JP3163421B2 - Adsorption decomposition deodorant - Google Patents
Adsorption decomposition deodorantInfo
- Publication number
- JP3163421B2 JP3163421B2 JP08982490A JP8982490A JP3163421B2 JP 3163421 B2 JP3163421 B2 JP 3163421B2 JP 08982490 A JP08982490 A JP 08982490A JP 8982490 A JP8982490 A JP 8982490A JP 3163421 B2 JP3163421 B2 JP 3163421B2
- Authority
- JP
- Japan
- Prior art keywords
- adsorptive
- deodorant
- platinum
- decomposition
- adsorption
- 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.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Treating Waste Gases (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は悪臭ガスまたは有害ガスを室温以下の温度で
を吸着除去するとともに加熱再生することにより脱着放
出される悪臭ガスまたは有害ガスをそのまま接触分解で
きる再生しながら連続脱臭処理が可能な吸着分解脱臭剤
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention adsorbs and removes a malodorous gas or a harmful gas at a temperature lower than room temperature, and directly contacts a malodorous gas or a harmful gas desorbed and released by heating and regenerating. The present invention relates to an adsorptive decomposition deodorant which can be decomposed and can be continuously deodorized while being regenerated.
従来悪臭ガスまたは有害ガスを吸着除去するために活
性炭、ゼオライト、シリカゲル、アルミナ等の吸着剤が
使用されてきた。また悪臭ガスまたは有害ガスを酸化分
解触媒を用いて接触分解する方法も広く行なわれてい
る。特開昭53−109874号には、有害ガス中の有害ガス成
分を吸着する吸着剤と、吸着剤の再生時に脱着した成分
を酸化燃焼する有害ガス処理装置において、吸着剤と酸
化触媒とを充分混合して一層とし、または吸着剤層と酸
化触媒層とを交互に配列してみかけ上一層とし、または
吸着剤表面に酸化触媒金属を付着させ吸着剤と酸化触媒
の両方の作用を有するものを充填して一層とすることを
特徴とする有害ガスの処理装置が開示されており、吸着
剤としては、活性炭、活性アルミナ、シリカゲル、ゼオ
ライトなどが用いられると記載されている。Conventionally, adsorbents such as activated carbon, zeolite, silica gel and alumina have been used to adsorb and remove odorous or harmful gases. Further, a method of catalytically decomposing a malodorous gas or a harmful gas using an oxidative decomposition catalyst has been widely used. JP-A-53-109874 discloses an adsorbent for adsorbing harmful gas components in a harmful gas and a harmful gas treatment apparatus for oxidizing and burning components desorbed during regeneration of the adsorbent. A mixture having a single layer, or an adsorbent layer and an oxidation catalyst layer alternately arranged to form an apparent upper layer, or a substance having both an adsorbent and an oxidation catalyst by adhering an oxidation catalyst metal to the surface of the adsorbent. An apparatus for treating harmful gas, which is characterized by being filled into a single layer, is disclosed. It is described that activated carbon, activated alumina, silica gel, zeolite, or the like is used as an adsorbent.
しかしながら、吸着剤として活性炭を用いることは、
再生時に高温にさらされると発火の恐れがあり危険であ
る。またアルミナ、ゼオライト等耐火性の大きい吸着剤
を用いても吸着能はかならずしも満足のいくものではな
く、また再生による吸着能の賦活化も十分でないという
欠点を有していた。However, using activated carbon as an adsorbent
Exposure to high temperatures during regeneration can cause ignition and is dangerous. Further, even if an adsorbent having high refractory properties such as alumina and zeolite is used, the adsorbing ability is not always satisfactory, and the adsorbing ability is not sufficiently activated by regeneration.
またセピオライトに酸化触媒を担持させた吸着分解脱
臭剤についても、再生時に脱着される悪臭ガスまたは有
害ガスをより低温で酸化分解することができ、再生時の
加熱により脱臭性能が低下しにくい長期間の反復再生使
用にも耐えうる優れた耐久性を有するものが要望されて
いる。In addition, the adsorbent decomposition deodorant in which the oxidation catalyst is supported on sepiolite can also oxidize and decompose the odorous or harmful gas desorbed at the time of regeneration at a lower temperature, and the deodorization performance is hardly reduced by heating during the regeneration. There is a demand for a material having excellent durability that can withstand repetitive use.
さらに、悪臭ガスの中に含まれる硫黄は強い触媒毒と
しての作用を持っているので、この硫黄による被毒に耐
えうるものが要請されている。Further, since sulfur contained in the odorous gas has a strong catalytic poisoning action, it is required that the sulfur can be poisoned by the sulfur.
