JPH04368341A - Process for simultaneous production of liquid hydrocarbon mixture and methane - Google Patents
Process for simultaneous production of liquid hydrocarbon mixture and methaneInfo
- Publication number
- JPH04368341A JPH04368341A JP3167407A JP16740791A JPH04368341A JP H04368341 A JPH04368341 A JP H04368341A JP 3167407 A JP3167407 A JP 3167407A JP 16740791 A JP16740791 A JP 16740791A JP H04368341 A JPH04368341 A JP H04368341A
- Authority
- JP
- Japan
- Prior art keywords
- methane
- catalyst
- liquid hydrocarbon
- hydrocarbon mixture
- carbon
- 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.)
- Withdrawn
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 46
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 46
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 230000008569 process Effects 0.000 title description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010457 zeolite Substances 0.000 claims abstract description 29
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- -1 hydrogen ions Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018404 Al2 O3 Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/06—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen in the presence of organic compounds, e.g. hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
Landscapes
- 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
Description
【0001】0001
【産業上の利用分野】本発明は、炭素酸化物を含むガス
状炭化水素を原料として、ガス状炭化水素を芳香族炭化
水素を含む液状炭化水素混合物に変換すると同時に、炭
素酸化物をメタンまたはメタンと一酸化炭素に還元する
ことによって、液状炭化水素混合物とメタンを同時に製
造する方法に関する。[Industrial Application Field] The present invention uses gaseous hydrocarbons containing carbon oxides as raw materials, converts the gaseous hydrocarbons into a liquid hydrocarbon mixture containing aromatic hydrocarbons, and at the same time converts the carbon oxides into methane or A method for simultaneously producing a liquid hydrocarbon mixture and methane by reduction to methane and carbon monoxide.
【0002】0002
【従来の技術】近年、天然ガスの重要性が認識され、そ
の化学的利用に関する研究が盛んに行なわれている。天
然ガスは、その主成分が化学的に安定なメタンであるた
め、そのほとんどが都市ガス、発電用燃料として利用さ
れており、化学工業原料としての利用は限定されている
。しかし、最近触媒の存在下でメタンを部分酸化して、
エタン,エチレンとし、これをさらに反応させて液体燃
料を製造する研究が盛んに行なわれるようになってきた
。この反応において重要なことは、エタン,エチレンの
収率を如何に高くするかということと同時に、一酸化炭
素、二酸化炭素などの炭素酸化物の生成を如何に低く抑
えるかということである。特に二酸化炭素は、炭素化合
物の酸化最終生成物で、反応性に乏しく、これが大量に
生成することは好ましくない。したがって、メタンから
エタン,エチレンを経て液体燃料を製造するプロセスに
おいて、この二酸化炭素をどのように処理するかが、そ
のプロセスの経済性を左右する重要なファクターの1つ
である。その1つとして、二酸化炭素をもとの原料すな
わち、メタンに戻して原料に混合することが考えられる
。BACKGROUND OF THE INVENTION In recent years, the importance of natural gas has been recognized, and research into its chemical utilization has been actively conducted. Since the main component of natural gas is methane, which is chemically stable, most of it is used as city gas and fuel for power generation, and its use as a raw material for the chemical industry is limited. However, recently methane was partially oxidized in the presence of a catalyst,
Research has been actively conducted to produce liquid fuel by further reacting ethane and ethylene. What is important in this reaction is how to increase the yield of ethane and ethylene, and at the same time how to suppress the production of carbon oxides such as carbon monoxide and carbon dioxide. In particular, carbon dioxide is the final product of oxidation of carbon compounds and has poor reactivity, so it is undesirable to generate large amounts of carbon dioxide. Therefore, in the process of producing liquid fuel from methane through ethane and ethylene, how this carbon dioxide is treated is one of the important factors that determines the economic efficiency of the process. One possibility is to return carbon dioxide to the original raw material, ie, methane, and mix it with the raw material.
【0003】二酸化炭素をメタンに変換する反応は公知
であり、そのための触媒も開発されている。したがって
、メタンの部分酸化反応を経て液体燃料を製造するプロ
セスにおいて、この反応を組込むことは容易に考えられ
る。たとえば、オーストラリア国のエドワーズら(’8
9環太平洋国際化学会議、メタンの活性化、変換、利用
に関する3Bシンポジウム講演予稿集、169ページ、
1989)は、本発明者らと同じ目的でメタンからエチ
レンを経て液体燃料を製造するプロセスにおいて、メタ
ンの部分酸化生成物の分離装置のあとに、炭素酸化物を
メタンに変換する工程を設け、メタンの利用効率の向上
を図っている。[0003] Reactions for converting carbon dioxide into methane are known, and catalysts for the conversion have also been developed. Therefore, it is easy to consider incorporating this reaction into a process for producing liquid fuel through a partial oxidation reaction of methane. For example, in Australia, Edwards et al.
