JP2006187760A - Catalyst for completely oxidizing and decomposing formaldehyde gas at room temperature and its using method - Google Patents
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Abstract
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本発明は常温環境下でホルムアルデヒドガスを酸化させるためになされたものであり、常温環境下でホルムアルデヒドガスを二酸化炭素と水とに転化させることができる。本発明の触媒は所定の期間内に極めて高いホルムアルデヒド酸化活性を有しており、本発明の触媒によるホルムアルデヒドの転化率は１００％に達している。 The present invention was made to oxidize formaldehyde gas in a normal temperature environment, and can convert formaldehyde gas into carbon dioxide and water in a normal temperature environment. The catalyst of the present invention has an extremely high formaldehyde oxidation activity within a predetermined period, and the conversion rate of formaldehyde by the catalyst of the present invention reaches 100%.
ホルムアルデヒドは家具や内装品に使われる汚染物のうち最も深刻な汚染物である。例えばペンキ、壁紙、プラスチック床材、合成繊維製カーペット、扉や窓など多くの内装材がホルムアルデヒドを含有しており、室内でホルムアルデヒドを放出するおそれがある。とりわけ合成板材では、フェノール樹脂などホルムアルデヒドを放出する恐れのある接着剤が多用されており、このような接着剤によるホルムアルデヒドの室内放出は数年続くとされている。長期間にわたって少しずつホルムアルデヒドを吸込むと慢性呼吸系疾病にかかるおそれがあり、鼻癌や咽喉癌、結腸癌、脳腫瘍、月経不順、細胞核の遺伝子突然変異、ＤＮＡ単鎖内交差結合およびタンパク質交差結合を誘発するとともに、ＤＮＡ損傷の回復が抑制され、妊娠症候群、新生児染色体異常、白血病、青少年記憶力や知力の低下などを誘発する恐れがある。中でも、子供や妊婦はホルムアルデヒドの影響を最も受けやすく、ホルムアルデヒドの与える被害が最も大きい。ホルムアルデヒドは毒性の高い物質であり、わが国では、有毒化学品リストの第二位にリストアップされている。ホルムアルデヒドは、世界保健機関（ＷＨＯ）によって発ガン性物質および催奇形性物質に指定されているほか、変異反応源であるとともに、潜在的な強変異誘発物質であるとされている。近年来、関係機関の宣伝や人々への科学知識の浸透により内装に起因する汚染問題に対して国民の関心が高くなっており、室内汚染問題の解決を目的とした研究が各国の研究者によって盛んに行われている。 Formaldehyde is the most serious contaminant used in furniture and interior items. For example, many interior materials such as paint, wallpaper, plastic flooring, synthetic fiber carpets, doors and windows contain formaldehyde and may release formaldehyde indoors. In particular, adhesives that may release formaldehyde, such as phenolic resins, are frequently used in synthetic board materials, and indoor release of formaldehyde by such adhesives is said to continue for several years. Inhalation of formaldehyde over a long period of time may cause chronic respiratory illness, including nasal cancer, throat cancer, colon cancer, brain tumor, irregular menstruation, gene mutation of cell nucleus, DNA single-strand cross-linking and protein cross-linking In addition to induction, the recovery of DNA damage is suppressed, which may induce pregnancy syndrome, neonatal chromosomal abnormalities, leukemia, youth memory and intellectual decline. Among them, children and pregnant women are most susceptible to formaldehyde, and formaldehyde is the most damaged. Formaldehyde is a highly toxic substance and is listed second in the toxic chemical list in Japan. Formaldehyde has been designated as a carcinogen and teratogen by the World Health Organization (WHO), and is also considered a potential source of mutation and a potential strong mutagen. In recent years, public interest in the pollution problem caused by the interior has increased due to the publicity of related organizations and the diffusion of scientific knowledge to people, and researchers aiming to solve the indoor pollution problem have been studied by researchers in various countries. It is actively done.
