JP2002126528A - Method for preparing reforming catalyst - Google Patents
Method for preparing reforming catalystInfo
- Publication number
- JP2002126528A JP2002126528A JP2000318477A JP2000318477A JP2002126528A JP 2002126528 A JP2002126528 A JP 2002126528A JP 2000318477 A JP2000318477 A JP 2000318477A JP 2000318477 A JP2000318477 A JP 2000318477A JP 2002126528 A JP2002126528 A JP 2002126528A
- Authority
- JP
- Japan
- Prior art keywords
- precipitate
- catalyst
- reforming
- producing
- reforming catalyst
- 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.)
- Pending
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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、一酸化炭素（Ｃ
Ｏ）と水素（Ｈ2 ）との混合ガスである合成ガスを、メ
タンなどの炭化水素と水、二酸化炭素、酸素、空気など
の改質物質とから得るためのリホーミング用触媒の製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to carbon monoxide (C
The present invention relates to a method for producing a reforming catalyst for obtaining a synthesis gas that is a mixed gas of O) and hydrogen (H 2 ) from a hydrocarbon such as methane and a reforming substance such as water, carbon dioxide, oxygen, and air. .
【０００２】[0002]
【従来の技術】従来より、メタン、天然ガス、石油ガ
ス、ナフサ、重油、原油などの炭化水素と、水、空気、
酸素あるいは二酸化炭素の改質物質とを高温で触媒の存
在下、反応させて、反応性に富む一酸化炭素と水素とか
らなる合成ガスを生成するリホーミングが行われてお
り、生成した合成ガスを原料としてメタノールや液体燃
料油が製造されている。このリホーミングに使用される
リホーミング用触媒としては、ニッケル／アルミナ触
媒、ニッケル／マグネシア／アルミナ触媒などが用いら
れる。2. Description of the Related Art Conventionally, hydrocarbons such as methane, natural gas, petroleum gas, naphtha, heavy oil, crude oil, water, air,
Reforming is performed in which a reformed substance of oxygen or carbon dioxide is reacted at a high temperature in the presence of a catalyst to generate a synthesis gas composed of highly reactive carbon monoxide and hydrogen. Is used as a raw material to produce methanol and liquid fuel oil. As the reforming catalyst used for this reforming, a nickel / alumina catalyst, a nickel / magnesia / alumina catalyst, or the like is used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
のリホーミング用触媒を用いた反応では、例えばメタン
と水蒸気とを化学等量反応させようとすると、炭素質
（カーボン）が多量に析出する問題がある。よって、こ
の炭素質の析出を防止するために大過剰の水蒸気を供給
し、リホーミング反応を促進する必要がある。このた
め、従来のリホーミングにあっては、多量の水蒸気を必
要とするためエネルギーコストが嵩み、設備が大型化す
る不都合があった。そこで本出願人は、大過剰の水蒸気
を供給しなくても炭素質（カーボン）の析出を抑制でき
るリホーミング用触媒として、コバルト／マグネシア系
触媒を特願平１０−１０３２０３号および特願平１１−
９８２２０号で報告したが、このような炭素質（カーボ
ン）の析出を抑制できる触媒を、より低コストで生産性
良く製造できる方法の開発が望まれていた。However, in the reactions using these reforming catalysts, if methane and water vapor are allowed to react in a stoichiometric manner, a large amount of carbonaceous material (carbon) is deposited. is there. Therefore, it is necessary to supply a large excess of steam in order to prevent this carbonaceous deposition and to promote the reforming reaction. For this reason, in the conventional reforming, a large amount of steam is required, so that the energy cost is increased and the equipment is disadvantageously increased in size. Accordingly, the present applicant has proposed a cobalt / magnesia catalyst as a reforming catalyst capable of suppressing the deposition of carbonaceous material (carbon) without supplying a large excess of water vapor, as disclosed in Japanese Patent Application Nos. 10-103203 and 11-113. −
No. 98220, it has been desired to develop a method capable of producing such a catalyst capable of suppressing the deposition of carbonaceous material (carbon) at lower cost and with higher productivity.
【０００４】本発明の目的は、炭化水素に化学等量もし
くはそれに近い量の改質物質を加えて合成ガスを製造す
る際にも炭素質が析出しない触媒を、生産性良く製造す
る方法を提供することである。[0004] An object of the present invention is to provide a method for producing a catalyst which does not deposit carbonaceous material even when producing a synthesis gas by adding a chemical equivalent or a similar amount of a reforming substance to a hydrocarbon with high productivity. It is to be.
【０００５】[0005]
【課題を解決するための手段】本発明のリホーミング用
触媒の製造方法は、下記式（１）で表される組成を有す
る複合酸化物からなり、Ｃｏが該複合酸化物中で高分散
化されていることを特徴とする炭化水素のリホーミング
触媒の製造方法であって、ＣｏとＭｇとＣａとを下記式
（１）で表された比率で含有する水溶液に、共沈剤を添
加して沈殿を生成させる沈殿生成工程と、前記沈殿を乾
燥し乾燥沈殿物とする乾燥工程と、前記乾燥沈殿物を焼
成する焼成工程を有し、沈殿生成工程を３１３〜３７３
Ｋで行うことを特徴とする。 ａＣｏ・ｂＭｇ・ｃＣａ・ｄＯ…（１） （式中、ａ，ｂ，ｃ，ｄはモル分率であり、ａ＋ｂ＋ｃ
＝１、０．００５≦ａ≦０．３０、０．７０≦（ｂ＋
ｃ）≦０．９９５、０＜ｂ≦０．９９５、０≦ｃ≦０．
９９５、ｄ＝元素が酸素と電荷均衡を保つのに必要な数
である。）The process for producing a reforming catalyst according to the present invention comprises a composite oxide having a composition represented by the following formula (1), wherein Co is highly dispersed in the composite oxide. A method for producing a hydrocarbon reforming catalyst, characterized in that a coprecipitant is added to an aqueous solution containing Co, Mg and Ca in a ratio represented by the following formula (1). A precipitate forming step of forming a precipitate by drying, a drying step of drying the precipitate to form a dried precipitate, and a firing step of firing the dried precipitate, wherein the precipitate generating step is performed at 313 to 373.
K is performed. aCo · bMg · cCa · dO (1) (where a, b, c, and d are mole fractions, and a + b + c
= 1, 0.005 ≦ a ≦ 0.30, 0.70 ≦ (b +
c) ≦ 0.995, 0 <b ≦ 0.995, 0 ≦ c ≦ 0.
995, d = number required to keep the element in charge balance with oxygen. )
【０００６】また、本発明のリホーミング用触媒の製造
方法は、下記式（２）で表される組成を有する複合酸化
物からなり、Ｎｉが該複合酸化物中で高分散化されてい
ることを特徴とする炭化水素のリホーミング触媒の製造
方法であって、ＮｉとＭｇとＣａとを下記式（２）で表
された比率で含有する水溶液に、共沈剤を添加して沈殿
を生成させる沈殿生成工程と、前記沈殿を乾燥し乾燥沈
殿物とする乾燥工程と、前記乾燥沈殿物を焼成する焼成
工程を有し、沈殿生成工程を３１３〜３７３Ｋで行うこ
とを特徴とする。 ａＮｉ・ｂＭｇ・ｃＣａ・ｄＯ…（２） （式中、ａ，ｂ，ｃ，ｄはモル分率であり、ａ＋ｂ＋ｃ
＝１、０．００５≦ａ≦０．３０、０．７０≦（ｂ＋
ｃ）≦０．９９５、０＜ｂ≦０．９９５、０≦ｃ≦０．
９９５、ｄ＝元素が酸素と電荷均衡を保つのに必要な数
である。）Further, the method for producing a reforming catalyst of the present invention comprises a composite oxide having a composition represented by the following formula (2), wherein Ni is highly dispersed in the composite oxide. A method for producing a hydrocarbon reforming catalyst, characterized in that a coprecipitant is added to an aqueous solution containing Ni, Mg and Ca at a ratio represented by the following formula (2) to form a precipitate: The method includes a step of generating a precipitate, a step of drying the precipitate to form a dried precipitate, and a step of firing the dried precipitate, wherein the step of generating the precipitate is performed at 313 to 373K. aNi.bMg.cCa.dO (2) (where a, b, c, and d are mole fractions, and a + b + c
= 1, 0.005 ≦ a ≦ 0.30, 0.70 ≦ (b +
c) ≦ 0.995, 0 <b ≦ 0.995, 0 ≦ c ≦ 0.
