JP2545734B2 - Hydrocarbon producing catalyst and hydrocarbon producing method - Google Patents
Hydrocarbon producing catalyst and hydrocarbon producing methodInfo
- Publication number
- JP2545734B2 JP2545734B2 JP5254988A JP25498893A JP2545734B2 JP 2545734 B2 JP2545734 B2 JP 2545734B2 JP 5254988 A JP5254988 A JP 5254988A JP 25498893 A JP25498893 A JP 25498893A JP 2545734 B2 JP2545734 B2 JP 2545734B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carbon dioxide
- copper
- reaction
- hydrogen
- 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.)
- Expired - Lifetime
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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭化水素製造用触媒及
び炭化水素の製造方法に関する。TECHNICAL FIELD The present invention relates to a catalyst for producing hydrocarbons and a method for producing hydrocarbons.
【０００２】[0002]
【従来技術とその問題点】近年、産業の発展とともに化
石燃料の使用量が増加し、それに伴って大気中に排出さ
れる二酸化炭素も増え続けている。このため、大気中の
二酸化炭素の濃度上昇による地球の温暖化が深刻な環境
問題となっている。二酸化炭素は、炭素資源として活用
することが可能であり、最近では二酸化炭素を回収して
リサイクル利用するための研究も進められているが、実
用化には至っていない。従って、二酸化炭素を回収して
その排出量を低減するとともに二酸化炭素を有効に利用
する技術の開発が急務となっている。2. Description of the Related Art In recent years, the amount of fossil fuels used has increased with the development of industry, and accompanying this, the amount of carbon dioxide emitted into the atmosphere has also continued to increase. Therefore, global warming due to an increase in the concentration of carbon dioxide in the atmosphere has become a serious environmental problem. Carbon dioxide can be utilized as a carbon resource, and recently, although research for collecting and recycling carbon dioxide is under way, it has not been put to practical use. Therefore, there is an urgent need to develop a technique for recovering carbon dioxide to reduce its emission amount and effectively utilizing carbon dioxide.
【０００３】二酸化炭素と水素とを反応させて炭化水素
を製造する方法に関しては、二酸化炭素をメタノールに
変換した後、これを炭化水素に変換する方法が知られて
いる(Masahiro Fujiwara and Yoshie Souma,J.Chem.So
c.Commun.,767(1992))。しかしながら、この方法では、
炭化水素の収率が第１段階で生成したメタノールの量に
制約されるため、二酸化炭素の炭化水素への転化率は低
く、せいぜい２０％程度である。Regarding a method for producing a hydrocarbon by reacting carbon dioxide with hydrogen, a method of converting carbon dioxide into methanol and then converting this into hydrocarbon is known (Masahiro Fujiwara and Yoshie Souma, J.Chem.So
c.Commun., 767 (1992)). However, with this method,
Since the yield of hydrocarbons is limited by the amount of methanol produced in the first stage, the conversion rate of carbon dioxide to hydrocarbons is low, about 20% at most.
【０００４】また、二酸化炭素から直接炭化水素を合成
することも試みられている (Jyh-Fu Lee, Wen-Shing
Chern and Min-Dar Lee,Can.J.Chem.Eng.,Vol 70,511(1
992). Min-Dar Lee,Jyh-Fu Lee, and Chau-Shang,Bul
l.Chem.Soc.Jpn.,62,2756-2758(1989)) 。しかしなが
ら、この方法では、高温・高圧の条件下でも、二酸化炭
素の反応率及び炭化水素の選択率が低く、工業的実施に
は適していない。It has also been attempted to directly synthesize hydrocarbons from carbon dioxide (Jyh-Fu Lee, Wen-Shing
Chern and Min-Dar Lee, Can.J.Chem.Eng., Vol 70,511 (1
992). Min-Dar Lee, Jyh-Fu Lee, and Chau-Shang, Bul
l. Chem. Soc. Jpn., 62 , 2756-2758 (1989)). However, according to this method, the reaction rate of carbon dioxide and the selectivity of hydrocarbons are low even under conditions of high temperature and high pressure, and are not suitable for industrial practice.
【０００５】このように、二酸化炭素の接触水素化につ
いての技術は未だ確立されておらず、また二酸化炭素か
ら炭化水素を製造するための有効な触媒等も知られてい
ないというのが現状である。As described above, the technology for catalytic hydrogenation of carbon dioxide has not been established yet, and no effective catalyst for producing hydrocarbons from carbon dioxide is known. .
