JPS63197548A - Manganese and ferrite catalyst - Google Patents
Manganese and ferrite catalystInfo
- Publication number
- JPS63197548A JPS63197548A JP2899487A JP2899487A JPS63197548A JP S63197548 A JPS63197548 A JP S63197548A JP 2899487 A JP2899487 A JP 2899487A JP 2899487 A JP2899487 A JP 2899487A JP S63197548 A JPS63197548 A JP S63197548A
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- manganese
- decomposition
- catalyst
- ammonium
- 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 27
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 24
- 239000011572 manganese Substances 0.000 title claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 23
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 150000002696 manganese Chemical class 0.000 abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001099 ammonium carbonate Substances 0.000 abstract description 2
- 235000012501 ammonium carbonate Nutrition 0.000 abstract description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 abstract description 2
- FRRMMWJCHSFNSG-UHFFFAOYSA-N diazanium;propanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC([O-])=O FRRMMWJCHSFNSG-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (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、オゾン分解用マンガン・フェライト触媒に関
する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a manganese ferrite catalyst for ozone decomposition.
又、酸素の存在下、一酸化炭素及び炭化水素から選ばれ
る化合物とオゾンの同時分解用マンガン・フェライト触
媒に関するものである。The present invention also relates to a manganese ferrite catalyst for simultaneous decomposition of ozone and a compound selected from carbon monoxide and hydrocarbons in the presence of oxygen.
（ロ）従来の技術
オゾンは、非常に強い酸化力を有し且つ分解生成物が無
害の酸素であることから、殺菌、消毒、脱臭及び脱色等
の目的で、産業界で広く利用されている。(b) Conventional technology Because ozone has very strong oxidizing power and the decomposition product is harmless oxygen, it is widely used in industry for purposes such as sterilization, disinfection, deodorization, and decolorization. .
しかし、その利用過程等においてオゾンが大気中に放出
されると、光化学スモッグ等の原因となるためオゾンの
分解の必要性がさけばれている。However, if ozone is released into the atmosphere during its utilization process, it may cause photochemical smog, etc., so the need to decompose ozone has been avoided.
従来から、オゾンの分解法として活性炭分解法、薬液洗
浄法、熱分解法及び固体触媒による分解法等が知られて
いる。Conventionally, methods for decomposing ozone include an activated carbon decomposition method, a chemical cleaning method, a thermal decomposition method, and a decomposition method using a solid catalyst.
（ハ）発明が解決しようとする問題点
活性炭分解法は、簡便で且つオゾンを確実に分解できる
ので広く利用されている。この方法では、オゾンは活性
炭表面に吸着され活性炭と反応して一酸化炭素及び炭酸
ガスを生成する。(c) Problems to be Solved by the Invention Activated carbon decomposition methods are widely used because they are simple and can reliably decompose ozone. In this method, ozone is adsorbed on the surface of activated carbon and reacts with the activated carbon to generate carbon monoxide and carbon dioxide gas.
Ｃ＋０３→ＣＯ＋Ｏ□＋２５３．２ ｋＪＣ＋２０：＋
→ＣＯ□＋２ｏｚ＋ ６７８．９ ｋＪ従って、この
方法は上記反応により高価な活性炭が消費され、しかも
大きな反応熱のため発火等の危険があり高濃度のオゾン
の分解には使用できない。C+03→CO+O□+253.2 kJC+20:+
→CO□+2oz+ 678.9 kJ Therefore, in this method, expensive activated carbon is consumed by the above reaction, and there is a risk of ignition due to the large heat of reaction, so it cannot be used to decompose highly concentrated ozone.
薬液洗浄法は、水酸化す） ＩＪウム水溶液等のアルカ
リ水溶液、又はチオ硫酸ナトリウム等の還元剤でオゾン
を分解する方法であるが薬剤費が高価であり、湿式法の
ためスクラバーを必要とし、更に廃液処理の必要がある
等の欠点がある。The chemical cleaning method is a method of decomposing ozone with an alkaline aqueous solution such as hydroxide solution or a reducing agent such as sodium thiosulfate, but the chemicals are expensive and the wet method requires a scrubber. Furthermore, there are drawbacks such as the need for waste liquid treatment.
