JP2016150042A - Iodine carrying composition, deodorant prepared with the composition and method for producing the same, and deodorization method using the same - Google Patents
Iodine carrying composition, deodorant prepared with the composition and method for producing the same, and deodorization method using the same Download PDFInfo
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Abstract
Description
本発明は、ヨウ素担持用組成物、その組成物を用いて調製した脱臭剤並びにその製造方法及びそれを用いた脱臭方法に関する。 The present invention relates to an iodine-supporting composition, a deodorizing agent prepared using the composition, a production method thereof, and a deodorizing method using the same.
し尿処理施設、下水処理施設、ゴミ処理施設、事務所ビルの廃水処理施設等から排出される排ガスには、硫化水素、硫化メチル、アンモニアなど、悪臭の原因となる物質が含まれている。そのため、排ガスを大気中に放出する前に、排ガスを脱臭処理して、悪臭の原因物質を除去する必要がある。このような脱臭処理は、ヨウ素化合物を担持した活性炭によって行われる場合がある。 Exhaust gas discharged from human waste treatment facilities, sewage treatment facilities, waste treatment facilities, wastewater treatment facilities in office buildings, and the like contains substances that cause bad odors such as hydrogen sulfide, methyl sulfide, and ammonia. Therefore, before releasing the exhaust gas into the atmosphere, it is necessary to deodorize the exhaust gas to remove the odor-causing substance. Such deodorizing treatment may be performed by activated carbon carrying an iodine compound.
例えば、特許文献１は、ヨウ素酸化物（例えば、Ｉ２Ｏ５）、ヨウ素酸（例えば、ＨＩＯ３）、及び過ヨウ素酸（例えば、ＨＩＯ４）を活性炭に添着させた脱臭剤を開示している。ただし、この脱臭剤では、酸性である硫化水素の除去については一定の効果を発揮するものの、その他の悪臭の原因物質、例えば、アルカリ性であるアンモニアや中性である硫化メチルに対しては必ずしも十分な効果がなかった。 For example, Patent Document 1 discloses a deodorizer in which iodine oxide (eg, I 2 O 5 ), iodic acid (eg, HIO 3 ), and periodic acid (eg, HIO 4 ) are attached to activated carbon. Yes. However, although this deodorizer exerts a certain effect on the removal of acidic hydrogen sulfide, it is not necessarily sufficient for other odor-causing substances such as alkaline ammonia and neutral methyl sulfide. There was no effect.
また、特許文献２は、ヨウ化カリウムと無機酸とを含む水溶液を、臭素ガスで処理した活性炭に噴霧して得られる脱臭剤を開示している。この方法においては、製造工程において臭素ガスを用いることから、取り扱いが容易ではない。また、アルカリ金属塩であるヨウ化カリウムを用いると、アルカリ金属塩が不純物として悪影響を与え、耐久性が低くなるという問題があった。 Patent Document 2 discloses a deodorizer obtained by spraying an aqueous solution containing potassium iodide and an inorganic acid onto activated carbon treated with bromine gas. In this method, since bromine gas is used in the manufacturing process, handling is not easy. Further, when potassium iodide, which is an alkali metal salt, is used, there is a problem that the alkali metal salt has an adverse effect as an impurity and the durability is lowered.
特許文献３は、ヨウ素酸及び／又はヨウ素酸化物等の担持に先立って、活性炭を洗浄することによって、不純物含有量を低減させた脱臭剤の製造方法を開示している。 Patent Document 3 discloses a method for producing a deodorant in which the content of impurities is reduced by washing activated carbon prior to supporting iodic acid and / or iodine oxide.
特許文献４は、活性炭に、活性二酸化マンガン及びヨウ素酸塩を担持させた脱臭剤を開示している。この活性二酸化マンガンは、過マンガン酸カリウムの分解生成物であり、活性二酸化マンガンの存在によって、ヨウ素酸塩が安定に存在することができ、脱臭剤の除去性能が長期的に優れたものになる、としている。しかし、この脱臭剤も、脱臭性能及び耐久性の点で、未だに改良の余地があった。 Patent Document 4 discloses a deodorizer in which activated manganese dioxide and iodate are supported on activated carbon. This active manganese dioxide is a decomposition product of potassium permanganate, and the presence of active manganese dioxide makes it possible for iodate to be stably present, and the removal performance of the deodorant is excellent in the long term. , And. However, this deodorizer still has room for improvement in terms of deodorization performance and durability.
そこで、本発明は、単純かつ安全な方法で製造でき、かつ高い耐久性及び脱臭性能を有する脱臭剤を調製するための組成物を与えることを目的とする。さらに、本発明は、この組成物を用いて調製した脱臭剤、並びにその脱臭剤の製造法及びその脱臭剤を用いて硫化水素を脱臭する方法に関する。 Then, an object of this invention is to provide the composition for preparing the deodorizing agent which can be manufactured with a simple and safe method, and has high durability and deodorizing performance. Furthermore, the present invention relates to a deodorant prepared using this composition, a method for producing the deodorant, and a method for deodorizing hydrogen sulfide using the deodorant.
