JPS62240777A - Production of ethylene and hydrogen from gas containing methane - Google Patents
Production of ethylene and hydrogen from gas containing methaneInfo
- Publication number
- JPS62240777A JPS62240777A JP61082320A JP8232086A JPS62240777A JP S62240777 A JPS62240777 A JP S62240777A JP 61082320 A JP61082320 A JP 61082320A JP 8232086 A JP8232086 A JP 8232086A JP S62240777 A JPS62240777 A JP S62240777A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- methane
- ethylene
- gas
- solid electrolyte
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000007789 gas Substances 0.000 title claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000005977 Ethylene Substances 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 13
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- -1 hydrogen ions Chemical class 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UKOQKFKQGKXJTN-UHFFFAOYSA-L [O-]O[O-].[Sr+2] Chemical compound [O-]O[O-].[Sr+2] UKOQKFKQGKXJTN-UHFFFAOYSA-L 0.000 description 1
- MDUBKEIEMKOUCO-UHFFFAOYSA-L [O-]O[O-].[Sr+2].[Ce+3] Chemical compound [O-]O[O-].[Sr+2].[Ce+3] MDUBKEIEMKOUCO-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新しいエチレンの製造方法に関し、更に詳しく
はメタン含有ガスよりエチレン及び水素を得る方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a new method for producing ethylene, and more particularly to a method for obtaining ethylene and hydrogen from methane-containing gas.
現在エチレンは天然ガス中のエタン、石油留分中のナフ
サ、灯軽油を原料とし８００℃以上の高温下で熱分解さ
せて製造しているが、エチレン以外の副生成物が多く分
離精製工程が複雑であるという問題点がある。さらに石
油の枯渇が将来予想される中で埋蔵量の多いメタンを当
成分とする天然ガスを原料とするエチレン製造プロセス
の開発も急務となっている。Currently, ethylene is produced from ethane in natural gas, naphtha in petroleum distillates, and kerosene by thermal decomposition at high temperatures of over 800°C, but there are many byproducts other than ethylene, and the separation and purification process is required. The problem is that it is complicated. Furthermore, as oil is expected to run out in the future, there is an urgent need to develop an ethylene production process that uses natural gas, which contains methane, which has large reserves, as a raw material.
〔発明が解決しようとする問題点３
以上の状況から、本発明は従来、例のない天然ガスなど
メタン含有ガスを原料として、副反応の少ないエチレン
を製造する方法を提供しようとするものである。[Problem to be Solved by the Invention 3] In light of the above circumstances, the present invention seeks to provide a method for producing ethylene with few side reactions using a methane-containing gas such as natural gas as a raw material, which has never been done before. .
本発明は両面に電極を取付けた水素イオン導電性固体電
解質隔膜のプラス電極を取付けだ側よりメタン含有ガス
を供給し、プラス電極側にエチレン、マイナス電蓮側に
水素を生成させることを特徴とするメタン含有ガスより
エチレン及び水素の製造方法である。The present invention is characterized in that a methane-containing gas is supplied from the side to which the positive electrode of a hydrogen ion conductive solid electrolyte membrane with electrodes attached on both sides is attached, and ethylene is generated on the positive electrode side and hydrogen is generated on the negative electrode side. This is a method for producing ethylene and hydrogen from methane-containing gas.
本発明でいうメタン含有ガスとは、メタンを９０％以上
含有するガスで、メタン以外にエタン、プロパンなどの
炭化水素ガス、その他のガスを含有するものであって、
代表的には天然ガスである。The methane-containing gas referred to in the present invention is a gas containing 90% or more of methane, and in addition to methane, it also contains hydrocarbon gases such as ethane and propane, and other gases,
A typical example is natural gas.
本発明における温度は一般的に６００〜９００℃が好ま
しい。The temperature in the present invention is generally preferably 600 to 900°C.
メタン分子中の水素は水素イオンとして水素イオン導電
性固体電解質隔膜中を移動してマイナスの電極界面で水
素ガスとして生成し、他方、分子中の水素を水素イオン
として放出したメタンはエチレンとなる。The hydrogen in the methane molecules moves as hydrogen ions through the hydrogen ion conductive solid electrolyte membrane and is generated as hydrogen gas at the negative electrode interface, while the methane that releases the hydrogen in the molecules as hydrogen ions becomes ethylene.
水素イオン導電性固体電解質隔膜内における水素イオン
の′酸導は同時に抵抗発熱作用があるので直皮は自動的
に保持され、加熱は最初に系全体を加熱するだけで十分
である。Since the acid conduction of hydrogen ions within the hydrogen ion conductive solid electrolyte membrane also has a resistance heating effect, the direct skin is automatically maintained, and it is sufficient to heat the entire system initially.
本発明の試験装置の概要を第１図によって説明する。The outline of the test apparatus of the present invention will be explained with reference to FIG.
