JPS6377546A - Catalyst for conversion of carbon monoxide and its production - Google Patents
Catalyst for conversion of carbon monoxide and its productionInfo
- Publication number
- JPS6377546A JPS6377546A JP61218916A JP21891686A JPS6377546A JP S6377546 A JPS6377546 A JP S6377546A JP 61218916 A JP61218916 A JP 61218916A JP 21891686 A JP21891686 A JP 21891686A JP S6377546 A JPS6377546 A JP S6377546A
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble
- catalyst
- salt
- compound
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011572 manganese Chemical class 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GFCDJPPBUCXJSC-UHFFFAOYSA-N [O-2].[Zn+2].[Cu]=O Chemical compound [O-2].[Zn+2].[Cu]=O GFCDJPPBUCXJSC-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WVYYHSKIGBEZCQ-UHFFFAOYSA-N [O-2].[O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[O-2].[Cr+3].[Fe+2] WVYYHSKIGBEZCQ-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 alkali hydroxide compound Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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
- Inorganic Compounds Of Heavy Metals (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、−酸化炭素と水から水素を製造する触媒に関
するものであり、詳しくは１５０〜３５０℃の低温でも
活性が高く、長期間使用しても活性低下が少ない組成式
Ｃｕ Ｍ ｎ Ｏ，で表される一酸化炭素転化用触媒及
びその欠造方法に関するものである。Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a catalyst for producing hydrogen from -carbon oxide and water. The present invention relates to a carbon monoxide conversion catalyst represented by the compositional formula CuMnO, which causes little decrease in activity even when used, and a method for producing the same.
（ロ）従来の技術
従来より、−酸化炭素転化用触媒としては酸化鉄−酸化
クロム系触媒等の高温用触媒並びに酸化銅−酸化亜鉛系
、酸化鋼−酸化亜鉛−酸化クロム系及び酸化銅−酸化亜
鉛−酸化アルミニウム系触媒等の低温用触媒の２種が使
用されている。(b) Conventional technology Conventionally, as catalysts for converting carbon oxide, high-temperature catalysts such as iron oxide-chromium oxide catalysts, copper oxide-zinc oxide catalysts, steel oxide-zinc oxide-chromium oxide catalysts, and copper oxide catalysts have been used. Two types of low-temperature catalysts are used, such as zinc oxide-aluminum oxide catalysts.
また、組成式ＣｕＭｎＯ２の化合物は、■クレドネライ
ト鉱石から採取する方法、■酸化第１１１Ｎと２，３酸
化マンガンを空気中で焼成する方法等で得ることができ
る。Further, the compound having the compositional formula CuMnO2 can be obtained by (1) a method of collecting from credonnelite ore, (2) a method of calcining 111N oxide and 2,3 manganese oxide in air, etc.
（ハ）発明が解決しようとする問題点
高温用の酸化鉄−酸化クロム系触媒等は比較的安価では
あるが低温での活性が低く水素の収率が低い。(c) Problems to be Solved by the Invention Although iron oxide-chromium oxide catalysts for high temperatures are relatively inexpensive, their activity at low temperatures is low and the yield of hydrogen is low.
又、低温用の酸化銅−酸化亜鉛系触媒等は、高温になる
とその活性が消失するという欠点を有している。Further, copper oxide-zinc oxide catalysts for low temperatures have the disadvantage that their activity disappears at high temperatures.
更に、クレドネライト鉱石から採取した組成式Ｃｕ Ｍ
ｎ Ｏ２の化合物及び酸化第１銅と２，３酸化マンガ
ンより製造した組成式ＣｕＭｎＯ２の化合物は共に、酸
化銅、酸化マンガン及び組成式Ｃｕ Ｍ ｎ 、○。の
化合物の夾雑物が存在し純粋な組成式Ｃｕ Ｍ ｎ Ｏ
２の化合物を得ることは極めて困難である。Furthermore, the composition formula Cu M extracted from crednellite ore
Both the compound of n O2 and the compound of the compositional formula CuMnO2 produced from cuprous oxide and manganese 2,3 oxide have copper oxide, manganese oxide and the compositional formula Cu M n , ○. The pure compositional formula Cu M n O
It is extremely difficult to obtain compound 2.