したがって、本発明は再生時の加熱による酸化分解能
の劣化が少くかつ硫黄被毒に耐える優れた耐久性を有し
連続脱臭処理を可能とする耐火性吸着分解脱臭剤を提供
することを目的とする。Accordingly, an object of the present invention is to provide a refractory adsorptive decomposer which has a small deterioration of oxidative resolution due to heating during regeneration, has excellent durability to withstand sulfur poisoning, and enables continuous deodorization treatment. .
本発明者等は上記目的に沿って鋭意研究をおこなった
結果、セピオライトに触媒成分を担持させた吸着分解脱
臭剤が、通常の処理温度で悪臭ガスまたは有害ガスを吸
着除去し、これを定期的もしくは非定期的に加熱するこ
とにより吸着した悪臭ガスまたは有害ガスを脱着すると
同時に脱着放出された悪臭ガスまたは有害ガスをより低
い温度でさらにより効果よく酸化分解することができ、
再生時の加熱により酸化分解能の劣化がすくなく、耐硫
黄被毒性を有する吸着分解脱臭剤を見出した。The present inventors have conducted intensive studies in accordance with the above-mentioned object, and as a result, the adsorptive decomposition deodorant obtained by supporting the catalyst component on sepiolite adsorbs and removes odorous gas or harmful gas at a normal processing temperature. Or, it can desorb adsorbed malodorous gas or harmful gas by heating irregularly and simultaneously oxidize and decompose malodorous gas or harmful gas desorbed and released at lower temperature even more effectively,
We have found an adsorptive decomposer that is resistant to sulfur poisoning with little degradation of oxidative resolution due to heating during regeneration.
すなわち、本発明の吸着分解脱臭剤はセピオライトを
担体として採用し、これに触媒成分を担持させたことを
特徴とする。That is, the adsorptive decomposition deodorant of the present invention is characterized in that sepiolite is used as a carrier and a catalyst component is supported on the carrier.
触媒成分は加熱時に悪臭成分または有害成分の分解能
を有するものであって、白金族金属およびセリウム、ラ
ンタン等の希土類金属よりなる群から選ばれたすくなく
とも一種の元素の金属、酸化物または複合物である。The catalyst component is capable of degrading odorous or harmful components when heated, and is a metal, oxide or composite of at least one element selected from the group consisting of platinum group metals and rare earth metals such as cerium and lanthanum. is there.
前記元素群のうち、白金族金属とりわけ白金または白
金とパラジウムが好ましい。Of the group of elements, platinum group metals, especially platinum or platinum and palladium are preferred.
また、触媒成分中に希土類金属とくにセリウムおよび
／またはランタンを併用すると触媒の耐熱性がさらに向
上するので好ましい。It is also preferable to use a rare earth metal, particularly cerium and / or lanthanum, in the catalyst component, since the heat resistance of the catalyst is further improved.
触媒成分は従来の方法によって担持することができ
る。The catalyst component can be supported by conventional methods.
白金族金属の担持量は0.5〜5g/、好ましくは１〜2g
/であり、希土類金属の担持量は１〜100g/、好まし
くは５〜20g/である。The loading amount of the platinum group metal is 0.5 to 5 g /, preferably 1 to 2 g.
/, And the loading of the rare earth metal is 1 to 100 g /, preferably 5 to 20 g /.
本発明の吸着分解脱臭剤は、室温以下の温度以下の温
度で効率よくトリメチルアミン等のアミン系悪臭物質、
メチルメルカプタン等のイオウ系悪臭物質、アンモニア
およびその他芳香族炭化水素やエステル類からなる有機
悪臭ガスまたは有害ガスを吸着除去し、定期的または不
定期的に加熱することにより吸着した悪臭ガスまたは有
害ガスを脱着させ吸着能を再生するとともに脱着した悪
臭ガスまたは有害ガスを担持した酸化触媒によって酸化
分解し処理ガスの浄化を行えるものであり、従来の酸化
触媒では不可欠であった連続加熱が不要になり、単なる
吸着脱臭剤では不可能であった長期連続使用を可能とす
るものであり、さらにより低い温度でより効率よく酸化
分解することができる。本発明の吸着分解脱臭剤は、繰
り返し再生加熱しても脱臭性能が落ちにくい優れた耐熱
性を有するものであり、また悪臭ガスまたは有害ガス中
に含まれる硫黄によって被毒されにくい優れた特性を有
する。The adsorption decomposition deodorant of the present invention is an amine-based malodorous substance such as trimethylamine efficiently at a temperature of room temperature or lower,
Adsorbs and removes sulfur-based malodorous substances such as methyl mercaptan, organic malodorous gas or harmful gas consisting of ammonia and other aromatic hydrocarbons and esters, and adsorbs by heating regularly or irregularly. And regenerates adsorption capacity, and oxidizes and decomposes the treated gas using an oxidation catalyst that carries the deodorized or odorous gas, eliminating the need for continuous heating, which was indispensable with conventional oxidation catalysts. It enables long-term continuous use, which was not possible with a mere adsorptive deodorant, and enables more efficient oxidative decomposition at lower temperatures. The adsorptive decomposition deodorant of the present invention has excellent heat resistance, in which the deodorizing performance is hardly deteriorated even after repeated regeneration heating, and also has excellent characteristics in which it is hardly poisoned by sulfur contained in a malodorous gas or a harmful gas. Have.
