JPH1043594A - Amorphous alloy catalyst for conversion of carbon dioxide into methane - Google Patents
Amorphous alloy catalyst for conversion of carbon dioxide into methaneInfo
- Publication number
- JPH1043594A JPH1043594A JP8204543A JP20454396A JPH1043594A JP H1043594 A JPH1043594 A JP H1043594A JP 8204543 A JP8204543 A JP 8204543A JP 20454396 A JP20454396 A JP 20454396A JP H1043594 A JPH1043594 A JP H1043594A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous alloy
- carbon dioxide
- catalyst
- methane
- atomic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 72
- 239000001569 carbon dioxide Substances 0.000 title claims description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 32
- 238000006243 chemical reaction Methods 0.000 title abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- -1 Iron group metals Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は二酸化炭素のメタン
化用アモルファス合金触媒に係り、特に、二酸化炭素を
効率的にメタンに変換し得る高活性アモルファス合金触
媒に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous alloy catalyst for methanation of carbon dioxide, and more particularly to a highly active amorphous alloy catalyst capable of efficiently converting carbon dioxide to methane.
【０００２】[0002]
【従来の技術】現在、世界中で大量に放出される二酸化
炭素による地球の温暖化が社会問題となっている。しか
し、現在の産業活動や市民生活の水準を維持しながら二
酸化炭素の放出量を減らすことは困難である。従って、
生成した二酸化炭素を大気に放出せずに回収し、メタン
等の有効物質に変換して再利用するための技術の開発が
要望されている。2. Description of the Related Art At present, global warming due to carbon dioxide emitted in large quantities worldwide has become a social problem. However, it is difficult to reduce carbon dioxide emissions while maintaining the current standards of industrial activity and civil life. Therefore,
There is a demand for the development of a technology for collecting the generated carbon dioxide without releasing it to the atmosphere, converting it into an effective substance such as methane, and reusing it.
【０００３】従来、二酸化炭素の処理法としては、触媒
の存在下、二酸化炭素を数十気圧の圧力で水素と反応さ
せてメタノールに変換する研究が行われている。Conventionally, as a method for treating carbon dioxide, research has been conducted to convert carbon dioxide into methanol by reacting it with hydrogen at a pressure of several tens of atmospheres in the presence of a catalyst.
【０００４】一方、本出願人らは、アモルファス合金に
酸化還元処理を施したものの中に、二酸化炭素と水素と
の反応で大気圧でも高速でメタンを生成させる触媒とし
て機能するものとして、従来、鉄族金属とＺｒ，Ｔｉ，
Ｎｂ，Ｔａなどのバルブメタルからなるアモルファス合
金に酸化還元処理を施した二酸化炭素のメタン化用アモ
ルファス合金触媒を開発した。[0004] On the other hand, the present applicants have proposed that, among those obtained by subjecting an amorphous alloy to oxidation-reduction treatment, a catalyst which functions as a catalyst for producing methane at a high speed even at atmospheric pressure by a reaction between carbon dioxide and hydrogen, Iron group metals and Zr, Ti,
We have developed an amorphous alloy catalyst for methanation of carbon dioxide by subjecting an amorphous alloy composed of valve metals such as Nb and Ta to redox treatment.
【０００５】[0005]
【発明が解決しようとする課題】大量に発生する二酸化
炭素を効率的に処理するためには、大量の二酸化炭素を
迅速にメタン等に変換することができるより高活性な触
媒の出現が望まれる。In order to efficiently treat a large amount of carbon dioxide generated, it is desired to have a more active catalyst capable of rapidly converting a large amount of carbon dioxide into methane or the like. .
【０００６】本発明は上記従来の実情に鑑みてなされた
ものであって、二酸化炭素を大気圧下における水素との
反応でメタンに変換する反応の促進作用に優れ、大量の
二酸化炭素を高速でメタンに変換することができる高活
性な触媒を提供することを目的とする。The present invention has been made in view of the above-mentioned conventional circumstances, and has an excellent effect of accelerating a reaction of converting carbon dioxide to methane by a reaction with hydrogen under atmospheric pressure, and is capable of producing a large amount of carbon dioxide at high speed. It is an object of the present invention to provide a highly active catalyst capable of converting methane.
