JPH0471643A - Catalyst for decomposing methane gas - Google Patents
Catalyst for decomposing methane gasInfo
- Publication number
- JPH0471643A JPH0471643A JP2180510A JP18051090A JPH0471643A JP H0471643 A JPH0471643 A JP H0471643A JP 2180510 A JP2180510 A JP 2180510A JP 18051090 A JP18051090 A JP 18051090A JP H0471643 A JPH0471643 A JP H0471643A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- methane gas
- platinum
- plating
- decomposing
- 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 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 239000012210 heat-resistant fiber Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 11
- 239000004917 carbon fiber Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000007747 plating Methods 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 210000002268 wool Anatomy 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000007740 vapor deposition Methods 0.000 abstract description 4
- 238000007772 electroless plating Methods 0.000 abstract description 3
- 238000009713 electroplating Methods 0.000 abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 229910052741 iridium Inorganic materials 0.000 abstract 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 44
- 238000000354 decomposition reaction Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000029058 respiratory gaseous exchange Effects 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はメタンガス分解用触媒に関し、特に閉鎖系空間
（宇宙船、核シェルタ、潜水艦等）で人間の呼吸により
排出される炭酸ガスを吸着・濃縮した後、脱着した炭酸
ガスを水素で還元して生成したメタンガスを分解する反
応に使用される触媒に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a catalyst for decomposing methane gas, and particularly to a catalyst for decomposing methane gas, and particularly for adsorbing and absorbing carbon dioxide emitted by human breathing in a closed space (spacecraft, nuclear shelter, submarine, etc.). The present invention relates to a catalyst used in a reaction that decomposes methane gas produced by reducing desorbed carbon dioxide gas with hydrogen after concentration.
従来のメタンガス分解法を実施する装置の一態様を第４
図によって説明する。One aspect of the device for implementing the conventional methane gas decomposition method is shown in the fourth example.
This will be explained using figures.
第４図の装置はメタンガス分解炉Ｊにセットされた反応
管にの内部に、ペレット状白金系触媒りを充填し、この
ペレット状白金系触媒りを保持するため、その両側部に
耐熱性繊維Ｍを充填することによりメタンガスを分解す
るようにしたものである。この装置を用いて、以下に示
す条件により、メタンガスを分解した場合のメタンガス
分解率は約３５％であり、また析出炭素によって反応管
に内ガス流路が閉塞されるまでの時間は約９時間であっ
た。The device shown in Figure 4 is a reaction tube set in a methane gas decomposition furnace J that is filled with pelleted platinum catalyst, and in order to hold the pelleted platinum catalyst, heat-resistant fibers are placed on both sides of the reaction tube. By filling the tank with M, methane gas is decomposed. When methane gas is decomposed using this device under the conditions shown below, the methane gas decomposition rate is approximately 35%, and the time it takes for the internal gas flow path in the reaction tube to be blocked by precipitated carbon is approximately 9 hours. Met.
◎メタンガス分解条件
・反応管寸法：内径 ３０φ（ｍｍ ）長さ １０００
（田ｍ）
・反応温度＋１Ｏ００℃
・ペレット状白金系触媒：アルミナ担体０，５％ルテニ
ウム触媒（０，０２ｃｍ３／個）・ベレット状白金系触
媒充填量及び充填体積：４１ｇ、４０ｃｍ’
・耐熱性繊維ニジリカウール
（線径１〜７μｍ）
・耐熱性繊維充填量及び充填体積：
３゜５ｇ、１００ ｃｍ３
、メタンガス流量： ０．１４１β／ｍｉｎ・Ｇ ＨＳ
Ｖ （Ｇａｓ Ｈｏｕｒｌｙ ５ｐａｃｅ νｅｌ
ｏｃｉｔｙ）：６０ｈｒ
〔発明が解決しようとする課題〕
従来のメタンガス分解炉の反応管に充填される従来の触
媒は次に示す欠点を有していた。◎Methane gas decomposition conditions/Reaction tube dimensions: Inner diameter 30φ (mm) Length 1000
(Tan m) ・Reaction temperature +100℃ ・Pellet-shaped platinum catalyst: 0.5% ruthenium catalyst on alumina carrier (0.02 cm3/unit) ・Bellet-shaped platinum catalyst loading amount and filling volume: 41 g, 40 cm' ・Heat resistance Fiber rainbow wool (wire diameter 1-7μm) Heat-resistant fiber filling amount and filling volume: 3°5g, 100cm3, methane gas flow rate: 0.141β/min・G HS
V (Gas Hourly 5 pace νel
[Problems to be Solved by the Invention] The conventional catalyst filled in the reaction tube of the conventional methane gas decomposition furnace had the following drawbacks.