冷却空気強制循環方式の冷蔵庫では冷却器に霜がつく
と冷却性能が低下するため除霜ヒーターにより定期的に
自動除霜している。本発明の吸着分解脱臭剤を冷却空気
の循環経路にある除霜ヒーター近傍に設置すると、冷蔵
庫の冷却運転中には庫内の空気はファンにより前記循環
経路を経て循環しているので、このとき貯蔵食品から発
生した悪臭ガスは前記吸着分解脱臭剤により吸着除去さ
れ冷蔵庫内の脱臭が行われる。また前記吸着分解脱臭剤
の吸着能の再生と吸着した悪臭ガスの酸化分解は前記除
霜ヒーターの熱を利用することにより行うことができる
ため、本発明の吸着分解脱臭剤は、冷蔵庫脱臭等に極め
て有効に適用できる。冷蔵庫の脱臭に用いるときには、
吸着分解脱臭剤に水分がたくさん付着したり、吸着した
りした条件で、凍結、加熱が繰り返されるため、セピオ
ライト製以外の板状担体は、自己破壊しやすく、原型を
とどめることが困難である。In the refrigerator of the forced air circulation system, when the frost is formed on the cooler, the cooling performance is reduced, so that the defrost heater is used to periodically perform automatic defrosting. If the adsorptive decomposition deodorant of the present invention is installed near the defrost heater in the cooling air circulation path, the air in the refrigerator is circulated through the circulation path by the fan during the cooling operation of the refrigerator. The malodorous gas generated from the stored food is adsorbed and removed by the adsorptive decomposition deodorant and deodorized in the refrigerator. In addition, since the regeneration of the adsorption capacity of the adsorptive decomposition deodorant and the oxidative decomposition of the adsorbed malodorous gas can be performed by utilizing the heat of the defrost heater, the adsorptive decomposition deodorant of the present invention can be used for refrigerator deodorization and the like. It can be applied very effectively. When we use for deodorization of refrigerator,
Since freezing and heating are repeated under the condition that a large amount of water adheres to or adsorbs to the adsorptive decomposition deodorant, plate carriers other than those made of sepiolite are liable to self-destruction, and it is difficult to keep the original form.
以下に本発明を実施例によりさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例１ １％硝酸溶液で前処理した粒状セピオライト担体50ml
（43.3g）を、ヘキサアンミン白金（IV）塩化物水溶液
（1.463％Pt含量）5.13mlに28％アンモニア水（和光純
薬製）0.74gを加えpH10.5に調整し340mlに希釈した溶液
に浸漬した、水洗、乾燥した後水素気流中500℃の温度
で還元しPt換算で1.47g/の白金を担持した吸着分解脱
臭剤Ａを得た。Example 1 50 ml of granular sepiolite carrier pretreated with 1% nitric acid solution
(43.3 g) was added to 5.13 ml of an aqueous solution of hexaammineplatinum (IV) chloride (1.463% Pt content) and 0.74 g of 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.) was added to adjust the pH to 10.5, and the solution was diluted to 340 ml. After being immersed, washed with water and dried, it was reduced at a temperature of 500 ° C. in a hydrogen stream to obtain an adsorption decomposition deodorant A carrying 1.47 g / platinum of platinum.
比較例１ 粒状アルミナ50ml（18.47g）を塩化白金酸溶液（4.58
7％Pt含量）1.635gを50mlに希釈した溶液に浸漬した。
水洗、乾燥した後水素気流中450℃の温度で還元しPt換
算で1.48g/の白金を担持した吸着分解脱臭剤Ｂを得
た。Comparative Example 1 50 ml (18.47 g) of granular alumina was added to a chloroplatinic acid solution (4.58
1.635 g (7% Pt content) was immersed in a solution diluted to 50 ml.
After washing with water and drying, it was reduced in a stream of hydrogen at a temperature of 450 ° C. to obtain an adsorption / decomposition deodorant B carrying 1.48 g / platinum of platinum in terms of Pt.
