JPH0333022B2 - - Google Patents
Info
- Publication number
- JPH0333022B2 JPH0333022B2 JP61198396A JP19839686A JPH0333022B2 JP H0333022 B2 JPH0333022 B2 JP H0333022B2 JP 61198396 A JP61198396 A JP 61198396A JP 19839686 A JP19839686 A JP 19839686A JP H0333022 B2 JPH0333022 B2 JP H0333022B2
- Authority
- JP
- Japan
- Prior art keywords
- zno
- tio
- white
- water
- aqueous solution
- 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 - Lifetime
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000011787 zinc oxide Substances 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- 150000003609 titanium compounds Chemical class 0.000 claims description 9
- 150000003752 zinc compounds Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 21
- 230000001877 deodorizing effect Effects 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- -1 Titanium sulfate-zinc sulfate Chemical compound 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は硫化水素、アンモニア、メルカプタ
ン、アミン及びアルデヒド等の各種悪臭ガスの脱
臭剤に関し、より具体的には酸化亜鉛と二酸化チ
タンの混成体を主体とし幾分の水分子を含み極め
て良好な吸着特性を有する白色微粉末状の全く新
規な脱臭剤を提供することに関する。
［従来技術］
近年、日常生活において発生する硫化水素、ア
ンモニア、メルカプタン、アミン及びアルデヒド
等の各種悪臭ガスが生活環境を著しく悪くしてい
ることから快適な生活環境を維持する為に、これ
らの悪臭ガスを除去する機能を有する脱臭剤につ
いての社会的関心が高まつており、様々な種類の
脱臭剤が実際に使用されている。
これらの脱臭剤は日常生活で使用されるもので
あるため、小なくとも次の様な条件を満たすもの
であることが要求される。
日常生活において発生する硫化水素、アンモ
ニア、メルカプタン、アミン及びアルデヒド等の
各種悪臭ガスに対し、良好な脱臭性能を有するも
のであること、安全性の高いものであること、
取扱いが容易なものであること、安価なもの
であること、清潔感を有するものであること。
しかしながら、従来上記のすべての条件を充分
に満足する脱臭剤は存在しなかつたし、最近の研
究によつても、まだ、開発されていなかつた。例
えば、脱臭剤として最も一般に使用されている活
性炭はメルカプタン及びアミン等の悪臭ガスの脱
臭効果は優れているものの日常生活において発生
する代表的な悪臭ガスである硫化水素やアンモニ
アに対する脱臭性は劣つたものである。この点を
改良する目的で活性炭に酸、アルカリあるいはあ
る種のハロゲン化物を担持させた添着炭と称され
る製品もつくられているが、そのような処理を行
つた製品は酸あるいはアルカリそのものと同様に
一種の危険物としての取扱いが必要となる為、日
常生活での使用には適さない。加うるに、活性炭
のもつ本質的な欠点として黒色であることがあげ
られ、この色調の為に活性炭を主体とする脱臭剤
の用途が狭くなつている。
又、硫酸鉄（FeSO4）にＬ−アスコルビン酸を
結合させた脱臭剤も上市されているが、この種の
ものはアンモニアやアミン等の塩基性の悪臭ガス
に対する脱臭効果は良好であるものの硫化水素、
メルカプタンおよびアルデヒド等に対する脱臭効
果はほとんど無く、又水に濡れると溶解する為、
湿潤ガスの脱臭には使用できないという欠点を有
している。
他の化学消臭剤として分類される脱臭剤もある
が、酸性やアルカリ性の強いものが多く、又消臭
できるガスの種類も限られており、吸湿又は乾燥
の影響を受け易いといつた欠点がある。
ほかに有機系脱臭剤もあるが、耐熱性が悪い為
加工し難いうえに高価である。
以上記したように従来の脱臭剤には前記〜
の条件をすべて充分に満たしているものはなかつ
た。
［目的］
