COの吸着と活性化が不充分となるため充分な活性を得ることができない。金属の平均粒子径が上記範囲の下限未満のものは担持させることが困難である。 Moreover, it is preferable that the average particle diameter of the supported Ru and Ru other than Ru obtained from the CO adsorption amount obtained above is in the range of 0.5 to 5 nm, more preferably 0.8 to 4 nm. If the average particle diameter of the metal exceeds the upper limit of the above range, sufficient adsorption cannot be obtained because CO adsorption and activation are insufficient. It is difficult to carry a metal whose average particle diameter is less than the lower limit of the above range.
なお、CO吸着量から求められる金属の平均粒子径は、担持した金属の割合より担持金属の平均原子量および平均原子半径を算出し、触媒分析装置(BEL−CAT)取扱説明書に記載されている計算式を用いて算出することができる。 In addition, the average particle diameter of the metal calculated | required from CO adsorption amount calculates the average atomic weight and average atomic radius of a supported metal from the ratio of the supported metal, and is described in a catalyst analyzer (BEL-CAT) instruction manual. It can be calculated using a calculation formula.
また、触媒の比表面積が30〜200m2/g、さらには60〜120m2/gの範囲にあることが好ましい。
触媒の比表面積が前記範囲の下限未満の場合は、活性が不充分となり、高いSV(空塔
速度)での運転か困難となる。触媒の比表面積が前記範囲の上限を越えて大きくても、長時間運転した場合に活性、選択性の低下が大きくなる傾向にある。
The specific surface area of the catalyst is preferably in the range of 30 to 200 m 2 / g, more preferably 60 to 120 m 2 / g.
When the specific surface area of the catalyst is less than the lower limit of the above range, the activity is insufficient and it becomes difficult to operate at a high SV (superficial velocity). Even if the specific surface area of the catalyst is larger than the upper limit of the above range, the activity and selectivity tend to decrease greatly when operated for a long time.
また、触媒の細孔容積は0.10〜0.45ml/g、さらには0.15〜0.30ml/gの範囲にあることが好ましい。
触媒の細孔容積が前記範囲の下限未満の場合は、充分な活性が得られないことがある。
The pore volume of the catalyst is preferably in the range of 0.10 to 0.45 ml / g, more preferably 0.15 to 0.30 ml / g.
When the pore volume of the catalyst is less than the lower limit of the above range, sufficient activity may not be obtained.
触媒の細孔容積が前記範囲の上限を越えて大きくすることは、本発明の組成範囲では得ることが困難である。
なお、細孔容積は、酸化物担体の比表面積に依存し、金属塩を中和してゲルを生成させるがこのときのゲルの大きさ、熟成条件などを制御することによって調整される。
Increasing the pore volume of the catalyst beyond the upper limit of the above range is difficult to obtain in the composition range of the present invention.
The pore volume depends on the specific surface area of the oxide carrier and neutralizes the metal salt to form a gel. The pore volume is adjusted by controlling the gel size, aging conditions, and the like.
本発明に係る一酸化炭素メタネーション用触媒は、担体成分および活性成分が前記した範囲にあり、触媒の比表面積および細孔容積が前記した範囲にあり、一酸化炭素のメタネーションに用いることができれば特に制限はなく従来公知の方法によって製造することができる。このほか、各種酸化物ゾルおよびシリカ源としては水ガラスを脱アルカリした珪酸液も好適に用いることができる。 In the catalyst for carbon monoxide methanation according to the present invention, the support component and the active component are in the above-mentioned range, the specific surface area and pore volume of the catalyst are in the above-mentioned range, and used for carbon monoxide methanation. If possible, there is no particular limitation, and it can be produced by a conventionally known method. In addition, as the various oxide sols and silica sources, silicic acid solutions obtained by dealkalizing water glass can be preferably used.
例えば、担体成分原料としてジルコニウム塩、ニッケル塩、コバルト塩、セリウム塩、アルミニウム塩、チタニウム塩、珪酸塩の1種以上金属塩水溶液、好ましくは2種以上の混合金属塩水溶液を調製する。 For example, zirconium salt, nickel salt, cobalt salt, cerium salt, aluminum salt, titanium salt, silicate aqueous solution of one or more metal salts, preferably two or more mixed metal salt aqueous solutions are prepared as a carrier component raw material.
ニッケル塩としては硝酸ニッケル、硫酸ニッケル、塩化ニッケル、酢酸ニッケル、炭酸ニッケル等が用いられ、コバルト塩としては硝酸コバルト、硫酸コバルト、塩化コバルト、酢酸コバルト等が用いられる。セリウム塩としては硝酸セリウム、塩化セリウム、硫酸セリウム、等が用いられる。ジルコニウム塩としては硝酸ジルコニウム、塩化ジルコニウム、塩化ジルコニル、硫酸ジルコニウム、酢酸ジルコニウム、硝酸ジルコニル、硫酸ジルコニル、炭酸ジルコニウム等が用いられ、アルミニウム塩としては塩化アルミニウム、硫酸アルミニウム、硝酸アルミニウム等が用いられ、チタニウム塩としては四塩化チタン、硫酸チタン等が用いられ、珪酸塩としては水ガラス等が主に用いられる。これを所望の酸化物組成となるように、必要に応じて混合する。 As the nickel salt, nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, nickel carbonate or the like is used, and as the cobalt salt, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetate or the like is used. As the cerium salt, cerium nitrate, cerium chloride, cerium sulfate, etc. are used. Zirconium nitrate, zirconium chloride, zirconyl chloride, zirconium sulfate, zirconium acetate, zirconyl nitrate, zirconyl sulfate, zirconium carbonate, etc. are used as the zirconium salt, and aluminum chloride, aluminum sulfate, aluminum nitrate, etc. are used as the aluminum salt. As the salt, titanium tetrachloride, titanium sulfate or the like is used, and as the silicate, water glass or the like is mainly used. This is mixed as needed so that it may become a desired oxide composition.