比較例２ 実施例１と同様にして粒状シリカゲル（和光純薬製）
50ml（42.46g）にPt換算で1.38g/の白金を担持した吸
着分解脱臭剤Ｃを得た。Comparative Example 2 Granular silica gel (manufactured by Wako Pure Chemical Industries, Ltd.) in the same manner as in Example 1.
An adsorptive decomposition deodorant C carrying 1.38 g / Pt equivalent of platinum in 50 ml (42.46 g) was obtained.
試験例１ トリメチルアミン反応試験 得られた吸着分解脱臭剤を16のガラス製の反応槽内
に設置し、トリメチルアミンを槽内濃度が3000ppmにな
るように注入し30分間室温に放置したのち15分間吸着分
解脱臭剤表面温度を350℃まで昇温加熱し、さらに25分
間放冷しトリメチルアミン濃度の変化を測定し、同様の
操作を繰り返し行った。その結果を第１図〜第３図に示
す。Test Example 1 Trimethylamine Reaction Test The obtained adsorptive decomposition deodorant was placed in a 16 glass reaction tank, trimethylamine was injected to a concentration of 3000 ppm in the tank, left at room temperature for 30 minutes, and adsorbed and decomposed for 15 minutes The surface temperature of the deodorant was raised to 350 ° C., and the mixture was allowed to cool for 25 minutes. The change in the concentration of trimethylamine was measured, and the same operation was repeated. The results are shown in FIGS.
第１図〜第３図よりセピオライトを担体とする本発明
の吸着分解脱臭剤がアルミナ、シリカゲル等従来の吸着
剤を担体とした吸着分解脱臭剤に比べて吸着能および酸
化分解能がすぐれているばかりでなく繰り返し反応を行
っても吸着酸化能が共に低下しないという優れた繰り返
し特性を有することがわかる。1 to 3, the adsorptive decomposer of the present invention using sepiolite as a carrier is superior in adsorption capacity and oxidative resolution as compared with the conventional adsorptive deodorizer using alumina, silica gel or the like as a carrier. However, it can be seen that they have excellent repetition characteristics that the adsorption oxidizing ability does not decrease even when the reaction is repeated.
試験例２ メチルメルカプタン反応試験 本発明の吸着分解脱臭剤Ａについて同様の試験をメチ
ルメルカプタンについて槽内の初期濃度を90ppmに調整
し、実施したときの結果を第４図に示す。Test Example 2 Methyl Mercaptan Reaction Test FIG. 4 shows the results when the same test was carried out for the adsorptive decomposition deodorant A of the present invention by adjusting the initial concentration of methyl mercaptan in the tank to 90 ppm.
試験例３ アンモニア反応試験 またアンモニアについて槽内の初期濃度を1000ppmに
調整し60分間室温に放置したのち350℃まで昇温加熱し
たときの結果を第５図に示す。Test Example 3 Ammonia Reaction Test FIG. 5 shows the results when the initial concentration of ammonia in the tank was adjusted to 1000 ppm, left at room temperature for 60 minutes, and then heated to 350 ° C. and heated.
実施例２ １％硝酸溶液で前処理した１枚当り50mm×18mm×6mm
の板状セピオライト36枚を、ヘキサンアンミン白金（I
V）塩化物水溶液（1.463％Pt含量）28.5mlにテトラアン
ミンパラジウム（II）塩化物水溶液（0.991％Pd含量）2
1.1mlを添加し28％アンモニア水（和光純薬製）3.2gを
さらに加え1,440mlに稀釈した溶液（PH10.5）に浸漬し
た。水洗、乾燥したのち水素気流中500℃の温度で還元
し、Pt換算で1.89g/の白金およびPd換算で0.99g/の
パラジウム担持した吸着分解脱臭剤Ｄを得た。Example 2 50 mm × 18 mm × 6 mm per sheet pretreated with 1% nitric acid solution
36 plate-shaped sepiolite of hexaneammine platinum (I
V) Chloride aqueous solution (1.463% Pt content) 28.5 ml in tetraammine palladium (II) chloride aqueous solution (0.991% Pd content) 2
1.1 ml was added, and 3.2 g of 28% aqueous ammonia (manufactured by Wako Pure Chemical Industries) was further added, followed by immersion in a solution (PH 10.5) diluted to 1,440 ml. After being washed with water and dried, it was reduced at a temperature of 500 ° C. in a stream of hydrogen to obtain an adsorptive decomposer D carrying 1.89 g / Pt equivalent and 0.99 g / Pd equivalent palladium on Pt basis.