第１図において１は水素イオン導電性固体電Ｉｖｊ質隔
膜よりなる反応管であり、反応管１の内側及び外側には
白金の多孔質′成極２が焼きつけられている。この電極
２の両極に電圧可変の直流電源４に接続のだめリード線
３を出している。In FIG. 1, reference numeral 1 denotes a reaction tube made of a hydrogen ion conductive solid electrolyte diaphragm, and porous platinum polarization 2 is baked onto the inside and outside of the reaction tube 1. Lead wires 3 for connection to a variable voltage DC power source 4 are extended to both poles of the electrode 2.
５は反応器であり、水素イオン導電性固体電解質隔膜反
応器１の外側をとり囲む容器である。5 is a reactor, which is a container surrounding the outside of the hydrogen ion conductive solid electrolyte membrane reactor 1.
６は前記反応管１を加熱するための電気炉である。７は
反応ガスとして使用するメタン含有ガス導入管、８は未
反応のメタンと反応により生シタガス（エチレン）の混
合物取出管、９はギヤリアガス（たとえば窒素）を導入
するキャリアガス導入管であり、１０は反応後ガス（水
素）取出管である。１１は測温用の熱電対である。6 is an electric furnace for heating the reaction tube 1. 7 is a methane-containing gas introduction pipe used as a reaction gas, 8 is a pipe for taking out a mixture of raw gas (ethylene) by reaction with unreacted methane, 9 is a carrier gas introduction pipe for introducing gear gas (for example, nitrogen), and 10 is the post-reaction gas (hydrogen) extraction pipe. 11 is a thermocouple for temperature measurement.
それぞれの取出管８，９には流量計とガスクロが接続さ
れており、（図示省略）オンラインでガス流量及び組成
の分析が可能なようになっている。A flow meter and a gas analyzer (not shown) are connected to each of the extraction pipes 8 and 9, making it possible to analyze the gas flow rate and composition online.
実施例 １゜
水素イオン導電性固体電解質として三酸化セリウムスト
ロンチウム（ＳｒＣｅ０３） ｆ母体とした５ｒＣｅ、
、、 Ｙｂ、、、、 Ｏ，ａ（ａ ：酸素欠損量）を用
いた。Example 1゜Cerium strontium trioxide (SrCe03) as a hydrogen ion conductive solid electrolyte, 5rCe as f matrix,
,, Yb,..., O,a (a: amount of oxygen vacancies) was used.
第１図に示した試験装置においてメタン含有ガス導入管
７のメタン流量を２０ｒｎｌＺ−、キャリアガス導入管
９の窒素流量を２０−／―として流通させた。熱電対１
１で検出する水素イオン導電性固体電解質隔膜反応管１
の温度を８００℃とし、直流電源４には１．Ｏｖの直流
電圧を印加した。In the test apparatus shown in FIG. 1, the methane flow rate through the methane-containing gas introduction pipe 7 was set to 20 rnlZ-, and the nitrogen flow rate through the carrier gas introduction pipe 9 was set to 20-/-. thermocouple 1
Hydrogen ion conductive solid electrolyte diaphragm reaction tube 1 for detection in 1
The temperature of the DC power supply 4 is 800°C, and the DC power supply 4 is set to 1. A DC voltage of Ov was applied.
このようにして反応後ガス取出管１０に流出するガスの
流量及び組成を測定すると、流凝は２１−／−であり、
５％の水素が含有されていた。また、一方の取出管８に
はエチレンが検出された。When the flow rate and composition of the gas flowing out into the gas extraction pipe 10 after the reaction are measured in this way, the flow condensation is 21-/-,
It contained 5% hydrogen. Furthermore, ethylene was detected in one of the extraction pipes 8.
以上の反応は
２ＣＨ，−→Ｃｚ Ｈ４＋ ２ Ｈ雪
と考えられ、メタンが電解されて水素を生成し、水素は
水素イオン導電性固体電解質隔膜内を水素イオンとして
移動し、他側へ水素ガスとして生成したものと考えられ
る。The above reaction can be considered as 2CH,-→Cz H4+ 2H snow, where methane is electrolyzed to produce hydrogen, which moves as hydrogen ions within the hydrogen ion conductive solid electrolyte membrane and is transferred to the other side as hydrogen gas. It is thought that it was generated.
実施例 ２
実施例１と同一の反応管を使用しメタン含有ガス導入管
７のメタン流量を２０−／―とじて流通させた。熱電対
１１で検出する水素イオン導電性固体電解質隔膜反応管
１の温度を７００〜１０００℃と変化させ、電圧を１．
Ｏｖとし、取出管８に流出するエチレンの景を測定した
。Example 2 The same reaction tube as in Example 1 was used, and the methane flow rate in the methane-containing gas introduction tube 7 was set at 20-/-. The temperature of the hydrogen ion conductive solid electrolyte diaphragm reaction tube 1 detected by the thermocouple 11 was varied from 700 to 1000°C, and the voltage was changed to 1.
Ov, and the appearance of ethylene flowing out into the take-out pipe 8 was measured.
その結果を第２図に示す。The results are shown in FIG.