995, d = number required to keep the element in charge balance with oxygen. )
【０００７】さらに、本発明のリホーミング用触媒の製
造方法は、下記式（３）で表される組成を有する複合酸
化物からなり、ＭおよびＮｉが該複合酸化物中で高分散
化されていることを特徴とする炭化水素のリホーミング
触媒の製造方法であって、ＭとＮｉとＭｇとＣａとを下
記式（３）で表された比率で含有する水溶液に、共沈剤
を添加して沈殿を生成させる沈殿生成工程と、前記沈殿
を乾燥し乾燥沈殿物とする乾燥工程と、前記乾燥沈殿物
を焼成する焼成工程を有し、沈殿生成工程を３１３〜３
７３Ｋで行うことを特徴とする。 ａＭ・ｂＮｉ・ｃＭｇ・ｄＣａ・ｅＯ…（３） （式中、ａ，ｂ，ｃ，ｄ，ｅはモル分率であり、ａ＋ｂ
＋ｃ＋ｄ＝１、０．０００１≦ａ≦０．１０、０．００
０１≦ｂ≦０．３０、０．６０≦（ｃ＋ｄ）≦０．９９
９８、０＜ｃ≦０．９９９８、０≦ｄ＜０．９９９８、
ｅ＝元素が酸素と電荷均衡を保つのに必要な数である。
また、Ｍは周期律表第６Ａ族元素、第７Ａ族元素、Ｎｉ
を除く第８族遷移元素、第１Ｂ族元索、第２Ｂ族元素、
第４Ｂ族元素およびランタノイド元素の少なくとも１種
類の元素である。）Further, the method for producing a reforming catalyst of the present invention comprises a composite oxide having a composition represented by the following formula (3), wherein M and Ni are highly dispersed in the composite oxide. A method for producing a hydrocarbon reforming catalyst, comprising: adding a coprecipitant to an aqueous solution containing M, Ni, Mg, and Ca in a ratio represented by the following formula (3). A precipitate forming step of forming a precipitate by drying, a drying step of drying the precipitate to form a dried precipitate, and a firing step of firing the dried precipitate.
It is characterized in that it is performed at 73K. aM · bNi · cMg · dCa · eO (3) (where a, b, c, d, and e are mole fractions, and a + b
+ C + d = 1, 0.0001 ≦ a ≦ 0.10, 0.00
01 ≦ b ≦ 0.30, 0.60 ≦ (c + d) ≦ 0.99
98, 0 <c ≦ 0.9998, 0 ≦ d <0.9998,
e = number of elements required to keep charge balance with oxygen.
M is a group 6A element, a group 7A element, Ni
Group 8 transition elements, except Group 1B origin element, Group 2B element,
It is at least one element of a Group 4B element and a lanthanoid element. )
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳しく説明する。
本発明の製造方法で製造されるリホーミング用触媒は、
下記式（１）で表される組成の複合酸化物からなるもの
である。 ａＣｏ・ｂＭｇ・ｃＣａ・ｄＯ…（１） （式中、ａ，ｂ，ｃ，ｄはモル分率であり、ａ＋ｂ＋ｃ
＝１、０．００５≦ａ≦０．３０、０．７０≦（ｂ＋
ｃ）≦０．９９５、０＜ｂ≦０．９９５、０≦ｃ≦０．
９９５、ｄ＝元素が酸素と電荷均衡を保つのに必要な数
である。） なお、ここでの周期律表はＩＵＰＡＣによるものとす
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The reforming catalyst produced by the production method of the present invention,
It is composed of a composite oxide having a composition represented by the following formula (1). aCo · bMg · cCa · dO (1) (where a, b, c, and d are mole fractions, and a + b + c
= 1, 0.005 ≦ a ≦ 0.30, 0.70 ≦ (b +
c) ≦ 0.995, 0 <b ≦ 0.995, 0 ≦ c ≦ 0.
995, d = number required to keep the element in charge balance with oxygen. The periodic table here is based on IUPAC.
【０００９】コバルト含有量（ａ）は、０．００５≦ａ
≦０．３０であり、好ましくは、０．００５≦ａ≦０．
２５、さらに好ましくは０．０１≦ａ≦０．２０であ
る。コバルト含有量（ａ）が０．００５未満ではコバル
トの含有量が少なすぎて反応活性が低く、０．３０を越
えると後述する高分散化が阻害され、炭素質析出防止効
果が十分得られない。The cobalt content (a) is 0.005 ≦ a
≦ 0.30, preferably 0.005 ≦ a ≦ 0.
25, more preferably 0.01 ≦ a ≦ 0.20. If the cobalt content (a) is less than 0.005, the cobalt content is too small and the reaction activity is low. If it exceeds 0.30, high dispersion described later is inhibited, and the effect of preventing carbonaceous deposition cannot be sufficiently obtained. .
【００１０】マグネシウム含有量（ｂ）とカルシウム含
有量（ｃ）との合計量（ｂ＋ｃ）は、０．７０≦（ｂ＋
ｃ）≦０．９９５であり、好ましくは０．７５≦（ｂ＋
ｃ）≦０．９９、さらに好ましくは０．８０≦（ｂ＋
ｃ）≦０．９９である。このうち、マグネシウム含有量
（ｂ）は０＜ｂ≦０．９９５であり、好ましくは０．７
５≦ｂ≦０．９９、さらに好ましくは０．５０≦ｂ≦
０．９９であり、カルシウム含有量（ｃ）は０≦ｃ＜
０．９９５、好ましくは０≦ｃ≦０．５、さらに好まし
くは０≦ｃ≦０．３であり、カルシウムを欠くものであ
ってもよい。The total amount (b + c) of the magnesium content (b) and the calcium content (c) is 0.70 ≦ (b +
c) ≦ 0.995, preferably 0.75 ≦ (b +
c) ≦ 0.99, more preferably 0.80 ≦ (b +
c) ≦ 0.99. Among them, the magnesium content (b) is 0 <b ≦ 0.995, preferably 0.7
5 ≦ b ≦ 0.99, more preferably 0.50 ≦ b ≦
0.99, and the calcium content (c) is 0 ≦ c <
0.995, preferably 0 ≦ c ≦ 0.5, more preferably 0 ≦ c ≦ 0.3, and may lack calcium.
【００１１】マグネシウム含有量（ｂ）とカルシウム含
有量（ｃ）との合計量（ｂ＋ｃ）は、コバルト含有量
（ａ）とのバランスで決められる。（ｂ＋ｃ）は上記範
囲内であればいかなる割合でもリホーミング反応に優れ
た効果を発揮するが、カルシウム（ｃ）の含有量が多い
と炭素質析出の抑制に効果があるものの、マグネシウム
（ｂ）が多い場合に比べて触媒活性が低い。よって、活
性を重視するのであれば、カルシウム含有量（ｃ）が
０．５を越えると活性が低下するので好ましくない。The total amount (b + c) of the magnesium content (b) and the calcium content (c) is determined by the balance with the cobalt content (a). (B + c) exhibits an excellent effect on the reforming reaction at any ratio as long as it is within the above range, but when the content of calcium (c) is large, the effect of suppressing the carbonaceous precipitation is improved, but magnesium (b) , The catalytic activity is lower than in the case where the amount is large. Therefore, if the activity is emphasized, it is not preferable that the calcium content (c) exceeds 0.5 because the activity decreases.
【００１２】本発明における複合酸化物とは、ＭｇＯ、
ＣａＯが岩塩型結晶構造をとり、その格子に位置するＭ
ｇまたはＣａ原子の一部がＣｏに置換した一種の固溶体
であって、単相をなすものであり、各元素の単独の酸化
物の混合物を言うものではない。そして、本発明の製造
方法で製造されるリホーミング用コバルト系触媒では、
Ｃｏがこの複合酸化物中で高分散状態となっている。In the present invention, the composite oxide is MgO,
CaO has a rock salt type crystal structure, and M
It is a kind of solid solution in which a part of g or Ca atom is replaced by Co, and forms a single phase, and does not mean a mixture of a single oxide of each element. In the reforming cobalt-based catalyst produced by the production method of the present invention,
Co is in a highly dispersed state in this composite oxide.
【００１３】本発明での分散とは、一般に触媒分野で定
義されているものであって、例えば「触媒講座 第５巻
触媒設計」第１４１頁（触媒学会編、講談社刊）など
にあるように、担持された金属の全原子数に対する触媒
表面に露出している原子数の比として定められるもので
ある。[0013] The dispersion in the present invention is generally defined in the field of catalysts, and is, for example, as described in “Catalysis Course, Vol. 5, Catalyst Design”, page 141 (edited by the Catalysis Society of Japan, published by Kodansha). And the ratio of the number of atoms exposed on the catalyst surface to the total number of atoms of the supported metal.
【００１４】これを、図１の模式図によって具体的に説
明すると、複合酸化物からなる触媒１の表面には活性中
心となる半球状などの微小粒子２、２…が無数存在して
おり、この微小粒子２は、後述する活性化（還元）処理
後ではＣｏの金属元素またはその化合物からなってい
る。この微小粒子２をなすＣｏの金属元素またはその化
合物の原子数をＡとし、これらの原子のうち粒子２の表
面に露出している原子の数をＢとすると、Ｂ／Ａが分散
度となる。This will be described in detail with reference to the schematic diagram of FIG. 1. In the surface of a catalyst 1 made of a composite oxide, numerous particles 2, 2,... The microparticles 2 are made of a Co metal element or a compound thereof after an activation (reduction) treatment described later. Assuming that the number of atoms of the metal element of Co or its compound forming the microparticles 2 is A, and the number of atoms of these atoms exposed on the surface of the particles 2 is B, B / A is the degree of dispersion. .
【００１５】触媒反応に関与するのは、微小粒子２の表
面に露出している原子であると考えれば、分散度が１に
近いものは多くの原子がその表面に分布することになっ
て、活性中心が増加し、高活性となりうると考えられ
る。また、微小粒子２の粒径が限りなく小さくなれば、
微小粒子２をなす原子の大部分は、粒子２表面に露出す
ることになって、分散度は１に近づく。したがって、微
小粒子２の粒径が分散度を表す指標にもなりうる。If it is considered that the atoms involved in the catalytic reaction are the atoms exposed on the surface of the fine particles 2, those having a dispersity close to 1 have many atoms distributed on the surface. It is thought that the number of active centers increases, and high activity can be achieved. Also, if the particle size of the microparticles 2 becomes infinitely small,
Most of the atoms forming the microparticles 2 are exposed on the surface of the particles 2, and the degree of dispersion approaches 1. Therefore, the particle size of the fine particles 2 can be an index indicating the degree of dispersion.
