WO2001007371A1 - Procede d'elimination des ions nocifs et agent d'elimination destine a etre utilise dans le cadre dudit procede - Google Patents

Procede d'elimination des ions nocifs et agent d'elimination destine a etre utilise dans le cadre dudit procede Download PDF

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Publication number
WO2001007371A1
WO2001007371A1 PCT/JP2000/004932 JP0004932W WO0107371A1 WO 2001007371 A1 WO2001007371 A1 WO 2001007371A1 JP 0004932 W JP0004932 W JP 0004932W WO 0107371 A1 WO0107371 A1 WO 0107371A1
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WO
WIPO (PCT)
Prior art keywords
acid
substance
salt
water
harmful
Prior art date
Application number
PCT/JP2000/004932
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English (en)
Japanese (ja)
Inventor
Kenji Tatsumi
Shinji Wada
Yasuhiro Yukawa
Original Assignee
Japan As Represented By Secretary Of Agency Of Industrial Science And Technology
Mitsubishi Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan As Represented By Secretary Of Agency Of Industrial Science And Technology, Mitsubishi Corporation filed Critical Japan As Represented By Secretary Of Agency Of Industrial Science And Technology
Priority to AU60235/00A priority Critical patent/AU6023500A/en
Publication of WO2001007371A1 publication Critical patent/WO2001007371A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds

Definitions

  • the present invention relates to a method for removing harmful ions and a remover used therefor.
  • the present invention relates to a method and a remover for removing dissolved harmful ions in water.
  • an alkaline substance such as sodium hydroxide and calcium hydroxide is added to water and precipitated as hydroxide.
  • an alkaline substance such as sodium hydroxide and calcium hydroxide is added to water and precipitated as hydroxide.
  • sodium hydroxide is used as the alkaline substance
  • the amount of generated sludge is small
  • the sludge particles are small and difficult to separate. Therefore, calcium hydroxide has been used exclusively until now, but in this case, there is a disadvantage that a large amount of sludge is generated.
  • the main method of removing fluorine ions contained in water has been to add lime or slaked lime (calcium hydroxide) to the water and precipitate fluorine as calcium fluoride.
  • this method has a drawback that the fluoride ion cannot be removed to a low concentration because the solubility of calcium fluoride is 16 mg / L.
  • the present invention provides a sludge that efficiently and reduces dissolved harmful ions contained in water. It is an object of the present invention to provide a method for removing harmful ions and a harmful ion remover used for the method.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
  • the method comprises the steps of: adding an anion group-containing hydrophilic polymer substance, an acidic substance, and, if necessary, a harmless polyvalent metal compound to the water;
  • a method for removing harmful ions, characterized by insolubilizing dissolved harmful ions contained in water by introducing and dispersing a remover composed of a mixture in the form of a powder or an aqueous liquid, is provided.
  • a remover for removing dissolved harmful ions contained in water comprising an anion group-containing hydrophilic polymer substance and an acidic substance, and if necessary, harmless polyvalent.
  • An agent for removing harmful ions, comprising a mixture with a metal compound is provided.
  • the harmful ion remover of the present invention (hereinafter, also simply referred to as a remover) comprises a mixture of an anion group-containing hydrophilic polymer substance, an acidic substance, and if necessary, a harmless polyvalent metal compound. It is.
  • the anion group-containing hydrophilic polymer substance includes various polymer substances containing an anion group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and both natural products and synthetic products can be used. From the viewpoint of conservation, it is preferable to use biodegradable materials.
  • Such polymeric substances include alginic acid, dielan gum, xanthan gum, tragacanth gum, pectin, pectic acid, pectinic acid, carrageenan, gelatin, agar, anionized starch, propylene glycol alginate, carboxymethyl cellulose, starch.
  • Polysaccharides such as glycolic acid, cellulose glycolic acid, starch phosphoric acid, and galatamannan and their alkali metal salts; polyatalylic acid, copolymers of atarylamide and ataryl acid and their metal salts; high water absorption Water-soluble polymer (for example, Sumitomo Chemical Co., Ltd., Sumikagel, Sanyo Chemical
  • anion group-containing hydrophilic polymer substances are usually used in powder form (including short fiber form), and have an average particle diameter of 10 to 500 ⁇ , preferably 20 to 200 ⁇ m. Preferably it is 50 to 150 ⁇ .
  • the anionic group-containing hydrophilic polymer substance used as a removing agent component in the present invention can be used alone or in the form of a mixture.
  • the removing agent of the present invention contains an acidic substance.
  • the acidic substances include ferrous chloride, ferric chloride, and mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid.
  • Such an acidic substance exerts an action such as controlling the solubility of the anionic group-containing hydrophilic high-molecular substance to the high-molecular substance.
  • the proportion of the acidic substance used is not particularly limited, and is appropriately selected depending on the type and amount of harmful ions dissolved in the water, ⁇ of the water to be treated, and the like.
  • the concentration of ferric chloride is not particularly limited, and the type and amount of metal ions dissolved in water and It is appropriately selected depending on the amount of the water to be treated, etc., and is 1 to 1000 parts by weight, preferably 20 to 500 parts by weight based on 100 parts by weight of the anionic group-containing hydrophilic polymer substance. The ratio is more preferably 100 to 2000 parts by weight.
  • the remover of the present invention contains a harmless polyvalent metal compound, if necessary.
  • a harmless polyvalent metal compound include iron salts such as ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, polyferric chloride, and ferric polysulfate, as well as aluminum sulfate and aluminum chloride.
  • Iron salts such as ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, polyferric chloride, and ferric polysulfate, as well as aluminum sulfate and aluminum chloride.
  • These polyvalent metal compounds form an ionic bond and a chelate bond to a hydrophilic polymer substance containing an anion group and exhibit an action of controlling the solubility of the polymer substance.
  • the proportion of the polyvalent metal compound used is not particularly limited, and may vary depending on the type and amount of the metal ion dissolved in the water and the ⁇ ⁇ ⁇ of the water to be treated. Generally selected, the amount is generally 1 to 1000 parts by weight, preferably 20 to 500 parts by weight, based on 100 parts by weight of the anionic group-containing hydrophilic polymer substance. The ratio is more preferably 100 to 2000 parts by weight.
  • a harmful ion collector in combination.
  • Such materials include crystalline hydrated iron oxides, and hazardous ion removing agents composed of a mixture of crystalline hydrated iron oxide and amorphous hydrated iron oxide and / or iron oxide.