実施例３ ヘキサンアンミン白金（IV）塩化物水溶液（1.463％P
t含量）14.3mlおよびテトラアンミンパラジウム（II）
塩化物水溶液（0.991％Pd含量）10.5mlを用いたことを
除いては実施例２と同様にしてPt換算で0.98g/の白金
およびPd換算で0.49g/のパラジウムを担持した吸着分
解脱臭剤Ｅを得た。Example 3 An aqueous solution of hexaneammineplatinum (IV) chloride (1.463% P
t content) 14.3 ml and tetraammine palladium (II)
Adsorbent decomposition deodorant carrying 0.98 g / Pt-equivalent platinum and 0.49 g / Pd-equivalent palladium in the same manner as in Example 2 except that 10.5 ml of an aqueous chloride solution (0.991% Pd content) was used. E was obtained.
実施例４ ヘキサンアンミン白金（IV）塩化物水溶液（1.463％P
t含量）21.4mlを用いたことを除いては実施例２と同様
にしてPt換算で1.48g/の白金を担持した吸着分解脱臭
剤Ｆを得た。Example 4 An aqueous solution of hexaneammineplatinum (IV) chloride (1.463% P
(t content) Except for using 21.4 ml, an adsorptive decomposition deodorant F carrying 1.48 g / platinum platinum was obtained in the same manner as in Example 2.
試験例４ トリメチルアミン反応試験 得られた吸着分解脱臭剤を16のガラス製の反応槽内
に設置し、トリメチルアミンを槽内濃度が3000ppmにな
るように注入し30分間室温に放置したのち15分間吸着分
解脱臭剤表面温度を350℃まで昇温加熱し、さらに25分
間放冷しトリメチルアミン濃度の変化を測定しその結果
を第６図に示す。Test Example 4 Trimethylamine Reaction Test The obtained adsorptive decomposition deodorant was placed in a 16 glass reaction tank, trimethylamine was injected to a concentration of 3000 ppm in the tank, left at room temperature for 30 minutes, and adsorbed and decomposed for 15 minutes The surface temperature of the deodorant was raised to 350 ° C., and the mixture was allowed to cool for 25 minutes. The change in the concentration of trimethylamine was measured, and the results are shown in FIG.
なお、残存率（％）は初期濃度Coと経時濃度Ctとの以
下の関係式により求めた。The residual ratio (%) was determined by the following relational expression between the initial concentration Co and the temporal concentration Ct.
残存率（％）＝Ct/Co×100 試験例５ 加速耐熱試験 得られた吸着分解脱臭剤を担持された白金およびパラ
ジウム粒子が変化を起し始める500℃の温度に保ち熱劣
化させたものを上記と同様の方法でトリメチルアミン反
応試験をおこないトリメチルアミン反応試験の45分経過
時の残存率（％）を測定しその結果を第７図に示す。Residual rate (%) = Ct / Co x 100 Test Example 5 Accelerated heat resistance test Platinum and palladium particles carrying the adsorptive decomposition deodorant obtained were thermally degraded while maintaining the temperature at 500 ° C at which change began to occur. A trimethylamine reaction test was conducted in the same manner as described above, and the residual rate (%) of the trimethylamine reaction test after 45 minutes was measured. The results are shown in FIG.
試験例６ 耐硫黄被毒試験 １枚当り54mm×18mm×6mmの板状吸着分解脱臭剤２枚
に硫化水素0.11gを吸着させたのち250℃の温度に25分間
保ち硫黄被毒処理した被毒吸着分解脱臭剤を上記と同様
の方法でトリメチルアミン反応試験をおこないその結果
を第８図から第10図に示す。Test Example 6 Sulfur poisoning resistance test 0.12 g of hydrogen sulfide was adsorbed on two 54 mm x 18 mm x 6 mm plate-shaped adsorptive decomposers, and then poisoned by sulfur poisoning at 250 ° C for 25 minutes. The adsorption decomposition deodorant was subjected to a trimethylamine reaction test in the same manner as described above, and the results are shown in FIGS. 8 to 10.
第６図より、白金とパラジウムを併用した吸着分解脱
臭剤の方が白金のみを担持した吸着分解脱臭剤よりもす
ぐれた脱臭性能を有することがわかる。From FIG. 6, it can be seen that the adsorptive decomposition deodorant using both platinum and palladium has a better deodorizing performance than the adsorptive decomposition deodorant carrying only platinum.
第７図より白金とパラジウムを併用した吸着分解脱臭
剤ＤおよびＥの方が白金のみを担持した吸着分解脱臭剤
Ｆよりも耐熱性が高いことがわかる。すなわち、白金と
パラジウムを併用した吸着分解脱臭剤は再生加熱を繰り
返えしおこなっても脱臭性能が落ちにくいことがわか
る。From FIG. 7, it can be seen that the adsorptive decomposition deodorants D and E using both platinum and palladium have higher heat resistance than the adsorptive decomposition deodorant F carrying only platinum. That is, it can be seen that the adsorptive decomposition deodorant using both platinum and palladium hardly deteriorates in deodorization performance even when regenerating and heating are repeated.
