JPH0352825A - Method for producing propane by hydrogenation of carbon dioxide - Google Patents

Method for producing propane by hydrogenation of carbon dioxide

Info

Publication number
JPH0352825A
JPH0352825A JP18449689A JP18449689A JPH0352825A JP H0352825 A JPH0352825 A JP H0352825A JP 18449689 A JP18449689 A JP 18449689A JP 18449689 A JP18449689 A JP 18449689A JP H0352825 A JPH0352825 A JP H0352825A
Authority
JP
Japan
Prior art keywords
carbon dioxide
metal
propane
catalyst
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP18449689A
Other languages
Japanese (ja)
Other versions
JP2841500B2 (en
Inventor
Tsutomu Shikada
鹿田　勉
Minoru Asanuma
稔 浅沼
Yakudo Tachibana
橘　躍動
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan Ltd
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Filing date
Publication date
Application filed by NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Priority to JP1184496A priority Critical patent/JP2841500B2/en
Publication of JPH0352825A publication Critical patent/JPH0352825A/en
Application granted granted Critical
Publication of JP2841500B2 publication Critical patent/JP2841500B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C07C2529/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • C07C2529/24—Iron group metals or copper

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

PURPOSE:To selectively obtain propane by reaction between CO2 and H2 in the presence of a catalyst consisting of a mixture of Cu, Zn or Cr or oxide thereof, etc., and a crystalline aluminosilicate. CONSTITUTION:The objective propane can be obtained by reaction between CO2 and H2 at the molar ratio H2/CO2=0.1-10 at 250-400 deg.C under 5-70kg/cm<2>G in the presence of a catalyst consisting of a mixture of (A) a metal having such catalytic activity as to hydrogenate CO2 or its compound and (B) a crystalline aluminosilicate. Said metal is e.g. Cu, Zn, Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Pa, Ir or Pt; said compound is e.g. an oxide, carbide or nitride, pref. an oxide of Cu, Zn or Cr. The component B is pref. zeolite with mordenite structure. And excess use such that the weight ratio B/A=(1-10):1 is more effective.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、二酸化炭素と水素とを反応させることにより
プロパンを製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing propane by reacting carbon dioxide and hydrogen.

〔従来の技術〕[Conventional technology]

二酸化炭素を接触的に水素化して炭化水素を製造する方
法は、これまでいくつか知られている。Several methods have been known to catalytically hydrogenate carbon dioxide to produce hydrocarbons.

例えば、ミクローマクロ二元構造を有するシリカ担体に
、ニッケル、酸化ランタンおよびルテニウムを担持した
触媒を用い、メタンを製造する方法（特公昭６１−２９
７７８号公報）、ロジウム、ニッケル等の遷移金属を添
加した鉄−グラファイト層間化合物を触媒として、エタ
ンおよびメタンに富む高発熱量燃料を製造する方法（特
開昭５３−７４５０２号公報）、鉄、コバルトまたはニ
ッケルを触媒として、液状炭化水素を合或する方法（フ
ィッシャートロプシュ合或法）、一酸化炭素還元触媒と
少なくとも１２のシリカ対アルξナ比をもつ結晶性アル
ミノシリケートの混合物を触媒とし、液状炭化水素を合
戒する方法（特開昭５０−１４２５０２号公報）などが
ある。For example, a method for producing methane using a catalyst in which nickel, lanthanum oxide, and ruthenium are supported on a silica carrier having a micro-macro binary structure (Japanese Patent Publication No. 61-29
778 Publication), a method for producing a high calorific value fuel rich in ethane and methane using an iron-graphite intercalation compound added with transition metals such as rhodium and nickel as a catalyst (Japanese Unexamined Patent Publication No. 53-74502), iron, A method of combining liquid hydrocarbons using cobalt or nickel as a catalyst (Fischer-Tropsch synthesis method), using a mixture of a carbon monoxide reduction catalyst and a crystalline aluminosilicate having a silica to alumina ratio of at least 12 as a catalyst; There is a method of mixing liquid hydrocarbons (Japanese Unexamined Patent Publication No. 142502/1983).

