JP2008056539A - Carbon monoxide methanation method - Google Patents
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Abstract
Description
本発明は、水素含有ガス中の一酸化炭素の除去方法に関する。
さらに詳しくは、シフト反応によって生成した高温の水素含有ガスのＣＯメタネーションにおいて、比較的低温で活性の高い触媒を充填した第１反応部と、比較的高温で活性の高い触媒（低温で選択性の高い触媒）を充填した第２反応部とからなる反応層でメタネーション反応を行う効率的な一酸化炭素の除去方法に関する。
The present invention relates to a method for removing carbon monoxide in a hydrogen-containing gas.
More specifically, in the CO methanation of the high-temperature hydrogen-containing gas produced by the shift reaction, a first reaction part filled with a catalyst having a high activity at a relatively low temperature and a catalyst having a high activity at a relatively high temperature (selectivity at a low temperature). The present invention relates to an efficient method for removing carbon monoxide in which a methanation reaction is performed in a reaction layer comprising a second reaction section filled with a high 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いことから、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 by 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 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, etc., 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), so if the fuel contains CO above a certain level, the power generation performance will 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。
The deterioration of the activity of the catalyst due to the CO poisoning is remarkable especially 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.
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。 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。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。
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. 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、特許文献１（特開平３−９３６０２号公報）、特許文献２（特開平１１−８６８９２号公報）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。しかしながら、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てしまい望ましくない。
Recently, a method of converting CO to methane by methanation with hydrogen (hereinafter also referred to as methanation) has been reviewed. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 3-93602) and Patent Document 2 (Japanese Patent Laid-Open No. 11-86892), a catalyst in which Ru is supported on a γ-alumina carrier (Ru / γ-alumina catalyst), A method of contacting hydrogen gas containing CO is disclosed. However, when carbon dioxide (CO 2 ) is included in the hydrogen gas, a methanation reaction of carbon dioxide, which is a side reaction, also occurs and hydrogen is consumed as much, which is not desirable.
したがって、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。
また、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２００２−０６８７０７号公報）。
In order to solve the above problems, a catalyst in which an Ru compound and an alkali metal compound and / or an alkaline earth metal compound are supported on an inorganic oxide carrier has been proposed (Patent Document 3: Japanese Patent Application Laid-Open No. 2002-068707). ).
しかしながら、１種類の触媒を１つの反応層に充填してメタネーションを行った場合、メタネーション反応が発熱反応であることから反応層の下部に行くに従って反応温度が高くなり、触媒の活性、選択性が最適温度からずれ、反応層の下部では触媒の性能を充分発現することができない場合があった。 However, when methanation is performed with one type of catalyst packed in one reaction layer, the reaction temperature increases toward the bottom of the reaction layer because the methanation reaction is exothermic, and the activity and selection of the catalyst. In some cases, the performance of the catalyst deviated from the optimum temperature, and the performance of the catalyst could not be fully exhibited in the lower part of the reaction layer.
このため、本発明者等は鋭意検討した結果、反応層を２段に分け、第1段目（第１反応
部）に比較的低温で活性の高い触媒を充填し、2段目（第２反応部）に比較的低温でもＣ
Ｏを選択的にメタン化できる触媒を充填してメタネーションを行うと反応温度の調整が容易で暴走反応を起こすことがなく、効率的に一酸化炭素を除去できることを見出して本発明を完成するに至った。
For this reason, as a result of intensive studies, the present inventors divided the reaction layer into two stages, filled the first stage (first reaction section) with a catalyst having a relatively low temperature and high activity, and the second stage (second stage). The reaction part) is C even at relatively low temperatures.
The present invention is completed by finding that when a catalyst capable of selectively methanating O is charged and methanation is performed, the reaction temperature can be easily adjusted and no runaway reaction occurs, and carbon monoxide can be efficiently removed. It came to.
本発明は、反応温度の調整が容易で、過度の発熱による暴走反応を起こすことのない、効率的な一酸化炭素の除去方法を提供することを目的としている。
本発明の構成要件は以下の通りである。
[1]一酸化炭素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一酸化
炭素のメタネーション方法において、反応層が第１反応部と第２反応部とからなり、
第１反応部に用いる一酸化炭素メタネーション触媒が、少なくともＮｉＯおよび／またはＣｏＯを含んでなる複合酸化物担体に４Ｂ族、７Ａ族および８族から選ばれる１種以上の金属が担持されてなり、下記条件(1)下、反応温度１２０℃でＣＯ除去率が９８％以上
である触媒であり、
第２反応部に用いる一酸化炭素メタネーション触媒が６Ａ族および８族から選ばれる１種以上の金属が、ＺｒＯ2、ＣｅＯ2、Ａｌ2Ｏ3、ＴiＯ2、ＳiＯ2から選ばれる１種以上の酸化物または複合酸化物である金属酸化物担体に担持されてなり、下記条件(1)下、反応
温度１８０℃でＣＯ除去率が９８％以上である触媒であることを特徴とする一酸化炭素のメタネーション方法。
An object of the present invention is to provide an efficient method for removing carbon monoxide, which is easy to adjust the reaction temperature and does not cause a runaway reaction due to excessive heat generation.
The configuration requirements of the present invention are as follows.
[1] In a carbon monoxide methanation method in which a carbon monoxide methanation catalyst and a carbon monoxide gas-containing hydrogen gas are brought into contact, the reaction layer comprises a first reaction part and a second reaction part,
The carbon monoxide methanation catalyst used in the first reaction part is formed by supporting at least one metal selected from Group 4B, Group 7A and Group 8 on a composite oxide support containing at least NiO and / or CoO. A catalyst having a CO removal rate of 98% or more at a reaction temperature of 120 ° C. under the following condition (1):
The carbon monoxide methanation catalyst used in the second reaction part is at least one metal selected from Group 6A and Group 8 selected from ZrO 2 , CeO 2 , Al 2 O 3 , TiO 2 , and SiO 2. A catalyst having a CO removal rate of 98% or more at a reaction temperature of 180 ° C. under the following condition (1): Carbon methanation method.
条件(1)：
ＳＶ：２，０００ｈ-1、原料ガス組成：Ｈ2濃度５１．４vol%、ＣＯ濃度０．６vol%、Ｃ
Ｏ2濃度２０vol%、ＣＨ4濃度２vol%、水蒸気濃度３３．３vol%
[2]前記第１反応部の入口（上部）反応温度（ＴENT）が１００〜１６０℃の範囲にあり、
前記第１反応部の出口（下部）反応温度（ＴEXIT）が１８０℃以下であることを特徴とする[1]の一酸化炭素のメタネーション方法。
[3]前記４Ｂ族の金属がＳｎであり、６Ａ族の金属がＭｏ、Ｗであり、７Ａ族の金属がＭ
ｎ、Ｒｅであり、８族の金属がＲｕ、Ｐｔ、Ｐｄ、Ｎｉ、ＦｅおよびＣｏであることを特徴とする[1]の一酸化炭素のメタネーション方法。
[4]前記第１反応部に用いる一酸化炭素メタネーション用触媒中の金属の担持量が０．５
〜９０重量％の範囲にあることを特徴とする[1]〜[3]の一酸化炭素メタネーション用触媒。
[5]前記第１反応部に用いる一酸化炭素メタネーション用触媒中に金属としてＲuを含んでなり、金属中のＲｕの割合が２０〜９０重量％の範囲にあることを特徴とする[1]の一酸
化炭素のメタネーション方法。
[6]前記第２反応部に、ＣＯ吸着剤が充填されたＣＯ吸着塔が接続されていることを特徴
とする[1]〜[5]の一酸化炭素のメタネーション方法。
[7]前記ＣＯ吸着剤が、４Ｂ族、６Ａ族、７Ａ族および８族から選ばれる１種以上の金属
が担持されたゼオライトからなり、該ＣＯ吸着剤中の金属の含有量が０．５〜１５重量％の範囲にあることを特徴とする[6]の一酸化炭素のメタネーション方法。
[8]前記ゼオライトがＺＳＭ−５型ゼオライト、モルデナイト型ゼオライト、フォージャ
サイト型ゼオライト、βゼオライトから選ばれる１種以上であることを特徴とする[7]の
一酸化炭素のメタネーション方法。
Condition 1):
SV: 2,000 h −1 , raw material gas composition: H 2 concentration 51.4 vol%, CO concentration 0.6 vol%, C
O 2 concentration 20 vol%, CH 4 concentration 2 vol%, water vapor concentration 33.3 vol%
[2] The inlet (upper) reaction temperature (T ENT ) of the first reaction section is in the range of 100 to 160 ° C.,
[1] The methanation method of carbon monoxide, wherein an outlet (lower) reaction temperature (T EXIT ) of the first reaction section is 180 ° C. or lower.
[3] The 4B group metal is Sn, the 6A group metal is Mo, W, and the 7A group metal is M.
[1] The methanation method of carbon monoxide, wherein n and Re, and the Group 8 metal is Ru, Pt, Pd, Ni, Fe, and Co.
[4] The amount of metal supported in the catalyst for carbon monoxide methanation used in the first reaction part is 0.5.
The catalyst for carbon monoxide methanation according to [1] to [3], which is in the range of -90% by weight.
[5] The carbon monoxide methanation catalyst used in the first reaction part contains Ru as a metal, and the ratio of Ru in the metal is in the range of 20 to 90% by weight. ] Carbon monoxide methanation method.
