JPH10272361A - Methanol synthesis and reforming catalyst - Google Patents
Methanol synthesis and reforming catalystInfo
- Publication number
- JPH10272361A JPH10272361A JP9080936A JP8093697A JPH10272361A JP H10272361 A JPH10272361 A JP H10272361A JP 9080936 A JP9080936 A JP 9080936A JP 8093697 A JP8093697 A JP 8093697A JP H10272361 A JPH10272361 A JP H10272361A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- catalyst
- zinc
- aluminum
- weight
- 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]
【発明の属する技術分野】本発明は、二酸化炭素又は一
酸化炭素もしくは二酸化炭素と一酸化炭素との混合ガス
を水素ガスと反応させてアルコール及び／又は炭化水素
を合成する際に用いる二酸化炭素又は一酸化炭素の水素
化反応用触媒、また、逆にアルコールと水とから水素を
製造する水蒸気改質用触媒に関するものである。BACKGROUND OF THE INVENTION The present invention relates to carbon dioxide or carbon dioxide used for synthesizing alcohol and / or hydrocarbon by reacting carbon dioxide or carbon monoxide or a mixed gas of carbon dioxide and carbon monoxide with hydrogen gas. The present invention relates to a catalyst for hydrogenation reaction of carbon monoxide and, on the contrary, to a catalyst for steam reforming for producing hydrogen from alcohol and water.
【０００２】[0002]
【従来の技術】メタノール合成触媒の開発研究の歴史は
古く、とりわけ銅、亜鉛、アルミニウムの酸化物より構
成される共沈法により作製した触媒は高いメタノール合
成活性を有することが知られており、この触媒を用いた
合成ガスからのメタノール製造プラントは工業化されて
いる。2. Description of the Related Art The research and development of methanol synthesis catalysts has a long history, and it is known that catalysts prepared by the coprecipitation method composed of oxides of copper, zinc and aluminum have high methanol synthesis activity. A plant for producing methanol from synthesis gas using this catalyst has been industrialized.
【０００３】最近になってからは二酸化炭素による地球
温暖化問題解決の方法として、こういったメタノール合
成触媒を用いて、二酸化炭素をメタノールに変換しよう
という動きが活発化してきている。しかしながら、化石
燃料を燃焼させることによって発生するような大量の二
酸化炭素をメタノールに交換するためには、極めて速い
燃焼反応に追従できるだけの高速変換性が必要になる。
したがって、従来よりも更に高活性な触媒が切望されて
いる。[0003] Recently, as a method of solving the global warming problem by carbon dioxide, a movement to convert carbon dioxide into methanol using such a methanol synthesis catalyst has been activated. However, in order to exchange a large amount of carbon dioxide generated by burning fossil fuel into methanol, a high-speed conversion property that can follow an extremely fast combustion reaction is required.
Therefore, a catalyst having a higher activity than before has been desired.
【０００４】例えば、メタノールの水蒸気改質反応は下
記反応式（１）に示されるものである。For example, a steam reforming reaction of methanol is represented by the following reaction formula (1).
【０００５】 ＣＨ3ＯＨ＋Ｈ2Ｏ → ３Ｈ2＋ＣＯ2 …（１） また、メタノールの合成反応は下記反応式（２）に示さ
れるものである。CH 3 OH + H 2 O → 3H 2 + CO 2 (1) Further, a synthesis reaction of methanol is represented by the following reaction formula (2).
【０００６】 ３Ｈ2＋ＣＯ2 → ＣＨ3ＯＨ＋Ｈ2Ｏ …（２） これらに関連した触媒としては次のようなものが知られ
ている。銅、亜鉛、アルミニウムの酸化物に更に添加物
を加えたものとして、特開昭６０−２０９２５５では希
土類やジルコニウムの添加、特開昭６０−１４７２４４
では、イットリウムやランタノイド、アクチノイドの添
加、特開平４−１２２４５０ではクロム酸化物、銀の添
加、特開平５−１６８９３６はクロム酸化物、ランタン
酸化物の添加、また特開平６−３１２１３８ではガリウ
ム、バナジウム、モリブデン、タングステンの添加、特
開平８−２２９３９９はチタン、ジルコニウムの酸化物
の添加が記載されている。銅、亜鉛、アルミニウムの酸
化物のみの三元系より構成された触媒についても、特開
昭５０−６８９８３、特開昭５５−１０６５４３、特開
昭５６−７０８３６、特開昭５７−１３０５４７、特開
昭５７−７２５６、特開昭５９−２２２２３２、特開昭
５９−１０２４４３、特開昭６０−１９０２３２、特開
昭６０−１７９１４５、特開昭６２−５３７３９、特開
平３−６８４５０、特開平６−１７０２３１等に示され
ている。又、これによると、銅、亜鉛、アルミニウムの
酸化物の組成範囲としては銅が３０〜７０重量％、亜鉛
が２０〜７０重量％、アルミニウムが１５重量％以下の
範囲の有効性が実施例として示されている。3H 2 + CO 2 → CH 3 OH + H 2 O (2) The following are known as catalysts related to these. Japanese Patent Application Laid-Open No. 60-209255 discloses the addition of rare earths and zirconium to copper, zinc, and aluminum oxides with additional additives.