本発明者らは、以下の態様を有する手段により、上記課題を解決できることを見出した。
《態様１》
０．１〜１０重量部のヨウ化物、及び１．０〜１２重量部の酸化剤を含み、前記酸化剤に対する前記ヨウ化物のモル比は、０．０５以上０．８０以下であり、前記酸化剤は、ヨウ素酸以外のハロゲンオキソ酸又はその塩である、ヨウ素担持用水系組成物。
《態様２》
前記ヨウ化物が、ヨウ化亜鉛、ヨウ化アンモニウム、ヨウ化カドミウム、ヨウ化カリウム、ヨウ化カルシウム、ヨウ化コバルト（ＩＩ）、ヨウ化ストロンチウム、ヨウ化セシウム、ヨウ化ナトリウム、ヨウ化ニッケル（ＩＩ）、ヨウ化バリウム、ヨウ化マグネシウム、ヨウ化リチウム、ヨウ化ルビジウム、並びにこれらの混合物からなる群より選択される、態様１に記載の水系組成物。
《態様３》
前記ハロゲンオキソ酸が、次亜塩素酸、亜塩素酸、塩素酸、過塩素酸、次亜臭素酸、亜臭素酸、臭素酸、及び過臭素酸からなる群より選択される、態様１又は２に記載の水系組成物。
《態様４》
０．１〜５．０重量部の無機酸をさらに含む、態様１〜３のいずれか一項に記載の水系組成物。
《態様５》
態様１〜４のいずれか一項に記載の水系組成物を、１００重量部の多孔質担体に担持させてなる、脱臭剤。
《態様６》
前記多孔質担体が、活性炭である、態様５に記載の脱臭剤。
《態様７》
脱臭剤１００ｇ当たりに１００ｍｇ以上のヨウ素を担持している活性炭からなる脱臭剤であって、
その１．５ｇを、エタノール２０ｍｌに浸漬させてヨウ素を溶解した液から、活性炭を除去して、１０ｇ／Ｌのデンプン水溶液を２ｍｌ添加して、さらに０．１０ｍｏｌ／Ｌの硝酸銀水溶液を２ｍｌで添加して得た液の沈殿物が、５ｍｇ以下である、脱臭剤。
《態様８》
０．１〜１０重量部のヨウ化物、及び１．０〜１２重量部の酸化剤を含む水系組成物を調製する工程；
前記水系組成物を、１００重量部の多孔質担体に吸水担持させる工程；及び
前記吸収担持した多孔質担体を乾燥する工程、
を含む脱臭剤の製造方法。
《態様９》
態様１〜７に記載の脱臭剤と硫化水素を含むガスとを接触させる工程を含む、ガスの脱臭方法。
The present inventors have found that the above problems can be solved by means having the following modes.
<< Aspect 1 >>
0.1 to 10 parts by weight of iodide, and 1.0 to 12 parts by weight of an oxidizing agent, wherein the molar ratio of the iodide to the oxidizing agent is 0.05 or more and 0.80 or less, and the oxidation The agent is an aqueous composition for iodine support, which is a halogen oxo acid other than iodic acid or a salt thereof.
<< Aspect 2 >>
The iodide is zinc iodide, ammonium iodide, cadmium iodide, potassium iodide, calcium iodide, cobalt (II) iodide, strontium iodide, cesium iodide, sodium iodide, nickel iodide (II). Aqueous composition according to aspect 1, selected from the group consisting of, barium iodide, magnesium iodide, lithium iodide, rubidium iodide, and mixtures thereof.
<< Aspect 3 >>
Aspect 1 or 2 wherein the halogen oxoacid is selected from the group consisting of hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, and perbromic acid An aqueous composition as described in 1.
<< Aspect 4 >>
The aqueous composition according to any one of aspects 1 to 3, further comprising 0.1 to 5.0 parts by weight of an inorganic acid.
<< Aspect 5 >>
A deodorant obtained by supporting the aqueous composition according to any one of Embodiments 1 to 4 on 100 parts by weight of a porous carrier.
<< Aspect 6 >>
The deodorizer according to aspect 5, wherein the porous carrier is activated carbon.
<< Aspect 7 >>
A deodorizer comprising activated carbon carrying 100 mg or more of iodine per 100 g of the deodorizer,
The activated carbon is removed from the solution in which 1.5 g is immersed in 20 ml of ethanol to dissolve iodine, 2 ml of 10 g / L starch aqueous solution is added, and further 0.10 mol / L silver nitrate aqueous solution is added in 2 ml. The deodorizer whose precipitation of the liquid obtained by this is 5 mg or less.
<< Aspect 8 >>
Preparing an aqueous composition comprising 0.1 to 10 parts by weight of iodide and 1.0 to 12 parts by weight of an oxidizing agent;
A step of water-absorbing and supporting the aqueous composition on 100 parts by weight of a porous carrier; and a step of drying the absorption-supported porous carrier;
The manufacturing method of the deodorizer containing.
<< Aspect 9 >>
A method for deodorizing a gas, comprising a step of bringing the deodorizing agent according to any one of aspects 1 to 7 into contact with a gas containing hydrogen sulfide.
本発明によれば、単純かつ安全な方法で製造でき、かつ高い耐久性及び脱臭性能を有する脱臭剤を提供することができる。また、本発明によれば、長期間、高い脱臭性能で硫化水素を脱臭する方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the deodorizer which can be manufactured by a simple and safe method, and has high durability and deodorizing performance can be provided. Moreover, according to this invention, the method of deodorizing hydrogen sulfide with high deodorizing performance for a long period of time can be provided.
本発明のヨウ素担持用水系組成物は、０．１〜１０重量部のヨウ化物、及び１．０〜１２重量部の酸化剤を含み、酸化剤に対するヨウ化物のモル比は、０．０５以上０．８０以下で、かつ酸化剤は、ヨウ素酸以外のハロゲンオキソ酸又はその塩である。 The iodine-supporting aqueous composition of the present invention contains 0.1 to 10 parts by weight of iodide and 1.0 to 12 parts by weight of an oxidizing agent, and the molar ratio of the iodide to the oxidizing agent is 0.05 or more. 0.80 or less, and the oxidizing agent is a halogen oxo acid other than iodic acid or a salt thereof.