従って、触媒として使用する場合触媒活性及び成形性等
の点で満足できるものではなかった。Therefore, when used as a catalyst, it was not satisfactory in terms of catalytic activity, moldability, etc.
（ニ）問題点を解決するための手段
本発明者らは、上記−酸化炭素転化用触媒の欠点を改良
すべく鋭意検討努力した結果、組成式Ｃｕ Ｍ ｎ Ｏ
２の化合物が、従来の銅−マンガン系のスピネル型のＣ
ｕ Ｍ ｎ 、○、触媒又は酸化銅と酸化マンガンの単
なる混合物と異なり、低温で活性が高く且つ長期間活性
が持続する触媒であることを見出し本発明を完成するに
至った。(d) Means for Solving the Problems As a result of intensive study and efforts by the present inventors to improve the shortcomings of the above-mentioned carbon oxide conversion catalyst, the composition formula Cu M n O
The compound No. 2 is a conventional copper-manganese spinel type C
u M n , ○, Unlike a catalyst or a mere mixture of copper oxide and manganese oxide, the present invention was completed by discovering that the catalyst is highly active at low temperatures and maintains its activity for a long period of time.
即ち、本発明は、組成式ＣｕＭｎＯ２で表される一酸化
炭素転化用触媒及び銅とマンガンの水溶性塩をほぼ等モ
ルの割合で混合した水溶液を水溶性塩の合計量に対して
当量以上の水酸化アルカリ水溶液中６０〜５５０℃で水
熱反応させることを特徴とする組成式ＣｕＭｎＯ２で表
される一酸化炭素転化用触媒の製造方法に関するもので
ある。That is, in the present invention, an aqueous solution in which a carbon monoxide conversion catalyst represented by the composition formula CuMnO2 and a water-soluble salt of copper and manganese are mixed in an approximately equimolar ratio, is added in an amount equivalent to or more relative to the total amount of the water-soluble salt. The present invention relates to a method for producing a carbon monoxide conversion catalyst represented by the compositional formula CuMnO2, which is characterized by carrying out a hydrothermal reaction at 60 to 550°C in an aqueous alkali hydroxide solution.
本発明に使用される銅及びマンガンの水溶性塩としては
、硫酸塩、塩化物、硝酸塩、蟻酸塩及び酢酸塩等が好ま
しい。Preferred water-soluble salts of copper and manganese used in the present invention include sulfates, chlorides, nitrates, formates, and acetates.
又、本発明に使用される銅は２価の水溶性塩であり、マ
ンガンは２価の水溶性塩である。Further, copper used in the present invention is a divalent water-soluble salt, and manganese is a divalent water-soluble salt.
水酸化アルカリ化合物としては水酸化カリウム及び水酸
化ナトリウム等が好ましい。Preferred examples of the alkali hydroxide compound include potassium hydroxide and sodium hydroxide.
銅の水溶性塩とマンガンの水溶性塩の混合モル比は０．
８：１から１．２：１の範囲、好ましくは０．９：１か
ら１．１：１が良い。The mixing molar ratio of water-soluble copper salt and manganese water-soluble salt is 0.
The range is 8:1 to 1.2:1, preferably 0.9:1 to 1.1:1.
銅に対するマンガンのモル比が０．８未満又は１．２を
越えると組成式Ｃｕ Ｍ ｎ○２の化合物以外の生成物
が副生するので好ましくない。If the molar ratio of manganese to copper is less than 0.8 or more than 1.2, products other than the compound of the compositional formula Cu M n○2 will be produced as by-products, which is not preferable.
又、水酸化アルカリの使用量は、水溶性塩の合計量に対
して当量以上であれば特に制限はない。Further, the amount of alkali hydroxide used is not particularly limited as long as it is equal to or more than the total amount of water-soluble salts.
反応方法としては、水酸化アルカリ水溶液に銅及びマン
ガンの水溶性塩の混合物を添加する方法並びに銅及びマ
ンガンの水溶性塩の混合水溶液に水酸化アルカリ水溶液
を添加する方法等が好ましい。Preferred reaction methods include a method of adding a mixture of water-soluble salts of copper and manganese to an aqueous alkali hydroxide solution, and a method of adding an aqueous alkali hydroxide solution to a mixed aqueous solution of water-soluble salts of copper and manganese.