混合塩水溶液は合計の酸化物としての濃度が概ね7.5重量%以下の範囲にあることが好ましい。
混合塩水溶液の濃度が合計の酸化物として7.5重量%を超えると得られる触媒の比表面積が小さく、十分な活性が得られないことがある。
The mixed salt aqueous solution preferably has a total oxide concentration in the range of 7.5% by weight or less.
When the concentration of the mixed salt aqueous solution exceeds 7.5% by weight as the total oxide, the resulting catalyst has a small specific surface area, and sufficient activity may not be obtained.
ついで、混合塩水溶液に塩基性化合物の水溶液を加えて中和し、必要に応じて熟成してヒドロゲルを調製する。
塩基性化合物としてはNaOH、KOH、Na2CO3等のアルカリ金属水溶液、アンモニア、テトラメチルアンモニウムハイドロオキサイド等を用いることができる。
Next, an aqueous solution of a basic compound is added to the mixed salt aqueous solution to neutralize it, and it is aged as necessary to prepare a hydrogel.
Examples of basic compounds that can be used include aqueous alkali metal solutions such as NaOH, KOH, Na 2 CO 3 , ammonia, tetramethylammonium hydroxide, and the like.
熟成する際の温度は通常30〜100℃の範囲が好ましく、時間は通常0.5〜24時間程度である。
ついで、ヒドロゲルを濾過し、洗浄する。洗浄方法は副生する塩化ナトリウム等の塩を除去できれば特に制限はなく従来公知の方法を採用することができる。例えば、温水を充分掛ける方法、アンモニア水を掛ける方法、限外濾過膜法等は好適に採用することができる。
The temperature for aging is usually preferably in the range of 30 to 100 ° C., and the time is usually about 0.5 to 24 hours.
The hydrogel is then filtered and washed. The washing method is not particularly limited as long as it can remove by-produced salt such as sodium chloride, and a conventionally known method can be adopted. For example, a method of sufficiently applying warm water, a method of applying ammonia water, an ultrafiltration membrane method and the like can be suitably employed.
ついで、ヒドロゲルから担体を調製するが、かかる方法には主に2つの方法があり、1
つは洗浄したゲルを乾燥し、焼成し、得られた混合酸化物粉体は必要に応じて粉砕し、錠剤成型器等で成型する方法である。
The carrier is then prepared from the hydrogel, and there are two main methods:
One is a method in which the washed gel is dried and fired, and the obtained mixed oxide powder is pulverized as necessary and molded with a tablet molding machine or the like.
他の1つの方法は、洗浄したゲルを、必要に応じてセルローズ等の成型助剤を加え、水分調整、加熱濃縮、捏和、混練等した後、押出成型器等によりペレットとし、必要に応じてペレットをマルメライザー、転動造粒機等で球状とし、ついで、乾燥し、焼成する方法である。このどちらも特に制限なく採用することができる。 Another method is to add a molding aid such as cellulose to the washed gel as necessary, adjust the moisture, heat and concentrate, knead, knead, etc., and then form a pellet with an extruder, etc. In this method, the pellets are formed into a spherical shape with a malmerizer, a rolling granulator or the like, then dried and fired. Both of these can be employed without any particular limitation.
焼成して得た担体に、ついでRuとRu以外の金属を担持するためにルテニウム成分とルテニウム以外の成分を担持する。
担持する方法としては、所定量のルテニウム成分とルテニウム以外の成分とを担持することができれば特に制限はないが、通常、担体の細孔容積に相当する容積のルテニウム塩水溶液とルテニウム以外の塩の水溶液との混合水溶液を調製し、担体に含浸させ、ついで乾燥する。
The carrier obtained by firing is then loaded with a ruthenium component and a component other than ruthenium in order to carry a metal other than Ru and Ru.
The loading method is not particularly limited as long as a predetermined amount of a ruthenium component and a component other than ruthenium can be loaded. Usually, a ruthenium salt aqueous solution having a volume corresponding to the pore volume of the carrier and a salt other than ruthenium are used. A mixed aqueous solution with an aqueous solution is prepared, impregnated into a carrier, and then dried.
ルテニウム塩としては塩化ルテニウム、硝酸ルテニウム等が用いられる。Ru以外の金属の塩としては4B族、6A族、7A族および8族から選ばれる1種または2種以上の金属の塩を用いることが好ましい。なかでも、4B族のSn、6A族のMo、W、7A族のRe、8族のPt、Pd、Rh、Ni、Co等の金属の塩は好適に用いることができる。 As the ruthenium salt, ruthenium chloride, ruthenium nitrate or the like is used. As the metal salt other than Ru, it is preferable to use a salt of one or more metals selected from Group 4B, Group 6A, Group 7A and Group 8. Among these, metal salts such as 4B group Sn, 6A group Mo, W, 7A group Re, 8 group Pt, Pd, Rh, Ni and Co can be preferably used.