現在、さまざまな空気洗浄器が開発されており、それらの空気洗浄器は主として活性炭の強吸着性を利用してホルムアルデヒドなどの汚染物を吸着するようにしている。吸着剤としてハニカム状活性炭、球状活性炭、活性炭繊維、新型活性炭などの多孔質炭素材料、および分子篩、ゼオライト、多孔質粘土や鉱石、活性アルミナおよびシリカゲルなどが多用されている。このような空気洗浄器は比較的簡単であるが、吸着剤は定期的に交換する必要がある。触媒技術によりホルムアルデヒドを無臭無害な物質に分解する従来の触媒分解法は、所定の温度（一般２００℃以上）を必要としており、常温におけるホルムアルデヒドの転化率が最高で８８％に止まり、利用コストが高い（例えば特許文献１）。プラズマ触媒技術は、常温常圧で有害ガスを分解することができるが、一酸化炭素、オゾンおよび窒化酸化物などの二次生成物を発生するとともに、高価なプラズマ発生装置を必要とする。現在、ナノメータ級の光触媒を用いてホルムアルデヒドを分解する技術が盛んに研究されているが、このような触媒は、主としてナノメータ級のＴｉＯ2パウダーまたはフィルムを光触媒として用いており、原料の製造方法は複雑で高度の技術を必要としているほか、ナノメータ級の光触媒を励起するには特殊の励起光源が必要である（例えば非特許文献１、２）。常温環境下では光は直接低濃度のホルムアルデヒドを無害の水と二酸化炭素へ酸化させることはできない。 Currently, various air scrubbers have been developed, and these air scrubbers mainly use the strong adsorptivity of activated carbon to adsorb contaminants such as formaldehyde. As the adsorbent, porous carbon materials such as honeycomb activated carbon, spherical activated carbon, activated carbon fiber, and new activated carbon, and molecular sieves, zeolites, porous clays and ores, activated alumina, and silica gel are frequently used. Such an air scrubber is relatively simple, but the adsorbent needs to be replaced periodically. The conventional catalytic decomposition method, which decomposes formaldehyde into odorless and harmless substances using catalytic technology, requires a predetermined temperature (generally 200 ° C or higher), and the conversion rate of formaldehyde at room temperature is only 88% at the maximum, and the usage cost is low. High (for example, Patent Document 1). Plasma catalyst technology can decompose harmful gases at normal temperature and pressure, but generates secondary products such as carbon monoxide, ozone and nitrided oxide, and requires an expensive plasma generator. At present, a technology for decomposing formaldehyde using a nanometer class photocatalyst has been actively researched, but such a catalyst mainly uses a nanometer class TiO 2 powder or a film as a photocatalyst, In addition to requiring complex and advanced technology, a special excitation light source is required to excite a nanometer-class photocatalyst (for example, Non-Patent Documents 1 and 2). Under normal temperature conditions, light cannot directly oxidize low concentrations of formaldehyde to harmless water and carbon dioxide.
本発明は、前記の課題に鑑みなされたものであり、常温環境下で低濃度のホルムアルデヒドを酸化させる高選択性の触媒を提供する。該触媒は入手しやすい金属酸化物および極めて少量の貴金属を原料とし、製造方法は簡単である。本発明はこれまでの研究結果を踏まえて研究を積み重ねてきた成果である。本発明により提供された触媒は、常温環境下でホルムアルデヒドを完全に酸化させて二酸化炭素と水とに転化するとともに、かなり長い期間において転化率を１００％に維持することができる。本発明は複雑な付属装置や外部環境を必要としない。 The present invention has been made in view of the above problems, and provides a highly selective catalyst that oxidizes formaldehyde at a low concentration in a normal temperature environment. The catalyst is made from a readily available metal oxide and a very small amount of a noble metal, and the production method is simple. The present invention is the result of repeated research based on previous research results. The catalyst provided by the present invention can completely oxidize formaldehyde and convert it into carbon dioxide and water in a normal temperature environment, and can maintain the conversion rate at 100% for a considerably long period. The present invention does not require complex accessory devices or external environments.
本発明の触媒は金属酸化物を担体として０．１〜５％の貴金属を担持させる。前記金属酸化物が、二酸化セリウム、二酸化ジルコニウム、二酸化チタン、三酸化二アルミニウム、三酸化二ランタン、酸化マグネシウム、酸化亜鉛、酸化カルシウム、酸化銅から選ばれた一種または複数種の酸化物の混合物であり、前記貴金属組成がプラチナ、金、ロジウム、パラジウムと銀から選ばれた一種又は複数種である。 The catalyst of the present invention supports 0.1 to 5% of a noble metal using a metal oxide as a support. The metal oxide is a mixture of one or more oxides selected from cerium dioxide, zirconium dioxide, titanium dioxide, dialuminum trioxide, dilanthanum trioxide, magnesium oxide, zinc oxide, calcium oxide, and copper oxide. And the noble metal composition is one or more selected from platinum, gold, rhodium, palladium and silver.