  • iron (II) is preferably used because it is inexpensive and easily obtained. Iron ⁇ of any origin can be used, but 100 parts by weight of iron powder is soaked with 10 parts by weight of concentrated hydrochloric acid, stirred, and left for 2 to 3 days. You can give what you get.
  • the use ratio of the iron compound is not particularly limited, and is appropriately selected depending on the type and amount of harmful ions dissolved in water, pH of the water to be treated, and the like.
  • the proportion is 1 to 100 parts by weight, preferably 10 to 100 parts by weight, and more preferably 10 to 50 parts by weight with respect to 0 parts by weight.
  • a floc growth promoting agent in combination.
  • C Such crystalline iron oxide hydrate, crystalline iron oxide hydrate and amorphous iron oxide hydrate And Z or a mixture of iron oxides and the like.
  • iron (II) is preferably used because it is inexpensive and easily obtained. Any source of iron can be used, but 100 parts by weight of iron powder is soaked in 100 parts by weight of concentrated hydrochloric acid, stirred, and allowed to stand for 2 to 3 days. Can be given.
  • the use ratio of the iron compound is not particularly limited, and is appropriately selected depending on the type and amount of the toxic ion soluble in water, the pH of the water to be treated, and the like. In general, the iron compound in the remover 1 The ratio is 1 to 100 parts by weight, preferably 10 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight.
  • the removing agent of the present invention is charged and dispersed in water in the form of a powder or an aqueous liquid.When the removing agent is charged and dispersed in water in this manner, the anion group-containing hydrophilic substance contained therein is not dissolved. Exists in an insoluble (insoluble) state.
  • One embodiment of the preferable removing agent according to the present invention is an aqueous liquid containing a hydrophilic polymer material containing an anion group and ferric chloride. In this aqueous liquid, the concentration of the ferric chloride is from 0.001 to 48% by weight, preferably from 0.1 to 45% by weight. The concentration of the anionic group-containing hydrophilic polymer substance is 0.0001 to 5% by weight, preferably 0.01 to 5% by weight.
  • Another preferred embodiment according to the present invention is an aqueous liquid containing a hydrophilic polymer substance containing an anion group, a mineral acid as an acidic substance, and a harmless polyvalent metal compound.
  • the concentration of the mineral acid is not particularly limited, and is appropriately selected depending on the type and amount of the metal ion dissolved in the water, the pH of the water to be treated, and the like.
  • the concentration of the harmless polyvalent metal compound is from 0.001 to 48% by weight, preferably from 0.1 to 45% by weight.
  • the concentration of the anion group-containing hydrophilic polymer substance is 0.0001 to 5% by weight, preferably 0.01 to 5% by weight. / 0 .
  • the remover was added to the water, and the anion group-containing hydrophilic polymer substance was dispersed without dissolving.
  • insolubilizes harmful ions In this case, the insolubilization of the harmful ion can be performed by various methods depending on the type of the harmful ion.
  • a metal ion insolubilizing agent eg, sodium sulfide, a hazardous collector, etc.
  • the removing agent of the present invention it is preferable to adjust the pH of the water to 7 to 12 by adding an alkaline substance to insolubilize harmful ions.
  • an alkaline substance it is particularly preferable to use sodium hydroxide.
  • the harmful ions are fluorine ions, nitrate ions, phosphate ions, arsenite ions, and arsenate, they can be insolubilized by adsorption to the added collecting agent or iron hydroxide.
  • a coagulant is preferably used in combination.
  • the flocculants in this case are those used for flocculation of flocks, such as chitosan, calcium chloride, bis (dihydrogen phosphate) calcium, ferrous chloride, ferric chloride. Ferrous sulfate, ferrous sulfate, ferric sulfate, aluminum sulfate, aluminum polychloride, etc.
  • cationically modified polyacrylamides In addition to inorganic flocculants, cationically modified polyacrylamides, cationic organic flocculants such as poly (methylaminoethyl ethyl acrylate), poly (dimethylaminoethyl methacrylate), polyethyleneimine, chitosan, polyacrylamide, etc. And anionic organic coagulants such as polyacrylic acid, copolymers of acrylamide and atalilic acid, and salts thereof.
  • the wastewater to which the present invention is applied includes dissolved polyvalent harmful ions such as copper ions, zinc ions, nickel ions, lead ions, chromium ions, iron ions, fluorine ions, nitrate ions, phosphate ions, and phosphite ions. Wastewater containing one or two or more of these. There is no particular restriction on the concentration of harmful ions in this wastewater, and there is no restriction on other coexisting ions.
  • the wastewater is preferably acidic wastewater, but if the wastewater is neutral or alkaline, the wastewater must be removed beforehand. It is preferred to adjust the pH of the effluent in the acidic region, usually ⁇ 1-7, preferably in the range 2-4. In this case, if it is difficult to adjust the pH to a predetermined value even when a removing agent containing an acidic substance is added, it is preferable to adjust the pH by adding an acidic substance such as a mineral acid.
  • a pH regulator When adjusting the pH of the water to be treated to an alkaline or acidic range, a pH regulator is used.
  • a pH regulator include sodium hydroxide and lithium hydroxide.
  • Alkaline substances such as sodium, sodium carbonate, potassium carbonate, and calcium hydroxide, or acidic substances such as hydrochloric acid, sulfuric acid, and nitric acid are used.
  • the gel formed by adsorbing or taking in the insolubilized harmful ions generated as described above is usually a floc that can be separated into solid and liquid.
  • the floc generated as described above is separated from water by a solid-liquid separation method.
  • solid-liquid separation methods include filtration, centrifugation, and sedimentation. Conventional methods such as the law can be adopted.