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

しかし前述の方法においては以下の問題点を有する。す
なわち、特公昭６１−２９７７８号公報記載の方法およ
び特開昭５３−７４５０２号公報記載の方法においては
、それぞれメタンおよびメタンとエタンが生成物の大部
分を占め、プロパンはほとんど生威しない。フィッシャ
ートロブシュ法においては、生成物の炭素数がいわゆる
シュルツ・フローリー則に従って、炭素数１のメタンか
ら炭素数５０程度のワックスまで幅広い炭素数分布を与
え、特定の範囲の炭化水素を選択的に合戒することはで
きない。However, the above method has the following problems. That is, in the method described in Japanese Patent Publication No. 61-29778 and the method described in Japanese Patent Application Laid-Open No. 53-74502, methane and methane and ethane account for the majority of the products, respectively, and propane is hardly viable. In the Fischer-Trobsch method, the carbon number of the product follows the so-called Schulz-Flory law, giving a wide carbon number distribution from methane with 1 carbon number to wax with about 50 carbon atoms, and selectively selecting hydrocarbons in a specific range. It is not possible to join together.

特開昭５０−１４２５０２号公報記載の方法においては
、ガソリン沸点範囲の炭化水素が主生成物であり、低級
炭化水素の生或は少ない。また特公昭６１−２９７７８
号公報記載の方法を除く他の方法は、いずれも反応原料
として一酸化炭素と水素の混合ガス、またはこれにさら
に二酸化炭素が含有される混合ガスを使用することを基
本とするものであり、一酸化炭素を含まない二酸化炭素
と水素の混合ガスを対象としたものとは言い難い。In the method described in JP-A-50-142502, hydrocarbons in the gasoline boiling point range are the main products, and lower hydrocarbons are produced in small quantities. Also, special public service No. 61-29778
All other methods except for the method described in the publication are based on the use of a mixed gas of carbon monoxide and hydrogen, or a mixed gas further containing carbon dioxide, as the reaction raw material, It is hard to say that it is intended for a mixed gas of carbon dioxide and hydrogen that does not contain carbon monoxide.

このように従来の方法においては、メタン、エタンある
いは液状炭化水素の製造を意図するものであり、プロパ
ンの製造に関しては未だ満足する方法が開発されていな
い。As described above, conventional methods are intended to produce methane, ethane, or liquid hydrocarbons, and a satisfactory method for producing propane has not yet been developed.

本発明はこのような問題点を解決して二酸化炭素と水素
からプロパンを選択的に製造する方法を提供するもので
ある。The present invention solves these problems and provides a method for selectively producing propane from carbon dioxide and hydrogen.

゜〔課題を解決するための手段〕 かかる本発明は、二酸化炭素を水素化する触媒活性を有
する金属または金属化合物と、結晶性アル稟ノシリケー
トとの混合物から或る触媒組威物の存在下で、二酸化炭
素と水素とを反応させることを特徴とするプロパンの製
造方法に関するものである。[Means for Solving the Problems] The present invention provides a method for hydrogenating carbon dioxide in the presence of a certain catalyst composition from a mixture of a metal or a metal compound having catalytic activity for hydrogenating carbon dioxide and a crystalline alkinosilicate. The present invention relates to a method for producing propane, which is characterized by reacting carbon dioxide and hydrogen.

本発明で使用される触媒は、上述したように特定の金属
または金属化合物と結晶性アルミノシリケートの両成分
を組み合せて戒るものである。二酸化炭素を水素化する
触媒活性を有する金属としては、銅、亜鉛、クロム、モ
リブデン、タングステン、鉄、コバルト、ニッケル、ル
テニウム、ロジウム、パラジウム、イリジウム、白金等
の金属を挙げることができる。また、上記活性を有する
金属化合物としては上記の金属の酸化物、炭化物、窒化
物及び硫化物をあげることができる。これらを単独で用
いるばか２種以上を混合して用いることもできる。これ
らのなかで特に銅、亜鉛、クロムの酸化物が好ましい。As mentioned above, the catalyst used in the present invention is a combination of a specific metal or metal compound and a crystalline aluminosilicate. Examples of metals having catalytic activity for hydrogenating carbon dioxide include metals such as copper, zinc, chromium, molybdenum, tungsten, iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, and platinum. Further, examples of the metal compound having the above-mentioned activity include oxides, carbides, nitrides, and sulfides of the above-mentioned metals. These may be used alone or two or more may be used in combination. Among these, oxides of copper, zinc, and chromium are particularly preferred.