熱分解法は、オゾンを高温で且つ滞留時間１秒以上で分
解する方法である。しかし、３５０°Ｃ程度の高温まで
オゾンを加熱しなければならず、燃料費が高（つく。又
、この方法は加熱装置の立上りに時間を要し間歇的使用
が困難である。The thermal decomposition method is a method of decomposing ozone at high temperature and residence time of 1 second or more. However, it is necessary to heat the ozone to a high temperature of about 350° C., which increases fuel costs.Furthermore, this method requires time for the heating device to start up, making it difficult to use it intermittently.
固体触媒による接触分解法は、二酸化マンガン、酸化鉄
及び酸化ニッケル等の金属酸化物、又は銀、白金等の貴
金属をアルミナ及び酸化珪素等に担持したものを触媒と
し、オゾンを接触分解する方法である。The catalytic cracking method using a solid catalyst is a method of catalytically decomposing ozone using metal oxides such as manganese dioxide, iron oxide, and nickel oxide, or precious metals such as silver and platinum supported on alumina and silicon oxide as catalysts. be.
Ｃａ １ｄｅｒｂａｎｋ及びＬｅｗｉｓによればオゾン
の分解機構は次の通りである。（Ｃｈｅｍ、 Ｅｎｄ、
Ｓｃｉ、、３１（１２）。According to Calderbank and Lewis, the decomposition mechanism of ozone is as follows. (Chem, End,
Sci., 31(12).
０３＋−Ｈ−→ −Ｈ−＋ Ｏ、（１）−Ｈ−＋０３
→ −Ｈ＋２０ｇ （２）■
酸化鉄、酸化ニッケル、銀及び白金等は、反応（１）に
比べて反応（２）の活性化エネルギーが大きくオゾン分
解活性が時間と共に低下するため、オゾンの分解活性を
持続するには５０°Ｃ以上の温度で使用する必要がある
。03+-H-→ -H-+ O, (1)-H-+03
→ -H+20g (2) ■ Iron oxide, nickel oxide, silver, platinum, etc. have a larger activation energy for reaction (2) than reaction (1), and their ozone decomposition activity decreases over time. To maintain this, it is necessary to use the product at a temperature of 50°C or higher.
酸化銅及び酸化コバルト等は、反応（２）に比べて反応
（１）の活性化エネルギーが大きくオゾン分解活性が時
間とともに増大するが初期活性が小さいため、間歇的な
使用には適さない。Copper oxide, cobalt oxide, etc. have a larger activation energy for reaction (1) than reaction (2), and their ozonolytic activity increases with time, but their initial activity is small, so they are not suitable for intermittent use.
又、酸化マンガンは低温での活性が小さい。Furthermore, manganese oxide has low activity at low temperatures.
上記触媒はいずれも常温では失活が著しいか低活性であ
り、５０°Ｃ以上で使用されているのが現状である。All of the above catalysts are significantly deactivated or have low activity at room temperature, and are currently used at temperatures above 50°C.
更に、半導体産業等から排出されるオゾン濃度は飲方ｐ
ｐｍに達しており、このような高濃度のオゾンを効率良
く分解する触媒は知られていない。Furthermore, the concentration of ozone emitted from the semiconductor industry, etc.
pm, and there are no known catalysts that can efficiently decompose ozone at such high concentrations.
（ニ）問題点を解決するための手段
゛本発明者らは、飲方ｐｐｍに達する高濃度のオゾンを
効率良く分解する触媒並びに一酸化炭素及び炭化水素か
ら選ばれる化合物とオゾンを同時に効率良く除去する触
媒について鋭意検討を行い、本発明を完成するに至った
。(d) Means for solving the problem ゛The present inventors have developed a catalyst that efficiently decomposes ozone at a high concentration reaching ppm in drinking water, and a compound selected from carbon monoxide and hydrocarbons that efficiently decomposes ozone at the same time. After conducting extensive research on the catalyst to be removed, the present invention was completed.
即ち、本発明は、常温で高濃度のオゾンの分解性能が高
く且つ活性低下の非常に少ないマンガン・フェライト触
媒に関するものである。That is, the present invention relates to a manganese ferrite catalyst that has high ozone decomposition performance at a high concentration at room temperature and exhibits very little reduction in activity.