また、本発明の触媒の使用方法は、上記触媒を水分添加量０．０２％以上の雰囲気で使用することを特徴とする。 Moreover, the method of using the catalyst of the present invention is characterized in that the catalyst is used in an atmosphere having a water addition amount of 0.02% or more.
本発明により提供された触媒は、常温環境下でホルムアルデヒドを完全に酸化させて二酸化炭素と水とに転化するとともに、かなり長い期間において転化率を１００％に維持することができる。本発明は複雑な付属装置や外部環境を必要としない。 The catalyst provided by the present invention can completely oxidize formaldehyde and convert it into carbon dioxide and water in a normal temperature environment, and can maintain the conversion rate at 100% for a considerably long period. The present invention does not require complex accessory devices or external environments.
本発明の触媒は金属酸化物を担体として０．１〜５％の貴金属を担持させる。前記金属酸化物が、二酸化セリウム、二酸化ジルコニウム、二酸化チタン、三酸化二アルミニウム、三酸化二ランタン、酸化マグネシウム、酸化亜鉛、酸化カルシウム、酸化銅から選ばれた一種または複数種の酸化物の混合物であり、前記貴金属組成がプラチナ、金、ロジウム、パラジウムと銀から選ばれた一種又は複数種である。 The catalyst of the present invention supports 0.1 to 5% of a noble metal using a metal oxide as a support. The metal oxide is a mixture of one or more oxides selected from cerium dioxide, zirconium dioxide, titanium dioxide, dialuminum trioxide, dilanthanum trioxide, magnesium oxide, zinc oxide, calcium oxide, and copper oxide. And the noble metal composition is one or more selected from platinum, gold, rhodium, palladium and silver.
また、前記金属酸化物が、三酸化二アルミニウム、酸化ニッケル、二酸化マンガン、二酸化ケイ素と三酸化二鉄から選ばれた一種または複数種の酸化物の混合物であってもよい。 The metal oxide may be a mixture of one or more oxides selected from dialuminum trioxide, nickel oxide, manganese dioxide, silicon dioxide and diiron trioxide.
前記触媒は、貴金属組成がそれぞれの可溶性化合物の水溶液を用いて、浸漬法、沈澱法、ゾル−ゲル法により金属酸化物に担持される。例えば、沈澱法を用いる場合には、攪拌しながら所定の金属酸化物を貴金属およびその他の金属のそれぞれ溶解しうる化合物の水溶液に１〜２４時間浸漬させ、８０〜１２０℃で乾燥し、空気または窒素ガスまたは水素ガスまたは真空中において段階的に１００℃から６００℃に昇温する。貴金属組成およびその他の金属組成の粒径は温度、時間および雰囲気などの要素を調整することにより制御することができる。本発明によれば、順番に拘ることなく前記方法により一種または複数種の貴金属組成を金属酸化物に担持させるとともに、同様の方法で他の貴金属組成を担持させることができる。本発明によれば、それぞれ異なる金属酸化物に貴金属組成を担持させてから混合して触媒を構成してもよい。
前記触媒は、必要に応じてさまざまな構造に形成してもよく、例えば、ハニカムセラミックや金属製スクリーン構造の壁表面に担持させることができ、または触媒の構造性担体として開孔泡沫体を用いてもよい。さらに触媒を球状または板状に形成してもよい。
The catalyst is supported on a metal oxide by a dipping method, a precipitation method, or a sol-gel method using an aqueous solution of each soluble compound having a noble metal composition. For example, when the precipitation method is used, a predetermined metal oxide is immersed in an aqueous solution of a compound capable of dissolving a noble metal and another metal with stirring for 1 to 24 hours, dried at 80 to 120 ° C., air or The temperature is raised stepwise from 100 ° C. to 600 ° C. in nitrogen gas, hydrogen gas or vacuum. The particle size of the noble metal composition and other metal compositions can be controlled by adjusting factors such as temperature, time and atmosphere. According to the present invention, one or more kinds of noble metal compositions can be supported on a metal oxide by the above method regardless of the order, and other noble metal compositions can be supported by the same method. According to the present invention, the catalyst may be configured by supporting a noble metal composition on different metal oxides and then mixing them.
