JP5353952B2 - Method for producing catalyst for methanation reaction of carbon oxide - Google Patents
Method for producing catalyst for methanation reaction of carbon oxide Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims description 68
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 58
- 238000006243 chemical reaction Methods 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 229910002090 carbon oxide Inorganic materials 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 28
- 230000000087 stabilizing effect Effects 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- -1 composed of these Chemical compound 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000012495 reaction gas Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、二酸化炭素、一酸化炭素および二酸化炭素、またはこれらを主成分とする混合ガスと、水素とを反応させてメタンを製造するための触媒の製造方法に関する。本発明はまた、その方法により製造した触媒を使用するメタン化方法にも関する。 The present invention relates to a method for producing a catalyst for producing methane by reacting carbon dioxide, carbon monoxide and carbon dioxide, or a mixed gas containing these as main components with hydrogen. The invention also relates to a methanation process using a catalyst produced by the process.
化石燃料を燃焼することによって排出される二酸化炭素が引き起こす、地球温暖化の問題が深刻となり、排出量を削減する対策が検討されている。その一つの方法として、二酸化炭素を水素と反応させてメタンを生成させる方法が、エネルギー生産法としても期待されている。それとともに、コークス、石炭、バイオマス燃料、汚泥廃棄物などのガス化で得られる水素、一酸化炭素、二酸化炭素からなる低カロリーガスをメタン化して、高カロリーのガスを製造する技術にも、期待がかかっている。 The problem of global warming caused by carbon dioxide emitted by burning fossil fuels becomes serious, and measures to reduce emissions are being studied. As one of the methods, a method of producing methane by reacting carbon dioxide with hydrogen is also expected as an energy production method. At the same time, the technology for producing high-calorie gas by methanation of low-calorie gas consisting of hydrogen, carbon monoxide and carbon dioxide obtained by gasification of coke, coal, biomass fuel, sludge waste, etc. is also expected. Is on.
二酸化炭素および一酸化炭素を含む混合ガスと水素とを接触的に反応させ、メタンを製造する反応の触媒として、これまで、ラネーニッケル、アルミナおよびシリカを担体とした触媒を用いることが試みられていた。しかしながら、既知のこの種の触媒では、メタンヘの転化の反応速度が遅いため、反応圧力を高圧にする必要があった。 Attempts have been made to use Raney nickel, alumina, and silica-supported catalysts as catalysts for the reaction of producing methane by catalytically reacting a mixed gas containing carbon dioxide and carbon monoxide with hydrogen. . However, with this type of known catalyst, the reaction rate of methane conversion was slow, so that the reaction pressure had to be increased.
メタン合成を効率よく行なうことができる触媒として、筆頭発明者を中心とする研究グループは、Ｎｉ，Ｃｏなどの鉄族金属と、Ｚｒ，Ｔｉ，Ｎｂ，Ｔａなどのバルブメタルとの合金の溶湯を、液体急冷法によってリボン状のアモルファス合金にしたものが、すぐれた触媒性能を有することを見出し、すでに開示した。(特許文献１、特許文献２，特許文献３)。この触媒は、メタンヘの選択率がほぼ１００％であり、大気圧下においてもきわめて高い転化率を示す。しかしながら、液体急冷法による触媒製造は、量産性に欠けるほか、触媒がリボン形状であるため、触媒反応システムが制限されるという問題がある。 As a catalyst that can efficiently synthesize methane, a research group led by the leading inventor uses a molten alloy of an iron group metal such as Ni and Co and a valve metal such as Zr, Ti, Nb, and Ta. The inventors have found that a ribbon-like amorphous alloy obtained by a liquid quenching method has excellent catalytic performance and has already been disclosed. (Patent Document 1, Patent Document 2, Patent Document 3). This catalyst has a selectivity to methane of almost 100% and exhibits a very high conversion even under atmospheric pressure. However, the catalyst production by the liquid quenching method has problems that it lacks mass productivity and the catalyst reaction system is limited because the catalyst has a ribbon shape.