又、本発明は、一酸化炭素及び炭化水素から選ばれる化
合物とオゾンの同時除去にも極めて高活性なマンガン・
フェライト触媒に関するものである。In addition, the present invention uses manganese, which is extremely active in simultaneously removing ozone and compounds selected from carbon monoxide and hydrocarbons.
It relates to ferrite catalysts.
本発明のマンガン・フェライト触媒は、例えばマンガン
及び鉄の可溶性塩の混合溶液と蟻酸アンモニウム、蓚酸
アンモニウム、マロン酸アンモニウム又は炭酸アンモニ
ウム等から、加熱により容易に炭酸ガスを発生する無機
酸又は有機酸のマンガン塩及び鉄塩を共沈させ、乾燥、
３００〜８゜ＯｏＣでの焼成を行いマンガン・フェライ
トを得た後、生成したマンガン・フェライトを通常の成
形法で成形して触媒として使用する。The manganese ferrite catalyst of the present invention is an inorganic or organic acid that easily generates carbon dioxide gas by heating, for example, from a mixed solution of soluble salts of manganese and iron and ammonium formate, ammonium oxalate, ammonium malonate, or ammonium carbonate. Co-precipitate manganese salt and iron salt, dry,
After obtaining manganese ferrite by performing calcination at 300 to 8° OoC, the produced manganese ferrite is molded by a conventional molding method and used as a catalyst.
（ホ）発明の効果
本発明のマンガン・フェライト触媒は、−１０〜５０°
Ｃの低温好ましくは０〜４０°Ｃにおいてもオゾン分解
性能が高く且つ活性低下が非常に少ない。(e) Effects of the invention The manganese ferrite catalyst of the present invention has a temperature of -10 to 50°
The ozone decomposition performance is high even at low temperatures of C, preferably from 0 to 40°C, and the decrease in activity is very small.
又、飲方ｐｐ＋ｍに達する高濃度のオゾンを効率良く分
解することができる。In addition, it is possible to efficiently decompose ozone at a high concentration reaching pp+m.
更に、本発明のマンガン・フェライト触媒は、酸素の存
在下、一酸化炭素及び炭化水素から選ばれる化合物とオ
ゾンの同時分解除去においても極めて活性が高い。Furthermore, the manganese ferrite catalyst of the present invention has extremely high activity in the simultaneous decomposition and removal of ozone and a compound selected from carbon monoxide and hydrocarbons in the presence of oxygen.
（ト）実施例
次に、本発明の実施例を具体的に説明するが、本発明は
これらによって限定されるものではない。(g) Examples Next, examples of the present invention will be specifically described, but the present invention is not limited thereto.
実施例１
硫酸第１マンガン７水和物９．２ｋｇを水１００１に溶
解した溶液と硫酸鉄アンモニウム６水和物７７．６ｋｇ
を水２００１に溶解した溶液を混合した。Example 1 A solution of 9.2 kg of manganous sulfate heptahydrate dissolved in 100 ml of water and 77.6 kg of ferrous ammonium sulfate hexahydrate
A solution of 2001 in water was mixed.
次に、蓚酸アンモニウム３７．２ｋｇを水３００１に溶
解した溶液を添加し数分間撹拌し１時間放置したところ
、蓚酸マンガンと蓚酸鉄の共沈澱物が得られた。Next, a solution of 37.2 kg of ammonium oxalate dissolved in 3001 of water was added, stirred for several minutes, and left to stand for 1 hour, resulting in a coprecipitate of manganese oxalate and iron oxalate.
この共沈澱物を濾過、水洗、乾燥、４００°Ｃでの焼成
及び粉砕を行いマンガン・フェライト粉末を得た。This coprecipitate was filtered, washed with water, dried, fired at 400°C, and pulverized to obtain manganese ferrite powder.
