JPH08215570A - Catalyst for synthesis of methanol, production thereof and synthesis of methanol - Google Patents
Catalyst for synthesis of methanol, production thereof and synthesis of methanolInfo
- Publication number
- JPH08215570A JPH08215570A JP7029394A JP2939495A JPH08215570A JP H08215570 A JPH08215570 A JP H08215570A JP 7029394 A JP7029394 A JP 7029394A JP 2939495 A JP2939495 A JP 2939495A JP H08215570 A JPH08215570 A JP H08215570A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- methanol
- alloy
- group
- oxide
- 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
Links
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]
【産業上の利用分野】本発明はＣＯ2を主成分とする燃
焼排ガスとＨ2ガスからメタノールを製造する触媒及び
その製造法並びにメタノールの合成法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing methanol from combustion exhaust gas containing CO 2 as a main component and H 2 gas, a method for producing the same, and a method for synthesizing methanol.
【０００２】[0002]
【従来の技術】経済活動の活発化に伴いＣＯ2の排出量
は年と共に増加の傾向にあり、このＣＯ2の蓄積による
地球温暖化が最近深刻化し、ＣＯ2排出量の削減が急務
となっている。その解決策の一つとして種々ＣＯ2削減
法が検討されているが、中でも有力な方法としてＣＯ2
をＨ2と反応させメタノールなどのアルコール原料に変
換し、再資源化する方法がある。この方法により得られ
るメタノールは、エネルギー源として利用することもで
きるが、化学品合成の際の基幹原料でもあるため、この
方法が確立できれば、ＣＯ2排出量の削減ができるだけ
でなく、石油資源の節約にも貢献できるのである。この
種の反応を行うための触媒は、従来から研究されてお
り、金属塩を出発原料とした共沈、含浸法などの化学的
手法を用いて作ったＣｕ−Ｚｎ系等の触媒が有望視され
ており、システム的なところまで検討がなされるように
なりはじめてきたが、副生成物の除去や未反応ガスのリ
サイクルに大きな電力を必要とするといった問題点があ
り、触媒性能の更なる向上が期待されていた。又、金属
塩を出発原料にしているため、不純物イオンの残存があ
ることや触媒粒子の分散度が小さい問題がある。さらに
特開昭６０−８７２３３号公報には、水素と一酸化炭素
とからなる合成ガスを触媒材料である非晶質合金に直接
接触させることによりメタノールを製造する方法が開示
されている。また、この方法では触媒として機能するの
は非晶質合金そのものであることが示されているが、非
晶質合金そのものは熱的に不安定であり、しかも表面積
も小さいため、そのままでは大きな活性を得ることがで
きない。2. Description of the Related Art CO 2 emissions tend to increase over the years as economic activities become more active, and global warming due to the accumulation of CO 2 has recently become more serious, and there is an urgent need to reduce CO 2 emissions. ing. Various CO 2 reduction method has been studied as one of the solutions, CO 2 as inter alia effective method
Is reacted with H 2 to be converted into an alcohol raw material such as methanol and then recycled. Methanol obtained by this method can be used as an energy source, but since it is also a basic raw material in the synthesis of chemical products, if this method can be established, not only CO 2 emissions can be reduced, but also petroleum resources can be reduced. It can also contribute to savings. A catalyst for carrying out this kind of reaction has been studied so far, and a Cu—Zn-based catalyst produced by a chemical method such as coprecipitation using a metal salt as a starting material or an impregnation method is considered promising. However, there is a problem that a large amount of electricity is required to remove by-products and recycle unreacted gas, and further improvement of catalyst performance has started. Was expected. Further, since a metal salt is used as a starting material, there are problems that impurity ions remain and the degree of dispersion of catalyst particles is small. Further, Japanese Patent Laid-Open No. 60-87233 discloses a method for producing methanol by directly contacting a synthetic gas composed of hydrogen and carbon monoxide with an amorphous alloy which is a catalyst material. In addition, although it is shown that the amorphous alloy itself functions as a catalyst in this method, the amorphous alloy itself is thermally unstable and has a small surface area. Can't get
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、従来
から知られている共沈法などで作ったＣｕ−Ｚｎ系や非
