JP4441625B2 - Harmful anion adsorption organic polymer gel - Google Patents
Harmful anion adsorption organic polymer gel Download PDFInfo
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- JP4441625B2 JP4441625B2 JP2003418783A JP2003418783A JP4441625B2 JP 4441625 B2 JP4441625 B2 JP 4441625B2 JP 2003418783 A JP2003418783 A JP 2003418783A JP 2003418783 A JP2003418783 A JP 2003418783A JP 4441625 B2 JP4441625 B2 JP 4441625B2
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- 229920000620 organic polymer Polymers 0.000 title claims description 28
- 238000001179 sorption measurement Methods 0.000 title claims description 15
- 150000001450 anions Chemical class 0.000 title description 28
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 18
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 18
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 7
- 229940000488 arsenic acid Drugs 0.000 claims description 7
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 claims description 7
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 4
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- RPPPKGJITXNWOW-UHFFFAOYSA-J [Cr](=O)(=O)(O)O[Cr](=O)(=O)O.[Cr](=O)(=O)(O)O[Cr](=O)(=O)O Chemical compound [Cr](=O)(=O)(O)O[Cr](=O)(=O)O.[Cr](=O)(=O)(O)O[Cr](=O)(=O)O RPPPKGJITXNWOW-UHFFFAOYSA-J 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229940000207 selenious acid Drugs 0.000 claims description 2
- 239000000499 gel Substances 0.000 description 37
- 150000002500 ions Chemical class 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009920 chelation Effects 0.000 description 4
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 rare earth compound Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZKIINMZZECFLGB-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate chloromethane Chemical compound ClC.C(C=C)(=O)OCCN ZKIINMZZECFLGB-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BHDFTVNXJDZMQK-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C(C)=C BHDFTVNXJDZMQK-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Description
本発明は、有害陰イオン、たとえば砒酸、亜砒酸、クロム酸といった陰イオンを吸着・除去する有機高分子ゲルに関する。 The present invention relates to an organic polymer gel that adsorbs and removes harmful anions such as arsenic acid, arsenous acid, and chromic acid.
近年、有害イオンたとえば鉛、銅、カドミウムといった陽イオンおよび有害陰イオンたとえば砒酸、亜砒酸、クロム酸といった陰イオンによる土壌汚染に対する認識が社会全般に高まりかつ広まってきた。この認識の高まり、広まりを受けて有害イオンの環境中への流出防止に関する研究や技術開発が進展してきた。 In recent years, the recognition of soil contamination by cations such as harmful ions such as lead, copper and cadmium and harmful anions such as arsenic acid, arsenous acid and chromic acid has increased and spread throughout society. In response to the growing awareness and spread, research and technology development related to prevention of harmful ions from flowing out into the environment have progressed.
しかしながら、一旦環境中へ流出した有害イオンは分解して消滅することなく、経時的に広範囲に拡散する。現在、工場等から排出される廃棄物としての有害イオンは、環境省によるマニュアルに従って、特殊廃液処理施設等で水酸化物として処理された後、有害物質含有量や環境・人体に与える影響当の基準によって分別され、以下の最終処分場において処分されている。
（１）安定型最終処分場：腐敗、分解することのない廃棄物を収容する処分場であって、地下水汚染防止対策は施されていない。
（２）管理型最終処分場：廃棄物の腐敗、降雨による汚水発生の虞がある廃棄物を収容する処分場であって、底面に遮水シートが敷設されている。また、滲出汚水回収施設が付属している。
（３）遮断型最終処分場：通常の方法では無害化することが困難な廃棄物を収容する処分場であって、鉄筋コンクリート製の遮蔽構造をもち、雨水進入防止のために屋根がついている。
However, harmful ions once flowing out into the environment are diffused over time without decomposing and disappearing. Currently, harmful ions as waste discharged from factories, etc. are treated as hydroxides at special waste liquid treatment facilities, etc. according to the manual of the Ministry of the Environment. Sorted according to standards and disposed of at the following final disposal sites.
(1) Stable final disposal site: A disposal site that contains waste that does not rot or decompose, and no measures are taken to prevent groundwater contamination.
(2) Management-type final disposal site: A disposal site that contains wastes that may be spoiled or generate sewage due to rain, and has a waterproof sheet on the bottom. In addition, an exudate sewage collection facility is attached.
(3) Blocking-type final disposal site: A disposal site that contains waste that is difficult to detoxify by ordinary methods, has a shielded structure made of reinforced concrete, and has a roof to prevent rainwater ingress.