本発明の水系組成物を、例えば吸水担持法を用いて、１００重量部の多孔質担体に担持させて、その後乾燥させて、脱臭剤を製造することができる。吸水担持法においては、ヨウ化物、酸化剤等を水に溶解して、水系組成物を得た後、この水系組成物に１０℃〜４０℃で多孔質担体を浸漬する。これにより、各化合物の実質的に全ての量を、多孔質担体に分散性高く吸着させることができる。吸着後、多孔質担体を取り出し、例えば８０℃〜１２０℃の温度で乾燥させる。 The water-based composition of the present invention can be supported on 100 parts by weight of a porous carrier using, for example, a water absorption support method, and then dried to produce a deodorant. In the water absorption support method, after an iodide, an oxidant, and the like are dissolved in water to obtain an aqueous composition, a porous carrier is immersed in the aqueous composition at 10 ° C to 40 ° C. Thereby, substantially all amounts of each compound can be adsorbed on the porous carrier with high dispersibility. After the adsorption, the porous carrier is taken out and dried at a temperature of 80 ° C. to 120 ° C., for example.
本発明者らは、ヨウ化物と特定の酸化剤とを特定の量で含む水系組成物を多孔質担体に担持させることで得られる脱臭剤が、高い耐久性及び脱臭性能を有することを見出した。理論に拘束されないが、これは特定の酸化剤によってヨウ化物が水中でＩ３ −を効果的に生成し、これが多孔質担体に担持されることによるものと考えられる。硫化水素は、ヨウ素に酸化されて除去されるが、事前にヨウ素を特定の酸化剤で酸化する事で、これを担持した脱臭剤はより強い酸化性を持つようになり、硫化水素の除去効率が上がり、耐久性が向上すると考えられる。 The present inventors have found that a deodorizer obtained by supporting an aqueous composition containing iodide and a specific oxidizing agent in a specific amount on a porous carrier has high durability and deodorizing performance. . Without being bound by theory, this is believed to be due to the fact that the iodide effectively produces I 3 − in water by a specific oxidant, which is supported on the porous support. Hydrogen sulfide is oxidized and removed by iodine, but by deoxidizing iodine with a specific oxidizer in advance, the deodorant carrying this becomes more oxidizable, and the removal efficiency of hydrogen sulfide It is considered that durability is improved.
本発明の脱臭剤は、特に硫化水素に対して高い脱臭性能を有する。例えば、本発明の脱臭剤は、下記の実施例に記載した評価方法に従って評価した場合に、７５％以上、８０％以上、又は８５％以上の浄化率を有する。また、本発明の脱臭剤は、下記の実施例に記載した耐久試験後の浄化率と、耐久試験前の浄化率との差が、好ましくは８％以下、６％以下、４％以下又は２％以下である。 The deodorizer of the present invention has a high deodorizing performance especially against hydrogen sulfide. For example, the deodorizer of the present invention has a purification rate of 75% or more, 80% or more, or 85% or more when evaluated according to the evaluation method described in the following examples. In the deodorizer of the present invention, the difference between the purification rate after the durability test described in the following examples and the purification rate before the durability test is preferably 8% or less, 6% or less, 4% or less, or 2 % Or less.
本発明の脱臭剤で用いられる担体が担持するヨウ素が、望ましいＩ３ −となっているのか、Ｉ−となっているのかは、ヨウ素が容易に溶解するエタノールに脱臭剤を浸漬し、担持体をろ過等によって分離し、助剤としてデンプンを少量添加した後に、硝酸銀を添加することによって評価することができる。すなわち、Ｉ−が多量に存在する場合、硝酸銀を添加すると、ヨウ素酸銀（ＡｇＩＯ３）を生成して多量の沈殿物を形成する。しかし、Ｉ３ −となっている場合には、沈殿物を生じない。なお、沈殿物がヨウ素酸銀であるかどうかは、例えばＸ線回折によって確認することができる。 Iodine to carrier bearing used in the deodorizing agent of the present invention, preferably I 3 - what has become, I - and is what has become, immersed deodorant ethanol in which iodine is readily soluble, carrier Can be separated by filtration or the like, and after adding a small amount of starch as an auxiliary agent, it can be evaluated by adding silver nitrate. That is, when I − is present in a large amount, addition of silver nitrate produces silver iodate (AgIO 3 ) and forms a large amount of precipitate. However, when it is I 3 − , no precipitate is formed. Whether the precipitate is silver iodate can be confirmed by, for example, X-ray diffraction.
本発明の一態様の脱臭剤では、１００ｇ当たり１００ｍｇ以上のヨウ素を活性炭が担持する。この脱臭剤は、従来にない水準でＩ３ −を担持しており、高い耐久性及び脱臭性能を有する。この脱臭剤の１．５ｇを、エタノール２０ｍｌに浸漬させてヨウ素を溶解し、そこから活性炭を除去し、この液に１０ｇ／Ｌのデンプン水溶液 を２ｍｌ添加 して、さらに０．１０ｍｏｌ／Ｌの硝酸銀水溶液 を２ｍｌで添加した際の沈殿物は、好ましくは５ｍｇ以下、３ｍｇ以下、又は１．５ｍｇ以下である。 In the deodorizer of one embodiment of the present invention, activated carbon supports 100 mg or more of iodine per 100 g. This deodorizer carries I 3 − at an unprecedented level and has high durability and deodorization performance. 1.5 g of this deodorant is immersed in 20 ml of ethanol to dissolve iodine, from which the activated carbon is removed, 2 ml of 10 g / L starch aqueous solution is added to this liquid, and further 0.10 mol / L silver nitrate is added. The precipitate when 2 ml of the aqueous solution is added is preferably 5 mg or less, 3 mg or less, or 1.5 mg or less.
