JP2013111524A - 有害物質吸着材及びその製造方法並びにそれを用いた環境浄化方法 - Google Patents
有害物質吸着材及びその製造方法並びにそれを用いた環境浄化方法 Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 54
- 239000003463 adsorbent Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004140 cleaning Methods 0.000 title 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims abstract description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002689 soil Substances 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 7
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 6
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 39
- 229910052742 iron Inorganic materials 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
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- 239000003440 toxic substance Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
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- 239000011669 selenium Substances 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
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- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000383 hazardous chemical Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
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- 230000000052 comparative effect Effects 0.000 description 13
- 235000013980 iron oxide Nutrition 0.000 description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000000523 sample Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Water Treatment By Sorption (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
【解決手段】有害物質吸着材として、ジルコニウム及びマンガンを含有する無水酸化鉄を含むものを用いる。また、前記有害物質吸着材は、鉄化合物、ジルコニウム化合物及びマンガン化合物を含む溶液を30〜80℃の範囲の温度下で、5.5〜8.0の範囲のpHで中和し、酸化してジルコニウム及びマンガンを含有する無水酸化鉄を生成させた後、得られた当該無水酸化鉄を固液分離することで製造される。
【効果】本発明は、有害物質、特にフッ素の吸着能力が高く、フッ素等の有害物質で汚染された水、土壌等を効果的に浄化できる。
【選択図】なし
Description
硫酸法酸化チタンの製造工程から発生した廃硫酸(硫酸鉄をFeとして10g/リットル、硫酸マンガンをMnとして0.90g/リットル含む)に、硫酸ジルコニウム(Zrとして0.82g/リットル)を添加し、この溶液を65℃に昇温し、pHが6.0となるように20%苛性ソーダを添加しながら、溶液中に空気を吹き込み、酸化率が70.2%にまるまで酸化した後、濾過、洗浄し、大気中40℃の温度で48時間乾燥し、本発明の有害物質吸着材(試料A)を得た。酸化率から、この鉄酸化物は、FeO1.44で表される化合物であると考えられる。
実施例1において、硫酸ジルコニウムを添加しなかった以外は、実施例1と同様にして、比較対象の有害物質吸着材(試料B)を得た。
実施例1において、反応温度を45℃、中和pHを8.5、酸化率100%をとした以外は、実施例1と同様にして、比較対象の有害物質吸着材(試料C)を得た。酸化率から、この鉄酸化物は、FeOOHで表されるオキシ化合物であると考えられる。
比較例2において、硫酸ジルコニウムを添加しなかった以外は、比較例2と同様にして、比較対象の有害物質吸着材(試料D)を得た。
実施例1、比較例1〜3試料(A〜D)について、X線回折、酸化ジルコニウム及び酸化マンガンの含有量、BET比表面積の測定結果を表1に示す。
実施例1、比較例1〜3試料(A〜D)について、各試料を12規定の塩酸に煮沸溶解した後、試料溶液に指示薬としてジフェニルアミンスルホン酸ソーダを添加し、重クロム酸カリウムを用いて酸化還元滴定を行い、2価鉄量を定量した。また、同様に調製した試料溶液に指示薬としてインジコカルミンを添加し、更に還元剤として三塩化チタンを加え、試料溶液の無色〜薄黄色が青色に変わるまで、3価鉄を2価鉄に還元させた。その後、同様に酸化還元滴定を行い、2価鉄量を定量し、これを全鉄量とし、全鉄量から先に求めた2価鉄量を差し引いて、3価鉄量とした。結果を、表2に示す。実施例1、比較例1は、「合計量」が95〜100重量%の範囲内であることから、無水酸化鉄であり、一方、比較例3、4は、「合計量」が前記範囲より小さいことから、含水酸化鉄であることが判る。
実施例1、比較例1〜3の試料(A〜D)を、フッ素を10mg/リットル含む模擬汚染水に、投入した後、pHを5に調整し、室温下2時間撹拌した。撹拌後、試料を固液分離した。模擬汚染水中の試料濃度は、1.0、5.0g/リットルの2水準とした。また、試料を投入せずに同様に処理した模擬汚染水を、比較例3とする。模擬汚染水中のフッ素濃度は、原子吸光分析で測定した。その結果を、表3に示す。本発明のフッ素吸着材は、フッ素の吸着能力が優れていることが判る。
Claims (9)
- ジルコニウム及びマンガンを含有する無水酸化鉄を含むことを特徴とする有害物質吸着材。
- Fe3O4換算の無水酸化鉄に対し、ジルコニウムの含有量がZrO2換算で0.1〜20重量%の範囲にあり、マンガンの含有量がMnO換算で0.1〜10重量%の範囲にあることを特徴とする請求項1記載の有害物質吸着材。
- 無水酸化鉄が磁着性を有していることを特徴とする請求項1に記載の有害物質吸着材。
- 無水酸化鉄がFeOx(1.33<x<1.5)の化学式で表される化合物であることを特徴とする請求項1に記載の有害物質吸着材。
- 無水酸化鉄がスピネル型の結晶構造を有することを特徴とする請求項1に記載の有害物質吸着材。
- 有害物質がフッ素、ヒ素、クロム、セレン、鉛、カドミウムから選ばれる少なくとも1種であることを特徴とする請求項1記載の有害物質吸着材。
- ジルコニウム及びマンガンを含有する無水酸化鉄を含む有害物質吸着材の製造方法であって、鉄化合物、ジルコニウム化合物及びマンガン化合物を含む溶液を30〜80℃の範囲の温度下で、5.5〜8の範囲のpHで中和し、酸化してジルコニウム及びマンガンを含有する無水酸化鉄を生成させた後、得られた当該無水酸化鉄を固液分離することを特徴とする有害物質吸着材の製造方法。
- 酸化チタンの製造工程から副生する鉄成分及びマンガン成分を含む廃硫酸にジルコニウム化合物を添加して当該溶液を調製することを特徴とする請求項7記載の有害物質吸着材の製造方法。
- 有害物質で汚染された水中又は土壌中に請求項1記載の有害物質吸着材を投入して有害物質を吸着させることを特徴とする環境浄化方法。
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KR20150085556A (ko) * | 2014-01-15 | 2015-07-24 | 한국지질자원연구원 | 망간이 치환된 철수산화물, 그 합성방법 및 이를 이용한 수처리방법 |
WO2017173737A1 (zh) * | 2016-04-06 | 2017-10-12 | 北京高能时代环境技术股份有限公司 | 一种用于处理铬污染土壤的稳定化药剂及其应用 |
CN115400734A (zh) * | 2022-08-26 | 2022-11-29 | 广西大学 | 一种用于从硫酸锰溶液中除去铝离子的吸附剂的制备方法及其应用 |
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KR20150085556A (ko) * | 2014-01-15 | 2015-07-24 | 한국지질자원연구원 | 망간이 치환된 철수산화물, 그 합성방법 및 이를 이용한 수처리방법 |
KR101586686B1 (ko) | 2014-01-15 | 2016-01-20 | 한국지질자원연구원 | 망간이 치환된 철수산화물, 그 합성방법 및 이를 이용한 수처리방법 |
WO2017173737A1 (zh) * | 2016-04-06 | 2017-10-12 | 北京高能时代环境技术股份有限公司 | 一种用于处理铬污染土壤的稳定化药剂及其应用 |
CN115400734A (zh) * | 2022-08-26 | 2022-11-29 | 广西大学 | 一种用于从硫酸锰溶液中除去铝离子的吸附剂的制备方法及其应用 |
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