晶質合金等の触媒よりも優れた活性、選択性を有するＣ
Ｏ2とＨ2ガスからメタノールを製造する触媒材料及びそ
の触媒の製造法並びにメタノールの合成法を提供するも
のである。The object of the present invention is to have a higher activity and selectivity than catalysts such as Cu--Zn type and amorphous alloys prepared by the conventionally known coprecipitation method. C
The present invention provides a catalyst material for producing methanol from O 2 and H 2 gas, a method for producing the catalyst, and a method for synthesizing methanol.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
には、触媒中の不純物イオンの除去、活性な金属粒
子の更なる微細化、金属超微粒子の更なる分散度の向
上を達成する必要があり、本発明は急速凝固した合金を
出発材料に用いることにより、〜を達成した内容を
開示したものである。本発明の第一は、一般式：ＴＭ
（ただし、Ｔは希土類元素〔Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎ
ｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅ
ｒ，Ｔｍ，Ｙｂ，Ｌｕ〕およびＭｇ，Ｃａ，Ｍｎ，Ｚ
ｒ，Ｈｆ，Ａｌ，Ｇａから選ばれる少なくとも一種の元
素、Ｍは周期律表ＩＢ族〔Ｃｕ，Ａｇ，Ａｕ〕およびVI
II族〔Ｆｅ，Ｃｏ，Ｎｉ，Ｒｕ，Ｒｈ，Ｐｄ，Ｏｓ，Ｉ
ｒ，Ｐｔ〕から選ばれる少なくとも一種の元素）で示さ
れる合金からなり、その表面がＴ元素からなる酸化物上
にＭ元素からなる金属微細粒子が分散にてなることを特
徴とするメタノール合成用触媒である。上記一般式にお
いて、原子パーセントでＴ元素は１〜９９％、Ｍ元素は
１〜９９％である。また、島状に分散したＭ元素からな
る金属微粒子の大きさはサブナノメートルから数十ナノ
メートル、より具体的には３０ｎｍ以下の微粒子が触媒
として特に有効に働く。In order to solve the above problems, it is necessary to remove impurity ions in the catalyst, further miniaturize active metal particles, and further improve the dispersity of ultrafine metal particles. Therefore, the present invention discloses the fact that is achieved by using a rapidly solidified alloy as a starting material. The first aspect of the present invention is the general formula: TM
(However, T is a rare earth element [Y, La, Ce, Pr, N
d, Pm, Sm, Eu, Gd, Tb, Dy, Ho, E
r, Tm, Yb, Lu] and Mg, Ca, Mn, Z
At least one element selected from r, Hf, Al and Ga, M is Group IB [Cu, Ag, Au] and VI of the periodic table.
Group II [Fe, Co, Ni, Ru, Rh, Pd, Os, I
[at least one element selected from r, Pt]), the surface of which is an oxide of T element and fine metal particles of M element dispersed therein for methanol synthesis. It is a catalyst. In the above general formula, T element is 1 to 99% and M element is 1 to 99% in atomic percent. In addition, the size of the metal fine particles composed of M elements dispersed in an island shape is from sub-nanometer to several tens of nanometers, and more specifically, fine particles of 30 nm or less work particularly effectively as a catalyst.
【０００５】一般式で示されるＴ元素とＭ元素とを組み
合わせることにより、その溶融合金の急速凝固体が非晶
質あるいは非晶質と微細結晶質相との混相からなる合金
（非晶質相を含む合金）又は微細結晶質相からなる合金
を得て、それを所定の酸化処理または酸化−還元処理を
してＴ元素よりなる酸化物上にＭ元素の金属微細粒子又
は表層が金属よりなる金属酸化物超微粒子が分散してな
る表面層を得ることができる。Ｔ元素よりなる酸化物
は、Ｍ元素よりなる金属微細粒子と強い相互作用で結び
つき、金属微細粒子をそのまま安定に固定し、大きな活
性を示す。Ｔ元素とＭ元素の組み合わせから外れると非
晶質相を前駆体としても活性は低い。By combining the T element and the M element represented by the general formula, the rapidly solidified body of the molten alloy is an amorphous alloy or a mixed phase of an amorphous and a fine crystalline phase (amorphous phase). Or an alloy containing a fine crystalline phase, and subjecting it to a predetermined oxidation treatment or oxidation-reduction treatment, the metal fine particles of the M element or the surface layer are formed of a metal on the oxide consisting of the T element. It is possible to obtain a surface layer in which ultrafine metal oxide particles are dispersed. The oxide composed of the T element is bound to the metal fine particles composed of the M element through a strong interaction, stably fixes the metal fine particles as they are, and exhibits great activity. If the combination of the T element and the M element deviates, the activity is low even if the amorphous phase is used as a precursor.