【００１６】本発明の製造方法で製造される触媒では、
微細粒子２の径は種々の測定法、例えばＸ線回析法など
の測定限界の３．５ｎｍ未満であり、このことから分散
度が高く、高分散状態であると言うことができる。この
ため、反応に関与するコバルトの原子数が増加し、高活
性となって、反応が化学量論的に進行し、炭素質（カー
ボン）の析出が防止される。In the catalyst produced by the production method of the present invention,
The diameter of the fine particles 2 is less than the measurement limit of 3.5 nm in various measuring methods, for example, an X-ray diffraction method, and it can be said that the fine particles 2 have a high degree of dispersion and are in a highly dispersed state. For this reason, the number of cobalt atoms involved in the reaction increases, the activity becomes high, the reaction proceeds stoichiometrically, and the deposition of carbonaceous (carbon) is prevented.
【００１７】また、本発明の製造方法で製造されるリホ
ーミング用触媒としては、上記式（１）におけるＣｏの
かわりにＮｉを使用した、下記式（２）で表される組成
の複合酸化物からなるものであってもよい。 ａＮｉ・ｂＭｇ・ｃＣａ・ｄＯ…（２） （式中、ａ，ｂ，ｃ，ｄはモル分率であり、ａ＋ｂ＋ｃ
＝１、０．００５≦ａ≦０．３０、０．７０≦（ｂ＋
ｃ）≦０．９９５、０＜ｂ≦０．９９５、０≦ｃ≦０．
９９５、ｄ＝元素が酸素と電荷均衡を保つのに必要な数
である。） なお、ここでの周期律表はＩＵＰＡＣによるものとす
る。この式（２）で表されるリホーミング用触媒も、Ｍ
ｇＯ、ＣａＯが岩塩型結晶構造をとり、その格子に位置
するＭｇまたはＣａ原子の一部がＮｉに置換した一種の
固溶体であって、単相をなす複合酸化物からなり、各元
素の単独の酸化物の混合物からなるものではない。そし
て、式（２）で表されるリホーミング用触媒において
は、式（１）におけるＣｏのかわりにＮｉがこの複合酸
化物中で高分散状態となっている。また、式（２）のリ
ホーミング用触媒における、Ｎｉの好ましい割合は式
（１）の複合酸化物からなるリフォーミング触媒におけ
るＣｏと同じであり、Ｍｇ、Ｃａの好ましい割合は式
（１）のリホーミング用触媒のＭｇ、Ｃａと同様であ
る。Further, as the reforming catalyst produced by the production method of the present invention, a composite oxide having a composition represented by the following formula (2) using Ni instead of Co in the above formula (1) is used. May be used. aNi.bMg.cCa.dO (2) (where a, b, c, and d are mole fractions, and a + b + c
= 1, 0.005 ≦ a ≦ 0.30, 0.70 ≦ (b +
c) ≦ 0.995, 0 <b ≦ 0.995, 0 ≦ c ≦ 0.
995, d = number required to keep the element in charge balance with oxygen. The periodic table here is based on IUPAC. The reforming catalyst represented by the formula (2) is also M
gO, CaO has a rock salt type crystal structure, and is a kind of solid solution in which a part of Mg or Ca atoms located in the lattice is replaced by Ni, and is composed of a single phase composite oxide, and each element is a single oxide. It does not consist of a mixture of oxides. In the reforming catalyst represented by the formula (2), Ni is in a highly dispersed state in the composite oxide instead of Co in the formula (1). Further, in the reforming catalyst of the formula (2), the preferable ratio of Ni is the same as that of Co in the reforming catalyst comprising the complex oxide of the formula (1), and the preferable ratio of Mg and Ca is as follows. It is the same as Mg and Ca of the reforming catalyst.
【００１８】さらに、本発明の製造方法で製造されるリ
ホーミング用触媒としては、下記式（３）の複合酸化物
からなるものであってもよい。この触媒においては、Ｎ
ｉとＭが複合酸化物中で高分散状態となっている。 ａＭ・ｂＮｉ・ｃＭｇ・ｄＣａ・ｅＯ…（３） （式中、ａ，ｂ，ｃ，ｄ，ｅはモル分率であり、ａ＋ｂ
＋ｃ＋ｄ＝１、０．０００１≦ａ≦０．１０、０．００
０１≦ｂ≦０．３０、０．６０≦（ｃ＋ｄ）≦０．９９
９８、０＜ｃ≦０．９９９８、０≦ｄ＜０．９９９８、
ｅ＝元素が酸素と電荷均衡を保つのに必要な数である。
また、Ｍは周期律表第６Ａ族元素、第７Ａ族元素、Ｎｉ
を除く第８族遷移元素、第１Ｂ族元索、第２Ｂ族元素、
第４Ｂ族元素およびランタノイド元素の少なくとも１種
類の元素である。） なお、ここでの周期律表はＩＵＰＡＣによるものとす
る。ここでＭは、マンガン、モリブデン、ロジウム、ル
テニウム、白金、パラジウム、銅、銀、亜鉛、錫、鉛、
ランタニウム、セリウムから選ばれる少なくとも１種で
あることが好ましい。また、この組成において、Ｍの含
有量（ａ）は、０．０００１≦ａ≦０．１０であり、好
ましくは０．０００１≦ａ≦０．０５、さらに好ましく
は０．０００１≦ａ≦０．０３である。Ｍの含有量
（ａ）が０．０００１未満では、炭素質析出抑制効果が
認められず、０．１０を越えるとリフォーミング反応の
活性を低下させ不都合である。Further, the reforming catalyst produced by the production method of the present invention may be composed of a complex oxide represented by the following formula (3). In this catalyst, N
i and M are in a highly dispersed state in the composite oxide. aM · bNi · cMg · dCa · eO (3) (where a, b, c, d, and e are mole fractions, and a + b
+ C + d = 1, 0.0001 ≦ a ≦ 0.10, 0.00
01 ≦ b ≦ 0.30, 0.60 ≦ (c + d) ≦ 0.99
98, 0 <c ≦ 0.9998, 0 ≦ d <0.9998,
e = number of elements required to keep charge balance with oxygen.
M is a group 6A element, a group 7A element, Ni
Group 8 transition elements, except Group 1B origin element, Group 2B element,
It is at least one element of a Group 4B element and a lanthanoid element. The periodic table here is based on IUPAC. Here, M is manganese, molybdenum, rhodium, ruthenium, platinum, palladium, copper, silver, zinc, tin, lead,
It is preferably at least one selected from lanthanum and cerium. In this composition, the content (a) of M satisfies 0.0001 ≦ a ≦ 0.10, preferably 0.0001 ≦ a ≦ 0.05, and more preferably 0.0001 ≦ a ≦ 0. 03. If the content (a) of M is less than 0.0001, no effect of suppressing carbonaceous deposition is observed, and if it exceeds 0.10, the activity of the reforming reaction is reduced, which is disadvantageous.
【００１９】ニッケル含有量（ｂ）は、０．０００１≦
ｂ≦０．３０であり、好ましくは、０．０００１≦ｂ≦
０．２５、さらに好ましくは０．０００１≦ｂ≦０．２
０である。ニッケル含有量（ｂ）が０．０００１未満で
はニッケルの含有量が少なすぎて反応活性が低く、０．
３０を越えると高分散化が阻害され、炭素質析出防止効
果が十分得られない。The nickel content (b) is 0.0001 ≦
b ≦ 0.30, preferably 0.0001 ≦ b ≦
0.25, more preferably 0.0001 ≦ b ≦ 0.2
0. If the nickel content (b) is less than 0.0001, the nickel content is too small and the reaction activity is low.
If it exceeds 30, high dispersion is hindered, and the effect of preventing carbonaceous deposition cannot be sufficiently obtained.
【００２０】マグネシウム含有量（ｃ）とカルシウム含
有量（ｄ）との合計量（ｃ＋ｄ）は、０．６０≦（ｃ＋
ｄ）≦０．９９９８であり、好ましくは０．７０≦（ｃ
＋ｄ）≦０．９９９８、さらに好ましくは０．７７≦
（ｃ＋ｄ）≦０．９９９８である。このうち、マグネシ
ウム含有量（ｃ）は０＜ｃ≦０．９９９８であり、好ま
しくは０．２０≦ｃ≦０．９９９８、さらに好ましくは
０．３７≦ｃ≦０．９９９８であり、カルシウム含有量
（ｄ）は０≦ｄ＜０．９９９８、好ましくは０≦ｄ≦
０．５、さらに好ましくは０≦ｄ≦０．３であり、カル
シウムを欠くものであってもよい。The total amount (c + d) of the magnesium content (c) and the calcium content (d) is 0.60 ≦ (c +
d) ≦ 0.9998, preferably 0.70 ≦ (c
+ D) ≦ 0.9998, more preferably 0.77 ≦
(C + d) ≦ 0.9998. Among them, the magnesium content (c) is 0 <c ≦ 0.9998, preferably 0.20 ≦ c ≦ 0.9998, more preferably 0.37 ≦ c ≦ 0.9998, and the calcium content is (D) is 0 ≦ d <0.9998, preferably 0 ≦ d ≦
0.5, more preferably 0 ≦ d ≦ 0.3, and may lack calcium.