反応温度は６ｏ〜５５０’Ｃ１好ましくは７０〜１５０
℃が良い、６０’Ｃ未満では組成式ＣｕＭｎＯ２の化合
物の生成が不十分で、５５０℃を越えると組成式Ｃｕ
Ｍ ｎ○２の化合物の粒子径が大きくなり表面積が小さ
くなると共に触媒としての成形性が悪くなる。The reaction temperature is 6o~550'C1, preferably 70~150'C1
℃ is good.If it is less than 60'C, the formation of the compound with the compositional formula CuMnO2 is insufficient, and if it exceeds 550℃, the compound with the compositional formula CuMnO2 is not formed.
The particle size of the compound of M n○2 becomes large, the surface area becomes small, and the moldability as a catalyst deteriorates.
反応は、空気が存在しても良いし、不活性ガス雰囲気中
でも行うことができる。The reaction may be carried out in the presence of air or in an inert gas atmosphere.
反応後、濾過、水洗及び乾燥することにより。After the reaction, by filtration, washing with water and drying.
組成式ＣｕＭｎＯ２の化合物を得ることができる。A compound with the composition formula CuMnO2 can be obtained.
更に１組成式ＣｕＭｎＯ２の化合物を触媒として使用す
る場合、必要に応じて成形することもできる。Furthermore, when a compound of one compositional formula CuMnO2 is used as a catalyst, it can be shaped as necessary.
（ホ）発明の効果
本発明による組成式Ｃｕ Ｍ ｎ○２の化合物は純度が
高く、触媒として使用し易い。(E) Effects of the Invention The compound of the compositional formula Cu M n○2 according to the present invention has high purity and is easy to use as a catalyst.
更に、−酸化炭素転化用触媒として使用した場合、低温
型の酸化銅−酸化亜鉛系触媒に比較して更に低温で活性
が高く且つ長期間活性が持続する。Furthermore, when used as a catalyst for converting -carbon oxide, it has higher activity at lower temperatures and remains active for a longer period of time than a low-temperature type copper oxide-zinc oxide catalyst.
（へ）実施例
以下１本発明について実施例を挙げて詳細に説明するが
１本発明はこれらに限定されるものではない。(f) Examples The present invention will be described in detail with reference to Examples below, but the present invention is not limited to these.
実施例１
水酸化ナトリウム（４ｍｏｌ）の水溶液ＩＱをオートク
レーブに仕込み、次に塩化第二銅（０，５ｍ０１）と塩
化マンガン（０，５ｍｏｌ）の混合水溶液２Ｑを攪拌し
ながら１時間でオートクレーブに注入した。Example 1 An aqueous solution IQ of sodium hydroxide (4 mol) was charged into an autoclave, and then a mixed aqueous solution 2Q of cupric chloride (0.5 m01) and manganese chloride (0.5 mol) was injected into the autoclave over 1 hour while stirring. did.
注入後の混合液のＰ ＩＩは１１．７０、温度は２８〜
３０’Ｃであった。The P II of the mixed solution after injection is 11.70, and the temperature is 28~
It was 30'C.
次に、オートクレーブ内の空気を窒素ガスで置換した後
、混合液を１５０℃で１５時間水熱処理した。Next, after replacing the air in the autoclave with nitrogen gas, the mixed solution was hydrothermally treated at 150° C. for 15 hours.
得られた＠濁液を濾過、水洗及び乾燥し組成式Ｃｕ Ｍ
ｎ Ｏ□の化合物を得た。この化合物は層状結晶構造
を有する板状の結晶であった。The obtained @turbid solution was filtered, washed with water, and dried to obtain the composition formula Cu M
A compound of n O□ was obtained. This compound was a plate-like crystal with a layered crystal structure.
