JP2006061885A - Deodorizing adsorbent - Google Patents
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Abstract
Description
本発明は、脱臭吸着剤に関するものである。 The present invention relates to a deodorizing adsorbent.
従来、下水、し尿、焼却場等のプラント設備等から発生する複合臭気を脱臭するために、それぞれの臭気に対応した薬剤を添着させた活性炭が用いられている。 Conventionally, in order to deodorize complex odors generated from plant facilities such as sewage, human waste, and incineration plants, activated carbon to which chemicals corresponding to the respective odors are attached is used.
例えば、特許文献１及び特許文献２には、活性炭の品質を均一にし、硫化ジメチル、二硫化ジメチルを満足できる程度まで除去可能にすることを目的として、不純物の含量が規定範囲内にあり、かつ臭素の含量が３質量％以上である臭素添着活性炭が開示されている。
For example, in
しかしながら、上記特許文献１及び特許文献２に記載されている臭素添着活性炭は、硫化メチル等の両性硫黄系ガスに対する除去性能が十分とは言えなかった。また、このような臭素添着活性炭は、製造の際に臭素ガス、液体臭素、あるいは、臭素水を用いることから、安全性にも問題があった。
本発明は、安全に製造でき、かつ両性硫黄系ガスに対する優れた除去性能を有する脱臭吸着剤を提供することを目的とするものである。 An object of the present invention is to provide a deodorizing adsorbent that can be produced safely and has excellent removal performance for amphoteric sulfur-based gases.
本発明に係る脱臭吸着剤は、鉄及び臭素を担持する多孔質担体を含むことを特徴とするものである。 The deodorizing adsorbent according to the present invention includes a porous carrier supporting iron and bromine.
本発明によれば、安全に製造でき、かつ両性硫黄系ガスに対する優れた除去性能を有する脱臭吸着剤を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the deodorizing adsorption agent which can be manufactured safely and has the outstanding removal performance with respect to amphoteric sulfur type gas can be provided.
前述した特許文献１には、不純物として活性炭中に含まれる鉄は、臭素添着活性炭の吸着性能を低下させることから、その含有量を０．３質量％以下に規定することが記載されている。しかしながら、本発明者らが鋭意研究した結果、臭素と共に鉄を多孔質体の表面に担持させることにより、脱臭吸着剤の両性硫黄系ガスに対する吸着性能を向上させることができるという知見を得た。本発明はこの知見に基づくものである。
以下、本発明に係る脱臭吸着剤の種々の実施形態を説明する。 Hereinafter, various embodiments of the deodorizing adsorbent according to the present invention will be described.
本発明に係る脱臭吸着剤は、鉄および臭素を担持する多孔質担体を含むことを特徴とするものである。 The deodorizing adsorbent according to the present invention includes a porous carrier supporting iron and bromine.
鉄は酸化触媒的な作用を有することから、臭素と共に鉄を多孔質担体表面に担持させることにより、硫化メチル、二硫化メチルなどの両性硫黄系ガスの除去性能を向上させることができるものと考えられる。 Since iron has an oxidation catalytic action, it is thought that the removal performance of amphoteric sulfur gases such as methyl sulfide and methyl disulfide can be improved by supporting iron together with bromine on the surface of the porous carrier. It is done.
鉄及び臭素は、少なくとも一部が鉄臭化物の形態で前記多孔質担体に担持されていることが好ましく、全てが鉄臭化物（ＦｅＢｒ2）の形態にあることが特に好ましい。 It is preferable that at least a part of iron and bromine is supported on the porous support in the form of iron bromide, and it is particularly preferable that all of them are in the form of iron bromide (FeBr 2 ).
鉄臭化物は、両性硫黄系ガスを化学吸着により除去する効果を有し、特に、下水のにおいの主な原因である硫化メチルに対する除去性能を向上させる効果を有する。鉄及び臭素の少なくとも一部を鉄臭化物の形態で担持させることにより、多孔質担体の物理吸着に加え、鉄、臭素及び鉄臭化物の化学吸着によって、臭気成分、特に硫化メチル等の両性硫黄系ガスに対する脱臭吸着剤の除去性能を向上させることができる。 Iron bromide has the effect of removing amphoteric sulfur gas by chemisorption, and in particular has the effect of improving the removal performance for methyl sulfide, which is the main cause of sewage odor. By supporting at least a part of iron and bromine in the form of iron bromide, in addition to the physical adsorption of the porous carrier, the chemisorption of iron, bromine and iron bromide will cause odorous components, in particular amphoteric sulfur gases such as methyl sulfide. It is possible to improve the removal performance of the deodorizing adsorbent.