【００２１】マグネシウム含有量（ｃ）とカルシウム含
有量（ｄ）との合計量（ｃ＋ｄ）は、Ｍ含有量（ａ）お
よびニッケル含有量（ｂ）とのバランスで決められる。
（ｃ＋ｄ）は上記範囲内であればいかなる割合でもリホ
ーミング反応に優れた効果を発揮するが、カルシウム
（ｄ）とＭ（ａ）の含有量が多いと炭素質析出の抑制に
効果があるものの、マグネシウム（ｃ）が多い場合に比
べて触媒活性が低い。よって、活性を重視するのであれ
ば、カルシウム含有量（ｃ）が０．５を越え、Ｍ含有量
（ａ）が０．１を越えると活性が低下するので好ましく
ない。The total amount (c + d) of the magnesium content (c) and the calcium content (d) is determined by the balance between the M content (a) and the nickel content (b).
(C + d) exhibits an excellent effect on the reforming reaction at any ratio as long as it is within the above range, but a large content of calcium (d) and M (a) is effective in suppressing carbonaceous precipitation. , The catalytic activity is lower than when magnesium (c) is high. Therefore, if the activity is emphasized, it is not preferable that the calcium content (c) exceeds 0.5 and the M content (a) exceeds 0.1 because the activity is reduced.
【００２２】以上説明したＣｏが複合酸化物（式
（１））中で高分散化されているリホーミング用触媒、
Ｎｉが複合酸化物（式（２））中で高分散化されている
リホーミング用触媒、ＭおよびＮｉが複合酸化物（式
（３））中で高分散化されているリホーミング用触媒
は、以下に説明する本発明の製造方法で効率的に製造で
きる。まず、式（１）で表される複合酸化物からなる触
媒の製造方法を説明する。本発明の製造方法は、Ｃｏと
ＭｇとＣａとを式（１）で表された比率で含有する水溶
液に、共沈剤を添加して沈殿を生成させる沈殿生成工程
と、前記沈殿を乾燥し乾燥沈殿物とする乾燥工程と、前
記乾燥沈殿物を焼成する焼成工程とを有し、沈殿生成工
程を３１３〜３７３Ｋで行う。A reforming catalyst in which Co described above is highly dispersed in the composite oxide (formula (1));
A reforming catalyst in which Ni is highly dispersed in the composite oxide (formula (2)), and a reforming catalyst in which M and Ni are highly dispersed in the composite oxide (formula (3)) It can be efficiently manufactured by the manufacturing method of the present invention described below. First, a method for producing a catalyst comprising a composite oxide represented by the formula (1) will be described. The production method of the present invention includes a precipitation forming step of adding a coprecipitant to an aqueous solution containing Co, Mg, and Ca at a ratio represented by the formula (1) to form a precipitate, and drying the precipitate. The method includes a drying step of forming a dried precipitate and a baking step of baking the dried precipitate, and the precipitation generation step is performed at 313 to 373K.
【００２３】沈殿生成工程における、ＣｏとＭｇとＣａ
とを式（１）で表された比率で含有する水溶液は、コバ
ルト、マグネシウム、カルシウムの酢酸塩などの有機塩
や、硝酸塩などの無機塩といった水溶性塩類を、所望の
比率で水に完全に溶解することによって得られる。In the precipitation step, Co, Mg and Ca
And an aqueous solution containing organic salts such as acetates of cobalt, magnesium and calcium, and water-soluble salts such as inorganic salts such as nitrates in water at a desired ratio. Obtained by dissolving.
【００２４】共沈剤は、水溶液から沈殿を生成させるこ
とができるものであれば特に制限はないが、ナトリウム
炭酸塩、カリウム炭酸塩、アンモニウム炭酸塩、ナトリ
ウム炭酸水素塩、カリウム炭酸水素塩、アンモニウム炭
酸水素塩、水酸化ナトリウム、水酸化カリウム、水酸化
アンモニウム、アンモニア水から選ばれる少なくとも１
種であることが好ましい。また、共沈剤の添加量は沈殿
生成当量の１．０〜１．２倍とすることが好ましい。こ
こで沈殿生成当量とは、Ｃｏ、Ｍｇ、Ｃａをすべて水酸
化物として沈殿させる場合に必要十分な共沈剤量の理論
値である。共沈剤の添加量が沈殿生成当量の１．２倍を
超えると、沈殿の生成量が多くゲル状のスラリーにな
り、このスラリーを十分に攪拌できなくなる場合があ
る。スラリーを十分に攪拌できないと、得られる触媒の
組成が不均一になったり、Ｃｏが高分散しなくなったり
する。また、スラリーがゲル状であると取扱いにくいう
え、沈殿の歩留まりが低下し、触媒の生産性が低下す
る。一方、共沈剤の添加量が沈殿生成当量の１．０倍未
満では、十分に沈殿を生成させることができない場合が
ある。共沈剤の添加量を沈殿生成当量の１．０〜１．２
倍とすることによって、水溶液のｐＨを８〜９．５に維
持でき、沈殿を含むスラリーがゲル化せず、高い歩留ま
り、すなわち高い収量で沈殿を得ることができる。The coprecipitant is not particularly limited as long as it can form a precipitate from an aqueous solution, but is not limited to sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate. At least one selected from hydrogen carbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, and aqueous ammonia
Preferably it is a seed. Further, the addition amount of the coprecipitant is preferably 1.0 to 1.2 times the equivalent of the precipitation. Here, the precipitation equivalent is a theoretical value of a necessary and sufficient amount of a coprecipitating agent when Co, Mg, and Ca are all precipitated as hydroxides. If the amount of the coprecipitating agent exceeds 1.2 times the equivalent of the amount of the precipitate, the amount of the precipitate formed is large, resulting in a gel slurry, which may not be sufficiently stirred. If the slurry cannot be sufficiently agitated, the composition of the resulting catalyst will be non-uniform or Co will not be highly dispersed. In addition, when the slurry is in a gel state, it is difficult to handle, and the yield of precipitation is reduced, and the productivity of the catalyst is reduced. On the other hand, if the added amount of the coprecipitant is less than 1.0 times the equivalent of the precipitation, it may not be possible to sufficiently generate the precipitate. The addition amount of the coprecipitant is set to 1.0 to 1.2 of the equivalent of precipitation.
By doubling the pH, the pH of the aqueous solution can be maintained at 8 to 9.5, the slurry containing the precipitate does not gel, and the precipitate can be obtained with a high yield, that is, a high yield.
【００２５】また、沈殿生成工程は、水溶液を３１３〜
３７３Ｋに維持して行うことが好ましい。水溶液の温度
が３１３Ｋ未満では、沈殿の生成量が多くゲル状のスラ
リーになり、このスラリーを十分に攪拌できなくなる場
合がある。スラリーを十分に攪拌できないと、得られる
触媒の組成が不均一になったり、Ｃｏが高分散しなくな
ったりする。また、スラリーがゲル状であると取扱いに
くいうえ、沈殿の歩留まりが低下し、触媒の生産性が低
下する。一方、３７３Ｋ以上では、沈殿の溶解度および
イオン積が大きくなるため、沈殿の歩留まりが低下し、
触媒の生産性が低下する。さらに、Ｃｏを高分散させる
ためには沈殿生成工程中、水溶液を攪拌することが好ま
しく、沈殿生成後も１０分間以上撹拌して沈殿の生成を
完結させることが好ましい。このようにして沈殿生成工
程を行うことによって、ＣｏとＭｇと必要に応じてＣａ
を有する成分からなる化合物が、熱分解性水酸化物の形
態で沈殿する。In the step of forming a precipitate, the aqueous solution is 313-
It is preferable to carry out at 373K. If the temperature of the aqueous solution is lower than 313 K, the amount of the precipitate formed is large, resulting in a gel-like slurry, and this slurry may not be sufficiently stirred. If the slurry cannot be sufficiently agitated, the composition of the resulting catalyst will be non-uniform or Co will not be highly dispersed. In addition, when the slurry is in a gel state, it is difficult to handle, and the yield of precipitation is reduced, and the productivity of the catalyst is reduced. On the other hand, at 373 K or more, the solubility of the precipitate and the ionic product increase, so that the yield of the precipitate decreases,
Catalyst productivity is reduced. Further, in order to highly disperse Co, it is preferable to stir the aqueous solution during the precipitation generation step, and it is preferable to stir for 10 minutes or more after the precipitation generation to complete the generation of the precipitate. By performing the precipitation generation step in this way, Co and Mg and, if necessary, Ca
Is precipitated in the form of a thermally decomposable hydroxide.