[6] The carbon monoxide methanation method of [1] to [5], wherein a CO adsorption tower filled with a CO adsorbent is connected to the second reaction section.
[7] The CO adsorbent is made of zeolite on which one or more metals selected from Group 4B, Group 6A, Group 7A and Group 8 are supported, and the content of the metal in the CO adsorbent is 0.5. [6] Carbon monoxide methanation method, characterized by being in the range of ˜15% by weight.
[8] The carbon monoxide methanation method according to [7], wherein the zeolite is at least one selected from ZSM-5 type zeolite, mordenite type zeolite, faujasite type zeolite, and β zeolite.
本発明によると、シフト反応によって生成した高温の水素含有ガスを比較的低温で活性・選択性の高い触媒を充填した第１反応部と、比較的高温で活性・選択性の高い触媒（比較的低温で選択性の高い触媒）を充填した第２反応部とからなる異なる触媒を充填した反応層でメタネーション反応を行う効率的な一酸化炭素の除去方法を提供することができる。 According to the present invention, a high-temperature hydrogen-containing gas generated by a shift reaction is filled with a catalyst having a relatively high activity and selectivity at a relatively low temperature, and a catalyst having a high activity and selectivity at a relatively high temperature (relatively It is possible to provide an efficient method for removing carbon monoxide in which a methanation reaction is performed in a reaction layer filled with a different catalyst composed of a second reaction section filled with a catalyst having high selectivity at a low temperature.
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のメタネーション方法は、反応層が第１反応部と第２反応部とからなる。
Hereinafter, modes for carrying out the present invention will be described.
In the methanation method for carbon monoxide according to the present invention, the reaction layer includes a first reaction part and a second reaction part.
第１反応部に用いる一酸化炭素メタネーション触媒が、少なくともＮｉＯおよび／またはＣｏＯを含んでなる複合酸化物担体に４Ｂ族、７Ａ族および８族から選ばれる１種以上の金属が担持されてなり、下記条件(1)下、反応温度１２０℃でＣＯ除去率が９８％以上
である触媒であり、
第２反応部に用いる一酸化炭素メタネーション触媒が６Ａ族および８族から選ばれる１種以上の金属が金属酸化物担体に担持されてなり、下記条件(1)下、反応温度１８０℃で
ＣＯ除去率が９８％以上である触媒である。
The carbon monoxide methanation catalyst used in the first reaction part is formed by supporting at least one metal selected from Group 4B, Group 7A and Group 8 on a composite oxide support containing at least NiO and / or CoO. A catalyst having a CO removal rate of 98% or more at a reaction temperature of 120 ° C. under the following condition (1):
The carbon monoxide methanation catalyst used in the second reaction part is formed by supporting one or more metals selected from Group 6A and Group 8 on a metal oxide carrier, and CO at a reaction temperature of 180 ° C. under the following condition (1). The catalyst has a removal rate of 98% or more.
条件(1)：
ＳＶ：２，０００ｈ-1、原料ガス組成：Ｈ2濃度５１．４vol%、ＣＯ濃度０．６vol%、Ｃ
Ｏ2濃度２０vol%、ＣＨ4濃度２vol%、水蒸気濃度３３．３vol%
第１反応部に反応温度１２０℃でＣＯ除去率が９８％以上の触媒を充填し、第２反応部に反応温度１８０℃でＣＯ除去率が９８％以上の触媒を充填した反応層を用いることにより、メタネーションの過度の発熱による暴走反応を抑制するとともの温度調整を容易にし、且つ、活性・選択性の低下を抑制し、効率的に一酸化炭素を除去することができる。
Condition 1):
SV: 2,000 h −1 , raw material gas composition: H 2 concentration 51.4 vol%, CO concentration 0.6 vol%, C
O 2 concentration 20 vol%, CH 4 concentration 2 vol%, water vapor concentration 33.3 vol%
Use a reaction layer in which the first reaction part is filled with a catalyst having a CO removal rate of 98% or more at a reaction temperature of 120 ° C., and the second reaction part is filled with a catalyst having a CO removal rate of 98% or more at a reaction temperature of 180 ° C. Thus, the runaway reaction due to excessive heat generation of methanation can be suppressed, temperature adjustment can be facilitated, the decrease in activity / selectivity can be suppressed, and carbon monoxide can be efficiently removed.
第１反応部にこのような触媒を用いると、ＣＯ濃度を容易に、概ね２０ｐｐｍ以下まで
低減することができる。第２反応部に用いる一酸化炭素メタネーション触媒は高温で活性が高いが、低温では必ずしも活性は高くないもののＣＯ2を殆どメタン化することなくＣ
Ｏを選択的にメタン化することができるため第２反応部で反応温度が上昇することなく好適に用いることができる。
When such a catalyst is used in the first reaction part, the CO concentration can be easily reduced to approximately 20 ppm or less. The carbon monoxide methanation catalyst used in the second reaction part is highly active at high temperatures, but is not necessarily highly active at low temperatures, but C 2 is almost never methanated.
Since O can be selectively methanated, it can be suitably used without increasing the reaction temperature in the second reaction section.
第２反応部にこのような触媒を用いると、第２反応部でＣＯ濃度を容易に、概ね１０ｐｐｍ以下まで低減することができる。
前記第１反応部の入口反応温度（ＴENT）は１００〜１６０℃の範囲にあり、前記第１
反応部の出口反応温度（ＴEXIT）はが１８０℃以下であることが好ましい。
When such a catalyst is used in the second reaction part, the CO concentration in the second reaction part can be easily reduced to approximately 10 ppm or less.
The inlet reaction temperature (T ENT ) of the first reaction part is in the range of 100 to 160 ° C.
The outlet reaction temperature (T EXIT ) of the reaction section is preferably 180 ° C. or lower.
第１反応部の入口反応温度（ＴENT）が低すぎると第１反応部に用いる触媒によっては
充分な活性が得られず、高濃度のＣＯが第２反応部へ供給されることになる。第１反応部の入口反応温度（ＴENT）が高すぎると、第１反応部の出口反応温度（ＴEXIT）が１８０
℃を超えることがあり、ＣＯ2のメタネーションが顕著となり選択性が低下する場合があ
る。
If the inlet reaction temperature (T ENT ) of the first reaction section is too low, sufficient activity cannot be obtained depending on the catalyst used in the first reaction section, and high concentration CO is supplied to the second reaction section. If the inlet reaction temperature (T ENT ) of the first reaction section is too high, the outlet reaction temperature (T EXIT ) of the first reaction section is 180
In some cases, the temperature may exceed 0 ° C., and the methanation of CO 2 may be remarkable and the selectivity may be lowered.
このとき、第１出口反応部の平均反応温度（Ｔ1）は１２０〜１７０℃、さらには１２
５〜１６０℃の範囲にあることが好ましい。なお、第１反応部の平均反応温度（Ｔ1）は
前記反応温度（ＴENT）と前記反応温度（ＴEXIT）との平均値を意味している。第１反応
部の平均反応温度（Ｔ1）が低い場合は、充分な活性が得られず、高濃度のＣＯが第２反
応部へ供給されることになる。第１反応部の平均反応温度（Ｔ1）が高いと、ＣＯ2のメタネーションが顕著になり選択性が低下する場合がある。
At this time, the average reaction temperature of the first outlet reaction section (T 1) is 120 to 170 ° C., more 12
It is preferable that it exists in the range of 5-160 degreeC. The average reaction temperature (T 1 ) in the first reaction part means the average value of the reaction temperature (T ENT ) and the reaction temperature (T EXIT ). When the average reaction temperature (T 1 ) of the first reaction part is low, sufficient activity cannot be obtained, and high-concentration CO is supplied to the second reaction part. If the average reaction temperature (T 1 ) in the first reaction part is high, the methanation of CO 2 becomes remarkable and the selectivity may be lowered.
また、第２反応部の入口の反応温度（第１反応部出口温度（ＴEXIT）と同じ）は１８０℃以下であり、第２反応部出口温度は後述する第２反応部に用いる一酸化炭素メタネーション用触媒を充填した場合、１０５〜１８０℃、好ましくは１１０〜１７０℃の範囲にある。 The reaction temperature at the inlet of the second reaction section (same as the first reaction section outlet temperature (T EXIT )) is 180 ° C. or lower, and the second reaction section outlet temperature is carbon monoxide used in the second reaction section described later. When the catalyst for methanation is filled, it is in the range of 105 to 180 ° C, preferably 110 to 170 ° C.
本発明の一酸化炭素のメタネーション方法では、このように第２反応部出口温度が第１反応部出口温度（ＴEXIT）を大きく上回ることがないので温度管理が容易であるとともにＣＯを選択的にメタン化することができる。 In the carbon monoxide methanation method of the present invention, the temperature of the second reaction section outlet does not greatly exceed the first reaction section outlet temperature (T EXIT ) as described above. Can be methanated.
前記第１反応部へ供給される一酸化炭素ガス含有水素ガスは、通常シフト反応生成ガスが用いられる。シフト反応生成ガスには水素ガス、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。 As the carbon monoxide gas-containing hydrogen gas supplied to the first reaction section, a shift reaction product gas is usually used. The shift reaction product gas contains hydrogen gas, carbon monoxide gas, carbon dioxide gas, water vapor, and the like, and may contain methane.