そこで発明者のグループは、上述の触媒を基礎にして、リボン状触媒に代わる、量産性の高い粉末触媒を製造する方法を開発し、これも開示した（特許文献４）。この触媒は、正方晶系ジルコニア担体にＮｉおよび（または）Ｃｏを担持した触媒であって、Ｚｒの酸化物中に正方晶を形成し安定化するための安定化元素（Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｅｕ，ＭｇおよびＣａ）のいずれかを加えた正方晶系ジルコニア担体を焼成により用意し、それにＮｉおよび（または）Ｃｏの化合物の溶液を含浸させ、加熱して乾燥した後、還元してＮｉおよび（または）Ｃｏを金属状態にしたものである。
特許文献４に記載されている触媒とその製造方法は、つぎのとおりである。
［触媒］ 正方晶ジルコニア系担体にＮｉ及び／又はＣｏを担持してなる二酸化炭素メタン化用触媒において、該正方晶ジルコニア系担体は、Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｅｕ、ＭｇおよびＣａよりなる群から選ばれる１種又は２種以上の安定化元素を含み、該ジルコニア担体中の安定化元素の含有量が、Ｚｒと安定化元素との合計に対して１５原子％以下であり、Ｎｉ及び／又はＣｏの担持量が、Ｚｒと安定化元素とＮｉ及び／又はＣｏとの合計に対して５〜５０%であることを特徴とする二酸化炭素メタン化用触媒。
The catalyst described in Patent Document 4 and the production method thereof are as follows.
[Catalyst] In the catalyst for carbon dioxide methanation formed by supporting Ni and / or Co on a tetragonal zirconia carrier, the tetragonal zirconia carrier is Y, La, Ce, Pr, Nd, Sm, Gd, Tb. , Dy, Eu, Mg and Ca, one or more kinds of stabilizing elements selected from the group consisting of, and the content of the stabilizing elements in the zirconia support is based on the total of Zr and stabilizing elements Carbon dioxide methanation, characterized in that the amount of Ni and / or Co supported is 5 to 50% with respect to the sum of Zr, stabilizing element and Ni and / or Co. Catalyst.
［製造方法］ 上記の二酸化炭素メタン化用触媒を製造する方法において、
ジルコニアゾル水溶液に、Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｅｕ，ＭｇおよびＣａよりなる群から選ばれる１種又は２種以上の塩を添加し、撹拌下、加熱蒸発乾固させて主成分が正方晶系構造のジルコニア系担体を製造する工程と、得られたジルコニア系担体をＮｉ及び／又はＣｏの水溶液に添加し、撹拌下、加熱蒸発乾固させた後焼成し、その後還元処理することを特徴とする二酸化炭素メタン化用触媒の製造方法。
[Production Method] In the method for producing the carbon dioxide methanation catalyst,
One or more salts selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Eu, Mg, and Ca are added to the zirconia sol aqueous solution, and the mixture is heated with stirring. A step of producing a zirconia-based support having a tetragonal structure as a main component by evaporating to dryness, and adding the obtained zirconia-based support to an aqueous solution of Ni and / or Co, followed by heating to dryness with stirring A method for producing a catalyst for methanation of carbon dioxide, characterized by calcining and then reduction treatment.
さらに二酸化炭素メタン化用触媒の改良を進めた発明者らは、特許文献４に開示したような、あらかじめ正方晶系ジルコニア構造の担体を用意して、それにＮｉおよび（または）Ｃｏを担持するという工程によるよりも、触媒を構成する上で必要な成分をすべて含む酸化物混合物をまず製造し、ついで還元処理を施すという工程による方が、高性能の触媒が得られることを見出し、本発明に到達した。 Further, the inventors who have further improved the catalyst for carbon dioxide methanation prepare a support having a tetragonal zirconia structure in advance as disclosed in Patent Document 4, and support Ni and / or Co on the support. It has been found that a high-performance catalyst can be obtained by first producing an oxide mixture containing all the components necessary for constituting the catalyst and then subjecting it to a reduction treatment, rather than by the process. Reached.