本発明は上記のごとき実情にかんがみてなされ
たものであり、その目的は日常生活において発生
する硫化水素、アンモニア、メルカプタン、アミ
ン及びアルデヒド等の悪臭ガスに対して良好な脱
臭効果を有し安全性が高くかつ取扱いの容易な全
く新しい組成の脱臭剤を提供することにある。
［構成］
本発明は上記目的を達成する為に鋭意研究を重
ねた結果、水可溶性チタン化合物および水可溶性
亜鉛化合物の混成水溶液とアルカリ性水溶液とを
最終的に得られる合体液のPHが６〜11、好ましく
は７〜９になるように同時に混合し、これにより
合体液中にZnO、TiO2及びH2Oより成る白色の
沈澱物を生成せしめ、次にこの沈澱物の合体液か
ら分離した後、乾燥して得られる白色の微粉末が
硫化水素、アンモニア、メルカプタン、アミン及
びアルデヒド等の悪臭ガスに対し極めて良好な脱
臭性能を有することを発見しこの発明を基礎とし
て完成したものである。
本発明の脱臭剤の製造において原料である水可
溶性チタン化合物としては硫酸チタン、硫酸チタ
ニル、塩化チタン、硝酸チタン等を使用すること
ができ、水可溶性亜鉛化合物としては硫酸亜鉛、
塩化亜鉛、硝酸亜鉛、酢酸亜鉛等を使用すること
ができる。又中和用に使用するアルカリ性水溶液
としては水酸化ナトリウム、水酸化カリウム、水
酸化マグネシウム、水酸化カルシウム、水酸化バ
リウム、アンモニア等の水溶液を使用することが
できる。但し水可溶性チタン化合物あるいは水可
溶性亜鉛化合物が硫酸塩の場合には中和用のアル
カリ性水溶液として水酸化カルシウムや水酸化バ
リウムを使用すると水に不溶性の塩が生成する為
好ましくない。水可溶性チタン化合物と水可溶性
亜鉛化合物との混合割合はTiO2対ZnOのモル比
で１対９から９対１の範囲好ましくは３対７から
７対３の範囲である。即ちTiO2対ZnOのモル比
で１対９よりもZnOの多い組成領域あるいは９対
１よりもTiO2の多い組成領域で生成する沈澱を
乾燥して得られる微粉末は各々端成分である酸化
亜鉛あるいははチタン酸とほぼ同様な吸着特性を
示し、これらの吸着特性は本発明の組成領域で得
られる微粉末の吸着特性に比べ実質的に劣つてい
ると認められる。
水可溶性チタン化合物および水可溶性亜鉛化合
物からなる混成水溶液とアルカリ性水溶液との混
合方法についてはこれら両水溶液の合体液のPHが
６〜11になるように同時に混合することが重要で
ある。即ち合体液のPHが６より低い場合及び11よ
り高い場合には水溶液中への水酸化亜鉛の溶解度
が大きく、沈澱物への亜鉛の歩留まりが悪くなる
為好ましくない。
更に水可溶性チタン化合物と水可溶性亜鉛化合
物との混成水溶液にアルカリ性水溶液を添加して
合体液のPHを６〜11に調整する方法あるいはこれ
とは逆にアルカリ性水溶液に混成水溶液を添加し
て合体液のPHを６〜11に調整する方法等の場合に
はチタン酸と水酸化亜鉛の沈澱生成領域が異なる
為にチタン酸と水酸化亜鉛とが別々の粒子を形成
し、これを乾燥して得られる粉末が端成分である
チタン酸粒子と酸化亜鉛粒子との単なる混合物に
なる為、特性の優れたものを得ることはできな
い。
水可溶性チタン化合物と水可溶性亜鉛化合物の
混成水溶液の濃度については特に制限はないが、
工業的観点からは、できるだけ濃い方が好まし
い。
又水可溶性チタン化合物および水可溶性亜鉛化
合物からなる混成水溶液とアルカリ性水溶液とを
混合してZnO・TiO2・H2Oから成る沈澱を生成
させる時の温度については20〜80℃の範囲を採用
できるが40〜60℃の範囲が好ましい。更に沈澱を
ロ過・洗浄した後の乾燥温度については100℃〜
200℃の広い範囲を不都合なく使用できるが、150
℃〜220℃の範囲が好ましい。
尚本発明によるZnO・TiO・H2O系の脱臭剤の
熱的安定性については220℃以上の加熱によりわ
ずかに吸着特性に変化を生ずるが400℃付近まで
は良好な特性を維持している。
［発明の効果］
本発明に係るZnO・TiO2・H2O系白色脱臭剤
は日常生活において発生する硫化水素、メルカプ
タン、アミン及びアルデヒド等の各種悪臭ガスの
脱臭に関し、極めて良好な特性を有するのみなら
ず無毒性のZnO、TiO2及びH2Oから構成されて
いる為安全性が高く、又微粉末である為、紙及び
シート等に容易に担持でき、熱的にも400℃程度
まで安定な為、プラスチツクへの練り込みも可能
であるなど加工性にも優れているので脱臭剤とし
て産業利用性の高いものであり、特に白色である
為化粧品、生理用品及び紙おむつ等の用途にも好
適であるなど種々の用途に使用され得る。
［実施例］
以下に実施例を挙げて更に詳細に説明するがこ
れらは単に例示のために記すものであり、発明の
範囲がこれらによつて制限されるものではない。
実施例 １
５ビーカーに純水１分取し、撹拌しながら
温度60℃に加熱保持した。ついで別途用意した
TiO2として144ｇ及びZnOとして16ｇを含む硫酸
チタン−硫酸亜鉛混成水溶液２とアンモニア水