シフト反応生成ガス中の水素ガスの濃度は概ね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。さらにシフト反応生成ガスには水蒸気が２０vol%〜７０vol%の割合で含まれている。 The concentration of hydrogen gas in the shift reaction product gas is approximately 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). Further, the shift reaction product gas contains water vapor at a rate of 20 vol% to 70 vol%.
本発明に用いるシフト反応生成ガス中のＣＯ濃度（ＣＦCO）は、０．３〜１．０Vol%、さらには０．５Vol%以下の範囲にあることが好ましい。ＣＯ濃度が大きいと、ＣＯメタネーション反応に伴い消費される水素量が多くなり、燃料電池に供給するための水素量が減少することがある。 The CO concentration (CF 2 CO 3 ) in the shift reaction product gas used in the present invention is preferably in the range of 0.3 to 1.0 Vol%, more preferably 0.5 Vol% or less. When the CO concentration is high, the amount of hydrogen consumed with the CO methanation reaction increases, and the amount of hydrogen supplied to the fuel cell may decrease.
また、第１反応部の出口ガス中のＣＯ濃度（Ｃ１CO）は５００ｐｐｍ以下、さらには１００ｐｐｍ以下の範囲にあることが好ましい。ＣＯ濃度（Ｃ１CO）が多いと、第２反応部での反応によりＣＯ濃度が充分に低下しない場合がある。 The CO concentration (C1 CO ) in the outlet gas of the first reaction section is preferably 500 ppm or less, more preferably 100 ppm or less. If the CO concentration (C1 CO 2 ) is large, the CO concentration may not be sufficiently lowered due to the reaction in the second reaction part.
また、第２反応部の出口ガス中のＣＯ濃度（Ｃ２CO）は１０ｐｐｍ以下、さらには５ｐｐｍ以下であることが好ましい。ＣＯ濃度（Ｃ２CO）が多いと、燃料電池へ供給した場合、ＣＯ濃度が高いために燃料電池の電極をＣＯにより短時間で被毒する問題がある。 Further, the CO concentration (C2 CO ) in the outlet gas of the second reaction section is preferably 10 ppm or less, more preferably 5 ppm or less. When the CO concentration (C 2 CO 2 ) is large, there is a problem that when the fuel cell is supplied, the CO concentration is high and the fuel cell electrode is poisoned by CO in a short time.
触媒として、第１反応部に用いる一酸化炭素メタネーション用触媒は、ＮｉＯおよび／またはＣｏＯを含んでなる複合酸化物担体に４Ｂ族、７Ａ族および８族から選ばれる１種以上の金属が担持されてなるものが好ましい。 As the catalyst, the catalyst for carbon monoxide methanation used in the first reaction part is supported by one or more metals selected from Group 4B, Group 7A and Group 8 on a composite oxide support containing NiO and / or CoO. What is made is preferable.
担持される金属成分として、これらの中でも、４Ｂ族の金属としてＳｎ、７Ａ族の金属としてＲｅ、８族の金属としてＲｕ、Ｐｔ、Ｐｄ、Ｒｔ、Ｎｉ、ＣｏおよびＩｒから選ばれる１種以上の金属が好適に用いられる。 Among these, as the metal component to be supported, one or more selected from Sn as the group 4B metal, Re as the group 7A metal, Ru, Pt, Pd, Rt, Ni, Co and Ir as the group 8 metal Metal is 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、Ｓｎまたは他の金属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。 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 Sn or another metal.
Ｒｅの場合、Ｒｅまたは他の金属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。Ｒｕ、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。 In the case of Re, it is considered that the activity is improved by promoting the adsorption and desorption of carbon species to Re or other metals. In the case of Ru, Pt, Pd, Rh, Ni, and Co, it is considered that the activity is improved by dissociating and adsorbing CO and H 2 .
なかでも、金属成分が８族から選ばれる１種以上の金属であることが好ましく、具体的にはＲｕ、Ｐｔ、Ｐｄ、Ｒｔ、Ｎｉ、Ｃｏ、Ｉｒ等が挙げられる。
特に、金属成分としてＲｕが含まれていると、低温での活性および選択性に優れている。このとき、このとき、金属成分中のＲｕの割合は金属として２０重量％以上、さらに２５重量％以上の範囲にあることが好ましい。金属成分中のＲｕの割合が金属として２０重量％未満の場合は、低温での活性が低く、反応による発熱が少ないため、第１反応部での反応性が低下し、結果としてＣＯ濃度を充分に低減できないことがある。
Especially, it is preferable that a metal component is 1 or more types of metals chosen from 8 groups, and specifically, Ru, Pt, Pd, Rt, Ni, Co, Ir etc. are mentioned.
In particular, when Ru is contained as a metal component, the activity and selectivity at low temperatures are excellent. At this time, the ratio of Ru in the metal component is preferably 20% by weight or more, more preferably 25% by weight or more as a metal. When the ratio of Ru in the metal component is less than 20% by weight as a metal, the activity at low temperature is low and the heat generated by the reaction is small, so the reactivity in the first reaction part is lowered, and as a result, the CO concentration is sufficient. May not be reduced.
このような金属成分の担持量は、第１反応部に用いる触媒中に金属として０．５〜１５重量％、さらには１〜１０重量％の範囲にあることが好ましい。担持量が少ないと、活性および選択性が不充分となることがあり、担持量が多すぎても活性は高いもののＣＯ2の
メタネーション反応が起こるために選択性が低下し、結果としてＣＯの除去効果が不充分となることがある。
The amount of such a metal component supported is preferably in the range of 0.5 to 15% by weight, more preferably 1 to 10% by weight as a metal in the catalyst used in the first reaction part. When the amount of supported is small, there is the activity and selectivity may be insufficient, although activity is higher too large supported amount reduces the selectivity for methanation reaction of CO 2 takes place, as a result of CO The removal effect may be insufficient.
担体としては、少なくともＮｉＯおよび／またはＣｏＯ（なお、酸化コバルトであればよくＣｏ3Ｏ4も含む）を含んでなる複合酸化物担体が用いられ、具体的にはＺｒＯ2-ＣｏＯ、ＺｒＯ2-ＮｉＯ、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−Ｃｏ3Ｏ4等が挙げられる。ＮｉＯおよび／またはＣｏＯを含むことで、低温での活
性および選択性を向上することができる。なお、かかる作用効果を発現するためには、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％以上含まれていることが望ましい。
As the support, a composite oxide support containing at least NiO and / or CoO (which may be cobalt oxide and also including Co 3 O 4 ) is used. Specifically, ZrO 2 —CoO, ZrO 2 — NiO, 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 — Examples thereof include CeO 2 —CoO, Al 2 O 3 —NiO, TiO 2 —CoO, TiO 2 —NiO, and TiO 2 —SiO 2 —Co 3 O 4 . By including NiO and / or CoO, the activity and selectivity at a low temperature can be improved. In order to exhibit such an effect, it is desirable that at least one of Ni and Co oxides is contained in the composite oxide in an amount of approximately 10% by weight or more, preferably 30% by weight or more.
第２反応部に用いる一酸化炭素メタネーション用触媒は、６Ａ族および８族から選ばれる１種以上の金属が金属酸化物担体に担持されている。金属成分として、６Ａ族の金属ではＭｏ、Ｗ、８族の金属ではＲｕが好適に用いられる。 In the catalyst for carbon monoxide methanation used in the second reaction section, one or more metals selected from Group 6A and Group 8 are supported on a metal oxide support. As the metal component, Mo or W is suitably used for the Group 6A metal, and Ru is suitably used for the Group 8 metal.
このような金属成分の担持量は、第２反応部に用いる触媒中に金属として１〜１５重量％、さらには２〜１２重量％の範囲にあることが好ましい。担持量が少ないと、活性およ
びＣＯメタネーション選択性が不充分となることがある。また、担持量が多すぎても、ＣＯ2のメタネーション反応が起こるために発熱が顕著になるとともに選択性が低下し、結
果としてＣＯの除去効果が不充分となることがある。
The amount of such a metal component supported is preferably in the range of 1 to 15% by weight, more preferably 2 to 12% by weight as a metal in the catalyst used in the second reaction part. If the loading is small, the activity and CO methanation selectivity may be insufficient. Even if the amount is too large, the methanation reaction of CO 2 occurs, so that the heat generation becomes remarkable and the selectivity is lowered, and as a result, the effect of removing CO may be insufficient.
金属酸化物担体成分としては、具体的にはＺｒＯ2、ＣｅＯ2、Ａｌ2Ｏ3、ＴiＯ2、Ｓi
Ｏ2から選ばれる１種以上の酸化物または複合酸化物である。具体的にはＺｒＯ2、ＣｅＯ2、Ａｌ2Ｏ3、ＴiＯ2、ＳiＯ2の他ＺｒＯ2-Ａｌ2Ｏ3、ＺｒＯ2-ＴiＯ2、ＺｒＯ2-ＳiＯ2
、Ａｌ2Ｏ3−ＣｅＯ2、ＴｉＯ2−ＳｉＯ2等の複合酸化物が挙げられる。
Specific examples of the metal oxide support component include ZrO 2 , CeO 2 , Al 2 O 3 , TiO 2 and Si.
One or more oxides or composite oxides selected from O 2 . Specifically, ZrO 2 , CeO 2 , Al 2 O 3 , TiO 2 , SiO 2 , ZrO 2 —Al 2 O 3 , ZrO 2 —TiO 2 , ZrO 2 —SiO 2.
, Al 2 O 3 —CeO 2 , TiO 2 —SiO 2 and other complex oxides.