（１） アルミナペレットを担体とする白金系金属触
媒はその体積が１個当り約０．０２ ｃｍ３と大きく、
ＧＨ３Ｖ＝６０ｈｒりでメタンガスを分解する場合、約
９時間経過（触媒１ ｋｇに対して炭素を約１００ｇ補
集）すると系内が閉塞してしまうため、反応管内の耐熱
性繊維及びペレット状白金系金属触媒を頻繁に交“換し
なければならない。(1) The platinum-based metal catalyst using alumina pellets as a carrier has a large volume of approximately 0.02 cm3 per piece.
When decomposing methane gas at GH3V = 60 hours, the system becomes clogged after about 9 hours (approximately 100 g of carbon is collected per 1 kg of catalyst), so the heat-resistant fibers and pelleted platinum in the reaction tube become clogged. The metal catalyst must be replaced frequently.
（２） ペレット状白金系金属触媒及び耐熱性繊維の
交換頻度が高いため、メタンガス分解炉の昇温及び降温
サイクル回数が多くなり電力消費量が大きい。(2) Since the pelleted platinum-based metal catalyst and heat-resistant fibers are frequently replaced, the number of temperature raising and cooling cycles of the methane gas decomposition furnace increases, resulting in large power consumption.
（３） ベレット状担体であるため、その重量が大き
い。(3) Since it is a pellet-shaped carrier, its weight is large.
（４） アルミナペレットを担体とする白金系金属触
媒は、その比表面積が小さいため触媒としての効果が少
なく反応に高温を必要とする。(4) A platinum-based metal catalyst using alumina pellets as a carrier has a small specific surface area, so it is less effective as a catalyst and requires high temperature for reaction.
本発明は以上のような欠点を解消するため、反応管に充
填されたペレット状白金系金属触媒及び耐熱性繊維の交
換頻度を低減し、低温度でメタンガス分解反応が可能と
なるメタンガス分解触媒を提供しようとするものである
。In order to eliminate the above-mentioned drawbacks, the present invention has developed a methane gas decomposition catalyst that reduces the frequency of replacing the pelleted platinum-based metal catalyst and heat-resistant fibers filled in the reaction tube, and enables the methane gas decomposition reaction at low temperatures. This is what we are trying to provide.
本発明は耐熱性繊維に白金系金属を担持してなることを
特徴とするメタンガス分解用触媒である。The present invention is a catalyst for decomposing methane gas characterized by having a platinum-based metal supported on heat-resistant fibers.
本発明をより詳細に説明すると、触媒担体として用いる
耐熱性繊維としてはシリカウール、アルミナウールまた
はカーボン繊維が、活性触又、触媒担体である耐熱繊維
に白金系金属を添着させる方法としては、めっき法（化
学めっき、無電解めっき、電解めっき）または蒸着法（
ＣＶ Ｄ ： Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐ
ｏｓｉｔｉｏｎ 、 Ｐ Ｖ Ｄ ：Ｐｈｙｓｉｃａ
ｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）を用いること
ができる。To explain the present invention in more detail, silica wool, alumina wool, or carbon fiber is used as the heat-resistant fiber used as the catalyst carrier, and plating is used as the method for impregnating the heat-resistant fiber that is the active catalyst or the catalyst carrier with the platinum metal. method (chemical plating, electroless plating, electrolytic plating) or vapor deposition method (
CVD: Chemical Vapor Dep
position, PVD: Physica
1 Vapor Deposition) can be used.
シリカウール、アルミナウールまたはカーボン繊維を触
媒担体とし、白金、ルテニウム、イリジウムまたはパラ
ジウムを活性触媒金属としてめっき法（化学めっき、無
電解約つき、電解めっき）または蒸着法（ＣＶＤ、ＰＶ
Ｄ）により添着した本発明の触媒をメタンガス分解用触
媒として適用することにより析出炭素補集量を増加させ
ることができ、また、担体の重量を低減することができ
るとともに触媒比表面積を大きくすることができる。Plating methods (chemical plating, electroless plating, electrolytic plating) or vapor deposition methods (CVD, PV
By applying the catalyst of the present invention impregnated by D) as a catalyst for decomposing methane gas, the amount of collected carbon can be increased, and the weight of the carrier can be reduced, and the specific surface area of the catalyst can be increased. I can do it.