In addition, addition of yttrium, lanthanoids and actinoids, addition of chromium oxide and silver in JP-A-4-122450, addition of chromium oxide and lanthanum oxide in JP-A-5-168936, and addition of gallium and vanadium in JP-A-6-313138 , Molybdenum and tungsten, and JP-A-8-229399 describes the addition of titanium and zirconium oxides. Catalysts composed of a ternary system containing only oxides of copper, zinc and aluminum are also disclosed in JP-A-50-68983, JP-A-55-106543, JP-A-56-70836, JP-A-57-13047, JP-A-57-7256, JP-A-59-222232, JP-A-59-102443, JP-A-60-190232, JP-A-60-179145, JP-A-62-53739, JP-A-3-68450, JP-A-3-68450 -170231. According to this, the composition range of the oxides of copper, zinc and aluminum is 30 to 70% by weight of copper, 20 to 70% by weight of zinc and 15% by weight or less of aluminum as an example. It is shown.
【０００７】[0007]
【発明が解決しようとする課題】上記の従来技術のう
ち、銅、亜鉛、アルミニウム酸化物に添加物を加える方
法は、添加物としてチタン、ジルコニウム、ガリウム、
バナジウム、モリブデン、タングステン、イットリウ
ム、ランタノイド、アクチノイド等と、銅、亜鉛、アル
ミニウムに比べると極めて高価な元素を必要とするた
め、工業的には不向きである。Among the above-mentioned prior arts, the method of adding an additive to copper, zinc, and aluminum oxide is as follows: titanium, zirconium, gallium,
Vanadium, molybdenum, tungsten, yttrium, lanthanoids, actinoids and the like, and extremely expensive elements as compared with copper, zinc and aluminum are not industrially suitable.
【０００８】それに対して、銅、亜鉛、アルミニウムの
酸化物のみより構成されている触媒は、コスト面での問
題はないが、銅が３０〜７０重量％、亜鉛が２０〜７０
重量％、アルミニウムが１５重量％以下の範囲において
は、共沈法などの一般的な触媒製造法では、高い触媒活
性は得られない。この範囲において我々が共沈法で作っ
た触媒の特性データから類推すると、最も有効な組成に
おいても、現状のメタノール合成に用いられている、
銅、亜鉛、アルミニウム酸化物系の工業触媒の２倍程度
の活性にしかならないことが予想される。したがって、
この範囲において更に高い性能を得るためには、例えば
特開平８−２１５５７１等に示されるような特殊な調製
法を用いない限り実現できないと思われる。On the other hand, a catalyst composed only of oxides of copper, zinc and aluminum has no problem in cost, but contains 30 to 70% by weight of copper and 20 to 70% by weight of zinc.
When the amount of aluminum is less than 15% by weight or less, high catalyst activity cannot be obtained by a general catalyst production method such as a coprecipitation method. By analogy with the characteristics data of the catalyst we made by the coprecipitation method in this range, even the most effective composition is used for the current methanol synthesis,
It is expected that the activity is only about twice as high as that of copper, zinc and aluminum oxide-based industrial catalysts. Therefore,
In order to obtain even higher performance in this range, it is considered that it cannot be realized unless a special preparation method as shown in, for example, JP-A-8-215571 is used.
【０００９】したがって、本発明では、銅、亜鉛、アル
ミニウムの酸化物に対して。それ以外の有害な添加元
素、あるいは高価な添加元素等は使わず、しかも製造コ
ストのかかる特別な手法を用いない、いわゆる最も一般
的な触媒製造法である共沈法で高活性が得られる触媒を
提供することを目的としている。Therefore, in the present invention, oxides of copper, zinc and aluminum are used. A catalyst that does not use any other harmful additive elements or expensive additive elements, and does not use special methods that require high production costs. It is intended to provide.