第２図において横軸は温度、縦軸はエチレン生成量を示
す。温度が高くなるほどエチレンの生成量が多くなるこ
とが認められる。同時に電流値を見ると、高温はど電流
の値が大きく水素イオンが水素イオン導電性固体胤解質
隔膜内を移動しやすいことが判明した。In FIG. 2, the horizontal axis shows temperature and the vertical axis shows the amount of ethylene produced. It is observed that the higher the temperature, the greater the amount of ethylene produced. At the same time, looking at the current value, it was found that the higher the temperature, the higher the current value, and the easier the hydrogen ions were to move within the hydrogen ion conductive solid solute diaphragm.
実施例 ５
水素イオン導電性固体電解質として三酸化セリウムスト
ロンチウムを母体とした５ｒＣｅ ａ？。Example 5 5rCe a? using cerium strontium trioxide as a hydrogen ion conductive solid electrolyte. .
８Ｃ，、。０．−〇（α；酸素欠損量）を用いた。8C... 0. −〇(α; amount of oxygen vacancies) was used.
第１図に示した試験装置を用い、メタン含有ガス導入管
７のメタン流量を１０ｄ／＋ｗキャリアガス導入管９の
窒素流量を２１］ｄ／ｍとして流通させた。焼電対１１
で検出する反応管の温度を９００℃とし、電圧を変化さ
せて、取出管８に流出するガスの着及び組成を調べた。Using the test apparatus shown in FIG. 1, the methane flow rate through the methane-containing gas introduction tube 7 was set to 10 d/+w, and the nitrogen flow rate through the carrier gas introduction tube 9 was set to 21] d/m. Baked pair 11
The temperature of the reaction tube to be detected was set to 900° C., and the voltage was varied to examine the deposition and composition of the gas flowing out into the take-out tube 8.
その結果を第５図に示す。The results are shown in FIG.
第３図において、横軸は印加電圧（Ｖ）、縦軸はエチレ
ン生成量を示す。この結果から電圧の上昇に伴い、エチ
レン生成量も増加することが判明した。また、一方の取
出１１０には水素の流出が（箱誌された。In FIG. 3, the horizontal axis shows the applied voltage (V), and the vertical axis shows the amount of ethylene produced. The results revealed that the amount of ethylene produced increased as the voltage increased. In addition, hydrogen was leaked from one outlet 110.
本発明に従えば、メタンからエチレンの生成が容易とな
り、併せて水素を採取することができる。According to the present invention, ethylene can be easily produced from methane, and hydrogen can also be extracted.
Ｍ１図は本発明の実施例に使用した試Ａ倹装置の概略図
。第２図は温度とエチレン生成量の関係を示す図表、第
３図は印加電圧とエチレン生成ｌの関係を示す図表であ
る。
復代理人 内 １） 明
復代理人 萩 原 亮 −
復代理人 安 西 篤 夫
第１図
温度（０Ｃ）Figure M1 is a schematic diagram of the trial A-sparing apparatus used in the examples of the present invention. FIG. 2 is a chart showing the relationship between temperature and ethylene production amount, and FIG. 3 is a chart showing the relationship between applied voltage and ethylene production l. Sub-agents 1) Meifuku agent Ryo Hagiwara - Sub-agent Atsuo Anzai Figure 1 Temperature (0C)
Claims (1)
のプラス電極を取付けた側よりメタン含有ガスを供給し
、プラス電極側にエチレン、マイナス電極側に水素を生
成させることを特徴とするメタン含有ガスよりエチレン
及び水素の製造方法。A methane-containing gas characterized by supplying methane-containing gas from the positive electrode side of a hydrogen ion conductive solid electrolyte diaphragm with electrodes attached on both sides, producing ethylene on the positive electrode side and hydrogen on the negative electrode side. A method for producing ethylene and hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61082320A JPS62240777A (en) | 1986-04-11 | 1986-04-11 | Production of ethylene and hydrogen from gas containing methane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61082320A JPS62240777A (en) | 1986-04-11 | 1986-04-11 | Production of ethylene and hydrogen from gas containing methane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62240777A true JPS62240777A (en) | 1987-10-21 |
Family
ID=13771272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61082320A Pending JPS62240777A (en) | 1986-04-11 | 1986-04-11 | Production of ethylene and hydrogen from gas containing methane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62240777A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017471A (en) * | 1998-06-30 | 2000-01-18 | Permelec Electrode Ltd | Hydrogen generator |
| US9932679B2 (en) | 2013-10-31 | 2018-04-03 | Exxonmobil Chemical Patents Inc. | Electrochemical conversion of hydrocarbons |
-
1986
- 1986-04-11 JP JP61082320A patent/JPS62240777A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017471A (en) * | 1998-06-30 | 2000-01-18 | Permelec Electrode Ltd | Hydrogen generator |
| US9932679B2 (en) | 2013-10-31 | 2018-04-03 | Exxonmobil Chemical Patents Inc. | Electrochemical conversion of hydrocarbons |
| US10865487B2 (en) | 2013-10-31 | 2020-12-15 | Exxonmobil Chemical Patents Inc. | Electrochemical conversion of hydrocarbons |
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