以下、本発明の一実施例を第１図によって説明する。 An embodiment of the present invention will be described below with reference to FIG.
第１図において、内径３０φ（ｍｍ）、長さ１００１０
００（の反応管Ａの均熱部に、表面を白金（１０ｗｔ％
）で被覆されたカーボン繊維（線径７〜１５μｍ）Ｂを
約１０ｇ充填する。次に白金で被覆されたカーボン繊維
Ｂを１０００ｔに加熱し、温度が安定した後メタンガス
流量をマスフローメータＣでＧ、 ｌ ４１ ｊ２／ｍ
ｉｎ （ＧＨ３Ｖ ： ６０ｈｒ−’）に調整し、反
応管Ａに流入させる。In Figure 1, the inner diameter is 30φ (mm) and the length is 10010 mm.
Platinum (10wt%) was added to the surface of the soaking section of reaction tube A of
) is filled with about 10 g of carbon fiber (wire diameter: 7 to 15 μm) B. Next, carbon fiber B coated with platinum was heated to 1,000 t, and after the temperature was stabilized, the methane gas flow rate was measured using a mass flow meter C as G, l 41 j2/m
in (GH3V: 60hr-') and flowed into reaction tube A.
次に系内圧力を背圧弁りを使用して０．５ｋｇ／ｃｍ’
Ｇ （ゲージ圧）に設定する。Next, adjust the system pressure to 0.5 kg/cm' using a back pressure valve.
Set to G (gauge pressure).
反応系が閉塞（反応管Ａ前後の圧力差が０．５ｋｇ／ｃ
ｍ’Ｇ以上）したときメタンガスの流入を止め、反応管
Ａが冷却した後、炭素が析出した白金で被覆したカーボ
ン繊維Ｂを取り出し、その重量を測定する。またメタン
ガス流入中のメタンガス分解率を求めるため、反応管出
口部のメタンガス及び水素ガス濃度をガスクロマトグラ
フ分析装置Ｅで分析する。The reaction system is blocked (pressure difference before and after reaction tube A is 0.5 kg/c
m'G or more), the flow of methane gas is stopped, and after the reaction tube A has cooled, the platinum-coated carbon fiber B on which carbon has precipitated is taken out and its weight is measured. Furthermore, in order to determine the methane gas decomposition rate during the inflow of methane gas, the methane gas and hydrogen gas concentrations at the outlet of the reaction tube are analyzed by a gas chromatograph analyzer E.
その結果白金で被覆したカーボン繊維已に析出した炭素
は５．５ｇであり、第２図に示す通り白金で被覆したカ
ーボン繊維１ ｋｇに対しテ約５５０ｇの析出炭素を補
集することができる。このときのメタンガス分解率は５
０％であった。As a result, 5.5 g of carbon was deposited on the carbon fiber coated with platinum, and as shown in FIG. 2, about 550 g of precipitated carbon could be collected for 1 kg of carbon fiber coated with platinum. At this time, the methane gas decomposition rate is 5
It was 0%.
なお、こ＼で使用した触媒のカーボン繊維への白金担持
方法は次の通りである。The method for supporting platinum on the carbon fibers of the catalyst used here is as follows.
カーボン繊維を硝酸１０％溶液中で２〜３時間加熱後濾
過水洗し、乾燥する。白金を王水で溶解後加熱濃縮して
塩酸酸性とした後、温水を加え約８０ｒｄとする。この
溶液に前記の乾燥したカーボン繊維を加えて、次いでこ
の溶液にホルマリン（３７ｖｏ１％）を約８ｍ１．加え
た後、ＮａＯＨ溶液（３０ｗｔ％）を溶液が弱アルカリ
性を示すまで加える。その後、カーボン繊維を溶液から
取り出し、水洗した後、１２０〜１５０℃で乾燥する。The carbon fibers are heated in a 10% nitric acid solution for 2 to 3 hours, filtered, washed with water, and dried. After dissolving platinum in aqua regia, heating and concentrating the solution to make it acidic with hydrochloric acid, warm water was added to make the solution about 80 rd. The dried carbon fibers were added to this solution, and then about 8 ml of formalin (37 vol. 1%) was added to this solution. After addition, NaOH solution (30 wt%) is added until the solution becomes slightly alkaline. Thereafter, the carbon fibers are taken out of the solution, washed with water, and then dried at 120 to 150°C.