9 Pacific Rim International Chemistry Conference, Proceedings of the 3B Symposium on Activation, Conversion, and Utilization of Methane, 169 pages,
(1989), for the same purpose as the present inventors, provided a process for converting carbon oxides to methane after a separation device for partial oxidation products of methane in a process for producing liquid fuel from methane via ethylene. Efforts are being made to improve the efficiency of methane use.
【0004】0004
【発明が解決しようとする課題】しかし、前記の方法の
場合は、炭素酸化物をメタンに変換する反応器が別に必
要であり、かつプロセスが複雑になり、また、コスト的
にも経済性のあるものとは言い難い。したがって、プロ
セスを簡略化し、経済性を高めるための工夫が要望され
る。[Problems to be Solved by the Invention] However, in the case of the above method, a separate reactor is required to convert carbon oxides into methane, the process is complicated, and it is not economical in terms of cost. It's hard to say that it is. Therefore, there is a need for ways to simplify the process and improve economic efficiency.
【0005】本発明の目的は、メタンの部分酸化反応で
生成した炭素酸化物を含むガス状炭化水素を芳香族炭化
水素を含む液状炭化水素混合物に変換するに際し、本変
換反応に活性な触媒と炭素酸化物をメタンまたはメタン
と一酸化炭素へ還元する反応に活性を有する触媒からな
る複合触媒を使用することによって、2つの反応を同時
に進行させ、これによって工程を短縮し、プロセス効率
を向上させた製造方法を提供することにある。An object of the present invention is to convert gaseous hydrocarbons containing carbon oxides produced in a partial oxidation reaction of methane into a liquid hydrocarbon mixture containing aromatic hydrocarbons, using a catalyst active in the conversion reaction. By using a composite catalyst consisting of a catalyst that is active in the reaction of reducing carbon oxides to methane or methane and carbon monoxide, two reactions can proceed simultaneously, thereby shortening the process and improving process efficiency. The purpose of this invention is to provide a manufacturing method.
【0006】[0006]
【課題を解決するための手段】本発明者らは、メタンの
部分酸化反応で生成した炭素酸化物を含むガス状炭化水
素を芳香族炭化水素を含む液状炭化水素混合物に変換す
るに際し、炭素酸化物をメタンまたはメタンと一酸化炭
素に還元し、これを原料系に戻すことによってメタンの
利用効率の向上と、液状炭化水素混合物の収率向上を図
ることを目的として鋭意研究を重ねた結果、ペンタシル
型ゼオライトと炭素酸化物還元触媒からなる複合触媒を
用いることによって、課題を解決できることを見出し、
本発明を完成した。[Means for Solving the Problems] The present inventors have developed a method for oxidizing carbon when converting gaseous hydrocarbons containing carbon oxides produced by a partial oxidation reaction of methane into a liquid hydrocarbon mixture containing aromatic hydrocarbons. As a result of extensive research aimed at improving the utilization efficiency of methane and improving the yield of liquid hydrocarbon mixtures by reducing methane to methane or methane and carbon monoxide and returning this to the raw material system, We discovered that the problem could be solved by using a composite catalyst consisting of pentasil-type zeolite and a carbon oxide reduction catalyst.
The invention has been completed.
【0007】すなわち、本発明の要旨は、メタンを除く
ガス状炭化水素であって、かつ炭素酸化物を含有するも
のを原料とし、触媒を用いて200〜700℃で反応さ
せて芳香族炭化水素を含む液状炭化水素混合物を製造す
る方法において、触媒としてガス状炭化水素を芳香族炭
化水素に変換しうる触媒と炭素酸化物還元触媒からなる
複合触媒を用い、前記ガス状炭化水素を芳香族炭化水素
を含む液状炭化水素混合物に変換すると同時に、炭素酸
化物をメタンまたはメタンと一酸化炭素に還元すること
を特徴とする液状炭化水素混合物とメタンの同時製造方
法に存する。That is, the gist of the present invention is to use gaseous hydrocarbons other than methane and containing carbon oxides as raw materials and react them at 200 to 700°C using a catalyst to produce aromatic hydrocarbons. In a method for producing a liquid hydrocarbon mixture containing a gaseous hydrocarbon, a composite catalyst consisting of a catalyst capable of converting gaseous hydrocarbons into aromatic hydrocarbons and a carbon oxide reduction catalyst is used as a catalyst, and the gaseous hydrocarbons are converted into aromatic hydrocarbons. The present invention relates to a method for simultaneously producing a liquid hydrocarbon mixture and methane, which is characterized in that carbon oxides are reduced to methane or methane and carbon monoxide at the same time as the hydrogen-containing liquid hydrocarbon mixture is converted.