これらの酸化物あるいは複合酸化物自体はＣＯメタネーション活性、ＣＯ2メタネーシ
ョン活性が極めて低いが、一方で比較的比表面積が高く、このため前記Ｍｏ、Ｗ、Ｒｕ等の金属を高分散状態で担持することができ、活性は必ずしも高くないもののＣＯメタネーション選択性が高く、ＣＯ2メタネーション選択性が低い前記金属成分の特性を充分に発
揮することができる。
These oxides or composite oxides themselves have very low CO methanation activity and CO 2 methanation activity, but on the other hand they have a relatively high specific surface area, so that metals such as Mo, W, and Ru are highly dispersed. Although it can be supported and has not necessarily high activity, it can exhibit the characteristics of the metal component with high CO methanation selectivity and low CO 2 methanation selectivity.
第２反応部に使用される触媒には、ＮｉＯおよび／またはＣｏＯは含まれない。その理由は、上記した作用効果を奏することが可能となるからである。
一酸化炭素メタネーション用触媒の調製
本発明の第１反応部および第２反応部に用い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、前記活性特性（所定条件でのＣＯ除去率が９８％以上）を有し、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。
The catalyst used in the second reaction part does not contain NiO and / or CoO. The reason for this is that the above-described effects can be achieved.
Preparation of catalyst for carbon monoxide methanation The catalyst for carbon monoxide methanation used in the first reaction section and the second reaction section of the present invention has the carrier component and the active component in the above-mentioned ranges, and the activity characteristics (predetermined conditions) The CO removal rate at 98% is 98% or more) and can be produced by a conventionally known method without particular limitation as long as it can be used for methanation of carbon monoxide.
第１反応部で使用される触媒の場合、例えば、担体成分原料としてニッケル塩、コバルト塩と必要に応じてジルコニウム塩、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。 In the case of the catalyst used in the first reaction part, for example, an aqueous solution of one or more metal salts of nickel salt, cobalt salt and optionally zirconium salt, cerium salt, aluminum salt, titanium salt, silicate as a carrier component raw material, Preferably, two or more mixed metal salt aqueous solutions are prepared.
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。 As the nickel salt, nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, nickel carbonate and the like are used, and as the cobalt salt, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetate and the like are 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 aluminum 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.
混合塩水溶液中のニッケル塩、コバルト塩の使用量は最終的に得られる複合酸化物担体中に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％以上含まれる量とする。 The amount of nickel salt and cobalt salt used in the mixed salt aqueous solution is such that at least one of Ni and Co oxides is approximately 10% by weight or more, preferably 30% by weight or more, in the finally obtained composite oxide support. Amount.
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. As the basic compound, an aqueous alkali metal solution such as NaOH, KOH, Na 2 CO 3 , ammonia, tetramethylammonium hydroxide and the like can be used.
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、担体を調製するが、主に２種類の方法があり、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。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。 Next, the carrier is prepared. There are mainly two methods, one is drying and baking the washed gel, and the resulting mixed oxide powder is pulverized as necessary, and a tablet molding machine, etc. It is a method of molding with. 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.
焼成して得た担体に、ついで４Ｂ族、７Ａ族および８族から選ばれる１種以上の金属の塩を担持する。担持する方法としては、所定量金属成分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金属塩水溶液を調製し、担体に吸収させ、ついで乾燥する。金属塩としては、水溶性のものであれば特に制限されるものではないが、具体的には、塩化スズ、酢酸スズ、硫酸スズ、シュウ酸スズ、塩化レニウム、過レニウム酸アンモニウム、塩化ルテニウム、硝酸ルテニウム、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。 The carrier obtained by firing is then loaded with one or more metal salts selected from Group 4B, Group 7A and Group 8. The method of supporting is not particularly limited as long as a predetermined amount of the metal component can be supported. Usually, an aqueous metal salt solution corresponding to the pore volume of the support is prepared, absorbed by the support, and then dried. The metal salt is not particularly limited as long as it is water-soluble, but specifically, tin chloride, tin acetate, tin sulfate, tin oxalate, rhenium chloride, ammonium perrhenate, ruthenium chloride, Ruthenium nitrate, chloroplatinic acid, dichlorotetraamine platinum, palladium nitrate, palladium chloride, rhodium nitrate, rhodium chloride, nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate and the like are preferably used.
金属塩水溶液の濃度は、通常、所定量、すなわち得られる触媒中の金属成分の合計の含有量が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吸収および乾燥を繰り返し行うこともできる。 The concentration of the metal salt aqueous solution is usually a predetermined amount, that is, a concentration that can be supported so that the total content of the metal components in the obtained catalyst is 0.5 to 15% by weight. When the amount is low or when the amount is large, absorption 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℃で還元して第１反応部に用いる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 used in the first reaction section can be obtained by reduction at 100 to 700 ° C., preferably 150 to 400 ° C. in a reducing gas atmosphere.
還元ガスとしては通常、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。還元温度が低すぎると、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り、また還元温度が高すぎると焼結が起こり、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。 As the reducing gas, hydrogen gas or a mixed gas of hydrogen gas and inert gas such as nitrogen gas is usually used. If the reduction temperature is too low, the reduction of the active metal becomes insufficient and sufficient activity may not be obtained, and if the reduction temperature is too high, sintering occurs, the specific surface area of the resulting catalyst is small, and the activity is low. It may be insufficient.
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。
また、第１反応部に用いる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。
Although the time for reduction varies depending on the temperature, it is usually 0.5 to 12 hours.
The shape of the carbon monoxide methanation catalyst used in the first reaction part is not particularly limited, and can be appropriately selected depending on the reaction method, reaction conditions, etc. Fine powder can be used as it is, It can also be used after being pressure-molded, and can be suitably used that which has been extrusion-molded into a honeycomb or pellet form, and further which has a pellet (spherical shape).
本発明の第２反応部に用いる一酸化炭素メタネーション用触媒も、前記した第１反応部に使用される触媒と同様の方法で調製できる。
例えば、担体成分原料としてジルコニウム塩、セリウム塩、アルミニウム塩、チタニウム塩、珪酸塩の１種以上の金属塩水溶液、好ましくは２種以上の混合金属塩水溶液を調製する。
The catalyst for carbon monoxide methanation used for the 2nd reaction part of this invention can also be prepared by the method similar to the catalyst used for an above described 1st reaction part.
For example, one or more metal salt aqueous solutions of zirconium salt, cerium salt, aluminum salt, titanium salt, and silicate, preferably two or more mixed metal salt aqueous solutions are prepared as carrier component raw materials.
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。
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.
ついで、混合塩水溶液に、第１反応部の触媒と同様にして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したのち、成型し、乾燥し、焼成する。 Next, the mixed salt aqueous solution is neutralized by adding an aqueous solution of a basic compound in the same manner as the catalyst in the first reaction part, and after aging as necessary to prepare a hydrogel, it is molded, dried, and calcined. .
焼成して得た担体に、６Ａ族および８族から選ばれる１種以上の金属の塩を担持する。担持する方法としては、所定量金属成分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金属塩水溶液を調製し、担体に吸収させ、ついで乾燥する。 One or more metal salts selected from Group 6A and Group 8 are supported on the carrier obtained by firing. The method of supporting is not particularly limited as long as a predetermined amount of the metal component can be supported. Usually, an aqueous metal salt solution corresponding to the pore volume of the support is prepared, absorbed by the support, and then dried.
前記６Ａ族のＭｏ、Ｗ、８族のＲｕ等の金属塩は好適に用いることができる。
具体的には、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、塩化ルテニウム、硝酸ルテニウム等が好適に用いられる。
金属塩水溶液の濃度は、通常、所定量、すなわち得られる触媒中の金属成分の合計の含有量が１〜１５重量％、好ましくは２〜１２重量％の範囲となるように担持できる濃度とするが、金属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吸収および乾燥を繰り返し行うこともできる。
Metal salts such as Group 6A Mo, W, Group 8 Ru and the like can be preferably used.
Specifically, molybdenum chloride, ammonium molybdate, ammonium tungstate, ruthenium chloride, ruthenium nitrate and the like are preferably used.
The concentration of the metal salt aqueous solution is usually a predetermined amount, that is, a concentration capable of being supported so that the total content of the metal components in the obtained catalyst is in the range of 1 to 15% by weight, preferably 2 to 12% by weight. However, when the concentration of the aqueous metal salt solution is low or when the supported amount is large, absorption 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℃で還元して第２反応部に用いる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 used in the second reaction part 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、第２反応部に用いる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。 The shape of the carbon monoxide methanation catalyst used in the second reaction section is not particularly limited, and can be appropriately selected depending on the reaction method, reaction conditions, etc. Fine powder can be used as it is, It can also be used after being pressure-molded, and can be suitably used that which has been extrusion-molded into a honeycomb or pellet form, and further which has a pellet (spherical shape).
本発明では、前記第２反応部に、ＣＯ吸着剤が充填されたＣＯ吸着塔が接続されていることが好ましい。
前記ＣＯ吸着剤としては、前記した第２反応部で生成したＨ2、Ｈ2Ｏ、ＣＯ2等を含む
ガス中のＣＯを吸着することができれば特に制限はないが、本発明では、前記ＣＯ吸着剤が、４Ｂ族、６Ａ族、７Ａ族および８族から選ばれる１種以上の金属が担持されたゼオライトからなり、該ＣＯ吸着剤中の金属の含有量が０．５〜１５重量％の範囲にあることが好ましい。
In the present invention, it is preferable that a CO adsorption tower filled with a CO adsorbent is connected to the second reaction section.