前記環境省のマニュアルによる最終処分場における処分によるときも、酸性雨等に起因して最終処分場における廃棄物の処分に、以下のような問題を生じている。即ち、安定型最終処分場にあっては、酸性雨による侵食、重金属の流出、管理型最終処分場においては、遮水シートの耐久性低下による液状廃棄物の漏泄や重金属の流出、また、遮断型最終処分場にあっても、酸性雨によるコンクリート製隔壁の耐久性低下に起因する破壊による重金属酸化物の滲出といった問題を惹起する。 Even when disposal is performed at the final disposal site according to the manual of the Ministry of the Environment, the following problems occur in the disposal of waste at the final disposal site due to acid rain and the like. That is, in stable final disposal sites, erosion due to acid rain and heavy metal spills, and in managed final disposal sites, liquid waste leaks and heavy metal spills due to reduced durability of the water shielding sheet. Even in the final disposal site of the mold, problems such as leaching of heavy metal oxides due to breakage due to deterioration of the durability of concrete partition walls due to acid rain are caused.
上記各種最終処分場から漏泄する有害イオンには、鉛、銅、カドミウムといった有害重金属陽イオンと共に、砒酸、亜砒酸、クロム酸、重クロム酸、亜セレン酸、セレン酸、硼酸等の陰イオンがある。これら陰イオンはきわめて有害であり、微量を吸収しただけでも人体に重大な悪影響を及ぼす。一方、人体に直接的な悪影響を及ぼすことはないけれども、海や湖沼の富栄養化によって、湖沼等を緑色に彩る微小な藻類である青粉（あおこ）やプランクトンの多量発生による湖沼、海洋汚染の原因となる燐酸イオンも有害陰イオンであるといえる。 The harmful ions leaked from the various final disposal sites include anions such as arsenic acid, arsenous acid, chromic acid, dichromic acid, selenous acid, selenic acid, boric acid as well as harmful heavy metal cations such as lead, copper, and cadmium. . These anions are extremely harmful, and even if only a small amount is absorbed, they can have a serious adverse effect on the human body. On the other hand, although there is no direct adverse effect on the human body, due to the eutrophication of the sea and lakes, lakes and oceans due to the abundance of blue powder (Ako) and plankton, which are microalgae that color the lakes etc. green It can be said that the phosphate ion causing the contamination is also a harmful anion.
このような有害陰イオンを吸着・除去する手段として、アルギン酸のゲル化球状体内に、有害陰イオン吸着剤たとえば希土類系化合物粉末が分散された有害陰イオン吸着粒子が知られている（たとえば、特許文献１参照）。
アルギン酸のゲル化球状体内に、たとえば希土類系化合物粉末を分散せしめた有害陰イオン吸着粒子は、吸着剤単位重量当りの吸着物質量が小さく、ハンドリング、運搬コストが高くなる問題がある。また、高分子凝集剤のキレーション能力を利用してフロックを形成し、イオンを除去する方法においては、有害陰イオン回収処理の際の極端な環境変動による網目構造の破壊があったり、キレーションによって形成されるフロックの大きさがばらついており、濾別等簡便な手段による溶液・フロックの分離が困難である問題がある。 For example, harmful anion adsorbing particles in which rare earth compound powder is dispersed in a gelled sphere of alginic acid have a problem that the amount of adsorbing substance per unit weight of adsorbent is small and handling and transportation costs are high. In addition, in the method of forming flocs by utilizing the chelating ability of the polymer flocculant and removing ions, the network structure may be destroyed due to extreme environmental fluctuations during the recovery of harmful anions, or it may be formed by chelation. The size of the flocs to be dispersed varies, and there is a problem that it is difficult to separate the solution and flocs by simple means such as filtration.
本発明は、有害陰イオンを、吸着剤単位重量当りの吸着物質量が大きく取り扱いも容易であり運搬コストも低くまた、形成されるフロックの大きさのばらつきが小さく濾別等簡便な手段による溶液・フロックの分離が可能な有害陰イオン吸着有機高分子ゲルを提供することを目的とする。 The present invention provides a solution of harmful anions by a simple means such as filtration with a large amount of adsorbed substance per unit weight of adsorbent, easy handling and low transportation cost, and small variation in the size of floc formed. An object is to provide a harmful anion-adsorbing organic polymer gel capable of separating flocs.
上記課題を解決するための本発明は、クロム酸、重クロム酸（二クロム酸）、砒酸、亜砒酸、セレン酸、亜セレン酸の吸着ゲルであって、架橋による三次元網目構造を有するとともに、網目を形成する主鎖が、正の電荷を有するイオン性の４級アンモニウム塩末端をもつ側鎖を派生した構造を有する点によって特徴づけられる有害陰イオン吸着有機高分子ゲルである。 The present invention for solving the above problems is an adsorption gel of chromic acid, dichromic acid (dichromic acid), arsenic acid, arsenous acid, selenic acid, selenious acid, and has a three-dimensional network structure by crosslinking, A harmful anion-adsorbing organic polymer gel characterized by the fact that the main chain forming a network has a structure derived from a side chain having a ionic quaternary ammonium salt terminal having a positive charge.