鉄臭化物は、鉄化合物と臭素化合物とを多孔質担体に吸着させ、多孔質担体上で反応させて得ることもできる。なお、臭化鉄は比較的高価であることから、鉄化合物及び臭素化合物から得られる鉄臭化物を担持させることが好ましい。 The iron bromide can also be obtained by adsorbing an iron compound and a bromine compound on a porous carrier and reacting them on the porous carrier. Since iron bromide is relatively expensive, it is preferable to carry iron bromide obtained from an iron compound and a bromine compound.
多孔質担体の材質は特に限定されるものではないが、例えば、ゼオライト、活性炭等を挙げることができる。特に、種々の臭気成分に対する吸着能に優れることから、多孔質担体には活性炭を用いることが好ましい。 The material of the porous carrier is not particularly limited, and examples thereof include zeolite and activated carbon. In particular, it is preferable to use activated carbon for the porous carrier because of its excellent ability to adsorb various odor components.
鉄の担持量と臭素の担持量との比率は、Ｆｅ：Ｂｒが原子比で０．３３：１〜０．７：１の範囲にあることが好ましい。ＦｅとＢｒの原子比が前記範囲から外れると、硫化メチル等の両性硫黄系ガスに対する脱臭吸着剤の除去性能が低下する傾向がある。鉄の担持量と臭素の担持量との比率のさらに好ましい範囲は、Ｆｅ：Ｂｒが原子比で０．４：１〜０．６：１である。ＦｅとＢｒの原子比をこの範囲にすると、硫化メチルの除去性能をさらに向上させることができる。 The ratio of the iron loading and bromine loading is preferably such that Fe: Br is in the range of 0.33: 1 to 0.7: 1 by atomic ratio. When the atomic ratio of Fe and Br is out of the above range, the removal performance of the deodorizing adsorbent with respect to amphoteric sulfur gases such as methyl sulfide tends to be lowered. A more preferable range of the ratio between the iron loading and the bromine loading is such that Fe: Br is 0.4: 1 to 0.6: 1 in atomic ratio. When the atomic ratio of Fe and Br is within this range, the removal performance of methyl sulfide can be further improved.
脱臭吸着剤における鉄の担持量は、０．８〜３．８質量％の範囲にあることが好ましい。鉄の担持量が、０．８質量％未満であると、硫化メチル等の両性硫黄系ガスに対する除去性能が十分に得られない恐れがある。一方、鉄の担持量が３．８質量％を超えると、多孔質担体の細孔が閉塞され、臭気成分を十分に吸着できなくなる傾向がある。鉄の担持量のさらに好ましい範囲は、２〜３質量％である。鉄の担持量がこの範囲内にある場合に、種々の臭気成分に対する脱臭吸着剤の除去性能を最も良好にすることができる。 The iron loading in the deodorizing adsorbent is preferably in the range of 0.8 to 3.8% by mass. If the amount of iron supported is less than 0.8% by mass, there is a risk that sufficient removal performance for amphoteric sulfur gases such as methyl sulfide may not be obtained. On the other hand, if the amount of iron supported exceeds 3.8% by mass, the pores of the porous carrier are blocked, and there is a tendency that odor components cannot be sufficiently adsorbed. A more preferable range of the iron loading is 2 to 3% by mass. When the iron loading is within this range, the removal performance of the deodorizing adsorbent for various odor components can be made the best.
前記多孔質担体は、さらに無機酸を担持することが好ましい。これは、鉄及び臭素を担持させることによる両性硫黄系ガスに対する除去性能の向上効果は、酸性条件下で特に良好に発揮されるためである。 It is preferable that the porous carrier further supports an inorganic acid. This is because the effect of improving the removal performance for the amphoteric sulfur-based gas by supporting iron and bromine is exhibited particularly well under acidic conditions.
無機酸としては、硫酸、塩酸等を挙げることができる。 Examples of inorganic acids include sulfuric acid and hydrochloric acid.
無機酸の担持量は、多孔質担体１００重量部に対して２〜２０重量部の範囲にあることが好ましい。無機酸の担持量がこの範囲内にあるときに、硫化メチルに対する脱臭吸着剤の除去性能が最も良好になる。 The amount of the inorganic acid supported is preferably in the range of 2 to 20 parts by weight with respect to 100 parts by weight of the porous carrier. When the supported amount of inorganic acid is within this range, the deodorizing adsorbent removal performance for methyl sulfide is the best.
かかる脱臭吸着剤は、例えば以下に説明する吸水担持法を用いて製造することができる。 Such a deodorizing adsorbent can be produced using, for example, a water absorption support method described below.