次に、マンガン・フェライト粉末６０部、アルミナ及び
酸化珪素を主成分とする粘土鉱物３０部、カルボキシメ
チルセルロース１０部及び水１０部を混合しスクリュー
押出機にて成型後、１０５°Ｃで１２時間乾燥し８０龍
φＸ３２０１龍（５００セル／１ｎ２）のマンガン・フ
ェライトハニカム触媒を得た。Next, 60 parts of manganese ferrite powder, 30 parts of clay mineral mainly composed of alumina and silicon oxide, 10 parts of carboxymethyl cellulose, and 10 parts of water were mixed, molded using a screw extruder, and dried at 105°C for 12 hours. A manganese ferrite honeycomb catalyst with a diameter of 80 mm and a diameter of 3201 mm (500 cells/1n2) was obtained.
このマンガン・フェライトハニカム触媒をステンレス反
応管に入れ、入口ガスとして５００００ｐｐｍのオゾン
（残りは空気）を、１０〜２０°Ｃで５Ｊ／ｍｉｎの流
量で通過させ、出口オゾン濃度を測定した。This manganese ferrite honeycomb catalyst was placed in a stainless steel reaction tube, and 50,000 ppm of ozone (the rest was air) was passed through the tube as an inlet gas at a flow rate of 5 J/min at 10 to 20° C., and the outlet ozone concentration was measured.
オゾンの分解率は６００時間経過後も９９．９％以上で
あった。第１表にその分解結果を示す。The ozone decomposition rate remained at 99.9% or higher even after 600 hours. Table 1 shows the decomposition results.
（以下、余白）
第１表 オゾン分解率
実施例２
実施例１と同様にして得たマンガン・フェライトハニカ
ム８０鰭φＸｌ０（ｌ關（５００セル／ｉｎ ”）をス
テンレス反応管に入れ、入口ガスとして５０００ｐｐｍ
のオゾン（残りは空気）を、１０〜２０ ’Ｃで１０１
／ｍｉｎの流量で通過させた。(The following is a blank space) Table 1 Ozone decomposition rate Example 2 Manganese ferrite honeycomb 80 φ 5000ppm
of ozone (the rest is air) at 10-20'C.
It was allowed to pass through at a flow rate of /min.
第２表にその分解結果を示す。Table 2 shows the decomposition results.
又、ｌ０００時間後も、出口オゾン濃度は０．１ｐｉ１
１以下を示した。Also, even after 1000 hours, the outlet ozone concentration remains 0.1pi1.
It showed 1 or less.
即ち、本触媒は常温でオゾン分解に対して極めて高い活
性を示し、しかも活性の低下が非常に少ないものである
ことが分かった。That is, it was found that the present catalyst exhibited extremely high activity against ozone decomposition at room temperature, and the decrease in activity was extremely small.
比較例Ｉ
低温酸化で優れた性能を発揮する触媒として知られてい
る市販銅マンガンポツプカライド粉末を実施例１と同様
にしてハニカム状に成形し、実施例２と同様にしてオゾ
ン分解反応を行った。Comparative Example I Commercially available copper manganese popcalide powder, which is known as a catalyst that exhibits excellent performance in low-temperature oxidation, was formed into a honeycomb shape in the same manner as in Example 1, and an ozone decomposition reaction was carried out in the same manner as in Example 2. went.
第２表にその結果を示す。Table 2 shows the results.
実施例３
実施例１のマンガン・フェライト粉末に１重量％の黒鉛
を添加後、３ ／ １６１ｎｃｈＸ ３ ／ １６１ｎ
ｃｈの円筒状に成形し、以下の条件でオゾン分解反応を
行った。第３表にその結果を示す。Example 3 After adding 1% by weight of graphite to the manganese ferrite powder of Example 1, 3/161nchX 3/161n
The sample was molded into a cylindrical shape, and an ozone decomposition reaction was performed under the following conditions. Table 3 shows the results.
入口オゾン２０ｐｐａ＋（残りは空気）ＳＶ＝ １００
００ｈｒ−’
比較例２
市販パラジウム触媒（０，１％パラジウム／酸化アルミ
ニウム）を使用し、実施例３と同様にしてオゾン分解反
応を行った。第３表にその結果を示す。Inlet ozone 20ppa + (remaining air) SV = 100
00hr-' Comparative Example 2 An ozone decomposition reaction was carried out in the same manner as in Example 3 using a commercially available palladium catalyst (0.1% palladium/aluminum oxide). Table 3 shows the results.