これらの金属及び金属化合物は一般の金属触媒あるいは
金属化合物触媒を調製する方法に従って調製することが
できる。These metals and metal compounds can be prepared according to methods for preparing general metal catalysts or metal compound catalysts.

一方、本発明で使用される触媒のもう一つの戒分である
結晶性アルミノシリケートとしてはＸ型、Ｙ型、Ｌ型、
モルデナイト等のゼオライトが用いられる。結晶性アル
ミノシリケートにおけるシリカ対アルミナの比はモル比
で５〜３０、すなわち、ＳｉＯｚがＡｌｚＯｚの５倍モ
ルから３０倍モルのものが使用される。特にモルデナイ
ト構造を有するゼオライトが好ましい。これらのゼオラ
イトは陽イオンがＨ型、金属イオン型、アンモニウム型
で使用される。金属イオンには前述の触媒活性を有する
金属等のイオンを用いることが好ましい。このような結
晶性アルミノシリケートも公知の方法に従って調製する
ことができ、例えば当該ゼオライトを必要によりイオン
交換させて所定のイオン型にした後、焼威して仕上げれ
ばよい。On the other hand, crystalline aluminosilicates, which are another component of the catalyst used in the present invention, include X-type, Y-type, L-type,
Zeolites such as mordenite are used. The ratio of silica to alumina in the crystalline aluminosilicate used is 5 to 30 in terms of molar ratio, that is, SiOz is 5 times to 30 times mole as much as AlzOz. Zeolite having a mordenite structure is particularly preferred. These zeolites are used with cations in H type, metal ion type, and ammonium type. As the metal ion, it is preferable to use an ion such as a metal having the above-mentioned catalytic activity. Such a crystalline aluminosilicate can also be prepared according to a known method. For example, the zeolite may be ion-exchanged if necessary to form a predetermined ion type, and then finished by burning.

上記触媒にはさらに他の戒分を含有させることができる
。例えば前述の金属または金属化合物触媒にさらに他の
金属化合物を併用することができる。このような金属化
合物は例えば助触媒作用を有するものであり、アルカリ
金属、アルカリ土類金属、土類金属、希土類等の化合物
などを挙げることができる。また、既存の触媒、例えば
メタノール合成触媒、混合アルコール合或触媒等を添加
することもできる。これらの他の金属化合物及びアルコ
ール合成触媒の含有量は５０重量％未満とする。The above catalyst may further contain other components. For example, other metal compounds can be used in combination with the above-mentioned metal or metal compound catalyst. Such metal compounds have, for example, a cocatalyst effect, and include compounds of alkali metals, alkaline earth metals, earth metals, rare earths, and the like. Furthermore, existing catalysts such as methanol synthesis catalysts, mixed alcohol synthesis catalysts, etc. can also be added. The content of these other metal compounds and alcohol synthesis catalyst is less than 50% by weight.

前述の両成分の混合方法は、両戒分を粉末にしたのち圧
縮戒形してペレット化してもよく、それぞれ戒分をペレ
ット化後に混合してもよく、あるいは結晶性アルミノシ
リケートに金属または金属化合物をイオン交換または含
浸担持するなどいずれの方法でもよい。The above-mentioned method of mixing the two ingredients may be as follows: the two components may be powdered and then compressed into pellets, the respective components may be pelletized and then mixed, or crystalline aluminosilicate may be mixed with metal or metal. Any method such as supporting the compound by ion exchange or impregnation may be used.

両戒分の混合割合は、特に限定されることなく各戒分の
種類あるいは反応条件等に応じて適宜選定すればよいが
通常は重量比で１：１〜２０：１程度であり、好ましく
は１：ｌ〜１０：ｌ程度であり、結晶性アルミノシリケ
ートが過剰の方が有効である。The mixing ratio of both precepts is not particularly limited and may be appropriately selected depending on the type of each precept or reaction conditions, but it is usually about 1:1 to 20:1 by weight, and is preferably about 1:1 to 20:1. The ratio is about 1:l to 10:l, and an excess of crystalline aluminosilicate is more effective.