The catalyst may be formed in various structures as required. For example, the catalyst can be supported on the wall surface of a honeycomb ceramic or a metal screen structure, or an open foam is used as a structural support for the catalyst. May be. Further, the catalyst may be formed in a spherical shape or a plate shape.
本発明は、製造プロセスが簡単であり、作業が簡単である。従来の技術に比べれば、本発明は以下の長所を有している。
（１）本発明の触媒は、構成原料が安価で入手しやすく、使用条件が簡単であり、常温環境下においてホルムアルデヒドを効率よく酸化させることができる。
（２）本発明の触媒は、常温環境下においてホルムアルデヒドを無害な二酸化炭素と水とに転化することができる。
（３）本発明の触媒は、有効期間中におけるホルムアルデヒドの転化率が１００％に達している。
（４）本発明の触媒は、使用量が少なく、電気や熱源などを必要とせず、エネルギーを節約することができる。
以下において比較例および実施例により本発明をさらに詳しく説明する。但し、これらは本発明の範囲を限定するものではない。
In the present invention, the manufacturing process is simple and the operation is simple. Compared to the prior art, the present invention has the following advantages.
(1) The catalyst of the present invention is inexpensive and easily available, and the usage conditions are simple, so that formaldehyde can be efficiently oxidized in a room temperature environment.
(2) The catalyst of the present invention can convert formaldehyde into harmless carbon dioxide and water in a room temperature environment.
(3) In the catalyst of the present invention, the conversion rate of formaldehyde reaches 100% during the effective period.
(4) The catalyst of the present invention is used in a small amount, does not require electricity or a heat source, and can save energy.
Hereinafter, the present invention will be described in more detail by way of comparative examples and examples. However, these do not limit the scope of the present invention.
比較例１．
三酸化二アルミニウム粉末１０グラムに所定量の脱イオン水を添加し、攪拌しながら１％のＡｕ（金）溶液を添加し、１時間攪拌した後に、７０℃で回転蒸発法により乾燥し、その後６００℃で５時間焼成して所望の触媒を得た。触媒は４０〜６０メッシュのフィルタにかけた。
Comparative Example 1
A predetermined amount of deionized water is added to 10 grams of dialuminum trioxide powder, a 1% Au (gold) solution is added with stirring, the mixture is stirred for 1 hour, and then dried by rotary evaporation at 70 ° C. The desired catalyst was obtained by calcining at 600 ° C. for 5 hours. The catalyst was filtered through a 40-60 mesh filter.
比較例２．
比較例１で得たフィルタで選別後の触媒０．０６６グラムを管状固定床反応器で反応させた。実験条件は下記のとおりである。
体積％で酸素ガス２０％、窒素ガス８０％であり、ホルムアルデヒドガスをホルムアルデヒドガス発生器で発生し、窒素ガスにより反応系に吹き込み、ホルムアルデヒドの濃度を０．０５％、反応空間速度（ＧＨＳＶ）を５０，０００／時間に制御した。常温環境下におけるホルムアルデヒドの転化率は０である。
Comparative Example 2
0.066 grams of the catalyst selected by the filter obtained in Comparative Example 1 was reacted in a tubular fixed bed reactor. The experimental conditions are as follows.
Oxygen gas is 20% by volume and nitrogen gas is 80%. Formaldehyde gas is generated by a formaldehyde gas generator and blown into the reaction system with nitrogen gas. The concentration of formaldehyde is 0.05% and the reaction space velocity (GHSV) is Controlled to 50,000 / hour. The conversion rate of formaldehyde in a room temperature environment is zero.
実施例１．
二酸化チタン粉末１０グラムに所定量の脱イオン水を添加し、攪拌しながら二酸化チタン重量の１％のＰｔ（白金）を含有する溶液を添加し、１時間攪拌した後に、７０℃で回転蒸発法により乾燥し、その後６００℃で５時間焼成して所望の触媒を得た。触媒は４０〜６０メッシュのフィルタにかけた。
Example 1.