溶液とをこれら合体液のPHが7.5を維持するよう
に注意しながら30分間かけて前記純水中に同時滴
下した。
生成物を過・洗浄後200℃で３時間乾燥し、
本発明のZnO・TiO2・T2O系の白色脱臭剤を製
造した。この白色脱臭剤をＸ線回折により調べた
ところ非晶質であつた。又BET比表面積は410
m2／ｇであり、化学分折によるZnOとTiO2のモ
ル比は1.0対9.0であつた。
この白色脱臭剤の硫化水素、アンモニア、エチ
ルメルカプタン、トリメチルアミン及びアルデヒ
ド等の悪臭ガスに対する吸着特性を次の様にして
調べた。
白色粉末100mgを内容積120mlのガラス製バイア
ル瓶に入れ、ゴム栓をした後マイクロシリンジを
使つて所定量の悪臭ガス成分をバイアル瓶内に注
入する。ガスを注入してから２時間後、バイアル
瓶内の空気をマイクロシリンジで取り出し、ガス
クロマトグラフを使用してガス濃度を分析する。
結果を（表−１）に示した。
実施例 ２〜９
硫酸チタン−硫酸亜鉛混成水溶液中のTiO2と
ZnOとの量的割合を種々変化させた以外は実施例
１とまつたく同様にして白色脱臭剤を得た。これ
らの白色脱臭剤の化学分析によるZnOとTiO2の
モル比、Ｘ線回折による同定相及び各種悪臭ガス
に対する吸着特性を（表−１）に示した。
比較例 １
５ビーカーに純水１を分取し、撹拌しなが
ら温度60℃に加熱保持した。ついで別途用意した
ZnOとして81ｇを含む硫酸亜鉛水溶液１とアン
モニア水溶液とをこれらの合体液のPHが7.5を維
持するように注意しながら30分間かけて前記純水
中に同時滴下した。
生成物を過・洗浄後200℃で３時間乾燥して
白色粉末を得た。この白色粉末のBET比表面積
は30m2／ｇでありＸ線回析により酸化亜鉛である
ことが判つた。この酸化亜鉛粉末の各種悪臭ガス
に対する吸着特性を（表−１）に示した。
比較例 ２
比較例１の硫酸亜鉛水溶液をTiO2として80ｇ
を含む硫酸チタン水溶液に変えた以外は比較例１
をまつたく同様にしてチタン酸を得た。このもの
のBET比表面積は420m2／ｇであつた。このチタ
ン酸粉末の各種悪臭ガスに対する吸着特性を（表
−１）に示した。
比較例 ３
市販活性炭について各種悪臭ガスに対する吸着
特性を調べた結果を（表−１）に示した。
【表】Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a deodorizing agent for various malodorous gases such as hydrogen sulfide, ammonia, mercaptans, amines and aldehydes, and more specifically to a hybrid of zinc oxide and titanium dioxide. The present invention relates to the provision of a completely new deodorizing agent in the form of a white fine powder, which is mainly composed of 100% water molecules and contains some water molecules, and has extremely good adsorption properties. [Prior art] In recent years, various foul-smelling gases such as hydrogen sulfide, ammonia, mercaptans, amines, and aldehydes generated in daily life have significantly worsened the living environment. There is increasing social interest in deodorizers that have the function of removing gas, and various types of deodorizers are actually used. Since these deodorants are used in daily life, they are required to satisfy at least the following conditions. It must have good deodorizing performance against various malodorous gases such as hydrogen sulfide, ammonia, mercaptans, amines, and aldehydes that are generated in daily life, and it must be highly safe.