【0008】本発明において、前記複合触媒としては、
ペンタシル型ゼオライト、またはこれを水素イオンもし
くはアルカリ土類金属またはガリウムで変性した触媒と
、ルテニウム,ニッケル,コバルトあるいはモリブテン
よりなる群から選ばれるいずれか一種または二種の金属
もしくはその酸化物からなる複合触媒が用いられる。
これを反応器に充填し、これに炭素酸化物を含む前記ガ
ス状炭化水素を、通常、重量時間空間速度(WHSV)
0.1〜400hr−1、温度200〜700℃、圧力
0.1〜100気圧(10〜10132キロパスカル)
の条件下で通して反応させることにより、液状炭化水素
混合物とメタンを同時に製造することができる。本発明
の方法で特に驚くべきことは、ペンタシル型ゼオライト
を単独で用いた場合に比べて、炭素酸化物還元触媒を混
合することによって芳香族炭化水素の生成率が増加する
ことである。[0008] In the present invention, the composite catalyst includes:
Composite consisting of pentasil type zeolite or a catalyst modified with hydrogen ions, alkaline earth metals or gallium, and one or two metals selected from the group consisting of ruthenium, nickel, cobalt or molybdenum or their oxides. A catalyst is used. This is charged into a reactor, and the gaseous hydrocarbons containing carbon oxides are usually charged at a weight hourly space velocity (WHSV).
0.1 to 400 hr-1, temperature 200 to 700°C, pressure 0.1 to 100 atm (10 to 10132 kilopascals)
A liquid hydrocarbon mixture and methane can be produced simultaneously by reacting the mixture under the following conditions. What is particularly surprising about the process of the present invention is that the production rate of aromatic hydrocarbons is increased by incorporating a carbon oxide reduction catalyst compared to when pentasil-type zeolite is used alone.
【0009】以下、本発明について、詳細に説明する。
本発明では、ガス状炭化水素を芳香族炭化水素を含む液
状炭化水素混合物に変換するゼオライト触媒と炭素酸化
物還元触媒からなる複合触媒を用いる。まず、ゼオライ
ト触媒としては、例えば自動車用液体燃料の原料として
使用可能な軽質芳香族炭化水素特に、ベンゼン,トルエ
ン,キシレン類の生成割合の高い触媒が望ましい。この
ようなゼオライト触媒としては、ペンタシル型ゼオライ
トを挙げることができる。より具体的には、アメリカ合
衆国モービル社が開発した特殊な合成ゼオライトである
、ZSM−5,ZSM−11,ZSM−12,ZSM−
23,ZSM−35,ZSM−48型のゼオライトを挙
げることができる。これらの中では、本発明の目的には
特にZSM−5型ゼオライトが好ましい。ペンタシル型
ゼオライトを構成するシリカとアルミナのモル比(Si
O2 /Al2 O3 比)は、15〜3000が好ま
しく、最も好ましくは20〜100である。The present invention will be explained in detail below. The present invention uses a composite catalyst consisting of a zeolite catalyst and a carbon oxide reduction catalyst that converts gaseous hydrocarbons into a liquid hydrocarbon mixture containing aromatic hydrocarbons. First, the zeolite catalyst is preferably a catalyst that can be used as a raw material for liquid fuel for automobiles, and can produce a high proportion of light aromatic hydrocarbons, particularly benzene, toluene, and xylenes. As such a zeolite catalyst, a pentasil type zeolite can be mentioned. More specifically, ZSM-5, ZSM-11, ZSM-12, and ZSM- are special synthetic zeolites developed by Mobil Corporation in the United States.
Zeolites of the type 23, ZSM-35 and ZSM-48 can be mentioned. Among these, ZSM-5 type zeolite is particularly preferred for the purpose of the present invention. The molar ratio of silica and alumina (Si
O2 /Al2 O3 ratio) is preferably 15-3000, most preferably 20-100.
【0010】ペンタシル型ゼオライトとしては、水熱合
成したのち有機塩基を取り除いた焼成品をそのまま用い
ることができるが、これを水素イオンで変性したものを
用いてもよい。水素イオン変性は、たとえば、次のよう
にして行なうことができる。硝酸アンモニウム(試薬特
級)40gを蒸留水1000mlに溶解し、これにZS
M−5型ゼオライト10gを加えて、80℃で3時間攪
拌後ゼオライトを溶液から濾別する。このゼオライトを
さらに上記の硝酸アンモニウム水溶液に懸濁し同様に処
理する。この操作を合計10回行なって、水素イオン変
性を終了する。その後、まず空気中、120℃で15時
間乾燥し、さらに空気中、550℃で2時間焼成する。As the pentasil type zeolite, a calcined product obtained by hydrothermally synthesizing and removing the organic base can be used as it is, but it may also be modified with hydrogen ions. Hydrogen ion modification can be performed, for example, as follows. Dissolve 40g of ammonium nitrate (special grade reagent) in 1000ml of distilled water, and add ZS to this.
After adding 10 g of M-5 type zeolite and stirring at 80°C for 3 hours, the zeolite was filtered from the solution. This zeolite is further suspended in the above aqueous ammonium nitrate solution and treated in the same manner. This operation is repeated 10 times in total to complete the hydrogen ion modification. Thereafter, it is first dried in air at 120°C for 15 hours, and then fired in air at 550°C for 2 hours.
