JP5039953B2 - 水溶液中のヒ素とクロムとを分離する方法 - Google Patents
水溶液中のヒ素とクロムとを分離する方法 Download PDFInfo
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- 229910052785 arsenic Inorganic materials 0.000 title claims description 153
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 153
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 111
- 229910052804 chromium Inorganic materials 0.000 title claims description 111
- 239000011651 chromium Substances 0.000 title claims description 111
- 239000007864 aqueous solution Substances 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 44
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 126
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 80
- 229910052802 copper Inorganic materials 0.000 claims description 80
- 239000010949 copper Substances 0.000 claims description 80
- 239000011163 secondary particle Substances 0.000 claims description 80
- 238000000926 separation method Methods 0.000 claims description 35
- 239000003755 preservative agent Substances 0.000 claims description 30
- 230000002335 preservative effect Effects 0.000 claims description 28
- 239000010875 treated wood Substances 0.000 claims description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 12
- 239000002023 wood Substances 0.000 claims description 11
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 9
- 239000012991 xanthate Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000010306 acid treatment Methods 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 230000002421 anti-septic effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000011656 manganese carbonate Substances 0.000 description 8
- 235000006748 manganese carbonate Nutrition 0.000 description 8
- 229940093474 manganese carbonate Drugs 0.000 description 8
- 150000002697 manganese compounds Chemical class 0.000 description 8
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 8
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000010840 domestic wastewater Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- -1 manganese oxide compound Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical group 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPJBONAWFAURGB-UHFFFAOYSA-L Lobenzarit disodium Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1NC1=CC(Cl)=CC=C1C([O-])=O QPJBONAWFAURGB-UHFFFAOYSA-L 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 230000005540 biological transmission 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
- 239000004566 building material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/78—Recycling of wood or furniture waste
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- Processing Of Solid Wastes (AREA)
- Removal Of Specific Substances (AREA)
- Extraction Or Liquid Replacement (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