【００２６】沈殿が生成した後、この沈殿物をろ過し、
水や炭酸アンモニウム水溶液で洗浄を繰り返す。つい
で、乾燥工程においてこの沈殿を３７３Ｋ以上の温度で
乾燥し、乾燥沈殿物とする。そして乾燥沈殿物を、通常
９７３〜１５７３Ｋ、好ましくは１１７３〜１５７３
Ｋ、より好ましくは１２２３〜１５２３Ｋで、１〜２０
時間焼成する焼成工程を行う。この焼成工程によって、
熱分解性水酸化物が熱分解して酸化物となり、目的のリ
ホーミング用触媒を得ることができる。焼成温度が９７
３Ｋ未満では、炭素質（カーボン）析出を防止できる触
媒が得られない場合がある。一方、１５７３Ｋを超える
と、触媒活性が著しく低下する場合がある。また、焼成
工程は空気中の他、不活性雰囲気中で行ってもよい。After a precipitate has formed, the precipitate is filtered,
Repeat washing with water or aqueous ammonium carbonate. Next, in a drying step, the precipitate is dried at a temperature of 373K or more to obtain a dried precipitate. And the dried precipitate is usually 973-1573K, preferably 1173-1573.
K, more preferably from 1223 to 1523 K, from 1 to 20
A firing step of firing for a time is performed. By this firing process,
The thermally decomposable hydroxide is thermally decomposed into an oxide, so that a desired reforming catalyst can be obtained. Firing temperature 97
If it is less than 3K, a catalyst capable of preventing carbonaceous (carbon) deposition may not be obtained. On the other hand, when it exceeds 1573K, the catalytic activity may be significantly reduced. Further, the firing step may be performed in an inert atmosphere other than in the air.
【００２７】このような沈殿生成工程、乾燥工程、焼成
工程で得られた触媒は、粉砕して粉末状として用いるこ
ともできるが、必要に応じて圧縮成型機により成型し
て、タブレット状として用いることもできる。また、こ
れらの触媒を石英砂、アルミナ、マグネシア、カルシ
ア、その他の希釈剤と合わせて用いることもできる。The catalyst obtained in such a precipitation forming step, drying step and calcining step can be pulverized and used as a powder. However, if necessary, it is molded by a compression molding machine and used as a tablet. You can also. In addition, these catalysts can be used in combination with quartz sand, alumina, magnesia, calcia, and other diluents.
【００２８】なお、式（２）で表される複合酸化物から
なる触媒を製造する場合には、沈殿生成工程において使
用する水溶液として、ＣｏのかわにりＮｉを含有する水
溶液を使用する以外には上述した式（１）で表される複
合酸化物の製造の場合と同様に行えばよい。このような
製造方法で製造することによって、Ｎｉが複合酸化物
（式（２））中で高分散化されているリホーミング用触
媒を製造できる。また、式（３）で表される複合酸化物
からなる触媒を製造する場合には、沈殿生成工程におい
て使用する水溶液として、ＣｏのかわにりＮｉとＭとを
含有する水溶液を使用する以外には上述した式（１）で
表される複合酸化物の製造の場合と同様に行えばよい。
このような製造方法で製造することによって、Ｎｉおよ
びＭが複合酸化物（式（３））中で高分散化されている
リホーミング用触媒を製造できる。In the case of producing a catalyst composed of the complex oxide represented by the formula (2), the aqueous solution used in the precipitation step is not limited to the use of an aqueous solution containing Ni but containing Co. May be performed in the same manner as in the case of producing the composite oxide represented by the above formula (1). By using such a manufacturing method, a reforming catalyst in which Ni is highly dispersed in the composite oxide (formula (2)) can be manufactured. In the case of producing a catalyst composed of the complex oxide represented by the formula (3), besides using an aqueous solution containing Ni and M, it is used as an aqueous solution used in the precipitation generation step. May be performed in the same manner as in the case of producing the composite oxide represented by the above formula (1).
By producing by such a production method, a reforming catalyst in which Ni and M are highly dispersed in the composite oxide (formula (3)) can be produced.
【００２９】次に、本発明の製造方法で製造したリホー
ミング用触媒を用いて合成ガスを製造する方法について
説明する。まず、予めリホーミング用触媒の活性化処理
を行う。この活性化処理は触媒を水素ガスなどの還元性
気体の存在下で、７７３〜１２７３Ｋ、好ましくは８７
３〜１２７３Ｋ、さらに好ましくは９２３〜１２７３Ｋ
の温度範囲で０．５〜３０時間程度加熱することによっ
て行われる。還元性気体は窒素ガスなどの不活性ガスで
希釈されていてもよい。この活性化処理をリホーミング
反応を行う反応器内で行うこともできる。この活性化処
理により、図１での触媒１表面の微小粒子２、２…が還
元されてＣｏまたはＭの金属元素またはその化合物とな
り、触媒活性が発現する。本発明での活性化処理は、従
来のＣｏ酸化物系触媒およびＮｉ酸化物系触媒の活性化
よりも高温で行う。従来のこれらの触媒ではすべて７７
３Ｋ未満で行われており、本発明の製造方法で得られる
触媒においては、このような高温での活性化処理も高分
散化に寄与している可能性がある。Next, a method for producing a synthesis gas using the reforming catalyst produced by the production method of the present invention will be described. First, an activation process of the reforming catalyst is performed in advance. In this activation treatment, the catalyst is treated in the presence of a reducing gas such as hydrogen gas at 773 to 1273K, preferably 87 to 1273K.
3 to 1273K, more preferably 923 to 1273K
This is performed by heating at a temperature in the range of about 0.5 to 30 hours. The reducing gas may be diluted with an inert gas such as nitrogen gas. This activation treatment can be performed in a reactor for performing a reforming reaction. By this activation treatment, the fine particles 2, 2,... On the surface of the catalyst 1 in FIG. 1 are reduced to become a metal element of Co or M or a compound thereof, thereby exhibiting catalytic activity. The activation treatment in the present invention is performed at a higher temperature than the activation of the conventional Co oxide-based catalyst and Ni oxide-based catalyst. For all these conventional catalysts, 77
In the catalyst obtained at less than 3K and obtained by the production method of the present invention, such an activation treatment at a high temperature may also contribute to high dispersion.
【００３０】合成ガスの原料となる炭化水素としては、
天然ガス、石油ガス、ナフサ、重油、原油などや石炭、
コールサンドなどから得られた炭化水素などが用いら
れ、その一部にメタンなどの炭化水素が含有されていれ
ば、特に限定されることはない。これらは２種以上が混
合されていてもよい。また、改質物質としては、水（水
蒸気）、二酸化炭素、酸素、空気などが用いられ、２種
以上が混合されていてもよい。Examples of hydrocarbons used as raw materials for synthesis gas include:
Natural gas, petroleum gas, naphtha, heavy oil, crude oil, coal,
There is no particular limitation as long as hydrocarbons or the like obtained from coal sand or the like are used and a part thereof contains a hydrocarbon such as methane. Two or more of these may be mixed. Further, as the modifying substance, water (steam), carbon dioxide, oxygen, air or the like is used, and two or more kinds may be mixed.
【００３１】反応に際しての炭化水素と改質物質との供
給割合は、炭化水素中の炭素原子の数を基準とするモル
比で表して、改質物質／炭素比＝０．３〜１００、好ま
しくは０．３〜１０、さらに好ましくは０．５〜３とさ
れ、本発明では、改質物質を大過剰に供給する必要はな
い。炭化水素と改質物質との混合気体には、希釈剤とし
て窒素などの不活性ガスを共存させてもよい。The supply ratio of the hydrocarbon and the reforming substance at the time of the reaction is represented by a molar ratio based on the number of carbon atoms in the hydrocarbon, and the reforming substance / carbon ratio is preferably from 0.3 to 100, more preferably Is from 0.3 to 10, more preferably from 0.5 to 3. In the present invention, it is not necessary to supply a large excess of the modifying substance. An inert gas such as nitrogen may coexist as a diluent in the mixed gas of the hydrocarbon and the reforming substance.
【００３２】具体的な反応としては、上述のリホーミン
グ用触媒を充填した反応管に、炭化水素と改質物質とか
らなる原料ガスを供給し、温度７７３〜１２７３Ｋ、好
ましくは８７３〜１２７３Ｋ、さらに好ましくは９２３
〜１２７３Ｋの温度条件で、圧力条件が０．１〜１０Ｍ
Ｐａ、好ましくは０．１〜５ＭＰａ、さらに好ましくは
０．１〜３ＭＰａの範囲で反応を行う。原料ガスの空間
速度（ＧＨＳＶ：原料ガスの供給速度を体積換算の触媒
量で除した値）は、５００〜２０００００ｈ-1、好まし
くは１０００〜１０００００ｈ -1、さらに好ましくは１
０００〜７００００ｈ-1の範囲とすることが望ましい。
また、触媒床の形態は、固定床、移動床、流動床などの
周知の形態を任意に選択できる。As a specific reaction, the above-mentioned reformin
Hydrocarbons and reforming substances are placed in a reaction tube filled with
Is supplied at a temperature of 773 to 1273 K,
Preferably 873-1273K, more preferably 923
Pressure condition is 0.1 to 10M under temperature condition of ~ 1273K
Pa, preferably 0.1 to 5 MPa, more preferably
The reaction is performed in the range of 0.1 to 3 MPa. Source gas space
Velocity (GHSV: catalyst in terms of volume converted from supply rate of raw material gas
500-200,000 h)-1, Preferred
1000 to 100000h -1, More preferably 1
000-70000h-1It is desirable to be within the range.
The form of the catalyst bed may be fixed bed, moving bed, fluidized bed, etc.
A well-known form can be arbitrarily selected.