【0011】さらに、本発明の目的をよりよく達成する
ためには、水素イオン変性ゼオライトをさらにアルカリ
土類金属またはガリウムにより変性することが必要であ
る。変性するために用いるアルカリ土類金属としては、
特にマグネシウムとカルシウムが好ましい。変性は、こ
れらのアルカリ土類金属またはガリウムの塩、酸化物、
水酸化物を用いて、イオン交換法や含浸法などにより行
なうことができる。アルカリ土類金属のイオン交換法に
よる変性の例を示せば以下の通りである。硝酸マグネシ
ウム(試薬特級)32gを蒸留水500mlに溶解し、
これに水素イオン交換したZSM−5型ゼオライト5g
を加えて、80℃で3時間攪拌する。ゼオライトを溶液
から濾別後、さらに上記の硝酸マグネシウム溶液に懸濁
し、同様の処理を合計5回行なう。その後、まず空気中
、120℃で15時間乾燥し、さらに空気中、550℃
で2時間焼成する。Furthermore, in order to better achieve the objects of the present invention, it is necessary to further modify the hydrogen ion modified zeolite with an alkaline earth metal or gallium. The alkaline earth metals used for modification are:
Especially preferred are magnesium and calcium. Modification involves the use of these alkaline earth metal or gallium salts, oxides,
This can be carried out by an ion exchange method, an impregnation method, etc. using a hydroxide. Examples of modification of alkaline earth metals by ion exchange method are as follows. Dissolve 32g of magnesium nitrate (special grade reagent) in 500ml of distilled water,
5g of ZSM-5 type zeolite with which hydrogen ions were exchanged
and stirred at 80°C for 3 hours. After the zeolite is filtered from the solution, it is further suspended in the above magnesium nitrate solution and the same treatment is performed a total of 5 times. After that, it was first dried in the air at 120°C for 15 hours, and then dried in the air at 550°C.
Bake for 2 hours.
【0012】一方、炭素酸化物還元触媒としては、ルテ
ニウム,ニッケル,コバルトあるいはモリブデンの有機
塩や塩化物,硝酸塩などの無機塩、または酸化物や水酸
化物を用いて調製する。場合によっては、これらをシリ
カ,アルミナあるいは活性炭などの担体に担持させたも
のを用いることもできる。炭素酸化物還元触媒は以下の
ようにして調製する。所定量の金属化合物を蒸留水に溶
解し、これに規定量のアルミナを加え、減圧下で30分
放置した後、水蒸気浴中で蒸発乾固する。その後、まず
空気中、120℃で15時間乾燥し、さらに空気中、5
50℃で2時間焼成する。On the other hand, the carbon oxide reduction catalyst is prepared using organic salts of ruthenium, nickel, cobalt or molybdenum, inorganic salts such as chlorides and nitrates, or oxides and hydroxides. Depending on the case, these may be supported on a carrier such as silica, alumina, or activated carbon. The carbon oxide reduction catalyst is prepared as follows. A predetermined amount of a metal compound is dissolved in distilled water, a predetermined amount of alumina is added thereto, the solution is left under reduced pressure for 30 minutes, and then evaporated to dryness in a steam bath. After that, it was first dried in the air at 120°C for 15 hours, and then dried in the air for 5 hours.
Bake at 50°C for 2 hours.
【0013】本発明の方法においては、このようにして
得られた炭素酸化物還元触媒とペンタシル型ゼオライト
触媒とを重量比1:1〜1:10、好ましくは1:4で
混合して用いる。混合は、固体粉末同士で行なってもよ
く、あるいは適当な分散媒を用いてスラリー状で混合し
てもよい。また、場合によってはルテニウム,ニッケル
,コバルトあるいはモリブデンの金属イオンを適当な溶
媒に溶解し、ゼオライト触媒に含浸担持してもよい。
これらの触媒はそのまま反応に用いてもよいが、空気中
または窒素気流中で焼成後用いてもよい。また、場合に
よっては水素または一酸化炭素などの気流中で還元して
もよい。混合触媒中に含有させるルテニウム,ニッケル
,コバルトあるいはモリブデンの金属量は、それぞれ金
属換算で0.1〜15重量%であり、ルテニウムについ
ては0.1〜5重量%、ニッケル,コバルトおよびモリ
ブデンについては0.2〜10重量%が好ましい。In the method of the present invention, the carbon oxide reduction catalyst thus obtained and the pentasil type zeolite catalyst are mixed at a weight ratio of 1:1 to 1:10, preferably 1:4. The mixing may be carried out in solid powder form or in the form of a slurry using an appropriate dispersion medium. Further, depending on the case, metal ions such as ruthenium, nickel, cobalt, or molybdenum may be dissolved in a suitable solvent and impregnated and supported on the zeolite catalyst. These catalysts may be used in the reaction as they are, or may be used after being calcined in air or in a nitrogen stream. Further, depending on the case, reduction may be carried out in a gas stream of hydrogen or carbon monoxide. The metal amount of ruthenium, nickel, cobalt or molybdenum to be contained in the mixed catalyst is 0.1 to 15% by weight in terms of metal, and 0.1 to 5% by weight for ruthenium and 0.1 to 5% by weight for nickel, cobalt and molybdenum. 0.2 to 10% by weight is preferred.