【０００６】Ｔ元素およびＭ元素の好ましい範囲は、合
金状態図上での共晶点付近が非晶質相や微細な結晶組織
を得るのに最も効果的であり、そのため触媒活性も高
い。原子パーセントでＴ元素が１〜９９％、Ｍ元素が９
９〜１％の範囲とすることにより酸化物上に金属微細粒
子が分散してなる組織がより顕著に表れ、高活性を示
す。具体例としては、ＬａＡｕ合金ではＬａbalＡｕ
10〜95、ＣｅＣｏ合金ではＣｅbalＣｏ5〜50、ＮｄＡｇ
合金ではＮｄbalＡｇ10〜95、ＧｄＡｕ合金ではＧｄbal
Ａｕ5〜90、ＭｇＰｄ合金ではＭｇbalＰｄ5〜30、Ｃａ
Ｃｕ合金ではＣａbalＣｕ10〜50、ＭｎＣｕ合金ではＭ
ｎbalＣｕ40〜80（但し、ｂａｌは残部、数字は原子パ
ーセントを示す）などが挙げられる。もちろん、他の組
み合わせ例でも同程度の範囲となる。又、それぞれの元
素の好ましい組成範囲はＴ元素３０〜７０％、Ｍ元素７
０〜３０％である。この範囲で大きな活性が得られる。
金属微粒子の大きさは前述のようにサブナノメートルか
ら数十ナノメートル、より具体的には３０ｎｍ以下、特
に１０ｎｍ以下で触媒効果が飛躍的に向上する。さらに
は５ｎｍ以下が好ましい。本発明触媒の対象反応は、下
記のＣＯ2の接触水素化によるメタノール合成反応であ
る。 ＣＯ2＋３Ｈ2 → ＣＨ3ＯＨ＋Ｈ2Ｏ 本発明の第二は上記一般式ＴＭに示す合金の溶融組成よ
り非晶質相および／又は微細結晶質相を含む合金を作製
し、これを酸化雰囲気下で５０〜７００℃に加熱し、Ｔ
元素からなる酸化物上にＭ元素からなる金属微細粒子を
析出分散せしめることを特徴とするメタノール合成用触
媒の製造法である。The preferred ranges of the T element and the M element are most effective near the eutectic point on the alloy phase diagram for obtaining an amorphous phase or a fine crystal structure, and therefore the catalytic activity is also high. 1 to 99% of T element and 9 of M element in atomic percent
When the content is in the range of 9 to 1%, a structure in which fine metal particles are dispersed on the oxide is more remarkably exhibited, and high activity is exhibited. As a specific example, for LaAu alloy, La bal Au is used.
10 to 95 , Ce bal Co 5 to 50 in CeCo alloy, NdAg
Nd bal Ag 10-95 for alloys, Gd bal for GdAu alloys
Au 5 to 90 , Mg bal Pd 5 to 30 in the case of MgPd alloy, Ca
Cu bal Cu 10-50 for Cu alloys, M for MnCu alloys
n bal Cu 40 to 80 (however, bal represents the rest and numbers represent atomic percentages) and the like. Of course, the range is about the same for other combinations. Further, the preferable composition range of each element is 30 to 70% of T element and 7 of M element.
0 to 30%. Great activity is obtained in this range.