【００３３】このようなリホーミング用触媒の製造方法
にあっては、ＣｏＯまたはＮｉＯまたはＮｉＯおよびＭ
Ｏｘが、ＭｇＯまたはＭｇＯ／ＣａＯとの複合酸化物と
なっていて、コバルトまたはニッケルまたはニッケルお
よびＭが高分散化している触媒を生産性よく製造でき
る。すなわち、高活性で、メタンなどの炭化水素と水蒸
気などの改質物質とを化学等量もしくはそれに近い量で
反応させても、炭素質（カーボン）の析出を抑制でき、
効率よく合成ガスを製造でき、寿命も長い高性能な触媒
を、低コストで製造できる。このため、触媒製造を含め
た合成ガス製造プロセス全体のコストを低く抑えること
ができる。In such a method for producing a reforming catalyst, CoO or NiO or NiO and M
Ox is a composite oxide of MgO or MgO / CaO, and a catalyst in which cobalt or nickel or nickel and M are highly dispersed can be produced with high productivity. That is, even if a hydrocarbon such as methane and a reforming substance such as steam are reacted in a chemical equivalent amount or a similar amount thereof, the precipitation of carbonaceous material (carbon) can be suppressed,
A high-performance catalyst that can efficiently produce synthesis gas and has a long life can be produced at low cost. For this reason, the cost of the whole synthesis gas production process including the production of the catalyst can be kept low.
【００３４】[0034]
【実施例】以下、具体例を示して本発明の作用、効果を
明確にするが、本発明はこれら具体例に限定されるもの
ではない。 ［実施例１］硝酸コバルト六水和物１６．２ｇ、硝酸マ
グネシウム六水和物２７０．７ｇを水５００ｍｌに溶解
した。ついで、溶液温度を３２３Ｋに保ちながら、共沈
剤として２ｍｏｌ／Ｌ炭酸カリウム水溶液５９０ｍｌ
（沈殿生成当量の約１．１倍）を加えることによってｐ
Ｈ９にし、コバルト、マグネシウムの２成分からなる沈
殿物を生成させた。沈殿を含むスラリー溶液はゲルしな
かった。最終的に沈殿を生成した溶液はｐＨ８．４とな
った。沈殿物をろ過し、洗浄を行なった後、空気中３９
３Ｋで１２時間以上乾燥した。乾燥後の沈殿の収量は８
５．８ｇであった。ついで、空気中、１４５３Ｋで５時
間焼成して触媒Ａを得た。EXAMPLES Hereinafter, the operation and effect of the present invention will be clarified by showing specific examples, but the present invention is not limited to these specific examples. Example 1 16.2 g of cobalt nitrate hexahydrate and 270.7 g of magnesium nitrate hexahydrate were dissolved in 500 ml of water. Then, while maintaining the solution temperature at 323 K, 590 ml of a 2 mol / L aqueous potassium carbonate solution as a coprecipitant.
(Approximately 1.1 times the precipitation equivalent) by adding p
The mixture was changed to H9 to form a precipitate composed of two components, cobalt and magnesium. The slurry solution containing the precipitate did not gel. The solution which finally formed a precipitate had a pH of 8.4. After the precipitate was filtered and washed, 39
Dry at 3K for 12 hours or more. The yield of the precipitate after drying is 8
It was 5.8 g. Then, the mixture was calcined at 1,453 K for 5 hours in the air to obtain a catalyst A.
【００３５】［実施例２］硝酸ニッケル六水和物９．６
９ｇ、硝酸マグネシウム六水和物２７６．３ｇを水５０
０ｍｌに溶解した。ついで、溶液温度を３２３Ｋに保ち
ながら、共沈剤として２ｍｏｌ／Ｌ炭酸カリウム水溶液
５９０ｍｌ（沈殿生成当量の約１．１倍）を加えること
によってｐＨ９にし、ニッケル、マグネシウムの２成分
からなる沈殿物を生成させた。沈殿を含むスラリー溶液
はゲルしなかった。最終的に沈殿を生成した溶液はｐＨ
８．４となった。沈殿物をろ過し、洗浄を行なった後、
空気中３９３Ｋで１２時間以上乾燥した。乾燥後の沈殿
の収量が８６．０ｇであった。ついで、空気中、１４５
３Ｋで５時間焼成して触媒Ｂを得た。Example 2 Nickel nitrate hexahydrate 9.6
9g and 276.3 g of magnesium nitrate hexahydrate in 50 parts of water.
Dissolved in 0 ml. Then, while maintaining the solution temperature at 323 K, 590 ml of a 2 mol / L aqueous potassium carbonate solution (approximately 1.1 times the precipitation equivalent) was added as a coprecipitating agent to adjust the pH to 9, and the two-component precipitate of nickel and magnesium was removed. Generated. The slurry solution containing the precipitate did not gel. The solution that finally formed the precipitate was pH
It was 8.4. After filtering the precipitate and washing,
Dry at 393K in air for 12 hours or more. The yield of the precipitate after drying was 86.0 g. Then, in the air, 145
The mixture was calcined at 3K for 5 hours to obtain a catalyst B.
【００３６】［実施例３］硝酸ニッケル六水和物１４．
５ｇ、硝酸マグネシウム六水和物２７２．１ｇ、硝酸マ
ンガン六水和物３．１９ｇを水５００ｍｌに溶解した。
ついで、溶液温度を３２３Ｋに保ちながら、共沈剤とし
て２ｍｏｌ／Ｌ炭酸カリウム水溶液５９０ｍｌ（沈殿生
成当量の約１．１倍）を加えることによってｐＨ９に
し、ニッケル、マグネシウム、マンガンの３成分からな
る沈殿物を生成させた。沈殿を含むスラリー溶液はゲル
しなかった。最終的に沈殿を生成した溶液はｐＨ８．４
となった。沈殿物をろ過し、洗浄を行なった後、空気中
３９３Ｋで１２時間以上乾燥した。乾燥後の沈殿の収量
が８５．５ｇであった。ついで、空気中、１４５３Ｋで
５時間焼成して触媒Ｃを得た。Example 3 Nickel nitrate hexahydrate
5 g, magnesium nitrate hexahydrate 272.1 g, and manganese nitrate hexahydrate 3.19 g were dissolved in water 500 ml.
Then, while maintaining the solution temperature at 323 K, 590 ml of a 2 mol / L aqueous potassium carbonate solution (approximately 1.1 times the precipitation generation equivalent) is added as a coprecipitating agent to adjust the pH to 9, and a precipitation comprising three components of nickel, magnesium and manganese is performed. Produced. The slurry solution containing the precipitate did not gel. The solution that finally formed a precipitate was pH 8.4.
It became. The precipitate was filtered, washed, and dried in air at 393K for 12 hours or more. The yield of the precipitate after drying was 85.5 g. Then, the mixture was calcined in air at 1,453 K for 5 hours to obtain a catalyst C.
【００３７】（比較例１）硝酸コバルト六水和物１６．
２ｇ、硝酸マグネシウム六水和物２７０．７ｇを水５０
０ｍｌに溶解した。ついで、溶液温度を２９３Ｋに保ち
ながら、共沈剤として２ｍｏｌ／Ｌ炭酸カリウム水溶液
５４０ｍｌ（沈殿生成当量の１．０倍）を加えることに
よってｐＨを９とし、コバルト、マグネシウムの２成分
からなる沈澱を生成させた。沈殿を含むスラリー溶液は
ゲル化し、攪拌できなかった。最終的に沈殿を生成した
溶液はｐＨ９．４となった。沈澱をろ過し、洗浄を行な
った後、空気中、３９３Ｋで１２時間以上乾燥した。乾
燥後の沈殿の収量は７１．０ｇであった。(Comparative Example 1) Cobalt nitrate hexahydrate
2 g, 270.7 g of magnesium nitrate hexahydrate in 50 parts of water
Dissolved in 0 ml. Then, while maintaining the solution temperature at 293 K, 540 ml of a 2 mol / L aqueous potassium carbonate solution (1.0 times the precipitation equivalent) was added as a coprecipitating agent to adjust the pH to 9, and the precipitate composed of two components of cobalt and magnesium was added. Generated. The slurry solution containing the precipitate gelled and could not be stirred. The solution which finally formed a precipitate had a pH of 9.4. The precipitate was filtered, washed, and dried in air at 393K for 12 hours or more. The yield of the precipitate after drying was 71.0 g.
【００３８】（比較例２）硝酸コバルト六水和物１６．
２ｇ、硝酸マグネシウム六水和物２７０．７ｇを水５０
０ｍｌに溶解した。ついで、溶液温度を２９３Ｋに保ち
ながら、共沈剤として２ｍｏｌ／Ｌ炭酸カリウム水溶液
８１５ｍｌ（沈殿生成当量の１．５倍）を加えることに
よってｐＨを１０とし、コバルト、マグネシウムの２成
分からなる沈澱を生成させた。沈殿を含むスラリー溶液
はゲル化し、攪拌できなかった。最終的に沈殿を生成し
た溶液はｐＨ１０．８となった。沈澱をろ過し、洗浄を
行なった後、空気中、３９３Ｋで１２時間以上乾燥し
た。乾燥後の沈殿の収量は７９．５ｇであった。Comparative Example 2 Cobalt nitrate hexahydrate
2 g, 270.7 g of magnesium nitrate hexahydrate in 50 parts of water
Dissolved in 0 ml. Then, while maintaining the solution temperature at 293 K, 815 ml of a 2 mol / L aqueous potassium carbonate solution (1.5 times the precipitation equivalent) was added as a coprecipitant to adjust the pH to 10, and a precipitate composed of two components of cobalt and magnesium was added. Generated. The slurry solution containing the precipitate gelled and could not be stirred. The solution in which the precipitate finally formed had a pH of 10.8. The precipitate was filtered, washed, and dried in air at 393K for 12 hours or more. The yield of the precipitate after drying was 79.5 g.