【0014】次に上記で得られた触媒を用いて、炭素酸
化物含有ガス状炭化水素から、芳香族炭化水素を含む液
状炭化水素混合物とメタンまたはメタンと一酸化炭素を
同時に製造する方法を述べる。反応は、温度200〜7
00℃、好ましくは350〜600℃、重量時間空間速
度0.1〜400hr−1、好ましくは1〜50hr−
1、全圧力0.1〜100気圧(10〜10132キロ
パスカル)、好ましくは0.1〜20気圧(10〜20
26キロパスカル)の条件下で行なうことができる。原
料としては、メタンの部分酸化反応により生成したエタ
ンおよびエチレンを含むガスをそのまま用いるが、これ
と同様の成分を有するガスであれば、いかなる起源のガ
スを用いてもよい。これらの原料は水蒸気あるいは、窒
素,ヘリウム,アルゴンなどの不活性ガスで希釈して触
媒上に供給することも可能である。生成物である芳香族
炭化水素と未反応原料は公知の方法によって互に分離、
精製される。この反応は、上記原料をガスとして供給し
、固体である触媒と充分接触させ得るものであればどん
な反応形式でもよく、固定床反応方式、流動床反応方式
、移動床反応方式などいずれの反応形式でも本発明の目
的を達成することができる。Next, a method for simultaneously producing a liquid hydrocarbon mixture containing an aromatic hydrocarbon and methane or methane and carbon monoxide from a gaseous hydrocarbon containing carbon oxides using the catalyst obtained above will be described. . The reaction takes place at a temperature of 200-7
00°C, preferably 350-600°C, weight hourly space velocity 0.1-400 hr-1, preferably 1-50 hr-
1. Total pressure 0.1 to 100 atm (10 to 10132 kilopascals), preferably 0.1 to 20 atm (10 to 20
26 kilopascals). As a raw material, a gas containing ethane and ethylene produced by a partial oxidation reaction of methane is used as it is, but any gas of any origin may be used as long as it has similar components. These raw materials can also be diluted with water vapor or an inert gas such as nitrogen, helium, or argon and then supplied onto the catalyst. The product aromatic hydrocarbon and unreacted raw material are separated from each other by a known method.
Refined. This reaction may be carried out in any reaction format as long as the above raw materials are supplied as a gas and can be brought into sufficient contact with the solid catalyst, such as a fixed bed reaction method, a fluidized bed reaction method, a moving bed reaction method, etc. However, the object of the present invention can be achieved.
【0015】[0015]
【実施例】以下、本発明を実施例に基づいて説明するが
、本発明はこれに限定されるものではない。
実施例1
(1)触媒の調製
イ)H−Z5触媒の調製
硝酸アンモニウム(試薬特級)40gを蒸留水1000
mlに溶解し、これにZSM−5型ゼオライト10gを
加えて、80℃で3時間攪拌した。ゼオライトを溶液か
ら濾別後、このゼオライトについて前記と同様の処理を
合計10回行なった。その後、空気中、120℃で15
時間乾燥し、さらに空気中、550℃で2時間焼成した
。
ロ)Mo/H−Z5触媒(複合触媒)の調製パラモリブ
デン酸アンモニウム(試薬特級)0.92gを蒸留水2
5mlに溶解した溶液に、H−Z5触媒9.50gを加
え、減圧下で30分放置した後、水蒸気浴中で蒸発乾固
した。その後、空気中、120℃で15時間乾燥し、さ
らに空気中、550℃で2時間焼成した。
(2)反応
上記ロ)で得られた触媒粉末を圧力400Kg/cm2
で打錠し、次いでこれを粉砕して20〜40メッシュ
に成粒したもの1gを内径10mmの石英ガラス製反応
管に充填した。反応は、大気圧下において、エチレンと
一酸化炭素を窒素で希釈した混合ガス(C2 H4 /
CO/N2 =20/5/75:体積比)を用い、W/
F=10g・h/mol 、400℃の条件で行なった
。反応管から出た生成物をそのままガスクロマトグラフ
に導き分析した。結果を表1に示す。[Examples] The present invention will be explained below based on Examples, but the present invention is not limited thereto. Example 1 (1) Preparation of catalyst a) Preparation of H-Z5 catalyst 40 g of ammonium nitrate (special grade reagent) was added to 1000 g of distilled water.
ml, 10 g of ZSM-5 type zeolite was added thereto, and the mixture was stirred at 80°C for 3 hours. After filtering the zeolite from the solution, the same treatment as above was performed on the zeolite 10 times in total. Then, in air at 120℃ for 15
It was dried for an hour and then fired in air at 550°C for 2 hours. b) Preparation of Mo/H-Z5 catalyst (composite catalyst)
9.50 g of H-Z5 catalyst was added to the solution dissolved in 5 ml, and after being left under reduced pressure for 30 minutes, it was evaporated to dryness in a steam bath. Thereafter, it was dried in air at 120°C for 15 hours, and further baked in air at 550°C for 2 hours. (2) Reaction The catalyst powder obtained in step (b) above was heated to a pressure of 400 kg/cm2.