具体的には、塩化スズ、酢酸スズ、硫酸スズ、シュウ酸スズ、塩化モリブデン、モリブデン酸アンモニウム、タングステン酸アンモニウム、塩化レニウム、過レニウム酸アンモニウム、塩化白金酸、ジクロロテトラアミン白金、硝酸パラジウム、塩化パラジウム、硝酸ロジウム、塩化ロジウム、硝酸ニッケル、硫酸ニッケル、塩化ニッケル、硝酸コバルト、塩化コバルト、硫酸コバルト等が好適に用いられる。 Specifically, tin chloride, tin acetate, tin sulfate, tin oxalate, molybdenum chloride, ammonium molybdate, ammonium tungstate, rhenium chloride, ammonium perrhenate, chloroplatinic acid, dichlorotetraamineplatinum, palladium nitrate, chloride Palladium, rhodium nitrate, rhodium chloride, nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate and the like are preferably used.
混合塩水溶液の濃度は、通常、所定量、すなわち得られる触媒中のRuとRu以外の金属の合計の含有量が0.5〜15重量%となるように担持できる濃度とするが、混合塩水溶液の濃度が低い場合、あるいは担持量が多い場合は含浸および乾燥を繰り返し行うこともできる。 The concentration of the mixed salt aqueous solution is usually a predetermined amount, that is, a concentration that can be supported so that the total content of metals other than Ru and Ru in the obtained catalyst is 0.5 to 15% by weight. When the concentration of the aqueous solution is low, or when the loading amount is large, the impregnation and drying can be repeated.
乾燥条件は特に制限はないが、通常80〜200℃で乾燥する。乾燥した後、還元ガス雰囲気下、100〜700℃、好ましくは150〜400℃で還元して一酸化炭素メタネーション用触媒を得ることができる。 The drying conditions are not particularly limited, but are usually dried at 80 to 200 ° C. After drying, the catalyst for carbon monoxide methanation can be obtained by reduction at 100 to 700 ° C., preferably 150 to 400 ° C. in a reducing gas atmosphere.
還元雰ガスとしては通常、水素ガスあるいは水素ガスと窒素ガス等不活性ガスとの混合ガスが用いられる。
還元する際の温度が100℃未満の場合は、活性金属の還元が不充分となり、充分な活性が得られないことがある。
As the reducing atmosphere gas, hydrogen gas or a mixed gas of hydrogen gas and inert gas such as nitrogen gas is usually used.
If the temperature during the reduction is less than 100 ° C., the reduction of the active metal becomes insufficient and sufficient activity may not be obtained.
還元する際の温度が700℃を超えると焼結が起こり、得られる触媒の比表面積が小さく、活性が不充分となることがある。
還元する際の時間は温度によっても異なるが、通常0.5〜12時間である。
If the temperature at the time of reduction exceeds 700 ° C., sintering occurs, the specific surface area of the resulting catalyst is small, and the activity may be insufficient.
Although the time for reduction varies depending on the temperature, it is usually 0.5 to 12 hours.
また、一酸化炭素メタネーション用触媒の形状等は特に制限はなく、反応方法、反応条件等によって適宜選択することができ、微粉体をそのまま用いることもでき、微粉体を加圧成型して用いることもでき、ハニカム状あるいはペレット状に押出成型したもの、さらにはペレットを球状(ビード状)にしたものも好適に用いることができる。 Further, the shape of the catalyst for carbon monoxide methanation is not particularly limited, and can be appropriately selected depending on the reaction method, reaction conditions, etc. The fine powder can be used as it is, and the fine powder is used after being pressure-molded. It is also possible to suitably use a honeycomb or pellet extruded product, or a pellet made into a spherical shape (bead shape).
つぎに、本発明に係る一酸化炭素のメタネーション方法について説明する。
本発明に係る一酸化炭素のメタネーション方法は、メタネーション用触媒と一酸化炭素ガス含有水素ガスと接触させることを特徴としている。メタネーション用触媒としては前記した触媒を用いる。
Next, the carbon monoxide methanation method according to the present invention will be described.
The methanation method for carbon monoxide according to the present invention is characterized in that the methanation catalyst is brought into contact with a hydrogen gas containing carbon monoxide gas. As the methanation catalyst, the aforementioned catalyst is used.
一酸化炭素ガス含有水素ガスとしては燃料ガス(改質ガス中の水素含有ガス)が用いられ、このガスは通常、水素ガス、一酸化炭素ガス、二酸化炭素ガス、および水蒸気等を含んでおり、メタンを含む場合もある。
本発明に用いる燃料ガス中の水素ガスの濃度は71〜89vol%、一酸化炭素ガス濃度は0.3〜1.0vol%、二酸化炭素ガス濃度は10〜25vol%、メタンガス濃度0〜3.0vol%(ガス組成)である。さらにその燃料中のガスに対して水蒸気を20vol%〜70vol%の割合で含んでいる。
As the carbon monoxide gas-containing hydrogen gas, a fuel gas (hydrogen-containing gas in the reformed gas) is used, and this gas usually contains hydrogen gas, carbon monoxide gas, carbon dioxide gas, water vapor, and the like. May contain methane.
The hydrogen gas concentration in the fuel gas used in the present invention is 71 to 89 vol%, the carbon monoxide gas concentration is 0.3 to 1.0 vol%, the carbon dioxide gas concentration is 10 to 25 vol%, and the methane gas concentration is 0 to 3.0 vol. % (Gas composition). Furthermore, it contains water vapor at a ratio of 20 vol% to 70 vol% with respect to the gas in the fuel.