臭素化合物、鉄化合物、及び、必要に応じて無機酸を水に溶解し、この水溶液に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、担体を取り出し、例えば８０℃〜１２０℃の温度で乾燥する。吸着された臭素化合物及び鉄化合物のうちの少なくとも一部は、多孔質担体上で反応し、鉄臭化物を形成する。この吸水担持法を用いることにより、鉄及び臭素を多孔質担体に高分散に担持させることができると共に、鉄臭化物を多孔質担体に高分散に担持させることができ、得られる脱臭吸着剤の除去性能及び耐久性を向上させることができる。 A bromine compound, an iron compound and, if necessary, an inorganic acid are dissolved in water, and the porous carrier is immersed in this aqueous solution at 10 ° C to 40 ° C. Thereby, substantially the entire amount of each compound can be adsorbed on the porous carrier with high dispersibility. After adsorption, the carrier is taken out and dried at a temperature of, for example, 80 ° C to 120 ° C. At least some of the adsorbed bromine compound and iron compound react on the porous support to form iron bromide. By using this water absorption loading method, iron and bromine can be supported on a porous carrier in a highly dispersed manner, and iron bromide can be supported on a porous carrier in a highly dispersed manner, and the resulting deodorizing adsorbent can be removed. Performance and durability can be improved.
臭素化合物としては、臭化水素、臭化アンモニウム等を挙げることができる。 Examples of the bromine compound include hydrogen bromide and ammonium bromide.
鉄化合物としては、塩化第二鉄、硫酸鉄、塩化第一鉄等を挙げることができる。 Examples of the iron compound include ferric chloride, iron sulfate, and ferrous chloride.
なお、この発明は、上記実施形態そのままに限定されるものではなく、実施段階ではその要旨を逸脱しない範囲で構成要素を変形して具体化できる。また、上記実施形態に開示されている複数の構成要素の適宜な組み合せにより種々の発明を形成できる。例えば、実施形態に示される全構成要素から幾つかの構成要素を削除してもよい。更に、異なる実施形態に亘る構成要素を適宜組み合せてもよい。 Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. Further, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, you may combine suitably the component covering different embodiment.
［実施例］
以下、本発明に係る脱臭吸着剤を実施例により説明する。
[Example]
Hereinafter, the deodorizing adsorbent according to the present invention will be described with reference to examples.
（実施例１及び比較例１〜３）
＜脱臭吸着剤の製造＞
（実施例１）
ベンゼン吸着量が３１質量％以上になるように賦活を進めたヤシ殻活性炭を用意し、これを塩酸で処理することにより不純物を除去して清浄化し、活性化したものを多孔質担体として用いた。
(Example 1 and Comparative Examples 1-3)
<Manufacture of deodorizing adsorbent>
Example 1
A coconut shell activated carbon whose activation was advanced so that the amount of benzene adsorbed was 31% by mass or more was prepared, and this was treated with hydrochloric acid to remove impurities to be purified, and the activated product was used as a porous carrier. .
この多孔質担体１００重量部を、臭素化合物として臭化水素１１重量部、鉄化合物として塩化第二鉄９．９重量部、及び、無機酸として硫酸７重量部を水に溶解することにより調製した水溶液に浸漬し、吸水担持を行った。その後、１００℃で５時間乾燥させて脱臭吸着剤を得た。 100 parts by weight of this porous carrier was prepared by dissolving 11 parts by weight of hydrogen bromide as a bromine compound, 9.9 parts by weight of ferric chloride as an iron compound, and 7 parts by weight of sulfuric acid as an inorganic acid. It was immersed in an aqueous solution to carry water. Then, it was made to dry at 100 degreeC for 5 hours, and the deodorizing adsorption agent was obtained.
このようにして得られた脱臭吸着剤の水浸ｐＨを以下に説明するように測定した。その結果を表１に示す。 The water immersion pH of the deodorized adsorbent thus obtained was measured as described below. The results are shown in Table 1.
水浸ｐＨは、１００ｃｃの水中に３ｇの試料を浸漬し、５分間煮沸し、冷却した後の水のｐＨを測定したものであり、その測定法はＪＩＳ規格に規定された方法に準ずる。 The immersion pH is obtained by immersing a 3 g sample in 100 cc of water, boiling it for 5 minutes, and measuring the pH of the water after cooling, and the measurement method conforms to the method defined in JIS standards.