The tablets were then crushed into granules of 20 to 40 mesh, and 1 g of the tablets were filled into a quartz glass reaction tube with an inner diameter of 10 mm. The reaction takes place under atmospheric pressure using a mixed gas of ethylene and carbon monoxide diluted with nitrogen (C2 H4 /
CO/N2 = 20/5/75: volume ratio), W/
The test was carried out under the conditions of F=10 g·h/mol and 400°C. The product released from the reaction tube was directly introduced into a gas chromatograph and analyzed. The results are shown in Table 1.
【表1】
表1において、エタン転化率は反応したエタンの割合を
示し、選択率は反応生成物の生成割合を示す。なお、表
中、C1 ,C2 ,C3,C4 はそれぞれC1 炭
化水素、C2 炭化水素、C3 炭化水素、C4 炭化
水素を表わす。
また、C5 + 脂肪族はC5 以上の炭化水素、芳香
族は芳香族炭化水素を表わし、両者の合計が液状炭化水
素混合物を表わす。[Table 1] In Table 1, the ethane conversion rate indicates the proportion of reacted ethane, and the selectivity indicates the proportion of reaction products produced. In addition, in the table, C1, C2, C3, and C4 represent C1 hydrocarbon, C2 hydrocarbon, C3 hydrocarbon, and C4 hydrocarbon, respectively. Further, C5 + aliphatic represents a hydrocarbon of C5 or higher, aromatic represents an aromatic hydrocarbon, and the sum of both represents a liquid hydrocarbon mixture.
【0016】比較例1
実施例1の(1)イ)で調製した、H−Z5触媒のみを
用いて、実施例1の(2)と同じ条件下で反応させた。
その結果を表1に示す。Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 (2) using only the H-Z5 catalyst prepared in Example 1 (1) A). The results are shown in Table 1.
【0017】実施例2
硝酸ニッケル(試薬特級)2.48gを用いたほかは、
実施例1の(1)ロ)と同様の操作でNi/H−Z5触
媒を調製し、実施例1の(2)と同じ条件で反応させた
。
その結果を表1に示す。Example 2 Except for using 2.48 g of nickel nitrate (special grade reagent),
A Ni/H-Z5 catalyst was prepared in the same manner as in (1) b) of Example 1, and reacted under the same conditions as in (2) of Example 1. The results are shown in Table 1.
【0018】実施例3
(1)Ru+H−Z5触媒(複合触媒)の調製三塩化ル
テニウム(試薬特級)1.03gを蒸留水25mlに溶
解した溶液に、アルミナ9.50gを加え、減圧下で3
0分放置した後、水蒸気浴中で蒸発乾固した。その後、
空気中、120℃で15時間乾燥し、さらに空気中、5
50℃で2時間焼成した。ここで得られた触媒粉末とH
−Z5触媒を重量比で1対4になるように秤量し、乳ば
ちで混合した。
(2)反応
実施例1の(2)と同様にして行なった。その結果を表
1に示す。Example 3 (1) Preparation of Ru+H-Z5 catalyst (composite catalyst) 9.50 g of alumina was added to a solution of 1.03 g of ruthenium trichloride (reagent grade) dissolved in 25 ml of distilled water, and 3.0 g of alumina was added under reduced pressure.
After standing for 0 minutes, it was evaporated to dryness in a steam bath. after that,
Dry in the air at 120°C for 15 hours, and then dry in the air for 5 hours.
It was baked at 50°C for 2 hours. The catalyst powder obtained here and H
-Z5 catalysts were weighed out at a weight ratio of 1:4 and mixed in a mortar. (2) The reaction was carried out in the same manner as (2) of Reaction Example 1. The results are shown in Table 1.
【0019】実施例4
硝酸コバルト(試薬特級)2.47gを用い、アルミナ
に代えてシリカ9.50gを用いたほかは、実施例3の
(1)と同様の操作でCo+H−Z5触媒を調製し、実
施例1の(2)と同じ条件で反応させた。その結果を表
2に示す。Example 4 A Co+H-Z5 catalyst was prepared in the same manner as in Example 3 (1), except that 2.47 g of cobalt nitrate (special grade reagent) was used and 9.50 g of silica was used in place of alumina. The reaction was carried out under the same conditions as in Example 1 (2). The results are shown in Table 2.