メタネーション用触媒と一酸化炭素ガス含有水素ガスとを接触させる際の温度(以下、反応温度という)は100〜250℃、さらには130〜190℃の範囲にあることが好ましい。 The temperature at which the methanation catalyst and carbon monoxide gas-containing hydrogen gas are brought into contact (hereinafter referred to as reaction temperature) is preferably in the range of 100 to 250 ° C, more preferably 130 to 190 ° C.
反応温度が100℃未満の場合は、反応ガス中に含まれる水蒸気が凝縮し、継続的に反応を行うことが困難である。
反応温度が250℃を超えると、COシフト反応(CO+H2O→CO2+H2)の温度
域となり、COシフト反応により転化することのできる一酸化炭素をメタネーション反応により、メタン化するため、燃料ガス中に含まれる、水素濃度が著しく低下してしまう。
When the reaction temperature is less than 100 ° C., the water vapor contained in the reaction gas is condensed and it is difficult to carry out the reaction continuously.
When the reaction temperature exceeds 250 ° C., it becomes the temperature range of the CO shift reaction (CO + H 2 O → CO 2 + H 2 ), and carbon monoxide that can be converted by the CO shift reaction is methanated by the methanation reaction. The hydrogen concentration contained in the fuel gas is significantly reduced.
このような、本発明に係る一酸化炭素のメタネーション方法で処理された燃料ガスは、一酸化炭素ガス濃度が20ppm以下に除去されている。
[実施例]
以下、実施例により本発明をより具体的に説明するが、本発明はこれら実施例により限定されるものではない。
[実施例1]
メタネーション用触媒(1)の調製
硝酸ジルコニル溶液(ZrO2濃度:25.0%)168.00g、硝酸セリウム・6
水和物50.20g、硝酸コバルト・6水和物100.89gおよび硝酸ニッケル・6水和物46.71gを水2800gに溶解させ、混合水溶液(1)を得た。
The fuel gas treated by such a carbon monoxide methanation method according to the present invention has a carbon monoxide gas concentration of 20 ppm or less.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of catalyst for methanation (1 ) Zirconyl nitrate solution (ZrO 2 concentration: 25.0%) 168.00 g, cerium nitrate-6
50.20 g of hydrate, 100.89 g of cobalt nitrate hexahydrate and 46.71 g of nickel nitrate hexahydrate were dissolved in 2800 g of water to obtain a mixed aqueous solution (1).
水酸化ナトリウム86.51gを水3200gに溶解し、攪拌しながらこれに混合水溶液(1)を添加してヒドロゲルスラリーを調製し、ついで80℃にて2時間熟成した。
熟成したヒドロゲルを濾過し、充分な温水を掛けて洗浄し、120℃で1昼夜乾燥し、ついで、550℃で1時間、大気中にて焼成を行い、複合酸化物粉体(1)を得た。
86.51 g of sodium hydroxide was dissolved in 3200 g of water, and the mixed aqueous solution (1) was added thereto while stirring to prepare a hydrogel slurry, and then aged at 80 ° C. for 2 hours.
The aged hydrogel is filtered, washed with sufficient warm water, dried at 120 ° C for one day, and then baked in the air at 550 ° C for 1 hour to obtain a composite oxide powder (1). It was.
ついで、複合酸化物粉体(1)を 錠剤成型器に充填し、50Kg/cm2で加圧成型し、粉砕し、粒度を20〜42メッシュに調整してメタネーション触媒用担体(1)を調製した。
塩化ルテニウムおよび塩化パラジウムを金属重量比でRu:Pd=1:0.8となり、金属濃度が10重量%となるように溶解し、含浸溶液(1)を調製した。含浸溶液(1)23.56gをメタネーション触媒用担体(1)50gに吸収させ、充分撹拌し、1時間静
置した後、120℃にて8時間乾燥し、ついで、pHを10〜11に調製した炭酸水素ナトリウム溶液2L中に攪拌し、その後、十分な温水を掛けて洗浄し、120℃にて5時間乾燥させ400℃にて1.5時間水素気流中にて還元処理を行い、メタネーション用触媒(1)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
メタネーション用触媒(1)4.2mlを、内径12mmのステンレス製反応管に充填し
、触媒層温度400℃で水素−窒素混合ガス(H2濃度10VOl%)の流通下で再び1時
間還元処理し、ついで、触媒層温度を120℃の反応温度にした後、反応用混合ガス(一酸化炭素0.6Vol%、二酸化炭素20.0Vol%、メタン2.0Vol%、水素51.37Vol%、水蒸気33.3Vol%)をSV=2,500h-1となるように流通させ、約1時間後の定常状態での生成ガスをガスクロマトグラフィーおよび赤外分光型ガス濃度計で分析し、反応管出口CO濃度、CO2濃度およびCH4濃度を測定した結果を表に示した。
Next, the complex oxide powder (1) is filled into a tablet molding machine, pressure-molded at 50 kg / cm 2 , pulverized, and the particle size is adjusted to 20 to 42 mesh to obtain the methanation catalyst carrier (1). Prepared.