As described above, when the size of the metal fine particles is from sub-nanometer to several tens of nanometers, more specifically 30 nm or less, particularly 10 nm or less, the catalytic effect is dramatically improved. Furthermore, 5 nm or less is preferable. The target reaction of the catalyst of the present invention is the following methanol synthesis reaction by catalytic hydrogenation of CO 2 . CO 2 + 3H 2 → CH 3 OH + H 2 O In the second aspect of the present invention, an alloy containing an amorphous phase and / or a fine crystalline phase is prepared from the molten composition of the alloy represented by the above general formula TM, and the alloy is prepared under an oxidizing atmosphere. Heat to 50-700 ° C with
A method for producing a catalyst for methanol synthesis, which comprises depositing and dispersing fine metal particles of M element on an oxide of element.
【０００７】上記非晶質相および／又は微細結晶質相を
含む合金を作製する手段としては、溶融金属の液体急冷
法により１０4〜１０6Ｋ／ｓの冷却速度で急速凝固させ
る方法やアトマイズ法、液中紡糸法、ＭＡ（メカニカル
アロイング）法、スパッタ法、メッキ法などがある。か
かる合金は酸化雰囲気下で加熱することにより表面層か
ら酸化され、Ｔ元素からなる酸化物（Ｔが二種以上の場
合は、それぞれの複合酸化物および／混合酸化物）上に
数十ナノメートルのＭ元素からなる金属微細粒子が分散
した状態になり、高い触媒活性を示す。上記に示す酸化
物上に金属微粒子が存在する触媒を製造する酸化雰囲気
としては酸化性の雰囲気なら、液相、気相いずれでもか
まわないが、操作性からすると気相の方が簡易で望まし
く、特に空気または酸素と不活性ガスの混合ガスで行う
ことが望ましい。不活性ガスと酸素との濃度比は、それ
ぞれの合金の酸化のされ易さによって異なり、酸化され
易い合金ほど急激に酸化され発熱し、微粒子の焼結等が
起こるため、不活性ガス濃度を高める必要がある。また
その時の酸化処理温度に関しては、５０〜７００℃の範
囲で行う必要がある。これも合金の種類により温度は異
なるが、高温で処理すると酸化はされ易いが、微粒子の
焼結等も起こり易いためできるかぎり低い温度で行うこ
とが望ましい。As means for producing the alloy containing the amorphous phase and / or the fine crystalline phase, a method of rapidly solidifying a molten metal by a liquid quenching method at a cooling rate of 10 4 to 10 6 K / s, or atomizing. Method, submerged spinning method, MA (mechanical alloying) method, sputtering method, plating method and the like. Such an alloy is oxidized from the surface layer by heating in an oxidizing atmosphere, and it is tens of nanometers on an oxide composed of T element (in the case of two or more kinds, each complex oxide and / or mixed oxide). The fine metal particles composed of the M element are dispersed and exhibit high catalytic activity. The oxidizing atmosphere for producing the catalyst in which the metal fine particles are present on the oxide shown above may be either a liquid phase or a gas phase as long as it is an oxidizing atmosphere, but in view of operability, the gas phase is simpler and desirable, In particular, it is desirable to use air or a mixed gas of oxygen and an inert gas. The concentration ratio of the inert gas and oxygen varies depending on the degree of oxidization of each alloy, and the more easily the alloy is oxidized, the more rapidly it is oxidized and heat is generated, and the sintering of fine particles occurs. There is a need. Further, the oxidation treatment temperature at that time needs to be in the range of 50 to 700 ° C. Although the temperature also varies depending on the type of alloy, it is desirable to carry out the treatment at a high temperature as low as possible because it is easily oxidized if it is treated at a high temperature, but sintering of fine particles is also likely to occur.