この化合物のＢ、Ｅ、Ｔ、比表面積は１６ ｍ ／ ｇ
であった・
得られた組成式ＣｕＭｎＯ２の化合物の透過型電子顕微
鏡写真（１００００倍）を参考図に示す。B, E, T, specific surface area of this compound is 16 m/g
A transmission electron micrograph (10,000 times magnification) of the obtained compound having the compositional formula CuMnO2 is shown in the reference figure.
次に、この化合物を常法により打錠成形し１／４１ｎｃ
ｈφＸ １ ／ ８１ｎｃｈの円筒状触媒を作製した。Next, this compound was formed into tablets by a conventional method to form tablets of 1/41 nc.
A cylindrical catalyst of hφX 1/81 nch was produced.
この成形触媒を使用して以下に示す条件で一酸化炭素の
転化反応を行なった。結果を表１に示す。Using this shaped catalyst, a carbon monoxide conversion reaction was carried out under the conditions shown below. The results are shown in Table 1.
触媒使用量 ５０ｃｃ
反応温度 ２００〜３５０℃
空間速度 ２０００ＩＩｒ’″１原料ガス組成
Ｃ○＝１５％
Ｈ，＝８５％
水蒸気添加率（水蒸気モル数／原料ガスモル数）０、４
又、触媒活性の持続性を調べるため反応温度を５００℃
とした他は上記反応条件に５時間保持した後、反応温度
を２００〜３００℃とした他は上記条件で一酸化炭素の
転化反応を行なった。結果を表２に示す。Catalyst usage amount 50cc Reaction temperature 200-350℃ Space velocity 2000IIr'''1 Raw material gas composition
C○ = 15% H, = 85% Steam addition rate (number of moles of steam/number of moles of raw material gas) 0, 4 In addition, the reaction temperature was set to 500°C to check the sustainability of catalyst activity.
After maintaining the above reaction conditions for 5 hours, the conversion reaction of carbon monoxide was carried out under the above conditions except that the reaction temperature was 200 to 300°C. The results are shown in Table 2.
実施例２
５００Ｑのオートクレーブに水酸化ナトリウム６４ｋｇ
を溶解した水溶液２６６Ｑを仕込み１次に硫酸マンガン
１水和物３４．６８ｋｇを溶解した水溶液１００ Ｑ
（２ｍｏｌ／ Ｑ）及び硫酸第二銅５水和物５０．１５
８ｋｇを溶解Ｌ タ水溶液２００Ｑ（１ｍｏｌ／ Ｑ
）を３０℃で１時間で注入した。Example 2 64 kg of sodium hydroxide in a 500Q autoclave
Firstly, prepare an aqueous solution 266Q in which 34.68 kg of manganese sulfate monohydrate was dissolved.
(2 mol/Q) and cupric sulfate pentahydrate 50.15
Dissolve 8kg in Lta aqueous solution 200Q (1 mol/Q
) was injected at 30°C for 1 hour.
注入後、３０分間熟成（ｐＨ１３，８５） し。After injection, it was aged for 30 minutes (pH 13,85).
次いで９５℃で１２時間加熱を行なった。Next, heating was performed at 95° C. for 12 hours.
得られた懸濁液を濾過、水洗及び乾燥し、組成式（：ｕ
ＭｎＯ，の化合物３０ｋｇを得た。The obtained suspension was filtered, washed with water and dried, and the composition formula (:u
30 kg of a compound of MnO was obtained.
この化合物のＢ、Ｅ、Ｔ、比表面積は３６ ｍ ／ ｇ
であった。B, E, T, specific surface area of this compound is 36 m/g
Met.
次に、この化合物より１ ／ ４１ｎｃｈφ×１／８ｉ
ｎｃｈの円筒状触媒を作製した。Next, from this compound, 1/41nchφ×1/8i
A cylindrical nch catalyst was prepared.
この成形触媒を使用して実施例１と同様に試験を行なっ
た。結果を表１に示す。A test was conducted in the same manner as in Example 1 using this shaped catalyst. The results are shown in Table 1.