Ruthenium chloride and palladium chloride were dissolved so that the metal weight ratio was Ru: Pd = 1: 0.8 and the metal concentration was 10% by weight to prepare an impregnation solution (1). 23.56 g of impregnation solution (1) was absorbed into 50 g of support (1) for methanation catalyst, stirred well, allowed to stand for 1 hour, dried at 120 ° C. for 8 hours, and then adjusted to pH 10-11. Stir in 2 L of the prepared sodium hydrogen carbonate solution, wash with sufficient warm water, dry at 120 ° C. for 5 hours, perform reduction treatment in a hydrogen stream at 400 ° C. for 1.5 hours, Nation catalyst (1) was prepared. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
The catalyst for activity test methanation (1) (4.2 ml) was filled into a stainless steel reaction tube with an inner diameter of 12 mm, and again for 1 hour under a flow of hydrogen-nitrogen mixed gas (H 2 concentration 10 VOL%) at a catalyst layer temperature of 400 ° C. Then, after reducing the catalyst layer temperature to 120 ° C., the reaction gas mixture (carbon monoxide 0.6 vol%, carbon dioxide 20.0 vol%, methane 2.0 vol%, hydrogen 51.37 vol%) , Water vapor 33.3 Vol%) is circulated so that SV = 2,500 h −1, and the product gas in a steady state after about 1 hour is analyzed by gas chromatography and an infrared spectroscopic gas densitometer. The results of measuring the tube outlet CO concentration, CO 2 concentration, and CH 4 concentration are shown in the table.
選択性としては、反応ガス中の二酸化炭素20.0Vol%からのCO2の増減を表に
示し、CO2の増減の少ない場合が選択性に優れるとして評価した。
同様にして、反応温度を140℃、160℃についても実施し、結果を表に示した。
[実施例2]
メタネーション用触媒(2)の調製
実施例1において、塩化ルテニウムおよび塩化パラジウムを金属重量比でRu:Pd=1:0.4となり、金属濃度が10重量%となるように溶解し、含浸溶液(2)を調製し、含浸溶液(2)18.13gを吸収させた以外は同様にしてメタネーション触媒(2)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[実施例3]
メタネーション用触媒(3)の調製
実施例1において、塩化ルテニウムおよび塩化パラジウムを金属重量比でRu:Pd=1:1.6となり、金属濃度が10重量%となるように溶解し、含浸溶液(3)を調製し、含浸溶液(3)34.76gを吸収させた以外は同様にしてメタネーション触媒(3)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[実施例4]
メタネーション用触媒(4)の調製
実施例1において、塩化ルテニウム、塩化パラジウム、塩化白金酸を金属重量比でRu:Pd:Pt=1:0.6:0.4となり、金属濃度が10重量%となるように溶解し、含浸溶液(4)を調製し、含浸溶液(4)26.32gを吸収させた以外は同様にしてメタネーション触媒(4)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[実施例5]
メタネーション用触媒(5)の調製
硝酸アルミニウム・9水和物154.47g、硝酸セリウム・6水和物50.20g、硝酸コバルト・6水和物100.89gおよび硝酸ニッケル・6水和物46.71gを水2780gに溶解させ、混合水溶液(2)を得た。
水酸化ナトリウム242.01gを水3220gに溶解し、攪拌しながらこれに混合水溶液(2)を添加してヒドロゲルスラリーを調製し、ついで80℃にて2時間熟成した。
As the selectivity, the increase / decrease in CO 2 from 20.0 Vol% of carbon dioxide in the reaction gas is shown in the table, and the case where the increase / decrease in CO 2 is small is evaluated as being excellent in selectivity.
Similarly, the reaction was carried out at 140 ° C. and 160 ° C., and the results are shown in the table.
[Example 2]
Preparation of catalyst for methanation (2) In Example 1, ruthenium chloride and palladium chloride were dissolved so that the metal weight ratio was Ru: Pd = 1: 0.4, and the metal concentration was 10% by weight. A methanation catalyst (2) was prepared in the same manner except that (2) was prepared and 18.13 g of the impregnation solution (2) was absorbed. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Example 3]
Preparation of catalyst for methanation (3) In Example 1, ruthenium chloride and palladium chloride were dissolved so that the metal weight ratio was Ru: Pd = 1: 1.6, and the metal concentration was 10% by weight. A methanation catalyst (3) was prepared in the same manner except that (3) was prepared and 34.76 g of the impregnation solution (3) was absorbed. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Example 4]
Preparation of catalyst for methanation (4) In Example 1, Ru: Pd: Pt = 1: 0.6: 0.4 in terms of metal weight ratio of ruthenium chloride, palladium chloride and chloroplatinic acid, and the metal concentration was 10 wt. The methanation catalyst (4) was prepared in the same manner except that the impregnation solution (4) was prepared and 26.32 g of the impregnation solution (4) was absorbed. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Example 5]
Preparation of catalyst for methanation (5) 154.47 g of aluminum nitrate nonahydrate, 50.20 g of cerium nitrate hexahydrate, 100.89 g of cobalt nitrate hexahydrate, and nickel nitrate hexahydrate 46 .71 g was dissolved in 2780 g of water to obtain a mixed aqueous solution (2).
242.01 g of sodium hydroxide was dissolved in 3220 g of water, and the mixed aqueous solution (2) was added thereto while stirring to prepare a hydrogel slurry, and then aged at 80 ° C. for 2 hours.
熟成したヒドロゲルを濾過し、充分な温水を掛けて洗浄し、120℃で1昼夜乾燥し、
ついで、550℃で1時間、大気中にて焼成を行い、複合酸化物粉体(2)を得た。ついで、複合酸化物粉体(2)を 錠剤成型器に充填し、50Kg/cm2で加圧成型し、ついで粉
砕し、粒度を20〜42メッシュに調整してメタネーション触媒用担体(2)を調製した。
The aged hydrogel is filtered, washed with sufficient warm water, dried at 120 ° C for one day,
Subsequently, it baked in air | atmosphere at 550 degreeC for 1 hour, and composite oxide powder (2) was obtained. Next, the complex oxide powder (2) is filled into a tablet molding machine, pressure-molded at 50 kg / cm 2 , then pulverized, and the particle size is adjusted to 20 to 42 mesh to adjust the carrier for methanation catalyst (2). Was prepared.