A predetermined amount of deionized water is added to 10 grams of titanium dioxide powder, a solution containing 1% Pt (platinum) by weight of titanium dioxide is added with stirring, and the mixture is stirred for 1 hour, followed by rotary evaporation at 70 ° C. And then calcined at 600 ° C. for 5 hours to obtain the desired catalyst. The catalyst was filtered through a 40-60 mesh filter.
実施例２．
実施例１で得たフィルタで選別後の触媒０．０６６グラムを管状固定床反応器で反応させた。実験条件は下記のとおりである。
体積％で酸素ガス２０％、窒素ガス８０％であり、ホルムアルデヒドガスをホルムアルデヒドガス発生器で発生し、窒素ガスにより反応系に吹き込み、ホルムアルデヒドの濃度を０．０５％、反応空間速度（ＧＨＳＶ）を５０，０００／時間に制御した。常温環境下におけるホルムアルデヒドの転化率は１００％であり、２４時間保持した後、転化率の低下が見られなかった。
Example 2
0.066 gram of the catalyst selected by the filter obtained in Example 1 was reacted in a tubular fixed bed reactor. The experimental conditions are as follows.
Oxygen gas is 20% by volume and nitrogen gas is 80%. Formaldehyde gas is generated by a formaldehyde gas generator and blown into the reaction system with nitrogen gas. The concentration of formaldehyde is 0.05% and the reaction space velocity (GHSV) is Controlled to 50,000 / hour. The conversion rate of formaldehyde in a room temperature environment was 100%, and no decrease in the conversion rate was observed after holding for 24 hours.
実施例３．
硝酸マンガン１００グラムを所定量の水に溶解させ、攪拌しながら水酸化ナトリウム溶液によりＰＨ＝１２〜１３に調整し、硝酸マンガンと次亜塩素酸ナトリウム溶液とのモル％が２〜３となるように緩やかに次亜塩素酸ナトリウム溶液を添加して一夜放置した。濾過、沈殿後に、硝酸銀溶液を用いた塩素イオンの検出で濾液から塩素イオンが検出されなくなるまで、脱イオン水で洗浄した。沈殿物を７０℃で加熱乾燥した。乾燥後の沈殿物を沈殿物重量の５％のＰｔを含有する溶液に浸漬し、回転蒸発後に７０℃で加熱乾燥した。加熱乾燥後の触媒を４０〜６０メッシュのフィルタにかけた。
こうして得た二酸化マンガンに銀が担持された触媒０．０６６グラムを管状固定床反応器で反応させた。実験条件は下記のとおりである。
体積％で酸素ガス２０％、窒素ガス８０％であり、ホルムアルデヒドガスをホルムアルデヒドガス発生器で発生し、窒素ガスにより反応系に吹き込み、ホルムアルデヒドの濃度を０．０５％、反応空間速度（ＧＨＳＶ）を５０，０００／時間に制御した。常温環境下におけるホルムアルデヒドの転化率は１００で％あり、この転化率は４８時間維持した。その後転化率が約７０％に降下したが、６０時間保持した後も転化率の更なる低下が見られなかった。
Example 3
100 g of manganese nitrate is dissolved in a predetermined amount of water and adjusted to PH = 12-13 with a sodium hydroxide solution while stirring, so that the molar percentage of manganese nitrate and sodium hypochlorite solution is 2-3. The sodium hypochlorite solution was slowly added and left overnight. After filtration and precipitation, the sample was washed with deionized water until chlorine ions were not detected from the filtrate by detection of chloride ions using a silver nitrate solution. The precipitate was heat-dried at 70 ° C. The dried precipitate was immersed in a solution containing 5% Pt of the precipitate weight, and dried by heating at 70 ° C. after rotary evaporation. The catalyst after heat drying was passed through a 40 to 60 mesh filter.
0.066 grams of the catalyst in which silver was supported on the manganese dioxide thus obtained was reacted in a tubular fixed bed reactor. The experimental conditions are as follows.
Oxygen gas is 20% by volume and nitrogen gas is 80%. Formaldehyde gas is generated by a formaldehyde gas generator and blown into the reaction system with nitrogen gas. The concentration of formaldehyde is 0.05% and the reaction space velocity (GHSV) is Controlled to 50,000 / hour. The conversion rate of formaldehyde in a normal temperature environment was 100%, and this conversion rate was maintained for 48 hours. Thereafter, the conversion rate dropped to about 70%, but no further decrease in the conversion rate was observed after holding for 60 hours.