比較例１
硫酸第二銅５水和物６９ｋｇ及び硫酸マンガン１水和物
８９ｋｇを水３２００ｆｌに溶解した水溶液に、過マン
ガン酸カリウム４８ｋｇ及び炭酸カリウム１２６ｋｇを
水６４００Ｑに溶解した水溶液を攪拌しながら添加した
。Comparative Example 1 To an aqueous solution in which 69 kg of cupric sulfate pentahydrate and 89 kg of manganese sulfate monohydrate were dissolved in 3200 fl of water, an aqueous solution in which 48 kg of potassium permanganate and 126 kg of potassium carbonate were dissolved in 6400 Q of water was added with stirring. did.
沈殿を３時間熟成後、濾過、水洗及び乾燥しホブカライ
ド型化合物を得た。After aging the precipitate for 3 hours, it was filtered, washed with water and dried to obtain a fobcalide type compound.
この化合物のＢ、Ｅ、Ｔ、比表面積は２００ｒ＋？／ｇ
であった。B, E, T, specific surface area of this compound is 200r+? /g
Met.
次に、この化合物より１７４１ｎｃｈφ×１／８ｉｎｃ
ｈの円筒状触媒を作製した。Next, from this compound, 1741nchφ×1/8inch
A cylindrical catalyst of h was prepared.
この成形触媒を使用して実施例１と同様に試験を行なっ
た。結果を表１及び表２に示す。−比較例２
硫酸亜鉛７水和物１０６４ｋｇ、硫酸第二銅５水和物４
１５ｋｇ及び硫酸アルミニウム１８永和物１０４ｋｇを
水４１７０Ｑに溶解した水溶液に、炭酸ナトリウム７４
０ｋｇを水６０１０Ｑに溶解した水溶液を攪拌しながら
添加した。A test was conducted in the same manner as in Example 1 using this shaped catalyst. The results are shown in Tables 1 and 2. - Comparative Example 2 Zinc sulfate heptahydrate 1064 kg, cupric sulfate pentahydrate 4
15 kg of aluminum sulfate and 104 kg of aluminum sulfate 18 permanent were dissolved in water 4170Q, and 74 kg of sodium carbonate was added to the solution.
An aqueous solution of 0 kg dissolved in water 6010Q was added with stirring.
沈殿を３時間熟成後、濾過、水洗及び乾燥し３７０℃で
４時間焼成して、銅、亜鉛の酸化物を得た。The precipitate was aged for 3 hours, filtered, washed with water, dried, and calcined at 370°C for 4 hours to obtain copper and zinc oxides.
この化合物のＢ、Ｅ、Ｔ、比表面積は６０ｍ／ｇであっ
た・
次に、この化合物より１７４１ｎｃｈφ×１／８ｉｎｃ
ｈの円筒状触媒を作製した。The B, E, and T specific surface areas of this compound were 60 m/g.Next, from this compound, 1741 nchφ×1/8 inch
A cylindrical catalyst of h was prepared.
この成形触媒を使用して実施例１と同様に試験を行なっ
た。結果を表１及び表２に示す。A test was conducted in the same manner as in Example 1 using this shaped catalyst. The results are shown in Tables 1 and 2.
第１表
第 ２ 表
実施例３（触媒製造例）
オートクレーブに水酸化ナトリウム６．９１２爾を溶解
した水溶液４３．２１ Ｑ （４ｍｏｌ／ Ｑ）を仕
込み、次に硝酸第二銅３水和物２．ＩＱ９ｋｇ及びマン
ガン粉末４７９ｇを硝酸水溶液ｃｐｈｔ１．３５９）に
溶解した混合水溶液４３．１Ｑ（ｐＨ１，８５）を攪拌
しながら３５分間でオートクレーブに注入した。Table 1 Table 2 Example 3 (Catalyst production example) An aqueous solution of 43.21 Q (4 mol/Q) in which 6.912 sodium hydroxide was dissolved was charged into an autoclave, and then cupric nitrate trihydrate 2 ．． A mixed aqueous solution 43.1Q (pH 1,85) in which 9 kg of IQ and 479 g of manganese powder were dissolved in an aqueous nitric acid solution (cpht 1.359) was injected into the autoclave over 35 minutes with stirring.
注入後３０分間熟成した後、９５℃で５時間加熱を行な
った。After the injection, the mixture was aged for 30 minutes and then heated at 95° C. for 5 hours.