【０００７】[0007]
【課題を解決するための手段】請求項１の二酸化炭素の
メタン化用アモルファス合金触媒は、アモルファス合金
よりなる前駆体に酸化還元処理を施してなる二酸化炭素
のメタン化用アモルファス合金触媒であって、該アモル
ファス合金が、Ｚｒと、Ｙ，Ｌａ，Ｃｅ，Ｎｄ，Ｓｍ，
Ｇｄ，Ｔｂ及びＤｙよりなる群から選ばれる１種又は２
種以上の希土類元素とを含み、残部が実質的にＣｏ及び
／又はＮｉよりなり、Ｚｒの含有量が８原子％以上、希
土類元素の含有量が５原子％以下で、Ｚｒと希土類元素
との合計の含有量が８０原子％以下であることを特徴と
する。The amorphous alloy catalyst for methanation of carbon dioxide according to claim 1 is an amorphous alloy catalyst for methanation of carbon dioxide obtained by subjecting a precursor comprising an amorphous alloy to a redox treatment. The amorphous alloy is composed of Zr, Y, La, Ce, Nd, Sm,
One or two selected from the group consisting of Gd, Tb and Dy
A rare earth element of at least one species, the balance substantially consisting of Co and / or Ni, a Zr content of 8 atomic% or more, a rare earth element content of 5 atomic% or less, The total content is 80 atomic% or less.
【０００８】請求項２の二酸化炭素のメタン化用アモル
ファス合金触媒は、アモルファス合金よりなる前駆体に
酸化還元処理を施してなる二酸化炭素のメタン化用アモ
ルファス合金触媒であって、該アモルファス合金が、Ｔ
ｉ，Ｎｂ及びＴａよりなる群から選ばれる１種又は２種
以上と、Ｚｒと、Ｙ，Ｌａ，Ｃｅ，Ｎｄ，Ｓｍ，Ｇｄ，
Ｔｂ及びＤｙよりなる群から選ばれる１種又は２種以上
の希土類元素とを含み、残部が実質的にＣｏ及び／又は
Ｎｉよりなり、Ｚｒの含有量が８原子％以上、希土類元
素の含有量が５原子％以下で、Ｔｉ，Ｎｂ及びＴａより
なる群から選ばれる１種又は２種以上とＺｒと希土類元
素との合計の含有量が８０原子％以下であることを特徴
とする。[0008] The amorphous alloy catalyst for methanation of carbon dioxide according to claim 2 is an amorphous alloy catalyst for methanation of carbon dioxide obtained by subjecting a precursor comprising an amorphous alloy to a redox treatment, wherein the amorphous alloy comprises: T
one or more selected from the group consisting of i, Nb and Ta, Zr, Y, La, Ce, Nd, Sm, Gd,
One or two or more rare earth elements selected from the group consisting of Tb and Dy, the balance substantially consisting of Co and / or Ni, a Zr content of at least 8 atomic%, and a rare earth element content Is 5 atomic% or less, and the total content of one or more selected from the group consisting of Ti, Nb and Ta, Zr and a rare earth element is 80 atomic% or less.
【０００９】即ち、本出願人らは、アモルファス合金の
特性について鋭意研究を重ねた結果、従来の鉄族金属と
Ｚｒ，Ｔｉ，Ｎｂ，Ｔａなどのバルブメタルからなるア
モルファス合金に、更に酸素との親和力が高い希土類元
素を加えたアモルファス合金を作製し、これに酸化還元
処理を施すと、従来の鉄族金属−バルブメタルアモルフ
ァス合金に酸化還元処理を施したものより、二酸化炭素
と水素との反応によるメタン生成に対して更に高い活性
を備えた触媒が得られることを見出し本発明を完成させ
た。That is, as a result of intensive studies on the properties of amorphous alloys, the present applicants have found that an amorphous alloy composed of a conventional iron group metal and a valve metal such as Zr, Ti, Nb, Ta, etc. When an amorphous alloy containing a high-affinity rare earth element is prepared and subjected to oxidation-reduction treatment, the reaction between carbon dioxide and hydrogen is reduced as compared with a conventional iron-group metal-valve metal amorphous alloy subjected to oxidation-reduction treatment. The present inventors have found that a catalyst having higher activity for methane generation by methane can be obtained and completed the present invention.