The CO adsorbent is not particularly limited as long as it can adsorb CO in a gas containing H 2 , H 2 O, CO 2 and the like generated in the second reaction section. In the present invention, the CO adsorbent is not limited. The adsorbent is made of zeolite on which one or more metals selected from Group 4B, Group 6A, Group 7A and Group 8 are supported, and the content of metal in the CO adsorbent is 0.5 to 15% by weight. It is preferable to be in the range.
ＣＯ吸着剤に用いるゼオライトとしてはＺＳＭ−５型ゼオライト、モルデナイト型ゼオライト、フォージャサイト型ゼオライト、βゼオライトから選ばれる１種以上のゼオライトが好適に用いられる。フォージャサイト型ゼオライトを用いる場合は骨格を構成するＳiＯ2とＡl2Ｏ3のモル比（ＳiＯ2／Ａl2Ｏ3）が１０以上、さらには１５以上であることが
好ましい。
As the zeolite used for the CO adsorbent, one or more zeolites selected from ZSM-5 type zeolite, mordenite type zeolite, faujasite type zeolite, and β zeolite are preferably used. When faujasite type zeolite is used, the molar ratio of SiO 2 to Al 2 O 3 constituting the framework (SiO 2 / Al 2 O 3 ) is preferably 10 or more, more preferably 15 or more.
このようなゼオライトは、他の無機酸化物あるいは複合酸化物に比べて比表面積が高く、イオン交換法によって金属イオンを担持し、還元処理することにより金属担持ゼオライト触媒が得られる。このとき、担持された活性成分が微細な金属微粒子であるためにＣＯ吸着容量が高く、好適に用いることができる。 Such a zeolite has a higher specific surface area than other inorganic oxides or composite oxides, and a metal-supported zeolite catalyst can be obtained by supporting metal ions by an ion exchange method and performing a reduction treatment. At this time, since the supported active ingredient is fine metal fine particles, the CO adsorption capacity is high and can be suitably used.
金属成分としては、４Ｂ族、６Ａ族、７Ａ族および８族から選ばれる１種以上の金属が好ましい。
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Ｍｎ、Ｒｅ、８族の金属としてはＲｕ、Ｐｔ、Ｒｈ、Ｐｄ、Ｆｅ、Ｎｉ、ＣｏおよびＩｒから選ばれる１種以上の金属が好適に用いられる。
As the metal component, one or more metals selected from Group 4B, Group 6A, Group 7A and Group 8 are preferable.
Among them, Sn as the 4B group metal, Mo, W as the 6A group metal, Mn, Re as the 7A group metal, Ru, Pt, Rh, Pd, Fe, Ni, Co as the 8th group metal. And one or more metals selected from Ir and Ir are preferably used.
このような金属成分の担持量は吸着剤中に金属として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。
金属の担持量が小さすぎるとＣＯ吸着容量が小さくなり、金属の担持量が多すぎたとしてもさらにＣＯ吸着容量が増加することもなく、金属の種類によっては担持金属の粒子径が大きくなるためかＣＯ吸着量が減少することがある。
The amount of such a metal component supported is preferably in the range of 0.5 to 15% by weight, more preferably 1.0 to 10% by weight as a metal in the adsorbent.
If the amount of supported metal is too small, the CO adsorption capacity will be small, and even if the amount of supported metal is too large, the CO adsorption capacity will not increase, and depending on the type of metal, the particle size of the supported metal will increase. The amount of CO adsorption may decrease.
このようなＣＯ吸着剤が充填されたＣＯ吸着塔が接続されていると、第２反応部で生成したガス中に残存するＣＯガスを吸着することができるので、ＣＯガスを実質的に含まない水素ガスを製造することができる。そして、このような水素ガスを燃料電池に用いると、燃料電池の電極の被毒を抑制することができるので燃料電池を長期にわたって使用することができる。 When a CO adsorption tower filled with such a CO adsorbent is connected, the CO gas remaining in the gas generated in the second reaction section can be adsorbed, and therefore substantially does not contain CO gas. Hydrogen gas can be produced. And when such hydrogen gas is used for a fuel cell, since poisoning of the electrode of a fuel cell can be suppressed, a fuel cell can be used over a long period of time.
なお、第２反応部に接続して用いる吸着塔は複数の吸着塔を並列に接続して用いることもでき、この場合、少なくとも１つの吸着塔は吸着に、他の吸着塔は再生し、繰り返し連続的に使用することができる。 The adsorption tower used by connecting to the second reaction section can also be used by connecting a plurality of adsorption towers in parallel. In this case, at least one adsorption tower is used for adsorption, and the other adsorption tower is regenerated and repeated. Can be used continuously.
本発明に用いる金属担持ゼオライトは、前記金属成分が所定量担持されていれば特に制限はなく従来公知の方法で製造することができる。
以下、本発明に好適に用いることのできる金属担持ゼオライトの製造方法について例示する。
The metal-supported zeolite used in the present invention is not particularly limited as long as a predetermined amount of the metal component is supported, and can be produced by a conventionally known method.
Hereinafter, a method for producing a metal-supported zeolite that can be suitably used in the present invention will be exemplified.
前記したゼオライト粉末に活性成分に用いる金属塩水溶液を、得られる吸着剤中の金属の含有量が前記範囲となるように吸収させ、ついで乾燥し、還元することによって一酸化炭素吸着剤を得ることができる。 A carbon monoxide adsorbent is obtained by absorbing the metal salt aqueous solution used as an active ingredient in the zeolite powder described above so that the metal content in the obtained adsorbent is within the above range, and then drying and reducing. Can do.
また、別の方法はゼオライト粉末を水に分散させ、これに、活性成分に用いる金属の塩あるいは金属塩水溶液を添加し、必要に応じて加熱してイオン交換を行う。このときの金属塩の使用量は、ゼオライトのＡｌ2Ｏ3のモル数を１とした時に、金属塩が０．１〜５モルの範囲とすることが好ましい。金属塩の使用量が０．１モル未満の場合はゼオライトにイオン交換される金属イオンの量が少なく、充分な吸着性能が得られないことがある。金属塩の使用量が５モルを超えてはイオン交換により担持できる金属イオンの量をさらに増やすことは困難で、また、イオン交換されない金属イオン、金属錯イオンが増加することから経済性が低下する問題がある。 In another method, zeolite powder is dispersed in water, a metal salt or an aqueous metal salt solution used as an active ingredient is added thereto, and ion exchange is performed by heating as necessary. The amount of the metal salt used at this time is preferably in the range of 0.1 to 5 moles of metal salt when the number of moles of Al 2 O 3 in the zeolite is 1. When the amount of metal salt used is less than 0.1 mol, the amount of metal ions ion-exchanged to zeolite is small, and sufficient adsorption performance may not be obtained. If the amount of metal salt used exceeds 5 moles, it is difficult to further increase the amount of metal ions that can be supported by ion exchange, and the economic efficiency decreases because the number of metal ions and metal complex ions that are not ion-exchanged increases. There's a problem.
イオン交換する際の温度は、通常、室温から９８℃、時間は０．５時間から１２時間の範囲である。
金属塩としては、Ｓｎ、Ｒｅ、Ｒｕ、Ｐｔ、Ｒｈ、Ｐｄ、Ｆｅ、Ｎｉ、Ｃｏ、Ｉｒ等の
１種以上の金属塩が用いられる。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、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。
The temperature at the time of ion exchange is usually from room temperature to 98 ° C., and the time is from 0.5 hours to 12 hours.
As the metal salt, one or more metal salts such as Sn, Re, Ru, Pt, Rh, Pd, Fe, Ni, Co, and Ir are used. Specifically, tin chloride, tin acetate, tin sulfate, tin oxalate, molybdenum chloride, ammonium molybdate, tungstic acid, ammonium tungstate, rhenium chloride, ammonium perrhenate, chloroplatinic acid, dichlorotetraamine platinum, nitric acid Palladium, palladium chloride, rhodium nitrate, rhodium chloride, nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt chloride, cobalt sulfate and the like are preferably used.
金属塩の吸収またはイオン交換後濾過洗浄した後、乾燥し、ついで還元することによって一酸化炭素吸着剤を得ることができる。
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１５０〜６００℃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。
A carbon monoxide adsorbent can be obtained by absorption after metal salt absorption or ion exchange, filtration, washing, drying, and reduction.
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 reducing at 100 to 700 ° C., preferably 150 to 600 ° 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。還元温度が低いと、還元が不充分となり、充分な吸着性能が得られないことがあり、高すぎても担持金属の粒子径が大きくなりすぎて吸着性能が不充分となったり、金属の焼結が起こり、吸着性能が不充分となることがある。 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 reduction temperature is low, the reduction may be insufficient and sufficient adsorption performance may not be obtained. If the reduction temperature is too high, the particle size of the supported metal may become too large, resulting in insufficient adsorption performance, or metal firing. Condensation may occur and the adsorption performance may be insufficient.