塩化ルテニウム、塩化パラジウム、塩化すず・2水和物を金属重量比でRu:Pd:Sn=1:0.4:0.6となり、金属濃度が10重量%となるように溶解し、含浸溶液(5)を調製し、含浸溶液(5)26.32gをメタネーション触媒用担体(2)50gへ吸収させた以外は実施例1と同様にしてメタネーション触媒(5)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[実施例6]
メタネーション用触媒(6)の調製
四塩化チタン(TiO2:28.1%)溶液149.47g、塩化セリウム・7水和物21.66g、塩化コバルト・6水和物152.28gを水2840gに溶解させ、混合水溶液(3)を得た。
Ruthenium chloride, palladium chloride, tin chloride dihydrate is dissolved so that the metal weight ratio is Ru: Pd: Sn = 1: 0.4: 0.6, and the metal concentration is 10% by weight. A methanation catalyst (5) was prepared in the same manner as in Example 1 except that (5) was prepared and 26.32 g of the impregnation solution (5) was absorbed into 50 g of the methanation catalyst support (2). The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Example 6]
Preparation of catalyst for methanation (6) 149.47 g of titanium tetrachloride (TiO2: 28.1%) solution, 21.28 g of cerium chloride heptahydrate and 152.28 g of cobalt chloride hexahydrate into 2840 g of water It was made to melt | dissolve and mixed aqueous solution (3) was obtained.
水酸化ナトリウム60.50gを水3200gに溶解し、攪拌しながらこれに混合水溶液(3)を添加してヒドロゲルスラリーを調製し、ついで80℃にて2時間熟成した。
熟成したヒドロゲルを濾過し、充分な温水を掛けて洗浄し、120℃で1昼夜乾燥し、ついで、550℃で1時間、大気中にて焼成を行い、複合酸化物粉体(3)を得た。ついで、複合酸化物粉体(3)を 錠剤成型器に充填し、50Kg/cm2で加圧成型し、ついで粉
砕し、粒度を20〜42メッシュに調整してメタネーション触媒用担体(3)を調製した。
60.50 g of sodium hydroxide was dissolved in 3200 g of water, and a mixed aqueous solution (3) was added thereto while stirring to prepare a hydrogel slurry, followed by aging at 80 ° C. for 2 hours.
The aged hydrogel was filtered, washed with sufficient warm water, dried at 120 ° C. for one day, and then baked in the air at 550 ° C. for 1 hour to obtain a composite oxide powder (3). It was. Next, the complex oxide powder (3) is filled into a tablet molding machine, pressure-molded at 50 kg / cm 2 , then pulverized, and the particle size is adjusted to 20-42 mesh to support the methanation catalyst carrier (3). Was prepared.
塩化ルテニウム、過レニウム酸、塩化モリブデンを重量比でRu:Re:Mo=1:0.4:0.6となり、金属濃度が10重量%となるように溶解し、含浸溶液(6)を調製し、含浸溶液(6)26.32gをメタネーション触媒用担体(3)50gへ吸収させた以外は実施例1と同様にしてメタネーション触媒(6)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[実施例7]
メタネーション用触媒(7)の調製
四塩化チタン(TiO2:28.1%)溶液149.47g、塩化セリウム・7水和物21.66g、塩化コバルト・6水和物101.52gおよび塩化にける・6水和物50.91gを水2852gに溶解させ、混合水溶液(4)を得た。
Ruthenium chloride, perrhenic acid, and molybdenum chloride are dissolved in a weight ratio of Ru: Re: Mo = 1: 0.4: 0.6 and the metal concentration is 10% by weight to prepare an impregnation solution (6). Then, a methanation catalyst (6) was prepared in the same manner as in Example 1 except that 26.32 g of the impregnation solution (6) was absorbed into 50 g of the support (3) for methanation catalyst. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Example 7]
Preparation of catalyst for methanation (7) 149.47g of titanium tetrachloride (TiO2: 28.1%) solution, 21.66g of cerium chloride heptahydrate, 101.52g of cobalt chloride hexahydrate and chlorinated -50.91 g of hexahydrate was dissolved in 2852 g of water to obtain a mixed aqueous solution (4).
水酸化ナトリウム60.57gを水3200gに溶解し、攪拌しながらこれに混合水溶液(4)を添加してヒドロゲルスラリーを調製し、ついで80℃にて2時間熟成した。
熟成したヒドロゲルを濾過し、充分な温水を掛けて洗浄し、120℃で1昼夜乾燥し、ついで、550℃で1時間、大気中にて焼成を行い、複合酸化物粉体(4)を得た。ついで、複合酸化物粉体(4)を 錠剤成型器に充填し、50Kg/cm2で加圧成型し、ついで粉
砕し、粒度を20〜42メッシュに調整してメタネーション触媒用担体(4)を調製した。
60.57 g of sodium hydroxide was dissolved in 3200 g of water, and a mixed aqueous solution (4) was added thereto with stirring to prepare a hydrogel slurry, and then aged at 80 ° C. for 2 hours.
The aged hydrogel was filtered, washed with sufficient warm water, dried at 120 ° C for one day and night, and then calcined at 550 ° C for 1 hour in the air to obtain a composite oxide powder (4). It was. Next, the complex oxide powder (4) is filled into a tablet molding machine, pressure-molded at 50 kg / cm 2 , then pulverized, and the particle size is adjusted to 20 to 42 mesh to support the methanation catalyst carrier (4). Was prepared.