【００１０】特定の化学反応に対する高い選択的触媒活
性を備えた触媒を得るためには、アルミナ、チタニア、
シリカなどのセラミックスに白金族元素などを担持する
よりは、有効元素を必要量含む合金を前駆体として用い
る方が有利である。しかし、通常の方法で作られる結晶
質金属の場合、多種多量の合金金属を添加すると、しば
しば、化学的性質の異なる多相構造となることが多く、
所定の特性を備えることができないだけでなく、また脆
いために触媒として必要な比表面積の大きな材料が得難
い。In order to obtain a catalyst with a high selective catalytic activity for a particular chemical reaction, alumina, titania,
It is more advantageous to use an alloy containing a necessary amount of an effective element as a precursor than to carry a platinum group element or the like on ceramics such as silica. However, in the case of crystalline metals made by ordinary methods, the addition of a large amount of various alloy metals often results in a multiphase structure with different chemical properties,
In addition to being unable to have the predetermined characteristics, it is difficult to obtain a material having a large specific surface area required as a catalyst because of its brittleness.
【００１１】これに対し、本発明組成のアモルファス合
金は、構成元素が局在することを許さず所定の元素を均
一に固溶している。このようなアモルファス合金を液体
急冷法、スパッター法、メカニカルアロイイング法など
を用いて作製すると、従来では実現しなかった本発明の
アモルファス合金固有の優れた触媒活性を備え、二酸化
炭素を迅速にメタンに変換し得る触媒が得られる。On the other hand, in the amorphous alloy of the composition of the present invention, a predetermined element is uniformly dissolved in a solid solution without allowing the constituent elements to be localized. When such an amorphous alloy is manufactured using a liquid quenching method, a sputtering method, a mechanical alloying method, etc., it has excellent catalytic activity unique to the amorphous alloy of the present invention, which has not been realized in the past, and rapidly converts carbon dioxide into methane. A catalyst which can be converted to
【００１２】上記組成のアモルファス合金に酸化還元処
理を施して得られる本発明の触媒によれば、大気圧で高
速に二酸化炭素をメタンに変換することができる。According to the catalyst of the present invention obtained by subjecting an amorphous alloy having the above composition to an oxidation-reduction treatment, carbon dioxide can be rapidly converted to methane at atmospheric pressure.
【００１３】[0013]
【発明の実施の形態】以下に本発明を詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
【００１４】本発明において、触媒の前駆体となるアモ
ルファス合金の組成は下記表に示す通りである。In the present invention, the composition of the amorphous alloy serving as a catalyst precursor is as shown in the following table.
【００１５】[0015]
【表１】 [Table 1]
【００１６】以下に、本発明に係るアモルファス合金の
各成分組成の限定理由を述べる。The reasons for limiting the composition of each component of the amorphous alloy according to the present invention will be described below.
【００１７】Ｎｉ及びＣｏは、本発明に係るアモルファ
ス合金の基礎となる元素であって、バルブメタルである
Ｚｒ又はＺｒの一部を他のバルブメタルであるＴａ，Ｔ
ｉ，Ｎｂの１種以上で置換したものとの共存で、アモル
ファス構造を形成する元素である。このアモルファス構
造の形成のためには、Ｎｉ及び／又はＣｏは２０原子％
以上必要であるため、他の元素の合計を８０原子％以下
とする。Ni and Co are elements that form the basis of the amorphous alloy according to the present invention. The valve metal Zr or a part of Zr is replaced with another valve metal Ta, T
It is an element that forms an amorphous structure in coexistence with one substituted by one or more of i and Nb. For the formation of this amorphous structure, Ni and / or Co are 20 atomic%.
Therefore, the total of other elements is set to 80 atomic% or less.
【００１８】また、Ｎｉ及びＣｏは活性元素として触媒
反応に寄与する元素でもある。Ni and Co are also elements that contribute to the catalytic reaction as active elements.
【００１９】ＺｒはＺｒＯ2 を生じてＮｉ及びＣｏに対
する担体として働く必須元素である。Ｚｒの含有量が８
原子％未満であると、この担体機能が十分に得られない
ため、Ｚｒの含有量は８原子％以上、好ましくは２５〜
７５原子％とする。Zr is an essential element that forms ZrO 2 and acts as a carrier for Ni and Co. Zr content of 8
When the content is less than atomic%, the carrier function cannot be sufficiently obtained, so that the Zr content is 8 atomic% or more, preferably 25 to
75 at%.