また、得られた脱臭吸着剤のＢｒ含有量、Ｆｅ含有量及びＮａ含有量を、試料を十分に乾燥させた後、微粉砕し、市販の蛍光Ｘ線分析装置（ＰＷ１４８０）を用いて測定した。その結果を表１に併記する。 Further, the Br content, Fe content and Na content of the obtained deodorizing adsorbent were measured using a commercially available fluorescent X-ray analyzer (PW1480) after the sample was sufficiently dried and then finely pulverized. . The results are also shown in Table 1.
（比較例１）
臭化ナトリウム１１重量部、及び、硫酸７重量部を水に溶解することにより調製した水溶液を用いて吸水担持を行ったこと以外は、実施例１と同様にして脱臭吸着剤を得た。
(Comparative Example 1)
A deodorizing adsorbent was obtained in the same manner as in Example 1 except that water absorption was carried out using an aqueous solution prepared by dissolving 11 parts by weight of sodium bromide and 7 parts by weight of sulfuric acid in water.
（比較例２）
臭化水素１１重量部、及び、硫酸７重量部を水に溶解することにより調製した水溶液を用いて吸水担持を行ったこと以外は、実施例１と同様にして脱臭吸着剤を得た。
(Comparative Example 2)
A deodorizing adsorbent was obtained in the same manner as in Example 1 except that water absorption was carried out using an aqueous solution prepared by dissolving 11 parts by weight of hydrogen bromide and 7 parts by weight of sulfuric acid in water.
（比較例３）
三角フラスコにおいて、臭化カリウム１３．４ｇ、及び、臭素酸カリウム（ＫＢｒＯ3）３．７７ｇを純水１Ｌに溶解した。この水溶液２５３．６ｍＬに硫酸３．３５ｇを反応させて臭素ガス（Ｂｒ2）を発生させ、この臭素ガスを、実施例１と同様な多孔質担体約３０ｍＬを充填したガラスカラムに導入した。このようにして、多孔質担体に臭素を担持させることにより比較例３の脱臭吸着剤を得た。
(Comparative Example 3)
In an Erlenmeyer flask, 13.4 g of potassium bromide and 3.77 g of potassium bromate (KBrO 3 ) were dissolved in 1 L of pure water. This aqueous solution 253.6 mL was reacted with 3.35 g of sulfuric acid to generate bromine gas (Br 2 ), and this bromine gas was introduced into a glass column packed with about 30 mL of the same porous carrier as in Example 1. Thus, the deodorizing adsorption agent of the comparative example 3 was obtained by carrying | supporting a bromine on a porous support | carrier.
得られた比較例１〜３の脱臭吸着剤についても、実施例１と同様にして水浸ｐＨ、Ｂｒ含有量、Ｆｅ含有量及びＮａ含有量を測定した。その結果を表１に示す。
＜評価方法＞
得られた実施例１及び比較例１〜３の脱臭吸着剤のサンプルを各６ｍＬずつ採取し、それぞれ３０ｍｍφガラスカラムに充填した。これらのガラスカラムに、硫化メチルを１０ｐｐｍ含み、かつ湿度を８０％に調整した空気ガスを温度２５℃で、５Ｌ／分の流速で６０分間通過させた。ＬＶ（線速度）は、０．１２ｍ／秒とし、ＳＶ（空間速度）は、５００００／時間とした。このときの所定時間経過時の入りガス及び出口ガスに含まれる硫化メチルの濃度をそれぞれ測定した。濃度測定には以下の装置を用い、ガスクロマトグラフィー（ＧＣ）により行った。
<Evaluation method>
6 mL of each sample of the obtained deodorizing adsorbents of Example 1 and Comparative Examples 1 to 3 was collected and packed in a 30 mmφ glass column. An air gas containing 10 ppm of methyl sulfide and adjusted to a humidity of 80% was passed through these glass columns at a temperature of 25 ° C. and a flow rate of 5 L / min for 60 minutes. The LV (linear velocity) was 0.12 m / second, and the SV (space velocity) was 50000 / hour. At this time, the concentrations of methyl sulfide contained in the inlet gas and the outlet gas when the predetermined time had elapsed were measured. The concentration was measured by gas chromatography (GC) using the following apparatus.
ＧＣ装置：島津製ＧＣ−８Ａｐ（ＦＰＤ）
カラム：β，β’−ＯＤＰＮ２５％ 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℃
得られた濃度より、下記（１）式に従って各経過時間ごとの硫化メチルの浄化率を算出した。
GC device: Shimadzu GC-8Ap (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.
From the obtained concentration, the purification rate of methyl sulfide for each elapsed time was calculated according to the following formula (1).