【００３９】［反応例１］実施例１で調製した触媒Ａ：
３０ｍｌを加圧固定床流通式反応器に充填して、メタン
の ＣＯ2／水蒸気改質を行った。触媒は予め水素気流中
で１１７３Ｋで還元処理を行った後、 ＣＨ4：ＣＯ2：
Ｈ2Ｏモル比＝１：０．４：１の原料ガスを、圧力 ２０
ｋｇ／ｃｍ2Ｇ、温度１１２３Ｋ、ＧＨＳＶ＝６０００
ｈｒ-1の条件で反応を行った。反応開始から１００時間
経過後の ＣＨ4転化率は５９％（反応条件下のＣＨ4の
平衡転化率＝５９％）であり、３０００時間経過後のＣ
Ｈ4転化率は５９％であった。[Reaction Example 1] Catalyst A prepared in Example 1:
30 ml was charged into a pressurized fixed bed flow reactor to perform CO 2 / steam reforming of methane. The catalyst was previously subjected to a reduction treatment at 1173 K in a hydrogen stream, and then CH 4 : CO 2 :
A source gas having an H 2 O molar ratio of 1: 0.4: 1 was applied at a pressure of 20.
kg / cm 2 G, temperature 1123K, GHSV = 6000
The reaction was performed under the conditions of hr -1 . 100 hours after the start of the reaction, the conversion of CH 4 was 59% (equilibrium conversion of CH 4 under the reaction conditions = 59%), and C after 3000 hours.
The H 4 conversion was 59%.
【００４０】［反応例２］実施例２で調製した触媒Ｂ：
３０ｍｌを加圧固定床流通式反応器に充填して、メタン
の ＣＯ2／水蒸気改質を行った。触媒は予め水素気流中
で１１７３Ｋで還元処理を行った後、 ＣＨ4：ＣＯ2：
Ｈ2Ｏモル比＝１：０．４：１の原料ガスを、圧力 ２０
ｋｇ／ｃｍ2Ｇ、温度１１２３Ｋ、ＧＨＳＶ＝６０００
ｈｒ-1の条件で反応を行った。反応開始から１００時間
経過後の ＣＨ4転化率は５９％（反応条件下のＣＨ4の
平衡転化率＝５９％）であった。[Reaction Example 2] Catalyst B prepared in Example 2:
30 ml was charged into a pressurized fixed bed flow reactor to perform CO 2 / steam reforming of methane. The catalyst was previously subjected to a reduction treatment at 1173 K in a hydrogen stream, and then CH 4 : CO 2 :
A source gas having an H 2 O molar ratio of 1: 0.4: 1 was applied at a pressure of 20.
kg / cm 2 G, temperature 1123K, GHSV = 6000
The reaction was performed under the conditions of hr -1 . 100 hours after the start of the reaction, the CH 4 conversion was 59% (equilibrium conversion of CH 4 under the reaction conditions = 59%).
【００４１】［反応例３］実施例３で調製した触媒Ｃ：
３０ｍｌを加圧固定床流通式反応器に充填して、メタン
の ＣＯ2／水蒸気改質を行った。触媒は予め水素気流中
で１１７３Ｋで還元処理を行った後、ＣＨ4：ＣＯ2：Ｈ
２Ｏモル比＝１：０．４：１の原料ガスを、圧力 ２０
ｋｇ／ｃｍ2Ｇ、温度１１２３Ｋ、ＧＨＳＶ＝６０００
ｈｒ-1の条件で反応を行った。反応開始から１００時間
経過後の ＣＨ4転化率は５９％（反応条件下のＣＨ4の
平衡転化率＝５９％）であった。[Reaction Example 3] Catalyst C prepared in Example 3:
30 ml was charged into a pressurized fixed bed flow reactor to perform CO 2 / steam reforming of methane. The catalyst was previously subjected to a reduction treatment at 1173 K in a hydrogen stream, and then CH 4 : CO 2 : H
A raw material gas having a 2O molar ratio of 1: 0.4: 1 was applied at a pressure of 20.
kg / cm 2 G, temperature 1123K, GHSV = 6000
The reaction was performed under the conditions of hr -1 . 100 hours after the start of the reaction, the CH 4 conversion was 59% (equilibrium conversion of CH 4 under the reaction conditions = 59%).
【００４２】[0042]
【発明の効果】以上説明したように本発明のリホーミン
グ用触媒の製造方法は、必須成分を特定の比率で含有す
る水溶液に、共沈剤を添加して沈殿を生成させる沈殿生
成工程と、前記沈殿を乾燥し乾燥沈殿物とする乾燥工程
と、前記乾燥沈殿物を焼成する焼成工程を有し、沈殿生
成工程を３１３〜３７３Ｋで行う。よって、ＣｏＯまた
はＮｉＯまたはＮｉＯおよびＭＯｘが、ＭｇＯまたはＭ
ｇＯ／ＣａＯとの複合酸化物となっていて、コバルトま
たはニッケルまたはニッケルおよびＭが高分散化してい
る触媒を、生産性よく製造できる。すなわち、高活性で
あり、メタンなどの炭化水素と水蒸気、二酸化炭素など
の改質物質とを化学等量もしくはそれに近い量で反応さ
せても、炭素質（カーボン）の析出を抑制でき、効率よ
く合成ガスを製造でき、寿命も長い高性能な触媒を、低
コストで製造できる。このため、触媒製造を含めた合成
ガス製造プロセス全体のコストを低く抑えることができ
る。As described above, the method for producing a reforming catalyst according to the present invention comprises the steps of: forming a precipitate by adding a coprecipitant to an aqueous solution containing an essential component at a specific ratio; The method includes a drying step of drying the precipitate to form a dried precipitate, and a baking step of baking the dried precipitate. The precipitation generation step is performed at 313 to 373K. Therefore, if CoO or NiO or NiO and MOx are MgO or M
A catalyst which is a composite oxide with gO / CaO and in which cobalt or nickel or nickel and M are highly dispersed can be produced with high productivity. In other words, it is highly active, and even when a hydrocarbon such as methane is reacted with a reforming substance such as water vapor or carbon dioxide in a chemical equivalent amount or a similar amount, it is possible to suppress the deposition of carbonaceous material (carbon), and to efficiently perform the reaction. A high-performance catalyst that can produce synthesis gas and has a long life can be produced at low cost. For this reason, the cost of the whole synthesis gas production process including the production of the catalyst can be kept low.
【図１】 本発明の触媒の表面状態を模式的に示した説
明図である。FIG. 1 is an explanatory view schematically showing a surface state of a catalyst of the present invention.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G040 EA03 EA05 EA06 EA07 EB01 EC01 EC02 EC03 EC04 EC05 EC07 4G069 AA08 AA09 BB04A BB04B BB06A BB06B BB16A BC02A BC03A BC09A BC10A BC10B BC21A BC22A BC31A BC32A BC35A BC42A BC43A BC59A BC62A BC62B BC67A BC67B BC68A BC68B BC70A BC71A BC72A BC75A BE17A CC17 EC30 FA01 FB09 FB30 FB57 FC03 FC07 FC08 4G140 EA03 EA05 EA06 EA07 EB01 EC01 EC02 EC03 EC04 EC05 EC07 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G040 EA03 EA05 EA06 EA07 EB01 EC01 EC02 EC03 EC04 EC05 EC07 4G069 AA08 AA09 BB04A BB04B BB06A BB06B BB16A BC02A BC03A BC09A BC10A BC10B BC21A BC22ABCA BCBC BCBC BC BC BC68B BC70A BC71A BC72A BC75A BE17A CC17 EC30 FA01 FB09 FB30 FB57 FC03 FC07 FC08 4G140 EA03 EA05 EA06 EA07 EB01 EC01 EC02 EC03 EC04 EC05 EC07
Claims (9)
合酸化物からなり、Ｃｏが該複合酸化物中で高分散化さ
れていることを特徴とする炭化水素のリホーミング触媒
の製造方法であって、 ＣｏとＭｇとＣａとを下記式（１）で表された比率で含
有する水溶液に、共沈剤を添加して沈殿を生成させる沈
殿生成工程と、前記沈殿を乾燥し乾燥沈殿物とする乾燥
工程と、前記乾燥沈殿物を焼成する焼成工程を有し、 沈殿生成工程を３１３〜３７３Ｋで行うことを特徴とす
るリホーミング用触媒の製造方法。 ａＣｏ・ｂＭｇ・ｃＣａ・ｄＯ…（１） （式中、ａ，ｂ，ｃ，ｄはモル分率であり、ａ＋ｂ＋ｃ
＝１、０．００５≦ａ≦０．３０、０．７０≦（ｂ＋
ｃ）≦０．９９５、０＜ｂ≦０．９９５、０≦ｃ≦０．
９９５、ｄ＝元素が酸素と電荷均衡を保つのに必要な数
である。）1. Production of a hydrocarbon reforming catalyst comprising a composite oxide having a composition represented by the following formula (1), wherein Co is highly dispersed in the composite oxide. A method of forming a precipitate by adding a coprecipitant to an aqueous solution containing Co, Mg, and Ca at a ratio represented by the following formula (1), and drying and drying the precipitate: A method for producing a reforming catalyst, comprising: a drying step of forming a precipitate; and a firing step of firing the dried precipitate, wherein the precipitation generation step is performed at 313 to 373K. aCo · bMg · cCa · dO (1) (where a, b, c, and d are mole fractions, and a + b + c
= 1, 0.005 ≦ a ≦ 0.30, 0.70 ≦ (b +
c) ≦ 0.995, 0 <b ≦ 0.995, 0 ≦ c ≦ 0.