塩化ルテニウム、タングステン酸を重量比でRu:W=1:1.2となり、金属濃度が10重量%となるように溶解し、含浸溶液(7)を調製し、含浸溶液(7)29.10gをメタネーション触媒用担体(4)50gへ吸収させた以外は実施例1と同様にしてメタネーション触媒(7)を調製した。活性成分、各担体成分の含有量、比表面積および細孔
容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[実施例8]
メタネーション用触媒(8)の調製
硝酸ジルコニル溶液(ZrO2濃度:25.0%)124.00g、硝酸セリウム・6
水和物25.10g、硝酸コバルト・6水和物147.46gを水2640gに溶解させ、混合水溶液(5)を得た。
Ruthenium chloride and tungstic acid are dissolved so that the weight ratio is Ru: W = 1: 1.2 and the metal concentration is 10% by weight to prepare an impregnation solution (7), and 29.10 g of the impregnation solution (7) A methanation catalyst (7) was prepared in the same manner as in Example 1 except that 50 g of the methanation catalyst support (4) was absorbed. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Example 8]
Preparation of catalyst for methanation (8 ) Zirconyl nitrate solution (ZrO 2 concentration: 25.0%) 124.00 g, cerium nitrate-6
Hydrate 25.10 g and cobalt nitrate hexahydrate 147.46 g were dissolved in water 2640 g to obtain a mixed aqueous solution (5).
水酸化ナトリウム61.30gおよび水ガラス(SiO2濃度:24.0%)を水320
0gに溶解し、攪拌しながらこれに混合水溶液(5)を添加してヒドロゲルスラリーを調製し、ついで80℃にて2時間熟成した。
Sodium hydroxide 61.30 g and water glass (SiO 2 concentration: 24.0%) were added to water 320
It melt | dissolved in 0g, mixed aqueous solution (5) was added to this with stirring, the hydrogel slurry was prepared, and it age | cure | ripened at 80 degreeC for 2 hours.
熟成したヒドロゲルを濾過し、充分な温水を掛けて洗浄し、120℃で1昼夜乾燥し、ついで、550℃で1時間、大気中にて焼成を行い、複合酸化物粉体(5)を得た。ついで、複合酸化物粉体(5)を 錠剤成型器に充填し、50Kg/cm2で加圧成型し、ついで粉
砕し、粒度を20〜42メッシュに調整してメタネーション触媒用担体(5)を調製した。
The aged hydrogel was filtered, washed with sufficient warm water, dried at 120 ° C for one day and night, and then baked in the air at 550 ° C for 1 hour to obtain a composite oxide powder (5). It was. Next, the complex oxide powder (5) is filled into a tablet molding machine, pressure-molded at 50 kg / cm 2 , then pulverized, and the particle size is adjusted to 20 to 42 mesh to adjust the carrier for methanation catalyst (5). Was prepared.
塩化ルテニウム、塩化ロジウム、塩化ニッケルを重量比でRu:Rh:Ni=1:0.2:1となり、金属濃度が10重量%となるように溶解し、含浸溶液(8)を調製し、含浸溶液(8)29.10gをメタネーション触媒用担体(5)50gへ吸収させた以外は実施例1と同様にしてメタネーション触媒(8)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[実施例9]
メタネーション用触媒(8)の調製
硝酸ジルコニル溶液(ZrO2濃度:25.0%)80.00g、硝酸セリウム・6水
和物25.10g、硝酸コバルト・6水和物124.17gおよび硝酸ニッケル・6水和物62.28gを水2640gに溶解させ、混合水溶液(6)を得た。
Ruthenium chloride, rhodium chloride, and nickel chloride are dissolved so that the weight ratio is Ru: Rh: Ni = 1: 0.2: 1, and the metal concentration is 10% by weight to prepare an impregnation solution (8). A methanation catalyst (8) was prepared in the same manner as in Example 1 except that 29.10 g of the solution (8) was absorbed into 50 g of the support (5) for methanation catalyst. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Example 9]
Preparation of catalyst for methanation (8) Zirconyl nitrate solution (ZrO 2 concentration: 25.0%) 80.00 g, cerium nitrate hexahydrate 25.10 g, cobalt nitrate hexahydrate 124.17 g and nickel nitrate -62.28 g of hexahydrate was dissolved in 2640 g of water to obtain a mixed aqueous solution (6).
水酸化ナトリウム61.30gおよび水ガラス(SiO2濃度:24.0%)を水320
0gに溶解し、攪拌しながらこれに混合水溶液(6)を添加してヒドロゲルスラリーを調製し、ついで80℃にて2時間熟成した。
Sodium hydroxide 61.30 g and water glass (SiO 2 concentration: 24.0%) were added to water 320
It melt | dissolved in 0g, mixed aqueous solution (6) was added to this, stirring, and the hydrogel slurry was prepared, and it matured at 80 degreeC for 2 hours then.
熟成したヒドロゲルを濾過し、充分な温水を掛けて洗浄し、120℃で1昼夜乾燥し、ついで、550℃で1時間、大気中にて焼成を行い、複合酸化物粉体(6)を得た。ついで、複合酸化物粉体(6)を 錠剤成型器に充填し、50Kg/cm2で加圧成型し、ついで粉
砕し、粒度を20〜42メッシュに調整してメタネーション触媒用担体(6)を調製した。
The aged hydrogel was filtered, washed with sufficient warm water, dried at 120 ° C. for one day, and then baked in the air at 550 ° C. for 1 hour to obtain a composite oxide powder (6). It was. Next, the complex oxide powder (6) is filled into a tablet molding machine, pressure-molded at 50 kg / cm 2 , then pulverized, and the particle size is adjusted to 20 to 42 mesh to adjust the carrier for methanation catalyst (6). Was prepared.