得られた懸濁液を濾過、水洗及び乾燥し、組成式ＣｕＭ
ｎＯ２の板状結晶を得た。The obtained suspension was filtered, washed with water and dried, and the composition formula: CuM
Plate crystals of nO2 were obtained.
この化合物のＩ３．Ｅ、Ｔ、比表面積は３０．１ｍ／ｇ
であった。I3 of this compound. E, T, specific surface area is 30.1m/g
Met.
出願人 口産ガードラー触媒株式会社正同化学工業株
式会社Applicant: Kochi Girdler Catalyst Co., Ltd. Seido Chemical Industry Co., Ltd.
Claims (1)
媒。 ２、銅とマンガンの水溶性塩をほぼ等モルの割合で混合
した水溶液を水溶性塩の合計量に対して当量以上の水酸
化アルカリ水溶液中６０〜５５０℃で水熱反応させるこ
とを特徴とする組成式ＣｕＭｎＯ＿２で表される一酸化
炭素転化用触媒の製造方法。[Claims] 1. A carbon monoxide conversion catalyst represented by the compositional formula CuMnO_2. 2. It is characterized by subjecting an aqueous solution of water-soluble salts of copper and manganese in approximately equimolar ratios to a hydrothermal reaction at 60 to 550°C in an aqueous alkali hydroxide solution in an amount equal to or more than the total amount of water-soluble salts. A method for producing a carbon monoxide conversion catalyst represented by the compositional formula CuMnO_2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61218916A JPS6377546A (en) | 1986-09-17 | 1986-09-17 | Catalyst for conversion of carbon monoxide and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61218916A JPS6377546A (en) | 1986-09-17 | 1986-09-17 | Catalyst for conversion of carbon monoxide and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6377546A true JPS6377546A (en) | 1988-04-07 |
| JPH0515501B2 JPH0515501B2 (en) | 1993-03-01 |
Family
ID=16727326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61218916A Granted JPS6377546A (en) | 1986-09-17 | 1986-09-17 | Catalyst for conversion of carbon monoxide and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6377546A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02164455A (en) * | 1988-12-15 | 1990-06-25 | Matsushita Electric Ind Co Ltd | Exhaust gas purifying catalyst |
| CN1304111C (en) * | 2004-12-31 | 2007-03-14 | 内蒙古工业大学 | Copper-manganese base high temperature transformation catalyst and preparation method thereof |
| JP2007335504A (en) * | 2006-06-13 | 2007-12-27 | Sumitomo Chemical Co Ltd | Thermoelectric conversion material and its manufacturing method |
| CN108862395A (en) * | 2018-06-25 | 2018-11-23 | 广东工业大学 | A kind of delafossite structure CuMnO2Powder and its preparation method and application |
| CN114669191A (en) * | 2022-03-31 | 2022-06-28 | 中国科学院生态环境研究中心 | Manganese copper ore material and application thereof in removing carbon monoxide at room temperature |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683583B (en) * | 2019-10-23 | 2020-06-05 | 山东大学 | Preparation method of manganese copper oxide supercapacitor electrode material |
-
1986
- 1986-09-17 JP JP61218916A patent/JPS6377546A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02164455A (en) * | 1988-12-15 | 1990-06-25 | Matsushita Electric Ind Co Ltd | Exhaust gas purifying catalyst |
| CN1304111C (en) * | 2004-12-31 | 2007-03-14 | 内蒙古工业大学 | Copper-manganese base high temperature transformation catalyst and preparation method thereof |
| JP2007335504A (en) * | 2006-06-13 | 2007-12-27 | Sumitomo Chemical Co Ltd | Thermoelectric conversion material and its manufacturing method |
| CN108862395A (en) * | 2018-06-25 | 2018-11-23 | 广东工业大学 | A kind of delafossite structure CuMnO2Powder and its preparation method and application |
| CN114669191A (en) * | 2022-03-31 | 2022-06-28 | 中国科学院生态环境研究中心 | Manganese copper ore material and application thereof in removing carbon monoxide at room temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0515501B2 (en) | 1993-03-01 |
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