(焼成)
磁性ルツボに入れた純度99.9%の炭酸マンガンの粉末(和光純薬社製、特級試薬)25gを電気炉中で、200℃で6時間焼成して焼成炭酸マンガンの粉末を得た。
(酸処理)
50gの焼成炭酸マンガン粉末を0.5mol/Lの希塩酸2Lに懸濁させ、1時間撹拌し、0.2マイクロメッシュのガラス繊維ろ紙(アドバンテック製、GS25)を用いて吸引ろ過を行い固液分離した。ガラス繊維ろ紙上に分離された固形物を再び0.5mol/Lの希塩酸1Lに懸濁させ、1時間撹拌し、再度吸引ろ過を行い固液分離した。
(乾燥)
さらに、大気圧下100℃で12時間乾燥し、R型の結晶構造を主成分とする物質:二酸化マンガン二次粒子を得た。乾燥後に得られる形状は、酸処理後にガラスろ紙上に吸引ろ過された直後の円形平板状が乾燥によって収縮したセンチメートル・オーダーの大きさのフレーク状や塊状であるため、必要に応じてメノウ乳鉢で粉砕してマイクロメートル・オーダーの粉末とすることもできる。
上述の乾燥処理によって得られたフレーク状、塊状、又は、それらをメノウ乳鉢で粉砕したR型二酸化マンガン二次粒子を、0.5mol/Lの希塩酸1Lに懸濁させ、1時間撹拌し、0.2マイクロメッシュのガラス繊維ろ紙(アドバンテック製、GS25)を用いて吸引ろ過を行い固液分離した。この酸処理にあったっては使用する酸を希塩酸の代わりに希硫酸、希硝酸を用いても同様な結果が得られた。この酸処理を施されたマンガン酸化物の主成分は、二酸化マンガンであった。このことは、粉末X線回折法によってR型の二酸化マンガンの回折ピークが得られること、及び、X線吸収分析法によって分析されたマンガンの価数が4価であること、から確認された。この再度の酸処理を施されたマンガン酸化物が、水素化したR型二酸化マンガン二次粒子(本発明の水素化した二次粒子)である。前記水素化した二次粒子は、ヒ素とクロムの分離に使用できる本発明のヒ素吸着組成物とすることができる。この再度の酸処理を施されたマンガン酸化物(水素化した二次粒子)の粉末X線回折パターン(図2のB)はR型二酸化マンガン二次粒子のそれ(図2のA)とほぼ同様であることから、結晶構造はR型の二酸化マンガンで、その表面が酸処理によってヒ素が吸着しやすい状態に改質されているものと考えられる。
ヒ素標準試薬(和光純薬製、原子吸光分析用試薬1000ppm)及びクロム標準試薬(和光純薬製、原子吸光分析用試薬1000ppm)を混合してヒ素及びクロムの濃度が30ppmの水溶液を1L調製した。また、5gのR型二酸化マンガン二次粒子(上述のように調製したもの)を0.5M濃度の希塩酸1L中に懸濁させて1時間保持した後、減圧ろ過器を用いてヒ素吸着組成物となる水素化したR型二酸化マンガン二次粒子をガラスろ紙(アドバンテック製、GS25)上にろ過回収した。次に、この水素化した二次粒子を、ヒ素とクロムを含んだ前記水溶液に懸濁させた。懸濁後、水溶液のpHを1M濃度の水酸化ナトリウム水溶液の添加によってpH3〜4に調整して1時間撹拌維持した。1時間経過時点で、ろ過器(アドバンテック製、DISMIC−GS25)を用いて水溶液中の水素化した二次粒子をろ過回収し、ICP発光分析装置を用いてサンプル中のヒ素とクロムの濃度を測定した。
CCA防腐剤で処理された木材から前記防腐剤成分である銅、ヒ素、及びクロムを抽出し、銅、ヒ素、クロムをそれぞれ分離回収した。本実施例における作業工程のフロー図を図4に示す。
Claims (5)
- ヒ素、クロム及び銅が溶存するヒ素、クロム及び銅の混合水溶液から銅及びヒ素を分離する分離方法であって、
前記水溶液にザンセート試薬を添加して、前記銅を硫化銅として分離する工程と、
銅が除かれた前記水溶液に水素化したR型二酸化マンガン二次粒子を接触させて前記ヒ素を前記水素化したR型二酸化マンガン二次粒子に吸着させることによりヒ素を分離する工程とを含む分離方法。 - 前記水素化したR型二酸化マンガン二次粒子との接触に先立って、前記銅が除かれた水溶液のpHをpH2.0〜4.0に調整することを含む、請求項1記載の分離方法。
- ヒ素、クロム及び銅が溶存する混合水溶液から銅及びヒ素を分離し、銅、ヒ素及びクロムから選択される少なくとも1つを回収する分離回収方法であって、
ヒ素、クロム及び銅が溶存する混合水溶液を請求項1又は2に記載の分離方法で処理することにより、ヒ素、クロム及び銅をそれぞれ分離する工程と
前記分離した銅、ヒ素及びクロムから選択される少なくとも1つを回収する工程と、を含む、分離回収方法。 - ヒ素、クロム及び銅が溶存するヒ素、クロム及び銅の混合水溶液からヒ素、クロム及び銅の少なくとも1つを製造する方法であって、前記混合水溶液を請求項1又は2に記載の方法で処理し、前記混合水溶液からヒ素、クロム及び銅をそれぞれ分離する工程を含む製造方法。
- 防腐剤処理木材の処理方法であって、
ヒ素、クロム及び銅を含む防腐剤で処理された木材から酸性水溶液を用いて前記防腐剤の成分を前記酸性水溶液に溶存する形態で抽出する工程と、
抽出されたヒ素、クロム及び銅が溶存するヒ素、クロム及び銅の混合水溶液を請求項1又は2に記載の分離方法で処理し、ヒ素、クロム及び銅をそれぞれ分離する工程とを含む処理方法。
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JP5317484B2 (ja) * | 2007-02-09 | 2013-10-16 | 国立大学法人京都大学 | 水から酸素ガスを製造するための触媒材料とその触媒材料を用いた酸素ガスの製造方法、二酸化炭素ガスから酢酸または有機物を合成するための触媒材料とその触媒材料を用いた酢酸または有機物の合成方法、電気エネルギー発生方法、水素ガスセンサー、廃液の再利用方法、r型二酸化マンガンの製造方法 |
WO2011118816A1 (ja) * | 2010-03-26 | 2011-09-29 | 国立大学法人京都大学 | ラムズデライト型結晶構造を有したナノメートルサイズの二酸化マンガンを合成する方法、二酸化マンガンを用いて水酸化物イオン起源のプロトン、電子および酸素を生成する方法 |
CN114769282B (zh) * | 2022-04-07 | 2023-10-27 | 楚雄滇中有色金属有限责任公司 | 一种铜冶炼污酸沉砷渣的无害化处理方法 |
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