（ヨウ化物）
ヨウ化物としては、水系組成物中で、酸化剤と反応してＩ３ −を生成するものであれば特に限定されない。本発明で用いるヨウ化物は、２０℃において２．０ｇ／１００ｇＨ２Ｏ以上、５．０ｇ／１００ｇＨ２Ｏ以上、１０ｇ／１００ｇＨ２Ｏ以上、又は５０ｇ／１００ｇＨ２Ｏ以上の水溶性を有することが好ましい。
(Iodide)
The iodide is not particularly limited as long as it generates I 3 − by reacting with an oxidizing agent in the aqueous composition. The iodide used in the present invention has a water solubility of 2.0 g / 100 gH 2 O or more, 20 g / 100 gH 2 O or more, 10 g / 100 gH 2 O or more, or 50 g / 100 gH 2 O or more at 20 ° C. preferable.
このようなヨウ化物としては、ヨウ化亜鉛、ヨウ化アンモニウム、ヨウ化カドミウム、ヨウ化カリウム、ヨウ化カルシウム、ヨウ化コバルト（ＩＩ）、ヨウ化ストロンチウム、ヨウ化セシウム、ヨウ化ナトリウム、ヨウ化ニッケル（ＩＩ）、ヨウ化バリウム、ヨウ化マグネシウム、ヨウ化リチウム、ヨウ化ルビジウム等を挙げることができ、これらの中から複数を組み合わせて用いてもよい。この中でも、劣化物生成の原因となる金属イオンを含まない、ヨウ化アンモニウムが特に好ましい。 Examples of such iodides include zinc iodide, ammonium iodide, cadmium iodide, potassium iodide, calcium iodide, cobalt (II) iodide, strontium iodide, cesium iodide, sodium iodide, nickel iodide. (II), barium iodide, magnesium iodide, lithium iodide, rubidium iodide and the like can be mentioned, and a plurality of these may be used in combination. Among these, ammonium iodide which does not contain a metal ion that causes degradation products is particularly preferable.
本発明で用いるヨウ化物は、脱臭効果を十分に与え、かつ多孔質担体の細孔の閉塞を防止する観点から、好ましくは担持させる多孔質担体１００重量部に対して、０．１重量部以上、０．５重量部以上、１．０重量部以上、又は１．５重量部以上で水系組成物中に含まれ、また１０重量部以下、９．０重量部以下、８．０重量部以下、又は６．０重量部以下で水系組成物中に含まれる。 The iodide used in the present invention is preferably 0.1 parts by weight or more with respect to 100 parts by weight of the porous carrier to be supported, from the viewpoint of sufficiently providing a deodorizing effect and preventing the pores of the porous carrier from being blocked. 0.5 parts by weight or more, 1.0 part by weight or more, or 1.5 parts by weight or more in the aqueous composition, and 10 parts by weight or less, 9.0 parts by weight or less, 8.0 parts by weight or less. Or 6.0 parts by weight or less in the aqueous composition.
（酸化剤）
酸化剤としては、ヨウ素酸以外のハロゲンオキソ酸を用いる。このような酸化剤は、水系組成物中で、溶解したヨウ化物と反応してＩ３ −を効果的に生成できる。
(Oxidant)
As the oxidizing agent, a halogen oxo acid other than iodic acid is used. Such an oxidizing agent can effectively generate I 3 − by reacting with dissolved iodide in an aqueous composition.
ハロゲンオキソ酸としては、次亜塩素酸、亜塩素酸、塩素酸、過塩素酸、次亜臭素酸、亜臭素酸、臭素酸、過臭素酸等を挙げることができる。塩としては、カリウム塩、ナトリウム塩、カルシウム塩、マグネシウム塩、アンモニウム塩等を用いることができる。 Examples of the halogen oxo acid include hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid and the like. As the salt, potassium salt, sodium salt, calcium salt, magnesium salt, ammonium salt and the like can be used.
酸化剤は、ヨウ素を十分に酸化し、かつヨウ素の析出を防止する観点から、好ましくは担持させる多孔質担体１００重量部に対して、１．０重量部以上、１．５重量部以上、１．８重量部以上、２．０重量部以上、又は３．０重量部以上で水系組成物中に含まれ、１２重量部以下、１０重量部以下、８重量部以下、又は６重量部以下で水系組成物中に含まれる。また、酸化剤は、その量と、上記のヨウ化物の量との比も重要であり、酸化剤に対するヨウ化物のモル比は、好ましくは０．０５以上、０．０８以上、又は０．１５以上であり、また０．８０以下、０．６０以下、又は０．５０以下である。 From the viewpoint of sufficiently oxidizing iodine and preventing precipitation of iodine, the oxidizing agent is preferably 1.0 part by weight or more, 1.5 part by weight or more with respect to 100 parts by weight of the porous carrier to be supported. 8 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, contained in the aqueous composition, 12 parts by weight or less, 10 parts by weight or less, 8 parts by weight or less, or 6 parts by weight or less. It is contained in an aqueous composition. In addition, the ratio of the amount of the oxidizing agent to the amount of the above-mentioned iodide is also important, and the molar ratio of the iodide to the oxidizing agent is preferably 0.05 or more, 0.08 or more, or 0.15. It is above, and is 0.80 or less, 0.60 or less, or 0.50 or less.
（その他）
本発明の水系組成物は、溶媒として水を含む。また水と混和性のある他の溶媒、例えばエタノールを含むこともできる。
(Other)
The aqueous composition of the present invention contains water as a solvent. It can also contain other solvents that are miscible with water, such as ethanol.
本発明で用いる水系組成物は、担持させる多孔質担体１００重量部に対して、０．１〜５．０重量部、又は０．５〜３．０重量部の無機酸を含んでもよい。水系組成物に無機酸を含有させることで、脱臭剤の耐久性を向上させることができる。理論に拘束されないが、これはヨウ素を含むハロゲン化物は、酸性域で酸化特性が向上される事が一般的に知られており、この酸化特性の向上が硫化水素を効率良く酸化除去し、耐久性を向上させていると考えられる。無機酸としては、塩酸、硫酸、硝酸、リン酸等を用いることができる。 The aqueous composition used in the present invention may contain 0.1 to 5.0 parts by weight, or 0.5 to 3.0 parts by weight of an inorganic acid with respect to 100 parts by weight of the porous carrier to be supported. By including an inorganic acid in the aqueous composition, the durability of the deodorizer can be improved. Although not bound by theory, it is generally known that halides containing iodine have improved oxidation characteristics in the acidic range, and this improvement in oxidation characteristics effectively oxidizes and removes hydrogen sulfide for durability. It is thought to improve the performance. As the inorganic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used.