ＣＬ＝｛（Ｃ0−Ｃ）／Ｃ0｝×１００ …（１）
ＣＬ；浄化率（％）
Ｃ0；入りガス濃度（ｐｐｍ）
Ｃ；出口ガス濃度（ｐｐｍ）
得られた結果を図１に示す。図１において、縦軸は、硫化メチルの浄化率（％）を示し、横軸は、経過時間（分）を示す。
CL = {(C 0 −C) / C 0 } × 100 (1)
CL: Purification rate (%)
C 0 ; Concentration of incoming gas (ppm)
C: outlet gas concentration (ppm)
The obtained results are shown in FIG. In FIG. 1, the vertical axis represents the purification rate (%) of methyl sulfide, and the horizontal axis represents the elapsed time (minutes).
図１から明らかなように、鉄及び臭素を担持する多孔質担体を含む実施例１の脱臭吸着剤は、臭素のみを担持する比較例３の脱臭吸着剤に比較して硫化メチル浄化率が高く、耐久性にも優れていた。これは、鉄が酸化触媒的な作用を有するため、また、吸水担持という簡便な方法で鉄臭化物を多孔質担体上に高分散に担持させることができたためと考えられる。また、比較例３の脱臭吸着剤は、多孔質担体に臭素ガスを担持させることにより得られるのに対して、実施例１の脱臭吸着剤は、製造時に、臭素ガス、液体臭素及び臭素水を使用する必要がないことから、安全性に優れるという効果も有する。 As is apparent from FIG. 1, the deodorizing adsorbent of Example 1 including the porous carrier supporting iron and bromine has a higher methyl sulfide purification rate than the deodorizing adsorbent of Comparative Example 3 supporting only bromine. Also, the durability was excellent. This is probably because iron has an oxidation catalytic action and iron bromide can be supported in a highly dispersed manner on the porous support by a simple method of supporting water absorption. The deodorizing adsorbent of Comparative Example 3 is obtained by supporting bromine gas on a porous carrier, whereas the deodorizing adsorbent of Example 1 contains bromine gas, liquid bromine and bromine water at the time of production. Since it is not necessary to use, it has the effect of being excellent in safety.
さらに実施例１の脱臭吸着剤は、臭化ナトリウムを担持させた比較例１の脱臭吸着剤、及び、臭化水素を担持させた比較例２の脱臭吸着剤に比較しても、硫化メチル浄化率が高く、耐久性にも優れていた。 Further, the deodorizing adsorbent of Example 1 is a methyl sulfide purifying agent as compared with the deodorizing adsorbent of Comparative Example 1 supporting sodium bromide and the deodorizing adsorbent of Comparative Example 2 supporting hydrogen bromide. The rate was high and the durability was excellent.
（実施例２〜８及び比較例４〜１０）
（実施例２〜８）
実施例１と同様な多孔質担体１００重量部を、臭化水素、塩化第二鉄及び硫酸を水に溶解することにより調製した水溶液に浸漬して吸水担持を行い、その後、１００℃で５時間乾燥させて脱臭吸着剤を得た。このとき、塩化第二鉄の添加量は９．９重量部とし、硫酸の添加量は７重量部とし、臭化水素の添加量は１３〜３８重量部の範囲で変化させて実施例２〜８の脱臭吸着剤とした。
(Examples 2-8 and Comparative Examples 4-10)
(Examples 2 to 8)
100 parts by weight of the same porous carrier as in Example 1 was immersed in an aqueous solution prepared by dissolving hydrogen bromide, ferric chloride and sulfuric acid in water to carry water absorption, and then at 100 ° C. for 5 hours. The deodorized adsorbent was obtained by drying. At this time, the addition amount of ferric chloride was 9.9 parts by weight, the addition amount of sulfuric acid was 7 parts by weight, and the addition amount of hydrogen bromide was changed in the range of 13 to 38 parts by weight. 8 deodorizing adsorbent.
（比較例４〜１０）
塩化第二鉄を添加しなかったこと以外は、実施例２〜８と同様にして比較例４〜１０の脱臭吸着剤を得た。このとき、実施例２と比較例４、実施例３と比較例５、実施例４と比較例６、実施例５と比較例７、実施例６と比較例８、実施例７と比較例９、実施例８と比較例１０は、それぞれ臭化水素の添加量を同量とした。
(Comparative Examples 4 to 10)
The deodorizing adsorbents of Comparative Examples 4 to 10 were obtained in the same manner as in Examples 2 to 8 except that ferric chloride was not added. At this time, Example 2 and Comparative Example 4, Example 3 and Comparative Example 5, Example 4 and Comparative Example 6, Example 5 and Comparative Example 7, Example 6 and Comparative Example 8, Example 7 and Comparative Example 9 In Example 8 and Comparative Example 10, the same amount of hydrogen bromide was added.