【表2】[Table 2]
【0020】実施例5
パラモリブデン酸アンモニウム(試薬特級)0.92g
を用いたほかは、実施例4と同様の操作でMo+H−Z
5触媒を調製し、実施例1の(2)と同じ条件で反応さ
せた。その結果を表2に示す。Example 5 Ammonium paramolybdate (special grade reagent) 0.92 g
Mo+H-Z was prepared in the same manner as in Example 4 except that Mo+H-Z
No. 5 catalyst was prepared and reacted under the same conditions as in Example 1 (2). The results are shown in Table 2.
【0021】実施例6
(1)触媒の調製
イ)Mg−Z5触媒の調製
硝酸マグネシウム(試薬特級)32gを蒸留水500m
lに溶解し、これにH−Z5触媒5gを加えて、80℃
で3時間攪拌した。ゼオライトを溶液から濾別後、この
ゼオライトについて前記と同様の処理を合計5回行なっ
た。その後、空気中、120℃で15時間乾燥し、さら
に空気中、550℃で2時間焼成した。ロ)Ni/Mg
−Z5触媒(複合触媒)の調製ゼオライトとして上記イ
)で得られたMg−Z5触媒を用いたほかは、実施例2
と同様にして調製した。
(2)反応
実施例1の(2)と同様にして行なった。その結果を表
2に示す。Example 6 (1) Preparation of catalyst a) Preparation of Mg-Z5 catalyst 32 g of magnesium nitrate (special grade reagent) was added to 500 m of distilled water.
1, add 5 g of H-Z5 catalyst, and heat to 80°C.
The mixture was stirred for 3 hours. After filtering the zeolite from the solution, the same treatment as above was performed on the zeolite five times in total. Thereafter, it was dried in air at 120°C for 15 hours, and further baked in air at 550°C for 2 hours. b) Ni/Mg
- Preparation of Z5 catalyst (composite catalyst) Example 2 except that the Mg-Z5 catalyst obtained in step (a) above was used as the zeolite.
Prepared in the same manner. (2) The reaction was carried out in the same manner as (2) of Reaction Example 1. The results are shown in Table 2.
【0022】比較例2
実施例2の(1)イ)で調製した、Mg−Z5触媒のみ
を用いて、実施例1の(2)と同じ条件で反応させた。
その結果を表2に示す。Comparative Example 2 A reaction was carried out under the same conditions as in Example 1 (2) using only the Mg-Z5 catalyst prepared in Example 2 (1) A). The results are shown in Table 2.
【0023】実施例7〜12、比較例3〜4原料ガス組
成のうち、COに代えてCO2 ガスを用いたほかは実
施例1〜6、比較例1〜2とそれぞれ同じ触媒を用い、
実施例1の(2)と同じ条件で反応させた。各々の結果
を表3および表4に示す。これらの表において、一酸化
炭素収率は炭素酸化物からの一酸化炭素生成量を表わす
。Examples 7 to 12 and Comparative Examples 3 to 4 The same catalysts as in Examples 1 to 6 and Comparative Examples 1 to 2 were used, except that CO2 gas was used instead of CO in the raw material gas composition.
The reaction was carried out under the same conditions as in Example 1 (2). The respective results are shown in Tables 3 and 4. In these tables, carbon monoxide yield represents the amount of carbon monoxide produced from carbon oxides.
【表3】[Table 3]
【表4】[Table 4]
【0024】比較例5〜10
原料ガス組成をC2 H4 /N2 =20/80とし
た以外は、実施例1〜6、比較例1〜2と同じ触媒を用
い、実施例1の(2)と同じ条件で反応させた。各々の
結果を表5および表6に示す。Comparative Examples 5 to 10 The same catalyst as in Examples 1 to 6 and Comparative Examples 1 to 2 was used except that the raw material gas composition was changed to C2 H4 /N2 = 20/80, and the same catalyst as in Example 1 (2) was used. The reaction was carried out under the same conditions. The respective results are shown in Tables 5 and 6.
【表5】[Table 5]
【表6】[Table 6]
【0025】[0025]
【発明の効果】本発明の方法によれば、炭素酸化物を含
むガス状炭化水素を、芳香族炭化水素を含む液状炭化水
素混合物に変換すると同時に、炭素酸化物をメタンまた
はメタンと一酸化炭素に還元することができ、プロセス
が簡略化できるとともに、芳香族炭化水素の生成率が顕
著に増大し、その工業的価値は大きい。According to the method of the present invention, gaseous hydrocarbons containing carbon oxides are converted into liquid hydrocarbon mixtures containing aromatic hydrocarbons, and at the same time, carbon oxides are converted into methane or methane and carbon monoxide. The process can be simplified, and the production rate of aromatic hydrocarbons can be significantly increased, so its industrial value is great.