（多孔質担体）
本発明の脱臭剤で用いる多孔質担体としては、ヨウ素を担持して脱臭剤として用いることができるのであれば特に限定されない。多孔質担体としては、破砕炭やペレット炭等の粒子状、ハニカム状、繊維状、シート状等の形態が挙げられる。
(Porous carrier)
The porous carrier used in the deodorizer of the present invention is not particularly limited as long as it can support iodine and can be used as a deodorizer. Examples of the porous carrier include particles such as crushed charcoal and pellet charcoal, honeycombs, fibers, sheets, and the like.
本発明の脱臭剤で用いる多孔質担体は、好ましくは粒子状の形態であり、好ましい粒子状の多孔質担体としては、活性炭、セピオライト、パリゴルスカイト、ゼオライト、活性炭素繊維、活性アルミナ、セピオライト混合紙、シリカゲル、活性白土、パーミキュライト、珪藻土等を挙げることができる。この中でも特に活性炭が好ましく、さらに好ましくはヤシ殻活性炭である。多孔質担体を酸洗浄してから用いることも好ましい。 The porous carrier used in the deodorizer of the present invention is preferably in a particulate form, and as a preferred particulate porous carrier, activated carbon, sepiolite, palygorskite, zeolite, activated carbon fiber, activated alumina, sepiolite mixed paper, Examples include silica gel, activated clay, permiculite, and diatomaceous earth. Among these, activated carbon is particularly preferable, and coconut shell activated carbon is more preferable. It is also preferred to use the porous carrier after acid cleaning.
本発明での脱臭剤用いる多孔質担体は、予め３５０℃で前処理後、窒素細孔分布測定装置（スペクトリス株式会社Ｑｕａｄｒａｓｏｒ）でＢＥＴ法にて測定した場合に、１００ｍ２／ｇ以上、２００ｍ２／ｇ以上、５００ｍ２／ｇ以上、又は８００ｍ２／ｇ以上、また２０００ｍ２／ｇ以下、１５００ｍ２／ｇ以下、又は１２００ｍ２／ｇ以下のＢＥＴ比表面積を有することが好ましい。 The porous carrier used for the deodorant in the present invention is pretreated at 350 ° C. in advance, and when measured by the BET method with a nitrogen pore distribution measuring device (Spectras Co., Ltd. Quadrasor), 100 m 2 / g or more, 200 m 2 / M or more, 500 m 2 / g or more, or 800 m 2 / g or more, preferably 2000 m 2 / g or less, 1500 m 2 / g or less, or 1200 m 2 / g or less.
＜脱臭方法＞
本発明の脱臭方法は、上記の脱臭剤と硫化水素を含む排ガスとを接触させる工程を含む。この方法は、例えばし尿処理施設、下水処理施設、ゴミ処理施設、事務所ビルの廃水処理施設、食品工場等で実施することができる。本発明の脱臭方法は、上記の脱臭剤を他の脱臭剤と組み合わせて使用することもできる。特に中性硫黄に対して高い脱臭性能を有する臭素又は遷移金属化合物を含む脱臭剤とを組み合わせることができる。
<Deodorization method>
The deodorizing method of the present invention includes a step of bringing the deodorizing agent into contact with an exhaust gas containing hydrogen sulfide. This method can be carried out, for example, in a human waste treatment facility, a sewage treatment facility, a waste treatment facility, a wastewater treatment facility in an office building, a food factory, or the like. In the deodorizing method of the present invention, the above deodorizing agent can be used in combination with other deodorizing agents. In particular, it can be combined with a deodorant containing bromine or a transition metal compound having high deodorization performance with respect to neutral sulfur.
（製造例）
実施例１
ヨウ化アンモニウム５重量部（０．０３４ｍｏｌ）及び次亜塩素酸ナトリウム（濃度１２ｗｔ％水溶液）７重量部（０．０１１ｍｏｌ）を水に溶解させ、この水系組成物をヤシ殻活性炭１００重量部に吸水担持させた。その後、１００℃で５時間乾燥させて、実施例１の脱臭剤を調製した。
(Production example)
Example 1
Ammonium iodide 5 parts by weight (0.034 mol) and sodium hypochlorite (concentration 12 wt% aqueous solution) 7 parts by weight (0.011 mol) were dissolved in water, and this aqueous composition was absorbed by 100 parts by weight of coconut shell activated carbon. Supported. Then, it was made to dry at 100 degreeC for 5 hours, and the deodorizer of Example 1 was prepared.
実施例２
３５％濃度の塩酸１．０重量部を水系組成物にさらに加えた以外は、実施例１と同じ方法で実施例２の脱臭剤を調製した。
Example 2
The deodorizer of Example 2 was prepared in the same manner as in Example 1 except that 1.0 part by weight of 35% hydrochloric acid was further added to the aqueous composition.
実施例３〜５
用いる次亜塩素酸ナトリウムの量を変えた以外は、実施例１と同じ方法で実施例３〜５の脱臭剤を調製した。
Examples 3-5
The deodorizers of Examples 3 to 5 were prepared in the same manner as in Example 1 except that the amount of sodium hypochlorite used was changed.
実施例６〜８
用いるヨウ化アンモニウムの量を変えた以外は、実施例１と同じ方法で実施例６〜８の脱臭剤を調製した。
Examples 6-8
Deodorizers of Examples 6 to 8 were prepared in the same manner as in Example 1 except that the amount of ammonium iodide used was changed.