比較例３
市販白金触媒（０，２％白金／酸化アルミニウム）を使
用し、実施例３と同様にしてオゾン分解反応を行った。Comparative Example 3 An ozone decomposition reaction was carried out in the same manner as in Example 3 using a commercially available platinum catalyst (0.2% platinum/aluminum oxide).
第３表にその結果を示す。Table 3 shows the results.
実施例４
実施例１のマンガン・フェライトハニカムを使用し、ｎ
−ブタン分解（酸化）反応を以下の条件で行った。第４
表にその結果を示す。Example 4 Using the manganese ferrite honeycomb of Example 1, n
-Butane decomposition (oxidation) reaction was carried out under the following conditions. Fourth
The results are shown in the table.
入口ｎ−ブタン１０１００ｐｐ残りは空気）ＳＶ＝５０
００ｈｒ−’
比較例４
比較例２の銅マンガンポツプカライドハニカムを使用し
、実施例４と同様にしてｎ−ブタン分解（酸化）反応を
行った。Inlet n-butane 10100pp, remaining air) SV=50
00hr-' Comparative Example 4 Using the copper manganese popcalide honeycomb of Comparative Example 2, an n-butane decomposition (oxidation) reaction was carried out in the same manner as in Example 4.
第４表にその結果を示す。Table 4 shows the results.
実施例５
実施例１のマンガンフェライトハニカム触媒を使用し、
−酸化炭素除去反応を以下の条件で行った。第５表にそ
の結果を示す。Example 5 Using the manganese ferrite honeycomb catalyst of Example 1,
-The carbon oxide removal reaction was carried out under the following conditions. Table 5 shows the results.
一酸化炭素２００ｐｐｍ（残りは空気）ＳＶ＝５０００
ｈｒ−’
比較例５
有害ガス浄化用に広く利用されている市販白金ハニカム
（０，２％白金／酸化アルミニウム）を使用し、実施例
５と同様にして一酸化炭素除去（酸化）反応を行った。Carbon monoxide 200ppm (the rest is air) SV=5000
hr-' Comparative Example 5 Using a commercially available platinum honeycomb (0.2% platinum/aluminum oxide) that is widely used for purifying harmful gases, carbon monoxide removal (oxidation) reaction was carried out in the same manner as in Example 5. Ta.
第５表にその結果を示す。Table 5 shows the results.
実施例６
実施例１のマンガン・フェライトハニカム触媒に、オゾ
ン２０００ｐｐｍＳｎ−ブタン１１００ｐｐ及び−酸化
炭素２００ ｐｐｎ＋を含む混合ガス（残りは空気）を
１５０°Ｃ，５Ｖ＝５０００ｈｒ−’の割合で通した。Example 6 A mixed gas containing 2000 ppm of ozone, 1100 ppm of Sn-butane, and 200 ppn+ of -carbon oxide (the rest being air) was passed through the manganese ferrite honeycomb catalyst of Example 1 at 150°C and at a rate of 5V = 5000 hr-'.
その結果は次の通りであった。The results were as follows.
゛オゾン分解率 １００％
ｎ−ブタン分解率 ８９．７％
一酸化炭素除去率 ９９．３％
実施例４及び実施例５と比較して混合ガスの場合、ｎ−
ブタン及び−酸化炭素の分解率は更に高くなった。゛Ozone decomposition rate 100% n-butane decomposition rate 89.7% Carbon monoxide removal rate 99.3% In the case of mixed gas, n-
The decomposition rates of butane and carbon oxide were even higher.
第５表 −酸化炭素除去率 日産ガードラー触媒株式会社Table 5 - Carbon oxide removal rate Nissan Girdler Catalyst Co., Ltd.