【０００６】[0006]
【発明が解決しようとする課題】二酸化炭素を「リサイ
クルエネルギー」の原料として利用するに際しては、こ
の原料から得られる炭化水素が化石燃料と同等のエネル
ギー密度をもっていることが望ましい。ここで、二酸化
炭素の接触水素化反応において生成する物質としてメタ
ノール、メタン及びＣ2 以上の炭化水素が挙げられる
が、常温常圧における単位体積当たりのエネルギー密度
の順序は、炭化水素（液状）＞メタノール＞＞メタンの
順となる。そのため、輸送性、貯蔵性等においても有利
な液状炭化水素を製造することが最も有効である。When carbon dioxide is used as a raw material for "recycling energy", it is desirable that the hydrocarbon obtained from this raw material has an energy density equivalent to that of fossil fuel. Here, examples of substances produced in the catalytic hydrogenation reaction of carbon dioxide include methanol, methane, and C 2 or higher hydrocarbons. The order of energy density per unit volume at room temperature and normal pressure is hydrocarbon (liquid)> Methanol >>> methane in that order. Therefore, it is most effective to produce a liquid hydrocarbon which is also advantageous in terms of transportability, storability and the like.
【０００７】従って、本発明は、二酸化炭素及び水素か
ら高収率で液状炭化水素を生成させることができるとと
もに、長期間高い活性が維持できる触媒、並びに二酸化
炭素及び水素から液状炭化水素を製造する方法を提供す
ることを主目的とする。Therefore, the present invention produces a liquid hydrocarbon from carbon dioxide and hydrogen in a high yield and can maintain a high activity for a long time, and a liquid hydrocarbon from carbon dioxide and hydrogen. The main purpose is to provide a method.
【０００８】[0008]
【課題を解決するための手段】本発明者は、上記目的を
達成すべく研究を重ねた結果、銅と鉄とを主成分とし、
これに特定の金属を含有させた触媒が上記目的を達成で
きることを見出し、本発明を完成するに至った。Means for Solving the Problems As a result of repeated research to achieve the above object, the present inventor has found that copper and iron are the main components,
The inventors have found that a catalyst containing a specific metal can achieve the above object, and completed the present invention.
【０００９】即ち、本発明は、下記の炭化水素製造用触
媒および炭化水素の製造方法を提供するものである； １．二酸化炭素と水素とを原料として炭化水素を製造す
るための触媒であって、鉄９９〜１：銅１〜９９（原子
比）からなる主成分と主成分の０．０１〜５％の割合で
アルカリ金属およびアルカリ土類金属の少なくとも１種
とを含むことを特徴とする炭化水素製造用触媒。 ２．二酸化炭素と水素とを原料として炭化水素を製造す
るに際し、鉄９９〜１：銅１〜９９（原子比）からなる
主成分と主成分の０．０１〜５％の割合でアルカリ金属
およびアルカリ土類金属の少なくとも１種とを含む触媒
の存在下に二酸化炭素と水素とを反応させることを特徴
とする方法。That is, the present invention provides the following catalyst for producing hydrocarbons and a method for producing hydrocarbons: A catalyst for producing a hydrocarbon using carbon dioxide and hydrogen as raw materials, the main component being iron 99-1: copper 1-99 (atomic ratio) and the proportion of 0.01-5% of the main component. A catalyst for hydrocarbon production, comprising at least one kind of alkali metal and alkaline earth metal. 2. When producing hydrocarbons using carbon dioxide and hydrogen as raw materials, the main component consisting of iron 99-1: copper 1-99 (atomic ratio) and the alkali metal and alkaline earth in a proportion of 0.01-5% of the main component. A method comprising reacting carbon dioxide and hydrogen in the presence of a catalyst containing at least one kind of metal.
【００１０】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１１】まず、本発明の触媒は、鉄及び銅を主成分
とし、さらにアルカリ金属及びアルカリ土類金属の少な
くとも１種を含むものである。鉄と銅との比率は、通常
９９：１〜１：９９程度、好ましくは９５：５〜１０：
９０とする。上記比率が範囲外となる場合、例えば鉄の
比率が極端に多い場合は二酸化炭素の転化率が低下す
る。また例えば、銅の比率が多い場合は液状炭化水素の
選択率が低下する。First, the catalyst of the present invention contains iron and copper as main components, and further contains at least one kind of alkali metal and alkaline earth metal. The ratio of iron to copper is usually about 99: 1 to 1:99, preferably 95: 5 to 10 :.