実施例９
次亜塩素酸ナトリウムの代わりに、次亜塩素酸を水系組成物に加えた以外は、実施例１と同じ方法で、実施例９の脱臭剤を調製した。
Example 9
The deodorizer of Example 9 was prepared in the same manner as in Example 1 except that hypochlorous acid was added to the aqueous composition instead of sodium hypochlorite.
実施例１０〜１２
ヨウ化アンモニウムの代わりに、ヨウ化カリウム、ヨウ化ナトリウム、及びヨウ素酸ナトリウムを水系組成物に加えた以外は、実施例１と同じ方法で、実施例１０〜１２の脱臭剤を調製した。ここでは、実施例１と同量のヨウ素量（０．０３４ｍｏｌ）となる様に、これらのヨウ素源を用いた。
Examples 10-12
Deodorizers of Examples 10 to 12 were prepared in the same manner as in Example 1 except that potassium iodide, sodium iodide, and sodium iodate were added to the aqueous composition instead of ammonium iodide. Here, these iodine sources were used so that the amount of iodine (0.034 mol) was the same as in Example 1.
比較例１〜６
同量のヨウ素量（０．０３４ｍｏｌ）となる様に各ヨウ化物又はヨウ素源を水に溶解させた後、実施例１と同様の処理を行い、比較例１〜６に記載の脱臭剤を調製した。但し、ここでは酸化剤を用いておらず、また比較例３については、水に溶解させる為、ヨウ素とヨウ化カリウムのヨウ素のモル数比が２：３となるように調製した（ＪＩＳヨウ素吸着力測定の調製方法）。
Comparative Examples 1-6
After each iodide or iodine source was dissolved in water so that the same amount of iodine (0.034 mol) was obtained, the same treatment as in Example 1 was performed to prepare the deodorizers described in Comparative Examples 1-6. did. However, no oxidizing agent was used here, and Comparative Example 3 was prepared so that the molar ratio of iodine to iodine of potassium iodide was 2: 3 in order to dissolve in water (JIS iodine adsorption). Force measurement preparation method).
比較例７
あらかじめ酸洗浄でカリウムを０．１重量％以下にさせたヤシ殻活性炭を用いた以外は比較例１と同じ方法で、比較例７の脱臭剤を調製した。
Comparative Example 7
The deodorizer of Comparative Example 7 was prepared by the same method as Comparative Example 1 except that coconut shell activated carbon in which potassium was previously adjusted to 0.1 wt% or less by acid washing was used.
比較例８〜１１
次亜塩素酸ナトリウムの代わりに、５重量部の塩酸、リン酸、硫酸、及び過マンガン酸カリウム（固形分）を水系組成物に加えた以外は、実施例１と同じ方法で、比較例８〜１１の脱臭剤を調製した。
Comparative Examples 8-11
Comparative Example 8 was the same as Example 1 except that 5 parts by weight of hydrochloric acid, phosphoric acid, sulfuric acid, and potassium permanganate (solid content) were added to the aqueous composition instead of sodium hypochlorite. -11 deodorants were prepared.
比較例１２
用いる次亜塩素酸ナトリウムの量を変えた以外は、実施例１と同じ方法で比較例１２の脱臭剤を調製した。
Comparative Example 12
A deodorant of Comparative Example 12 was prepared in the same manner as in Example 1 except that the amount of sodium hypochlorite used was changed.
比較例１３及び１４
ヨウ化アンモニウムを用いなかったこと以外は、実施例１と同じ方法で比較例１３の脱臭剤を調製した。また、用いるヨウ化アンモニウムの量を変えた以外は、実施例１と同じ方法で比較例１４の脱臭剤を調製した。
Comparative Examples 13 and 14
A deodorant of Comparative Example 13 was prepared in the same manner as Example 1 except that ammonium iodide was not used. Moreover, the deodorizer of the comparative example 14 was prepared by the same method as Example 1 except having changed the quantity of ammonium iodide to be used.
比較例１５
次亜塩素酸ナトリウムの代わりに、５重量部の過マンガン酸ナトリウム（固形分）を水系組成物に加えた以外は、実施例１と同じ方法で、比較例１５の脱臭剤を調製した。
Comparative Example 15
A deodorizer of Comparative Example 15 was prepared in the same manner as in Example 1 except that 5 parts by weight of sodium permanganate (solid content) was added to the aqueous composition instead of sodium hypochlorite.
下記の表１に上記の実施例１〜１２及び比較例１〜１５の脱臭剤の構成を示す。なお、ここで用いたヤシ殻活性炭は、窒素細孔分布測定装置で測定したＢＥＴ比表面積が１０００ｍ２／ｇであった。 Table 1 below shows configurations of the deodorizers of Examples 1 to 12 and Comparative Examples 1 to 15 described above. The coconut shell activated carbon used here had a BET specific surface area of 1000 m 2 / g as measured with a nitrogen pore distribution measuring device.
（評価方法）
脱臭性能の評価
３０ｍｍφガラスカラムに脱臭剤１０ｍｌを入れて、硫化水素１０ｐｐｍを含み、かつ室温で相対湿度を８０％に調整したガスを、カラムに５Ｌ／ｍｉｎで、ワンパスで通過させ続けた。１２０分後、入りガスと出口ガスの濃度を測定し、以下の式で定義される浄化率を算出した。カラムに流通させる際の線速度（ＬＶ）は、０．１２ｍ／ｓｅｃとし、空間速度（ＳＶ）は３０，０００／ｈであった。
浄化率（％）＝｛（Ｃ０−Ｃ）／Ｃ０｝×１００
（Ｃ０：入りガス濃度（ｐｐｍ）、Ｃ：出口ガス濃度（ｐｐｍ））
(Evaluation method)
Evaluation of Deodorizing Performance 10 ml of a deodorizing agent was placed in a 30 mmφ glass column, and a gas containing 10 ppm of hydrogen sulfide and having a relative humidity adjusted to 80% at room temperature was continuously passed through the column at 5 L / min in one pass. After 120 minutes, the concentrations of the inlet gas and the outlet gas were measured, and the purification rate defined by the following equation was calculated. The linear velocity (LV) when flowing through the column was 0.12 m / sec, and the space velocity (SV) was 30,000 / h.