このようにして得られた触媒に、二酸化炭素と水素を接
触させることにより、プロパンが選択的に得られる。二
酸化炭素と水素の混合割合（Ｈ．／Ｃｏ．比）はモル比
で０．０５〜２０の範囲、好ましくは０．１〜１０の範
囲である。二酸化炭素と水素は混合ガスとして反応塔に
供給してもよく、また、別々に供給してもよい。また二
酸化炭素と水素のほかに窒素、ヘリウム、アルゴン等の
不活性ガスを存在させてもよい。反応は常圧下または加
圧下で行われ、好ましくは５〜７０ｋｇ／ｃｍ”　−　
Ｇで行われる。By bringing carbon dioxide and hydrogen into contact with the thus obtained catalyst, propane can be selectively obtained. The mixing ratio of carbon dioxide and hydrogen (H./Co. ratio) is in the range of 0.05 to 20 in terms of molar ratio, preferably in the range of 0.1 to 10. Carbon dioxide and hydrogen may be supplied to the reaction tower as a mixed gas, or may be supplied separately. In addition to carbon dioxide and hydrogen, an inert gas such as nitrogen, helium, or argon may also be present. The reaction is carried out under normal pressure or increased pressure, preferably 5 to 70 kg/cm"-
It is done in G.

反応温度は２００〜４５０゜Ｃ、好ましくは２５０〜４
００゜Ｃである。The reaction temperature is 200-450°C, preferably 250-450°C.
It is 00°C.

本発明による；′触媒は、固定床、流動床、移動床のい
ずれの反応方式においても用いることができる。According to the present invention, the catalyst can be used in any fixed bed, fluidized bed or moving bed reaction system.

〔作用〕[Effect]

本発明における触媒は、二酸化炭素を水素化する触媒活
性を有する金属または金属化合物と、結晶性アルξノシ
リケートとを混合することを特徴とするものであり、こ
の混合により以下の作用が発現する。The catalyst of the present invention is characterized by mixing a metal or metal compound having catalytic activity for hydrogenating carbon dioxide with crystalline alkinosilicate, and the following effects are achieved by this mixing: .

（１）二酸化炭素の水素化反応、例えばアルコール合或
反応は熱力学的な平衡制約を受けるが、上述のような混
合触媒を用いることによって、すなわちアルコール合戒
反応とアルコール転化反応を組み合せることによって、
炭化水素がアルコールの熱力学的平衡値を越えて高い収
率で生成する。(1) Hydrogenation reactions of carbon dioxide, such as alcohol synthesis reactions, are subject to thermodynamic equilibrium constraints, but by using the above-mentioned mixed catalyst, it is possible to combine alcohol synthesis reactions and alcohol conversion reactions. By,
Hydrocarbons are produced in high yields above the thermodynamic equilibrium value of the alcohol.

（２）モルデナイト構造を有する結晶性アルくノシリケ
ートを使用することにより、プロパンが高い選択率で生
戒する。(2) By using a crystalline alkinosilicate having a mordenite structure, propane is produced with high selectivity.

（３）二酸化炭素からのプロパン製造において、二酸化
炭素を一酸化炭素に交換する工程、さらに一酸化炭素を
アルコールに変換する工程を必要とせず、一段で二酸化
炭素からプロパンを合戒することができる。なお、反応
の中間体であるアルコールは二酸化炭素が一酸化炭素に
還元された後、一酸化炭素と水素から生成するものでは
なく、二酸化炭素と水素から直接生或することが明らか
にされている。このことは二酸化炭素と水素からの炭化
水素合威が一酸化炭素と水素からの炭化水素合戊と根本
的に異なることを示唆するものである。(3) Propane production from carbon dioxide does not require the step of exchanging carbon dioxide to carbon monoxide and the step of converting carbon monoxide to alcohol, making it possible to produce propane from carbon dioxide in one step. . It has been revealed that alcohol, which is an intermediate in the reaction, is not produced from carbon monoxide and hydrogen after carbon dioxide is reduced to carbon monoxide, but is produced directly from carbon dioxide and hydrogen. . This suggests that hydrocarbon synthesis from carbon dioxide and hydrogen is fundamentally different from hydrocarbon synthesis from carbon monoxide and hydrogen.