【００２０】希土類元素は触媒の多孔性を向上させて触
媒活性を高める元素であるが、アモルファス合金作製の
過程でも酸化され易いため、合金作製工程における取り
扱い性や作業性等の面から、希土類元素の含有量は５原
子％以下とする。なお、希土類元素はその添加効果を十
分に得るために０．１原子％以上含有されていることが
好ましく、特に０．３〜５原子％とするのが好ましい。The rare earth element is an element that enhances the catalyst activity by improving the porosity of the catalyst. However, since the rare earth element is easily oxidized even in the process of producing the amorphous alloy, the rare earth element is difficult to handle and work in the alloy production process. Is 5 atomic% or less. The rare earth element is preferably contained in an amount of 0.1 atomic% or more in order to sufficiently obtain the effect of its addition, and particularly preferably 0.3 to 5 atomic%.
【００２１】Ｔｉ，Ｎｂ，ＴａはＺｒを置換してＮｉ及
び／又はＣｏとアモルファス構造を形成する有効元素で
あるが、酸化物となって担体として機能する際、触媒活
性に対するＺｒＯ2 の作用をしのぐことはないため、Ｔ
ｉ，Ｎｂ，Ｔａを含む場合、その含有量は、８原子％以
上のＺｒと５原子％以下の希土類元素との合計で８０原
子％以下の範囲とする必要がある。Ｔｉ，Ｎｂ，Ｔａの
１種又は２種以上を含む場合、その含有量は特に５０原
子％以下、とりわけ１０〜４０原子％であることが好ま
しい。Ti, Nb, and Ta are effective elements that form an amorphous structure with Ni and / or Co by substituting Zr, but when they function as oxides and as carriers, they exert an effect of ZrO 2 on catalytic activity. Because it cannot surpass, T
When i, Nb, and Ta are contained, the content thereof must be in a range of 80 atomic% or less in total of Zr of 8 atomic% or more and a rare earth element of 5 atomic% or less. When one or more of Ti, Nb, and Ta are contained, the content is preferably 50 atomic% or less, particularly preferably 10 to 40 atomic%.
【００２２】なお、本発明に係るアモルファス合金にお
いて、Ｎｉ及び／又はＣｏの一部を小量のＦｅで置換す
ることは本発明の目的に何ら支障を与えるものではな
い。It should be noted that substituting a part of Ni and / or Co with a small amount of Fe in the amorphous alloy according to the present invention does not affect the object of the present invention.
【００２３】本発明の二酸化炭素のメタン化用アモルフ
ァス合金触媒は、液体急冷法、スパッター法、メカニカ
ルアロイイング法等により得られた上記組成のアモルフ
ァス合金を前駆体とし、これを酸化還元処理することに
より得られる。The amorphous alloy catalyst for methanation of carbon dioxide of the present invention is obtained by subjecting an amorphous alloy having the above composition obtained by a liquid quenching method, a sputtering method, a mechanical alloying method or the like to a precursor, and subjecting it to a redox treatment. Is obtained by
【００２４】このアモルファス合金の酸化還元処理は、
例えば、アモルファス合金を酸素雰囲気中３００〜７０
０℃で１〜１２時間加熱して酸化した後、水素雰囲気中
１００〜５００℃で１〜２４時間加熱して還元すること
により行うことができる。The oxidation-reduction treatment of this amorphous alloy is performed by
For example, an amorphous alloy is placed in an oxygen atmosphere at 300-70.
After oxidizing by heating at 0 ° C. for 1 to 12 hours, reduction can be performed by heating at 100 to 500 ° C. for 1 to 24 hours in a hydrogen atmosphere.
【００２５】このようにして得られる本発明の二酸化炭
素のメタン化用アモルファス合金触媒は、二酸化炭素と
水素とを所定のモル比で反応させるメタン化反応の触媒
として高い触媒活性を示す。The thus obtained amorphous alloy catalyst for methanation of carbon dioxide of the present invention exhibits high catalytic activity as a catalyst for the methanation reaction of reacting carbon dioxide and hydrogen at a predetermined molar ratio.
【００２６】なお、本発明の二酸化炭素のメタン化用ア
モルファス合金触媒を用いて、二酸化炭素のメタン化を
行なうには、例えば、本発明の二酸化炭素のメタン化用
アモルファス合金触媒１ｇを充填した反応管に、二酸化
炭素と水素とをＣＯ2 ：Ｈ2＝１：１〜４（モル比）の
割合で混合したガスを１００〜３００℃で１５〜３００
ｍｌ／ｍｉｎで流通させて反応させれば良い。In order to methanize carbon dioxide using the amorphous carbon dioxide methanation catalyst of the present invention, for example, a reaction filled with 1 g of the carbon dioxide methanation amorphous alloy catalyst of the present invention is performed. A gas in which carbon dioxide and hydrogen are mixed in a ratio of CO 2 : H 2 = 1: 1 to 4 (molar ratio) in a tube at 15 to 300 ° C. at 100 to 300 ° C.
