JP6297266B2 - Antibacterial deodorant - Google Patents
Antibacterial deodorant Download PDFInfo
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- JP6297266B2 JP6297266B2 JP2013100769A JP2013100769A JP6297266B2 JP 6297266 B2 JP6297266 B2 JP 6297266B2 JP 2013100769 A JP2013100769 A JP 2013100769A JP 2013100769 A JP2013100769 A JP 2013100769A JP 6297266 B2 JP6297266 B2 JP 6297266B2
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- 230000000844 anti-bacterial effect Effects 0.000 title claims description 38
- 239000002781 deodorant agent Substances 0.000 title claims description 19
- 150000002500 ions Chemical class 0.000 claims description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims description 27
- 229910001424 calcium ion Inorganic materials 0.000 claims description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 239000010457 zeolite Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000001506 calcium phosphate Substances 0.000 claims description 12
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 12
- 235000011010 calcium phosphates Nutrition 0.000 claims description 12
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 12
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 146
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 146
- 238000001179 sorption measurement Methods 0.000 description 76
- 239000000243 solution Substances 0.000 description 58
- 239000007789 gas Substances 0.000 description 48
- 238000002474 experimental method Methods 0.000 description 40
- 239000007791 liquid phase Substances 0.000 description 26
- 239000012071 phase Substances 0.000 description 20
- 230000003247 decreasing effect Effects 0.000 description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 239000011575 calcium Substances 0.000 description 13
- 238000010828 elution Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000012901 Milli-Q water Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052586 apatite Inorganic materials 0.000 description 8
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
- 238000010908 decantation Methods 0.000 description 7
- LPSWFOCTMJQJIS-UHFFFAOYSA-N sulfanium;hydroxide Chemical compound [OH-].[SH3+] LPSWFOCTMJQJIS-UHFFFAOYSA-N 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- -1 furniture Substances 0.000 description 5
- 239000007792 gaseous phase Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- IXHBTMCLRNMKHZ-LBPRGKRZSA-N levobunolol Chemical compound O=C1CCCC2=C1C=CC=C2OC[C@@H](O)CNC(C)(C)C IXHBTMCLRNMKHZ-LBPRGKRZSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 description 1
- 229910014456 Ca-Ag Inorganic materials 0.000 description 1
- 101100352919 Caenorhabditis elegans ppm-2 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-NJFSPNSNSA-N iodine-129 atom Chemical compound [129I] ZCYVEMRRCGMTRW-NJFSPNSNSA-N 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Description
この発明は、抗菌消臭剤に関するものであり、特に抗菌性金属成分が水中に溶出しない抗菌性消臭剤および抗菌性消臭剤の製造方法に関するものである。 The present invention relates to an antibacterial deodorant, and particularly to an antibacterial deodorant that does not elute an antibacterial metal component into water and a method for producing the antibacterial deodorant.
特許文献１には、抗菌消臭剤として、抗菌性金属成分をゼオライトに担持した抗菌消臭剤は公知であるとされている。この抗菌消臭剤は、樹脂、塗料、繊維、皮革、家具類、化粧品などに添加または塗布して用いられる。しかし、従来公知であるとされていた抗菌性金属成分を担持したゼオライトは、継時的に徐々に変色したり、透明性が得られないという課題があった。 In Patent Document 1, an antibacterial deodorant having an antibacterial metal component supported on zeolite is known as an antibacterial deodorant. This antibacterial deodorant is added to or applied to resins, paints, fibers, leather, furniture, cosmetics and the like. However, the zeolite carrying an antibacterial metal component, which has been conventionally known, has a problem in that it gradually changes color over time and transparency cannot be obtained.
特許文献１はこのような課題に対して、平均一次粒子径（Ｄ１）が２０〜２００ｎｍの範囲にあり、平均二次粒子径（Ｄ２）が２０〜４００ｎｍの範囲にあり、（Ｄ２）／（Ｄ１）が１〜５の範囲にあるコロイド状フォージャサイト型ゼオライトに、銀、銅、亜鉛、錫、鉛、ビスマス、カドミウム、クロム、水銀から選ばれる１種または２種以上の金属イオンおよび／または金属錯イオンを含むことを特徴とする抗菌消臭剤を開示している。 In Patent Document 1, the average primary particle diameter (D1) is in the range of 20 to 200 nm, the average secondary particle diameter (D2) is in the range of 20 to 400 nm, and (D2) / ( D1) is a colloidal faujasite type zeolite in the range of 1 to 5, and one or more metal ions selected from silver, copper, zinc, tin, lead, bismuth, cadmium, chromium, mercury and / or Or the antibacterial deodorizer characterized by including a metal complex ion is disclosed.
また、ゼオライト中にＡｇやＣａを含ませることで、ヨウ素１２９の吸蔵性が高くなり、またヨウ素を吸蔵させた後、表面をアパタイトでコーティングすることで、ヨウ素を封じ込める発明が特許文献２に開示されている。 Further, Patent Document 2 discloses an invention in which iodine is contained by adding Ag or Ca in the zeolite, and the iodine 129 is occluded, and after occlusion of iodine, the surface is coated with apatite to contain iodine. Has been.
ゼオライトは、多孔質性を有しており、吸着能を有している点はよく知られている。これにＡｇ、Ｃｕ、Ｚｎといった抗菌性金属成分を含有させることで、抗菌性を有する点も、上記のようにすでに知られている。 It is well known that zeolite has porosity and adsorbability. The point which has antimicrobial property by making this contain antimicrobial metal components, such as Ag, Cu, and Zn, is already known as mentioned above.
これらの抗菌性金属成分は、ゼオライトのＳｉとＡｌの電荷の差によって、−１価になるサイトにイオン交換によって吸着されている。そのため、特に水中に曝される環境で使用される場合は、継時的にこれらの抗菌性金属成分が脱離するという課題が生じる。抗菌性金属成分の脱離は、抗菌能力の低下を招くだけでなく、環境負荷の原因ともなる。 These antibacterial metal components are adsorbed by ion exchange at sites that become −1 valence due to the difference in charge between Si and Al in the zeolite. Therefore, especially when used in an environment exposed to water, there arises a problem that these antibacterial metal components are detached over time. Desorption of the antibacterial metal component not only causes a decrease in antibacterial ability, but also causes an environmental burden.
本発明は上記の課題に鑑み、液相中でも抗菌性金属成分が溶出することのない、抗菌性消臭剤を提供する。 In view of the above problems, the present invention provides an antibacterial deodorant that does not elute an antibacterial metal component even in a liquid phase.
より具体的に、本発明に係る抗菌性消臭剤は、水酸化ナトリウムとメタ珪酸ナトリウムから調製されたＬＴＡ型ゼオライトのナトリウムイオンを銀イオンに交換した後、前記銀イオンの一部をカルシウムイオンに交換し、βサイトにＣａイオン、αサイトにＣａイオンとＡｇイオン、γサイトにＡｇイオンが含まれ、前記αサイトのＣａイオンはＡｇイオンより多いＬＴＡ型ゼオライトとし、さらにリン酸アンモニウムを作用させリン酸カルシウムで表面をコートし、前記ＬＴＡ型ゼオライト中にリン酸イオンを含んでいないことを特徴とする。 More specifically, the antibacterial deodorant according to the present invention replaces sodium ions of LTA-type zeolite prepared from sodium hydroxide and sodium metasilicate with silver ions, and then converts some of the silver ions into calcium ions. replace the, Ca ions β site, Ca ions and Ag ions into α site is Ag ions contained in the γ site, said Ca ions α site and often LTA type zeolite of Ag ions, act more ammonium phosphate coating the surface with calcium phosphate is characterized in that it does not contain phosphate ions in the LTA type zeolite.
本発明に係る抗菌性消臭剤は、抗菌性金属成分をＬＴＡ型ゼオライトに含有させ、その周囲をＣａでコーティングしたので、抗菌性金属成分の溶出量を抑制することができる。また、コーティングしたＣａの周囲をさらにアパタイトでコーティングしたものは、より抗菌性金属成分の溶出を抑制することができる。また、抗菌性金属成分を有しているので、抗菌能を有する消臭剤を提供できる。 Since the antibacterial deodorant according to the present invention contains an antibacterial metal component in LTA-type zeolite and the periphery thereof is coated with Ca, the amount of the antibacterial metal component eluted can be suppressed. Moreover, what coated the circumference | surroundings of coated Ca with apatite can suppress the elution of an antibacterial metal component more. Moreover, since it has an antibacterial metal component, a deodorant having antibacterial activity can be provided.
また、本発明に係る抗菌性消臭剤は、水分中でも抗菌剤および消臭剤として効果を有する。すなわち、水分を含む雰囲気中でも持続して効果を発揮する消臭剤として用いることができ、また、水分を含む雰囲気中でも持続して効果を発揮する抗菌剤として用いることもできる。 In addition, the antibacterial deodorant according to the present invention is effective as an antibacterial agent and a deodorant even in moisture. That is, it can be used as a deodorant that exhibits an effect in an atmosphere containing moisture, and can also be used as an antibacterial agent that exhibits an effect in an atmosphere containing moisture.
以下、本発明をさらに詳しく説明する。なお、以下は本発明の一例を示すのであり、本発明の趣旨を逸脱しない限り、以下の実施形態および実施例を変更しても本発明の技術的範囲に含まれるのは言うまでもない。 Hereinafter, the present invention will be described in more detail. In addition, the following shows an example of the present invention, and it goes without saying that the following embodiments and examples are included in the technical scope of the present invention without departing from the gist of the present invention.
本発明に係る抗菌性消臭剤は、ＬＴＡ型ゼオライトを用いる。そして、通常ＬＴＡ型は、Ｎａ（ナトリウム）イオンを有する形で得られるが、このＮａを抗菌性金属イオンに交換する。ここで、抗菌性金属は、Ａｇ（銀）、Ｃｕ（銅）、Ｚｎ（亜鉛）が好適に利用することができる。ゼオライトは結晶の形によって、特性が大きく変わることが知られている。悪臭となるアンモニア、硫化水素、メチルメルカプタン、トリメチルアミン等の物質（以後、「悪臭物質」と呼ぶ。）を吸着できるほどの細孔を有する。 The antibacterial deodorant according to the present invention uses LTA type zeolite. And normally LTA type | mold is obtained in the form which has Na (sodium) ion, This Na is exchanged for an antibacterial metal ion. Here, Ag (silver), Cu (copper), and Zn (zinc) can be suitably used as the antibacterial metal. It is known that the properties of zeolite vary greatly depending on the crystal form. It has pores that can adsorb substances such as ammonia, hydrogen sulfide, methyl mercaptan, trimethylamine and the like (hereinafter referred to as “bad odor substances”) that cause bad odor.