【００１０】[0010]
【課題を解決するための手段】本発明は、上記問題点を
鑑みて、一般的に知られる硝酸銅、硝酸亜鉛、硝酸アル
ミニウムの混合水溶液に炭酸アルカリ、炭酸水素アルカ
リ、水酸化アルカリ、アンモニア等、アルカリ性溶液を
加え、反応させて得た沈殿物を洗浄、濾過し、焼成する
いわゆる共沈法を用いて作った、銅、亜鉛、アルミニウ
ム酸化物より構成される触媒において、詳細な組成調査
を行った。その結果、これらの最適な組み合わせにおい
て特異的に高い活性を示すポイントを見いだし、本発明
を完成させるに至った。この高活性を発現する組成とし
ては、銅：６８．０〜８６．０重量％、アルミニウム：
２．０〜２０．０重量％、亜鉛：４．５〜２１．０重量
％であり、好ましくは、銅：６８．０〜８４．０重量
％、アルミニウム：４．０〜１７．０重量％、亜鉛：
５．０〜２１．０重量％である。SUMMARY OF THE INVENTION In view of the above problems, the present invention is directed to a generally known mixed aqueous solution of copper nitrate, zinc nitrate, and aluminum nitrate. A detailed composition study was conducted on a catalyst composed of copper, zinc, and aluminum oxide, which was formed using a so-called coprecipitation method in which an alkaline solution was added, the precipitate obtained by the reaction was washed, filtered, and calcined. went. As a result, a point showing specifically high activity in these optimal combinations was found, and the present invention was completed. As a composition exhibiting this high activity, copper: 68.0 to 86.0% by weight, aluminum:
2.0 to 20.0% by weight, zinc: 4.5 to 21.0% by weight, preferably copper: 68.0 to 84.0% by weight, aluminum: 4.0 to 17.0% by weight ,zinc:
5.0 to 21.0% by weight.
【００１１】ここで銅：６８．０〜８６．０重量％とし
たのはこの反応における活性元素は銅であるため、６
８．０重量％より少ないと大きな活性の発現には至らな
い、逆に銅が８６．０重量％を越えると、シンタリング
により銅の分散性が悪くなり、高い活性を発現できない
上、耐久性が著しく低下するためである。アルミニウム
においては、銅や亜鉛と相互作用し、更に活性を高める
働きと同時に、銅を安定に高分散させる作用を担ってい
る。したがって、アルミニウムの量が２．０重量％より
少ないと、銅の分散性が悪くなり、高活性を発現できな
い上、耐久性も著しく低下する。逆にアルミニウムが２
０．０重量％より多いと、銅や亜鉛と相互作用のバラン
スが崩れ、活性は著しく低下する。亜鉛については、触
媒表面に存在する銅の酸化状態のバランスを制御する働
きをし、これにより触媒活性が大きく左右される。銅、
アルミニウムが上記組成範囲をとる場合においては亜鉛
は４．５〜２１．０重量％の存在で触媒活性を大きく発
現させるよう働く、逆にこの範囲からはずれると銅の酸
化状態のバランスが損なわれ、高い活性が得られない。
こういった理由から銅：６８．０〜８６．０重量％、ア
ルミニウム：２．０〜２０．０重量％、亜鉛：４．５〜
２１．０重量％において工業触媒並の耐久性を保持し
た。極めて高い触媒活性を有する触媒が、簡易な共沈法
で得られるわけである。Here, copper: 68.0 to 86.0% by weight is used because the active element in this reaction is copper.
If the amount is less than 8.0% by weight, large activity is not exhibited. On the other hand, if the amount of copper exceeds 86.0% by weight, the dispersibility of copper is deteriorated due to sintering, high activity cannot be exhibited, and durability is high. Is significantly reduced. Aluminum interacts with copper and zinc to further increase the activity and at the same time to stably and highly disperse copper. Therefore, when the amount of aluminum is less than 2.0% by weight, the dispersibility of copper is deteriorated, high activity cannot be exhibited, and the durability is significantly reduced. Conversely, aluminum is 2
If the content is more than 0.0% by weight, the balance of the interaction with copper and zinc is lost, and the activity is significantly reduced. Zinc acts to control the balance of the oxidation state of copper present on the catalyst surface, which greatly affects the catalytic activity. copper,
In the case where aluminum has the above composition range, zinc acts to greatly develop catalytic activity in the presence of 4.5 to 21.0% by weight. Conversely, if it is out of this range, the balance of the oxidation state of copper is impaired, High activity cannot be obtained.