It must be easy to handle, inexpensive, and clean. However, no deodorizing agent that fully satisfies all of the above conditions has hitherto existed, and even with recent research, no deodorizing agent has been developed yet. For example, activated carbon, which is most commonly used as a deodorizing agent, has an excellent deodorizing effect on malodorous gases such as mercaptans and amines, but it has poor deodorizing properties against hydrogen sulfide and ammonia, which are typical malodorous gases generated in daily life. It is something. In order to improve this point, a product called impregnated carbon, in which activated carbon is loaded with acid, alkali, or a certain type of halide, is also produced, but products that have undergone such treatment may not contain the acid or alkali itself. Similarly, it is not suitable for use in daily life as it needs to be handled as a type of hazardous material. In addition, an essential drawback of activated carbon is that it is black, and this color tone has limited the use of deodorizing agents based on activated carbon. In addition, deodorizing agents made by combining L-ascorbic acid with iron sulfate (FeSO 4 ) are also on the market, but although this type of deodorizing agent has a good deodorizing effect on basic malodorous gases such as ammonia and amines, it hydrogen,
It has almost no deodorizing effect on mercaptans and aldehydes, and dissolves when wet with water.
It has the disadvantage that it cannot be used to deodorize wet gas. There are deodorants that are classified as other chemical deodorants, but many of them are strongly acidic or alkaline, the types of gases that can be deodorized are limited, and they have the drawbacks of being easily affected by moisture absorption or dryness. There is. There are other organic deodorizers, but they have poor heat resistance, making them difficult to process and expensive. As mentioned above, conventional deodorizers include
There was no one that satisfactorily met all of the conditions. [Purpose] The present invention was made in view of the above-mentioned circumstances, and its purpose is to have a good deodorizing effect on malodorous gases such as hydrogen sulfide, ammonia, mercaptans, amines and aldehydes generated in daily life. The object of the present invention is to provide a deodorizing agent having a completely new composition that is highly safe and easy to handle. [Structure] As a result of extensive research in order to achieve the above object, the present invention has revealed that the combined solution of a mixed aqueous solution of a water-soluble titanium compound and a water-soluble zinc compound and an alkaline aqueous solution has a pH of 6 to 11. , preferably 7 to 9 at the same time, thereby forming a white precipitate consisting of ZnO, TiO 2 and H 2 O in the combined liquid, and then after separating this precipitate from the combined liquid. The present invention was completed based on the discovery that the white fine powder obtained by drying has extremely good deodorizing performance against foul-smelling gases such as hydrogen sulfide, ammonia, mercaptans, amines, and aldehydes. In the production of the deodorizing agent of the present invention, titanium sulfate, titanyl sulfate, titanium chloride, titanium nitrate, etc. can be used as the water-soluble titanium compound that is a raw material, and as the water-soluble zinc compound, zinc sulfate,
Zinc chloride, zinc nitrate, zinc acetate, etc. can be used. As the alkaline aqueous solution used for neutralization, aqueous solutions of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonia, etc. can be used. However, if the water-soluble titanium compound or water-soluble zinc compound is a sulfate, it is not preferable to use calcium hydroxide or barium hydroxide as the alkaline aqueous solution for neutralization because water-insoluble salts will be formed. The mixing ratio of the water-soluble titanium compound and the water-soluble zinc compound is in the molar ratio of TiO 2 to ZnO in the range of 1:9 to 9:1, preferably in the range of 3:7 to 7:3. In other words, the fine powder obtained by drying the precipitate produced in a composition region containing more ZnO than 1 :9 or a composition region containing more TiO 2 than 9:1 in the molar ratio of TiO 2 to ZnO is an oxidized end component. It shows adsorption properties almost similar to those of zinc or titanic acid, and it is recognized that these adsorption properties are substantially inferior to those of fine powders obtained in the composition range of the present invention. Regarding the method of mixing a mixed aqueous solution consisting of a water-soluble titanium compound and a water-soluble zinc compound with an alkaline aqueous solution, it is important to