Claims (1)
素の存在下、一酸化炭素及び炭化水素から選ばれる化合
物とオゾンの同時分解用マンガン・フェライト触媒(1) Manganese ferrite catalyst for ozone decomposition (2) Manganese ferrite catalyst for simultaneous decomposition of ozone and a compound selected from carbon monoxide and hydrocarbons in the presence of oxygen
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2899487A JP2509600B2 (en) | 1987-02-10 | 1987-02-10 | Manganese / ferrite catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2899487A JP2509600B2 (en) | 1987-02-10 | 1987-02-10 | Manganese / ferrite catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63197548A true JPS63197548A (en) | 1988-08-16 |
| JP2509600B2 JP2509600B2 (en) | 1996-06-19 |
Family
ID=12263966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2899487A Expired - Lifetime JP2509600B2 (en) | 1987-02-10 | 1987-02-10 | Manganese / ferrite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2509600B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004531381A (en) * | 2001-05-15 | 2004-10-14 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Treatment of air pollutants |
| EP2246305A1 (en) * | 2009-04-29 | 2010-11-03 | IFP Energies nouvelles | Mixed iron-manganese oxides for high temperature oxygen production |
| CN116510782A (en) * | 2023-04-28 | 2023-08-01 | 浙江工业大学 | ZIFs-derived core-shell magnetic nano ozone catalyst, preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6776970B1 (en) | 1995-08-07 | 2004-08-17 | Giorgio Vergani | Getter materials for deoxygenating ammonia/oxygen gas mixtures at low temperature |
-
1987
- 1987-02-10 JP JP2899487A patent/JP2509600B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004531381A (en) * | 2001-05-15 | 2004-10-14 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Treatment of air pollutants |
| EP2246305A1 (en) * | 2009-04-29 | 2010-11-03 | IFP Energies nouvelles | Mixed iron-manganese oxides for high temperature oxygen production |
| FR2945036A1 (en) * | 2009-04-29 | 2010-11-05 | Inst Francais Du Petrole | FER-MANGANESE MIXED OXIDES FOR THE PRODUCTION OF HIGH TEMPERATURE OXYGEN |
| US8211212B2 (en) | 2009-04-29 | 2012-07-03 | Ifp | Mixed iron-manganese oxides for high-temperature oxygen production |
| CN116510782A (en) * | 2023-04-28 | 2023-08-01 | 浙江工业大学 | ZIFs-derived core-shell magnetic nano ozone catalyst, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2509600B2 (en) | 1996-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW520998B (en) | Catalyst and method for decomposing nitrous oxide and process for producing the catalyst | |
| CN102580525A (en) | Method for using activated carbon load copper oxide composite catalyst to absorb nitrogenous oxide | |
| JPH02198639A (en) | Catalyst for decomposing ammonia | |
| JPS5915022B2 (en) | Catalyst for removing nitrogen oxides from exhaust gas | |
| JP2007054714A (en) | Decomposition catalyst of nitrous oxide and decomposition method of nitrous oxide using the catalyst | |
| JP4861018B2 (en) | Nitric oxide oxidation catalyst and nitric oxide oxidation method | |
| JP2002355558A (en) | Method for oxidation removal of formaldehyde | |
| JPS63197548A (en) | Manganese and ferrite catalyst | |
| JP5483723B2 (en) | Nitrous oxide decomposition catalyst and purification method of gas containing nitrous oxide using the same | |
| JPH11502152A (en) | Process and apparatus for wastewater treatment by oxidation in the presence of a heterogeneous catalyst | |
| JP2711463B2 (en) | Exhaust gas purification method | |
| JPH0510973B2 (en) | ||
| JP4246584B2 (en) | Method for purifying ammonia-containing exhaust gas and ammonia-containing wastewater | |
| JPH0239297B2 (en) | ||
| JPH04371228A (en) | Gold catalyst for removal of malodorous substance | |
| JPH09313940A (en) | Ammonia oxidation decomposition catalyst | |
| JPH09155364A (en) | Treatment of waste water | |
| JP2001104781A (en) | Material for removing nitrogen oxide and method for removing it | |
| JPS61274729A (en) | Removal of hydrogen cyanide in exhaust gas | |
| JP3622211B2 (en) | Methane oxidation method | |
| JP2013056295A (en) | Method for regeneration of nitrous oxide decomposition catlyst | |
| JPS6152729B2 (en) | ||
| KR940006400B1 (en) | Method and apparatus for processing nitrogen oxide gas | |
| JP4092538B2 (en) | Method for producing hydrogen-containing gas | |
| JP2017094309A (en) | Aldehyde removal catalyst, method for producing the same, and aldehyde gas removal method |