90. When the ratio is out of the range, for example, when the ratio of iron is extremely large, the conversion rate of carbon dioxide decreases. Further, for example, when the proportion of copper is large, the selectivity of liquid hydrocarbons is lowered.
【００１２】アルカリ金属・アルカリ土類金属として
は、ナトリウム、カリウム、マグネシウム、カルシウム
等いずれのものも適用できる。上記主成分に対するアル
カリ金属・アルカリ土類金属の比率は、通常０．０１〜
５％程度、好ましくは０．１〜３％程度とする。アルカ
リ金属・アルカリ土類金属が少なすぎると二酸化炭素の
転化率が低下し、一方多すぎると耐久性が低下するので
好ましくない。As the alkali metal or alkaline earth metal, any of sodium, potassium, magnesium, calcium and the like can be applied. The ratio of alkali metal / alkaline earth metal to the main component is usually 0.01 to
It is set to about 5%, preferably about 0.1 to 3%. If the amount of the alkali metal or alkaline earth metal is too small, the conversion rate of carbon dioxide will decrease, while if it is too large, the durability will decrease, such being undesirable.
【００１３】本発明触媒は、その形状は特に限定され
ず、例えば粒状、成形体等の形状で使用できる。なお、
粒状で用いる場合は、原料ガスの流量を考慮してその粒
度を８〜４０メッシュ（約０．６４〜２．４ｍｍ）程度
とすることが望ましい。The shape of the catalyst of the present invention is not particularly limited, and it can be used in the shape of, for example, granules or molded bodies. In addition,
When used in a granular form, it is desirable that the grain size be about 8 to 40 mesh (about 0.64 to 2.4 mm) in consideration of the flow rate of the raw material gas.
【００１４】また、本発明の触媒は、そのままでも使用
できるが、例えばシリカ、アルミナ等の通常の触媒にお
ける担体として用いられる物質に担持させて用いても良
い。この場合、担持量は通常２〜１０％程度とする。Although the catalyst of the present invention can be used as it is, it may be used by supporting it on a substance such as silica or alumina which is used as a carrier in a usual catalyst. In this case, the supported amount is usually about 2 to 10%.
【００１５】上記触媒の製造方法は、例えば次のように
して行なうことができる。すなわち、硝酸鉄水溶液と硝
酸銅水溶液との混合水溶液に、水酸化ナトリウム等のア
ルカリ金属・アルカリ土類金属の水溶性化合物を溶解さ
せた水溶液を滴下してｐＨ７〜１０程度とする。その
後、室温で５〜１５時間程度熟成し、生成した共沈殿物
を濾過・洗浄した後、１００〜１２０℃程度で６〜１０
時間程度乾燥し、さらに３５０〜４００℃程度で３〜５
時間程度焼成することにより本発明触媒が得られる。な
お、担体を用いる場合には、含浸法等によって担持を行
なえば良い。The method for producing the above catalyst can be performed, for example, as follows. That is, an aqueous solution in which a water-soluble compound of an alkali metal or an alkaline earth metal such as sodium hydroxide is dissolved is added dropwise to a mixed aqueous solution of an aqueous iron nitrate solution and an aqueous copper nitrate solution to adjust the pH to about 7 to 10. Then, after aging at room temperature for about 5 to 15 hours, filtering and washing the generated coprecipitate, at about 100 to 120 ° C. for 6 to 10 hours.
Dry for about 3 hours, and then at 350-400 ℃ for 3-5
The catalyst of the present invention can be obtained by calcination for about an hour. When a carrier is used, it may be supported by an impregnation method or the like.
【００１６】本発明による炭化水素の製造方法において
は、鉄及び銅を主成分とし、さらにアルカリ金属及びア
ルカリ土類金属の少なくとも１種を含む触媒の存在下
に、二酸化炭素と水素とを反応させる。上記原料は、そ
の二酸化炭素と水素の比率が１／６〜１／３程度とす
る。In the method for producing hydrocarbons according to the present invention, carbon dioxide and hydrogen are reacted in the presence of a catalyst containing iron and copper as main components and at least one of alkali metals and alkaline earth metals. . The above raw material has a carbon dioxide to hydrogen ratio of about 1/6 to 1/3.