したがって本発明の目的は、炭素酸化物のメタン化反応において２５０℃またはそれ以下の低温でも高い活性を示す触媒であって、同時に、バイオマスその他をガス化して得られる二酸化炭素、一酸化炭素および水素からなる混合ガスからメタンを製造する場合にも好適な触媒の製造方法を提供することにある。 Accordingly, an object of the present invention is a catalyst exhibiting high activity even at a low temperature of 250 ° C. or lower in carbon oxide methanation reaction, and at the same time, carbon dioxide, carbon monoxide and hydrogen obtained by gasifying biomass and others. It is another object of the present invention to provide a catalyst production method suitable for producing methane from a mixed gas comprising:
本発明のメタン化反応用触媒の製造方法は、二酸化炭素、一酸化炭素と二酸化炭素との混合物、またはこれらを主成分とする混合物を水素化してメタンを得るためのメタン化反応用触媒を製造する方法であって、下記の諸工程からなり、
１）ジルコニアのヒドロゾルに、Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｄｙ，Ｃａ，およびＭｇからなるグループから選んだ１種または２種以上の安定化元素の塩の水溶液、ならびに鉄族元素の塩の水溶液を混合すること、
２）混合物を濃縮乾固させて焼成すること、および
３）混合物を還元処理すること、
元素状態の金属を基準とした原子％で、
Ａ）Ｚｒ：１８〜７０原子％、
Ｂ）上記安定化元素の１種または２種以上（２種以上の場合は合計で）：１〜２０原子％、および
Ｃ）鉄族元素：２５〜８０原子％、
からなる組成を有し、安定化元素とともに鉄族元素の一部をも結晶構造に取り込んで安定化された正方晶系ジルコニア構造の酸化物からなる担体に、金属状態の鉄族元素が触媒活性を担う活性種として担持された触媒を得ることを特徴とするメタン化反応用触媒の製造方法である。
The method for producing a catalyst for methanation reaction of the present invention produces a methanation reaction catalyst for obtaining methane by hydrogenating carbon dioxide, a mixture of carbon monoxide and carbon dioxide, or a mixture containing these as main components. Comprising the following steps:
1) An aqueous solution of a salt of one or more stabilizing elements selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Ca, and Mg, and iron Mixing an aqueous solution of a salt of a group element,
2) concentrating the mixture to dryness and calcining; and 3) reducing the mixture.
Atomic% based on elemental metal,
A) Zr: 18-70 atomic%,
B) One or more of the above stabilizing elements (in the case of two or more): 1 to 20 atomic%, and C) an iron group element: 25 to 80 atomic%,
The metal-state iron group element has catalytic activity on a support made of a tetragonal zirconia structure oxide that is stabilized by incorporating a part of the iron group element together with the stabilizing element into the crystal structure. It is a method for producing a catalyst for methanation reaction, characterized in that a catalyst supported as an active species that bears the above is obtained.
本発明の方法により製造した、正方晶系ジルコニア構造の複酸化物を担体とし、金属状態のＮｉまたはＮｉとＦｅおよび（または）Ｃｏである鉄族元素を活性成分として担持した触媒は、反応選択率がほぼ１００％メタンであって、反応平衡は、常圧でも極端に生成物側に片寄っているため、反応混合物から不純物を除去して未反応原料を循環させ、反応を高圧で何度も繰り返さなければならない、という問題は解消した。したがって、メタンとともに生成する水を除去するだけで、原料循環のための複雑な設備を要せずに、かつ、高圧でなく常圧で操業する単純な装置を用いて、迅速に、二酸化炭素または一酸化炭素と二酸化炭素との混合ガスを水素と反応させ、メタンに転換させることができる。 The catalyst produced by the method of the present invention using a tetragonal zirconia-structured double oxide as a support and supporting an iron group element as Ni or Ni and Fe and / or Co in the metal state as active components is selected by reaction. The rate is almost 100% methane, and the reaction equilibrium is extremely shifted to the product side even at normal pressure. Therefore, impurities are removed from the reaction mixture, unreacted raw materials are circulated, and the reaction is repeated many times at high pressure. The problem of having to repeat was solved. Therefore, simply removing the water produced with methane, without the need for complicated equipment for material circulation, and using simple equipment operating at normal pressure instead of high pressure, carbon dioxide or A mixed gas of carbon monoxide and carbon dioxide can be reacted with hydrogen and converted to methane.
本発明の方法により製造した触媒を用いれば、対象が一酸化炭素と二酸化炭素との混合ガスである場合、有毒な一酸化炭素をまずすべてメタンに転換し、残る水素で二酸化炭素をメタンに転換する、という理想的な機構を実現することができる。この触媒の製造は、きわめて容易である。 When the catalyst produced by the method of the present invention is used, when the target is a mixed gas of carbon monoxide and carbon dioxide, all toxic carbon monoxide is first converted to methane, and the remaining hydrogen is used to convert carbon dioxide to methane. This makes it possible to realize an ideal mechanism. The production of this catalyst is very easy.