For these reasons, copper: 68.0-86.0% by weight, aluminum: 2.0-20.0% by weight, zinc: 4.5-8.5%
At 21.0% by weight, durability equivalent to that of an industrial catalyst was maintained. A catalyst having extremely high catalytic activity can be obtained by a simple coprecipitation method.
【００１２】中でも、銅：７２．０〜８２．０重量％、
アルミニウム：６．０〜１５．０重量％、亜鉛：７．７
〜１８．０重量％の範囲では、銅、亜鉛、アルミニウム
酸化物より構成される市販の工業触媒の３倍以上、とり
わけ、銅：７４．０〜８１．０重量％、アルミニウム：
６．６〜１３．０重量％、亜鉛：１０．０〜１４．０重
量％の範囲では工業触媒の３．５倍以上の活性が得られ
た。Among them, copper: 72.0 to 82.0% by weight,
Aluminum: 6.0 to 15.0% by weight, zinc: 7.7
In the range of 〜18.0% by weight, it is more than three times that of a commercially available industrial catalyst composed of copper, zinc and aluminum oxide, especially copper: 74.0 to 81.0% by weight, aluminum:
In the range of 6.6 to 13.0% by weight and zinc in the range of 10.0 to 14.0% by weight, an activity 3.5 times or more that of the industrial catalyst was obtained.
【００１３】[0013]
【発明の実施の形態】以下、発明の実施の形態を実施例
並びに比較例によって説明する。Embodiments of the present invention will be described below with reference to examples and comparative examples.
【００１４】実施例 硝酸銅３水和物、硝酸亜鉛６水和物、硝酸アルミニウム
９水和物の所定量を１リットルのイオン交換水に溶解し
たａ液、および炭酸ナトリウム５３ｇを１リットルのイ
オン交換水に溶解したｂ液を用意し、スターラーで撹拌
しながらｂ液をａ液に滴下し、沈殿を形成させた。沈殿
物中のナトリウムイオンを取り除くため、洗浄を繰り返
した後、濾過し、８０℃で１２時間乾燥、その後３００
℃で１時間、焼成を行い、上記請求範囲に示した組成の
触媒（実施例１〜２０）を得た。この触媒について、二
酸化炭素の接触水素化反応に関する触媒特性を固定床加
圧流通式反応装置を用い、反応温度２５０℃、反応圧力
５ＭＰａの条件下、Ｈ2／ＣＯ2混合ガス（Ｈ2：ＣＯ2＝
３：１）を流通させ、生成物をオンラインガスクロマト
グラフにより分析し、二酸化炭素からのメタノール合成
における触媒特性を調べた。なお、得られた触媒の組成
分析結果及び、１０％の二酸化炭素転化率を示すように
触媒の重量に対するとＨ2／ＣＯ2混合ガス比〔Ｗ／Ｆ：
Ｗ＝触媒重量（ｇ）、Ｆ＝混合ガス流速（ｍｏｌ／
ｈ）〕を変化させた際の触媒特性〔メタノール空時収
量：接触単位重量（１ｋｇ）、単位反応時間（１ｈｒ）
当りのメタノール収量（ｇ）〕を表１に示す。Example 1 Liquid a prepared by dissolving predetermined amounts of copper nitrate trihydrate, zinc nitrate hexahydrate and aluminum nitrate nonahydrate in 1 liter of ion-exchanged water, and 53 g of sodium carbonate in 1 liter of ion Solution b dissolved in exchange water was prepared, and solution b was dropped into solution a while stirring with a stirrer to form a precipitate. To remove sodium ions in the precipitate, washing was repeated, followed by filtration and drying at 80 ° C. for 12 hours.
Calcination was performed at a temperature of 1 hour for 1 hour to obtain a catalyst having the composition shown in the claims (Examples 1 to 20). For this catalyst, the catalytic properties of the catalytic hydrogenation reaction of carbon dioxide were measured using a fixed bed pressurized flow reactor under the conditions of a reaction temperature of 250 ° C. and a reaction pressure of 5 MPa, and a mixed gas of H 2 / CO 2 (H 2 : CO 2). 2 =
3: 1), the product was analyzed by on-line gas chromatography, and the catalytic properties in methanol synthesis from carbon dioxide were examined. The H 2 / CO 2 mixed gas ratio [W / F: based on the weight of the catalyst so as to show a composition analysis result of the obtained catalyst and a carbon dioxide conversion of 10%.