  • the treatment time for removing dissolved harmful ions from water according to the invention is very short, usually within 1 hour, especially within 30 minutes, preferably 3 to 10 minutes.
  • the anion group-containing hydrophilic polymer substance a water-soluble substance such as alginic acid or an alkali metal salt thereof is used. Even a polymer substance can be used smoothly. That is, even if the anionic group-containing hydrophilic polymer substance is water-soluble, it can be dispersed in water as a mixture with an acidic substance and a harmless polyvalent metal compound to form a high molecular weight polymer. Dissolution of the substance can be prevented. Therefore, in the case of the present invention, the harmful ions may be insolubilized and solid-liquid separated under the condition that the powder of the polymer substance is not completely dissolved.
  • a flocculant can be added as needed.
  • the addition of the flocculant has the effect of aggregating insolubles of harmful ions, as well as anionic group-containing hydrophilic high-molecular substances dispersed in water, and generating a giant floc.
  • a remover is added to the acidic water, and if necessary, an alkali is added and the whole is stirred. Thereby, the harmful ions contained in the water are insolubilized. At this time, some of the harmful ions contained in the water react with the anionic group-containing hydrophilic polymer substance to form an insoluble salt of the polymer and precipitate. At this time, the presence of the anionic group-containing hydrophilic high molecular weight substance allows the generated flocs of the harmful hydroxide to grow larger, thereby achieving the conventional treatment of slaked lime and lime alone.
  • the use of calcium and magnesium can be greatly reduced compared to that, and as a result sludge can be significantly reduced. Furthermore, by adding a flocculant, larger and stronger flocs can be precipitated.
  • hazardous wastewater used as raw water to be treated includes wastewater from various factories such as a semiconductor manufacturing industry, a steel and non-ferrous metal industry, an electrical equipment manufacturing industry, a machine and equipment manufacturing industry, and a wastewater from a plating plant. Includes wastewater from various laboratories. Most of these wastewaters contain harmful ions.
  • the present invention generally comprises Cu, Zn, Cd, Pd, Ag, Al, Cr, Pb, Mn, Fe, Ni, F, N03, HPO
  • Ferric chloride (reagent) After stirring a 20 wt% aqueous solution at 80 ° C or more for 3 hours, sodium alginate 2.4 wt. / 0 was stirred added for 3 hours, was c which removing agent becomes brown suspension [I b]. This remover [lb] was added to the water to be treated at pH 2 containing 100 ppm of copper, nickel, lead, and zinc so as to be 300 ppm as ferric chloride, and sodium hydroxide was added. The pH was set at 10. A polymer flocculant was added to the mixture at 5 ppm, and the mixture was stirred for several minutes, followed by solid-liquid separation, and the residual metal ion concentration was measured.
  • Ferric chloride (industrial) 37.5 wt. /. After adjusting the pH of the aqueous solution to 1 with sodium hydroxide, 4.8% by weight of sodium alginate was added, and the mixture was stirred for 3 hours to form a brown suspension. This was used as the remover [IIa].
  • This remover [IIa] is added to the pH 2 treated water containing 100 ppm of copper, nickel, lead, and zinc so that the concentration of ferric chloride becomes 300 ppm.
  • the pH was adjusted to 10 with sodium hydroxide.
  • a polymer flocculant was added thereto at 5 ppm, and the mixture was stirred for several minutes, followed by solid-liquid separation, and the residual metal ion concentration was measured.
  • Ferric chloride (industrial) 37.5 wt. /.
  • the aqueous solution was adjusted to pH 1 with sodium hydroxide, stirred at 80 ° C. or higher for 3 hours, and then added with 4.8% by weight of sodium alginate, and stirred for 3 hours to form a brown suspension. .
  • This remover [lib] was added to the pH 2 treated water containing 100 ppm of copper, nickel, lead and zinc so that the concentration of ferric chloride would be 300 ppm.
  • the pH was adjusted to pH10 with sodium hydroxide. To this, a polymer flocculant was added at 5 ppm, and the mixture was stirred for several minutes, followed by solid-liquid separation, and the residual metal ion concentration was measured.
  • a 40-fold dilution of the remover [lib] l OOO ppm was added to actual wastewater containing 12.8 ppm of fluorine, 84.8 ppm of nitric acid, and 1.2.75 ppm of TOC, and then added with sodium hydroxide.
  • the pH was adjusted to 13, and after stirring for several minutes, solid-liquid separation was performed.
  • good results were obtained when the fluorine ion was 0 ppm, the nitric acid was 46.98 ppm, and the TOC was 2.24 ppm.
  • the harmful ion contained in the to-be-processed water containing various dissolved harmful ions can be efficiently removed at a high removal rate and with a reduced amount of sludge generated.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un procédé permettant d'éliminer les ions nocifs contenus dans l'eau, caractérisé en ce qu'il consiste à ajouter dans cette eau un agent d'élimination renfermant d'une part, un mélange d'un polymère hydrophile comportant des groupes anioniques et d'une substance acide, et éventuellement, un composé inoffensif d'un métal polyvalent, lequel mélange se présente sous la forme d'une poudre ou d'un fluide aqueux, et à disperser l'agent d'élimination de manière à insolubiliser les ions nocifs dissous contenus dans l'eau.
PCT/JP2000/004932 1999-07-23 2000-07-24 Procede d'elimination des ions nocifs et agent d'elimination destine a etre utilise dans le cadre dudit procede WO2001007371A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU60235/00A AU6023500A (en) 1999-07-23 2000-07-24 Method for removing harmful ion and remover for use in the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/209779 1999-07-23
JP20977999A JP3621963B2 (ja) 1999-07-23 1999-07-23 有害性イオンを除去するための方法及びそれに用いる除去剤