995, d = number required to keep the element in charge balance with oxygen. )
合酸化物からなり、Ｎｉが該複合酸化物中で高分散化さ
れていることを特徴とする炭化水素のリホーミング触媒
の製造方法であって、 ＮｉとＭｇとＣａとを下記式（２）で表された比率で含
有する水溶液に、共沈剤を添加して沈殿を生成させる沈
殿生成工程と、前記沈殿を乾燥し乾燥沈殿物とする乾燥
工程と、前記乾燥沈殿物を焼成する焼成工程を有し、 沈殿生成工程を３１３〜３７３Ｋで行うことを特徴とす
るリホーミング用触媒の製造方法。 ａＮｉ・ｂＭｇ・ｃＣａ・ｄＯ…（２） （式中、ａ，ｂ，ｃ，ｄはモル分率であり、ａ＋ｂ＋ｃ
＝１、０．００５≦ａ≦０．３０、０．７０≦（ｂ＋
ｃ）≦０．９９５、０＜ｂ≦０．９９５、０≦ｃ≦０．
９９５、ｄ＝元素が酸素と電荷均衡を保つのに必要な数
である。）2. A hydrocarbon reforming catalyst comprising a composite oxide having a composition represented by the following formula (2), wherein Ni is highly dispersed in the composite oxide. A method comprising the steps of: adding a coprecipitant to an aqueous solution containing Ni, Mg and Ca at a ratio represented by the following formula (2) to form a precipitate; and drying and drying the precipitate. A method for producing a reforming catalyst, comprising: a drying step of forming a precipitate; and a firing step of firing the dried precipitate, wherein the precipitation generation step is performed at 313 to 373K. aNi.bMg.cCa.dO (2) (where a, b, c, and d are mole fractions, and a + b + c
= 1, 0.005 ≦ a ≦ 0.30, 0.70 ≦ (b +
c) ≦ 0.995, 0 <b ≦ 0.995, 0 ≦ c ≦ 0.
995, d = number required to keep the element in charge balance with oxygen. )
合酸化物からなり、ＭおよびＮｉが該複合酸化物中で高
分散化されていることを特徴とする炭化水素のリホーミ
ング触媒の製造方法であって、 ＭとＮｉとＭｇとＣａとを下記式（３）で表された比率
で含有する水溶液に、共沈剤を添加して沈殿を生成させ
る沈殿生成工程と、前記沈殿を乾燥し乾燥沈殿物とする
乾燥工程と、前記乾燥沈殿物を焼成する焼成工程を有
し、 沈殿生成工程を３１３〜３７３Ｋで行うことを特徴とす
るリホーミング用触媒の製造方法。 ａＭ・ｂＮｉ・ｃＭｇ・ｄＣａ・ｅＯ…（３） （式中、ａ，ｂ，ｃ，ｄ，ｅはモル分率であり、ａ＋ｂ
＋ｃ＋ｄ＝１、０．０００１≦ａ≦０．１０、０．００
０１≦ｂ≦０．３０、０．６０≦（ｃ＋ｄ）≦０．９９
９８、０＜ｃ≦０．９９９８、０≦ｄ＜０．９９９８、
ｅ＝元素が酸素と電荷均衡を保つのに必要な数である。
また、Ｍは周期律表第６Ａ族元素、第７Ａ族元素、Ｎｉ
を除く第８族遷移元素、第１Ｂ族元索、第２Ｂ族元素、
第４Ｂ族元素およびランタノイド元素の少なくとも１種
類の元素である。）3. A hydrocarbon reforming catalyst comprising a composite oxide having a composition represented by the following formula (3), wherein M and Ni are highly dispersed in the composite oxide. A method for producing a precipitate, comprising: adding a coprecipitant to an aqueous solution containing M, Ni, Mg, and Ca in a ratio represented by the following formula (3) to form a precipitate; A method for producing a reforming catalyst, comprising: a drying step of drying a dried precipitate to form a dried precipitate; and a firing step of firing the dried precipitate, wherein the precipitation generation step is performed at 313 to 373K. aM · bNi · cMg · dCa · eO (3) (where a, b, c, d, and e are mole fractions, and a + b
+ C + d = 1, 0.0001 ≦ a ≦ 0.10, 0.00
01 ≦ b ≦ 0.30, 0.60 ≦ (c + d) ≦ 0.99
98, 0 <c ≦ 0.9998, 0 ≦ d <0.9998,
e = number of elements required to keep charge balance with oxygen.
M is a group 6A element, a group 7A element, Ni
Group 8 transition elements, except Group 1B origin element, Group 2B element,
It is at least one element of a Group 4B element and a lanthanoid element. )
ム、ルテニウム、白金、パラジウム、銅、銀、亜鉛、
錫、鉛、ランタニウム、セリウムから選ばれる少なくと
も１種であることを特徴とする請求項３に記載のリホー
ミング用触媒の製法。4. M is manganese, molybdenum, rhodium, ruthenium, platinum, palladium, copper, silver, zinc,
4. The method for producing a reforming catalyst according to claim 3, wherein the catalyst is at least one selected from tin, lead, lanthanum, and cerium.
を、沈殿生成当量の１．０〜１．２倍とすることを特徴
とする請求項１ないし４のいずれかに記載のリホーミン
グ用触媒の製造方法。5. The reforming method according to claim 1, wherein the amount of the coprecipitant added in the precipitation generation step is 1.0 to 1.2 times the equivalent of the precipitation generation. Method for producing catalyst.
行うことを特徴とする請求項１ないし５のいずれかに記
載のリホーミング用触媒の製造方法。6. The method for producing a reforming catalyst according to claim 1, wherein the calcination step is performed at a temperature of 973 to 1573K.
炭酸塩、アンモニウム炭酸塩、ナトリウム炭酸水素塩、
カリウム炭酸水素塩、アンモニウム炭酸水素塩、水酸化
ナトリウム、水酸化カリウム、水酸化アンモニウム、ア
ンモニア水から選ばれる少なくとも１種であることを特
徴とする請求項１ないし６のいずれかに記載のリホーミ
ング用触媒の製造方法。7. The coprecipitant comprises sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate,
7. Reforming according to any one of claims 1 to 6, characterized in that it is at least one selected from potassium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide and aqueous ammonia. Production method of catalyst for use.
法で得られたリホーミング用触媒を用いて、炭化水素と
改質物質とから合成ガスを得ることを特徴する合成ガス
の製法。8. A method for producing a synthesis gas, wherein a synthesis gas is obtained from a hydrocarbon and a reforming substance by using the reforming catalyst obtained by the method according to any one of claims 1 to 7.
て、炭化水素と改質物質との供給比を、改質物質／炭索
比＝０．３〜１００とすることを特徴とする合成ガスの
製法。9. The synthesis gas production method according to claim 8, wherein a supply ratio of the hydrocarbon and the reforming substance is set to a reforming substance / coal cable ratio = 0.3 to 100. Gas production method.
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| JP2002145604A (en) * | 2000-11-08 | 2002-05-22 | Japan Petroleum Exploration Co Ltd | Method for producing hydrogen |
| WO2002078840A1 (en) * | 2001-03-29 | 2002-10-10 | Idemitsu Kosan Co., Ltd. | Catalyst for reforming hydrocarbon and method for preparation thereof, and process for reforming hydrocarbon using said catalyst |
| JP2004141860A (en) * | 2002-10-04 | 2004-05-20 | Japan National Oil Corp | Catalyst for hydrocarbon reforming, and its manufacturing method |
| WO2009048083A1 (en) | 2007-10-11 | 2009-04-16 | Japan Petroleum Exploration Co., Ltd. | Catalyst for hydrocarbon reforming and process for producing synthesis gas with the same |
| WO2010010857A1 (en) | 2008-07-23 | 2010-01-28 | 石油資源開発株式会社 | Complex oxide for hydrocarbon reforming catalyst, method for producing the same, and method for producing synthetic gas using the same |
| JP2013237048A (en) * | 2013-07-22 | 2013-11-28 | Nippon Steel & Sumitomo Metal Corp | Modifying catalyst of tar containing gas, method for manufacturing the same, and modifying method of the tar containing gas |
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| KR20190027762A (en) | 2017-09-07 | 2019-03-15 | 한국화학연구원 | Nickel-based catalyst and system for producing the synthesis gas using the same |
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| EP2311560A4 (en) * | 2008-07-23 | 2011-12-28 | Japan Petroleum Exploration Co | Complex oxide for hydrocarbon reforming catalyst, method for producing the same, and method for producing synthetic gas using the same |
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