第８図より第10図から白金とパラジウムを併用した吸
着分解脱臭剤Ｄおよび吸着分解脱臭剤Ｅの方が白金のみ
を担持した吸着分解Ｆよりも耐硫黄被毒性がすぐれてい
ることがわかる。From FIG. 8, it can be seen from FIG. 10 that the adsorptive / decomposable deodorizer D and the adsorptive / decomposable deodorant E using both platinum and palladium are more resistant to sulfur poisoning than the adsorptive / decomposable F carrying only platinum.
実施例５ １％硝酸溶液で前処理した１枚当り50mm×18mm×6mm
の板状セピオライト36枚を、ヘキサアミン白金（IV）塩
化物溶液（1.465％Pt含量）14.253gにテトラアミンパラ
ジウム（II）塩化物水溶液（0.991％Pd含量）10.535gを
添加し28％アンモニア水（和光純薬剤）1.260gをさらに
加えpH10.0に調整し1440mlに稀釈した溶液に浸漬した。
水洗、乾燥したのち水素気流中500℃の温度で還元し、P
t換算で1.0g/の白金およびPd換算で0.5g/のパラジ
ウムを担持した吸着分解脱臭剤Ｇを得た。Example 5 50 mm × 18 mm × 6 mm per sheet pretreated with a 1% nitric acid solution
36 plate-like sepiolites were added to 14.253 g of hexaamine platinum (IV) chloride solution (1.465% Pt content) and 10.535 g of tetraamine palladium (II) chloride aqueous solution (0.991% Pd content) were added, and 28% ammonia water ( 1.260 g of Wako Pure Chemicals was further added to adjust the pH to 10.0, and the resultant was immersed in a solution diluted to 1440 ml.
After washing with water and drying, reducing in a stream of hydrogen at a temperature of 500 ° C,
An adsorptive decomposition deodorant G carrying 1.0 g / t of platinum in terms of t and 0.5 g / palladium in terms of Pd was obtained.
実施例６ １％硝酸溶液で前処理した１枚当り50mm×18mm×6mm
の板状セピオライト36枚を、硝酸セリウム（III）〔Ce
（NO3）３・6H2O〕20.22gを水に溶かし全量を1500mlと
した溶液に浸漬した。水洗、乾燥したのち550℃の温度
で２時間焼成し、Ce換算で11.2g/のセリウムを担持し
たのち実施例５と同様にしてさらにPt換算で1.0g/の
白金およびPd換算で0.5g/のパラジウムを担持した吸
着分解脱臭剤Ｈを得た。Example 6 50 mm × 18 mm × 6 mm per sheet pretreated with 1% nitric acid solution
Of cerium (III) nitrate [Ce
And the (NO 3) 3 · 6H 2 O ] 20.22g immersed in solution with 1500ml of total amount dissolved in water. After washing with water and drying, the mixture was calcined at a temperature of 550 ° C. for 2 hours, loaded with cerium at 11.2 g / Ce, and further treated in the same manner as in Example 5 with 1.0 g / Pt equivalent and 0.5 g / Pd equivalent. Thus, an adsorption decomposition deodorant H carrying palladium was obtained.
試験例７ メチルメルカプタンの繰り返し性能試験 得られた吸着分解脱臭剤ＧおよびＨを16のガラス製
の反応槽内にそれぞれ２枚設置し、メチルメルカプタン
を槽内濃度が90ppmになるように注入し、室温でファン
を使用し槽内大気を循環させながら30分間放置したのち
のメチルメルカプタン残存率（吸着性能）を測定した。
その後ファンを止め30分間触媒表面温度を300℃まで昇
温加熱し、その時のメチルメルカプタン残存率（分解性
能）を測定しその後30分ファンを回し放冷した。同様の
操作を繰り返し行った。その結果を第１表に示す。Test Example 7 Methyl mercaptan repetitive performance test Two obtained adsorption-decomposition deodorizers G and H were placed in each of 16 glass reaction tanks, and methyl mercaptan was injected so that the concentration in the tank was 90 ppm. The methyl mercaptan residual ratio (adsorption performance) was measured after standing for 30 minutes while circulating the atmosphere in the tank using a fan at room temperature.
Thereafter, the fan was stopped and the catalyst surface temperature was raised to 300 ° C. for 30 minutes, and the residual ratio of methyl mercaptan (decomposition performance) at that time was measured. Thereafter, the fan was rotated for 30 minutes and allowed to cool. The same operation was repeated. Table 1 shows the results.