Purification rate (%) = {(C 0 −C) / C 0 } × 100
(C 0 : incoming gas concentration (ppm), C: outlet gas concentration (ppm))
なお、上記のガス濃度は、以下の条件のガスクロマトグラフによって測定した。
測定機器：島津製作所製ＧＣ−１４Ｂ（ＦＰＤ）
カラム：β，β’−ＯＤＰＮ ２５％ Ｃｈｒｏｍｏｓｏｒｂ ６０〜８０メッシュ、内径３．０ｍｍφ×３０００ｍｍ、ガラスパックドカラム
温度：注入口／検出器１５０℃；カラム７０℃
In addition, said gas concentration was measured with the gas chromatograph of the following conditions.
Measuring equipment: Shimadzu GC-14B (FPD)
Column: β, β′-ODPN 25% Chromosorb 60-80 mesh, inner diameter 3.0 mmφ × 3000 mm, glass packed column temperature: inlet / detector 150 ° C .; column 70 ° C.
耐久性の評価
３０ｍｍφガラスカラムに脱臭剤１０ｍｌを入れて、硫化水素を約３５００ｐｐｍ含む２０Ｌテドラーバッグに定量ポンプを介して接続し、平衡になるまで循環させた。脱臭剤自重の１１ｗｔ％に相当する硫化水素を吸着処理させ、これを耐久後の脱臭剤とした。耐久試験前の脱臭剤の浄化率と、耐久試験後の脱臭剤の浄化率との差を、耐久性の評価に用いた。
Evaluation of durability 10 ml of a deodorizing agent was placed in a 30 mmφ glass column, connected to a 20 L Tedlar bag containing about 3500 ppm of hydrogen sulfide via a metering pump, and circulated until equilibrium was reached. Hydrogen sulfide corresponding to 11 wt% of the deodorizer's own weight was adsorbed and used as a deodorizer after durability. The difference between the purification rate of the deodorant before the durability test and the purification rate of the deodorant after the durability test was used for evaluating the durability.
担持されているヨウ素形態の評価
脱臭剤に担持されているヨウ素が、Ｉ３ −となっているのか、Ｉ−となっているのかを次のようにして評価した：
１．５ｇの脱臭剤を、エタノール２０ｍｌに浸漬し、活性炭微粉を濾過で除去し、助剤としてデンプン（１０ｇ／Ｌ)をビュレットで数滴添加して評価溶液を調製した。その直後に硝酸銀（０．１０ｍｏｌ／Ｌ)をビュレットで数滴添加して、遠心分離で沈殿物を分離し、上澄み液を除去後、乾燥させて沈殿物の重量測定を行った。
Evaluation of supported iodine form Whether the iodine supported on the deodorizer is I 3 − or I − was evaluated as follows:
An evaluation solution was prepared by immersing 1.5 g of deodorant in 20 ml of ethanol, removing activated carbon fine powder by filtration, and adding a few drops of starch (10 g / L) as an auxiliary with a burette. Immediately after that, several drops of silver nitrate (0.10 mol / L) were added with a burette, the precipitate was separated by centrifugation, the supernatant was removed, and then dried and the weight of the precipitate was measured.
（評価結果−脱臭性能及び耐久性）
以下の表１に実施例１〜１２及び比較例１〜１５の脱臭剤の脱臭性能及び耐久性についての評価結果を示す。
(Evaluation results-deodorization performance and durability)
Table 1 below shows the evaluation results of the deodorizing performance and durability of the deodorizers of Examples 1 to 12 and Comparative Examples 1 to 15.
実施例１は、次亜塩素酸ナトリウムを添加していない比較例１と比較して、耐久前後での浄化率の差が小さく、高い耐久性が得られていることがわかる。比較例１〜６及び実施例９〜１２を参照すると、次亜塩素酸ナトリウム及び次亜塩素酸の添加の効果を確認することができる。また、活性炭に担持させるヨウ素源としては、ヨウ化アンモニウムが最も好ましいことも確認することができる。 As compared with Comparative Example 1 in which sodium hypochlorite is not added, Example 1 shows that the difference in purification rate before and after durability is small and high durability is obtained. Referring to Comparative Examples 1 to 6 and Examples 9 to 12, the effect of adding sodium hypochlorite and hypochlorous acid can be confirmed. It can also be confirmed that ammonium iodide is most preferable as an iodine source to be supported on activated carbon.
実施例１と実施例２とを比較すると、水系組成物に塩酸を添加して調製した脱臭剤の方が有意な効果を与えることが分かる。 Comparing Example 1 and Example 2, it can be seen that the deodorizer prepared by adding hydrochloric acid to the aqueous composition gives a significant effect.