simultaneously mix the two aqueous solutions so that the combined liquid has a pH of 6 to 11. That is, when the pH of the combined fluid is lower than 6 or higher than 11, the solubility of zinc hydroxide in the aqueous solution is high and the yield of zinc in the precipitate becomes poor, which is not preferable. Furthermore, an alkaline aqueous solution is added to a mixed aqueous solution of a water-soluble titanium compound and a water-soluble zinc compound to adjust the pH of the combined liquid to 6 to 11, or conversely, a mixed aqueous solution is added to an alkaline aqueous solution to form a combined liquid. In the case of methods such as adjusting the PH to 6 to 11, titanic acid and zinc hydroxide form separate particles because the precipitate formation regions of titanic acid and zinc hydroxide are different, and these particles are dried to obtain the precipitate. Since the resulting powder is simply a mixture of end components titanic acid particles and zinc oxide particles, it is not possible to obtain powder with excellent properties. There are no particular restrictions on the concentration of the mixed aqueous solution of a water-soluble titanium compound and a water-soluble zinc compound, but
From an industrial point of view, it is preferable that it be as dark as possible. Further, the temperature range of 20 to 80°C can be adopted when mixing a mixed aqueous solution consisting of a water-soluble titanium compound and a water-soluble zinc compound and an alkaline aqueous solution to form a precipitate consisting of ZnO, TiO 2 , H 2 O. is preferably in the range of 40 to 60°C. Furthermore, the drying temperature after filtering and washing the precipitate is 100℃~
Although it can be used in a wide range of 200℃ without any inconvenience,
A range of ℃ to 220℃ is preferred. Regarding the thermal stability of the ZnO/TiO/H 2 O-based deodorizer according to the present invention, the adsorption properties slightly change when heated above 220°C, but good properties are maintained up to around 400°C. . [Effect of the invention] The ZnO・TiO 2・H 2 O-based white deodorizer according to the present invention has extremely good properties in deodorizing various malodorous gases such as hydrogen sulfide, mercaptans, amines, and aldehydes that are generated in daily life. In addition, it is highly safe because it is composed of non-toxic ZnO, TiO 2 and H 2 O, and since it is a fine powder, it can be easily supported on paper and sheets, and it can be thermally resistant up to about 400℃. Because it is stable and can be kneaded into plastics, it has excellent processability, making it highly useful as a deodorizing agent, and because it is white, it can also be used in cosmetics, sanitary products, disposable diapers, etc. It can be used for various purposes such as suitable. [Examples] The following examples will be described in more detail, but these are merely for illustration purposes and the scope of the invention is not limited thereto. Example 1 One portion of pure water was placed in 5 beakers, and heated and maintained at a temperature of 60°C while stirring. I then prepared a separate
Titanium sulfate-zinc sulfate mixed aqueous solution 2 containing 144 g of TiO 2 and 16 g of ZnO and an ammonia aqueous solution were simultaneously dropped into the pure water over 30 minutes while being careful to maintain the pH of the combined solution at 7.5. . After filtering and washing the product, dry it at 200℃ for 3 hours.
A ZnO.TiO 2 .T 2 O-based white deodorizer of the present invention was manufactured. When this white deodorizer was examined by X-ray diffraction, it was found to be amorphous. Also, BET specific surface area is 410
m 2 /g, and the molar ratio of ZnO to TiO 2 by chemical analysis was 1.0:9.0. The adsorption properties of this white deodorizer for malodorous gases such as hydrogen sulfide, ammonia, ethyl mercaptan, trimethylamine, and aldehyde were investigated as follows. Put 100 mg of white powder into a glass vial with an internal volume of 120 ml, and after sealing with a rubber stopper, use a microsyringe to inject a predetermined amount of malodorous gas component into the vial. Two hours after injecting the gas, the air inside the vial is taken out with a microsyringe, and the gas concentration is analyzed using a gas chromatograph. The results are shown in (Table 1). Examples 2 to 9 TiO 2 in titanium sulfate-zinc sulfate mixed aqueous solution
A white deodorizer was obtained in the same manner as in Example 1 except that the quantitative ratio with ZnO was varied. Table 1 shows the molar ratio of ZnO and TiO 2 based on chemical analysis of these white deodorizers, the identified phases based on X-ray diffraction, and the adsorption characteristics for various malodorous gases. Comparative Example 1 Pure water 1 was taken into 5 beakers and heated and maintained at a temperature of 60°C while stirring. I then prepared a separate