実施例４．
硝酸ニッケル１００グラムを所定量の水に溶解させ、攪拌しながら水酸化ナトリウム溶液によりＰＨ＝１２〜１３に調整し、硝酸ニッケルと次亜塩素酸ナトリウム溶液とのモル％が２〜３となるように緩やかに次亜塩素酸ナトリウム溶液を添加して一夜放置した。濾過、沈殿後に、硝酸銀溶液を用いた塩素イオンの検出で濾液から塩素イオンが検出されなくなるまで、脱イオン水で洗浄した。沈殿物を７０℃で加熱乾燥した。乾燥後の沈殿物を沈殿物重量の１％のＡｕを含有する溶液に浸漬し、回転蒸発後に７０℃で加熱乾燥した。加熱乾燥後の触媒を４０〜６０メッシュのフィルタにかけた。
こうして得た酸化ニッケルに銀が担持された触媒０．０６６グラムを管状固定床反応器で反応させた。実験条件は下記のとおりである。
体積％で酸素ガス２０％、窒素ガス８０％であり、ホルムアルデヒドガスをホルムアルデヒドガス発生器で発生し、窒素ガスにより反応系に吹き込み、ホルムアルデヒドの濃度を０．０５％、反応空間速度（ＧＨＳＶ）を５０，０００／時間に制御した。常温環境下におけるホルムアルデヒドの転化率は１００％であり、この転化率は４８時間維持した。その後転化率が約８０％に降下したが、４８時間保持した後も転化率の更なる低下が見られなかった。
Example 4
100 g of nickel nitrate is dissolved in a predetermined amount of water, adjusted to PH = 12-13 with a sodium hydroxide solution while stirring, so that the molar percentage of nickel nitrate and sodium hypochlorite solution is 2-3. The sodium hypochlorite solution was slowly added and left overnight. After filtration and precipitation, the sample was washed with deionized water until chlorine ions were not detected from the filtrate by detection of chloride ions using a silver nitrate solution. The precipitate was heat-dried at 70 ° C. The dried precipitate was dipped in a solution containing 1% Au of the precipitate weight, and dried by heating at 70 ° C. after rotary evaporation. The catalyst after heat drying was passed through a 40 to 60 mesh filter.
0.066 grams of the catalyst in which silver was supported on the nickel oxide thus obtained was reacted in a tubular fixed bed reactor. The experimental conditions are as follows.
Oxygen gas is 20% by volume and nitrogen gas is 80%. Formaldehyde gas is generated by a formaldehyde gas generator and blown into the reaction system with nitrogen gas. The concentration of formaldehyde is 0.05% and the reaction space velocity (GHSV) is Controlled to 50,000 / hour. The conversion rate of formaldehyde in a normal temperature environment was 100%, and this conversion rate was maintained for 48 hours. Thereafter, the conversion rate dropped to about 80%, but no further decrease in the conversion rate was observed after holding for 48 hours.
実施例５．
硝酸ニッケル１００グラムを所定量の水に溶解させ、攪拌しながら水酸化ナトリウム溶液によりＰＨ＝１２〜１３に調整し、硝酸ニッケルと次亜塩素酸ナトリウム溶液とのモル％が２〜３となるように緩やかに次亜塩素酸ナトリウム溶液を添加して一夜放置した。濾過、沈殿後に、硝酸銀溶液を用いた塩素イオンの検出で濾液から塩素イオンが検出されなくなるまで、脱イオン水で洗浄した。沈殿物を７０℃で加熱乾燥した。乾燥後の沈殿物を沈殿物重量の０．５％のＡｕ−０．５％のＰｄを含有する溶液に浸漬し、回転蒸発後に７０℃で加熱乾燥した。加熱乾燥後の触媒を４０〜６０メッシュのフィルタにかけた。
こうして得た酸化ニッケルに銀が担持された触媒０．０６６グラムを管状固定床反応器で反応させた。実験条件は下記のとおりである。
体積％で酸素ガス２０％、窒素ガス８０％であり、ホルムアルデヒドガスをホルムアルデヒドガス発生器で発生し、窒素ガスにより反応系に吹き込み、ホルムアルデヒドの濃度を０．０５％、反応空間速度（ＧＨＳＶ）を５０，０００／時間に制御した。常温環境下におけるホルムアルデヒドの転化率は１００％であり、この転化率は４８時間維持した。その後転化率が約７０％に降下したが、７８時間保持した後も転化率の更なる低下が見られなかった。
Embodiment 5 FIG.