【０００８】さらに合金の種類によっては、この酸化処
理によってＭ元素まで完全に酸化されてしまう場合もあ
る。その時は水素気流中、または水素と不活性ガスの混
合ガス気流中などの還元雰囲気下で加熱し、Ｍ元素又は
Ｍ元素表面を還元する必要もでてくる。またこの還元処
理温度に関しても、５０〜７００℃の範囲で行う必要が
ある。これも合金の種類により温度は異なるが、高温で
処理すると、微粒子の焼結等も起こり易いためできるか
ぎり低い温度で行うことが望ましい。上記発明により、
反応温度２００〜３００℃、圧力３０〜１００気圧の範
囲のＣＯ2の接触水素化反応で高活性、高選択性を示す
結果となった。なお、本発明の触媒は、ＣＯとＨ2ガス
からメタノールを合成する際にも適用できる。本発明の
第三は、上記一般式ＴＭに示す合金よりなる触媒に二酸
化炭素と水素を導入するとともに加圧、加熱することを
特徴とするメタノール合成用触媒の製造法である。かか
る方法により、反応温度２００〜３００℃、圧力３０〜
１００気圧の範囲の前記ＣＯ2の接触水素化反応におい
て、触媒の高活性、高選択性により、高効率でメタノー
ルを合成することができる。Further, depending on the type of alloy, even the M element may be completely oxidized by this oxidation treatment. At that time, it is also necessary to reduce the M element or the surface of the M element by heating in a reducing atmosphere such as a hydrogen stream or a mixed gas stream of hydrogen and an inert gas. Also, regarding the reduction treatment temperature, it is necessary to perform the reduction treatment within the range of 50 to 700 ° C. The temperature also varies depending on the type of alloy, but if the treatment is performed at a high temperature, sintering of fine particles and the like are likely to occur, so it is desirable to perform the treatment at a temperature as low as possible. According to the above invention,
The catalytic hydrogenation reaction of CO 2 at a reaction temperature of 200 to 300 ° C. and a pressure of 30 to 100 atm resulted in high activity and high selectivity. The catalyst of the present invention can also be applied when synthesizing methanol from CO and H 2 gas. A third aspect of the present invention is a method for producing a catalyst for methanol synthesis, which comprises introducing carbon dioxide and hydrogen into a catalyst made of an alloy represented by the general formula TM, and applying pressure and heat. According to this method, the reaction temperature is 200 to 300 ° C. and the pressure is 30 to
In the catalytic hydrogenation reaction of CO 2 in the range of 100 atm, methanol can be synthesized with high efficiency due to the high activity and high selectivity of the catalyst.
【０００９】[0009]
【実施例】以下、本発明を実施例に基づき具体的に説明
する。 実施例１ アーク溶解炉によりＹ40Ａｇ60の合金を作り、これを先
端に小孔を有する石英管に挿入し、加熱溶融後、その石
英管を２００ｍｍの銅ロール直上に設置し、回転数４０
００ｒ．ｐ．ｍの高速回転下、石英管内の溶融金属をＡ
ｒ加圧下０．４ｋｇ／ｃｍ2により石英管の小孔から噴
出し、ロールの表面と接触することにより急速凝固させ
て幅約１ｍｍの薄体を得た。この際の冷却速度は１０5
Ｋ／ｓである。かかる薄体を用いて空気中３００℃で５
時間酸化処理し、Ｙ2Ｏ3上にＡｇ超微粒子が高密度で分
散した状態の触媒とした。EXAMPLES The present invention will be specifically described below based on examples. Example 1 An alloy of Y 40 Ag 60 was made by an arc melting furnace, inserted into a quartz tube having a small hole at the tip, heated and melted, and the quartz tube was placed directly on a 200 mm copper roll at a rotation speed of 40.
00r. p. The molten metal inside the quartz tube was
It was jetted from a small hole of a quartz tube under a pressure of 0.4 kg / cm 2 and rapidly solidified by coming into contact with the surface of a roll to obtain a thin body having a width of about 1 mm. The cooling rate at this time is 10 5
K / s. Using such a thin body, in air at 300 ℃ 5
Oxidation treatment was carried out for a period of time to obtain a catalyst in which Ag ultrafine particles were dispersed in high density on Y 2 O 3 .