得られた実施例２〜８及び比較例４〜１０の脱臭吸着剤について、実施例１と同様にして水浸ｐＨ、Ｂｒ含有量及びＦｅ含有量を測定した。その結果を表２に示す。さらに、得られたＢｒ含有量及びＦｅ含有量から、Ｆｅ／Ｂｒ原子比を求めた。その結果を表１に併記する。ここで、Ｆｅ／Ｂｒ原子比とは、Ｂｒ原子の数を１とおいたときのＦｅ原子の数を示すものである。 About the obtained deodorizing adsorption agent of Examples 2-8 and Comparative Examples 4-10, it carried out similarly to Example 1, and measured water immersion pH, Br content, and Fe content. The results are shown in Table 2. Furthermore, Fe / Br atomic ratio was calculated | required from the obtained Br content and Fe content. The results are also shown in Table 1. Here, the Fe / Br atomic ratio indicates the number of Fe atoms when the number of Br atoms is 1.
得られた実施例２〜８及び比較例４〜１０の脱臭吸着剤を用いて、実施例１と同様にして硫化メチル浄化率の評価を行った。６０分経過時の硫化メチル浄化率の結果を表２に示す。また、この硫化メチル浄化率とＦｅ／Ｂｒ原子比及びＢｒ含有量との関係を図２に示す。図２において、縦軸は、硫化メチル浄化率（％）を示し、下側の横軸は、Ｆｅ／Ｂｒ原子比を示し、上側の横軸は、Ｂｒ含有量（質量％）を示す。
表２及び図２から明らかなように、鉄及び臭素を担持する多孔質担体を含む実施例２〜８の脱臭吸着剤は、Ｆｅ／Ｂｒ原子比がいかなる範囲にあっても、鉄を担持しない比較例４〜１０の脱臭吸着剤に比較して硫化メチル浄化率が高く、硫化メチル除去性能に優れていた。 As is apparent from Table 2 and FIG. 2, the deodorizing adsorbents of Examples 2 to 8 including the porous support supporting iron and bromine do not support iron regardless of the Fe / Br atomic ratio. Compared with the deodorizing adsorbents of Comparative Examples 4 to 10, the methyl sulfide purification rate was high, and the methyl sulfide removal performance was excellent.
また、得られた実施例２及び比較例４の脱臭吸着剤の硫化メチル浄化率より、下記（２）式に従って実施例２の脱臭吸着剤の硫化メチル除去性能の向上率を算出した。 Moreover, the improvement rate of the methyl sulfide removal performance of the deodorizing adsorbent of Example 2 was calculated from the methyl sulfide purification rate of the obtained deodorizing adsorbent of Example 2 and Comparative Example 4 according to the following formula (2).
ＣＬup＝{（ＣＬe−ＣＬc）／ＣＬe}×１００ …（２）
ＣＬup；実施例２の脱臭吸着剤の硫化メチル除去性能の向上率（％）
ＣＬe；実施例２の脱臭吸着剤の硫化メチル浄化率（％）
ＣＬc；比較例４の脱臭吸着剤の硫化メチル浄化率（％）
実施例３〜８の脱臭吸着剤についても同様に、同量の臭化水素を添加して得られた比較例５〜１０の脱臭吸着剤に対する性能向上率を算出した。この結果を図３に示す。図３において、縦軸は、硫化メチル除去性能の向上率（％）を示し、横軸は、Ｆｅ／Ｂｒ原子比を示す。
CL up = {(CL e −CL c ) / CL e } × 100 (2)
CL up : Improvement rate (%) of methyl sulfide removal performance of the deodorizing adsorbent of Example 2
CL e ; methyl sulfide purification rate (%) of the deodorizing adsorbent of Example 2
CL c ; methyl sulfide purification rate (%) of the deodorizing adsorbent of Comparative Example 4
Similarly, for the deodorizing adsorbents of Examples 3 to 8, the performance improvement rate for the deodorizing adsorbents of Comparative Examples 5 to 10 obtained by adding the same amount of hydrogen bromide was calculated. The result is shown in FIG. In FIG. 3, the vertical axis represents the improvement rate (%) of the methyl sulfide removal performance, and the horizontal axis represents the Fe / Br atomic ratio.