本発明に係る抗菌性消臭剤は、この抗菌性金属イオンでイオン交換されたゼオライトの抗菌性金属イオンの一部をＣａ（カルシウム）イオンにイオン交換する。また、Ｃａをイオン交換したものにアパタイト（リン酸カルシウム）コーティングを行う。このようにすることで、悪臭物質は吸着し、なおかつ液中への抗菌性金属イオンの溶出が抑制される。また、このようなアパタイトコーティングを行っても、抗菌性は保持される。以下、実施例に基づいて本発明に係る抗菌性消臭剤を説明する。 The antibacterial deodorant according to the present invention ion-exchanges a part of the antibacterial metal ion of the zeolite ion-exchanged with the antibacterial metal ion to Ca (calcium) ion. Moreover, apatite (calcium phosphate) coating is performed on the ion exchanged Ca. By doing so, malodorous substances are adsorbed and the elution of antibacterial metal ions into the liquid is suppressed. Moreover, even if such apatite coating is performed, antibacterial properties are maintained. Hereinafter, the antibacterial deodorant according to the present invention will be described based on examples.
＜イオン交換ゼオライト＞
（ＬＴＡの合成）
ＬＴＡ型ゼオライトを以下の手順で合成した。超純水（ミリＱ水、Ｍｉｌｌｉｐｏｒｅ製、Ｄｉｒｅｃｔ−Ｑより採取）８０ｍｌをメスシリンダーで秤量し、上皿天秤（ｓｅｆｉ製、ＩＢＡ−２００）で秤量した水酸化ナトリウム（キシダ化学、特級）０．７２３ｇをガラス棒で攪拌して溶解させ水酸化ナトリウム溶液を得た。メスシリンダーで等量の水酸化ナトリウム溶液を秤量し、二つの三角フラスコにわけた。
<Ion exchange zeolite>
(Synthesis of LTA)
LTA type zeolite was synthesized by the following procedure. 80 ml of ultrapure water (Milli-Q water, manufactured by Millipore, collected from Direct-Q) was weighed with a graduated cylinder, and sodium hydroxide (Kishida Chemical, special grade) was weighed with an upper pan balance (Sef, IBA-200). 723 g was stirred and dissolved with a glass rod to obtain a sodium hydroxide solution. An equal volume of sodium hydroxide solution was weighed with a graduated cylinder and divided into two Erlenmeyer flasks.
片方の溶液（溶液Ａ）に、アルミン酸ナトリウム（和光純薬工業、一級）８．２５８ｇを、もう片方の溶液（溶液Ｂ）にメタ珪酸ナトリウム５水和物（ＳＴＲＥＭ ＣＨＥＭＩＣＡＬＳ）１５．４８０ｇを、それぞれ加えた。三角フラスコ中に攪拌子を入れ、ホットスターラー（アズワン製、ＲＳＨ−１０）で攪拌子を６００ｒｐｍで回転させてアルミン酸ナトリウムとメタ珪酸ナトリウムを溶解させた。 In one solution (solution A), sodium aluminate (Wako Pure Chemical Industries, grade 1) 8.258 g, in the other solution (solution B) sodium metasilicate pentahydrate (STREM CHEMICALS) 15.480 g, Added each. A stirrer was placed in the Erlenmeyer flask, and the stirrer was rotated at 600 rpm with a hot stirrer (manufactured by ASONE, RSH-10) to dissolve sodium aluminate and sodium metasilicate.
次に、溶液Ａに溶液Ｂを速やかに加え、８０℃でホットスターラーを用い５００ｒｐｍで攪拌した。得られた溶液をポリプロピレン容器（２５０ｍＬ）に入れ、１００℃に設定した水浴（アズワン製、ＡＮＡＬＯＧ ＢＡＴＨ ＥＷ−１００ ）中で４時間湯煎した。 Next, the solution B was quickly added to the solution A and stirred at 80 ° C. using a hot stirrer at 500 rpm. The obtained solution was put into a polypropylene container (250 mL) and bathed in a water bath set at 100 ° C. (manufactured by ASONE, ANALOG BATH EW-100) for 4 hours.
得られた溶液を遠心分離器（Ｋｕｂｏｔａ製、６９００）を用いて、１０００ｒｐｍで５分間、遠心分離し、固液分離した。デカンテーションで上澄み液を除去し、固形物をシャーレに移し、プログラム定温乾燥器（アズワン製、ＤＯＶ−４５０Ｐ）中、９０℃で２４時間乾燥し、白色粉末を得た。これをＮａ−ＬＴＡ型ゼオライト（以下単に「Ｎａ−ＬＴＡ」とも呼ぶ。）とした。 The obtained solution was centrifuged at 1000 rpm for 5 minutes using a centrifuge (manufactured by Kubota, 6900), and solid-liquid separation was performed. The supernatant was removed by decantation, the solid was transferred to a petri dish, and dried at 90 ° C. for 24 hours in a program constant temperature dryer (manufactured by ASONE, DOV-450P) to obtain a white powder. This was designated as Na-LTA type zeolite (hereinafter also simply referred to as “Na-LTA”).
＜イオン交換型ゼオライトの作製＞
（Ａｇ置換型ゼオライトの作製）
上記のＮａ−ＬＴＡのＮａイオンに対して、Ａｇイオン交換反応を以下のように行った。ミリＱ水をメスシリンダーで１Ｌ秤量し、２Ｌビーカー中に入れた。ついで硝酸銀（和光純薬工業、特級）を０．８５０ｇを秤量して加え、ホットスターラー（ＲＳＨ−１０、アズワン製）上で５００ｒｐｍで攪拌、溶解して０．００５Ｍ硝酸銀水溶液を得た。
<Production of ion exchange type zeolite>
(Preparation of Ag-substituted zeolite)
Ag ion exchange reaction was performed on the Na ions of the Na-LTA as follows. Milli-Q water was weighed 1 L with a graduated cylinder and placed in a 2 L beaker. Next, 0.850 g of silver nitrate (Wako Pure Chemical Industries, Special Grade) was weighed and added, and stirred and dissolved at 500 rpm on a hot stirrer (RSH-10, manufactured by ASONE) to obtain a 0.005M silver nitrate aqueous solution.
得られた０．００５Ｍ硝酸銀水溶液１Ｌに、Ｎａ−ＬＴＡの１．０００ｇを秤量して加え、５０℃に保持し、攪拌子を用いて、ホットスターラー上で、５００ｒｐｍで１時間攪拌した。生成した固形物は、ろ紙（ＫＩＲＩＹＡＭＡ製、５Ｃ）と吸引ろ過機（ＫＩＲＩＹＡＭＡ製）でろ別し、ミリＱ水を用いて十分に水洗し、未反応物質を除去した。上述と同様に、遠心分離、デカンテーションで、上澄み液を除去した固形物はシャーレに移し、プログラム定温乾燥器（ＤＯＶ−４５０Ｐ、アズワン製）中、９０℃で２４時間乾燥し、灰色粉末を得た。 To 1 L of the obtained 0.005 M silver nitrate aqueous solution, 1.000 g of Na-LTA was weighed and added, and the mixture was kept at 50 ° C. and stirred for 1 hour at 500 rpm on a hot stirrer using a stir bar. The produced solid was filtered off with a filter paper (manufactured by KIRIYAMA, 5C) and a suction filter (manufactured by KIRIYAMA), and sufficiently washed with Milli-Q water to remove unreacted substances. As described above, the solid material from which the supernatant was removed by centrifugation and decantation was transferred to a petri dish and dried at 90 ° C. for 24 hours in a program constant temperature dryer (DOV-450P, manufactured by ASONE) to obtain a gray powder. It was.
０．００５Ｍ硝酸銀水溶液中での攪拌、ろ別、遠心分離、デカンテーション、乾燥の作業をｎ（最大５）回繰り返した。得られた試料をＡｇ−ＬＴＡ［ｎ］とした。ここで、「［ｎ］」は、０．００５Ｍ硝酸銀水溶液中での攪拌、ろ別、遠心分離、デカンテーション、乾燥の作業の回数後の試料を意味する。 The operations of stirring, filtering, centrifuging, decanting, and drying in 0.005M silver nitrate aqueous solution were repeated n (maximum 5) times. The obtained sample was designated as Ag-LTA [n]. Here, “[n]” means a sample after the number of operations of stirring, filtration, centrifugation, decantation, and drying in a 0.005 M silver nitrate aqueous solution.
（Ｃａ置換型ゼオライトの作製）
上記のＮａ−ＬＴＡのＮａイオンに対して、Ｃａイオン交換反応を以下のように行った。塩化カルシウム（和光純薬工業、特級）１１．０００ｇをミリＱ水２００ｍｌにガラス棒で溶解して０．５Ｍ塩化カルシウム水溶液を得た。Ｎａ−ＬＴＡを１．０００ｇ秤量し、０．５Ｍ塩化カルシウム水溶液２００ｍｌ中に入れ、ホットスターラー（ＲＳＨ−１０、アズワン製）上で５０℃、攪拌子を用い、５００ｒｐｍで２４時間攪拌した。
(Production of Ca-substituted zeolite)
The Ca ion exchange reaction was performed on the Na ions of the Na-LTA as follows. 11.000 g of calcium chloride (Wako Pure Chemical Industries, special grade) was dissolved in 200 ml of milli-Q water with a glass rod to obtain a 0.5 M calcium chloride aqueous solution. 1.000 g of Na-LTA was weighed, placed in 200 ml of 0.5 M aqueous calcium chloride solution, and stirred for 24 hours at 500 rpm on a hot stirrer (RSH-10, manufactured by ASONE) using a stirrer.
