JPS61222540A - Carbon monoxide converting catalyst - Google Patents
Carbon monoxide converting catalystInfo
- Publication number
- JPS61222540A JPS61222540A JP60063475A JP6347585A JPS61222540A JP S61222540 A JPS61222540 A JP S61222540A JP 60063475 A JP60063475 A JP 60063475A JP 6347585 A JP6347585 A JP 6347585A JP S61222540 A JPS61222540 A JP S61222540A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carbon monoxide
- manganese nodule
- cuo
- total amount
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は一酸化炭素と水蒸気から水素を製造する一酸化
炭素転化反応に使用する触媒に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a catalyst used in a carbon monoxide conversion reaction for producing hydrogen from carbon monoxide and steam.
（従来の技術）
今日の市民生活にとって都市ガスは欠くべからざるもの
となっている。従来から都市ガスの原料として用いられ
てきた石炭ならびに石油類が大都市およびその周辺部に
おいては液化石油ガスや液化天然ガスに置き換えられつ
つあるが、中小の都市においては石油改質ガスがいまだ
に主流をなしている。との改質ガスは毒性を有する一酸
化炭素を含有しているため、該−酸化炭素の含有量を低
減することが各方面から強く望まれてお〕、現行のプロ
セスＫかいては下記の接触反応によシー酸化炭素の低減
がなされている。(Conventional technology) City gas has become indispensable for today's citizen life. Coal and petroleum, which have traditionally been used as raw materials for city gas, are being replaced by liquefied petroleum gas and liquefied natural gas in large cities and their surrounding areas, but reformed petroleum gas is still the mainstream in small and medium-sized cities. is doing. Since the reformed gas containing carbon monoxide contains toxic carbon monoxide, there is a strong desire from various quarters to reduce the content of carbon monoxide. Sea oxide carbon is reduced by catalytic reaction.
前記反応には一般にペレット状に成型した酸化鉄−酸化
クロム系触媒が高温−酸化炭素転化反応に用いられてい
る。クロムは助触媒として酸化鉄の表面積を増加させる
と同時にその焼結を防止する目的で用いられているもの
の、その毒性のため特定化学物質とされ、総理府令や労
働安全衛生法等によシ種々の規制を受けている。In the above reaction, an iron oxide-chromium oxide catalyst formed into pellets is generally used for the high-temperature carbon oxide conversion reaction. Although chromium is used as a promoter to increase the surface area of iron oxide and to prevent its sintering, it is classified as a specified chemical substance due to its toxicity, and is subject to various regulations such as the Prime Minister's Office Ordinance and the Industrial Safety and Health Act. is subject to regulations.
例えば水質汚濁防止法によって、排水中の全り臣ム２
ｗＩ／ Ｌ以下、六価クロム１５岬／を以下とされ、又
有害外産業廃棄物に係る判定基準は総理府令で定められ
た方法によって溶出させた場合、六価クロム化合物の溶
出量がｔｓｑ以下とされ、更に労働安全衛生法によって
、作業環境中のクロム化合物は１ ａｔｍ 、 ２５℃
において空気１ ｍ”中に１１岬以下とされている。従
って鉄−クロム系触媒を製造する場合、かかる規制を満
足するように作業環境及び工程よシ出る排水には万全の
対策を取らねばならず、又工業的に使用済の触媒はクロ
ムを含有しているためにしばしばその処理に困る。For example, according to the Water Pollution Control Law, all waste water in wastewater is
wI/L or less, hexavalent chromium is 15 capes/or less, and the criteria for non-hazardous industrial waste is that when eluted by the method specified by the Prime Minister's Office Ordinance, the amount of hexavalent chromium compounds eluted is less than tsq. Furthermore, according to the Industrial Safety and Health Act, chromium compounds in the working environment must be kept at 1 atm and 25°C.
Accordingly, when manufacturing iron-chromium catalysts, it is necessary to take all possible measures for the working environment and the wastewater emitted from the process to satisfy these regulations. Furthermore, industrially used catalysts often contain chromium and are therefore difficult to dispose of.
（発明が解決しようとする問題点）
本発明はかかる欠点を有する鉄−クロム系触媒に代る触
媒を提供しようセするものである。(Problems to be Solved by the Invention) The present invention seeks to provide a catalyst that can replace iron-chromium catalysts that have the above drawbacks.
（問題点を解決するための手段）
本発明は、種々研究の結果、マンガンΦノジュールが同
上の目的を満足する物質であることを見い出し、本発明
に到達したものである。(Means for Solving the Problems) As a result of various studies, the present invention has been achieved by discovering that manganese Φ nodules are a substance that satisfies the above objects.