【００１０】実施例２ Ｌａ70Ａｕ30合金から実施例１と同様な方法により、Ｌ
ａ2Ｏ3上にＡｕ超微粒子が高密度で分散した触媒を作っ
た。 実施例３ Ｃｅ40Ａｇ50Ｃｕ10合金から実施例１と同様な方法によ
り、ＣｅＯ2上にＣｕ，Ａｇの超微粒子が高密度で分散
した触媒を作った。 比較例 触媒塩を出発原料として共沈法で作ったＣｕ−Ｚｎ−Ｏ
系触媒を用いた。上記これらの材料１ｇに２５０℃、５
０気圧の条件でＣＯ2とＨ2の混合ガス（ＣＯ2：Ｈ2＝
１：３）を１００ｍｌ／ｍｉｎの流速で通過させたとき
の、このＣＯ2接触水素化反応に体する触媒性能評価の
結果を以下に示す。Example 2 From the La 70 Au 30 alloy, by the same method as in Example 1, L
A catalyst was prepared in which Au ultrafine particles were dispersed at high density on a 2 O 3 . Example 3 A catalyst in which ultrafine particles of Cu and Ag were dispersed at high density on CeO 2 was prepared from the Ce 40 Ag 50 Cu 10 alloy by the same method as in Example 1. Comparative Example Cu-Zn-O prepared by a coprecipitation method using a catalyst salt as a starting material
A system catalyst was used. 250g for 5g of these materials
A mixed gas of CO 2 and H 2 (CO 2 : H 2 =
The results of the evaluation of the catalyst performance involved in this CO 2 catalytic hydrogenation reaction when passing 1: 3) at a flow rate of 100 ml / min are shown below.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【発明の効果】本発明の触媒はＣＯ2の接触水素化反応
に対して、高い活性と選択性を兼ね備えた性質を有する
ため、従来の触媒に比較して、副生成物の除去設備を簡
略化でき、また未反応ガスのリサイクル回転も減らすこ
とが出来るなどの点で有利である。これらにより、本発
明ではＣＯ2よりメタノールを合成し再資源化技術とし
て有効である。EFFECTS OF THE INVENTION Since the catalyst of the present invention has the property of having both high activity and selectivity for the catalytic hydrogenation reaction of CO 2 , the by-product removal facility is simpler than that of conventional catalysts. It is advantageous in that it is possible to reduce the number of recycles of unreacted gas. As a result, the present invention is effective as a resource recycling technology by synthesizing methanol from CO 2 .
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/68 Ｂ０１Ｊ 23/78 Ｚ 23/76 23/89 Ｚ 23/78 Ｃ０７Ｃ 29/154 23/835 29/156 23/889 9155−4Ｈ 31/04 23/89 Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｃ 29/154 Ｂ０１Ｊ 23/56 ３０１Ｚ 29/156 23/64 １０４Ｚ 31/04 23/82 Ｚ // Ｃ０７Ｂ 61/00 ３００ 23/84 ３１１Ｚ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location B01J 23/68 B01J 23/78 Z 23/76 23/89 Z 23/78 C07C 29/154 23 / 835 29/156 23/889 9155-4H 31/04 23/89 C07B 61/00 300 C07C 29/154 B01J 23/56 301Z 29/156 23/64 104Z 31/04 23/82 Z // C07B 61/00 300 23/84 311Z
Claims (8)
〔Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇ
ｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕ〕およ
びＭｇ，Ｃａ，Ｍｎ，Ｚｒ，Ｈｆ，Ａｌ，Ｇａから選ば
れる少なくとも一種の元素、Ｍは周期律表ＩＢ族〔Ｃ
ｕ，Ａｇ，Ａｕ〕およびVIII族〔Ｆｅ，Ｃｏ，Ｎｉ，Ｒ
ｕ，Ｒｈ，Ｐｄ，Ｏｓ，Ｉｒ，Ｐｔ〕から選ばれる少な
くとも一種の元素）で示される合金からなり、その表面
がＴ元素からなる酸化物上にＭ元素からなる金属微細粒
子が分散してなることを特徴とするメタノール合成用触
媒。1. A general formula: TM (where T is a rare earth element [Y, La, Ce, Pr, Nd, Pm, Sm, Eu, G
d, Tb, Dy, Ho, Er, Tm, Yb, Lu] and at least one element selected from Mg, Ca, Mn, Zr, Hf, Al and Ga, and M is a group IB [C] of the periodic table.
u, Ag, Au] and Group VIII [Fe, Co, Ni, R]
u, Rh, Pd, Os, Ir, Pt], and at least one element selected from the group consisting of an alloy of which the surface is an oxide of T element and fine metal particles of M element dispersed therein. A catalyst for methanol synthesis characterized by the following.