第１表より明らかにセリウムを添加することによって
メチルメルカプタンの吸着性能の向上が認められるのみ
ならず繰り返し反応を行っても吸着性能および酸化分解
性能とも劣化しにくい優れた繰り返し特性を有すること
がわかる。 Table 1 clearly shows that the addition of cerium not only improves the adsorption performance of methyl mercaptan, but also has excellent repetition characteristics in which the adsorption performance and the oxidative decomposition performance are hardly deteriorated even when the reaction is repeated. .
試験例８ 耐熱試験 吸着分解脱臭剤Ｇおよび吸着分解脱臭剤Ｈを500℃の
温度で96時間電気炉中で熱処理を行ったものについて試
験例７と同様の方法で繰り返し性能試験を行いその結果
を第２表に示す。Test Example 8 Heat resistance test A heat treatment was performed on the adsorption-decomposition deodorant G and the adsorption-decomposition deodorant H in an electric furnace at a temperature of 500 ° C. for 96 hours, and a performance test was repeated in the same manner as in Test Example 7, and the results were obtained. It is shown in Table 2.
第１表および第２表より、セリウムを添加することに
よって加熱処理したものについても同様に繰り返し反応
を行っても吸着性能および酸化分解性能とも劣化しにく
い優れた繰り返し特性を有することがわかる。すなわ
ち、セリウムを添加することによって吸着性能および酸
化分解性能の向上に相まって耐熱性および熱安定性をも
改善されていることが認められる。 From Tables 1 and 2, it can be seen that those heat-treated by adding cerium also have excellent repetition characteristics in which the adsorption performance and the oxidative decomposition performance are hardly deteriorated even when the reaction is repeated. That is, it is recognized that the addition of cerium improves the heat resistance and the thermal stability in addition to the improvement of the adsorption performance and the oxidative decomposition performance.
本発明の吸着分解脱臭剤は、吸着能が高く、定期的ま
たは不定期的に行う再生時に脱着放出される悪臭ガスま
たは有害ガスを効率よく酸化分解でき、さらに反復使用
しても吸着酸化性能が落ちにくい優れた繰り返し性能を
有し連続脱臭処理を可能とする耐火性吸着分解脱臭剤で
あり、酸化分解のために連続的に加熱する必要がなく、
また吸着剤に触媒を担持させたものであるので処理装置
をコンパクトに設計することができ、再生のために複雑
な付帯設備を必要としない。The adsorptive decomposition deodorant of the present invention has a high adsorptivity, and can efficiently oxidize and decompose odorous or harmful gases that are desorbed and released at the time of regular or irregular regeneration. It is a refractory adsorptive decomposer that has excellent repetitive performance and is capable of continuous deodorization.It does not require continuous heating for oxidative decomposition.
Further, since the catalyst is supported on the adsorbent, the processing apparatus can be designed compact, and no complicated auxiliary equipment is required for regeneration.
白金とパラジウムをセピオライトに併用担持した吸着
分解脱臭剤は白金のみを担持した吸着分解脱臭剤よりも
すぐれた脱臭分解性能を有し、再生加熱を繰り返しおこ
なっても脱臭性能が落ちにくい繰り返し性能、熱安定性
および耐熱性について改善されているのみならず耐硫黄
被毒性をも兼ね備えている。The adsorptive decomposer that supports platinum and palladium in combination with sepiolite has better deodorizing and decomposing performance than the adsorptive decomposer that supports only platinum. It has not only improved stability and heat resistance, but also sulfur poisoning resistance.
さらに希土類金属とくにセリウムを併用担持するとメ
チルメルカプタンの様なイオウ系悪臭物質に対する吸着
分解性能が著しく改善された耐熱性も向上する。Further, when a rare earth metal, especially cerium, is used in combination, the heat resistance, which significantly improves the adsorptive decomposition performance for sulfur-based malodorous substances such as methyl mercaptan, is also improved.