The reaction may be carried out at a flow rate of ml / min.
【００２７】[0027]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明する。The present invention will be described more specifically below with reference to examples and comparative examples.
【００２８】実施例１，２，比較例１ 表２に示す組成となるように原料金属を混合し、アルゴ
ンアーク溶融により原料合金を作製した。この合金をア
ルゴン雰囲気中で再溶融し、図１に示す単ロール法で超
急冷凝固させることにより、厚さ０．０１〜０．０５ｍ
ｍ、幅１〜３ｍｍ、長さ３〜２０ｍのアモルファス合金
薄板を得た。Examples 1, 2 and Comparative Example 1 Raw materials were mixed so as to have the compositions shown in Table 2, and raw material alloys were prepared by argon arc melting. This alloy was re-melted in an argon atmosphere and was rapidly quenched and solidified by the single roll method shown in FIG.
m, a width of 1 to 3 mm, and a length of 3 to 20 m were obtained.
【００２９】図１において、１は石英管であり、高周波
コイル２の加熱機構を備える。この石英管１内に入れた
原料合金をアルゴンガス雰囲気中で加熱溶融させ、溶融
合金３を高速回転させた銅ロール４の表面に高圧のアル
ゴンガスで吹きつけてアモルファス合金薄板５を得る。In FIG. 1, reference numeral 1 denotes a quartz tube having a heating mechanism for the high-frequency coil 2. The raw material alloy placed in the quartz tube 1 is heated and melted in an argon gas atmosphere, and the molten alloy 3 is sprayed with high-pressure argon gas onto the surface of a copper roll 4 rotated at high speed to obtain an amorphous alloy thin plate 5.
【００３０】得られた薄板５のアモルファス構造形成の
確認はＸ線回析によって行なった。The formation of an amorphous structure in the obtained thin plate 5 was confirmed by X-ray diffraction.
【００３１】次いで、得られたアモルファス合金薄板の
試料を、酸素雰囲気中にて５００℃で３時間酸化した
後、水素雰囲気中にて３００℃で１時間還元して触媒を
得た。Next, the obtained sample of the amorphous alloy sheet was oxidized in an oxygen atmosphere at 500 ° C. for 3 hours, and then reduced in a hydrogen atmosphere at 300 ° C. for 1 hour to obtain a catalyst.
【００３２】得られた触媒１ｇを内径８ｍｍのガラス管
に５ｃｍの長さにつめて反応管とし、これを電気炉内に
設置した。この反応管に、所定の温度にてＣＯ2 とＨ2
をモル比で１：４含むガスを流速６０ｍｌ／ｍｉｎで流
し、反応管出口におけるＣＯ2 ，Ｈ2 ，ＣＨ4 ，その他
検出される物質の量をガスクロマトグラフで測定した。
その結果、検出される物質はＣＯ2 ，Ｈ2 ，ＣＨ4 のみ
であって、選択率１００％でＣＨ4 が生じることが確認
された。各反応温度におけるＣＯ2 からＣＨ4への変換
率を表２に示す。1 g of the obtained catalyst was packed in a glass tube having an inner diameter of 8 mm to a length of 5 cm to form a reaction tube, which was placed in an electric furnace. CO 2 and H 2 are added to the reaction tube at a predetermined temperature.
Was flowed at a flow rate of 60 ml / min, and the amounts of CO 2 , H 2 , CH 4 , and other detected substances at the outlet of the reaction tube were measured by gas chromatography.
As a result, it was confirmed that only the detected substances were CO 2 , H 2 , and CH 4 , and CH 4 was generated at a selectivity of 100%. Table 2 shows the conversion from CO 2 to CH 4 at each reaction temperature.
【００３３】[0033]
【表２】 [Table 2]
【００３４】表２より、Ｎｉ−４０原子％Ｚｒ−１．６
原子％Ｓｍ及びＮｉ−４０原子％Ｚｒ−３．５原子％Ｃ
ｅ合金に酸化還元処理を施して得られる本発明の触媒は
ＣＯ2 からＣＨ4 への変換用高活性触媒であることが明
らかである。From Table 2, it can be seen that Ni-40 atomic% Zr-1.6.