【００１７】反応方式は特に制限はなく、例えば上記触
媒の粒状物等を充填した反応装置中に上記原料を通過さ
せる方法（固定床流通方式）によれば良い。この場合の
反応条件としては、温度は通常１５０〜５００℃程度、
好ましくは２００〜４００℃とし、圧力は１〜７０気圧
程度、好ましくは１０〜５０気圧とし、及びＳＶ１００
０〜１２０００ｍｌ／ｇ−ｃａｔ・ｈ程度とする。本発
明の製造方法における二酸化炭素の炭化水素への転化率
は、用いる触媒、反応条件等によって異なるが通常３０
〜３５％程度である。また、本発明の製造方法によって
得られる液状炭化水素としては、触媒の種類、反応条件
等によって一様ではないが、主に例えばペンタン、ヘキ
サン、ヘプタン、オクタン、ノナン等が例示される。The reaction system is not particularly limited, and for example, a method of passing the above-mentioned raw materials through a reaction apparatus filled with the above-mentioned catalyst particles (fixed bed circulation method) may be used. As the reaction conditions in this case, the temperature is usually about 150 to 500 ° C,
The pressure is preferably 200 to 400 ° C., the pressure is about 1 to 70 atm, preferably 10 to 50 atm, and SV100.
It is about 0 to 12000 ml / g-cat · h. Although the conversion rate of carbon dioxide to hydrocarbons in the production method of the present invention varies depending on the catalyst used, reaction conditions and the like, it is usually 30
It is about 35%. The liquid hydrocarbon obtained by the production method of the present invention is not uniform depending on the type of catalyst, reaction conditions, etc., but mainly pentane, hexane, heptane, octane, nonane, etc. are exemplified.
【００１８】[0018]
【作用】本発明における触媒において、特に、銅は水素
を活性化し、反応し易い状態にする作用を有し、鉄は二
価の銅イオンを金属銅に還元する作用と、炭化水素が生
成して成長する過程でその反応場を提供する作用とを有
する。In the catalyst of the present invention, in particular, copper has an action of activating hydrogen to make it easily reactive, and iron has the action of reducing divalent copper ions to metallic copper and the formation of hydrocarbons. And the action of providing the reaction field in the process of growing.
【００１９】[0019]
【発明の効果】本発明の触媒及び炭化水素の製造方法に
よれば、二酸化炭素及び水素から高収率で液状炭化水素
を合成することができる。しかも、安定性に優れている
ので、本発明触媒は、高温における長期間の使用に対し
ても高い活性を維持することが可能である。According to the catalyst and the method for producing hydrocarbons of the present invention, liquid hydrocarbons can be synthesized from carbon dioxide and hydrogen in high yield. Moreover, because of its excellent stability, the catalyst of the present invention can maintain high activity even when used for a long period of time at high temperature.
【００２０】従って、本発明触媒は、民生用燃料供給、
化成品製造工業、エネルギー変換工業などの各種化学工
業分野において極めて有用であり、地球の温暖化問題の
解決、石油資源の節約等に大きく貢献できるものであ
る。Therefore, the catalyst of the present invention is used for supplying fuel for consumer use,
It is extremely useful in various chemical industries, such as the chemical product manufacturing industry and the energy conversion industry, and can greatly contribute to solving the global warming problem and saving petroleum resources.
【００２１】[0021]
【実施例】以下に実施例および比較例を示し、本発明の
特徴とするところをより一層明確にする。EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention.
【００２２】実施例１ 銅−鉄系触媒（Ｆｅ／Ｃｕ＝７／３ 原子比）を以下の
ようにして製造した。硝酸鉄九水和物２８．３ｇと硝酸
銅三水和物７．２６ｇを蒸留水に溶解させて全容を１０
０ｍｌとした。これに、水酸化カリウム５６．１ｇを蒸
留水に溶解させて全容を１０００ｍｌとした溶液を湯浴
中攪拌しながらｐＨ＝８（７０℃）となるまで滴下し
た。その後、室温で１５時間攪拌した後、濾過洗浄し、
１２０℃で６時間乾燥後、３５０℃で３時間焼成した。Example 1 A copper-iron catalyst (Fe / Cu = 7/3 atomic ratio) was produced as follows. 28.3 g of iron nitrate nonahydrate and 7.26 g of copper nitrate trihydrate were dissolved in distilled water to obtain a total volume of 10
The volume was 0 ml. A solution of 56.1 g of potassium hydroxide dissolved in distilled water to a total volume of 1000 ml was added dropwise to this while stirring in a water bath until pH = 8 (70 ° C.). After that, the mixture is stirred at room temperature for 15 hours, filtered and washed,
After drying at 120 ° C. for 6 hours, it was baked at 350 ° C. for 3 hours.