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。
このようにして得られた吸着剤は、そのまま粉体を吸着剤として用いることもできるが、通常、必要に応じて粉砕し、そのまま錠剤成型機等で成型したり、あるいはシリカゾル、アルミナゾル等のバインダーを混合し、必要に応じて成形助剤を混合し、押出成型機にて成型して用いることができる。また、ハニカム基材に吸着剤の層を形成して用いることもできる。
[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]
第１反応部用メタネーション触媒(1-1)の調製
硝酸コバルト・６水和物１５４．８ｇ、硝酸ジルコニル水溶液（ＺｒＯ2濃度：２５％
）２０１．６ｇおよび硝酸ニッケル・６水和物３６．８ｇを水２５００ｇに加えて混合水溶液(1-1)を調製した。
Although the time for reduction varies depending on the temperature, it is usually 0.5 to 12 hours.
The adsorbent thus obtained can be used directly as a powder as an adsorbent, but is usually pulverized if necessary and molded as it is with a tablet molding machine, or a binder such as silica sol or alumina sol. Can be mixed and, if necessary, a molding aid can be mixed and molded by an extrusion molding machine. Further, an adsorbent layer may be formed on the honeycomb substrate.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of methanation catalyst (1-1) for first reaction part 154.8 g of cobalt nitrate hexahydrate, aqueous zirconyl nitrate solution (ZrO 2 concentration: 25%)
) 201.6 g and 36.8 g of nickel nitrate hexahydrate were added to 2500 g of water to prepare a mixed aqueous solution (1-1).
水酸化ナトリウム８５．５ｇを水１５１９．５ｇに溶解し、撹拌しながらこれに混合水溶液(1-1)を添加してヒドロゲルを調製し、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(1-1)を得た。
85.5 g of sodium hydroxide was dissolved in 1519.5 g of water, and a mixed aqueous solution (1-1) was added thereto while stirring to prepare a hydrogel, 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 then fired at 550 ° C for 1 hour in the air to obtain a composite oxide powder (1-1) Got.
ついで、複合酸化物粉体(1-1)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第１反応部用メタネーション触媒担体(1-1)を調製した。 Next, the composite oxide powder (1-1) 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 first reaction part meta. Nation catalyst carrier (1-1) was prepared.
塩化ルテニウムを金属濃度が１０重量％となるように溶解し、含浸溶液（1-1）を調製
した。含浸溶液(1-1)２６．５ｇをメタネーション触媒用担体(1-1)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中に分散させて攪拌し、その後、濾過し、十分な温水を掛けて洗浄し、１２０℃にて５時間乾燥し、４００℃にて１．５時間水素気流中にて還元処理を行い、第1反応部用メタネーション触媒（1-1）を調製した。触媒組成、比表面積および細孔容積を測定し、結果を表１に示した。
第２反応部用メタネーション用触媒(1-2)の調製
硝酸ジルコニル水溶液（ＺｒＯ2濃度：２５％）４００．０ｇを水２２００．０ｇに加
えてよく攪拌し、その溶液に水酸化ナトリウム６５．０ｇを水１３２１．０ｇに溶解した溶液を添加し、ついで、８０℃にて２時間熟成した。
Ruthenium chloride was dissolved so that the metal concentration was 10% by weight to prepare an impregnation solution (1-1). 26.5 g of the impregnation solution (1-1) is absorbed in 50 g of the support (1-1) for methanation catalyst, sufficiently stirred, allowed to stand for 1 hour, dried at 120 ° C. for 8 hours, and then adjusted to pH. Disperse in 2 L of sodium bicarbonate solution prepared in 10 to 11 and stir, then filter, wash with sufficient warm water, dry at 120 ° C. for 5 hours, and dry at 400 ° C. for 1.5 hours. Reduction treatment was performed in a hydrogen stream to prepare a methanation catalyst (1-1) for the first reaction part. The catalyst composition, specific surface area and pore volume were measured, and the results are shown in Table 1.
Preparation of zirconyl nitrate solution (ZrO 2 concentration: 25%) for the second reaction portion methanation catalyst (1-2) was 400.0g was well stirred in water 2200.0G, sodium hydroxide to the solution 65. A solution prepared by dissolving 0 g in 1321.0 g of water was added, followed by aging 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、酸化ジルコニウム粉体を得た。
ついで、酸化ジルコニウム粉体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第２反応部用メタネーション触媒担体(1-2)を得た。
The aged hydrogel was filtered, washed with sufficient warm water, dried at 120 ° C. for 1 day, and then fired at 550 ° C. for 1 hour in the air to obtain zirconium oxide powder.
Next, the zirconium oxide powder is filled into a tablet molding machine, press-molded at 50 kg / cm 2 , then pulverized, and the particle size is adjusted to 20 to 42 mesh to adjust the methanation catalyst carrier for the second reaction part (1- 2) was obtained.
得られた第２反応部用メタネーション触媒担体５０ｇに、塩化ルテニウムを金属濃度が１０重量％となるように溶解した含浸用溶液１６．２ｇを吸収させ、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中に分散させて攪拌し、その後、十分な温水を掛けて洗浄し、１２０℃にて５時間乾燥し、さらに七モリブデン酸六アンモニウム四水和物をＭｏ金属濃度１０重量％となるように溶解した含浸溶液２７．０ｇを吸収させ、一時間静置した後、１２０℃にて４時間乾燥し、ついで５５０℃で１時間、大気中にて焼成を行い、４００℃で水素−窒素混合ガス(Ｈ2濃度１０Vol%)の流通下で１時間還元処理して第２反応部用メタネーション触媒（1-2）を調製した。 Into the obtained second reaction part methanation catalyst support 50 g, 16.2 g of impregnation solution in which ruthenium chloride was dissolved so that the metal concentration was 10% by weight was absorbed, and allowed to stand at 120 ° C. for 1 hour. For 8 hours, and then dispersed in 2 L of sodium bicarbonate solution adjusted to pH 10-11 and stirred, then washed with sufficient warm water, dried at 120 ° C. for 5 hours, 27.0 g of an impregnation solution in which hexaammonium heptamolybdate tetrahydrate is dissolved so that the Mo metal concentration is 10% by weight is absorbed, left to stand for 1 hour, dried at 120 ° C. for 4 hours, and then 550 ° C. Calcination in the atmosphere for 1 hour, and reduction treatment at 400 ° C. for 1 hour under the flow of hydrogen-nitrogen mixed gas (H 2 concentration 10 Vol%) for the second reaction part methanation catalyst (1-2) Was prepared.
吸着剤(1)の調製
Ｙ型ゼオライト（ＳｉＯ2／Ａｌ2Ｏ3＝５モル比）１００ｇを水１９００ｇに懸濁した
後、６０℃に加温し、塩化白金酸水溶液（Ｐｔ濃度２％）を攪拌しながら１１２０．０ｇ添加し、さらに６０℃にて２時間保持した。その後、濾過し、充分な温水を掛けて洗浄し、１２０℃で１昼夜乾燥し、４５０℃で３時間、大気中にて焼成を行い、４００℃で水素−窒素混合ガス(Ｈ2濃度１０Vol%)の流通下で１時間還元処理し、ついで、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吸着剤(1)を調製した。
Preparation of adsorbent (1) 100 g of Y-type zeolite (SiO 2 / Al 2 O 3 = 5 molar ratio) was suspended in 1900 g of water, and then heated to 60 ° C. to obtain an aqueous chloroplatinic acid solution (Pt concentration 2%). While stirring, 1120.0 g was added, and further maintained at 60 ° C. for 2 hours. Thereafter, it is filtered, washed with sufficient warm water, dried at 120 ° C. for one day and night, baked in the atmosphere at 450 ° C. for 3 hours, and mixed with hydrogen-nitrogen gas (H 2 concentration 10 Vol% at 400 ° C.). ) Under the flow of 1), then filled into a tablet molding machine, pressure-molded at 50 Kg / cm 2 , then pulverized, adjusted the particle size to 20-42 mesh, and adsorbent (1) Prepared.
第1反応部用メタネーション触媒(1-1)および第２反応部用メタネーション触媒(1-2)の
ＣＯ除去率の測定
メタネーション用触媒(1-1)４．２ｍｌを、内径１２ｍｍのステンレス製反応管（第２
反応部）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、触媒層の入口ガス温度を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%）を全触媒量に対してＳＶ=２，０００ｈ-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濃度を測定し、ＣＯ除去率を求め、結果を表に示した。同様にメタネーション用触媒(1-2)についても反応温度を１８０℃とした
以外は同様にしてＣＯ除去率を求め、結果を表１に示した。
Of the methanation catalyst (1-1) for the first reaction part and the methanation catalyst (1-2) for the second reaction part
Measurement of CO removal rate 4.2 ml of methanation catalyst (1-1) was added to a stainless steel reaction tube (second
In the reaction zone) and reduced 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., and the inlet gas temperature of the catalyst layer is set to a reaction temperature of 120 ° C. After that, the reaction mixed gas (carbon monoxide 0.6 Vol%, carbon dioxide 20.0 Vol%, methane 2.0 Vol%, hydrogen 51.37 Vol%, water vapor 33.3 Vol%) was added to the total catalyst amount by SV. = 2,000 h -1 circulated and the product gas in the steady state after about 1 hour was analyzed by gas chromatography and infrared spectroscopic gas concentration meter to measure the CO concentration at the outlet of the reaction tube, and the CO removal rate And the results are shown in the table. Similarly, for the methanation catalyst (1-2), the CO removal rate was determined in the same manner except that the reaction temperature was 180 ° C. The results are shown in Table 1.