Atomic% Sm and Ni-40 atomic% Zr-3.5 atomic% C
It is clear that the catalyst of the present invention obtained by subjecting the e-alloy to a redox treatment is a highly active catalyst for converting CO 2 into CH 4 .
【００３５】実施例３〜１６ 実施例１において、合金組成を表３に示す組成としたこ
と以外は同様にして触媒を調製し、同様に二酸化炭素の
メタン化反応を行い、その時のＣＯ2 からＣＨ4 への変
換率を調べ、結果を表３に示した。[0035] In Example 3-16 Example 1, the alloy composition in the same manner except for using the composition shown in Table 3 to prepare a catalyst, likewise performed methanation reaction of carbon dioxide, from the CO 2 at that time The conversion to CH 4 was determined and the results are shown in Table 3.
【００３６】[0036]
【表３】 [Table 3]
【００３７】表３より、本発明の二酸化炭素のメタン化
用アモルファス合金触媒は極めて高活性であることが明
らかである。From Table 3, it is clear that the amorphous alloy catalyst for methanation of carbon dioxide of the present invention has extremely high activity.
【００３８】[0038]
【発明の効果】以上詳述した通り、本発明の二酸化炭素
のメタン化用アモルファス合金触媒によれば、大気圧下
の反応で大量の二酸化炭素を効率的にメタンに変換する
ことが可能とされている。As described in detail above, according to the amorphous alloy catalyst for methanation of carbon dioxide of the present invention, a large amount of carbon dioxide can be efficiently converted to methane by a reaction under atmospheric pressure. ing.
【図１】本発明に係るアモルファス合金を製造するため
の装置の一例を示す断面図である。FIG. 1 is a sectional view showing an example of an apparatus for producing an amorphous alloy according to the present invention.
１ 石英管 ２ 高周波コイル ３ 溶融合金 ４ 銅ロール ５ アモルファス合金薄板 DESCRIPTION OF SYMBOLS 1 Quartz tube 2 High frequency coil 3 Molten alloy 4 Copper roll 5 Amorphous alloy thin plate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 嶋村 和郎 千葉県市原市八幡海岸通１番地 三井造船 株式会社千葉事業所内 (72)発明者 吉田 健 宮城県仙台市太白区三神峯２丁目14−18 (72)発明者 幅崎 浩樹 宮城県仙台市太白区長町８丁目２−31 (72)発明者 秋山 英二 宮城県仙台市太白区向山２丁目13−５ ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuo Shimamura 1-Yawata Kaigandori, Ichihara-shi, Chiba Mitsui Engineering & Shipbuilding Chiba Works Co., Ltd. 72) Inventor Hiroki Hirosaki 8-2-31 Nagamachi 8-chome, Taihaku-ku, Sendai City, Miyagi Prefecture
Claims (2)
還元処理を施してなる二酸化炭素のメタン化用アモルフ
ァス合金触媒であって、 該アモルファス合金が、Ｚｒと、Ｙ，Ｌａ，Ｃｅ，Ｎ
ｄ，Ｓｍ，Ｇｄ，Ｔｂ及びＤｙよりなる群から選ばれる
１種又は２種以上の希土類元素とを含み、残部が実質的
にＣｏ及び／又はＮｉよりなり、Ｚｒの含有量が８原子
％以上、希土類元素の含有量が５原子％以下で、Ｚｒと
希土類元素との合計の含有量が８０原子％以下であるこ
とを特徴とする二酸化炭素のメタン化用アモルファス合
金触媒。1. An amorphous alloy catalyst for methanation of carbon dioxide obtained by subjecting a precursor made of an amorphous alloy to a redox treatment, wherein the amorphous alloy comprises Zr, Y, La, Ce, and N.
one or two or more rare earth elements selected from the group consisting of d, Sm, Gd, Tb, and Dy, and the balance is substantially composed of Co and / or Ni, and the Zr content is at least 8 atomic%. An amorphous alloy catalyst for methanation of carbon dioxide, characterized in that the content of rare earth element is 5 atomic% or less and the total content of Zr and rare earth element is 80 atomic% or less.