〔実施例〕〔Example〕

？下、実施例によって本発明を具体的に説明するが、本
発明はこれらの実施例によって制限されるものではない
。? The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

（１）触媒の調製 酸化銅一酸化亜鉛一アルミナ触媒を次のように調製した
。硝酸１ｉｉ１（Ｃｕ（ＮＯＩ）Ｚ・３Ｈ！Ｏ）１８．
１ｇ，硝酸亜鉛（Ｚｎ（ＮＯｚ）ｚ・６｝１ｚＯ）１１
５．２ｇおよび硝酸アルミニウム（ＡＩ　（ＮＯｚ）　
３・９Ｈ．Ｏ）９１．９　ｇを水約５００ｄに溶解した
水溶液と炭酸ナトリウム（Ｎａ・．ｃｏ．）　１５０ｇ
を水約５００ｍｌに溶解した水溶液とを、１約９０゜Ｃ
に保温した水約２２の入ったビーカー中にｐＨが７．０
±０．５に保持されるように調節しながら滴下した。滴
下終了後、生威した沈澱を濾過、洗浄し１２０゜Ｃで２
４時間乾燥した後、空気中３５０゜Ｃで５時間焼或して
目的の触媒を得た。このものの組戒は６１−ｔ％ＣｕＯ
−３２−ｔ％ＺｎＯ−７ｗｔ％Ａｌｚ（ｈであった。(1) Preparation of catalyst A copper oxide zinc monoxide-alumina catalyst was prepared as follows. Nitric acid 1ii1 (Cu(NOI)Z・3H!O)18.
1g, zinc nitrate (Zn(NOz)z・6}1zO) 11
5.2g and aluminum nitrate (AI (NOz)
3.9H. An aqueous solution of 91.9 g of O) dissolved in approximately 500 d of water and 150 g of sodium carbonate (Na.co.)
and an aqueous solution prepared by dissolving it in about 500 ml of water at about 90°C.
The pH is 7.0 in a beaker containing approx.
The mixture was added dropwise while adjusting the amount to be maintained within ±0.5. After the dropwise addition, the precipitate was filtered, washed, and incubated at 120°C for 2 hours.
After drying for 4 hours, the catalyst was calcined in air at 350°C for 5 hours to obtain the desired catalyst. The composition of this thing is 61-t%CuO
-32-t%ZnO-7wt%Alz (h).

結晶性アルミノシリケートは、ナトリウム型モルデナイ
ト（東ソー■製品，　ＴＳＺ−６２０ＮＡＡ，　ＳｉＯ
■／Ａｈ（ｈ＝１４．９）を１モル／ｌの硝酸アンモニ
ウム水溶液で７０゜Ｃ，　　１２０時間イオン交換を行
った後、１２０゜Ｃで２４時間乾燥し、さらに空気中、
５００゜Ｃで６時間焼威して得た。Crystalline aluminosilicate is sodium type mordenite (Tosoh product, TSZ-620NAA, SiO
■/Ah (h=14.9) was ion-exchanged with a 1 mol/l ammonium nitrate aqueous solution at 70°C for 120 hours, then dried at 120°C for 24 hours, and further in air.
It was obtained by burning at 500°C for 6 hours.

（２）反応 ２０〜４０メッシュに分級した上記ＣｕＯ−ＺｎＯ−Ａ
ｌｚＯ３と、圧縮戒形後２０〜４０メッシュに分級した
上記のＨ型モルデナイトを所定量ずつとり、均一に混合
してステンレス製反応器に充填した。これを水素気流中
、３２０゜Ｃで３時間処理した後、所定の反応温度、反
応圧力において、Ｈ２／Ｃｏ２がモル比で２の水素と二
酸化炭素の混合ガスを流通させ、反応を行った。(2) The above CuO-ZnO-A classified into reaction 20-40 mesh
Predetermined amounts of lzO3 and the above-mentioned H-type mordenite, which had been compressed and classified into 20 to 40 mesh, were taken, uniformly mixed, and charged into a stainless steel reactor. After this was treated at 320° C. for 3 hours in a hydrogen stream, a mixed gas of hydrogen and carbon dioxide having a molar ratio of H2/Co2 of 2 was passed through at a predetermined reaction temperature and reaction pressure to carry out the reaction.

以上の操作により得られた反応生戒物ならびに未反応物
はガスクロマトグラフにより分析した。The reacted substances and unreacted substances obtained by the above operations were analyzed by gas chromatography.

結果を第１表に示す。The results are shown in Table 1.