反応試験
メタネーション用触媒(1-2)４．２ｍｌを、内径１２ｍｍのステンレス製反応管（第２
反応部）に充填し、ついで、その上部（第１反応部）にメタネーション触媒(1-1)を４．
２ｍｌ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、触媒層の入口ガス温度を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%）を全触媒量に対してＳＶ=２，０００ｈ-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各触媒の後段にて取り出し、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濃度を測定した
結果を表に示した。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。また、
第２反応部用触媒の後段のガス温度を測定し、出口反応温度とした。
4.2 ml of reaction test methanation catalyst (1-2) was added to a stainless steel reaction tube with an inner diameter of 12 mm (second
3. Next, the methanation catalyst (1-1) is added to the upper part (first reaction part).
After filling with 2 ml, reduction treatment was performed again for 1 hour under the flow of hydrogen-nitrogen mixed gas (H 2 concentration 10 Vol%) at a catalyst layer temperature of 400 ° C., and then the inlet gas temperature of the catalyst layer was set to a reaction temperature of 120 ° C. , A 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 SV = 2, based on the total catalyst amount. The gas produced in the steady state after about 1 hour is circulated to be 000 h -1 and taken out at the subsequent stage of each catalyst and analyzed by gas chromatography and an infrared spectroscopic gas concentration meter to measure the CO concentration at the outlet of the reaction tube. The results are shown in the table. Selectivity includes CO 2 from 20.0 Vol% of carbon dioxide in the reaction gas.
The increase / decrease was shown in the table, and the case where the increase / decrease in CO 2 was small was evaluated as having excellent selectivity. Also,
The gas temperature at the latter stage of the catalyst for the second reaction section was measured and used as the outlet reaction temperature.
さらに、吸着剤(1)８．４ｍｌを内径１２ｍｍのステンレス製反応管（吸着塔）に充填
し、吸着剤層温度３００℃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、吸着剤層温度を１２０℃にした後、第２反応部で生成したガスをＳＶ＝１，０００ｈ-1となるように流通させ、約１時間後の出口ＣＯ濃度を赤外分光型ガス濃度計で分析しＣＯ濃度を測定した結果を表１に示した。
[実施例２]
反応試験
実施例1において、触媒層の入口ガス温度を１３５℃とした以外は同様に行い、結果を
表１に示した。
[実施例３]
反応試験
実施例1において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を
表１に示した。
[実施例４]
第２反応部用メタネーション触媒(2-2)の調製
実施例１において調製した第２反応部用担体５０ｇに塩化ルテニウムを金属濃度が１０重量％となるように溶解した含浸用溶液１０．６ｇを吸収させ、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中に分散させて攪拌し、その後、十分な温水を掛けて洗浄し、１２０℃にて５時間乾燥し、さらに七モリブデン酸六アンモニウム四水和物をＭｏ金属濃度１０重量％となるように溶解した含浸溶液２１．２ｇを吸収させ、一時間静置した後、１２０℃にて４時間乾燥し、ついで５５０℃で１時間、大気中にて焼成を行い、４００℃で水素−窒素混合ガス(Ｈ2濃度１０Vol%)の流通下で１時間還元処理して第２反応部用メタネーション触媒（2-2）を調製した。触媒組成、比表面積、細孔容積およびＣＯ除去率を測定し、結果を表１に示した。
吸着剤(2)の調製
Ｙ型ゼオライト（ＳｉＯ2／Ａｌ2Ｏ3＝５モル比）１００ｇを水１９００ｇに懸濁した
後、６０℃に加温し、塩化銅水溶液（Ｃｕとして濃度２重量％）９２５．０ｇを添加し、さらに６０℃にて２時間撹拌した。その後、濾過し、充分な温水を掛けて洗浄し、１２０℃で１昼夜乾燥し、４５０℃で３時間、大気中にて焼成を行い、４００℃で水素−窒素混合ガス(Ｈ2濃度１０Vol%)の流通下で１時間還元処理し、ついで、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吸着剤(2)を調製した。
反応試験
実施例１において、第２反応部用触媒にメタネーション触媒(2-2)、および吸着塔に吸
着剤(2)を用いた以外は同様に行い、結果を表１に示した。
[実施例５]
反応試験
実施例４において、触媒層の入口ガス温度を１３５℃とした以外は同様に行い、結果を表１に示した。
[実施例６]
反応試験
実施例４において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を表１に示した。
[実施例７]
第２反応部用メタネーション触媒(3-2)の調製
実施例１において調製した第２反応部用担体５０ｇに塩化ルテニウム、タングステン酸を重量比でＲｕ：Ｗ＝１：１．２５となるように混合し、金属濃度が１０重量％となるように溶解した溶液４９．０５ｇを吸収させ、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中に分散させて攪拌し、その後、十分な温水を掛けて洗浄し、１２０℃にて５時間乾燥し、ついで５５０℃で１時間、大気中にて焼成を行い、４００℃で水素−窒素混合ガス(Ｈ2濃度１０Vol%)の
流通下で１時間還元処理して第２反応部用メタネーション触媒（3-2）を調製した。触媒
組成、比表面積、細孔容積およびＣＯ除去率を測定し、結果を表１に示した。
反応試験
実施例１において、第２反応部用触媒にメタネーション触媒(3-2)を用いた以外は同様
に行い、結果を表１に示した。
[実施例８]
反応試験
実施例７において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を表１に示した。
[実施例９]
第１反応部用メタネーション触媒(2-1)の調製
硝酸コバルト・６水和物１３１．９ｇ、硝酸ジルコニル水溶液（ＺｒＯ2濃度：２５％
）２４４．０ｇおよび硝酸ニッケル・６水和物１９．５ｇを水２５００ｇに加えて混合水溶液(2-1)を調製した。
Further, 8.4 ml of the adsorbent (1) is filled into a stainless steel reaction tube (adsorption tower) having an inner diameter of 12 mm, and again under a flow of hydrogen-nitrogen mixed gas (H 2 concentration 10 vol%) at an adsorbent layer temperature of 300 ° C. After reducing for 1 hour and then setting the adsorbent layer temperature to 120 ° C., the gas produced in the second reaction section was circulated so that SV = 1,000 h −1, and the outlet CO concentration after about 1 hour Table 1 shows the result of analyzing the CO concentration with an infrared spectroscopic gas concentration meter and measuring the CO concentration.
[Example 2]
The reaction was conducted in the same manner as in Example 1 except that the inlet gas temperature of the catalyst layer was 135 ° C. The results are shown in Table 1.
[Example 3]
The reaction was performed in the same manner as in Example 1 except that the inlet gas temperature of the catalyst layer was 150 ° C. Table 1 shows the results.
[Example 4]
Preparation of methanation catalyst for second reaction part (2-2) 10.6 g of impregnation solution prepared by dissolving ruthenium chloride in 50 g of second reaction part support prepared in Example 1 so that the metal concentration becomes 10% by weight. The sample was allowed to stand for 1 hour, then dried at 120 ° C. for 8 hours, then dispersed in 2 L of sodium bicarbonate solution adjusted to pH 10 to 11 and stirred, and then sufficiently warm water was applied. Washed and dried at 120 ° C. for 5 hours. Further, 21.2 g of an impregnated solution in which hexaammonium hexamolybdate tetrahydrate was dissolved to a Mo metal concentration of 10% by weight was absorbed and allowed to stand for 1 hour. Then, it is dried at 120 ° C. for 4 hours, then calcined in the atmosphere at 550 ° C. for 1 hour, and reduced at 400 ° C. for 1 hour under the flow of a hydrogen-nitrogen mixed gas (H 2 concentration 10 Vol%). The second reaction part methanation touch Medium (2-2) was prepared. The catalyst composition, specific surface area, pore volume and CO removal rate were measured and the results are shown in Table 1.
Preparation of adsorbent (2) After suspending 100 g of Y-type zeolite (SiO 2 / Al 2 O 3 = 5 mole ratio) in 1900 g of water, the mixture was heated to 60 ° C. to obtain an aqueous copper chloride solution (concentration of 2% by weight as Cu). ) 925.0 g was added and the mixture was further stirred at 60 ° C. for 2 hours. Thereafter, it is filtered, washed with sufficient warm water, dried at 120 ° C. for one day and night, baked in the atmosphere at 450 ° C. for 3 hours, and mixed with hydrogen-nitrogen gas (H 2 concentration 10 Vol% at 400 ° C.). ) For 1 hour under the distribution of
An adsorbent (2) was prepared by pressure molding at 50 kg / cm 2 and then pulverizing to adjust the particle size to 20 to 42 mesh.
Reaction Example 1 was performed in the same manner as in Example 1 except that the methanation catalyst (2-2) was used as the second reaction section catalyst and the adsorbent (2) was used as the adsorption tower. The results are shown in Table 1.
[Example 5]
Reaction Example 4 was performed in the same manner as in Example 4 except that the catalyst layer inlet gas temperature was 135 ° C. Table 1 shows the results.
[Example 6]
Reaction Example 4 was performed in the same manner as in Example 4 except that the catalyst layer inlet gas temperature was 150 ° C. The results are shown in Table 1.
[Example 7]
Preparation of Methanation Catalyst for Second Reaction Part (3-2) 50 g of the second reaction part support prepared in Example 1 was mixed with ruthenium chloride and tungstic acid so that Ru: W = 1: 1.25. The mixture was absorbed to absorb 49.05 g of the solution so that the metal concentration was 10% by weight, allowed to stand for 1 hour, dried at 120 ° C. for 8 hours, and then adjusted to pH 10-11. Disperse in 2 L of sodium hydrogen carbonate solution and stir, then wash with sufficient warm water, dry at 120 ° C. for 5 hours, and then calcinate at 550 ° C. for 1 hour in the atmosphere at 400 ° C. Then, a methanation catalyst (3-2) for the second reaction part was prepared by reduction treatment for 1 hour under the flow of a hydrogen-nitrogen mixed gas (H 2 concentration 10 Vol%). The catalyst composition, specific surface area, pore volume and CO removal rate were measured and the results are shown in Table 1.