表２及び図３から明らかなように、鉄の担持量と臭素の担持量との割合が、原子比（Ｆｅ：Ｂｒ）で０．３３：１〜０．７：１の範囲にある実施例２〜６の脱臭吸着剤は、性能向上率が５．０％以上と高く、原子比が前記範囲から外れる実施例７，８の脱臭吸着剤に比較して優れた硫化メチル浄化率の向上効果が得られた。また、原子比が０．４：１〜０．６：１の範囲にある実施例４，５は、原子比が前記範囲から外れる実施例２，３，６の脱臭吸着剤に比較して性能向上率がさらに高かった。さらに、Ｆｅ：Ｂｒが原子比でほぼ０．５：１にあるときに性能向上率が最も高くなることが確認できた。 As is clear from Table 2 and FIG. 3, the ratio of the amount of iron loaded to the amount of bromine loaded is in the range of 0.33: 1 to 0.7: 1 in terms of atomic ratio (Fe: Br). The deodorizing adsorbents 2 to 6 have a high performance improvement rate of 5.0% or more, and the improvement effect of the methyl sulfide purification rate superior to the deodorizing adsorbents of Examples 7 and 8 in which the atomic ratio is out of the above range. was gotten. In addition, Examples 4 and 5 having an atomic ratio in the range of 0.4: 1 to 0.6: 1 have performance compared to the deodorizing adsorbents of Examples 2, 3, and 6 in which the atomic ratio is out of the range. The improvement rate was even higher. Furthermore, it was confirmed that the performance improvement rate was the highest when Fe: Br was approximately 0.5: 1 by atomic ratio.
（実施例９〜１１及び比較例２）
（実施例９）
臭化水素１１重量部、塩化第二鉄１９．８重量部、及び、硫酸７重量部を水に溶解することにより調製した水溶液を用いて吸水担持を行ったこと以外は、実施例１と同様にして脱臭吸着剤を得た。
(Examples 9 to 11 and Comparative Example 2)
Example 9
Except that water absorption was carried out using an aqueous solution prepared by dissolving 11 parts by weight of hydrogen bromide, 19.8 parts by weight of ferric chloride and 7 parts by weight of sulfuric acid in water, the same as in Example 1. Thus, a deodorizing adsorbent was obtained.
（実施例１０）
臭化水素１１重量部、塩化第二鉄１２．６重量部、及び、硫酸７重量部を水に溶解することにより調製した水溶液を用いて吸水担持を行ったこと以外は、実施例１と同様にして脱臭吸着剤を得た。
(Example 10)
Except that water absorption was carried out using an aqueous solution prepared by dissolving 11 parts by weight of hydrogen bromide, 12.6 parts by weight of ferric chloride and 7 parts by weight of sulfuric acid in water, the same as in Example 1. Thus, a deodorizing adsorbent was obtained.
（実施例１１）
臭化水素１１重量部、塩化第二鉄８．０重量部、及び、硫酸７重量部を水に溶解することにより調製した水溶液を用いて吸水担持を行ったこと以外は、実施例１と同様にして脱臭吸着剤を得た。
(Example 11)
Except that water absorption was carried out using an aqueous solution prepared by dissolving 11 parts by weight of hydrogen bromide, 8.0 parts by weight of ferric chloride, and 7 parts by weight of sulfuric acid in water, the same as in Example 1. Thus, a deodorizing adsorbent was obtained.
得られた実施例９〜１１の脱臭吸着剤についても、実施例１と同様にして水浸ｐＨ、Ｂｒ含有量及びＦｅ含有量を測定した。その結果を表３に示す。さらに、得られたＢｒ含有量及びＦｅ含有量から、Ｆｅ／Ｂｒ原子比を求めた。その結果を表３に併記する。 For the obtained deodorized adsorbents of Examples 9 to 11, water immersion pH, Br content and Fe content were measured in the same manner as in Example 1. The results are shown in Table 3. Furthermore, Fe / Br atomic ratio was calculated | required from the obtained Br content and Fe content. The results are also shown in Table 3.