100 g of nickel nitrate is dissolved in a predetermined amount of water, adjusted to PH = 12-13 with a sodium hydroxide solution while stirring, so that the molar percentage of nickel nitrate and sodium hypochlorite solution is 2-3. The sodium hypochlorite solution was slowly added and left overnight. After filtration and precipitation, the sample was washed with deionized water until chlorine ions were not detected from the filtrate by detection of chloride ions using a silver nitrate solution. The precipitate was heat-dried at 70 ° C. The dried precipitate was dipped in a solution containing 0.5% Au-0.5% Pd of the precipitate weight, and dried by heating at 70 ° C. after rotary evaporation. The catalyst after heat drying was passed through a 40 to 60 mesh filter.
0.066 grams of the catalyst in which silver was supported on the nickel oxide thus obtained was reacted in a tubular fixed bed reactor. The experimental conditions are as follows.
Oxygen gas is 20% by volume and nitrogen gas is 80%. Formaldehyde gas is generated by a formaldehyde gas generator and blown into the reaction system with nitrogen gas. The concentration of formaldehyde is 0.05% and the reaction space velocity (GHSV) is Controlled to 50,000 / hour. The conversion rate of formaldehyde in a normal temperature environment was 100%, and this conversion rate was maintained for 48 hours. Thereafter, the conversion rate dropped to about 70%, but no further reduction in the conversion rate was observed after holding for 78 hours.
実施例６．
二酸化チタン粉末５０ｇに所定量の水を添加、攪拌しながら、１．０％のＰｔ溶液を添加し、1時間攪拌し、酸化チタンとＰｔの混合溶液を得た。その次にロータリーエバポレータを用いて、得られた混合溶液を７０℃で乾燥し、その後、４００℃で５時間焼成した。焼成後の粉末を乳鉢で粉砕し、粒子径が５μm程度の粉末を得た後、純水を添加し、ハニカム浸漬用のスラリーとした。
次にコージライト製のハニカムをスラリー中に浸漬し、ハニカム全体に粉末を塗布した後、１００℃で５時間乾燥させた。塗布量を稼ぐために、この処理を５回繰り返した。
Example 6
While adding a predetermined amount of water to 50 g of titanium dioxide powder and stirring, a 1.0% Pt solution was added and stirred for 1 hour to obtain a mixed solution of titanium oxide and Pt. Next, using a rotary evaporator, the obtained mixed solution was dried at 70 ° C., and then calcined at 400 ° C. for 5 hours. The fired powder was pulverized in a mortar to obtain a powder having a particle size of about 5 μm, and then pure water was added to prepare a slurry for dipping the honeycomb.
Next, a cordierite honeycomb was immersed in the slurry, and the powder was applied to the entire honeycomb, followed by drying at 100 ° C. for 5 hours. This process was repeated 5 times in order to earn a coating amount.
その後、３００℃で５時間焼成した。
それにより得たハニカムを管状固定床反応器で反応させた。実験条件は下記のとおりである。
体積％で酸素ガス２０％、窒素ガス８０％であり、ホルムアルデヒドガスをホルムアルデヒドガス発生器で発生し、水中のバブリングにより１．７％の水分を添加した後、窒素ガスにより反応系に吹き込み、ホルムアルデヒドの濃度を０．０５％、反応空間速度（ＧＨＳＶ）を５０，０００／時間に制御した。常温環境下におけるホルムアルデヒドの転化率は１００％であり、この転化率は４８時間維持した。その後、わずかに転化率は低下したが、１００時間保持した後においても、転化率は９８％を維持し、２００時間保持した後、転化率の低下は見られなかった。
Then, it baked at 300 degreeC for 5 hours.
The honeycomb thus obtained was reacted in a tubular fixed bed reactor. The experimental conditions are as follows.