本発明の触媒の製造方法の特徴は、既知の、すなわち特許文献４に開示した製造方法のように、まず正方晶系ジルコニアからなる担体を形成した後に、活性金属の塩の水溶液を混合し、還元するという二段の工程によるのではなく、必要な成分をすべて水溶液の形で混合し、この混合物を蒸発乾固し、還元処理するという、一段の焼成プロセスによって触媒を得ることにある。 The characteristics of the catalyst production method of the present invention are known, ie, as in the production method disclosed in Patent Document 4, first, after forming a support made of tetragonal zirconia, an aqueous solution of an active metal salt is mixed, Rather than the two-step process of reducing, the catalyst is obtained by a one-step calcination process in which all necessary components are mixed in the form of an aqueous solution, this mixture is evaporated to dryness and subjected to a reduction treatment.
この一段プロセスによるときは、蒸発乾固から焼成までの過程で、安定化元素だけでなく鉄族元素の一部も含んだ正方晶系ジルコニア構造の複酸化物と、鉄族元素の酸化物との混合物が生成する。続く還元によって、鉄族元素の酸化物が還元され、その結果、金属状態の鉄族元素が、正方晶系ジルコニア構造の複酸化物に担持された構造の触媒ができる。このように、還元処理後も、担体である正方晶系ジルコニア構造の複酸化物には、安定化元素とともに鉄族元素の一部が含まれたままである。 In this one-stage process, during the process from evaporation to dryness to firing, a double oxide of tetragonal zirconia structure containing not only a stabilizing element but also a part of an iron group element, an oxide of an iron group element, A mixture of Subsequent reduction reduces the oxide of the iron group element. As a result, a catalyst having a structure in which the iron group element in the metal state is supported on a double oxide having a tetragonal zirconia structure is formed. As described above, even after the reduction treatment, the tetragonal zirconia structure double oxide as a carrier still contains a part of the iron group element together with the stabilizing element.
上述した触媒製造方法において、ジルコニアヒドロゾルに正方晶ジルコニア構造安定化元素の塩と鉄族元素の塩とを添加したものに、触媒粒子の核となるアルミナ、シリカなどの粒子とバインダーとなるケイ酸塩、チタン酸塩、アルミン酸塩、ジルコン酸塩などを混合し、蒸発乾固し焼成することによって、最大３mm径の粒状触媒を形成することが可能である。バインダーの使用は、いったん製造した粉末状の触媒に対して混合し、加熱焼成するという手順によって行なうことも可能である。 In the catalyst production method described above, particles of alumina, silica, etc., which are the core of the catalyst particles, and silica, which is the binder, are added to the zirconia hydrosol to which a tetragonal zirconia structure stabilizing element salt and an iron group element salt are added. By mixing acid salt, titanate, aluminate, zirconate, etc., evaporating to dryness and firing, it is possible to form a granular catalyst having a maximum diameter of 3 mm. The use of the binder can also be performed by a procedure in which the binder is once mixed with the powdered catalyst that has been manufactured and then heated and fired.
以下、本発明の触媒の構成について説明する。安定化元素である、Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｄｙ，ＣａおよびＭｇからなるグループから選んだ１種または２種以上は、酸化ジルコニウムがゾルから結晶に変化する際に、正方晶系ジルコニア構造を安定化する作用をする成分である。１原子％以上添加する必要があるが、過剰に存在すると、安定化元素独自の酸化物を形成し触媒活性にとって有害になるため、添加量は２０原子％以下にする必要がある。 Hereinafter, the structure of the catalyst of this invention is demonstrated. One or more selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Ca and Mg, which are stabilizing elements, are used when zirconium oxide changes from sol to crystal. It is a component that acts to stabilize the tetragonal zirconia structure. Although it is necessary to add 1 atomic% or more, if it is present in excess, an oxide unique to the stabilizing element is formed, which is harmful to the catalytic activity, so the addition amount needs to be 20 atomic% or less.