塩化ルテニウム、塩化白金酸、塩化コバルトを重量比でRu:Pt:Co=1:0.2:1となり、金属濃度が10重量%となるように溶解し、含浸溶液(9)を調製し、含浸溶液(9)29.10gをメタネーション触媒用担体(6)50gへ吸収させた以外は実施例1と同様にしてメタネーション触媒(9)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[比較例1]
メタネーション用触媒(R1)の調製
実施例1においてメタネーション触媒用担体(1)を金属を担持することなく用いた。活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[比較例2]
メタネーション用触媒(R2)の調製
実施例1において、Ruとしての濃度1.0重量%の塩化ルテニウム水溶液26.32gを吸収させた以外は同様にしてメタネーション用触媒(R2)を調製した。活性成分、各
担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[比較例3]
メタネーション用触媒(R3)の調製
実施例1において、塩化ルテニウムおよび塩化パラジウムを金属重量比でRu:Pd=1:0.66となり、金属濃度が10重量%となるように溶解し、含浸溶液(R3)を調製し、含浸溶液(R3)166.67gを吸収させた後乾燥する工程を4回繰り返して行った以外は同様にしてメタネーション用触媒(R3)を調製した。活性成分、各担体成分の
含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
[比較例4]
メタネーション用触媒(R4)の調製
実施例1において、塩化ルテニウムおよび塩化パラジウムを金属重量比でRu:Pd=1:0.80となり、金属濃度が1.0重量%となるように溶解し、含浸溶液(R4)を調製し、含浸溶液(R4)22.60gを吸収させた後乾燥する工程を4回繰り返して行った以外は同様にしてメタネーション用触媒(R4)を調製した。活性成分、各担体成分の含有量、比表面積および細孔容積を測定し、結果を表に示した。
活性試験
実施例1と同様にして活性試験を行い、CO濃度、CO2濃度およびCH4濃度を表に示した。
Ruthenium chloride, chloroplatinic acid, and cobalt chloride were dissolved so that the weight ratio was Ru: Pt: Co = 1: 0.2: 1 and the metal concentration was 10% by weight to prepare an impregnation solution (9). A methanation catalyst (9) was prepared in the same manner as in Example 1 except that 29.10 g of the impregnation solution (9) was absorbed into 50 g of the support (6) for methanation catalyst. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Comparative Example 1]
Preparation of catalyst for methanation (R1) In Example 1, the support for methanation catalyst (1) was used without supporting a metal. Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Comparative Example 2]
Preparation of catalyst for methanation (R2) A catalyst for methanation (R2) was prepared in the same manner as in Example 1 except that 26.32 g of a ruthenium chloride aqueous solution having a concentration of 1.0% by weight as Ru was absorbed. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Comparative Example 3]
Preparation of catalyst for methanation (R3) In Example 1, ruthenium chloride and palladium chloride were dissolved so that the metal weight ratio was Ru: Pd = 1: 0.66, and the metal concentration was 10% by weight. A catalyst for methanation (R3) was prepared in the same manner except that the step of preparing (R3) and absorbing 166.67 g of the impregnation solution (R3) and then drying was repeated four times. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
[Comparative Example 4]
Preparation of catalyst for methanation (R4) In Example 1, ruthenium chloride and palladium chloride were dissolved so that the metal weight ratio was Ru: Pd = 1: 0.80, and the metal concentration was 1.0 wt%. A catalyst for methanation (R4) was prepared in the same manner except that the impregnation solution (R4) was prepared, and the step of absorbing and drying 22.60 g of the impregnation solution (R4) was repeated four times. The active component, the content of each carrier component, the specific surface area and the pore volume were measured, and the results are shown in the table.
Activity test An activity test was conducted in the same manner as in Example 1, and the CO concentration, CO 2 concentration and CH 4 concentration were shown in the table.
Claims (9)
RuとRu以外の金属の担持量が触媒中に0.5〜15重量%の範囲にあることを特徴とする一酸化炭素メタネーション用触媒。 A metal other than Ru and Ru is supported on a metal oxide support,
A catalyst for carbon monoxide methanation, wherein the supported amount of metal other than Ru and Ru is in the range of 0.5 to 15% by weight in the catalyst.
あることを特徴とする請求項1に記載の一酸化炭素メタネーション用触媒。 The catalyst for carbon monoxide methanation according to claim 1, wherein the metal other than Ru is one or more metals selected from Group 4B, Group 6A, Group 7A and Group 8.
なる群から選ばれる少なくとも1種であることを特徴とする請求項1または2に記載の一
酸化炭素メタネーション用触媒。 3. The monoxide according to claim 1, wherein the metal other than Ru is at least one selected from the group consisting of Sn, Mo, W, Re, Pt, Pd, Rh, Ni, and Co. 4. Catalyst for carbon methanation.
%の範囲にあることを特徴とする請求項1〜3のいずれかに記載の一酸化炭素メタネーション用触媒。 The carbon monoxide according to any one of claims 1 to 3, wherein the ratio of Ru is in the range of 20 to 90 wt% when the total of the metals other than Ru and Ru is 100 wt%. Catalyst for methanation.
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