％、Ｍ元素は９９〜１％である請求項１記載のメタノー
ル合成用触媒。2. The atomic percentage of T element is 1 to 99.
%, M element is 99-1%, The catalyst for methanol synthesis according to claim 1.
サブナノメートルから数十ナノメートルである請求項１
記載のメタノール合成用触媒。3. The size of the fine metal particles composed of M element is from sub-nanometer to several tens of nanometers.
The described catalyst for synthesizing methanol.
〔Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇ
ｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕ〕およ
びＭｇ，Ｃａ，Ｍｎ，Ｚｒ，Ｈｆ，Ａｌ，Ｇａから選ば
れる少なくとも一種の元素、Ｍは周期律表ＩＢ族〔Ｃ
ｕ，Ａｇ，Ａｕ〕およびVIII族〔Ｆｅ，Ｃｏ，Ｎｉ，Ｒ
ｕ，Ｒｈ，Ｐｄ，Ｏｓ，Ｉｒ，Ｐｔ〕から選ばれる少な
くとも一種の元素）の溶融組成より非晶質相および／又
は微細結晶質相を含む合金を作製し、これを酸化雰囲気
又はメタノール合成と同等の雰囲気中で５０〜７００℃
に加熱し、合金表面を酸化させＴ元素からなる酸化物上
にＭ元素からなる金属微細粒子を析出分散せしめること
を特徴とするメタノール合成用触媒の製造方法。4. A general formula: TM (where T is a rare earth element [Y, La, Ce, Pr, Nd, Pm, Sm, Eu, G
d, Tb, Dy, Ho, Er, Tm, Yb, Lu] and at least one element selected from Mg, Ca, Mn, Zr, Hf, Al and Ga, and M is a group IB [C] of the periodic table.
u, Ag, Au] and Group VIII [Fe, Co, Ni, R]
u, Rh, Pd, Os, Ir, Pt] and at least one element selected from the melting composition of an alloy containing an amorphous phase and / or a fine crystalline phase. 50 to 700 ℃ in an equivalent atmosphere
A method for producing a catalyst for methanol synthesis, which comprises heating the alloy surface to oxidize the surface of the alloy to deposit and disperse fine metal particles of M element on an oxide of T element.
後、さらに還元雰囲気で５０〜７００℃に加熱すること
により、Ｔ元素からなる酸化物上にＭ元素からなる金属
微細粒子を析出分散せしめることを特徴とするメタノー
ル合成用触媒の製造法。5. After the heat treatment in the oxidizing atmosphere according to claim 4, by further heating to 50 to 700 ° C. in a reducing atmosphere, the fine metal particles of the M element are deposited and dispersed on the oxide of the T element. A method for producing a catalyst for methanol synthesis, characterized by comprising:
処理を繰り返すことにより、Ｔ元素からなる酸化物上に
Ｍ元素からなる金属微細粒子を析出分散せしめることを
特徴とするメタノール合成用触媒の製造法。6. A method for synthesizing methanol, characterized in that fine metal particles consisting of M element are deposited and dispersed on an oxide consisting of T element by repeating the oxidation treatment and the reduction treatment described in claim 4. Catalyst manufacturing method.