Ｚｒは、いうまでもなく正方晶系ジルコニア構造をもつ担体を構成する基本の成分であって、１８原子％以上添加する必要がある。しかし、過剰に添加すると、触媒活性に必要な鉄族元素の濃度を十分に高くできなくなるため、７０原子％を上限とする。 Needless to say, Zr is a basic component constituting a support having a tetragonal zirconia structure, and it is necessary to add 18 atomic% or more. However, if added excessively, the concentration of the iron group element necessary for the catalytic activity cannot be made sufficiently high, so 70 atomic% is made the upper limit.
鉄族元素は、触媒活性を担う重要な成分であって、２５原子％以上存在する必要があるが、過剰に添加すると、それ自体で凝集して分散が悪くなり、かえって十分な活性が得られなくなるから、８０原子％以下とする必要がある。鉄族元素としてはＮｉが必要であるが、その一部を他の鉄族元素であるＦｅおよびＣｏの１種または２種で置換することができる。ただしその場合、原子比にして鉄族元素全体の少なくも６割を、Ｎｉが占めなければならない。 The iron group element is an important component responsible for the catalytic activity and needs to be present in an amount of 25 atomic% or more. However, if added excessively, it itself aggregates and disperses, resulting in sufficient activity. Therefore, it is necessary to make it 80 atomic% or less. Ni is required as the iron group element, but a part thereof can be substituted with one or two of Fe and Co, which are other iron group elements. However, in that case, Ni must occupy at least 60% of the total iron group element in terms of atomic ratio.
本発明の製造方法により得られる触媒が高活性を有し、かつその高活性が長期にわたって維持される理由として、発明者らは以下のように考えている。すなわち、ジルコニアの安定相は単斜晶系であるが、それを単独では安定でない正方晶系とし、これに鉄族元素を担持した触媒が、二酸化炭素および一酸化炭素のメタン化に対して高活性を呈する。このことは、特許文献４に明らかにした。本発明はそれから進んで、ジルコニアゾルに安定化元素の塩と鉄族元素の塩とを混合して焼成すると、酸化ジルコニウム結晶格子中に、酸化状態の安定化元素と酸化状態の鉄族元素の一部を含んだ正方晶系ジルコニア構造の複酸化物と、鉄族元素の酸化物とが均一に混じり合った酸化物混合体が得られ、この酸化物混合体に水素処理による還元を施すと、酸素との親和力が高いジルコニウムや安定化元素が主体の複酸化物は酸化状態に止まり、水素と直接接した鉄族元素の酸化物のみが金属状態に還元される、という事実を利用する。このようにして、正方晶系ジルコニア構造の複酸化物上に、触媒活性点である金属状態の鉄族元素が微細に分散した触媒が形成される。 The inventors consider the following as the reason why the catalyst obtained by the production method of the present invention has high activity and the high activity is maintained over a long period of time. In other words, the stable phase of zirconia is a monoclinic system, but it is a tetragonal system that is not stable by itself, and a catalyst that supports an iron group element is highly resistant to methanation of carbon dioxide and carbon monoxide. Exhibits activity. This is clarified in Patent Document 4. The present invention is further advanced, and when a stabilizing element salt and an iron group element salt are mixed and fired in a zirconia sol, an oxidized state stabilizing element and an oxidized state iron group element are contained in a zirconium oxide crystal lattice. When an oxide mixture is obtained in which a mixed oxide of a tetragonal zirconia structure containing a part of the oxide and an oxide of an iron group element are uniformly mixed. When this oxide mixture is reduced by hydrogen treatment, The fact that zirconium oxide, which has a high affinity with oxygen, and a double oxide mainly composed of a stabilizing element remains in an oxidized state, and only the oxide of an iron group element in direct contact with hydrogen is reduced to a metal state is utilized. In this way, a catalyst is formed in which a metallic iron group element, which is a catalytic active point, is finely dispersed on a double oxide having a tetragonal zirconia structure.
このような触媒は、反応ガスによって攪乱され、表面が摩耗して外表面にある金属状態の鉄族元素が失われても、その下から現れる酸化状態の鉄族元素が反応ガス中の水素によって還元されて金属状態になり、触媒活性点として働くため、常に担体上に十分な量の活性点が分散した、高活性の状態を維持することができる。 Such a catalyst is disturbed by the reaction gas, and even if the surface wears and the iron group element in the metallic state on the outer surface is lost, the iron group element in the oxidized state that appears from below is lost by the hydrogen in the reaction gas. Since it is reduced to a metal state and serves as a catalyst active site, a high activity state in which a sufficient amount of active sites are always dispersed on the support can be maintained.