得られた固形物を吸引ろ過によりろ別し、さらにミリＱ水を用いて十分に水洗し、未反応物質を除去した。上述と同様に、遠心分離、デカンテーションで上澄み液を除去した固形物をシャーレに移し、プログラム定温乾燥器（ＤＯＶ−４５０Ｐ、アズワン製）中、９０℃で２４時間乾燥し、白色粉末を得た。得られた試料をＣａ−ＬＴＡとした。 The obtained solid matter was separated by suction filtration, and further washed thoroughly with Milli-Q water to remove unreacted substances. As described above, the solid material from which the supernatant was removed by centrifugation and decantation was transferred to a petri dish and dried at 90 ° C. for 24 hours in a program constant temperature dryer (DOV-450P, manufactured by ASONE) to obtain a white powder. . The obtained sample was named Ca-LTA.
（Ｃａ−Ａｇ置換型ゼオライトの作製）
Ａｇ−ＬＴＡ［５］１．０００ｇを塩化カルシウム水溶液（０．００５Ｍ）１Ｌ中に分散して陽イオン交換反応を以下のように行った。塩化カルシウム（和光純薬工業、特級）０．５５０ｇをミリＱ水１Ｌに溶かし塩化カルシウム水溶液を得た。ホットスターラー（ＲＳＨ−１０、アズワン製）上で５０℃、攪拌子を用い５００ｒｐｍで１時間攪拌した。
(Preparation of Ca-Ag substituted zeolite)
Cation exchange reaction was performed as follows by dispersing 1.000 g of Ag-LTA [5] in 1 L of an aqueous calcium chloride solution (0.005M). 0.550 g of calcium chloride (Wako Pure Chemical Industries, special grade) was dissolved in 1 L of milli-Q water to obtain an aqueous calcium chloride solution. The mixture was stirred for 1 hour at 500 rpm using a stir bar on a hot stirrer (RSH-10, manufactured by ASONE).
得られた固形物を吸引ろ過によりろ別し、ミリＱ水を用いて十分に水洗し、未反応物質を除去した。上述と同様に、遠心分離、デカンテーションで上澄み液を除去した固形物をシャーレに移し、プログラム定温乾燥器（ＤＯＶ−４５０Ｐ、アズワン製）中、９０℃で２４時間乾燥し、Ａｇイオンの一部をＣａイオンに置換したＡｇ−ＬＴＡを得た。得られた試料をＣａ−Ａｇ−ＬＴＡとした。 The obtained solid was filtered off by suction filtration and washed thoroughly with Milli-Q water to remove unreacted substances. As described above, the solid material from which the supernatant was removed by centrifugation and decantation was transferred to a petri dish and dried at 90 ° C. for 24 hours in a program constant temperature dryer (DOV-450P, manufactured by ASONE). Ag-LTA was obtained by substituting Ca with Ca ions. The obtained sample was designated as Ca-Ag-LTA.
（Ａｇ−Ｃａ置換型ゼオライトの作製）
Ｃａ−ＬＴＡ１．０００ｇを硝酸銀水溶液（０．００５Ｍ）１Ｌ中に分散して陽イオン交換反応を以下のように行った。硝酸銀（和光純薬工業、特級）０．８５０ｇをミリＱ水１Ｌに溶かし、硝酸銀水溶液を得た。ホットスターラー（ＲＳＨ−１０、アズワン製）上で５０℃、スターラーを用い５００ｒｐｍで１時間攪拌した。
(Preparation of Ag-Ca substituted zeolite)
A cation exchange reaction was carried out as follows by dispersing 1.000 g of Ca-LTA in 1 L of an aqueous silver nitrate solution (0.005 M). 0.850 g of silver nitrate (Wako Pure Chemical Industries, special grade) was dissolved in 1 L of milli-Q water to obtain a silver nitrate aqueous solution. The mixture was stirred for 1 hour at 500 rpm using a stirrer on a hot stirrer (RSH-10, manufactured by ASONE).
得られた固形物を吸引ろ過によりろ別し、ミリＱ水を用いて十分に水洗し、未反応物質を除去した。上述と同様に、遠心分離、デカンテーションで上澄み液を除去した固形物をシャーレに移し、プログラム定温乾燥器（ＤＯＶ−４５０Ｐ、アズワン製）中、９０℃で２４時間乾燥し、Ｃａイオンの一部をＡｇイオンに置換したＣａ−ＬＴＡを得た。得られた試料をＡｇ−Ｃａ−ＬＴＡとした。 The obtained solid was filtered off by suction filtration and washed thoroughly with Milli-Q water to remove unreacted substances. In the same manner as described above, the solid material from which the supernatant was removed by centrifugation and decantation was transferred to a petri dish and dried at 90 ° C. for 24 hours in a program constant temperature dryer (DOV-450P, manufactured by ASONE). Ca-LTA was substituted with Ag ions. The obtained sample was named Ag-Ca-LTA.
（リン酸カルシウムコーティング）
Ｃａ−Ａｇ−ＬＴＡをリン酸アンモニウム水溶液（２Ｍ）１００ｍｌ中に入れ、密栓したポリ瓶をプログラム定温乾燥器（ＤＯＶ−４５０Ｐ、アズワン製）中、８０℃で８時間保持した。得られた固形物を吸引ろ過によりろ別し、ミリＱ水を用いて十分に水洗し、未反応物質を除去した。
(Calcium phosphate coating)
Ca-Ag-LTA was put in 100 ml of an aqueous ammonium phosphate solution (2M), and the sealed plastic bottle was kept at 80 ° C. for 8 hours in a programmed constant temperature dryer (DOV-450P, manufactured by ASONE). The obtained solid was filtered off by suction filtration and washed thoroughly with Milli-Q water to remove unreacted substances.
上述と同様に、遠心分離、デカンテーションで上澄み液を除去した固形物をシャーレに移し、プログラム定温乾燥器中、９０℃で２４時間乾燥し、試料を得た。得られた試料をＡＰ−Ｃａ−Ａｇ−ＬＴＡとした。なお、リン酸アンモニウム水溶液は、リン酸アンモニウム（和光純薬工業、特級）２３．０００ｇをミリＱ水１００ｍｌに溶かしたものを用いた。 In the same manner as described above, the solid material from which the supernatant was removed by centrifugation and decantation was transferred to a petri dish and dried at 90 ° C. for 24 hours in a programmed constant temperature dryer to obtain a sample. The obtained sample was named AP-Ca-Ag-LTA. In addition, the ammonium phosphate aqueous solution used what melt | dissolved ammonium phosphate (Wako Pure Chemical Industries, special grade) 23.000g in 100 ml of milli Q water.
＜イオン交換による硫化水素ガス吸着の効果＞
図１に硫化水素ガスの吸着実験装置を示す。吸着容器１は、容量が１０Ｌのつぼ型蓋付きガラス容器である。吸着容器１内部には、シャーレ１０が配置されている。吸着容器１の蓋２には、吸着容器１の中の気体を採取するためのセプタム３と、吸着容器１内に硫化水素ガスを注入する注入口４と、試料を吸着容器１内部のシャーレ１０に投入できるすり合わせガラスコック付分液ロート５が設けられている。
<Effect of hydrogen sulfide gas adsorption by ion exchange>
FIG. 1 shows a hydrogen sulfide gas adsorption experimental apparatus. The adsorption container 1 is a glass container with a pot type lid having a capacity of 10L. A petri dish 10 is disposed inside the adsorption container 1. The lid 2 of the adsorption container 1 has a septum 3 for collecting gas in the adsorption container 1, an inlet 4 for injecting hydrogen sulfide gas into the adsorption container 1, and a petri dish 10 inside the adsorption container 1. A separatory funnel 5 with a laminated glass cock that can be put into the container is provided.
実験方法は、以下の通りである。まず、吸着容器１内を脱気し、窒素ガスでパージした。次に硫化水素ガスをシリンジ６で吸着容器１内に注入した。硫化水素ガスは、吸着容器１内の硫化水素濃度が３０±２ｐｐｍになるように注入した。次にガラスコック付分液ロート５を介して、試料をシャーレ１０中に導入した。なお、シャーレ１０中の試料を符号７で示した。試料投入後０．５時間、１時間、１．５時間、２時間後にセプタム３から吸着容器１内の気体をシリンジ６で採取した。採取した気体は、ガスクロマトグラフ質量分析装置（ＧＣＭＳ ＱＰ５０００：島津製作所株式会社製）を用いて硫化水素ガス濃度を測定した。 The experimental method is as follows. First, the inside of the adsorption container 1 was deaerated and purged with nitrogen gas. Next, hydrogen sulfide gas was injected into the adsorption container 1 with a syringe 6. Hydrogen sulfide gas was injected so that the concentration of hydrogen sulfide in the adsorption vessel 1 was 30 ± 2 ppm. Next, the sample was introduced into the petri dish 10 through a separatory funnel 5 with a glass cock. A sample in the petri dish 10 is denoted by reference numeral 7. 0.5 hours, 1 hour, 1.5 hours, and 2 hours after sample introduction, the gas in the adsorption container 1 was collected from the septum 3 with a syringe 6. The collected gas was measured for hydrogen sulfide gas concentration using a gas chromatograph mass spectrometer (GCMS QP5000: manufactured by Shimadzu Corporation).
図２にＮａ−ＬＴＡと、Ａｇ−ＬＴＡ［１］、Ａｇ−ＬＴＡ［３］、Ａｇ−ＬＴＡ［５］（Ａｇ−ＬＴＡ）の硫化水素ガス吸着能力の結果を示す。横軸は時間（ｈ）であり、縦軸は硫化水素濃度（％）である。縦軸は実験開始の初期濃度と経過時間後の濃度の割合を示す。コントロールとして、何も入れない状態をＢｌａｎｋとして入れた。 FIG. 2 shows the results of the hydrogen sulfide gas adsorption ability of Na-LTA and Ag-LTA [1], Ag-LTA [3], and Ag-LTA [5] (Ag-LTA). The horizontal axis is time (h), and the vertical axis is hydrogen sulfide concentration (%). The vertical axis indicates the ratio of the initial concentration at the start of the experiment and the concentration after the elapsed time. As a control, a blank state was entered as Blank.
図２を参照して、ＮａをＡｇに置換することにより、吸着能が向上していることがわかる。また、Ａｇのイオン交換の作業は、回数を増やす毎に吸着能が向上している。また、ＮａをＡｇに交換することで、細孔径が大きくなり、硫化水素を吸着しやすくなると考えられる。 Referring to FIG. 2, it can be seen that the adsorption ability is improved by substituting Na for Ag. Further, the adsorption capacity of the Ag ion exchange work is improved every time the number of times is increased. Moreover, it is thought that by exchanging Na for Ag, the pore diameter becomes large and it becomes easy to adsorb hydrogen sulfide.