W = catalyst weight (g), F = mixed gas flow rate (mol /
h)] [Methanol space-time yield: contact unit weight (1 kg), unit reaction time (1 hr)]
Table 1 shows the yield of methanol per unit (g).
【００１５】比較例 硝酸銅３水和物、硝酸亜鉛６水和物、硝酸アルミニウム
９水和物、及び炭酸ナトリウムを用いて上記実施例と同
様な方法で請求範囲からはずれた組成の触媒（比較例１
〜１３）を得た。また実施例と同様な方法で二酸化炭素
からのメタノール合成における触媒特性を評価した。得
られた触媒の組成分析結果及び触媒特性を表１に示す。Comparative Example A catalyst having a composition deviating from the claims in the same manner as in the above example using copper nitrate trihydrate, zinc nitrate hexahydrate, aluminum nitrate nonahydrate, and sodium carbonate (comparative example) Example 1
To 13). The catalytic properties in the synthesis of methanol from carbon dioxide were evaluated in the same manner as in the examples. Table 1 shows the composition analysis results and catalyst characteristics of the obtained catalyst.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】また、表１の実施例及び比較例に示した触
媒の各組成（銅、亜鉛の重量％、残部はアルミニウム）
における触媒特性（メタノール空時収量）の関係を図１
に示す。●は実施例、▲は比較例の触媒特性のデータで
あるが、これより明らかに、実施例に示した範囲の組成
での触媒特性は、従来の発明により示されている範囲の
触媒特性より高いことがわかる。Each composition of the catalysts shown in the examples and comparative examples in Table 1 (% by weight of copper and zinc, balance being aluminum)
Fig. 1 shows the relationship between catalyst characteristics (space-time yield of methanol)
Shown in The solid circles represent the catalyst characteristics of the examples and the solid triangles represent the data of the catalyst characteristics of the comparative examples. The catalyst characteristics of the compositions in the ranges shown in the examples are clearly clearer than those of the ranges shown by the conventional invention. It turns out that it is high.
【００１９】[0019]
【発明の効果】本発明により従来より知られる銅、亜
鉛、アルミニウム酸化物より構成される触媒で、高価な
添加元素や、特殊な調製法を使用しなくても、非常に高
活性な二酸化炭素又は一酸化炭素の水素化反応用触媒を
含むメタノールの合成及び改質触媒を得ることができ
る。According to the present invention, a catalyst composed of copper, zinc, and aluminum oxides which has been conventionally known, and has a very high activity of carbon dioxide without using an expensive additive element or a special preparation method. Alternatively, a catalyst for synthesizing and reforming methanol containing a catalyst for hydrogenating carbon monoxide can be obtained.
【図１】実施例並びに比較例の触媒組成と触媒特性の関
係を示すグラフである。FIG. 1 is a graph showing the relationship between catalyst composition and catalyst characteristics of Examples and Comparative Examples.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０７Ｃ 29/154 Ｃ０７Ｃ 29/154 31/04 31/04 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 小林 正幸 宮城県黒川郡富谷町富ケ丘１−15−22 (72)発明者 山口 正志 宮城県仙台市太白区泉崎１−16−23 (72)発明者 荒川 裕則 東京都千代田区霞が関１丁目３番１号 工 業技術院内 (72)発明者 岡部 清美 茨城県つくば市東１丁目１番 物質工学工 業技術研究所内 (72)発明者 佐山 和弘 茨城県つくば市東１丁目１番 物質工学工 業技術研究所内 (72)発明者 草間 仁 茨城県つくば市東１丁目１番 物質工学工 業技術研究所内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI C07C 29/154 C07C 29/154 31/04 31/04 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Kobayashi Masayuki 1-15-22, Tomigaoka, Tomiya-cho, Kurokawa-gun, Miyagi Prefecture (72) Inventor Masashi Yamaguchi 1-16-23, Izumizaki, Taihaku-ku, Sendai, Miyagi Prefecture (72) Inventor Hironori Arakawa 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (72) Inventor, Kiyomi Okabe 1-1-1, Higashi, Tsukuba-shi, Ibaraki Pref. 72) Inventor Hitoshi Kusama 1-1-1 Higashi, Tsukuba, Ibaraki Pref.