実施例１と、比較例８〜１１及び比較例１５とを比較すると、次亜塩素酸ナトリウムを添加することで、最も耐久性が高い脱臭剤を得られることが分かる。これについて、比較例８〜１０で用いられた塩酸、リン酸及び硫酸に関しては、酸化剤としての特性が殆どないために効果が得られていないと考えられ、また比較例１１及び１５の過マンガン酸塩については比較的高い耐久性が得られているが、本願発明の脱臭剤の耐久性には至らなかった。これは、過マンガン酸塩は、分子が大きいために活性炭の細孔が閉塞していることが考えられる。そして、過マンガン酸塩については、環境負荷及び取扱い時の安全性を考慮しても、次亜塩素酸の方が酸化剤として好ましい。 When Example 1 is compared with Comparative Examples 8 to 11 and Comparative Example 15, it can be seen that the most durable deodorizer can be obtained by adding sodium hypochlorite. Regarding this, the hydrochloric acid, phosphoric acid and sulfuric acid used in Comparative Examples 8 to 10 are considered to have no effect due to almost no characteristics as an oxidizing agent, and permanganese in Comparative Examples 11 and 15 Although the comparatively high durability was acquired about the acid salt, it did not reach the durability of the deodorizer of this invention. This is probably because permanganate has a large molecule and thus the pores of activated carbon are clogged. And about permanganate, hypochlorous acid is more preferable as an oxidizing agent even if environmental load and the safety at the time of handling are considered.
実施例１０〜１２を参照すると、ヨウ化アンモニウムの他、ヨウ化カリウムやヨウ化ナトリウム等のヨウ化物であっても本願発明の効果を与えることが分かる。これは、酸化剤との組合せによってヨウ化物が水中でＩ３ −を生成する、という本願発明の機構を考慮すれば理解することができる。 Referring to Examples 10 to 12, it can be seen that, in addition to ammonium iodide, iodides such as potassium iodide and sodium iodide give the effect of the present invention. This can be understood in view of the mechanism of the present invention that iodide produces I 3 − in water in combination with an oxidizing agent.
実施例３〜５及び比較例１２を参照すると、用いることができる酸化剤の量は、非常に限られた範囲であることが分かる。これは、酸化剤の量が多い場合には、ヨウ素が析出し、水系組成物中で安定して存在できなくなり、活性炭への担持効率が低下するためであると考えられる。なお、実施例３〜５及び比較例１２の、次亜塩素酸ナトリウムに対するヨウ化アンモニウムのモル比は、それぞれ０．０８４、０．１８７、０．３２７、及び０．６０８であった。 Referring to Examples 3-5 and Comparative Example 12, it can be seen that the amount of oxidizing agent that can be used is in a very limited range. This is considered to be because when the amount of the oxidizing agent is large, iodine is precipitated and cannot stably exist in the aqueous composition, and the supporting efficiency on the activated carbon decreases. In addition, the molar ratios of ammonium iodide to sodium hypochlorite in Examples 3 to 5 and Comparative Example 12 were 0.084, 0.187, 0.327, and 0.608, respectively.
実施例６〜８、比較例１３及び１４を参照すると、用いることができるヨウ化物の量も、非常に限られた範囲であることが分かる。比較例１４の脱臭剤は、ヨウ化物の量が多かったことで、活性炭の細孔が閉塞したものと考えられる。 Referring to Examples 6-8 and Comparative Examples 13 and 14, it can be seen that the amount of iodide that can be used is also in a very limited range. The deodorizer of Comparative Example 14 is considered to have clogged the pores of the activated carbon due to the large amount of iodide.
（評価−担持されているヨウ素形態）
以下の表２に、実施例１〜８並びに比較例１及び１５の脱臭剤についての担持されているヨウ素形態についての評価結果を示す。
(Evaluation-supported iodine form)
Table 2 below shows the evaluation results for the supported iodine forms for the deodorizers of Examples 1 to 8 and Comparative Examples 1 and 15.
実施例１〜８の脱臭剤については、ヨウ素酸銀の沈殿物が非常にわずかであり、脱臭剤に担持されているヨウ素が、望ましい形態であるＩ３ −となっていたことがわかる。一方で、比較例１及び１５の脱臭剤は沈殿物が非常に多く、Ｉ−を多く含んでいたことが示唆された。 The deodorant of Example 1-8, a very slight precipitate of iodate silver, iodine carried on deodorant, a desirable form I 3 - which has been a can be seen. On the other hand, it was suggested that the deodorizers of Comparative Examples 1 and 15 contained a large amount of precipitates and contained a large amount of I − .
Claims (9)
その１．５ｇを、エタノール２０ｍｌに浸漬させてヨウ素を溶解した液から、活性炭を除去して、１０ｇ／Ｌのデンプン水溶液を２ｍｌ添加して、さらに０．１０ｍｏｌ／Ｌの硝酸銀水溶液を２ｍｌで添加して得た液の沈殿物が、５ｍｇ以下である、脱臭剤。 A deodorizer comprising activated carbon carrying 100 mg or more of iodine per 100 g of the deodorizer,
The activated carbon is removed from the solution in which 1.5 g is immersed in 20 ml of ethanol to dissolve iodine, 2 ml of 10 g / L starch aqueous solution is added, and further 0.10 mol / L silver nitrate aqueous solution is added in 2 ml. The deodorizer whose precipitation of the liquid obtained by this is 5 mg or less.
前記水系組成物を、１００重量部の多孔質担体に吸水担持させる工程；及び
前記吸収担持した多孔質担体を乾燥する工程、
を含む脱臭剤の製造方法。 Preparing an aqueous composition comprising 0.1 to 10 parts by weight of iodide and 1.0 to 12 parts by weight of an oxidizing agent;
A step of water-absorbing and supporting the aqueous composition on 100 parts by weight of a porous carrier; and a step of drying the absorption-supported porous carrier;
The manufacturing method of the deodorizer containing.
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| CN115397477A (en) * | 2020-04-23 | 2022-11-25 | 理研香料控股株式会社 | Deodorant agent |
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| JPS62161372A (en) * | 1986-01-13 | 1987-07-17 | 清水建設株式会社 | Deodorant and its production |
| JPH04320641A (en) * | 1991-04-18 | 1992-11-11 | Nippon Kayaku Co Ltd | Freshness-retaining agent or ethylene-removing agent |
| JP2001129392A (en) * | 1999-11-08 | 2001-05-15 | Takeda Chem Ind Ltd | Adsorbent |
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