次に、これらの試料の気相液相共存下での気相中の硫化水素吸着について調べた。図３に実験装置を示す。使用する吸着容器１は、図１で説明したものと同じものである。同じ部分には同様の符号を付し、説明を省略する。吸着容器１の中には、超純水１５０ｍｌを入れたビーカー１１が配置されている。また、ビーカー１１の中には、攪拌子１２が入れられており、吸着容器１外からマグネチックスターラー（図示せず）で、回転させることができる。 Next, the adsorption of hydrogen sulfide in the gas phase in the presence of the gas phase liquid phase of these samples was investigated. FIG. 3 shows the experimental apparatus. The adsorption container 1 to be used is the same as that described in FIG. The same parts are denoted by the same reference numerals, and description thereof is omitted. A beaker 11 containing 150 ml of ultrapure water is disposed in the adsorption container 1. Further, a stirrer 12 is placed in the beaker 11 and can be rotated from the outside of the adsorption vessel 1 by a magnetic stirrer (not shown).
実験は以下のようにして行った。まず、吸着容器１内を超純水が室温で沸騰しない程度まで減圧し、その後窒素ガスでパージした。次に吸着容器１内に４８．５ｐｐｍの硫化水素ガスを注入口４から導入する。吸着容器１内の硫化水素ガスが均一になったら、ガラスコック付分液ロート５から、試料０．２ｇを吸着容器１内のビーカー１１に投入する。以後ビーカー１１内の液体を溶液１３と呼ぶ。投入後０．２５時間、０．５時間、０．７５時間、１時間、２時間、４時間、８時間、２４時間後に、セプタム３から吸着容器１内部の気体をシリンジ６で採取する。採取したガス中の硫化水素濃度を炎光光度検出器付ガスクロマトグラフ（ＧＣ−ＦＰＤ）によって測定した。 The experiment was performed as follows. First, the inside of the adsorption vessel 1 was depressurized to such an extent that ultrapure water did not boil at room temperature, and then purged with nitrogen gas. Next, 48.5 ppm of hydrogen sulfide gas is introduced into the adsorption vessel 1 from the inlet 4. When the hydrogen sulfide gas in the adsorption vessel 1 becomes uniform, 0.2 g of the sample is put into the beaker 11 in the adsorption vessel 1 from the separatory funnel 5 with a glass cock. Hereinafter, the liquid in the beaker 11 is referred to as a solution 13. After 0.25 hours, 0.5 hours, 0.75 hours, 1 hour, 2 hours, 4 hours, 8 hours, and 24 hours after the introduction, the gas inside the adsorption container 1 is collected from the septum 3 by the syringe 6. The concentration of hydrogen sulfide in the collected gas was measured by a gas chromatograph with a flame photometric detector (GC-FPD).
（気相液相共存下での気相中の硫化水素吸着実験の結果）
Ｎａ−ＬＴＡ、Ａｇ−ＬＴＡ、Ｃａ−ＬＴＡ、Ａｇ−Ｃａ−ＬＴＡ、Ｃａ−Ａｇ−ＬＴＡ、ＡＰ−Ｃａ−Ａｇ−ＬＴＡをそれぞれ用い、吸着容器１内の硫化水素濃度変化を図４に示す。図４は横軸が時間（ｈ）で、縦軸が吸着容器１内の硫化水素濃度（％）を表す。なお、コントロールとして吸着材を入れていないものを「Ｂｌａｎｋ」として入れている。
(Results of hydrogen sulfide adsorption experiment in the gas phase in the coexistence of the gas phase and liquid phase)
FIG. 4 shows changes in the concentration of hydrogen sulfide in the adsorption vessel 1 using Na-LTA, Ag-LTA, Ca-LTA, Ag-Ca-LTA, Ca-Ag-LTA, and AP-Ca-Ag-LTA, respectively. In FIG. 4, the horizontal axis represents time (h), and the vertical axis represents the hydrogen sulfide concentration (%) in the adsorption vessel 1. In addition, the thing which does not put the adsorbent as control is put as "Blank".
Ｎａ−ＬＴＡ、Ａｇ−ＬＴＡ、Ａｇ−Ｃａ−ＬＴＡ、Ｃａ−Ａｇ−ＬＴＡは、４時間以内に吸着容器１内の硫化水素濃度がゼロになった。アパタイトコーティングしたＡＰ−Ｃａ−Ａｇ−ＬＴＡは１２時間後には、硫化水素濃度がゼロになった。 As for Na-LTA, Ag-LTA, Ag-Ca-LTA, and Ca-Ag-LTA, the hydrogen sulfide concentration in the adsorption vessel 1 became zero within 4 hours. The apatite-coated AP-Ca-Ag-LTA had a hydrogen sulfide concentration of zero after 12 hours.
Ｎａ−ＬＴＡの場合、試料を吸着容器１内に投入してから２時間後に、硫化水素濃度は０ｐｐｍになった。吸着容器１内に所定濃度の硫化水素水がある場合、吸着容器１内の硫化水素濃度は迅速に低下した。吸着容器１内では、硫化水素は気相と液相で平衡状態になっていると思われる。 In the case of Na-LTA, the hydrogen sulfide concentration became 0 ppm 2 hours after the sample was put into the adsorption vessel 1. When there was a predetermined concentration of hydrogen sulfide water in the adsorption vessel 1, the concentration of hydrogen sulfide in the adsorption vessel 1 quickly decreased. In the adsorption vessel 1, hydrogen sulfide seems to be in an equilibrium state between the gas phase and the liquid phase.
Ｎａ−ＬＴＡは硫化水素水中に投入するが、Ｎａ−ＬＴＡは水分子とともに水中の硫化水素を吸着し、吸着容器１内の気相と液相の平衡状態が崩れ、気相中の硫化水素濃度が低下したと思われる。また、水中ではＮａ−ＬＴＡの交換性カチオンであるＮａが溶解し、ｐＨがアルカリ性に傾き、その結果、硫化水素が溶液１３の中に溶け込んだと考えられる。よって、今回Ｎａ−ＬＴＡでの硫化水素吸着実験において硫化水素濃度が大幅に減少したのは、Ｎａ−ＬＴＡの吸着能と溶液１３のｐＨの変化による溶液１３への硫化水素溶解のためと考えられる。 Na-LTA is introduced into hydrogen sulfide water, but Na-LTA adsorbs hydrogen sulfide in water together with water molecules, and the equilibrium state between the gas phase and the liquid phase in the adsorption vessel 1 collapses, and the hydrogen sulfide concentration in the gas phase Seems to have declined. In addition, it is considered that Na, which is an exchange cation of Na-LTA, dissolves in water, the pH is inclined to be alkaline, and as a result, hydrogen sulfide is dissolved in the solution 13. Therefore, the hydrogen sulfide concentration in the hydrogen sulfide adsorption experiment with Na-LTA was greatly reduced this time because of the hydrogen sulfide dissolution in the solution 13 due to the change in the adsorption ability of the Na-LTA and the pH of the solution 13. .
Ａｇ−ＬＴＡの場合、試料を投入してから０．７５時間（４５分）後、硫化水素濃度は０ｐｐｍになった。銀の置換工程を５回繰り返したＡｇ−ＬＴＡの場合、ＮａはほとんどＡｇに置換している。したがって、Ｎａ溶出によるｐＨ変化は乏しいと思われる。 In the case of Ag-LTA, the hydrogen sulfide concentration became 0 ppm after 0.75 hours (45 minutes) from the introduction of the sample. In the case of Ag-LTA in which the silver substitution step is repeated 5 times, Na is almost substituted by Ag. Therefore, the pH change due to Na elution seems to be poor.
一方、Ａｇ−ＬＴＡで気相液相共存下での硫化水素吸着実験を行なった場合、１．０〜１．５時間を過ぎたあたりから、溶液１３の上に銀色のものが浮き始め、次第に増えていった。２４時間吸着実験を行った後に、遠心分離機を用いて回収し、洗浄、ろ過を繰り返し、乾燥させた。このようにして得られた試料をＳＥＭおよびＥＤＸにて観察した（図５および表１参照）。 On the other hand, when a hydrogen sulfide adsorption experiment was performed with Ag-LTA in the coexistence of the gas phase and liquid phase, a silver-colored thing started to float on the solution 13 after about 1.0 to 1.5 hours. It increased. After performing an adsorption experiment for 24 hours, the sample was collected using a centrifuge, washed and filtered repeatedly and dried. The sample thus obtained was observed with SEM and EDX (see FIG. 5 and Table 1).
この結果からＡｇ２Ｓが析出していることが考えられる。また、後述する銀イオン溶出において示されるように、Ａｇ−ＬＴＡを溶液に入れた際、Ａｇイオンが溶出している結果となった。溶出したＡｇイオンと硫化水素が反応し、Ａｇ２Ｓとして析出し、硫化水素濃度が下がったと考えられる。気相液相共存下においてもＡｇ−ＬＴＡが高い硫化水素吸着能を示したのは、Ａｇ−ＬＴＡの硫化水素吸着能によって硫化水素を吸着、溶出するＡｇイオンによって硫化水素を吸着したことが主要因と考えられる。 From this result, it is considered that Ag 2 S is precipitated. Moreover, as shown in the silver ion elution mentioned later, when Ag-LTA was put into the solution, the result was that the Ag ions were eluted. It is considered that the eluted Ag ions and hydrogen sulfide reacted to precipitate as Ag 2 S, and the hydrogen sulfide concentration decreased. Ag-LTA showed high hydrogen sulfide adsorption ability even in the coexistence of the gas phase and liquid phase, mainly because hydrogen sulfide was adsorbed by the adsorbed and eluted Ag ions by the hydrogen sulfide adsorption ability of Ag-LTA. It is thought to be the cause.