Claims (4)
成され、かつ、それぞれの金属元素の割合が、銅：６
８．０〜８６．０重量％、亜鉛：４．５〜２１．０重量
％、アルミニウム：２．０〜２０．０重量％であるメタ
ノール合成及び改質触媒。1. An oxide of copper, zinc, or aluminum, and the ratio of each metal element is copper: 6.
A methanol synthesis and reforming catalyst containing 8.0 to 86.0% by weight, zinc: 4.5 to 21.0% by weight, and aluminum: 2.0 to 20.0% by weight.
成され、かつ、それぞれの金属元素の割合が、銅：６
８．０〜８４．０重量％、亜鉛：５．０〜２１．０重量
％、アルミニウム：４．０〜１７．０重量％であるメタ
ノール合成及び改質触媒。2. It is composed of oxides of copper, zinc and aluminum, and the ratio of each metal element is copper: 6.
A methanol synthesis and reforming catalyst containing 8.0 to 84.0% by weight, 5.0 to 21.0% by weight of zinc, and 4.0 to 17.0% by weight of aluminum.
成され、かつ、それぞれの金属元素の割合が、銅：７
２．０〜８２．０重量％、亜鉛：７．７〜１８．０重量
％、アルミニウム：６．０〜１５．０重量％であるメタ
ノール合成及び改質触媒。3. It is composed of an oxide of copper, zinc and aluminum, and the ratio of each metal element is copper: 7.
A methanol synthesis and reforming catalyst containing 2.0 to 82.0% by weight, zinc: 7.7 to 18.0% by weight, and aluminum: 6.0 to 15.0% by weight.
成され、かつ、それぞれの金属元素の割合が、銅：７
４．０〜８１．０重量％、亜鉛：１０．０〜１４．０重
量％、アルミニウム：６．６〜１３．０重量％であるメ
タノール合成及び改質触媒。4. It is composed of oxides of copper, zinc and aluminum, and the ratio of each metal element is copper: 7
A methanol synthesis and reforming catalyst containing 4.0 to 81.0% by weight, zinc: 10.0 to 14.0% by weight, and aluminum: 6.6 to 13.0% by weight.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9080936A JPH10272361A (en) | 1997-03-31 | 1997-03-31 | Methanol synthesis and reforming catalyst |
| US09/050,207 US6114279A (en) | 1997-03-31 | 1998-03-30 | Catalyst for methanol synthesis and reforming |
| DE69808983T DE69808983T2 (en) | 1997-03-31 | 1998-03-30 | Methanol synthesis and reforming catalyst consisting of copper, zinc and aluminum |
| EP98105792A EP0868943B1 (en) | 1997-03-31 | 1998-03-30 | Copper, zinc and aluminium based catalyst for methanol synthesis and reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9080936A JPH10272361A (en) | 1997-03-31 | 1997-03-31 | Methanol synthesis and reforming catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10272361A true JPH10272361A (en) | 1998-10-13 |
Family
ID=13732358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9080936A Pending JPH10272361A (en) | 1997-03-31 | 1997-03-31 | Methanol synthesis and reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10272361A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001185190A (en) * | 1999-12-28 | 2001-07-06 | Mitsubishi Gas Chem Co Inc | Producing method of hydrogen for fuel cell |
| JP2013163675A (en) * | 2007-10-30 | 2013-08-22 | Toyama Univ | Hydrogen reduction method of carbon dioxide |
| US8623782B2 (en) | 2009-02-23 | 2014-01-07 | Mitsui Chemicals, Inc. | Process for preparing copper-based catalyst, copper-based catalyst, and pretreatment method of the same |
| US10252963B2 (en) | 2014-10-20 | 2019-04-09 | Mitsubishi Gas Chemical Company, Inc. | Method for producing methanol and apparatus for producing methanol |
-
1997
- 1997-03-31 JP JP9080936A patent/JPH10272361A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001185190A (en) * | 1999-12-28 | 2001-07-06 | Mitsubishi Gas Chem Co Inc | Producing method of hydrogen for fuel cell |
| JP2013163675A (en) * | 2007-10-30 | 2013-08-22 | Toyama Univ | Hydrogen reduction method of carbon dioxide |
| US8623782B2 (en) | 2009-02-23 | 2014-01-07 | Mitsui Chemicals, Inc. | Process for preparing copper-based catalyst, copper-based catalyst, and pretreatment method of the same |
| US10252963B2 (en) | 2014-10-20 | 2019-04-09 | Mitsubishi Gas Chemical Company, Inc. | Method for producing methanol and apparatus for producing methanol |
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