Reaction Example 1 was performed in the same manner as in Example 1 except that the methanation catalyst (3-2) was used as the second reaction part catalyst. The results are shown in Table 1.
[Example 8]
In Reaction Test Example 7, the reaction was performed in the same manner except that the inlet gas temperature of the catalyst layer was 150 ° C., and the results are shown in Table 1.
[Example 9]
Preparation of methanation catalyst (2-1) for first reaction part 131.9 g of cobalt nitrate hexahydrate, zirconyl nitrate aqueous solution (ZrO 2 concentration: 25%
) 244.0 g and 19.5 g of nickel nitrate hexahydrate were added to 2500 g of water to prepare a mixed aqueous solution (2-1).
水酸化ナトリウム８１．３ｇを水１４８９．５ｇに溶解し、撹拌しながらこれに混合水溶液(2-1)を添加してヒドロゲルを調製し、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(2-1)を得た。
81.3 g of sodium hydroxide was dissolved in 1489.5 g of water, and a mixed aqueous solution (2-1) was added thereto while stirring to prepare a hydrogel, followed by aging at 80 ° C. for 2 hours.
The aged hydrogel was filtered, washed with sufficient warm water, and dried at 120 ° C. overnight. 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 (2-1) Got.
ついで、複合酸化物粉体(2-1)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(2-1)を
調製した。塩化ルテニウムを金属濃度が１０重量％となるように溶解し、含浸溶液（2-1
）を調製した。含浸溶液(2-1)２６．５ｇをメタネーション触媒用担体(2-1)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、第1反応部用メタネーション触媒（2-1）を調製した。触媒組成、比表面積、細孔容積およびＣＯ除去率を測定し、結果を表１に示した。
反応試験
実施例１において、第１反応部に第１反応部用触媒(2-1)を用いた以外は同様に行い、
結果を表１に示した。
[実施例10]
反応試験
実施例９において、触媒層の入口ガス温度を１３５℃とした以外は同様に行い、結果を表１に示した。
[実施例11]
反応試験
実施例９において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を表１に示した。
[比較例１]
反応試験
実施例１において、第１反応部用触媒(1-1)を第１反応部および第２反応部に充填して
反応した以外は同様に行い、結果を表１に示した。
[比較例２]
反応試験
比較例１において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を表１に示した。
[比較例３]
反応試験
実施例１において、第２反応部用触媒(1-2)を第１反応部および第２反応部に充填して
反応した以外は同様に行い、結果を表１に示した。
[比較例４]
反応試験
比較例３において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を表１に示した。
[比較例５]
反応試験
実施例４において、第２反応部用触媒(3-2)を第１反応部および第２反応部に充填して
反応した以外は同様に行い、結果を表１に示した。
[比較例６]
反応試験
比較例５において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を表１に示した。
[比較例７]
反応試験
実施例９において、第２反応部用触媒を用いずに、第１反応部用触媒(2-1)のみを用い
た以外は同様に行い、結果を表１に示した。
[比較例８]
反応試験
比較例７において、触媒層の入口ガス温度を１５０℃とした以外は同様に行い、結果を表１に示した。
Next, the composite oxide powder (2-1) 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 ( 2-1) was prepared. Ruthenium chloride is dissolved so that the metal concentration becomes 10% by weight, and the impregnation solution (2-1
) Was prepared. 26.5 g of the impregnation solution (2-1) is absorbed into 50 g of the support (2-1) for methanation catalyst, sufficiently stirred, allowed to stand for 1 hour, dried at 120 ° C. for 8 hours, and then adjusted to pH. Stir in 2 L of sodium hydrogen carbonate solution prepared to 10-11, then wash with enough warm water, dry at 120 ° C. for 5 hours, and reduce at 400 ° C. for 1.5 hours in a hydrogen stream. To prepare a methanation catalyst (2-1) for the first reaction part. The catalyst composition, specific surface area, pore volume and CO removal rate were measured and the results are shown in Table 1.
In Reaction Test Example 1, the same procedure was performed except that the first reaction part catalyst (2-1) was used in the first reaction part.
The results are shown in Table 1.
[Example 10]
Reaction Example 9 was performed in the same manner as in Example 9 except that the catalyst layer inlet gas temperature was 135 ° C. Table 1 shows the results.
[Example 11]
Reaction Example 9 was performed in the same manner as in Example 9 except that the catalyst layer inlet gas temperature was 150 ° C. Table 1 shows the results.
[Comparative Example 1]
Reaction Example 1 was conducted in the same manner as in Example 1 except that the first reaction part catalyst (1-1) was charged in the first reaction part and the second reaction part, and the results are shown in Table 1.
[Comparative Example 2]
The reaction was performed in the same manner as in Comparative Example 1 except that the inlet gas temperature of the catalyst layer was 150 ° C. Table 1 shows the results.
[Comparative Example 3]
Reaction Example 1 was conducted in the same manner as in Example 1 except that the second reaction part catalyst (1-2) was charged in the first reaction part and the second reaction part, and the results are shown in Table 1.
[Comparative Example 4]
The reaction was performed in the same manner as in Comparative Example 3 except that the inlet gas temperature of the catalyst layer was 150 ° C. Table 1 shows the results.
[Comparative Example 5]
The reaction was carried out in the same manner as in Example 4 except that the second reaction part catalyst (3-2) was charged in the first reaction part and the second reaction part and reacted, and the results are shown in Table 1.
[Comparative Example 6]
In Reaction Test Comparative Example 5, the reaction was performed in the same manner except that the inlet gas temperature of the catalyst layer was 150 ° C., and the results are shown in Table 1.
[Comparative Example 7]
Reaction Example 9 was carried out in the same manner as in Example 9 except that only the first reaction part catalyst (2-1) was used without using the second reaction part catalyst, and the results are shown in Table 1.
[Comparative Example 8]
In Reaction Test Comparative Example 7, the reaction was performed in the same manner except that the inlet gas temperature of the catalyst layer was 150 ° C., and the results are shown in Table 1.
Claims (8)
第１反応部に用いる一酸化炭素メタネーション触媒が、少なくともＮｉＯおよび／またはＣｏＯを含んでなる複合酸化物担体に４Ｂ族、７Ａ族および８族から選ばれる１種以上の金属が担持されてなり、下記条件(1)下、反応温度１２０℃でＣＯ除去率が９８％以上
である触媒であり、
第２反応部に用いる一酸化炭素メタネーション触媒が６Ａ族および８族から選ばれる１種以上の金属が、ＺｒＯ2、ＣｅＯ2、Ａｌ2Ｏ3、ＴiＯ2、ＳiＯ2から選ばれる１種以上の酸化物または複合酸化物である金属酸化物担体に担持されてなり、下記条件(1)下、反応
温度１８０℃でＣＯ除去率が９８％以上である触媒であることを特徴とする一酸化炭素のメタネーション方法。
条件(1)：
ＳＶ：２，０００ｈ-1、原料ガス組成：Ｈ2濃度５１．４vol%、ＣＯ濃度０．６vol%、Ｃ
Ｏ2濃度２０vol%、ＣＨ4濃度２vol%、水蒸気濃度３３．３vol% In the carbon monoxide methanation method in which the catalyst for carbon monoxide methanation and the hydrogen gas containing carbon monoxide gas are brought into contact, the reaction layer comprises a first reaction part and a second reaction part,
The carbon monoxide methanation catalyst used in the first reaction part is formed by supporting at least one metal selected from Group 4B, Group 7A and Group 8 on a composite oxide support containing at least NiO and / or CoO. A catalyst having a CO removal rate of 98% or more at a reaction temperature of 120 ° C. under the following condition (1):
The carbon monoxide methanation catalyst used in the second reaction part is at least one metal selected from Group 6A and Group 8 selected from ZrO 2 , CeO 2 , Al 2 O 3 , TiO 2 , and SiO 2. A catalyst having a CO removal rate of 98% or more at a reaction temperature of 180 ° C. under the following condition (1): Carbon methanation method.
Condition 1):
SV: 2,000 h −1 , raw material gas composition: H 2 concentration 51.4 vol%, CO concentration 0.6 vol%, C
O 2 concentration 20 vol%, CH 4 concentration 2 vol%, water vapor concentration 33.3 vol%
前記第１反応部の出口（下部）反応温度（ＴEXIT）が１８０℃以下であることを特徴とする請求項１に記載の一酸化炭素のメタネーション方法。 The inlet (upper) reaction temperature (T ENT ) of the first reaction section is in the range of 100-160 ° C;
2. The carbon monoxide methanation method according to claim 1, wherein an outlet (lower) reaction temperature (T EXIT ) of the first reaction section is 180 ° C. or less.
なり、金属中のＲｕの割合が２０〜９０重量％の範囲にあることを特徴とする請求項１に記載の一酸化炭素のメタネーション方法。 The catalyst for carbon monoxide methanation used in the first reaction part contains Ru as a metal, and the ratio of Ru in the metal is in the range of 20 to 90% by weight. Carbon monoxide methanation method.
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