Ｃａ−ＬＴＡの場合、試料を投入してから１時間後まで硫化水素濃度が減少していた。その後、１２時間後まで次第に硫化水素濃度が上昇した。１２時間後の硫化水素濃度が１１．２ｐｐｍで、２４時間後の硫化水素濃度が１１．３ｐｐｍであったことから、ほぼ平衡に達したと考えられた。Ｎａ−ＬＴＡと比較すると、実験を開始してから１時間後までは、Ｎａ−ＬＴＡと同様に硫化水素濃度は低下した。Ｎａ−ＬＴＡを用いた場合より、硫化水素濃度の低下はやや早かった。その要因としては、Ｃａ−ＬＴＡの方がＮａ−ＬＴＡよりも細孔径が大きいために、硫化水素を吸着しやすかったと考えられる。 In the case of Ca-LTA, the hydrogen sulfide concentration decreased until 1 hour after the sample was added. Thereafter, the hydrogen sulfide concentration gradually increased until 12 hours later. Since the hydrogen sulfide concentration after 12 hours was 11.2 ppm and the hydrogen sulfide concentration after 24 hours was 11.3 ppm, it was considered that the equilibrium was almost reached. Compared with Na-LTA, the hydrogen sulfide concentration decreased in the same manner as Na-LTA until 1 hour after the start of the experiment. The decrease in hydrogen sulfide concentration was slightly faster than when Na-LTA was used. As the cause, it is considered that Ca-LTA has a larger pore diameter than Na-LTA, so that hydrogen sulfide was easily adsorbed.
また、アルカリ金属のＮａと比べ、アルカリ土類金属のＣａの溶出量、ｐＨ低下の程度が異なることも、原因と考えられる。しかし、Ａｇイオンのように、硫化水素吸着能を大幅に上昇させるような効果は見られなかった。実験を開始してから１時間後が経過したあたりから硫化水素濃度が上昇したのは、Ｃａ−ＬＴＡ内部のＣａイオンおよび、Ｃａ−ＬＴＡから溶出したＣａイオンが原因と考えられる。硫化水素と水の共存下での水溶液中においては、下記の反応が進むことが報告されている。 Moreover, it is also considered that the elution amount of alkaline earth metal Ca and the degree of pH decrease are different from those of alkali metal Na. However, as in the case of Ag ions, the effect of greatly increasing the hydrogen sulfide adsorption ability was not observed. The reason why the hydrogen sulfide concentration increased after about 1 hour after the start of the experiment is thought to be due to Ca ions inside Ca-LTA and Ca ions eluted from Ca-LTA. It has been reported that the following reaction proceeds in an aqueous solution in the presence of hydrogen sulfide and water.
この反応によりいったん吸着した硫化水素が気体となって出て行き、硫化水素濃度が上昇したと考えられる。 It is considered that the hydrogen sulfide once adsorbed by this reaction went out as a gas and the hydrogen sulfide concentration increased.
Ｃａ−Ａｇ−ＬＴＡの場合、試料を投入してから４時間後に、硫化水素濃度は０（ゼロ）になった。硫化水素濃度が０になった時間は正確ではないが、ほぼ傾向を把握することができた。Ｎａ−ＬＴＡと比較すると、硫化水素濃度の減少が小さかった。これは、Ｎａ−ＬＴＡに比べてｐＨの変化があまりなかったのではないかと考えられる。また、Ｃａ−ＬＴＡにおいて、Ｃａイオンによる硫化水素濃度上昇が考えられる。Ｃａ−Ａｇ−ＬＴＡでは、Ｃａイオンが含まれているにも関わらず硫化水素濃度は減少し続け、上昇することはなかった。これは、Ｃａイオンによる硫化水素濃度上昇よりもＡｇイオンによる硫化水素吸着の方が勝ったためだと考えられる。 In the case of Ca-Ag-LTA, the hydrogen sulfide concentration became 0 (zero) after 4 hours from the introduction of the sample. Although the time when the hydrogen sulfide concentration became zero was not accurate, the tendency could be almost grasped. Compared with Na-LTA, the decrease in hydrogen sulfide concentration was small. This is considered that there was not much change of pH compared with Na-LTA. In Ca-LTA, an increase in hydrogen sulfide concentration due to Ca ions can be considered. In Ca-Ag-LTA, the hydrogen sulfide concentration continued to decrease and did not increase despite the inclusion of Ca ions. This is probably because hydrogen sulfide adsorption by Ag ions was superior to the increase in hydrogen sulfide concentration by Ca ions.
Ａｇ−Ｃａ−ＬＴＡの場合、試料を投入してから０．７５時間（４５分）後、硫化水素濃度は０ｐｐｍになった。Ａｇ−ＬＴＡと比較すると、硫化水素吸着能が劣っていることがわかる。これは、Ａｇの総量がＡｇ−ＬＴＡよりもＡｇ−Ｃａ−ＬＴＡの方が少なかったためと考えられる。また、Ｃａイオンの影響については、Ｃａ−Ａｇ−ＬＴＡと同様の理由で影響がでなかったと考えられる。 In the case of Ag-Ca-LTA, the hydrogen sulfide concentration became 0 ppm after 0.75 hours (45 minutes) from the introduction of the sample. Compared with Ag-LTA, it turns out that hydrogen sulfide adsorption ability is inferior. This is probably because the total amount of Ag was less in Ag-Ca-LTA than in Ag-LTA. Moreover, about the influence of Ca ion, it is thought that there was no influence for the same reason as Ca-Ag-LTA.
ＡＰ−Ｃａ−Ａｇ−ＬＴＡの場合、試料を投入してから１２時間後、硫化水素濃度は０ｐｐｍになった。硫化水素濃度が０ｐｐｍになった時間は正確ではないが、ほぼ傾向を把握することができた。Ｃａ−Ａｇ−ＬＴＡと比較すると、ＡＰ−Ｃａ−Ａｇ−ＬＴＡの方が硫化水素濃度の低下が遅い。 In the case of AP-Ca-Ag-LTA, the hydrogen sulfide concentration became 0 ppm after 12 hours from the introduction of the sample. Although the time when the hydrogen sulfide concentration reached 0 ppm was not accurate, the tendency could be almost grasped. Compared to Ca-Ag-LTA, AP-Ca-Ag-LTA has a slower decrease in hydrogen sulfide concentration.
また、リン酸カルシウムでゼオライトが被覆されることにより、硫化水素吸着能が減少したとも考えられる。リン酸カルシウムは様々なカチオン、アニオンをイオン交換で取り込むことが知られているが、硫化物に関しては、リン酸カルシウムが持つリン酸や炭酸と硫化物とはサイズや価数が異なるため、それほど取り込むことはないと考えられる。また、Ａｇが溶出しても、リン酸カルシウムに取り込まれると思われる。溶液１３の中にＡｇイオンが溶出していないため、Ａｇ−ＬＴＡやＣａ−Ａｇ−ＬＴＡ、Ａｇ−Ｃａ−ＬＴＡよりも硫化水素吸着能が劣ったとも考えられる。 Moreover, it is thought that the hydrogen sulfide adsorption ability was reduced by coating the zeolite with calcium phosphate. Calcium phosphate is known to incorporate various cations and anions by ion exchange, but with regard to sulfides, phosphoric acid, carbonic acid, and sulfides possessed by calcium phosphate are different in size and valence, so they are not so much incorporated. it is conceivable that. Moreover, even if Ag elutes, it seems that it is taken in by calcium phosphate. Since Ag ions are not eluted in the solution 13, it is considered that the hydrogen sulfide adsorption ability is inferior to Ag-LTA, Ca-Ag-LTA, and Ag-Ca-LTA.
次にこれら試料の液相中（溶液中）での硫化水素の吸着に関して調べた。図６に実験装置を示す。実験装置２０は、二ッ口ガラスフラスコ２２に、コック付漏斗２３を密着させたものである。側管口２６には、セプタム２５を介して、シリンジ２７の針を二ッ口ガラスフラスコ２２内に浸入させ、内部の気体３０もしくは液体３２を抽出することができる。 Next, the adsorption of hydrogen sulfide in the liquid phase (in solution) of these samples was examined. FIG. 6 shows an experimental apparatus. The experimental apparatus 20 is a two-necked glass flask 22 in which a funnel 23 with a cock is brought into close contact. Through the septum 25, the needle of the syringe 27 can enter the two-necked glass flask 22 into the side tube port 26, and the internal gas 30 or liquid 32 can be extracted.
気相液相共存下での硫化水素吸着は以下のように実験を行った。まず、超純水中に硫化水素水ガスを導入し、硫化水素水を作製した。この硫化水素水を超純水で希釈し、所定濃度の硫化水素水を調製した。次に、二ッ口ガラスフラスコ２２に、硫化水素水を側管口２６の下まで満たし密閉した。これで、セプタム２５を介して、二ッ口ガラスフラスコ２２内の液体（以下「溶液」とも呼ぶ。）３２の両方をシリンジ２７で採取可能にした。なお、二ッ口ガラスフラスコ２２内の溶液３２がない部分はヘッドスペースと呼ぶ。ヘッドスペース中の気体を気体３０と呼ぶ。 The hydrogen sulfide adsorption in the coexistence of the gas phase and the liquid phase was conducted as follows. First, hydrogen sulfide water gas was introduced into ultrapure water to produce hydrogen sulfide water. This hydrogen sulfide water was diluted with ultrapure water to prepare hydrogen sulfide water having a predetermined concentration. Next, the two-necked glass flask 22 was filled with hydrogen sulfide water to the bottom of the side pipe port 26 and sealed. Thus, both the liquid (hereinafter also referred to as “solution”) 32 in the two-necked glass flask 22 can be collected by the syringe 27 through the septum 25. Note that the portion without the solution 32 in the two-necked glass flask 22 is called a head space. The gas in the head space is referred to as gas 30.
そして、コック付漏斗２３から、試料０．２ｇを、二ッ口ガラスフラスコ２２内に投入した。投入後０．２５時間、０．５時間、０．７５時間、１時間、２時間、４時間、８時間、２４時間後に、セプタム２５から、二ッ口ガラスフラスコ２２内の溶液３２をシリンジ２７で採取した。採取した溶液３２中の硫化水素濃度を炎光光度検出器付ガスクロマトグラフ（ＧＣ−ＦＰＤ）で測定した。 Then, 0.2 g of the sample was put into the two-necked glass flask 22 from the funnel 23 with a cock. After 0.25 hours, 0.5 hours, 0.75 hours, 1 hour, 2 hours, 4 hours, 8 hours, and 24 hours after charging, the solution 32 in the two-necked glass flask 22 is transferred from the septum 25 to the syringe 27. Collected at The concentration of hydrogen sulfide in the collected solution 32 was measured by a gas chromatograph with a flame photometric detector (GC-FPD).
（溶液中の硫化水素濃度測定の結果）
Ｎａ−ＬＴＡ、Ａｇ−ＬＴＡ、Ｃａ−ＬＴＡ、Ａｇ−Ｃａ−ＬＴＡ、Ｃａ−Ａｇ−ＬＴＡ、ＡＰ−Ｃａ−Ａｇ−ＬＴＡをそれぞれ用い、溶液３２中の硫化水素濃度の経時変化を図７に示す。図７は横軸が時間（ｈ）であり、縦軸は溶液の硫化水素濃度（％）を表す。なお、それぞれの初期濃度を表２に示す。図７の縦軸は％表示であるので、それぞれの試料で具体的な濃度の値が異なる。以下の説明では、濃度（ｐｐｍ）表示した物で、図７に記載されているものは、表２の初期値に基づいて％表示を括弧で示す。
(Results of measuring hydrogen sulfide concentration in solution)
FIG. 7 shows changes with time in the hydrogen sulfide concentration in the solution 32 using Na-LTA, Ag-LTA, Ca-LTA, Ag-Ca-LTA, Ca-Ag-LTA, and AP-Ca-Ag-LTA, respectively. . In FIG. 7, the horizontal axis represents time (h), and the vertical axis represents the hydrogen sulfide concentration (%) of the solution. The initial concentrations are shown in Table 2. Since the vertical axis in FIG. 7 is expressed in%, the specific concentration value differs for each sample. In the following description, what is indicated in concentration (ppm) and described in FIG. 7 is indicated by parentheses in% based on the initial values in Table 2.
Ｂｌａｎｋでも、２４時間後硫化水素濃度が５７．２ｐｐｍ（９７．６％）に減少した．マイクロシリンジでの採取の際に大気が入り込んだため、あるいは、容器内壁へ硫化水素が吸着したためと考えられる。 Even in Blank, the hydrogen sulfide concentration decreased to 57.2 ppm (97.6%) after 24 hours. This is probably because the atmosphere entered during collection with the microsyringe or because hydrogen sulfide was adsorbed on the inner wall of the container.
Ｎａ−ＬＴＡの場合、実験を開始してから１時間後まで溶液３２の硫化水素濃度が２７．９ｐｐｍ（５０．４％）まで減少し、２時間後一旦４１．４ｐｐｍ（７４．７％）まで上昇し、その後また減少した。１２時間後の溶液３２の硫化水素濃度が３４．７ｐｐｍ（６２．６％）で２４時間後の硫化水素濃度が３４．１ｐｐｍ（６１．６％）であることから、濃度平衡は確認されなかったと考えられる。 In the case of Na-LTA, the hydrogen sulfide concentration of the solution 32 decreased to 27.9 ppm (50.4%) until 1 hour after the start of the experiment, and once after 2 hours, it decreased to 41.4 ppm (74.7%). It rose and then decreased again. Since the hydrogen sulfide concentration of the solution 32 after 12 hours was 34.7 ppm (62.6%) and the hydrogen sulfide concentration after 24 hours was 34.1 ppm (61.6%), the concentration equilibrium was not confirmed. Conceivable.
図３および図４の気相液相共存下における硫化水素実験のＮａ−ＬＴＡの結果では、２時間後に、気体の硫化水素濃度が０ｐｐｍになった。その要因として、水の中にＮａ−ＬＴＡが入ると、溶液１３（図３参照）のｐＨがアルカリ性に傾き、その結果、硫化水素が溶液１３（図３参照）の中に溶け込んだと考えられた。これを考慮に入れると、図６および図７の実験を開始してから２時間後Ｎａ−ＬＴＡの硫化水素濃度が、一旦上昇した理由としては、溶液３２中の硫化水素濃度が減少した際に、ヘッドスペースから硫化水素が溶液３２に溶け込んだためと考えられる。 As a result of Na-LTA in the hydrogen sulfide experiment in the coexistence of the gas phase liquid phase in FIGS. 3 and 4, the hydrogen sulfide concentration of the gas became 0 ppm after 2 hours. As a factor, when Na-LTA enters water, the pH of the solution 13 (see FIG. 3) is inclined to be alkaline, and as a result, hydrogen sulfide is dissolved in the solution 13 (see FIG. 3). It was. Taking this into account, the reason why the hydrogen sulfide concentration of Na-LTA increased once two hours after the start of the experiments of FIGS. 6 and 7 was that the hydrogen sulfide concentration in the solution 32 decreased. This is probably because hydrogen sulfide was dissolved in the solution 32 from the head space.
図７において、実験を開始してから４時間後以降、Ｎａ−ＬＴＡの硫化水素濃度が減少したのは、図３および図４に示す気相液相共存下における硫化水素実験のＮａ−ＬＴＡの結果より、ヘッドスペースの硫化水素がすべて溶液３２の中に溶け込んでいると考えられるので、Ｎａ−ＬＴＡによる硫化水素吸着が行われたと考えられる。 In FIG. 7, after 4 hours from the start of the experiment, the hydrogen sulfide concentration of Na-LTA decreased because of the Na-LTA of the hydrogen sulfide experiment in the coexistence of the gas phase liquid phase shown in FIGS. From the results, it is considered that all of the hydrogen sulfide in the head space is dissolved in the solution 32, so that it is considered that hydrogen sulfide adsorption by Na-LTA was performed.
Ａｇ−ＬＴＡの場合、実験を開始してから２時間後の時点で、溶液３２の硫化水素濃度は０ｐｐｍになった。実験を開始してから１時間後の時点で、溶液３２の硫化水素濃度は、０．７ｐｐｍ（０．１％）になっていた。その為、実験を開始してから２時間後までに溶液３２の硫化水素濃度が０ｐｐｍになっている可能性が高い。硫化水素濃度が０ｐｐｍになった時間は正確ではないが、ほぼ傾向を把握することができた。 In the case of Ag-LTA, the hydrogen sulfide concentration of the solution 32 became 0 ppm at 2 hours after the start of the experiment. At one hour after the start of the experiment, the hydrogen sulfide concentration of the solution 32 was 0.7 ppm (0.1%). Therefore, there is a high possibility that the hydrogen sulfide concentration of the solution 32 is 0 ppm by 2 hours after the start of the experiment. Although the time when the hydrogen sulfide concentration reached 0 ppm was not accurate, the tendency could be almost grasped.
図３および図４に示した気相液相共存下における硫化水素実験のＡｇ−ＬＴＡにおいて、Ａｇ−ＬＴＡが高い硫化水素吸着能を示したのは、Ａｇ−ＬＴＡの硫化水素吸着能によって硫化水素を吸着、溶出するＡｇイオンによって硫化水素を吸着、またｐＨの変化による溶液１３への硫化水素溶解これらが要因と考えられた。しかし、図６および図７に示す液相の実験では、溶液３２の硫化水素濃度が０ｐｐｍになっていることからｐＨの変化による溶液３２への硫化水素溶解は考えにくいことがわかった。すなわち、Ａｇ−ＬＴＡが高い硫化水素吸着能を示したのは、Ａｇ−ＬＴＡの硫化水素吸着能によって硫化水素を吸着、溶出するＡｇイオンによって硫化水素を吸着によるものだと考えられる。 In Ag-LTA of hydrogen sulfide experiment in the coexistence of gas phase liquid phase shown in FIG. 3 and FIG. 4, Ag-LTA showed high hydrogen sulfide adsorption ability because of hydrogen sulfide adsorption ability of Ag-LTA. It was considered that hydrogen sulfide was adsorbed by Ag ions that adsorbed and eluted, and dissolved in the solution 13 due to pH change. However, in the liquid phase experiments shown in FIG. 6 and FIG. 7, it was found that the hydrogen sulfide concentration in the solution 32 due to the change in pH is unlikely because the hydrogen sulfide concentration of the solution 32 is 0 ppm. That is, the high hydrogen sulfide adsorption ability of Ag-LTA is considered to be due to the adsorption of hydrogen sulfide by the Ag ions adsorbed and eluted by the hydrogen sulfide adsorption ability of Ag-LTA.
Ｃａ−ＬＴＡの場合、実験を開始してから１時間後まで溶液３２の硫化水素濃度が３１．２ｐｐｍ（５６．４％）まで減少し、２時間後一旦４５．０ｐｐｍ（８１．４％）まで上昇し、その後また減少した。４時間後の溶液３２の硫化水素濃度が４４．０ｐｐｍ（７９．６％）で２４時間後の硫化水素濃度が４４．９ｐｐｍ（８１．２％）であり、濃度平衡に達したと考えられる。 In the case of Ca-LTA, the hydrogen sulfide concentration of the solution 32 is reduced to 31.2 ppm (56.4%) until 1 hour after the start of the experiment, and after 2 hours to 45.0 ppm (81.4%) once. It rose and then decreased again. The hydrogen sulfide concentration of the solution 32 after 4 hours was 44.0 ppm (79.6%) and the hydrogen sulfide concentration after 24 hours was 44.9 ppm (81.2%), which is considered to have reached the concentration equilibrium.
図３および図４に示した気相液相共存下における硫化水素実験のＣａ−ＬＴＡの結果では、２時間後から８時間後にいたるまで、気体の硫化水素濃度が上昇していた。これは、Ｃａ−ＬＴＡ内部のＣａイオンおよび、Ｃａ−ＬＴＡから溶出したＣａイオンが硫化水素と反応し、再度硫化水素を発生し、硫化水素濃度が上昇すると考えられた。図６および図７に示した実験の溶液３２の硫化水素濃度が４時間後以降ほとんど変化しなかった（図７参照）ことを考えると、４時間後から８時間後まではヘッドスペースに硫化水素が出て行く反応の方が多く起こり、その後、濃度平衡に達したと考えられる。 In the results of Ca-LTA in the hydrogen sulfide experiment in the coexistence of the gas phase and liquid phase shown in FIGS. 3 and 4, the gas hydrogen sulfide concentration increased from 2 hours to 8 hours later. It was thought that this is because Ca ions inside Ca-LTA and Ca ions eluted from Ca-LTA react with hydrogen sulfide to generate hydrogen sulfide again, increasing the hydrogen sulfide concentration. Considering that the hydrogen sulfide concentration of the solution 32 of the experiment shown in FIG. 6 and FIG. 7 hardly changed after 4 hours (see FIG. 7), hydrogen sulfide in the head space from 4 hours to 8 hours later. It is thought that more reactions occurred, and then concentration equilibrium was reached.
以上の事からＮａ−ＬＴＡと同じような挙動を示しているが、挙動のメカニズムは異なっていると考えられる。また、図３および図４に示した気相液相共存下における硫化水素吸着実験において、Ｃａ−ＬＴＡがＮａ−ＬＴＡよりも吸着能が少し高い要因として、Ｃａ−ＬＴＡの方がＮａ−ＬＴＡよりも細孔径が大きいために、硫化水素をより多く吸着したと考えられた。しかし、図６および図７の実験における溶液３２の硫化水素濃度測定において、２時間後以降の挙動をみると、Ｎａ−ＬＴＡの方が溶液３２の硫化水素濃度が減少している。これについては、Ｃａ−ＬＴＡの方が細孔径が大きいために、水溶液の水分子をより多く吸着し、硫化水素濃度が上昇した可能性が考えられる。 Although the same behavior as Na-LTA is shown from the above, the mechanism of the behavior is considered to be different. Further, in the hydrogen sulfide adsorption experiment in the coexistence of the gas phase liquid phase shown in FIG. 3 and FIG. 4, Ca-LTA is slightly higher than Na-LTA because Ca-LTA has a slightly higher adsorption capacity than Na-LTA. It was thought that more hydrogen sulfide was adsorbed due to the large pore diameter. However, in the measurement of the hydrogen sulfide concentration of the solution 32 in the experiments of FIG. 6 and FIG. 7, when the behavior after 2 hours is observed, the hydrogen sulfide concentration of the solution 32 is decreased with Na-LTA. About this, since Ca-LTA has a larger pore diameter, more water molecules in the aqueous solution may be adsorbed, and the hydrogen sulfide concentration may have increased.
Ｃａ−Ａｇ−ＬＴＡの場合、実験を開始してから１時間後まで溶液３２の硫化水素濃度が１３．４ｐｐｍ（２５．０％）まで減少し、２時間後一旦３２．６ｐｐｍ（６０．８％）まで上昇し、その後また減少した。１２時間後の溶液３２の硫化水素濃度が２６．４ｐｐｍ（４９．２％）で２４時間後の硫化水素濃度が２５．８ｐｐｍ（４８．１％）であることから、濃度平衡は確認されなかったと考えられる。 In the case of Ca-Ag-LTA, the hydrogen sulfide concentration of the solution 32 decreased to 13.4 ppm (25.0%) until 1 hour after the start of the experiment, and 32.6 ppm (60.8%) after 2 hours. ) And then decreased again. Since the hydrogen sulfide concentration of the solution 32 after 12 hours was 26.4 ppm (49.2%) and the hydrogen sulfide concentration after 24 hours was 25.8 ppm (48.1%), the concentration equilibrium was not confirmed. Conceivable.
図３および図４の気相液相共存下における硫化水素吸着実験のＣａ−Ａｇ−ＬＴＡの結果では、実験を開始してから４時間後の時点で、硫化水素濃度は０ｐｐｍになった。また、気相液相共存下における硫化水素吸着実験において、Ｎａ−ＬＴＡと比較すると、硫化水素濃度があまり減少していなかった。これは、Ｎａ−ＬＴＡに比べてｐＨの変化があまりなかったのではないかと考えられた。 In the results of the Ca-Ag-LTA in the hydrogen sulfide adsorption experiment in the coexistence of the gas phase liquid phase in FIGS. 3 and 4, the hydrogen sulfide concentration became 0 ppm at 4 hours after the start of the experiment. Further, in the hydrogen sulfide adsorption experiment in the coexistence of the gas phase and the liquid phase, the hydrogen sulfide concentration did not decrease much compared to Na-LTA. This was considered that there was not much change of pH compared with Na-LTA.
しかし、図６および図７の液相の吸着実験では、溶液３２の硫化水素濃度測定では、Ｃａ−Ａｇ−ＬＴＡは、Ｎａ−ＬＴＡよりも硫化水素濃度が減少していた。ｐＨの変化があまりなかったと考えると、Ｃａ−Ａｇ−ＬＴＡの内部のＡｇによって硫化水素が吸着され、Ｎａ−ＬＴＡよりも硫化水素濃度が減少したと考えられる。 However, in the liquid phase adsorption experiments of FIGS. 6 and 7, in the measurement of the hydrogen sulfide concentration of the solution 32, Ca-Ag-LTA had a reduced hydrogen sulfide concentration than Na-LTA. Considering that there was not much change in pH, it is considered that hydrogen sulfide was adsorbed by Ag inside Ca-Ag-LTA, and the hydrogen sulfide concentration was reduced compared to Na-LTA.
Ａｇ−Ｃａ−ＬＴＡの場合、実験を開始してから２時間後の時点で、溶液３２の硫化水素濃度は０ｐｐｍ（０％）になった。実験を開始してから１時間後の時点で、溶液３２の硫化水素濃度は、１．０ｐｐｍ（２．０％）になった。その為、実験を開始してから２時間後までに溶液３２の硫化水素濃度が０ｐｐｍ（０％）になっている可能性が高い。硫化水素濃度が０ｐｐｍ（０％）になった時間は正確ではないが、ほぼ傾向を把握することができた。 In the case of Ag-Ca-LTA, the hydrogen sulfide concentration of the solution 32 became 0 ppm (0%) at 2 hours after the start of the experiment. At one hour after the start of the experiment, the hydrogen sulfide concentration of the solution 32 was 1.0 ppm (2.0%). Therefore, it is highly possible that the hydrogen sulfide concentration of the solution 32 is 0 ppm (0%) by 2 hours after the start of the experiment. Although the time when the hydrogen sulfide concentration was 0 ppm (0%) was not accurate, the tendency could be almost grasped.
図３および図４の気相液相共存下における硫化水素吸着実験のＡｇ−Ｃａ−ＬＴＡの結果では、硫化水素吸着能が劣っているもののＡｇ−ＬＴＡと同様の吸着反応がみられた。図６および図７の実験における溶液３２の硫化水素濃度測定においても、硫化水素吸着能が劣っているもののＡｇ−ＬＴＡと同様の吸着反応がみられた。どちらにおいても硫化水素吸着能が劣った要因は、Ａｇイオンの割合がＡｇ−ＬＴＡに比べ、Ａｇ−Ｃａ−ＬＴＡの方が少ないからだと考えられる。よって、内部にあるＣａイオンは、硫化水素吸着反応には特に影響を与えないと考えられる。 In the results of Ag-Ca-LTA in the hydrogen sulfide adsorption experiment in the coexistence of the gas phase liquid phase in FIGS. 3 and 4, the adsorption reaction similar to that of Ag-LTA was observed although the hydrogen sulfide adsorption ability was inferior. In the hydrogen sulfide concentration measurement of the solution 32 in the experiments of FIGS. 6 and 7, the same adsorption reaction as that of Ag-LTA was observed although the hydrogen sulfide adsorption ability was inferior. In either case, the reason why the hydrogen sulfide adsorption ability is inferior is considered to be because the proportion of Ag ions is smaller in Ag-Ca-LTA than in Ag-LTA. Therefore, it is considered that the Ca ions inside do not particularly affect the hydrogen sulfide adsorption reaction.
図６および図７に示す実験の場合、ＡＰ−Ｃａ−Ａｇ−ＬＴＡの場合、実験を開始してから１２時間後と２４時間後の硫化水素濃度は、それぞれ２８．７ｐｐｍ（５５．４％）と２７．１ｐｐｍ（５２．３％）であった。２４時間後の方が硫化水素濃度は減少しており、少なくとも１２時間後の時点では濃度平衡は確認されなかった。Ｃａ−Ａｇ−ＬＴＡと比べると、Ｃａ−Ａｇ−ＬＴＡのような一旦下がって一旦上がりまた下がるといった現象は起きなかった。よって、リン酸カルシウムが被覆されることによってｐＨの影響がなかったと考えられる。 In the case of the experiments shown in FIGS. 6 and 7, in the case of AP-Ca-Ag-LTA, the hydrogen sulfide concentrations after 12 hours and 24 hours from the start of the experiment were 28.7 ppm (55.4%), respectively. And 27.1 ppm (52.3%). The concentration of hydrogen sulfide decreased after 24 hours, and no concentration equilibrium was confirmed at least 12 hours later. Compared with Ca-Ag-LTA, there was no phenomenon such as Ca-Ag-LTA that once lowered, then raised and lowered. Therefore, it is thought that there was no influence of pH by being coated with calcium phosphate.
しかし、図３および図４の気相液相共存下における硫化水素吸着実験のＡＰ−Ｃａ−Ａｇ−ＬＴＡの結果では、硫化水素吸着能が劣っているもののＡｇ−ＬＴＡやＡｇ−Ｃａ−ＬＴＡ、Ｃａ−Ａｇ−ＬＴＡと同様の吸着反応がみられ、１２時間後には気体中の硫化水素濃度が０ｐｐｍになっていた。すなわち、ｐＨの影響による溶液１３への硫化水素溶解が十分に考えられる。 However, in the results of AP-Ca-Ag-LTA in the hydrogen sulfide adsorption experiment in the coexistence of the gas phase liquid phase in FIGS. 3 and 4, although the hydrogen sulfide adsorption ability is poor, Ag-LTA and Ag-Ca-LTA, The same adsorption reaction as Ca-Ag-LTA was observed, and the hydrogen sulfide concentration in the gas was 0 ppm after 12 hours. That is, the dissolution of hydrogen sulfide in the solution 13 due to the influence of pH is considered sufficiently.
図７の液相下での吸着におけるＮａ−ＬＴＡやＣａ−ＬＴＡ、Ｃａ−Ａｇ−ＬＴＡで見られた、一旦下がって一旦上がる現象は、ｐＨ以外に要因があると考えられる。とくに、ＡＰ−Ｃａ−Ａｇ−ＬＴＡとＣａ−Ａｇ−ＬＴＡとが大きく異なっているのは、Ｃａイオンがアパタイトコーティングされているかどうかである。すなわち、アパタイトコーティングされることによって下記の反応が妨げられたと考えられる。 It is considered that the phenomenon of once decreasing and once increasing with Na-LTA, Ca-LTA, and Ca-Ag-LTA in the adsorption in the liquid phase of FIG. 7 is caused by factors other than pH. In particular, the difference between AP-Ca-Ag-LTA and Ca-Ag-LTA is whether Ca ions are apatite-coated. That is, it is considered that the following reaction was hindered by the apatite coating.
また、Ｎａイオンに関しても、下記の反応がおこることが報告されている。 In addition, it has been reported that the following reaction occurs with respect to Na ions.
図６および図７に示した硫化水素吸着実験を行った際、溶液３２のｐＨは酸性に傾いている。よって、上記の式は、右に進むと考えられる。しかし、試料を投入したことにより、ｐＨがアルカリ性に傾くため、上記の反応式が左に進むと考えられる。そのため、一旦、硫化水素の濃度が減少し、その後一旦硫化水素濃度が増加したと考えられる。 When the hydrogen sulfide adsorption experiment shown in FIG. 6 and FIG. 7 is performed, the pH of the solution 32 tends to be acidic. Therefore, the above formula is considered to advance to the right. However, it is considered that the above reaction formula advances to the left because the pH is inclined to be alkaline by introducing the sample. Therefore, it is considered that the concentration of hydrogen sulfide once decreased, and then the concentration of hydrogen sulfide once increased.
（銀イオン溶出実験）
次に、Ａｇ−ＬＴＡ、Ｃａ−Ａｇ−ＬＴＡ、Ａｇ−Ｃａ−ＬＴＡ、ＡＰ−Ｃａ−Ａｇ−ＬＴＡを用い、銀イオンの溶出実験を行った。超純水１００ｍｌに各試料１．０ｇを投入し、マグネチックスターターで２４時間攪拌した。攪拌後の溶液をろ過し、ろ液を回収した。回収したろ液をＦａｊａｎｓ法を用いた滴定で銀濃度を決定した。結果を表３に示す。
(Silver ion elution experiment)
Next, the elution experiment of silver ion was conducted using Ag-LTA, Ca-Ag-LTA, Ag-Ca-LTA, and AP-Ca-Ag-LTA. 1.0 g of each sample was put into 100 ml of ultrapure water and stirred for 24 hours with a magnetic starter. The stirred solution was filtered and the filtrate was recovered. The silver concentration of the collected filtrate was determined by titration using the Fajans method. The results are shown in Table 3.
Ａｇの溶出量が最も大きいのは、Ａｇ−ＬＴＡである。Ｃａ−Ａｇ−ＬＴＡと比べ、Ａｇ−Ｃａ−ＬＴＡの方が溶出量が多い。Ａｇ−Ｃａ−ＬＴＡの方がＡｇイオンの割合も多いためと思われる。一方、Ａｇ−ＬＴＡ、Ｃａ−Ａｇ−ＬＴＡ、Ａｇ−Ｃａ−ＬＴＡそれぞれのＡｇ含有量に比較して、Ｃａ−Ａｇ−ＬＴＡの溶出Ａｇ量が多い。 The largest elution amount of Ag is Ag-LTA. Compared with Ca-Ag-LTA, Ag-Ca-LTA has a larger amount of elution. This is probably because Ag-Ca-LTA has a higher proportion of Ag ions. On the other hand, compared to the Ag contents of Ag-LTA, Ca-Ag-LTA, and Ag-Ca-LTA, the amount of eluted Ag of Ca-Ag-LTA is large.
図８には、ＬＴＡ型ゼオライトの結晶構造を示す。Ｃａ−Ａｇ−ＬＴＡは、βサイトにＣａイオン、αサイトにＣａイオンとＡｇイオン（存在量はＣａ＞Ａｇ）、γサイトにＡｇイオンが含まれていると考えられる。一方、Ａｇ−Ｃａ−ＬＴＡでは、βサイトにＡｇイオン、αサイトにＡｇイオンとＣａイオン（存在量はＡｇ＞Ｃａ）、γサイトにＡｇイオンが含まれている。 FIG. 8 shows the crystal structure of LTA-type zeolite. Ca-Ag-LTA is considered to contain Ca ions at the β site, Ca ions and Ag ions at the α site (abundance is Ca> Ag), and Ag ions at the γ site. On the other hand, in Ag-Ca-LTA, Ag ions are contained in β sites, Ag ions and Ca ions (abundance is Ag> Ca) in α sites, and Ag ions are contained in γ sites.
Ａｇ含有量に比例せず、Ｃａ−Ａｇ−ＬＴＡの溶出Ａｇ量が多くなったのは、αサイトにあるＣａイオンの影響によってαサイトのＡｇが多く溶出したと考えられる。 The reason why the Ca-Ag-LTA elution Ag amount increased without being proportional to the Ag content is considered that a large amount of Ag at the α site was eluted due to the influence of Ca ions at the α site.
Ｃａ−Ａｇ−ＬＴＡとＡＰ−Ｃａ−Ａｇ−ＬＴＡを比較すると、ＡＰ−Ｃａ−Ａｇ−ＬＴＡの方がＡｇ溶出量がかなり少ない。表面に析出したリン酸カルシウムの影響であると思われる。また、リン酸カルシウムは種々のイオンを結晶格子に取り込むことができるため、αサイトのＡｇの溶出を妨げたと考えられる。 Comparing Ca-Ag-LTA and AP-Ca-Ag-LTA, AP-Ca-Ag-LTA has a much smaller amount of Ag elution. This is probably due to the influence of calcium phosphate deposited on the surface. Moreover, since calcium phosphate can take in various ions into the crystal lattice, it is considered that the elution of α-site Ag was hindered.
Ｃａ−Ａｇ−ＬＴＡは、βサイトにＣａイオン、αサイトにＣａイオンとＡｇイオン（存在量はＣａ＞Ａｇ）、γサイトにＡｇイオンが含まれていると考えられる。一方、Ａｇ−Ｃａ−ＬＴＡでは、βサイトにＡｇイオン、αサイトにＡｇイオンとＣａイオン（存在量はＡｇ＞Ｃａ）、γサイトにＡｇイオンが含まれている。 Ca-Ag-LTA is considered to contain Ca ions at the β site, Ca ions and Ag ions at the α site (abundance is Ca> Ag), and Ag ions at the γ site. On the other hand, in Ag-Ca-LTA, Ag ions are contained in β sites, Ag ions and Ca ions (abundance is Ag> Ca) in α sites, and Ag ions are contained in γ sites.
なお、リン酸カルシウム（アパタイト）コートによって、Ａｇイオンの流出は抑制されたが、Ａｇイオンの存在によって、抗菌性は維持されている。むしろ、Ａｇの溶出量が減少したために、抗菌性の持続期間が長くなることが期待される。 In addition, although the outflow of Ag ions was suppressed by the calcium phosphate (apatite) coat, the antibacterial property was maintained by the presence of Ag ions. Rather, since the elution amount of Ag is reduced, it is expected that the antibacterial duration will be longer.
本発明に係る抗菌性消臭剤は、繊維、化粧品、塗料、建物、構造物といった場所で好適に利用することができる。 The antibacterial deodorant according to the present invention can be suitably used in places such as fibers, cosmetics, paints, buildings, and structures.
１ 吸着容器
２ 蓋
３ セプタム
４ 注入口
５ ガラスコック付分液ロート
６ シリンジ
７ 試料
１０ シャーレ
１１ ビーカー
１２ 攪拌子
１３ 溶液
２０ 実験装置
２２ 二ッ口ガラスフラスコ
２３ コック付漏斗
２５ セプタム
２６ 側管口
２７ シリンジ
３０ 気体
３２ 液体（溶液）
DESCRIPTION OF SYMBOLS 1 Adsorption container 2 Lid 3 Septum 4 Inlet 5 Separation funnel 6 with a glass cock Syringe 7 Sample 10 Petri dish 11 Beaker 12 Stirrer 13 Solution 20 Experimental apparatus 22 Two-necked glass flask 23 Funnel 25 with a cock Septum 26 Side pipe 27 Syringe 30 Gas 32 Liquid (solution)
Claims (1)
前記銀イオンの一部をカルシウムイオンに交換し、βサイトにＣａイオン、αサイトにＣａイオンとＡｇイオン、γサイトにＡｇイオンが含まれ、前記αサイトのＣａイオンはＡｇイオンより多いＬＴＡ型ゼオライトとし、
さらにリン酸アンモニウムを作用させリン酸カルシウムで表面をコートし、前記ＬＴＡ型ゼオライト中にリン酸イオンを含んでいない抗菌性消臭剤。 After exchanging the sodium ion of the LTA type zeolite prepared from sodium hydroxide and sodium metasilicate with silver ion,
A portion of the silver ion exchanged calcium ions, Ca ions β sites, alpha site Ca ions and Ag ions, is Ag ions contained in the γ site, Ca ion is greater LTA type of Ag ions of the alpha site Zeolite,
Furthermore, an antibacterial deodorant which does not contain phosphate ions in the LTA-type zeolite, wherein the surface is coated with calcium phosphate by the action of ammonium phosphate .
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Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS60178810A (en) * | 1984-02-23 | 1985-09-12 | Kanebo Ltd | Deodorizing cosmetic |
| JP2598956B2 (en) * | 1988-04-07 | 1997-04-09 | 品川燃料株式会社 | Antibacterial aluminosilicate |
| JP2567719B2 (en) * | 1990-05-14 | 1996-12-25 | 日本化学工業株式会社 | Antibacterial zeolite |
| JP2985973B2 (en) * | 1990-12-25 | 1999-12-06 | 日本化学工業株式会社 | Zeolite antibacterial agent and resin composition |
| JPH0826956A (en) * | 1994-07-19 | 1996-01-30 | Shinagawa Fuel Co Ltd | Deodorant cosmetic |
| JP3490605B2 (en) * | 1998-03-02 | 2004-01-26 | カネボウ株式会社 | Antibacterial zeolite composition |
| JP3705920B2 (en) * | 1998-03-02 | 2005-10-12 | カネボウ株式会社 | Antibacterial zeolite |
| JP2000169317A (en) * | 1998-12-08 | 2000-06-20 | Tokyo Aoki:Kk | Microbial deodorizer and its manufacture |
| WO2000038524A1 (en) * | 1998-12-25 | 2000-07-06 | Kao Corporation | Aluminosilicate antibacterial agents |
| JP4295029B2 (en) * | 2003-07-02 | 2009-07-15 | レンゴー株式会社 | Method for producing inorganic insoluble salt-hydrophilic polymer composite |
| JP2009209089A (en) * | 2008-03-04 | 2009-09-17 | Jgc Catalysts & Chemicals Ltd | Antibacterial deodorant |
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