メタンガス分解反応は炭酸ガス還元・酸素回収システム
の一部に用いることができる。第３図に示す通り、炭酸
ガス還元・酸素回収システムは人間の呼吸により排出さ
れた炭酸ガスを分離・濃縮Ｆ後、その炭酸ガスを水素で
還元Ｇすることにより、メタンガスと水が生成する。メ
タンガスは分解工されることにより、固体炭素及び水素
が生成し、水素は炭酸ガス還元用として再利用される。The methane gas decomposition reaction can be used as part of a carbon dioxide reduction/oxygen recovery system. As shown in Fig. 3, the carbon dioxide reduction/oxygen recovery system separates and concentrates carbon dioxide gas emitted by human breathing, and then reduces the carbon dioxide gas with hydrogen, thereby producing methane gas and water. Methane gas is decomposed to produce solid carbon and hydrogen, and the hydrogen is reused for reducing carbon dioxide gas.
また炭酸ガスを還元することにより得られる水は、酸素
と水素とに電気分解Ｈされ、酸素は人間の呼吸用として
、水素は炭酸ガス還元用として再利用される。メタンガ
ス分解反応とは、以上の反応中Ｉの反応を示す。Furthermore, water obtained by reducing carbon dioxide gas is electrolyzed into oxygen and hydrogen, and the oxygen is reused for human respiration and the hydrogen is reused for reducing carbon dioxide gas. The methane gas decomposition reaction refers to reaction I in the above reactions.
本発明のメタンガス分解を用いてメタンガスを熱分解す
ることにより、触媒交換頻度を約２倍に延長できるため
、メタン分解炉の昇温、降温サイクルに要する電力を低
減できる。またメタンガス分解率を反応温度１０００℃
で約１５％向上することができるとともに触媒重量を約
スに軽減できるため、宇宙船等に使用する場合有利であ
る。By thermally decomposing methane gas using the methane gas decomposition method of the present invention, the frequency of catalyst replacement can be approximately doubled, thereby reducing the power required for the temperature raising and temperature lowering cycles of the methane decomposition furnace. In addition, the methane gas decomposition rate was measured at a reaction temperature of 1000°C.
The catalyst weight can be improved by about 15% and the weight of the catalyst can be reduced by about 100%, which is advantageous when used in spacecraft and the like.
第１図は本発明の一実施例のメタンガス分解用触媒の効
果を把握するために使用したメタン分解分解装置の概略
図、第２図は本発明の一実施例のメタンガス分解用触媒
の効果を示す図表、第３図はメタンガス分解反応が組み
込まれる反応系を説明するためのフロー、第４図は従来
のメタンガス分解装置の一態様を示す概略図である。
明Figure 1 is a schematic diagram of a methane decomposition device used to understand the effects of the methane gas decomposition catalyst of one embodiment of the present invention, and Figure 2 is a schematic diagram of the methane gas decomposition device used to understand the effects of the methane gas decomposition catalyst of one embodiment of the present invention. FIG. 3 is a flowchart for explaining a reaction system in which a methane gas decomposition reaction is incorporated, and FIG. 4 is a schematic diagram showing an embodiment of a conventional methane gas decomposition apparatus. Akira
Claims (1)
るメタンガス分解用触媒。A catalyst for decomposing methane gas, which is made by supporting a platinum-based metal on heat-resistant fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2180510A JPH0471643A (en) | 1990-07-10 | 1990-07-10 | Catalyst for decomposing methane gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2180510A JPH0471643A (en) | 1990-07-10 | 1990-07-10 | Catalyst for decomposing methane gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0471643A true JPH0471643A (en) | 1992-03-06 |
Family
ID=16084512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2180510A Pending JPH0471643A (en) | 1990-07-10 | 1990-07-10 | Catalyst for decomposing methane gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0471643A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005536866A (en) * | 2002-07-22 | 2005-12-02 | オヴォニック バッテリー カンパニー インコーポレイテッド | Coated catalyst material |
| JP2006255533A (en) * | 2005-03-15 | 2006-09-28 | Toyota Central Res & Dev Lab Inc | Gas cleaning material and its manufacturing method |
-
1990
- 1990-07-10 JP JP2180510A patent/JPH0471643A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005536866A (en) * | 2002-07-22 | 2005-12-02 | オヴォニック バッテリー カンパニー インコーポレイテッド | Coated catalyst material |
| JP4785384B2 (en) * | 2002-07-22 | 2011-10-05 | オヴォニック バッテリー カンパニー インコーポレイテッド | Coated catalyst material |
| JP2006255533A (en) * | 2005-03-15 | 2006-09-28 | Toyota Central Res & Dev Lab Inc | Gas cleaning material and its manufacturing method |
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