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WO2001007371A1 true WO2001007371A1 (fr) 2001-02-01

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110918068A (zh) * 2019-12-12 2020-03-27 西安工业大学 一种纳米零价铁微凝胶复合材料及其制备方法和再生方法
CN113683729A (zh) * 2021-08-24 2021-11-23 武汉科创伟业生物科技有限公司 一种复合型凝聚剂及其制备方法与应用

Families Citing this family (8)

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Publication number Priority date Publication date Assignee Title
EP1493716A4 (fr) * 2002-03-25 2007-10-03 Mitsubishi Gas Chemical Co Procede de traitement des eaux usees
JP4232019B2 (ja) 2003-09-16 2009-03-04 三菱瓦斯化学株式会社 フッ素含有排水の処理方法
JP2008142683A (ja) * 2006-12-13 2008-06-26 National Institute Of Advanced Industrial & Technology 水処理方法
KR20090104007A (ko) * 2007-01-24 2009-10-05 쿠리타 고교 가부시키가이샤 역침투막 처리 방법
JP5256503B2 (ja) * 2009-06-29 2013-08-07 株式会社アイ・イー・ジェー 廃水から多価金属を除去する方法
JP5884493B2 (ja) * 2012-01-11 2016-03-15 栗田工業株式会社 重金属含有排水の処理方法
JP5924683B2 (ja) * 2012-08-31 2016-05-25 前山　勝也 高分子ゲルとその製造方法並びにフッ化物イオン捕集剤
NO346509B1 (no) * 2017-09-04 2022-09-12 M Vest Water As Produkt, fremgangsmåte og anvendelse for vannrensing

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JPS50105578A (fr) * 1974-01-18 1975-08-20
JPS5670893A (en) * 1979-11-09 1981-06-13 Norihiko Base Treatment of muddy water
JPH0739754A (ja) * 1993-07-30 1995-02-10 Ebara Res Co Ltd リン酸イオン吸着材、その製造方法及び水処理方法
JPH07100304A (ja) * 1993-09-30 1995-04-18 Nippon Synthetic Chem Ind Co Ltd:The 懸濁液の凝集方法
JPH07236802A (ja) * 1994-02-28 1995-09-12 Yoshikawa Enbi Kogyosho:Kk 汚水処理助剤

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50105578A (fr) * 1974-01-18 1975-08-20
JPS5670893A (en) * 1979-11-09 1981-06-13 Norihiko Base Treatment of muddy water
JPH0739754A (ja) * 1993-07-30 1995-02-10 Ebara Res Co Ltd リン酸イオン吸着材、その製造方法及び水処理方法
JPH07100304A (ja) * 1993-09-30 1995-04-18 Nippon Synthetic Chem Ind Co Ltd:The 懸濁液の凝集方法
JPH07236802A (ja) * 1994-02-28 1995-09-12 Yoshikawa Enbi Kogyosho:Kk 汚水処理助剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110918068A (zh) * 2019-12-12 2020-03-27 西安工业大学 一种纳米零价铁微凝胶复合材料及其制备方法和再生方法
CN110918068B (zh) * 2019-12-12 2022-12-20 西安工业大学 一种纳米零价铁微凝胶复合材料及其制备方法和再生方法
CN113683729A (zh) * 2021-08-24 2021-11-23 武汉科创伟业生物科技有限公司 一种复合型凝聚剂及其制备方法与应用
CN113683729B (zh) * 2021-08-24 2023-08-18 武汉科创伟业生物科技有限公司 一种复合型凝聚剂及其制备方法与应用

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AU6023500A (en) 2001-02-13
JP3621963B2 (ja) 2005-02-23

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