Claims (5)
、かつ炭素酸化物を含有するものを原料とし、触媒を用
いて200〜700℃で反応させて芳香族炭化水素を含
む液状炭化水素混合物を製造する方法において、触媒と
してガス状炭化水素を芳香族炭化水素に変換しうる触媒
と炭素酸化物還元触媒からなる複合触媒を用い、前記ガ
ス状炭化水素を芳香族炭化水素を含む液状炭化水素混合
物に変換すると同時に、炭素酸化物をメタンまたはメタ
ンと一酸化炭素に還元することを特徴とする、液状炭化
水素混合物とメタンの同時製造方法。Claim 1: A liquid hydrocarbon mixture containing aromatic hydrocarbons obtained by reacting gaseous hydrocarbons other than methane and containing carbon oxides at 200 to 700°C using a catalyst. In the method for producing a liquid hydrocarbon containing aromatic hydrocarbons, a composite catalyst consisting of a catalyst capable of converting gaseous hydrocarbons into aromatic hydrocarbons and a carbon oxide reduction catalyst is used as a catalyst, and the gaseous hydrocarbons are converted into liquid hydrocarbons containing aromatic hydrocarbons. A method for the simultaneous production of a liquid hydrocarbon mixture and methane, characterized in that carbon oxides are reduced to methane or methane and carbon monoxide at the same time as the mixture is converted.
に変換しうる触媒として、ペンタシル型ゼオライトまた
はこれを水素イオンあるいはアルカリ土類金属またはガ
リウムで変性したゼオライトを、炭素酸化物還元触媒と
して、ルテニウム,ニッケル,コバルト,モリブデンよ
りなる群から選ばれるいずれか一種または二種の金属も
しくはその金属の酸化物をそれぞれ用いる、請求項1の
液状炭化水素混合物とメタンの同時製造方法。2. As a catalyst capable of converting the gaseous hydrocarbon into an aromatic hydrocarbon, a pentasil type zeolite or a zeolite modified with hydrogen ions, an alkaline earth metal, or gallium is used as a carbon oxide reduction catalyst, 2. The method for simultaneously producing a liquid hydrocarbon mixture and methane according to claim 1, wherein one or two metals selected from the group consisting of ruthenium, nickel, cobalt, and molybdenum or oxides of the metals are used.
−5型合成ゼオライトである、請求項2の液状炭化水素
混合物とメタンの同時製造方法。[Claim 3] The pentasil type zeolite is ZSM.
The method for simultaneously producing a liquid hydrocarbon mixture and methane according to claim 2, wherein the method is a -5 type synthetic zeolite.
性するためのアルカリ土類金属がマグネシウムまたはカ
ルシウムである、請求項2または請求項3の液状炭化水
素混合物とメタンの同時製造方法。4. The method for simultaneously producing a liquid hydrocarbon mixture and methane according to claim 2 or 3, wherein the alkaline earth metal for modifying the pentasil type zeolite catalyst is magnesium or calcium.
メタンの部分酸化反応で生成したエタン、エチレンおよ
び炭素酸化物を含む混合ガスである、請求項1ないし4
の何れかの項の液状炭化水素混合物とメタンの同時製造
方法。[Claim 5] The gaseous hydrocarbon containing carbon oxide is
Claims 1 to 4, wherein the gas is a mixed gas containing ethane, ethylene, and carbon oxide produced by a partial oxidation reaction of methane.
A method for simultaneously producing a liquid hydrocarbon mixture and methane according to any of the above.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3167407A JPH04368341A (en) | 1991-06-13 | 1991-06-13 | Process for simultaneous production of liquid hydrocarbon mixture and methane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3167407A JPH04368341A (en) | 1991-06-13 | 1991-06-13 | Process for simultaneous production of liquid hydrocarbon mixture and methane |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04368341A true JPH04368341A (en) | 1992-12-21 |
Family
ID=15849125
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3167407A Withdrawn JPH04368341A (en) | 1991-06-13 | 1991-06-13 | Process for simultaneous production of liquid hydrocarbon mixture and methane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04368341A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006249065A (en) * | 2005-02-10 | 2006-09-21 | Masaru Ichikawa | Method for producing aromatic hydrocarbon |
JP2019081165A (en) * | 2017-10-31 | 2019-05-30 | 株式会社豊田中央研究所 | Catalyst for synthesizing hydrocarbons, and hydrocarbons manufacturing device and hydrocarbon fuel manufacturing method equipped with the same |
-
1991
- 1991-06-13 JP JP3167407A patent/JPH04368341A/en not_active Withdrawn
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006249065A (en) * | 2005-02-10 | 2006-09-21 | Masaru Ichikawa | Method for producing aromatic hydrocarbon |
JP2019081165A (en) * | 2017-10-31 | 2019-05-30 | 株式会社豊田中央研究所 | Catalyst for synthesizing hydrocarbons, and hydrocarbons manufacturing device and hydrocarbon fuel manufacturing method equipped with the same |
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