すなわち、本発明はＦｅ、 Ｎｉ、 Ｃｏ、 ＣｕがＦ
ｅ１Ｏ１゜Ｎｉｐ、 Ｃｏｏ、 ＣｕＯ換算でその合計
量が１５−以上であるマンガン・ノジユールから々る還
元ガス中の一酸化炭素転化用触媒である。That is, in the present invention, Fe, Ni, Co, and Cu are F
This is a catalyst for converting carbon monoxide in reducing gas from manganese nodule, in which the total amount in terms of e1O1°Nip, Coo, and CuO is 15 or more.
本発明におけるマンガン・ノジユールはマンガンと鉄を
主成分として広く海底面に分布し、これらの成分は結晶
化したものが少なく、無定形の酸化物または水酸化物の
形態で存在している。マンガン・ノジユールは中心核と
その周囲を取りまく部分とが明らかにわかるものが多く
、周縁部の黒色層はマンガン、鉄を主成分とする殻であ
シ、中心核は軽石、風化した岩石によシ構成されている
。The manganese nodule according to the present invention has manganese and iron as its main components and is widely distributed on the ocean floor, and these components are rarely crystallized and exist in the form of amorphous oxides or hydroxides. In many cases of manganese nodule, the central core and surrounding parts are clearly visible.The black layer on the periphery is a shell mainly composed of manganese and iron, and the central core is made of pumice and weathered rock. is configured.
マンガン・ノジユールを構成する化学成分の組成範囲を
下記に示す。The composition range of the chemical components that make up manganese nodule is shown below.
Ｍｎ ： ６． Ｏ〜５５．０ ％Ｆｅ： １
．０〜５（１０％
Ｎｉ： （ＬＯＩ 〜１５０％
ｃｏ： ａｏｌ 〜１．５０％
Ｃｕ ： （Ｌ Ｏ１〜ｔ ００ ％前記微量成分の
内Ｎｉ、 Ｃｏ、 Ｃｕ は−酸化炭素転化反応の活性
促進作用があると言われている。Mn: 6. O~55.0%Fe: 1
．． 0 to 5 (10% Ni: (LOI ~150% co: aol ~1.50% Cu: (LOI ~ t 00%) Ni, Co, and Cu among the minor components have an activity-promoting effect on the carbon oxide conversion reaction. It is said that there is.
本発明における一酸化炭素転化触媒としてのマンガン・
ノジユールはＦｅ、 Ｎｉ、 Ｃｏ、 Ｃｕ がＦｅ１
Ｏ１，Ｎｉｐ、 Ｃｏｏ、 ＣｕＯ換算で、その合計が
１５チ以上のものである。以下、本発明の一酸化炭素転
化触媒を実施例に従い説明する。Manganese as a carbon monoxide conversion catalyst in the present invention
Fe, Ni, Co, and Cu are Fe1
The total is 15 or more in terms of O1, Nip, Coo, and CuO. Hereinafter, the carbon monoxide conversion catalyst of the present invention will be explained according to Examples.
〈実施例〉
試料Ａ１試料Ｂ及び試料Ｃはそれぞれ表１゜２及び３に
示す組成のマンガン・ノジユールな粒径５■以下に粉砕
し、円柱状（１０１φ×１０１ｈ）に加圧成型したもの
を用いた。<Example> Sample A1, Sample B and Sample C are manganese nodule particles having the compositions shown in Tables 1゜2 and 3, respectively, which are pulverized to a particle size of 5 cm or less, and pressure molded into a cylindrical shape (101φ x 101h). Using.
表１ 試料Ａマンガン・ノジユールの化学組成表２
試料Ｂマンガン・ノジユールの化学組成表３ 試料
Ｃマンガン・ノジユールの化学組成触媒の性能評価は表
４に示す試験条件につき、触媒層出口ガス中のＣＯガス
濃度を測定し、−酸化炭素転化率を求めた。なお比較の
ため、市販Ｆｅ −Ｃｒ系触媒（日量ガードラー製Ｇ
−５Ａ）についても同一条件にて一酸化炭素転化率を求
めた。Table 1 Chemical composition table 2 of sample A manganese nodule
Chemical composition of sample B manganese nodule Table 3 Chemical composition of sample C manganese nodule To evaluate the performance of the catalyst, measure the CO gas concentration in the catalyst layer outlet gas under the test conditions shown in Table 4, and calculate the -carbon oxide conversion rate. I asked for it. For comparison, a commercially available Fe-Cr catalyst (Girder Girder)
-5A), the carbon monoxide conversion rate was also determined under the same conditions.
表４ 活性試験条件
実施例における一酸化炭素転化率の経時変化を第１図に
示す。Table 4 Activity Test Conditions Figure 1 shows the change over time in the carbon monoxide conversion rate in Examples.