本発明の触媒の製造工程を一般的に説明すれば、Ｚｒのヒドロゾルに、Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｄｙ，ＣａおよびＭｇからなるグループから選んだ１種または２種以上の水可溶性の塩を混合し、これに、水に溶解したＮｉの塩、またはＮｉの塩と、Ｆｅおよび（または）Ｃｏを含む鉄族元素の塩の水溶液を添加する。この混合物を濃縮し、蒸発乾固したのち、大気中で約５００℃に加熱焼成して、正方晶系ジルコニア構造の複酸化物と、鉄族元素の酸化物との混合物を得る。ついでこの混合酸化物を、水素気流中で約３００℃に加熱し、還元処理することにより、正方晶ジルコニア構造の複酸化物担体に金属状態の鉄族金属が担持された触媒を得る。 The process for producing the catalyst of the present invention will be generally described. One or two kinds selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Ca and Mg are added to the Zr hydrosol. The above water-soluble salt is mixed, and an aqueous solution of an Ni salt dissolved in water, or an Ni salt and an iron group element salt containing Fe and / or Co is added thereto. The mixture is concentrated, evaporated to dryness, and then heated and fired at about 500 ° C. in the atmosphere to obtain a mixture of a tetragonal zirconia double oxide and an iron group element oxide. Then, the mixed oxide is heated to about 300 ° C. in a hydrogen stream and subjected to a reduction treatment to obtain a catalyst in which a metallic iron group metal is supported on a double oxide support having a tetragonal zirconia structure.
本発明の触媒元素の構成を一覧すれば、表1に示すとおりであり、各成分の組成を、Ｚｒ，安定化元素および鉄族元素の三成分で表したダイアグラムは、図１に示すとおりである。 The composition of the catalytic element of the present invention is listed as shown in Table 1, and the diagram showing the composition of each component with three components of Zr, stabilizing element and iron group element is as shown in FIG. is there.
表１
ジルコニアのヒドロゾル「Ｚｒ３０ＡＨ」（日産化学工業（株）製、Ｚｒ：３０重量％、ｐＨ＝４．０）１５．０ｇに、硝酸サマリウム六水和物の固体を１．９６９ｇ加え、ガラス棒で、均一なクリーム状スラッジになるまで撹拌した。別に硝酸ニッケル六水和物１９．８０６ｇを２０mlの純水に溶解し、硝酸ニッケル水溶液を用意した。この水溶液を上記のスラッジに加え、均一な溶液になるまで撹拌した。この溶液を１時間静置したのちマッフル炉に入れ、１５０℃で４時間保持し、水分および自由水を除去し、乾固した。ついで５００℃で８時間焼成し、灰黒色の固形物１０．３ｇを得た。固形物をメノウ乳鉢で粉砕し、１００μmメッシュのふるいにかけて通過分を採取することにより、触媒の前駆体となる酸化物を得た。この前駆体は、元素構成が、金属状態の元素を基準にしてＮｉを６２．５原子％含む、
ＮｉＯ0.625（Ｚｒ0.892Ｓｍ0.108Ｏ1.946）0.375
の組成を有する。ジルコニアが正方晶系であることは、Ｃｕ−Ｋα線を用いたＸ線回折により確認した。この触媒前駆体の比表面積は、約８０ｍ２／ｇであった。
Add 1.969 g of samarium nitrate hexahydrate solid to 15.0 g of zirconia hydrosol “Zr30AH” (Nissan Chemical Industry Co., Ltd., Zr: 30 wt%, pH = 4.0). Stir until uniform creamy sludge. Separately, 19.806 g of nickel nitrate hexahydrate was dissolved in 20 ml of pure water to prepare an aqueous nickel nitrate solution. This aqueous solution was added to the sludge and stirred until a homogeneous solution was obtained. This solution was allowed to stand for 1 hour and then placed in a muffle furnace and kept at 150 ° C. for 4 hours to remove moisture and free water and to dry. Subsequently, it was baked at 500 ° C. for 8 hours to obtain 10.3 g of a grayish black solid. The solid matter was pulverized in an agate mortar and passed through a 100 μm mesh sieve to collect the passing portion, thereby obtaining an oxide serving as a catalyst precursor. This precursor contains 62.5 atomic% of Ni based on the elemental configuration of the element in the metal state.