Oxygen gas is 20% by volume and nitrogen gas is 80%. Formaldehyde gas is generated by a formaldehyde gas generator, 1.7% water is added by bubbling in water, and then blown into the reaction system by nitrogen gas. Was controlled at 0.05%, and the reaction space velocity (GHSV) was controlled at 50,000 / hour. The conversion rate of formaldehyde in a normal temperature environment was 100%, and this conversion rate was maintained for 48 hours. Thereafter, although the conversion rate slightly decreased, the conversion rate was maintained at 98% even after being held for 100 hours, and no reduction in the conversion rate was observed after holding for 200 hours.
実施例７．
二酸化チタン粉末１０ｇに所定量の水を添加、攪拌しながら、二酸化チタン粉末重量の０．５％のＰｔを含有する溶液を添加し、1時間攪拌し、二酸化チタンとＰｔの混合溶液を得た。その次にロータリーエバポレータを用いて、得られた混合溶液を８０℃で乾燥し、その後、４００℃で５時間焼成した。
それにより得た二酸化チタンにＰｔが担持された触媒０．５グラムを管状固定床反応器で反応させた。実験条件は下記のとおりである。
体積％で酸素ガス２０％、窒素ガス８０％であり、ホルムアルデヒドガスをホルムアルデヒドガス発生器で発生させた。これらガスを混合した後、水中でバブリングして水分を添加したガスを反応系に吹き込み、ホルムアルデヒドの濃度を０．０１％に、反応空間速度（ＧＨＳＶ）を５０，０００／時間に制御した。添加水分量をバブリング無しの０．０１％（供給酸素、窒素ガスの残留水分量）から変化させた。その結果、水分添加の有無にかかわらず、２４時間後の常温環境下におけるホルムアルデヒドの転化率は１００％であり、１００時間後においては、水分添加が無い場合（添加しない場合で残留水分量として０．０１％含有）のホルムアルデヒド転化率は８５％、水分を０．０２％加えた系のホルムアルデヒド転化率は９２％、水分を０．５％加えた系のホルムアルデヒド転化率は９５％、水分を１．７％加えた系のホルムアルデヒド転化率は９８％、水分を３．５％添加した場合のホルムアルデヒド転化率は９７％であった。２００時間後において、水分を０．０２％以上加えた場合は各ホルムアルデヒド転化率を保ったが、無添加の場合は、ホルムアルデヒド転化率が７０％へと低下した。
Example 7
While adding a predetermined amount of water to 10 g of titanium dioxide powder and stirring, a solution containing 0.5% Pt of the titanium dioxide powder weight was added and stirred for 1 hour to obtain a mixed solution of titanium dioxide and Pt. . Next, the obtained mixed solution was dried at 80 ° C. using a rotary evaporator, and then calcined at 400 ° C. for 5 hours.
0.5 g of the catalyst in which Pt was supported on the titanium dioxide thus obtained was reacted in a tubular fixed bed reactor. The experimental conditions are as follows.
By volume%, oxygen gas was 20%, nitrogen gas was 80%, and formaldehyde gas was generated by a formaldehyde gas generator. After mixing these gases, a gas added with water by bubbling in water was blown into the reaction system to control the concentration of formaldehyde to 0.01% and the reaction space velocity (GHSV) to 50,000 / hour. The amount of water added was changed from 0.01% without bubbling (the amount of residual water supplied oxygen and nitrogen gas). As a result, regardless of the presence or absence of moisture addition, the conversion rate of formaldehyde in a normal temperature environment after 24 hours is 100%, and after 100 hours, when there is no moisture addition (the amount of residual moisture is 0 when not added). 0.01% content) formaldehyde conversion is 85%, 0.02% moisture added to formaldehyde is 92%, 0.5% moisture added to formaldehyde is 95%, and moisture is 1 The formaldehyde conversion rate of the system with 0.7% added was 98%, and when the water content was added 3.5%, the formaldehyde conversion rate was 97%. After 200 hours, each formaldehyde conversion was maintained when water was added in an amount of 0.02% or more, but when no water was added, the formaldehyde conversion was reduced to 70%.
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| CN114392736A (en) * | 2022-02-17 | 2022-04-26 | 苏州道一至诚纳米材料技术有限公司 | Catalytic membrane for purifying formaldehyde at normal temperature and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1795970A (en) | 2006-07-05 |
| CN1795970B (en) | 2011-04-13 |
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