第１図に示した結果の如く、本発明外の試料Ｂのマンガ
ン・ノジユールは市販のＦｅ−Ｃｒ系触媒に比較し、て
著しく性能が低いことがわかる。As shown in the results shown in FIG. 1, it can be seen that the manganese nodule of Sample B, which is outside the scope of the present invention, has significantly lower performance than the commercially available Fe--Cr catalyst.
−志木発明にかかる試料Ａ及び試料Ｃのマンガン・ノジ
ユールは市販のＦｅ−Ｃｒ系触媒に比較して遜色のない
活性を示すことから、実用触媒として用いることができ
ることが実証された。なお本発明の触媒は燃料電池用水
素製造用、アンモニア合成の水素製造用等水性ガス転化
反応においでも有効な触媒であり、都市ガス製造用に限
定されるものではない。- Shiki Since the manganese nodule of Sample A and Sample C according to the invention showed activity comparable to that of commercially available Fe-Cr-based catalysts, it was demonstrated that they can be used as practical catalysts. The catalyst of the present invention is also effective in water gas conversion reactions such as hydrogen production for fuel cells and hydrogen production in ammonia synthesis, and is not limited to use in city gas production.
第１１図は本発明の一酸化炭素転化触媒の性能試験結果
を示す図である。
復代理人 内 １） 明
復代理人 萩 原 亮 −FIG. 11 is a diagram showing the performance test results of the carbon monoxide conversion catalyst of the present invention. Sub-agents 1) Meifuku agent Ryo Hagiwara -
Claims (1)
ｏＯ、ＣｕＯ換算でその合計量が１５％以上であるマン
ガン・ノジユールからなる、還元ガス中の一酸化炭素転
化用触媒。Fe, Ni, Co, and Cu are Fe_2O_3, NiO, and C
A catalyst for converting carbon monoxide in a reducing gas, comprising manganese nodule whose total amount is 15% or more in terms of oO and CuO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60063475A JPS61222540A (en) | 1985-03-29 | 1985-03-29 | Carbon monoxide converting catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60063475A JPS61222540A (en) | 1985-03-29 | 1985-03-29 | Carbon monoxide converting catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61222540A true JPS61222540A (en) | 1986-10-03 |
Family
ID=13230291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60063475A Pending JPS61222540A (en) | 1985-03-29 | 1985-03-29 | Carbon monoxide converting catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61222540A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2604921A1 (en) * | 1986-10-10 | 1988-04-15 | Didier Werke Ag | USE OF MANGANIFEROUS NODULES OR MANGANESE-CONTAINING DEPTH DEPTHS IN CATALYSTS TO REDUCE THE NITROGEN NITROGEN OF RESIDUAL GAS NITROGEN |
| KR100460433B1 (en) * | 2001-12-11 | 2004-12-08 | (주)에너피아 | Catalyst for Purifying Reformate Gas and Process for Selectively Removing Carbon Monoxide Contained in Hydrogen-enriched Reformate Gas Using the Same |
| WO2004058634A3 (en) * | 2002-12-20 | 2005-01-13 | Honda Motor Co Ltd | Catalyst formulations for hydrogen generation |
| CN105983425A (en) * | 2015-03-03 | 2016-10-05 | 焦作正恒实业有限公司 | Novel gas-atomization contact agent powder |
| CN105983419A (en) * | 2015-02-09 | 2016-10-05 | 焦作正恒实业有限公司 | Novel water atomized catalyst powder |
-
1985
- 1985-03-29 JP JP60063475A patent/JPS61222540A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2604921A1 (en) * | 1986-10-10 | 1988-04-15 | Didier Werke Ag | USE OF MANGANIFEROUS NODULES OR MANGANESE-CONTAINING DEPTH DEPTHS IN CATALYSTS TO REDUCE THE NITROGEN NITROGEN OF RESIDUAL GAS NITROGEN |
| KR100460433B1 (en) * | 2001-12-11 | 2004-12-08 | (주)에너피아 | Catalyst for Purifying Reformate Gas and Process for Selectively Removing Carbon Monoxide Contained in Hydrogen-enriched Reformate Gas Using the Same |
| WO2004058634A3 (en) * | 2002-12-20 | 2005-01-13 | Honda Motor Co Ltd | Catalyst formulations for hydrogen generation |
| US7179442B2 (en) | 2002-12-20 | 2007-02-20 | Honda Giken Kogyo Kabushiki Kaisha | Catalyst formulations containing Group 11 metals for hydrogen generation |
| CN105983419A (en) * | 2015-02-09 | 2016-10-05 | 焦作正恒实业有限公司 | Novel water atomized catalyst powder |
| CN105983425A (en) * | 2015-03-03 | 2016-10-05 | 焦作正恒实业有限公司 | Novel gas-atomization contact agent powder |
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