得られた実施例９〜１１、及び、前述の比較例２の脱臭吸着剤を用いて、実施例１と同様にして硫化メチル浄化率の評価を行った。６０分経過時の硫化メチル浄化率の結果を表３に示す。また、この硫化メチル浄化率とＦｅ担持量（Ｆｅ含有量）との関係を図４に示す。図４において、縦軸は、硫化メチル浄化率（％）を示し、横軸は、Ｆｅ担持量（質量％）を示す。
表３から明らかなように、鉄及び臭素を担持する多孔質担体を含む実施例９〜１１の脱臭吸着剤は、鉄を担持しない比較例２の脱臭吸着剤に比較して硫化メチル浄化率が高く、硫化メチル除去性能に優れていた。また、鉄の担持量が、０．８〜３．８質量％の範囲にある実施例１０，１１の脱臭吸着剤は、鉄の担持量が前記範囲を外れる実施例９の脱臭吸着剤に比較して硫化メチル浄化率が高かった。図４から明らかなように、鉄の担持量が、０．８〜３．８質量％の範囲にあるときに、６０％以上の硫化メチル浄化率が得られ、２〜３質量％の範囲にあるときに、６５％を超える硫化メチル浄化率が得られることを確認できた。 As apparent from Table 3, the deodorizing adsorbents of Examples 9 to 11 including the porous carrier supporting iron and bromine have a methyl sulfide purification rate as compared with the deodorizing adsorbent of Comparative Example 2 not supporting iron. High methyl sulfide removal performance. Moreover, the deodorizing adsorbents of Examples 10 and 11 in which the iron loading is in the range of 0.8 to 3.8% by mass are compared with the deodorizing adsorbing agent of Example 9 in which the iron loading is outside the above range. The methyl sulfide purification rate was high. As apparent from FIG. 4, when the iron loading is in the range of 0.8 to 3.8% by mass, a methyl sulfide purification rate of 60% or more is obtained, and in the range of 2 to 3% by mass. In some cases, it was confirmed that a purification rate of methyl sulfide exceeding 65% was obtained.
（実施例１，１２，１３及び比較例２）
（実施例１２）
臭化水素１１重量部、硫酸鉄９．５重量部、及び、硫酸７重量部を水に溶解することにより調製した水溶液を用いて吸水担持を行ったこと以外には、実施例１と同様にして脱臭吸着剤を得た。
(Examples 1, 12, 13 and Comparative Example 2)
(Example 12)
Except that water absorption was carried out using an aqueous solution prepared by dissolving 11 parts by weight of hydrogen bromide, 9.5 parts by weight of iron sulfate, and 7 parts by weight of sulfuric acid in water, the same manner as in Example 1 was performed. Thus, a deodorizing adsorbent was obtained.
（実施例１３）
臭化鉄９．８重量部、及び、硫酸７重量部を水に溶解することにより調製した水溶液を用いて吸水担持を行ったこと以外には、実施例１と同様にして脱臭吸着剤を得た。
(Example 13)
A deodorized adsorbent was obtained in the same manner as in Example 1 except that water absorption was carried out using an aqueous solution prepared by dissolving 9.8 parts by weight of iron bromide and 7 parts by weight of sulfuric acid in water. It was.
得られた実施例１２，１３の脱臭吸着剤についても、実施例１と同様にして水浸ｐＨ、Ｂｒ含有量及びＦｅ含有量を測定した。その結果を表４に示す。
得られた実施例１２，１３、前述の実施例１、及び、前述の比較例２の脱臭吸着剤を用いて、実施例１と同様にして硫化メチルの浄化率の評価を行った。６０分経過時の硫化メチル浄化率の結果を図５に示す。 Using the deodorized adsorbents obtained in Examples 12 and 13, Example 1 described above, and Comparative Example 2 described above, the purification rate of methyl sulfide was evaluated in the same manner as Example 1. The result of the methyl sulfide purification rate after 60 minutes is shown in FIG.
図５から明らかなように、種々異なる化合物を用いて得られた鉄臭化物または臭化鉄を担持する実施例１，１２，１３の脱臭吸着剤は、鉄臭化物及び臭化鉄を担持しない比較例２の脱臭吸着剤に比較して硫化メチル浄化率が高かった。また、臭化水素及び塩化第二鉄を用いた実施例１の脱臭吸着剤は、臭化鉄を直接担持した実施例１３の脱臭吸着剤に比較して硫化メチル浄化率が高く、硫化メチル除去性能に優れていた。 As is apparent from FIG. 5, the deodorizing adsorbents of Examples 1, 12, and 13 carrying iron bromide or iron bromide obtained using different compounds are comparative examples not carrying iron bromide and iron bromide. The methyl sulfide purification rate was higher than that of No. 2 deodorizing adsorbent. In addition, the deodorizing adsorbent of Example 1 using hydrogen bromide and ferric chloride has a higher methyl sulfide purification rate than the deodorizing adsorbent of Example 13 directly supporting iron bromide, and removes methyl sulfide. Excellent performance.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012011281A (en) * | 2010-06-29 | 2012-01-19 | Cataler Corp | Combined odor deodorant |
| JP2012011282A (en) * | 2010-06-29 | 2012-01-19 | Cataler Corp | Sulfur based odor deodorant |
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| JP2012011281A (en) * | 2010-06-29 | 2012-01-19 | Cataler Corp | Combined odor deodorant |
| JP2012011282A (en) * | 2010-06-29 | 2012-01-19 | Cataler Corp | Sulfur based odor deodorant |
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