NiO 0.625 (Zr 0.892 Sm 0.108 O 1.946 ) 0.375
Having a composition of It was confirmed by X-ray diffraction using Cu—Kα rays that zirconia was tetragonal. The specific surface area of this catalyst precursor was about 80 m 2 / g.
内径１５mmの石英管を反応管として使用し、その中に、上に得た触媒前駆体酸化物５．０ｇを、石英ウールで固定した。反応管を電気炉内に置き、３００℃に加熱し、水素気流中で２時間還元して、触媒を得た。 A quartz tube having an inner diameter of 15 mm was used as a reaction tube, in which 5.0 g of the catalyst precursor oxide obtained above was fixed with quartz wool. The reaction tube was placed in an electric furnace, heated to 300 ° C., and reduced in a hydrogen stream for 2 hours to obtain a catalyst.
二酸化炭素と水素の割合が、モル比で１：４とした反応ガスを、触媒の温度を２５０℃に保った反応管に通した。反応管出口をガスクロマトグラフィと直結させ、反応ガス成分を分析して、水素および二酸化炭素の導入ガス量と未反応量のガスの比率から、転換率を求めた。 A reaction gas having a molar ratio of carbon dioxide and hydrogen of 1: 4 was passed through a reaction tube in which the temperature of the catalyst was maintained at 250 ° C. The reaction tube outlet was directly connected to gas chromatography, the reaction gas component was analyzed, and the conversion rate was determined from the ratio of the introduced gas amount of hydrogen and carbon dioxide to the unreacted gas amount.
その結果、触媒前駆体酸化物１．０ｇ当り反応ガスを５．４Ｌ／Ｈｒ通したときの二酸化炭素の転換率は、８２．２％であった。ガスクロマトグラフィで検出されたものは未反応の水素、二酸化炭素と生成物であるメタンのみであり、メタンへ反応選択率が１００%であることが確認された。 As a result, the conversion rate of carbon dioxide when the reaction gas was passed through 5.4 L / Hr per 1.0 g of the catalyst precursor oxide was 82.2%. Only unreacted hydrogen and carbon dioxide and the product methane were detected by gas chromatography, and it was confirmed that the reaction selectivity to methane was 100%.
特許文献４には、そこに開示した触媒のうち、５０原子％のＮｉを含む５０Ｎｉ／５０（Ｚｒ0.9Ｓｍ0.1Ｏ1.95）の組成を有する触媒は、上記の反応条件において、二酸化炭素の転換率が５２．６％であったと記載されている。 Patent Document 4 discloses that among the catalysts disclosed therein, a catalyst having a composition of 50Ni / 50 (Zr 0.9 Sm 0.1 O 1.95 ) containing 50 atomic% of Ni is obtained under the above reaction conditions. Was 52.6%.
実施例１と同様の成分混合および焼成の方法に従い、Ｎｉの含有量および種々の安定化元素の含有割合およびＺｒの含有量割合を変化させて触媒を製造し、実施例１と同じ反応条件で、各触媒の二酸化炭素転換率を測定した。その結果を表２に示す。いずれの触媒も、反応温度２００℃および２５０℃でメタンヘの高い転換率を示し、すぐれた触媒であることが確認された。 According to the same component mixing and firing method as in Example 1, the catalyst was produced by changing the Ni content, the various stabilizing element content ratios, and the Zr content ratio, under the same reaction conditions as in Example 1. The carbon dioxide conversion rate of each catalyst was measured. The results are shown in Table 2. Both catalysts showed high conversion to methane at reaction temperatures of 200 ° C. and 250 ° C., and were confirmed to be excellent catalysts.