【００２３】このようにして得られた粒状触媒１ｇ（２
４−４０メッシュ）を内径１ｃｍのステンレススチール
製反応管に充填し、固定床加圧流通反応装置にセットし
た。これに反応ガス（Ｈ2 ／ＣＯ2 ＝３／１）を５０ｋ
ｇ／ｃｍ2 、ＳＶ＝３０００ｍｌ／ｇ−ｃａｔ・ｈで供
給し、表１に示す各反応温度における反応生成物の分布
をオンラインガスクロマトグラフにより分析した。その
結果を表１に示す。1 g (2 g of the granular catalyst thus obtained)
4-40 mesh) was filled in a stainless steel reaction tube having an inner diameter of 1 cm and set in a fixed bed pressure distribution reactor. 50 k of reaction gas (H 2 / CO 2 = 3/1)
It was supplied at g / cm 2 and SV = 3000 ml / g-cat · h, and the distribution of reaction products at each reaction temperature shown in Table 1 was analyzed by an online gas chromatograph. Table 1 shows the results.
【００２４】[0024]
【表１】 実施例２ 水酸化カリウム５６．１ｇの代わりに水酸化ナトリウム
４０ｇを用いた以外は実施例１と同様にして得られた触
媒を用い、実施例１と同様の反応方式に従って、この触
媒に反応ガス（Ｈ2 ／ＣＯ2 ＝３／１）を４００℃、Ｓ
Ｖ＝３０００ｍｌ／ｇ−ｃａｔ・ｈで接触させ、反応圧
力の変化による反応生成物の分布をオンラインガスクロ
マトグラフにより分析した。その結果を表２に示す。[Table 1] Example 2 A catalyst obtained in the same manner as in Example 1 was used except that 40 g of sodium hydroxide was used instead of 56.1 g of potassium hydroxide, and a reaction gas was added to this catalyst according to the same reaction scheme as in Example 1. (H 2 / CO 2 = 3/1) at 400 ° C., S
The contact was made at V = 3000 ml / g-cat · h, and the distribution of reaction products due to changes in the reaction pressure was analyzed by an online gas chromatograph. The results are shown in Table 2.
【００２５】[0025]
【表２】 実施例３ 表３に示すように銅と鉄の比率を変えた以外は実施例２
と同様にして触媒を製造した。得られた触媒１ｇを用
い、実施例１と同様の反応方式に従って、これに反応ガ
ス（Ｈ2 ／ＣＯ2 ＝３）を４００℃、５０ｋｇ／ｃｍ2
でＳＶ＝３０００ｍｌ／ｇ−ｃａｔ・ｈで接触させ、各
触媒における反応生成物の分布をオンラインガスクロマ
トグラフにより分析した。その結果を表３に示す。[Table 2] Example 3 Example 2 except that the ratio of copper to iron was changed as shown in Table 3.
A catalyst was produced in the same manner as in. Using 1 g of the obtained catalyst, a reaction gas (H 2 / CO 2 = 3) was added thereto at 400 ° C. and 50 kg / cm 2 according to the same reaction method as in Example 1.
SV = 3000 ml / g-cat · h, and the distribution of the reaction product in each catalyst was analyzed by online gas chromatography. Table 3 shows the results.
【００２６】[0026]
【表３】 試験例１ 表４に示す組成（原子％）の触媒Ａ〜Ｄを実施例１と同
様にして調製し、これらに反応ガス（Ｈ2 ／ＣＯ2 ＝３
／１）を４００℃、５０ｋｇ／ｃｍ2 でＳＶ＝３０００
ｍｌ／ｇ−ｃａｔ・ｈで供給し、各触媒における反応生
成物の分布をオンラインガスクロマトグラフにより分析
した。その結果を表４に示す。[Table 3] Test Example 1 Catalysts A to D having the compositions (atomic%) shown in Table 4 were prepared in the same manner as in Example 1 and reaction gases (H 2 / CO 2 = 3) were prepared.
/ 1) at 400 ° C. and 50 kg / cm 2 SV = 3000
It was supplied at ml / g-cat · h, and the distribution of reaction products in each catalyst was analyzed by an online gas chromatograph. The results are shown in Table 4.