第 ｌ 表 〔発明の効果〕 以上のように、本発明の方法によれば、二酸化炭素と水
素の混合ガスから一酸化炭素を経由せず、一段でプロパ
ンを高い選択率、収率で合成することができる。Table I [Effects of the Invention] As described above, according to the method of the present invention, propane can be synthesized in one step with high selectivity and yield from a mixed gas of carbon dioxide and hydrogen without passing through carbon monoxide. be able to.

また、反応が一段で行なわれるところから反応器も１つ
でよく、反応装置全体をコンパクトにすることができる
。Furthermore, since the reaction is carried out in one stage, only one reactor is required, and the entire reaction apparatus can be made compact.

さらに、近年化石資源の大量消費により大気中への二酸
化炭素の放出量が著しく増大し、これにより大気中の二
酸化炭素の濃度が増大して大気温度の上昇あるいは気候
の激変をもたらす等、環境への影響が懸念されている。Furthermore, the amount of carbon dioxide released into the atmosphere has increased significantly in recent years due to the mass consumption of fossil resources, which has led to an increase in the concentration of carbon dioxide in the atmosphere, causing an increase in atmospheric temperature and drastic changes in the climate. There are concerns about the impact of

このような状況において、本発明の方法は、二酸化炭素
を大気中に放出することなく、再び優れた燃料であると
同時に貴重な化学工業原料であるプロパンに変換する方
法に関するものであり、上述の環境保全の観点からも利
点を有するものである。In this situation, the method of the present invention relates to a method for converting carbon dioxide into propane, which is again an excellent fuel and at the same time a valuable raw material for chemical industry, without releasing it into the atmosphere. This also has advantages from the perspective of environmental conservation.

Claims (1)

【特許請求の範囲】[Claims] 二酸化炭素を水素化する触媒活性を有する金属または金
属化合物と結晶性アルミノシリケートとの混合物から成
る触媒組成物の存在下で、二酸化炭素と水素とを反応さ
せることを特徴とする二酸化炭素の水素化によるプロパ
ンの製造方法Hydrogenation of carbon dioxide, characterized in that carbon dioxide and hydrogen are reacted in the presence of a catalyst composition consisting of a mixture of a crystalline aluminosilicate and a metal or metal compound having catalytic activity for hydrogenating carbon dioxide. Propane production method by
JP1184496A 1989-07-19 1989-07-19 Method for producing propane by hydrogenation of carbon dioxide Expired - Fee Related JP2841500B2 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014051472A (en) * 2012-09-10 2014-03-20 Kitakyushu Foundation For The Advancement Of Industry Science And Technology Method for producing hydrocarbon
EP2862849A1 (en) * 2013-09-23 2015-04-22 i2 Gesellschaft für Innovation mbH Method for the conversion of CO2 to hydrocarbons
JP2019188340A (en) * 2018-04-25 2019-10-31 日本製鉄株式会社 Process for producing catalyst for producing hydrocarbon from carbon dioxide and hydrogen, and process for producing hydrocarbon from carbon dioxide and hydrogen
WO2023199557A1 (en) * 2022-04-15 2023-10-19 古河電気工業株式会社 Catalyst for liquefied petroleum gas synthesis, and method for producing liquefied petroleum gas

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4916194A (en) * 1972-04-15 1974-02-13
JPS50142502A (en) * 1974-04-24 1975-11-17
JPS6313664A (en) * 1986-07-04 1988-01-20 Kubota Ltd Joining method for different kinds of materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4916194A (en) * 1972-04-15 1974-02-13
JPS50142502A (en) * 1974-04-24 1975-11-17
JPS6313664A (en) * 1986-07-04 1988-01-20 Kubota Ltd Joining method for different kinds of materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014051472A (en) * 2012-09-10 2014-03-20 Kitakyushu Foundation For The Advancement Of Industry Science And Technology Method for producing hydrocarbon
EP2862849A1 (en) * 2013-09-23 2015-04-22 i2 Gesellschaft für Innovation mbH Method for the conversion of CO2 to hydrocarbons
JP2019188340A (en) * 2018-04-25 2019-10-31 日本製鉄株式会社 Process for producing catalyst for producing hydrocarbon from carbon dioxide and hydrogen, and process for producing hydrocarbon from carbon dioxide and hydrogen
WO2023199557A1 (en) * 2022-04-15 2023-10-19 古河電気工業株式会社 Catalyst for liquefied petroleum gas synthesis, and method for producing liquefied petroleum gas

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