表２
ジルコニアのヒドロゾルに、硝酸サマリウムまたは硝酸カルシウムと、硝酸ニッケルとともに、硝酸コバルトと硝酸第二鉄のいずれか1種または２種を所定の割合で混合し、蒸発乾固、焼成および還元を行なって触媒を合成した。実施例１と同じ反応条件における、二酸化炭素転換率を測定した。その結果を、表３に示す。ここでも、各触媒は、反応温度２００℃および２５０℃において、メタンヘの高い転換率を示した。 A zirconia hydrosol is mixed with samarium nitrate or calcium nitrate and nickel nitrate together with one or two of cobalt nitrate and ferric nitrate at a predetermined ratio, and evaporated to dryness, calcined and reduced to form a catalyst. Was synthesized. The carbon dioxide conversion rate under the same reaction conditions as in Example 1 was measured. The results are shown in Table 3. Again, each catalyst showed high conversion to methane at reaction temperatures of 200 ° C and 250 ° C.
表３
実施例１と同様に、ジルコニアのヒドロゾルに、硝酸サマリウムまたは硝酸カルシウムと硝酸ニッケルとを種々の割合で混合し、蒸発乾固、焼成および還元を行なって、触媒を得た。ＣＯ，ＣＯ2およびＨ2の割合がモル％で１５．５％、１４．５％、７０％となるように混合した反応ガスを、触媒の温度を３００℃保った反応管に通した。反応ガスの流量は、前駆体の状態における触媒１．０ｇ当たり５．４Ｌ／Ｈｒである。反応管出口をガスクロマトグラフィと直結させ、反応ガス成分を分析し、導入したガスの量と未反応のガスの量との比率から、転換率を求めた。 In the same manner as in Example 1, samarium nitrate or calcium nitrate and nickel nitrate were mixed in various proportions with zirconia hydrosol, and evaporated to dryness, calcined and reduced to obtain a catalyst. The reaction gas mixed so that the proportions of CO, CO 2 and H 2 were 15.5%, 14.5%, and 70% in mol% was passed through a reaction tube in which the temperature of the catalyst was maintained at 300 ° C. The flow rate of the reaction gas is 5.4 L / Hr per 1.0 g of catalyst in the precursor state. The reaction tube outlet was directly connected to gas chromatography, the reaction gas components were analyzed, and the conversion rate was determined from the ratio of the amount of introduced gas and the amount of unreacted gas.
結果を、表４に示した。いずれの触媒も、反応温度３００℃では、まず一酸化炭素を１００％メタンに変換し、その反応で残った水素が、二酸化炭素をメタンに変換することが判明した。 The results are shown in Table 4. In any catalyst, at a reaction temperature of 300 ° C., carbon monoxide was first converted to 100% methane, and hydrogen remaining in the reaction was found to convert carbon dioxide to methane.
表４
Claims (3)
１）ジルコニアのヒドロゾルに、Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｄｙ，Ｃａ，およびＭｇからなるグループから選んだ１種または２種以上の安定化元素の塩の水溶液、ならびに鉄族元素の塩の水溶液を混合すること、
２）混合物を濃縮乾固させて焼成すること、および
３）混合物を還元処理すること、
元素状態の金属を基準とした原子％で、
Ａ）Ｚｒ：１８〜７０原子％、
Ｂ）上記安定化元素の１種または２種以上（２種以上の場合は合計で）：１〜２０原子％、ならびに
Ｃ）鉄族元素：２５〜８０原子％、
からなる組成を有し、安定化元素とともに鉄族元素の一部をも結晶構造に取り込んで安定化された正方晶系ジルコニア構造の酸化物からなる担体に、金属状態の鉄族元素が触媒活性を担う活性種として担持された触媒を得ることを特徴とするメタン化反応用触媒の製造方法。 A method for producing a catalyst for methanation reaction for obtaining methane by hydrogenating carbon dioxide, a mixture of carbon monoxide and carbon dioxide, or a mixture mainly composed of these, comprising the following steps:
1) An aqueous solution of a salt of one or more stabilizing elements selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Ca, and Mg, and iron Mixing an aqueous solution of a salt of a group element,
2) concentrating the mixture to dryness and calcining; and 3) reducing the mixture.
Atomic% based on elemental metal,
A) Zr: 18-70 atomic%,
B) One or more of the above stabilizing elements (in the case of two or more): 1 to 20 atomic%, and C) an iron group element: 25 to 80 atomic%,
The metal-state iron group element has catalytic activity on a support made of a tetragonal zirconia structure oxide that is stabilized by incorporating a part of the iron group element together with the stabilizing element into the crystal structure. A method for producing a catalyst for methanation reaction, characterized in that a catalyst supported as an active species that bears the above is obtained.
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