Zinc sulfate aqueous solution 1 containing 81 g of ZnO and ammonia aqueous solution were simultaneously dropped into the pure water over 30 minutes while being careful to maintain the pH of the combined solution at 7.5. After filtering and washing the product, it was dried at 200°C for 3 hours to obtain a white powder. This white powder had a BET specific surface area of 30 m 2 /g and was found to be zinc oxide by X-ray diffraction. The adsorption properties of this zinc oxide powder for various malodorous gases are shown in Table 1. Comparative Example 2 80g of the zinc sulfate aqueous solution of Comparative Example 1 as TiO 2
Comparative Example 1 except that the titanium sulfate aqueous solution containing
Titanic acid was obtained in the same manner as above. The BET specific surface area of this product was 420 m 2 /g. The adsorption properties of this titanic acid powder for various malodorous gases are shown in Table 1. Comparative Example 3 The adsorption properties of commercially available activated carbon for various malodorous gases were investigated and the results are shown in Table 1. 【table】
Claims (1)
よび水（H2O）の緊密結合体粒子の集合体から
なる白色微粉末であることを特徴とする白色脱臭
剤。 ２ ZnOとTiO2との割合がモル比で１対９から
９対１の範囲にある特許請求の範囲第１項に記載
の白色脱臭剤。 ３ ZnOとTiO2との割合がモル比で３対７から
７対３の範囲にある特許請求の範囲第２項に記載
の白色脱臭剤。 ４ 水可溶性チタン化合物および水可溶性亜鉛化
合物を含む混成水溶液とアルカリ性水溶液とを、
両者合体後の合体液のPHが６〜11の範囲の値とな
るように注意しながら、一部ずつ、または全部同
時に合体させて沈澱物を生成させ、該沈澱物を合
体液から分離した後乾燥して、ZnO・TiO2およ
びH2Oからなる白色微粉末を得ることを特徴と
する白色脱臭剤の製造方法。 ５ ZnOとTiO2との割合がモル比で１対９から
９対１の範囲にある特許請求の範囲第４項に記載
の白色脱臭剤の製造方法。 ６ ZnOとTiO2との割合がモル比で３対７から
７対３の範囲にある特許請求の範囲第５項に記載
の白色脱臭剤の製造方法。 ７ 前記沈澱生成の反応温度が40〜60℃であり、
粉末の乾燥温度が150〜220℃である特許請求の範
囲第４〜６項のいずれかに記載の方法。[Scope of Claims] 1. A white deodorizer characterized in that it is a white fine powder consisting of an aggregate of tightly bound particles of zinc oxide (ZnO), titanium dioxide (TiO 2 ), and water (H 2 O). 2. The white deodorizer according to claim 1, wherein the molar ratio of ZnO to TiO 2 is in the range of 1:9 to 9:1. 3. The white deodorizer according to claim 2, wherein the molar ratio of ZnO and TiO 2 is in the range of 3:7 to 7:3. 4 A mixed aqueous solution containing a water-soluble titanium compound and a water-soluble zinc compound and an alkaline aqueous solution,
After combining both parts or all at the same time to form a precipitate, taking care to ensure that the pH of the combined liquid after combining is in the range of 6 to 11, and separating the precipitate from the combined liquid. A method for producing a white deodorizer, which comprises drying to obtain a white fine powder consisting of ZnO, TiO 2 and H 2 O. 5. The method for producing a white deodorizer according to claim 4, wherein the molar ratio of ZnO and TiO 2 is in the range of 1:9 to 9:1. 6. The method for producing a white deodorizer according to claim 5, wherein the molar ratio of ZnO and TiO 2 is in the range of 3:7 to 7:3. 7. The reaction temperature for forming the precipitate is 40 to 60°C,
The method according to any one of claims 4 to 6, wherein the drying temperature of the powder is 150 to 220°C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61198396A JPS6354935A (en) | 1986-08-25 | 1986-08-25 | White deodorant and its production |
| US07/541,207 US5108739A (en) | 1986-08-25 | 1990-06-21 | White colored deodorizer and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61198396A JPS6354935A (en) | 1986-08-25 | 1986-08-25 | White deodorant and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6354935A JPS6354935A (en) | 1988-03-09 |
| JPH0333022B2 true JPH0333022B2 (en) | 1991-05-15 |
Family
ID=16390431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61198396A Granted JPS6354935A (en) | 1986-08-25 | 1986-08-25 | White deodorant and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6354935A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6411554A (en) * | 1987-07-02 | 1989-01-17 | Nippon Kasei Chem | Deodorant containing metal oxide and/or metal carbonate |
| JP2544788B2 (en) * | 1988-09-28 | 1996-10-16 | 株式会社クラレ | Deodorant synthetic fiber |
| JPH0299541A (en) * | 1988-10-05 | 1990-04-11 | Mitsui Toatsu Chem Inc | Polypropylene resin composition |
| JP2544224B2 (en) * | 1989-02-23 | 1996-10-16 | 鈴木総業株式会社 | Deodorant granule and method for producing the same |
| JPH02242999A (en) * | 1989-03-13 | 1990-09-27 | Suzuki Sogyo Kk | Paper material for deodorization |
| JPH0726281A (en) * | 1993-07-06 | 1995-01-27 | Suzuki Sogyo Co Ltd | Deodorization of oil |
-
1986
- 1986-08-25 JP JP61198396A patent/JPS6354935A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6354935A (en) | 1988-03-09 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |