JP2015193000A - Adsorbent and halitosis remover - Google Patents
Adsorbent and halitosis remover Download PDFInfo
- Publication number
- JP2015193000A JP2015193000A JP2015058802A JP2015058802A JP2015193000A JP 2015193000 A JP2015193000 A JP 2015193000A JP 2015058802 A JP2015058802 A JP 2015058802A JP 2015058802 A JP2015058802 A JP 2015058802A JP 2015193000 A JP2015193000 A JP 2015193000A
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- Prior art keywords
- hydrotalcite
- hydrogen sulfide
- carbonate
- type
- 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.)
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 27
- 206010006326 Breath odour Diseases 0.000 title claims abstract description 12
- 208000032139 Halitosis Diseases 0.000 title abstract 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 157
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 157
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 157
- 239000007791 liquid phase Substances 0.000 claims abstract description 29
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 56
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 56
- 239000007789 gas Substances 0.000 abstract description 29
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 239000012071 phase Substances 0.000 abstract description 19
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000007796 conventional method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 71
- 239000011701 zinc Substances 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- 239000000460 chlorine Substances 0.000 description 27
- 229910052801 chlorine Inorganic materials 0.000 description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000011777 magnesium Substances 0.000 description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 18
- 238000007689 inspection Methods 0.000 description 18
- 229910021642 ultra pure water Inorganic materials 0.000 description 17
- 239000012498 ultrapure water Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- -1 hydrogen sulfide Chemical class 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000012670 alkaline solution Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 229910019089 Mg-Fe Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
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- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 210000003128 head Anatomy 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000000551 dentifrice Substances 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 210000000214 mouth Anatomy 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QWCKCWSBAUZZLF-UHFFFAOYSA-L zinc sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O QWCKCWSBAUZZLF-UHFFFAOYSA-L 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 241000605986 Fusobacterium nucleatum Species 0.000 description 1
- BIVBRWYINDPWKA-VLQRKCJKSA-L Glycyrrhizinate dipotassium Chemical compound [K+].[K+].O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@H]1CC[C@]2(C)[C@H]3C(=O)C=C4[C@@H]5C[C@](C)(CC[C@@]5(CC[C@@]4(C)[C@]3(C)CC[C@H]2C1(C)C)C)C(O)=O)C([O-])=O)[C@@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O BIVBRWYINDPWKA-VLQRKCJKSA-L 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 235000012711 vitamin K3 Nutrition 0.000 description 1
- 239000011652 vitamin K3 Substances 0.000 description 1
- 229940041603 vitamin k 3 Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- Cosmetics (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は揮発性硫黄化合物、特に硫化水素をよく吸着する吸着剤に関わるものである。 The present invention relates to an adsorbent that adsorbs volatile sulfur compounds, particularly hydrogen sulfide, well.
ハイドロタルサイトは、アニオン交換機能を有する層状複水酸化物で一般式は、(1)式のように表される。
[Mm 2+Mn 3+(OH)2m+2n]Xn/z Z− bH2O (1)
Hydrotalcite is a layered double hydroxide having an anion exchange function, and the general formula is represented by the formula (1).
[M m 2+ M n 3+ ( OH) 2m + 2n] X n / z Z- bH 2 O (1)
ここで、Mm 2+は、Mg、Ca、Sr、Cu、Ba、Zn、Cd、Pb、NiおよびSnから選択される少なくとも1つの2価の金属であり、Mn 3+はAl、Fe、Cr、Ga、Ni、Co、Fe、Mn、Cr、V、Ti、Inであり、m、nは実数であり、XZ−はZ価アニオンであり、bは実数である。 Here, M m 2+ is at least one divalent metal selected from Mg, Ca, Sr, Cu, Ba, Zn, Cd, Pb, Ni, and Sn, and M n 3+ is Al, Fe, Cr , Ga, Ni, Co, Fe, Mn, Cr, V, Ti, and In, m and n are real numbers, XZ− is a Z-valent anion, and b is a real number.
例えばMm 2+としてZnを選択した場合においても、ハイドロタルサイトは、さまざまな局面で吸着剤として利用されている。例えば特許文献1では、亜硝酸イオンを吸着させている。また、特許文献2では、硝酸イオンを吸着させている。 For example, even when Zn is selected as M m 2+ , hydrotalcite is used as an adsorbent in various aspects. For example, in Patent Document 1, nitrite ions are adsorbed. In Patent Document 2, nitrate ions are adsorbed.
また特許文献3では、銀を回収するために、ハイドロタルサイトに銀を吸着させている。また特許文献4では、フッ化水素を除去するために、ハイドロタルサイトにフッ化水素を吸着させている。 Moreover, in patent document 3, in order to collect | recover silver, silver is made to adsorb | suck to a hydrotalcite. Moreover, in patent document 4, in order to remove hydrogen fluoride, hydrogen fluoride is made to adsorb | suck to a hydrotalcite.
被吸着物質の中でも、硫黄化合物が主となる硫化水素やメチルメルカプタンといった悪臭原物質を吸着し消臭する要望は高い。特許文献5では、硫酸ヒドロキシルアミンと有機ヒドラジド化合物と、酸化亜鉛とスメクタイトの混合物にハイドロタルサイトを含有させたものが硫化水素に対する吸着性(消臭性)を有するという報告がされている。 Among the substances to be adsorbed, there is a high demand for adsorbing and deodorizing malodorous substances such as hydrogen sulfide and methyl mercaptan mainly composed of sulfur compounds. Patent Document 5 reports that a mixture of hydroxylamine sulfate, an organic hydrazide compound, and a mixture of zinc oxide and smectite containing hydrotalcite has an adsorptivity (deodorant) to hydrogen sulfide.
また、口臭除去剤として、液相中の揮発性硫黄化合物(VSC:Volatile Sulfer Compounds)をハイドロタルサイトに吸着させるという発明がある(特許文献6参照)。ここでは、Mm 2+としてMgが選ばれた例が開示されている。 In addition, as a bad breath remover, there is an invention in which a volatile sulfur compound (VSC: Volatile Sulfur Compounds) in a liquid phase is adsorbed on hydrotalcite (see Patent Document 6). Here, an example in which Mg is selected as M m 2+ is disclosed.
特許文献1乃至5を参照すると、硫化水素等の揮発性硫黄化合物は、吸着剤(結果として消臭剤ともいえる。)の需要があるが、吸着性の高いものは得られていないという現状がある。 Referring to Patent Documents 1 to 5, volatile sulfur compounds such as hydrogen sulfide are in demand for adsorbents (and can be said to be deodorants as a result), but the present situation is that high adsorbents have not been obtained. is there.
一方特許文献6では、水中の揮発性硫黄化合物をよく吸着するハイドロタルサイトが紹介されている。しかし、これはハイドロタルサイトを合成した後、さらに加熱したハイドロタルサイト[Mg2+ 1−x+Al3+ x(OH)2][CO3 2− X/2]である。したがって、この材料は湿気を含む雰囲気や水分中で、徐々にその効果を失っていくという課題があった。また、層構造を解消させるために500℃という高温での熱処理が必要であるという課題もあった。 On the other hand, Patent Document 6 introduces a hydrotalcite that adsorbs volatile sulfur compounds in water well. However, this is hydrotalcite [Mg 2+ 1-x + Al 3 + x (OH) 2 ] [CO 3 2 −X / 2 ] which is further heated after the synthesis of hydrotalcite. Therefore, this material has a problem of gradually losing its effect in an atmosphere or moisture containing moisture. There is also a problem that heat treatment at a high temperature of 500 ° C. is necessary to eliminate the layer structure.
本発明は上記の課題に鑑みて想到されたものであり、合成後に高温での熱処理を必要とせず、しかも水中に保持しておいても、揮発性硫黄化合物の吸着能を維持できる吸着剤を提供するものである。 The present invention has been conceived in view of the above problems, and an adsorbent that does not require heat treatment at a high temperature after synthesis and can maintain the adsorption ability of a volatile sulfur compound even when kept in water. It is to provide.
より具体的に本発明に係る吸着剤は、(2)式の構造を有するハイドロタルサイトを含有することを特徴とする。
[Zn2+ 1−x+Al3+ x(OH)2][CO3 2− X/2・mH2O] (2)
ここで1<x<1であり、mはゼロより大きな整数である。
More specifically, the adsorbent according to the present invention is characterized by containing hydrotalcite having the structure of the formula (2).
[Zn 2+ 1-x + Al 3+ x (OH) 2 ] [CO 3 2− X / 2 · mH 2 O] (2)
Here, 1 <x <1, and m is an integer greater than zero.
また、(3)式および(4)式の構造を有するハイドロタルサイトを含有することを特徴とする。
[Mg2+ 1−x+Fe3+ x(OH)2][CO3 2− X/2・mH2O] (3)
[Mg2+ 1−x+Fe3+ x(OH)2][Cl− X・mH2O] (4)
以後、(2)式、(3)式、(4)式のそれぞれのハイドロタルサイトを「Znハイドロタルサイト」、「炭酸型Feハイドロタルサイト」、「塩素型Feハイドロタルサイト」と呼ぶ。
Moreover, the hydrotalcite which has a structure of (3) Formula and (4) Formula is contained, It is characterized by the above-mentioned.
[Mg 2+ 1-x + Fe 3+ x (OH) 2 ] [CO 3 2− X / 2 · mH 2 O] (3)
[Mg 2+ 1-x + Fe 3+ x (OH) 2] [Cl - X · mH 2 O] (4)
Hereinafter, the hydrotalcites of the formulas (2), (3), and (4) are referred to as “Zn hydrotalcite”, “carbonated Fe hydrotalcite”, and “chlorine type Fe hydrotalcite”.
本発明に係るハイドロタルサイトは、揮発性硫黄化合物の吸着能を発揮させるのに、加熱処理を行う必要がない。また、水中に保持しておいても、揮発性硫黄化合物の吸着能が低下しない。例えば、口腔内のように液相若しくは高湿気相環境に保持しておいても、長時間に渡って揮発性硫黄化合物を吸着するので、口臭予防に効果的であるという効果を奏する。 The hydrotalcite according to the present invention does not need to be subjected to heat treatment in order to exhibit the adsorption ability of volatile sulfur compounds. Moreover, even if it hold | maintains in water, the adsorption capacity of a volatile sulfur compound does not fall. For example, even if it is kept in a liquid phase or a high-humidity gas phase environment as in the oral cavity, the volatile sulfur compound is adsorbed over a long period of time, so that it is effective in preventing bad breath.
また、気相若しくは液相であれば、口腔内に限定されるものではなく、トイレ、ゴミ箱といった場所での揮発性硫黄化合物の吸着(結果として消臭)が可能である。 Moreover, if it is a gaseous phase or a liquid phase, it will not be limited to an intraoral area, but adsorption | suction (as a result of deodorizing) of a volatile sulfur compound in places, such as a toilet and a trash can, is possible.
以下に本発明に係るZnハイドロタルサイトの製造方法について、図面を参照しながら説明を行う。なお、以下の説明は本発明の一実施形態を示すものであり、本発明の趣旨を逸脱しない限りにおいて、以下の説明は改変することができる。 Below, the manufacturing method of Zn hydrotalcite concerning the present invention is explained, referring to drawings. The following description shows one embodiment of the present invention, and the following description can be modified without departing from the gist of the present invention.
Znハイドロタルサイトは、他のハイドロタルサイトと同様の方法で作製することができる。すなわち、2価の亜鉛を塩水溶液として用意する。また3価のアルミニウムも塩水溶液として用意する。これらはホスト層の原料となる。そしてこれらの塩水溶液に、アルカリ溶液を加え共沈させることでZnハイドロタルサイトを得ることができる。この時加えるアルカリ溶液によってゲスト層の元素が決まる。 Zn hydrotalcite can be produced in the same manner as other hydrotalcites. That is, divalent zinc is prepared as an aqueous salt solution. Trivalent aluminum is also prepared as an aqueous salt solution. These are the raw materials for the host layer. Then, Zn hydrotalcite can be obtained by coprecipitation by adding an alkaline solution to these salt aqueous solutions. The element of the guest layer is determined by the alkaline solution added at this time.
亜鉛の塩水溶液としては、硝酸亜鉛、硫酸亜鉛、リン酸亜鉛、炭酸亜鉛などが好適に利用できる。またアルミニウムの塩水溶液も硝酸アルミニウム、硫酸アルミニウム、リン酸アルミニウム等が好適に利用することができる。特に硝酸亜鉛は好適に利用することができる。 As the zinc salt aqueous solution, zinc nitrate, zinc sulfate, zinc phosphate, zinc carbonate and the like can be suitably used. Also, aluminum nitrate, aluminum sulfate, aluminum phosphate and the like can be suitably used as the aqueous salt solution of aluminum. In particular, zinc nitrate can be preferably used.
また、アルカリ溶液は、炭酸が含まれるものが好適に利用することができる。炭酸塩水溶液としては、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸バリウム、炭酸マグネシウム、炭酸リチウム、炭酸アンモニウム等、およびその混合物(ドロマイト等であってもよい。)が利用できる。特に炭酸ナトリウムは好適に利用することができる。 In addition, an alkaline solution containing carbonic acid can be suitably used. Examples of the carbonate aqueous solution that can be used include sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, ammonium carbonate, and mixtures thereof (may be dolomite). In particular, sodium carbonate can be suitably used.
これらの溶液は混合され反応させる。反応は攪拌若しくは加熱といった方法を用いてよい。反応によって生成した生成物は、熱処理が施される。熱は100℃乃至400℃で、4乃至10時間程度の温度で処理してZnハイドロタルサイトを得る。 These solutions are mixed and reacted. For the reaction, a method such as stirring or heating may be used. The product produced by the reaction is subjected to a heat treatment. The heat is 100 ° C. to 400 ° C. and the temperature is about 4 to 10 hours to obtain Zn hydrotalcite.
また、本発明に係る吸着剤に用いるZnハイドロタルサイトは、熱処理を施さなくてもよい。通常ハイドロタルサイトは、反応生成後に熱処理をすることで、無水物となり、吸着能を発揮する。しかし、本発明に係る吸着剤に用いるZnハイドロタルサイトは、熱処理を施さなくても、揮発性硫黄化合物の吸収能を有するからである。 Moreover, the Zn hydrotalcite used for the adsorbent according to the present invention may not be subjected to heat treatment. Usually, hydrotalcite becomes an anhydrate by heat treatment after the reaction is generated, and exhibits an adsorption ability. However, this is because the Zn hydrotalcite used in the adsorbent according to the present invention has the ability to absorb volatile sulfur compounds without being subjected to heat treatment.
また、本発明に係る炭酸型Feハイドロタルサイトおよび塩素型Feハイドロタルサイトも同様にして得ることができる。すなわち、2価のマグネシウムを塩水溶液として用意する。また、3価の鉄も塩水溶液として用意する。これらがホスト層の原料となる。そしてこれらの塩水溶液に、アルカリ溶液を加え共沈させる。この時加えるアルカリ溶液の種類によってゲスト層の元素が決まる。 Carbonic acid type Fe hydrotalcite and chlorine type Fe hydrotalcite according to the present invention can also be obtained in the same manner. That is, divalent magnesium is prepared as an aqueous salt solution. Trivalent iron is also prepared as an aqueous salt solution. These are the raw materials for the host layer. Then, an alkaline solution is added to these salt aqueous solutions to cause coprecipitation. The element of the guest layer is determined by the kind of the alkaline solution added at this time.
マグネシウムの塩水溶液としては、硝酸マグネシウム、硫酸マグネシウム、リン酸マグネシウム、炭酸マグネシウムなどが好適に利用できる。また、鉄の塩水溶液に硝酸鉄、硫酸鉄、リン酸鉄等が好適に利用できる。特にマグネシウムおよび鉄ともに硝酸塩は好適に利用できる。 As the magnesium salt aqueous solution, magnesium nitrate, magnesium sulfate, magnesium phosphate, magnesium carbonate and the like can be suitably used. Moreover, iron nitrate, iron sulfate, iron phosphate, etc. can be utilized suitably for the salt solution of iron. In particular, nitrates can be preferably used for both magnesium and iron.
また、アルカリ溶液としては、炭酸が含まれるものが利用できる。しかし、反応液中のpHがアルカリになっていればよく、水酸化ナトリウム等の強アルカリ溶液でpHを調整しながら調製してもよい。炭酸型Feハイドロタルサイトでは、アルカリ溶液として炭酸ナトリウム等が好適に利用できる。 Moreover, as an alkaline solution, what contains carbonic acid can be utilized. However, it is sufficient that the pH in the reaction solution is alkaline, and the reaction solution may be prepared while adjusting the pH with a strong alkali solution such as sodium hydroxide. In carbonated Fe hydrotalcite, sodium carbonate or the like can be suitably used as the alkaline solution.
また、塩素型Feハイドロタルサイトでは、水酸化ナトリウムを加えながら塩化ナトリウム溶液を加える。共沈はアルカリ側で安定して得ることができるからである。 In the case of chlorine type Fe hydrotalcite, a sodium chloride solution is added while adding sodium hydroxide. This is because coprecipitation can be stably obtained on the alkali side.
本発明に係るハイドロタルサイトはVOCの吸着能を有するため、口臭除去剤に添加してもよい。口臭除去剤は、モノグリセリドなどを主剤とし、ポリオール等の添加剤と、口臭除去剤を含むものである。 Since the hydrotalcite according to the present invention has the ability to adsorb VOC, it may be added to the bad breath remover. The bad breath remover is mainly composed of monoglyceride and the like, and contains an additive such as polyol and a bad breath remover.
また、本発明に係る口臭除去剤は、錬歯磨剤、口腔咽頭薬を含んでよい。錬歯磨剤は、リン酸水素カルシウム、炭酸カルシウム、水酸化アルミニウムといった研磨剤と、ラウロイルサルコシソーダ、ラウリル硫酸ナトリウム、ショ糖脂肪酸エステル等の発泡剤と、ソルビトール、グリセリン、プロピレングリコールなどの保湿剤、アルギン酸などの結合剤と共に本発明のハイドロタルサイトを含めてよい。 Moreover, the bad breath removing agent according to the present invention may include a dentifrice and an oropharyngeal drug. Dentifrices include abrasives such as calcium hydrogen phosphate, calcium carbonate, and aluminum hydroxide, foaming agents such as lauroyl sarcosoda, sodium lauryl sulfate, and sucrose fatty acid esters, and humectants such as sorbitol, glycerin, and propylene glycol The hydrotalcite of the present invention may be included with a binder such as alginic acid.
また、口腔咽頭薬は、セチルピリジニウム塩化物水和物、グリチルリチン酸ニカリウム、キキョウエキスといった成分が含まれている。本発明の吸着剤は、これらの成分とともに口頭咽薬に含めることができる。 In addition, the oropharyngeal drug contains components such as cetylpyridinium chloride hydrate, dipotassium glycyrrhizinate, and a red pepper extract. The adsorbent of the present invention can be included in an oropharyngeal drug along with these components.
次に生成物の特性の測定方法を説明する。生成物の揮発性硫黄化合物の吸着能(吸着性)については、液相および液相に接している気相中の硫化水素の吸着能について測定を行った。図1には、吸着能を測定する検査装置1を示す。検査装置1は、市販の200mLガラスフラスコ2にネジ付側管を取り付け、側管にセプタム付ホールキャップ6を取り付けている。また、ガラスフラスコ2の口には、シリコン栓を介してコック付分液漏斗3を取り付けた。セプタム付ホールキャップ6からは、シリンジ5の針をガラスフラスコ2内に浸入させ、内部の気体もしくは液体を抽出することができる。なお、検査装置1内には、攪拌子を入れてある。この検査装置1は以下のようにして用いた。 Next, a method for measuring the characteristics of the product will be described. About the adsorption capacity (adsorbability) of the volatile sulfur compound of the product, the adsorption capacity of hydrogen sulfide in the gas phase in contact with the liquid phase and the liquid phase was measured. FIG. 1 shows an inspection apparatus 1 that measures adsorption capacity. The inspection apparatus 1 has a threaded side tube attached to a commercially available 200 mL glass flask 2 and a septum-attached hole cap 6 attached to the side tube. Moreover, the separatory funnel 3 with a cock was attached to the opening | mouth of the glass flask 2 through the silicone stopper. From the hole cap 6 with a septum, the needle of the syringe 5 can enter the glass flask 2 to extract the internal gas or liquid. Note that a stirring bar is placed in the inspection apparatus 1. This inspection apparatus 1 was used as follows.
まず、ガラスフラスコ2には、硫化水素水溶液150mLを満たした(符号10)。硫化水素水溶液10の部分が液相部分であり、それに接するヘッドスペース11が気相部分である。硫化水素水は、硫化水素ガスをバブリングし、初期濃度が一定値になるように調整した。後述する実施例および比較例の試料毎に検査装置1を準備した。試料(実施例および比較例の吸着剤)各々所定量を検査装置1の硫化水素水溶液に導入し、1時間、2時間、3時間、4時間、6時間、18時間後の気相および液相のVSC濃度を調べた。なお、実施例によっては5時間目も測定を行った。 First, the glass flask 2 was filled with 150 mL of an aqueous hydrogen sulfide solution (reference numeral 10). The portion of the hydrogen sulfide aqueous solution 10 is a liquid phase portion, and the head space 11 in contact with it is a gas phase portion. Hydrogen sulfide water was adjusted so that hydrogen sulfide gas was bubbled and the initial concentration became a constant value. An inspection apparatus 1 was prepared for each sample of Examples and Comparative Examples described later. A predetermined amount of each of the samples (adsorbents of Examples and Comparative Examples) was introduced into the hydrogen sulfide aqueous solution of the inspection apparatus 1, and the gas phase and liquid phase after 1 hour, 2 hours, 3 hours, 4 hours, 6 hours and 18 hours The VSC concentration was examined. Depending on the example, the measurement was also performed for 5 hours.
VSC濃度は、ガラスフラスコ2内の気相(ヘッドスペース11)および液相(水溶液内)から、検査成分(気体若しくは液体)の所定量をシリンジ5で採取してFPD/GC(Flame Photometric Detection/Gas Chromatography)により硫化水素(H2S)を定量した。 The VSC concentration is obtained by sampling a predetermined amount of a test component (gas or liquid) from the gas phase (head space 11) and the liquid phase (in the aqueous solution) in the glass flask 2 with a syringe 5, and using FPD / GC (Frame Photometric Detection / Hydrogen sulfide (H 2 S) was quantified by Gas Chromatography.
<実施例1>
硫酸亜鉛六水和物(Zn(NO3)2・6H2O)の0.02molと、硝酸アルミニウム九水和物(Al(NO3)3・9H2O)の0.01molを超純水100mLに溶解し、金属塩水溶液とした。
<Example 1>
And 0.02mol of zinc sulfate hexahydrate (Zn (NO 3) 2 · 6H 2 O), ultrapure water 0.01mol of aluminum nitrate nonahydrate (Al (NO 3) 3 · 9H 2 O) It melt | dissolved in 100 mL and it was set as the metal salt aqueous solution.
炭酸ナトリウム(Na2CO3)の0.047molを超純水300mLに溶解し炭酸塩水溶液とした。この炭酸塩水溶液を70℃に保持し、攪拌しながら金属塩水溶液を加えた。さらに、0.05molのNaOHを純水100mLに溶解したものを、pHが10になるまで添加した。その後24時間撹拌熟成を行った。得られた生成物は、遠心分離し、洗浄液のpHが7.5程度になるまで洗浄した。その後80℃の温度で12時間乾燥処理し、Znハイドロタルサイトを得た。得られた生成物は、(2)式において、X=0.33となる。 0.047 mol of sodium carbonate (Na 2 CO 3 ) was dissolved in 300 mL of ultrapure water to obtain a carbonate aqueous solution. This carbonate aqueous solution was kept at 70 ° C., and the metal salt aqueous solution was added while stirring. Further, 0.05 mol of NaOH dissolved in 100 mL of pure water was added until the pH reached 10. Thereafter, the mixture was aged and stirred for 24 hours. The obtained product was centrifuged and washed until the pH of the washing solution reached about 7.5. Thereafter, it was dried at a temperature of 80 ° C. for 12 hours to obtain Zn hydrotalcite. The obtained product is X = 0.33 in the formula (2).
なお、Znハイドロタルサイトをさらに500℃2時間の熱処理を行ったサンプルを作製した。これをZnハイドロタルサイト500と呼ぶ。 In addition, a sample in which the Zn hydrotalcite was further heat-treated at 500 ° C. for 2 hours was produced. This is called Zn hydrotalcite 500.
<比較例1>
実施例1の硫酸亜鉛六水和物を硝酸マグネシウム六水和物(Mg(NO3)2・6H2O)とした以外は、実施例1と同じ材料および手順を繰り返し、ハイドロタルサイトを得た。これをMgハイドロタルサイトと呼ぶ。Mgハイドロタルサイトを500℃2時間の温度処理を行った。このサンプルをMgハイドロタルサイト500と呼ぶ。
<Comparative Example 1>
The same materials and procedures as in Example 1 were repeated except that the zinc sulfate hexahydrate of Example 1 was changed to magnesium nitrate hexahydrate (Mg (NO 3 ) 2 .6H 2 O) to obtain hydrotalcite. It was. This is called Mg hydrotalcite. The Mg hydrotalcite was temperature-treated at 500 ° C. for 2 hours. This sample is referred to as Mg hydrotalcite 500.
<比較例2>
超純水に炭酸ナトリウム(Na2CO3)を溶解し、次いで硝酸アルミニウム九水和物(Al(NO3)3・9H2O)と硝酸マグネシウム六水和物(Mg(NO3)2・6H2O)を溶解して作製した水溶液を、pH10に保持しながら滴下した。組成式Mg1−xAlx(OH)2An− x/n・nH2Oにおいてx=0.33(実施例1および比較例1と同じ)となるように調整した。
<Comparative Example 2>
It was dissolved sodium carbonate (Na 2 CO 3) in ultrapure water, and then aluminum nitrate nonahydrate (Al (NO 3) 3 · 9H 2 O) and magnesium nitrate hexahydrate (Mg (NO 3) 2 · An aqueous solution prepared by dissolving 6H 2 O) was added dropwise while maintaining the pH at 10. Composition formula Mg 1-x Al x (OH ) 2 A n- x / n · nH x = 0.33 in 2 O was adjusted to (the same as in Example 1 and Comparative Example 1).
70℃で24時間攪拌して得られた沈殿をろ別し、超純水で洗浄、80℃で12時間処理し試料を得た。この試料をMg33ハイドロタルサイト(「Mg33HT」とも記載する)と呼ぶ。また、Mg33ハイドロタルサイトをさらに500℃で30分熱処理を行った。このサンプルをMg33ハイドロタルサイト500(「Mg33HT500」とも記載する)と呼ぶ。 A precipitate obtained by stirring at 70 ° C. for 24 hours was filtered off, washed with ultrapure water, and treated at 80 ° C. for 12 hours to obtain a sample. This sample is referred to as Mg33 hydrotalcite (also referred to as “Mg33HT”). Further, the Mg33 hydrotalcite was further heat-treated at 500 ° C. for 30 minutes. This sample is referred to as Mg33 hydrotalcite 500 (also referred to as “Mg33HT500”).
図2には、試料としてMg33ハイドロタルサイトを入れた場合の検査装置1内の硫化水素濃度(μmol)の時間変化を示す。縦軸は硫化水素濃度(H2S濃度(μmol)と記した)であり、横軸は時間(hr)である。液相(A)の硫化水素濃度は初期(0時間)から2乃至4時間までは上昇傾向を示し、その後、緩やかな減少傾向を示した。 In FIG. 2, the time change of the hydrogen sulfide concentration (micromol) in the test | inspection apparatus 1 at the time of putting Mg33 hydrotalcite as a sample is shown. The vertical axis represents hydrogen sulfide concentration (denoted as H 2 S concentration (μmol)), and the horizontal axis represents time (hr). The hydrogen sulfide concentration in the liquid phase (A) showed an increasing tendency from the initial stage (0 hour) to 2 to 4 hours, and thereafter showed a gradual decreasing tendency.
一方、気相(B)では、試料投入後1時間でほぼ検出限界以下の濃度になった。すなわち、Mg33ハイドロタルサイトは、水溶液中の硫化水素を吸収することはできなかったが、硫化水素が溶解している水溶液に接している気相中の硫化水素を吸収した。 On the other hand, in the gas phase (B), the concentration was almost below the detection limit in 1 hour after the sample was charged. That is, Mg33 hydrotalcite could not absorb hydrogen sulfide in the aqueous solution, but absorbed hydrogen sulfide in the gas phase in contact with the aqueous solution in which hydrogen sulfide was dissolved.
図3には、Mg33ハイドロタルサイト500を入れた場合の検査装置内の硫化水素濃度(μmol)の時間変化を示す。縦軸は硫化水素濃度(H2S濃度(μmol)と記した)であり、横軸は時間(hr)である。液相(A)の硫化水素濃度は初期(0時間)から1時間までは上昇傾向を示し、その後、減少傾向を示した。 In FIG. 3, the time change of the hydrogen sulfide density | concentration (micromol) in a test | inspection apparatus at the time of putting Mg33 hydrotalcite 500 is shown. The vertical axis represents hydrogen sulfide concentration (denoted as H 2 S concentration (μmol)), and the horizontal axis represents time (hr). The hydrogen sulfide concentration in the liquid phase (A) showed an increasing tendency from the initial stage (0 hour) to 1 hour, and thereafter showed a decreasing tendency.
さらに、18時間後には液相(A)の硫化水素濃度は15%にまで減少した。また、気相(B)では、Mg33ハイドロタルサイトと同様に、試料投入後1時間でほぼ検出限界以下の濃度になった。 Furthermore, after 18 hours, the hydrogen sulfide concentration in the liquid phase (A) decreased to 15%. Further, in the gas phase (B), as in the case of Mg33 hydrotalcite, the concentration was almost below the detection limit in 1 hour after the sample was charged.
すなわち、Mg33ハイドロタルサイト500は、水溶液(液相)中の硫化水素を吸収し、なおかつ、硫化水素が溶解している水溶液に接している気相中の硫化水素をも吸収することができた。 That is, the Mg33 hydrotalcite 500 was able to absorb hydrogen sulfide in the aqueous solution (liquid phase) and also absorb hydrogen sulfide in the gas phase in contact with the aqueous solution in which hydrogen sulfide was dissolved. .
図4には、Mg33ハイドロタルサイト500のX線回折を調べた結果を示す。縦軸は強度(Intensity)(任意単位)であり、横軸は2θ(度)である。線源はCoのKαを用いた。図4には、3つの回折結果を示した。(a)は合成直後のMg33ハイドロタルサイト(図4中で「MG33HDT」と記した。)の回折結果である。 In FIG. 4, the result of having investigated the X-ray diffraction of Mg33 hydrotalcite 500 is shown. The vertical axis represents intensity (arbitrary unit), and the horizontal axis represents 2θ (degrees). Co Kα was used as the radiation source. FIG. 4 shows three diffraction results. (A) is a diffraction result of Mg33 hydrotalcite (denoted as “MG33HDT” in FIG. 4) immediately after synthesis.
次に(b)はMg33ハイドロタルサイトを500℃、2時間の条件で熱処理した結果得たMg33ハイドロタルサイト500の回折結果である。(a)と(b)は明瞭にピークのパターンが変わっており、500℃の熱処理によってハイドロタルサイトの層状構造が変化したと考えられる。 Next, (b) is a diffraction result of Mg33 hydrotalcite 500 obtained as a result of heat-treating Mg33 hydrotalcite at 500 ° C. for 2 hours. In (a) and (b), the peak pattern clearly changed, and it is considered that the layered structure of hydrotalcite was changed by the heat treatment at 500 ° C.
一方、(c)は、図3で示した吸収実験後のMg33ハイドロタルサイト500のX線回折結果である。これは(a)で示した合成直後のMg33ハイドロタルサイトと同じ回折結果を得た。 On the other hand, (c) is an X-ray diffraction result of the Mg33 hydrotalcite 500 after the absorption experiment shown in FIG. This gave the same diffraction results as the Mg33 hydrotalcite immediately after synthesis shown in (a).
以上の結果より、500℃で熱処理したMg33ハイドロタルサイト500は層状構造が変化し、液相に投入された後、層状構造を再構成する。そこで、図2に示すように液相中および気相中の硫化水素が吸収されていることを考慮すると、層状構造の再構成の際に、層状構造の間に硫化水素をインターカーレーションすることで取り込んでいると考えられる。言い換えると、Mg33ハイドロタルサイトでは、水分によって吸着能が劣化すると言える。 From the above results, the Mg33 hydrotalcite 500 heat-treated at 500 ° C. changes its layered structure, and after being put into the liquid phase, restructures the layered structure. Therefore, considering that hydrogen sulfide in the liquid phase and gas phase is absorbed as shown in FIG. 2, intercalation of hydrogen sulfide between the layered structures is performed when the layered structure is reconfigured. It is thought that it is taken in. In other words, in Mg33 hydrotalcite, it can be said that the adsorptive capacity deteriorates due to moisture.
図5は、Mgハイドロタルサイト500(比較例1)とZnハイドロタルサイト500の吸着能の比較を示す図である。横軸は時間(hr)であり、縦軸は硫化水素濃度の変化(%)である。ここで縦軸は液相および気相の硫化水素を合わせた濃度変化を表す。黒丸は試料を入れていない場合の変化であり、黒菱形は試料をMg33ハイドロタルサイト500(図中「Mg33HDT500」と記載した。)にした場合の変化であり、黒三角は試料をZnハイドロタルサイト500(図中「ZnHDT500」と記載した。)にした場合の変化を表す。 FIG. 5 is a diagram showing a comparison of the adsorption capacities of Mg hydrotalcite 500 (Comparative Example 1) and Zn hydrotalcite 500. The horizontal axis represents time (hr), and the vertical axis represents the change (%) in hydrogen sulfide concentration. Here, the vertical axis represents the concentration change of the liquid phase and gas phase hydrogen sulfide combined. The black circle is the change when the sample is not inserted, the black rhombus is the change when the sample is Mg33 hydrotalcite 500 (described as “Mg33HDT500” in the figure), and the black triangle is the Zn hydrotalcite. A change in the case of the site 500 (described as “ZnHDT500” in the drawing) is shown.
Mgハイドロタルサイト500(比較例1)は、図3のMg33ハイドロタルサイト500(比較例2)同様、液相中の硫化水素の吸収は気相ほど速やかに行われないと考えられる。一方、Znハイドロタルサイト500(実施例)は、Mgハイドロタルサイト500と比較して、液相および気相の硫化水素を急速に吸着できることがわかる。 It is considered that the Mg hydrotalcite 500 (Comparative Example 1) does not absorb hydrogen sulfide in the liquid phase as quickly as the gas phase, like the Mg33 hydrotalcite 500 (Comparative Example 2) in FIG. On the other hand, it can be seen that Zn hydrotalcite 500 (Example) can rapidly adsorb liquid and gas phase hydrogen sulfide as compared with Mg hydrotalcite 500.
図6には、ZnハイドロタルサイトとZnハイドロタルサイト500の吸着能の比較を示す。横軸は時間(hr)であり、縦軸は硫化水素濃度の変化(%)である。白四角は試料が無い場合の硫化水素濃度の時間変化を表す。Znハイドロタルサイト(図中「ZnHDT」と記載した。)は白菱形であり、またZnハイドロタルサイト500(図中「ZnHDT500」と記載した。)は黒三角で表した。図6からも明らかなように、ZnハイドロタルサイトとZnハイドロタルサイト500の吸着能は殆ど変らなかった。 FIG. 6 shows a comparison of the adsorption capacities of Zn hydrotalcite and Zn hydrotalcite 500. The horizontal axis represents time (hr), and the vertical axis represents the change (%) in hydrogen sulfide concentration. The white square represents the time change of the hydrogen sulfide concentration when there is no sample. Zn hydrotalcite (described as “ZnHDT” in the figure) is a white rhombus, and Zn hydrotalcite 500 (described as “ZnHDT500” in the figure) is represented by a black triangle. As is clear from FIG. 6, the adsorption capacity of Zn hydrotalcite and Zn hydrotalcite 500 was hardly changed.
図7には、Znハイドロタルサイト(「ZnHDT」と記した。)とZnハイドロタルサイト500(「ZnHDT500」と記した。)および吸着試験後のZnハイドロタルサイト500(「吸着後ZnHDT500」と記した。)のX線回折パターンを示す。 In FIG. 7, Zn hydrotalcite (denoted as “ZnHDT”), Zn hydrotalcite 500 (denoted as “ZnHDT500”), and Zn hydrotalcite 500 after the adsorption test (“ZnHDT500 after adsorption”) X-ray diffraction pattern of
横軸は2θ(度)であり、縦軸は強度(任意単位)である。500℃の熱処理によって、X線回折プロファイルが変化した。これよりZnハイドロタルサイト500は、Znハイドロタルサイトから層状構造が変化したといえる。しかし、吸着試験後はまた層状構造が再構成されていた。 The horizontal axis is 2θ (degrees), and the vertical axis is intensity (arbitrary unit). The heat treatment at 500 ° C. changed the X-ray diffraction profile. Accordingly, it can be said that the layer structure of the Zn hydrotalcite 500 is changed from that of the Zn hydrotalcite. However, after the adsorption test, the layered structure was reconstructed again.
これは、図4で示したMg33ハイドロタルサイトの場合と同じである。しかし、Mg33ハイドロタルサイトの場合と異なるのは、Znハイドロタルサイトは、層状構造が変化してしまっても、硫化水素の吸着能はほとんど変化しない(図6の結果より)点にある。つまり、Znハイドロタルサイトでは、層状構造の変化と再構成は硫化水素(H2S)の吸着とあまり関係がないといえる。 This is the same as the case of Mg33 hydrotalcite shown in FIG. However, the difference from the case of Mg33 hydrotalcite is that the adsorption capacity of hydrogen sulfide hardly changes even if the layered structure of Zn hydrotalcite changes (from the result of FIG. 6). That is, in Zn hydrotalcite, it can be said that the change in the layered structure and the reconstruction are not so much related to the adsorption of hydrogen sulfide (H 2 S).
言い換えるとZnハイドロタルサイトは、水分によって吸着能が変化しない。したがって、Znハイドロタルサイトを含む吸着剤は、湿気を含む環境に放置してもその吸着性能は変わることがなく、また、悪臭元の硫化水素を急速に吸収し、消臭することができる。また、この吸着剤は、液相、気相を選ばず、悪臭のある部分に粉末状のZnハイドロタルサイトを振りかけてしまえば消臭できるので、非常に使いやすい。 In other words, the adsorption capacity of Zn hydrotalcite is not changed by moisture. Therefore, the adsorption performance of the adsorbent containing Zn hydrotalcite does not change even if it is left in an environment containing moisture, and can quickly absorb and deodorize hydrogen odor source. Also, this adsorbent is very easy to use because it can be deodorized by sprinkling powdered Zn hydrotalcite on a malodorous part, regardless of liquid phase or gas phase.
また、予め液相中にZnハイドロタルサイトを含有させておき、液相ごと悪臭のある部分に投入してもよい。つまり、口臭除去剤や錬歯磨剤、口腔咽頭薬中に含有させておくことで、口腔内の揮発性硫黄化合物を除去することができる。 Moreover, Zn hydrotalcite may be previously contained in the liquid phase, and the whole liquid phase may be added to a portion having a bad odor. That is, the volatile sulfur compound in the oral cavity can be removed by containing it in the bad breath remover, dentifrice, oropharyngeal drug.
なお、以上の実験では、硫化水素水溶液の初期濃度は30ppmであり、検査装置1に導入した試料は0.2gである。また、液相および気相とも0.2gずつサンプリングし濃度測定を行った。 In the above experiment, the initial concentration of the aqueous hydrogen sulfide solution is 30 ppm, and the sample introduced into the inspection apparatus 1 is 0.2 g. Also, the concentration was measured by sampling 0.2 g each for the liquid phase and the gas phase.
<実施例1−1>
次にZnハイドロタルサイトのより具体的な効果を歯周病関連菌を用いて確認した。使用した供試細菌は、F.nucleatum(ATCC25586)である。この菌種は硫化水素を産生することが確認されている。
<Example 1-1>
Next, more specific effects of Zn hydrotalcite were confirmed using periodontal disease-related bacteria. The test bacteria used were F. nucleatum (ATCC 25586). This species has been confirmed to produce hydrogen sulfide.
供試細菌を以下のようにして培養した。0.5%酵母エキス、5μg/mLヘミン、0.5μg/mLメナジオンを含むBrain Heart Infusion培地(BHI培地、BD、東京)を用い、48時間嫌気培養した培養菌液2mLを、含硫アミノ酸である0.05%L−システインを添加し、あらかじめ1日嫌気状態にしておいた40mLの培地に供試細菌を接種した。 The test bacteria were cultured as follows. Using Brain Heart Infusion medium (BHI medium, BD, Tokyo) containing 0.5% yeast extract, 5 μg / mL hemin, and 0.5 μg / mL menadione, 2 mL of cultured bacterial solution was anaerobically cultured for 48 hours with sulfur-containing amino acids. A certain amount of 0.05% L-cysteine was added, and the test bacteria were inoculated into 40 mL of a medium that had been anaerobic for 1 day.
アシストチューブ(アシスト、東京)に培養した菌液を2mLずつ分注し、37℃で嫌気培養を行った。熱処理を行っていないMg33ハイドロタルサイト(Mg33HDT)、500℃で加熱処理したMg33ハイドロタルサイト(Mg33HDT500)、そしてZnハイドロタルサイト(ZnHDT)をそれぞれ0.01g加えたものと「吸着材なし」の4種類を作製した。 2 mL each of the bacterial solution cultured in the assist tube (Assist, Tokyo) was dispensed, and anaerobic culture was performed at 37 ° C. Mg33 hydrotalcite (Mg33HDT) without heat treatment, Mg33 hydrotalcite (Mg33HDT500) heat-treated at 500 ° C., and 0.01 g of Zn hydrotalcite (ZnHDT) and “no adsorbent” Four types were produced.
Mgハイドロタルサイト500は、事前に電気炉にて500℃で30分熱処理を行った。また、細菌の産生物質が外気に逃げるのを防ぐためにシリコンゴムをアシストチューブに被せた。硫化水素の測定の際には、アシストチューブ内の気体をガスタイトシリンジにて3mL採取し、直ちにガスクロマトグラフに注入し、硫化水素のピーク面積を算出した。測定時間は2時間おきに8時間行い、合計2回実施した。8時間経過後の計測結果を表1に示す。 The Mg hydrotalcite 500 was previously heat-treated at 500 ° C. for 30 minutes in an electric furnace. In addition, in order to prevent bacterial product from escaping to the outside air, silicon rubber was put on the assist tube. When measuring hydrogen sulfide, 3 mL of gas in the assist tube was collected with a gas tight syringe and immediately injected into a gas chromatograph, and the peak area of hydrogen sulfide was calculated. Measurement time was performed every 2 hours for 8 hours, and was performed twice in total. Table 1 shows the measurement results after 8 hours.
実際の細菌では、硫化水素の産生量が菌株のロットによって異なる。したがって1回と2回の硫化水素量は異なる(「吸着材なし」を参照)。しかし、Znハイドロタルサイトは、いずれの実験においても最も硫化水素の発生を抑えた結果となった。 In actual bacteria, the amount of hydrogen sulfide produced varies depending on the lot of the strain. Therefore, the amount of hydrogen sulfide is different between the first time and the second time (see “No adsorbent”). However, Zn hydrotalcite has the result of suppressing the generation of hydrogen sulfide most in any experiment.
<実施例2>
以下の手順の共沈法により炭酸型Feハイドロタルサイトを作製した。超純水167mLに炭酸ナトリウム(和光純薬工業、容量分析用標準物質)8.83gを溶解させ、炭酸ナトリウム溶液を調製した。また超純水100mLに水酸化ナトリウム(和光純薬工業、特級)8.00gを溶解させ、水酸化ナトリウム溶液、及び超純水83mLに硝酸鉄(III)九水和物(和光純薬工業、特級)8.42gと硝酸マグネシウム六水和物(和光純薬工業、特級)16.03gを溶解させた硝酸塩の混合溶液をそれぞれ調製した。鉄とマグネシウムがホスト層の原料となる。
<Example 2>
Carbonated Fe hydrotalcite was prepared by the coprecipitation method of the following procedure. To 167 mL of ultrapure water, 8.83 g of sodium carbonate (Wako Pure Chemical Industries, volumetric analysis standard substance) was dissolved to prepare a sodium carbonate solution. Moreover, 8.00 g of sodium hydroxide (Wako Pure Chemical Industries, special grade) is dissolved in 100 mL of ultrapure water, and iron nitrate (III) nonahydrate (Wako Pure Chemical Industries, Ltd.) is dissolved in 83 mL of sodium hydroxide solution and ultrapure water. A mixed solution of nitrate in which 8.42 g of special grade and 16.03 g of magnesium nitrate hexahydrate (Wako Pure Chemical Industries, special grade) were dissolved was prepared. Iron and magnesium are the raw materials for the host layer.
炭酸ナトリウム溶液をホットスターラー(ASONE、REXIM RSH−10)で4cmの攪拌子を用いて室温で800rpmで攪拌しながら、硝酸塩の混合溶液をビュレットを用い炭酸ナトリウム溶液に10mm±0.5/minの速度で滴下した。炭酸はゲスト層の原料となる。 While stirring the sodium carbonate solution with a hot stirrer (ASONE, REXIM RSH-10) using a 4 cm stirrer at 800 rpm at room temperature, the nitrate mixed solution was added to the sodium carbonate solution at 10 mm ± 0.5 / min using a burette. It was dripped at a speed. Carbonic acid is a raw material for the guest layer.
炭酸ナトリウム溶液は初期pHが11.7であったが、硝酸塩の混合溶液滴下により直ちに酸化されるため、pHメーターで溶液のpHが10.5±0.2になるよう、水酸化ナトリウム溶液を加えた。 Although the initial pH of the sodium carbonate solution was 11.7, it was immediately oxidized by the dropwise addition of the nitrate mixed solution, so the sodium hydroxide solution was adjusted so that the pH of the solution would be 10.5 ± 0.2 with a pH meter. added.
この溶液を40℃で24h、800rpmで攪拌させ、得られた溶液を吸引ろ過により固液分離し、超純水200mLで3回洗浄した。得られた生成物を80℃で18時間乾燥させた後、乳鉢で解砕し、炭酸型Feハイドロタルサイト(炭酸型Mg−Fe系LDHとも言う。)を得た。なお、炭酸型Feハイドロタルサイトは、(3)式の組成式では、An−=CO3 2−、x=0.33である。 This solution was stirred at 800 rpm for 24 h at 40 ° C., and the resulting solution was subjected to solid-liquid separation by suction filtration and washed three times with 200 mL of ultrapure water. The obtained product was dried at 80 ° C. for 18 hours and then crushed in a mortar to obtain carbonated Fe hydrotalcite (also referred to as carbonated Mg—Fe LDH). Note that the carbonate-type Fe hydrotalcite is A n− = CO 3 2− and x = 0.33 in the composition formula (3).
また、pH測定は、pHメーター(HORIBA、D−51)を用い、超純水は、超純水製造装置(Direct−Q、ミリポア製)から採取して実験に供した。 The pH was measured using a pH meter (HORIBA, D-51), and ultrapure water was collected from an ultrapure water production apparatus (Direct-Q, manufactured by Millipore) and used for experiments.
<実施例3>
以下の手順の共沈法により塩素型Feハイドロタルサイトを作製した。超純水1000mLを溶存している炭酸イオンを減らすために煮沸させた。その超純水167mLに塩化ナトリウム(和光純薬工業、特級)9.74gを溶解させ、塩化ナトリウム溶液を調製した。
<Example 3>
Chlorine-type Fe hydrotalcite was prepared by the coprecipitation method of the following procedure. In order to reduce the carbonate ion which dissolved 1000 mL of ultrapure water, it was boiled. 9.74 g of sodium chloride (Wako Pure Chemical Industries, special grade) was dissolved in 167 mL of the ultrapure water to prepare a sodium chloride solution.
また超純水150mLに水酸化ナトリウム(和光純薬工業、特級)12.00gを溶解させ、水酸化ナトリウム溶液、及び超純水83mLに硝酸鉄(III)九水和物(和光純薬工業、特級)8.42gと硝酸マグネシウム六水和物(和光純薬工業、特級)16.03gを溶解させた硝酸塩の混合溶液をそれぞれ調製した。鉄とマグネシウムがホスト層となる。 Further, 12.00 g of sodium hydroxide (Wako Pure Chemical Industries, special grade) is dissolved in 150 mL of ultrapure water, and iron (III) nitrate nonahydrate (Wako Pure Chemical Industries, Ltd.) is dissolved in 83 mL of sodium hydroxide solution and ultrapure water. A mixed solution of nitrate in which 8.42 g of special grade and 16.03 g of magnesium nitrate hexahydrate (Wako Pure Chemical Industries, special grade) were dissolved was prepared. Iron and magnesium are the host layer.
炭酸ナトリウム溶液をホットスターラーで、4cmの攪拌子を用いて室温で800rpmで攪拌しながら、硝酸塩の混合溶液をビュレットを用い塩化ナトリウム溶液に10±0.5mm/minの速度で滴下した。 While stirring the sodium carbonate solution with a hot stirrer at 800 rpm at room temperature using a 4 cm stirrer, the mixed solution of nitrate was dropped into the sodium chloride solution at a rate of 10 ± 0.5 mm / min using a burette.
塩化ナトリウム溶液は初期pHが7.9であったので、水酸化ナトリウム溶液を入れpHが11.7になった後に硝酸塩の混合溶液を滴下し、pHメーターで溶液のpHが10.5±0.2になるよう、水酸化ナトリウム溶液を加えた。 Since the initial pH of the sodium chloride solution was 7.9, the mixed solution of nitrate was dropped after the sodium hydroxide solution was added and the pH reached 11.7, and the pH of the solution was adjusted to 10.5 ± 0 with a pH meter. The sodium hydroxide solution was added to reach .2.
この溶液を40℃で24h、800rpmで攪拌させ、得られた溶液を吸引ろ過により固液分離し、超純水200mLで3回洗浄した。得られた生成物を80℃で18時間乾燥させた後、乳鉢で解砕し、塩素型Feハイドロタルサイト(塩素型Mg−Fe系LDHとも言う。)を得た。なお、炭酸型Feハイドロタルサイトは、(4)式の組成式では、An−=Cl−、x=0.33である。 This solution was stirred at 800 rpm for 24 h at 40 ° C., and the resulting solution was subjected to solid-liquid separation by suction filtration and washed three times with 200 mL of ultrapure water. The obtained product was dried at 80 ° C. for 18 hours and then crushed in a mortar to obtain chlorine-type Fe hydrotalcite (also referred to as chlorine-type Mg—Fe-based LDH). Incidentally, carbonate type Fe hydrotalcite, (4) In the composition formula of formula, A n- = Cl -, is x = 0.33.
図8には、検査装置1中の液相中および気相中にある全硫化水素量の経時変化を示す。縦軸は全硫化水素量の変化(%)であり、横軸は時間(h)である。縦軸の100%は、試料投入前の検査装置1の溶液とヘッドスペースの硫化水素の合計濃度である。 FIG. 8 shows changes over time in the total amount of hydrogen sulfide in the liquid phase and gas phase in the inspection apparatus 1. The vertical axis represents the change (%) in the total hydrogen sulfide amount, and the horizontal axis represents time (h). 100% on the vertical axis is the total concentration of the solution of the inspection apparatus 1 and the hydrogen sulfide in the head space before the sample is charged.
なお、ここでは硫化水素水溶液を以下のようにして調製した。500mL四口フラスコの主管に分液漏斗、2つの側管をそれぞれシリコン栓、ガラス管付シリコン栓を取り付けた。また、200mLガラスフラスコに超純水を150mL入れ、ガラス管、円筒ガス噴射管をシリコン栓に通して取り付けた。四口フラスコのガラス管とガラスフラスコの円筒ガス噴射管をシリコンチューブと二方コックを介して接続した。 Here, an aqueous hydrogen sulfide solution was prepared as follows. A 500 mL four-necked flask was fitted with a separatory funnel, two side tubes each with a silicon stopper and a glass stopper with a glass tube. In addition, 150 mL of ultrapure water was placed in a 200 mL glass flask, and a glass tube and a cylindrical gas injection tube were attached through a silicon stopper. The glass tube of the four-neck flask and the cylindrical gas injection tube of the glass flask were connected to the silicon tube via a two-way cock.
さらに、ガラスフラスコのガラス管には、シリコンチューブを介して1mol/Lの水酸化ナトリウム水溶液を満たしたガス洗浄瓶に接続した。ガス洗浄瓶にはシリコンチューブを介して塩化カルシウム管を取り付けた。500mL四口フラスコに硫化鉄(FeS、和光純薬工業、硫化水素発生用)を3g入れ、次いで分液漏斗から硫酸(和光純薬工業、試薬特級)を希釈した濃度1mol/L希硫酸を15mL加え、フラスコ内で硫化水素を発生させた。発生した硫化水素をガラスフラスコ内の超純水に通し、約15分間バブリングさせた。 Furthermore, the glass tube of the glass flask was connected to a gas cleaning bottle filled with 1 mol / L sodium hydroxide aqueous solution through a silicon tube. A calcium chloride tube was attached to the gas cleaning bottle via a silicon tube. Add 3 g of iron sulfide (FeS, Wako Pure Chemical Industries, for hydrogen sulfide generation) to a 500 mL four-necked flask, and then dilute sulfuric acid (Wako Pure Chemical Industries, reagent grade) from a separatory funnel at a concentration of 1 mL / L dilute sulfuric acid. In addition, hydrogen sulfide was generated in the flask. The generated hydrogen sulfide was passed through ultrapure water in a glass flask and bubbled for about 15 minutes.
図8を参照して、白四角は吸着剤(炭酸型Feハイドロタルサイト若しくは塩素型Feハイドロタルサイト)が含まれていない場合である。バツ印は炭酸型Feハイドロタルサイト(図中「炭酸型FeHDT」と記した。)であり、黒菱形印は塩素型ハイドロタルサイト(図中「塩素型FeHDT」と記した。)を示す。 Referring to FIG. 8, white squares are cases where no adsorbent (carbonated Fe hydrotalcite or chlorine type Fe hydrotalcite) is contained. The cross mark indicates carbonate type Fe hydrotalcite (indicated as “carbonate type FeHDT” in the figure), and the black diamond mark indicates chlorine type hydrotalcite (indicated as “chlorine type FeHDT”).
炭酸型Feハイドロタルサイトも塩素型Feハイドロタルサイトも、試料を投入すると直ちに大幅に減少し、1時間で90%減少した。その後時間と共に減少を続け、5時間後には、検出装置1中の硫化水素濃度は、測定機の検出限界以下まで減少した。このように炭酸型Feハイドロタルサイトも塩素型ハイドロタルサイトも、液相中および液相中から漏れた気相中のVSCを吸着することができ、吸着剤、口臭除去剤に好適に利用することができる。 Both carbonate-type Fe hydrotalcite and chlorine-type Fe hydrotalcite were greatly reduced as soon as the sample was added, and decreased by 90% in 1 hour. After that, it continued to decrease with time, and after 5 hours, the hydrogen sulfide concentration in the detector 1 decreased to below the detection limit of the measuring device. Thus, both carbonate-type Fe hydrotalcite and chlorine-type hydrotalcite can adsorb VSC in the gas phase leaked from the liquid phase and the liquid phase, and are preferably used as an adsorbent and a bad breath removing agent. be able to.
表2には、図8の実測データを示す。炭酸型Feハイドロタルサイトと、塩素型ハイドロタルサイトは同様の挙動を示した。しかし、細かく見ると、塩素型Feハイドロタルサイトの方が、炭酸型Feハイドロタルサイトより硫化水素を多く吸着する傾向があった。層状複水酸化物の構造では、ゲスト層の元素として、塩素より炭酸の方が安定なので、硫化物は塩素の方がよりイオン交換しやすかったためと考えられた。 Table 2 shows the actual measurement data of FIG. Carbonated Fe hydrotalcite and chlorine hydrotalcite showed similar behavior. However, when viewed closely, chlorine-type Fe hydrotalcite tended to adsorb more hydrogen sulfide than carbonate-type Fe hydrotalcite. In the structure of the layered double hydroxide, carbon dioxide is more stable than chlorine as an element of the guest layer, so it is considered that the sulfide was more easily ion-exchanged with chlorine.
図9に生成し乾燥した直後の炭酸型Feハイドロタルサイトと塩素型FeハイドロタルサイトのX線回折の結果を示す。横軸は2θ(°)であり、縦軸は強度(任意単位)である。線源はCoのKα線を用いた。(a)は炭酸型Feハイドロタルサイト(図中「炭酸型FeHDT」と記した。)であり、(b)は塩素型Feハイドロタルサイト(図中「塩素型FeHDT」と記した。)である。 FIG. 9 shows the results of X-ray diffraction of carbonate-type Fe hydrotalcite and chlorine-type Fe hydrotalcite immediately after being produced and dried. The horizontal axis is 2θ (°), and the vertical axis is intensity (arbitrary unit). Co Kα radiation was used as the radiation source. (A) is carbonate type Fe hydrotalcite (denoted as “carbonate type FeHDT” in the figure), and (b) is chlorine type Fe hydrotalcite (denoted as “chlorine type FeHDT” in the figure). is there.
図中に(c)JCPDSのMg−Fe系ハイドロタルサイト(Pyroaurite#70−2150)の回折線図(図中「Pyroaurite」と記した。)も示した。何れの試料も、回折線図のピークとほぼ同じ位置にピークがあった。未知のピークは見当たらず、Pyroauriteと同様の結晶構造を有すると判断される。 Also shown in the figure is a diffraction diagram of (c) JCPDS Mg—Fe hydrotalcite (Pyroaurite # 70-2150) (denoted as “Pyroaurite” in the figure). Each sample had a peak at almost the same position as the peak of the diffraction diagram. An unknown peak is not found, and it is judged to have a crystal structure similar to Pyroaurite.
図10には、図9の2θが10〜40°の拡大図を示す。横軸は2θ(°)であり、縦軸は強度(cps)である。塩素型Feハイドロタルサイト(b)の回折ピークは炭酸型Feハイドロタルサイト(a)と比較して低角側にあることがわかる。したがって、C面の面間隔(層間距離)は、塩素型Feハイドロタルサイトの方が炭酸型Feハイドロタルサイトより大きいと考えられる。 FIG. 10 shows an enlarged view of 2θ in FIG. 9 of 10 to 40 °. The horizontal axis is 2θ (°), and the vertical axis is intensity (cps). It can be seen that the diffraction peak of the chlorine-type Fe hydrotalcite (b) is on the lower angle side compared to the carbonate-type Fe hydrotalcite (a). Therefore, the C-plane spacing (interlayer distance) is considered to be greater for chlorine-type Fe hydrotalcite than for carbonate-type Fe hydrotalcite.
図11には、検査装置1で硫化水素水溶液に浸漬した後の炭酸型Feハイドロタルサイトと塩素型FeハイドロタルサイトのX線回折の結果を示す。横軸は2θ(°)であり、縦軸は強度(任意単位)である。図中にJCPDSのMg−Fe系ハイドロタルサイト(Pyroaurite#70−2150)の回折線図も示し、ミラー指数(hkl)も示した。 In FIG. 11, the result of the X-ray diffraction of the carbonate type Fe hydrotalcite and the chlorine type Fe hydrotalcite after being immersed in the hydrogen sulfide aqueous solution by the inspection apparatus 1 is shown. The horizontal axis is 2θ (°), and the vertical axis is intensity (arbitrary unit). In the figure, a diffraction diagram of JCPDS Mg-Fe hydrotalcite (Pyroaurite # 70-2150) is also shown, and a Miller index (hkl) is also shown.
どちらの試料もMg−Fe系ハイドロタルサイトの回折線図とほぼ一致している。図9の吸着試験前のX線回折図とピーク位置を比較すると炭酸型Feハイドロタルサイト(a)ではあまり変化がなかった。しかし、塩素型Feハイドロタルサイト(b)では、ピークの位置が高角側にシフトしていた。 Both samples almost coincide with the diffraction diagram of Mg-Fe hydrotalcite. When the peak position was compared with the X-ray diffraction pattern before the adsorption test in FIG. 9, there was not much change in the carbonate type Fe hydrotalcite (a). However, in the chlorine type Fe hydrotalcite (b), the peak position was shifted to the high angle side.
図12に塩素型Feハイドロタルサイトの浸漬前と浸漬後のX線回折図を示す。横軸は2θ(°)であり、縦軸は強度(任意単位)である。(a)は浸漬前であり、(b)は浸漬後である。(b)の浸漬後の方が高角側にシフトしている。これはC面間隔が狭くなったことを示している。塩素イオンは6.7オングストロームであり、硫化水素イオンは4.2オングストロームであるので、ゲスト層の塩素イオンがより小さい硫化水素イオンに置換したためと考えられる。 FIG. 12 shows X-ray diffraction patterns before and after immersion of chlorine-type Fe hydrotalcite. The horizontal axis is 2θ (°), and the vertical axis is intensity (arbitrary unit). (A) is before immersion, and (b) is after immersion. The direction after immersion of (b) is shifted to the high angle side. This indicates that the C-plane spacing has become narrower. Since chlorine ions are 6.7 angstroms and hydrogen sulfide ions are 4.2 angstroms, it is considered that the chlorine ions in the guest layer were replaced with smaller hydrogen sulfide ions.
図13(a)には、炭酸型Feハイドロタルサイトの赤外吸収スペクトルを示し、図13(b)には塩素型Feハイドロタルサイトの赤外吸収スペクトルを示す。いずれも横軸は波数(cm−1)であり、縦軸は透過率(任意単位)である。 FIG. 13A shows an infrared absorption spectrum of carbonate-type Fe hydrotalcite, and FIG. 13B shows an infrared absorption spectrum of chlorine-type Fe hydrotalcite. In either case, the horizontal axis represents the wave number (cm −1 ), and the vertical axis represents the transmittance (arbitrary unit).
図13(a)では、3440cm−1付近のブロードなピークは、層状複水酸化物のブルーサイト状シート構造の水酸基の吸収、2850cm−1から2950cm−1のピークは、層間水とアニオンの水素結合の吸収、1650cm−1付近のピークは層間水の水酸基の吸収によるものである。 In FIG. 13 (a), the broad peak near 3440 cm −1 is the hydroxyl absorption of the brucite sheet structure of the layered double hydroxide, and the peaks from 2850 cm −1 to 2950 cm −1 are the hydrogen of the interlayer water and anions. Absorption of bonds, the peak near 1650 cm −1 is due to absorption of hydroxyl groups in interlayer water.
また1380cm−1、1050cm−1付近、860cm−1、770cm−1、700cm−1のピークは炭酸イオンによるものである。400cm−1から580cm−1に見られるピークはFe−Oの結合による吸収と考えられる。 The 1380 cm -1, 1050 cm -1 vicinity, 860cm -1, 770cm -1, the peak of 700 cm -1 is due to carbonate ions. Peaks seen from 400 cm -1 to 580 cm -1 is believed to absorption by binding Fe-O.
図13(b)も図13(a)とほぼ同じようなスペクトルである。しかし炭酸イオンに相当する700cm−1あたりの吸収ピークは、塩素系Feハイドロタルサイトでは明瞭でない。ほかの炭酸イオンに帰属できる吸収ピークは観察されるため、まったく炭酸イオンがないわけではない。塩素イオンはイオン結合性が強いことからIRでは確認されないとされており、図13(b)でも塩素イオンのピークは見られなかった。 FIG. 13B also has a spectrum that is almost the same as that in FIG. However, the absorption peak per 700 cm −1 corresponding to carbonate ions is not clear in chlorine-based Fe hydrotalcite. Absorption peaks that can be attributed to other carbonate ions are observed, so they are not completely free of carbonate ions. Chlorine ions are considered not to be confirmed by IR because of their strong ion binding properties, and no peak of chlorine ions was observed in FIG. 13 (b).
また、図14(a)、図14(b)にそれぞれ炭酸型Feハイドロタルサイトと塩素型FeハイドロタルサイトのEDS(Energy Dispersive X−ray Spectroscopy)プロファイルを示す。 FIGS. 14A and 14B show EDS (Energy Dispersive X-ray Spectroscopy) profiles of carbonate-type Fe hydrotalcite and chlorine-type Fe hydrotalcite, respectively.
図14を参照して、横軸はエネルギー(keV)であり、縦軸はカウント数である。図14(b)には、図14(a)には見られない塩素のピークが確認された。 Referring to FIG. 14, the horizontal axis is energy (keV), and the vertical axis is the count number. In FIG. 14 (b), a peak of chlorine not found in FIG. 14 (a) was confirmed.
以上のように、図9、図11の粉末X線回折図形の結果および図13の赤外吸収スペクトルの結果と併せて、炭酸型Feハイドロタルサイトおよび塩素型Feハイドロタルサイトは、ともにMg−FeLDH構造を持つが、炭酸型Feハイドロタルサイトは炭酸型であり、塩素型Feハイドロタルサイトでは、炭酸イオンも含むが、塩素型であると判断される。 As described above, together with the results of the powder X-ray diffraction patterns of FIGS. 9 and 11 and the result of the infrared absorption spectrum of FIG. 13, both the carbonate-type Fe hydrotalcite and the chlorine-type Fe hydrotalcite are Mg— Although it has an FeLDH structure, carbonate-type Fe hydrotalcite is carbonate-type, and chlorine-type Fe hydrotalcite contains carbonate ions, but is judged to be chlorine-type.
表3および4には、図14で示したEDSのより詳細な元素分析結果を示す。測定箇所は5箇所である。Mg−FeLDHのFe/Mg比((3)式(4)式中の「x」)はx=0.20〜0.33とされている。表2および3の結果より、炭酸型Feハイドロタルサイトではx=0.27であり、塩素型Feハイドロタルサイトではx=0.25であった。 Tables 3 and 4 show more detailed elemental analysis results of the EDS shown in FIG. There are five measurement points. The Fe / Mg ratio of Mg—FeLDH (“x” in equation (3) and equation (4)) is x = 0.20 to 0.33. From the results shown in Tables 2 and 3, the carbonic acid type Fe hydrotalcite was x = 0.25, and the chlorine type Fe hydrotalcite was x = 0.25.
本発明に係る吸着剤は、Znハイドロタルサイトまたは炭酸型Feハイドロタルサイトまたは塩素型Feハイドロタルサイトを含有するので、液相および気相を選ばず、特に悪臭元となる硫化水素を大変よく吸着する。したがって、吸着剤や口臭除去剤だけでなく消臭剤としても使用することができる。 The adsorbent according to the present invention contains Zn hydrotalcite, carbonate-type Fe hydrotalcite, or chlorine-type Fe hydrotalcite, so that it does not select liquid phase or gas phase, and particularly hydrogen sulfide which is a source of bad odor is very good. Adsorb. Therefore, it can be used not only as an adsorbent and a bad breath remover but also as a deodorant.
1 検査装置
2 ガラスフラスコ
3 漏斗
4 コック
5 シリンジ
6 ねじ口
10 硫化水素水溶液
11 ヘッドスペース
DESCRIPTION OF SYMBOLS 1 Inspection apparatus 2 Glass flask 3 Funnel 4 Cock 5 Syringe 6 Screw port 10 Hydrogen sulfide aqueous solution 11 Head space
Claims (5)
[Zn2+ 1−xAl3+ x(OH)2][CO3 2− X/2・mH2O] (2)
ここで0<x<1であり、mはゼロより大きな整数である (2) An adsorbent comprising hydrotalcite having a structure of the formula and adsorbing a volatile sulfur compound in a liquid phase.
[Zn 2+ 1-x Al 3+ x (OH) 2 ] [CO 3 2− X / 2 · mH 2 O] (2)
Where 0 <x <1 and m is an integer greater than zero
[Mg2+ 1−x+Fe3+ x(OH)2][CO3 2− X/2・mH2O] (3)
[Mg2+ 1−x+Fe3+ x(OH)2][Cl− X・mH2O] (4)
ここで0<x<1であり、mはゼロより大きな整数である (3) An adsorbent comprising hydrotalcite having a structure of formula (4) or formula (4) and adsorbing a volatile sulfur compound in a liquid phase.
[Mg 2+ 1-x + Fe 3+ x (OH) 2 ] [CO 3 2− X / 2 · mH 2 O] (3)
[Mg 2+ 1-x + Fe 3+ x (OH) 2] [Cl - X · mH 2 O] (4)
Where 0 <x <1 and m is an integer greater than zero
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