第１図は吸着分解脱臭剤Ａ、第２図は吸着分解脱臭剤
Ｂ、第３図は吸着分解脱臭剤Ｃについてそれぞれのトリ
メチルアミンの残存率を示すグラフである。 第４図はメチルメルカプタンの残存率を示すグラフであ
る。 第５図はアンモニアの残存率を示すグラフである。 第６図は白金担持型と白金・パラジウム併用担持型の両
吸着分解脱臭剤についてのトリメチルアミンの残存率を
示すグラフである。 第７図は白金担持型と白金・パラジウム併用担持型の両
吸着分解脱臭剤についての耐熱性を示すグラフである。 第８図は吸着分解脱臭剤Ｄ、第９図は吸着分解脱臭剤
Ｅ、第10図は吸着分解脱臭剤Ｆの耐硫黄被毒性を示すグ
ラフである。FIG. 1 is a graph showing the residual ratio of trimethylamine for the adsorptive decomposition deodorant A, FIG. 2 is a graph for the adsorptive decomposition deodorant B, and FIG. FIG. 4 is a graph showing the residual ratio of methyl mercaptan. FIG. 5 is a graph showing the residual ratio of ammonia. FIG. 6 is a graph showing the residual ratio of trimethylamine for both the adsorption-decomposition deodorizers of the platinum-supported type and the platinum-palladium combined-supported type. FIG. 7 is a graph showing the heat resistance of both adsorption-decomposition deodorants of the platinum-supported type and the platinum-palladium combined-supported type. FIG. 8 is a graph showing the sulfur-detoxification resistance of the adsorptive decomposition deodorant D, FIG. 9 is a graph showing the adsorptive decomposition deodorant E, and FIG.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ０１Ｊ 23/63 (72)発明者 相原 孝 神奈川県平塚市四之宮1212番地 (72)発明者 毛利 悦朗 神奈川県平塚市四之宮1212番地 (72)発明者 飯田 栄紀 神奈川県平塚市四之宮1212番地 (56)参考文献 特開 平２−275823（ＪＰ，Ａ) 特開 平１−119255（ＪＰ，Ａ) 特開 昭63−147518（ＪＰ，Ａ) 実開 平１−136377（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 53/86 A61L 9/00 B01J 21/00 - 37/36 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI B01J 23/63 (72) Takashi Aihara 1212 Shinomiya, Hiratsuka-shi, Kanagawa (72) Inventor Etsuro Mochi 1212 Shinomiya, Hiratsuka-shi, Kanagawa (72) Inventor Eiki Iida 1212 Yonomiya, Hiratsuka-shi, Kanagawa (56) References JP-A-2-275823 (JP, A) JP-A-1-119255 (JP, A) JP-A-63-147518 (JP, A) A) Japanese Utility Model 1-136377 (JP, U) (58) Field surveyed (Int. Cl. 7 , DB name) B01D 53/86 A61L 9/00 B01J 21/00-37/36
Claims (4)
に担持させたことを特徴とする吸着分解脱臭剤。1. An adsorptive decomposition deodorant characterized in that a platinum group metal is supported on sepiolite as a catalyst component.
してセピオライトに担持させたことを特徴とする吸着分
解脱臭剤。2. An adsorptive decomposer comprising a platinum group metal and a rare earth metal as catalyst components supported on sepiolite.
ジウムである請求項１または２記載の吸着分解脱臭剤。3. The adsorptive decomposition deodorant according to claim 1, wherein the platinum group metal is platinum and / or palladium.
ランタンである請求項２記載の吸着分解脱臭剤。4. The adsorptive decomposition deodorant according to claim 2, wherein the rare earth metal is cerium and / or lanthanum.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08982490A JP3163421B2 (en) | 1989-10-19 | 1990-04-04 | Adsorption decomposition deodorant |
| GB9022835A GB2236952B (en) | 1989-10-19 | 1990-10-19 | Adsorptive decomposition deodorizer |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27022389 | 1989-10-19 | ||
| JP1-270223 | 1989-10-19 | ||
| JP1-282850 | 1989-10-30 | ||
| JP28285089 | 1989-10-30 | ||
| JP08982490A JP3163421B2 (en) | 1989-10-19 | 1990-04-04 | Adsorption decomposition deodorant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03249921A JPH03249921A (en) | 1991-11-07 |
| JP3163421B2 true JP3163421B2 (en) | 2001-05-08 |
Family
ID=27306246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08982490A Expired - Fee Related JP3163421B2 (en) | 1989-10-19 | 1990-04-04 | Adsorption decomposition deodorant |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3163421B2 (en) |
| GB (1) | GB2236952B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1103817B (en) * | 1978-06-27 | 1985-10-14 | Guaber Spa | GRANULAR DEODORANT COMPOSITION FOR ASHTRAY |
| JPS63212363A (en) * | 1987-02-27 | 1988-09-05 | ダイソー株式会社 | Deodorant |
| GB8808359D0 (en) * | 1988-04-09 | 1988-05-11 | Kitty Little Ltd | Deodorizing composition |
-
1990
- 1990-04-04 JP JP08982490A patent/JP3163421B2/en not_active Expired - Fee Related
- 1990-10-19 GB GB9022835A patent/GB2236952B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB9022835D0 (en) | 1990-12-05 |
| GB2236952B (en) | 1993-05-05 |
| JPH03249921A (en) | 1991-11-07 |
| GB2236952A (en) | 1991-04-24 |
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