〔Ｙ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇ
ｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕ〕およ
びＭｇ，Ｃａ，Ｍｎ，Ｚｒ，Ｈｆ，Ａｌ，Ｇａから選ば
れる少なくとも一種の元素、Ｍは周期律表ＩＢ族〔Ｃ
ｕ，Ａｇ，Ａｕ〕およびVIII族〔Ｆｅ，Ｃｏ，Ｎｉ，Ｒ
ｕ，Ｒｈ，Ｐｄ，Ｏｓ，Ｉｒ，Ｐｔ〕から選ばれる少な
くとも一種の元素）で示される合金からなり、その表面
がＴ元素からなる酸化物上にＭ元素からなる金属微細粒
子が分散してなる触媒に二酸化炭素と水素を導入すると
ともに、加圧、加熱することを特徴とするメタノールの
合成法。7. The general formula: TM (where T is a rare earth element [Y, La, Ce, Pr, Nd, Pm, Sm, Eu, G
d, Tb, Dy, Ho, Er, Tm, Yb, Lu] and at least one element selected from Mg, Ca, Mn, Zr, Hf, Al and Ga, and M is a group IB [C] of the periodic table.
u, Ag, Au] and Group VIII [Fe, Co, Ni, R]
u, Rh, Pd, Os, Ir, Pt], and at least one element selected from the group consisting of an alloy of which the surface is an oxide of T element and fine metal particles of M element dispersed therein. A method for synthesizing methanol, which comprises introducing carbon dioxide and hydrogen into a catalyst, and applying pressure and heating.
Ｍ元素は９９〜１％である触媒を用いる請求項７記載の
メタノールの合成法。8. The T element is 1 to 99% in atomic percent,
The method for synthesizing methanol according to claim 7, wherein a catalyst in which the M element is 99 to 1% is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7029394A JPH08215570A (en) | 1995-02-17 | 1995-02-17 | Catalyst for synthesis of methanol, production thereof and synthesis of methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7029394A JPH08215570A (en) | 1995-02-17 | 1995-02-17 | Catalyst for synthesis of methanol, production thereof and synthesis of methanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08215570A true JPH08215570A (en) | 1996-08-27 |
Family
ID=12274934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7029394A Pending JPH08215570A (en) | 1995-02-17 | 1995-02-17 | Catalyst for synthesis of methanol, production thereof and synthesis of methanol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08215570A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102437C (en) * | 1999-05-24 | 2003-03-05 | 中国科学院山西煤炭化学研究所 | Methanol synthesizing catalyst |
| JP2009215263A (en) * | 2008-03-12 | 2009-09-24 | Tokyo Electric Power Co Inc:The | Method for synthesizing methanol |
| WO2012105631A1 (en) | 2011-02-02 | 2012-08-09 | 独立行政法人産業技術総合研究所 | Noble metal-oxide joined nanoparticles and method for high-purity production of the same |
| WO2012122057A3 (en) * | 2011-03-04 | 2012-11-22 | Felix Studt | Catalysts for the reduction of carbon dioxide to methanol |
-
1995
- 1995-02-17 JP JP7029394A patent/JPH08215570A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102437C (en) * | 1999-05-24 | 2003-03-05 | 中国科学院山西煤炭化学研究所 | Methanol synthesizing catalyst |
| JP2009215263A (en) * | 2008-03-12 | 2009-09-24 | Tokyo Electric Power Co Inc:The | Method for synthesizing methanol |
| WO2012105631A1 (en) | 2011-02-02 | 2012-08-09 | 独立行政法人産業技術総合研究所 | Noble metal-oxide joined nanoparticles and method for high-purity production of the same |
| US9675964B2 (en) | 2011-02-02 | 2017-06-13 | National Institute Of Advanced Industrial Science And Technology | Noble metal-oxide combined nanoparticle, and, method of producing the same with high purity |
| WO2012122057A3 (en) * | 2011-03-04 | 2012-11-22 | Felix Studt | Catalysts for the reduction of carbon dioxide to methanol |
| EP2680964A2 (en) * | 2011-03-04 | 2014-01-08 | The Board Of Trustees Of The University Of the Leland Stanford Junior University | Catalysts for the reduction of carbon dioxide to methanol |
| CN103547366A (en) * | 2011-03-04 | 2014-01-29 | 里兰斯坦福初级大学理事会 | Catalysts for the reduction of carbon dioxide to methanol |
| EP2680964A4 (en) * | 2011-03-04 | 2014-11-19 | Univ Leland Stanford Junior | Catalysts for the reduction of carbon dioxide to methanol |
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