【００２７】[0027]
【表４】 試験例２ 実施例３で得られた本発明触媒（Ｆｅ／Ｃｕ＝５／５
原子比）を用い、これに反応ガス（Ｈ2 ／ＣＯ2 ＝３／
１）を４００℃、５０ｋｇ／ｃｍ2 、ＳＶ＝３０００ｍ
ｌ／ｇ−ｃａｔ・ｈで供給し、時間の経過による転化率
の変化について調べた。その結果を表５に示す。[Table 4] Test Example 2 The catalyst of the present invention obtained in Example 3 (Fe / Cu = 5/5
Atomic ratio is used, and the reaction gas (H 2 / CO 2 = 3 /
1) at 400 ° C., 50 kg / cm 2 , SV = 3000 m
It was supplied at 1 / g-cat · h, and the change in conversion rate over time was examined. The results are shown in Table 5.
【００２８】[0028]
【表５】 [Table 5]
Claims (2)
を製造するための触媒であって、鉄９９〜１：銅１〜９
９（原子比）からなる主成分と主成分の０．０１〜５％
の割合でアルカリ金属およびアルカリ土類金属の少なく
とも１種とを含むことを特徴とする炭化水素製造用触
媒。1. A catalyst for producing a hydrocarbon using carbon dioxide and hydrogen as raw materials, which is iron 99-1: copper 1-9.
Main component consisting of 9 (atomic ratio) and 0.01 to 5% of the main component
A catalyst for hydrocarbon production, comprising at least one of an alkali metal and an alkaline earth metal in a proportion of.
を製造するに際し、鉄９９〜１：銅１〜９９（原子比）
からなる主成分と主成分の０．０１〜５％の割合でアル
カリ金属およびアルカリ土類金属の少なくとも１種とを
含む触媒の存在下に二酸化炭素と水素とを反応させるこ
とを特徴とする方法。2. When producing hydrocarbons using carbon dioxide and hydrogen as raw materials, iron 99-1: copper 1-99 (atomic ratio)
A method of reacting carbon dioxide and hydrogen in the presence of a catalyst containing a main component consisting of: and a catalyst containing 0.01 to 5% of the main component and at least one of an alkali metal and an alkaline earth metal. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5254988A JP2545734B2 (en) | 1993-09-16 | 1993-09-16 | Hydrocarbon producing catalyst and hydrocarbon producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5254988A JP2545734B2 (en) | 1993-09-16 | 1993-09-16 | Hydrocarbon producing catalyst and hydrocarbon producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0780309A JPH0780309A (en) | 1995-03-28 |
| JP2545734B2 true JP2545734B2 (en) | 1996-10-23 |
Family
ID=17272654
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5254988A Expired - Lifetime JP2545734B2 (en) | 1993-09-16 | 1993-09-16 | Hydrocarbon producing catalyst and hydrocarbon producing method |
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| Country | Link |
|---|---|
| JP (1) | JP2545734B2 (en) |
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|---|---|---|---|---|
| JP5747499B2 (en) * | 2009-12-25 | 2015-07-15 | 東ソー株式会社 | Hydrogenation catalyst, method for producing the same, and use thereof |
| JP2015077575A (en) * | 2013-10-18 | 2015-04-23 | 岩谷産業株式会社 | Hydrocarbon synthesis catalyst, and hydrocarbon production device using the same and method for producing hydrocarbon |
| JP2016132644A (en) * | 2015-01-21 | 2016-07-25 | 岩谷産業株式会社 | Hydrocarbon production apparatus and hydrocarbon production method |
| JP6599223B2 (en) * | 2015-12-16 | 2019-10-30 | 岩谷産業株式会社 | Method for producing hydrocarbon synthesis catalyst, method for producing hydrocarbon |
| JP6978844B2 (en) * | 2017-03-22 | 2021-12-08 | 岩谷産業株式会社 | Hydrocarbon synthesis catalyst manufacturing method, hydrocarbon manufacturing method |
| JP7392854B2 (en) * | 2020-06-22 | 2023-12-06 | 株式会社Ihi | Hydrocarbon generation system |
| JP2022064671A (en) * | 2020-10-14 | 2022-04-26 | 国立研究開発法人産業技術総合研究所 | Production method of hydrocarbon |
| WO2022138910A1 (en) | 2020-12-25 | 2022-06-30 | Ｅｎｅｏｓ株式会社 | Hydrocarbon production method |
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| JPS536862A (en) * | 1976-07-08 | 1978-01-21 | Nippon Electric Co | Method of making thinnfilm resistor |
| JPS624438A (en) * | 1985-06-28 | 1987-01-10 | Mitsubishi Acetate Co Ltd | Composition generating sol-gel transition |
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