還元処理を施してなる二酸化炭素のメタン化用アモルフ
ァス合金触媒であって、 該アモルファス合金が、Ｔｉ，Ｎｂ及びＴａよりなる群
から選ばれる１種又は２種以上と、Ｚｒと、Ｙ，Ｌａ，
Ｃｅ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ及びＤｙよりなる群から
選ばれる１種又は２種以上の希土類元素とを含み、残部
が実質的にＣｏ及び／又はＮｉよりなり、Ｚｒの含有量
が８原子％以上、希土類元素の含有量が５原子％以下
で、Ｔｉ，Ｎｂ及びＴａよりなる群から選ばれる１種又
は２種以上とＺｒと希土類元素との合計の含有量が８０
原子％以下であることを特徴とする二酸化炭素のメタン
化用アモルファス合金触媒。2. An amorphous alloy catalyst for methanation of carbon dioxide obtained by subjecting a precursor comprising an amorphous alloy to a redox treatment, wherein the amorphous alloy is one selected from the group consisting of Ti, Nb and Ta. Or two or more, Zr, Y, La,
One or more rare earth elements selected from the group consisting of Ce, Nd, Sm, Gd, Tb and Dy, and the balance substantially consisting of Co and / or Ni, and having a Zr content of 8 atoms %, The content of the rare earth element is 5 atom% or less, and the total content of one or more selected from the group consisting of Ti, Nb and Ta, Zr and the rare earth element is 80% or less.
An amorphous alloy catalyst for methanation of carbon dioxide, which is at most atomic%.
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|---|---|---|---|
| JP20454396A JP3819486B2 (en) | 1996-08-02 | 1996-08-02 | Amorphous alloy catalysts for methanation of carbon dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20454396A JP3819486B2 (en) | 1996-08-02 | 1996-08-02 | Amorphous alloy catalysts for methanation of carbon dioxide |
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| Publication Number | Publication Date |
|---|---|
| JPH1043594A true JPH1043594A (en) | 1998-02-17 |
| JP3819486B2 JP3819486B2 (en) | 2006-09-06 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090042998A1 (en) * | 2007-08-03 | 2009-02-12 | Daiki Ataka Engineering Co., Ltd. | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| JP2009034650A (en) * | 2007-08-03 | 2009-02-19 | Daiki Ataka Engineering Co Ltd | Methanation catalyst of carbon oxide, its manufacturing method and methanation method |
| US10343147B2 (en) | 2014-07-19 | 2019-07-09 | Hitachi Zosen Corporation | Methanation reaction catalyst, method for producing methanation reaction catalyst and method for producing methane |
| CN111116346A (en) * | 2019-12-31 | 2020-05-08 | 上海师范大学 | Supercritical CO based on amorphous alloy2Hydrogenation process |
-
1996
- 1996-08-02 JP JP20454396A patent/JP3819486B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090042998A1 (en) * | 2007-08-03 | 2009-02-12 | Daiki Ataka Engineering Co., Ltd. | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| JP2009034650A (en) * | 2007-08-03 | 2009-02-19 | Daiki Ataka Engineering Co Ltd | Methanation catalyst of carbon oxide, its manufacturing method and methanation method |
| EP2033943A1 (en) | 2007-08-03 | 2009-03-11 | Daiki Ataka Engineering Co., Ltd. | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| US9617196B2 (en) * | 2007-08-03 | 2017-04-11 | Hitachi Zosen Corporation | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| US9732010B2 (en) | 2007-08-03 | 2017-08-15 | Hitachi Zosen Corporation | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| US9731278B2 (en) | 2007-08-03 | 2017-08-15 | Hitachi Zosen Corporation | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| US10343147B2 (en) | 2014-07-19 | 2019-07-09 | Hitachi Zosen Corporation | Methanation reaction catalyst, method for producing methanation reaction catalyst and method for producing methane |
| CN111116346A (en) * | 2019-12-31 | 2020-05-08 | 上海师范大学 | Supercritical CO based on amorphous alloy2Hydrogenation process |
| WO2021135387A1 (en) * | 2019-12-31 | 2021-07-08 | 上海师范大学 | Amorphous alloy-based process for use in supercritical co2 hydrogenation |
| CN111116346B (en) * | 2019-12-31 | 2021-10-22 | 上海师范大学 | Supercritical CO based on amorphous alloy2Hydrogenation process |
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| Publication number | Publication date |
|---|---|
| JP3819486B2 (en) | 2006-09-06 |
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