本発明によれば、通常のイオン交換樹脂に比し、イオン吸着に寄与する官能基の密度が高い。従って、有害陰イオンがイオン性官能基に遭遇する割合が高く吸着効率が高い。また、本発明の有害陰イオン吸着有機高分子ゲルは、Ｃ、Ｈ、Ｏ、Ｎ等の軽い元素のみで構成されているから、原子量の大きな元素を多く含むゼオライト等の陰イオン吸着剤に比し、吸着剤それ自体も安価でありまた、吸着剤単位重量当りの吸着物質量が大きく取り扱いが容易で運搬等のコストも低くできる。 According to the present invention, the density of functional groups contributing to ion adsorption is higher than that of a normal ion exchange resin. Therefore, the rate at which harmful anions encounter ionic functional groups is high and the adsorption efficiency is high. In addition, the harmful anion-adsorbing organic polymer gel of the present invention is composed only of light elements such as C, H, O, and N, and therefore, compared to an anion adsorbent such as zeolite containing a large amount of elements having a large atomic weight. In addition, the adsorbent itself is inexpensive, and the amount of adsorbent per unit weight of adsorbent is large and easy to handle, so that the cost of transportation and the like can be reduced.
さらに、本発明の有害陰イオン吸着有機高分子ゲルは、共有結合によって網目が形成されている処から、外部環境変化に対し網目構造が比較的安定である。従って、高分子凝集剤のキレーション能力を利用してフロックを形成するイオン除去方法においては、フロックの大きさがばらついているから濾別等簡便な溶液・フロック分離が困難であるが、本発明の有害陰イオン吸着有機高分子ゲルは、高分子網目構造が予定した大きさに揃えられて作られているので、濾別等簡便な手段での溶液・フロック分離が可能である。 Furthermore, the harmful anion-adsorbing organic polymer gel of the present invention has a relatively stable network structure against changes in the external environment since the network is formed by covalent bonds. Therefore, in the ion removal method that forms flocs using the chelation ability of the polymer flocculant, the size of the flocs varies, so that simple solution / floc separation such as filtration is difficult. Since the harmful anion-adsorbing organic polymer gel is made with a polymer network having a predetermined size, solution / floc separation can be performed by simple means such as filtration.
発明者らは先に、特願２００３−３２０２０９号にて、廃液中の金属多価イオン（陽イオン）を吸着・除去する架橋剤無添加生分解性高分子ゲルを提案した。発明者らは今般、低濃度であっても毒性の高い漏洩有害陰イオンを吸着・除去する吸着用ゲルとして、有害陰イオンを静電的な相互作用で吸着するカチオン性の側鎖を有する有機高分子ゲルを発明した。 The inventors previously proposed, in Japanese Patent Application No. 2003-320209, a biodegradable polymer gel without a crosslinking agent that adsorbs and removes metal polyvalent ions (cations) in the waste liquid. The present inventors have now developed an organic gel having a cationic side chain that adsorbs harmful anions by electrostatic interaction as an adsorbing gel that adsorbs and removes harmful anions with high toxicity even at low concentrations. A polymer gel was invented.
本発明において、吸着剤として高分子ゲルという形態を採った理由は、低濃度であっても有害な漏泄有害陰イオンの吸着・回収に際し、次の利点を有することによる。（１）通常のイオン交換樹脂に比し、有機高分子ゲルはイオン吸着に寄与する官能基の密度が高いために、有害陰イオンがイオン性官能基に遭遇する割合がより高く、有害陰イオン吸着効率が高い。（２）陰イオン吸着物質としてよく知られているゼオライトは、ＡｍＢｎＯ２ｎ・ＣＨ２Ｏ（Ａ＝Ｎａ，Ｃａ，Ｋ，まれにＢａ，Ｓｒ、Ｂ＝Ｓｉ＋Ａｌ（Ｓｉ：Ａｌ＞１）、Ｃ＝不定）という組成をもつが、原子量の大きな元素を多く含むので、吸着剤単位重量当りの吸着物質重量が小さい。これに対し有機高分子ゲルの場合は、Ｃ、Ｈ、Ｏ、Ｎ等の軽い元素のみで構成されているから、ゼオライト等に比し吸着剤単位重量当りの吸着物質重量が大きい。従って、取り扱いが容易でありまた、運搬コストも低くできる。（３）共有結合によって網目が形成されている有機高分子ゲルは、外部環境変化に対し網目構造が比較的安定である。従って、高分子凝集剤のキレーション能力を利用しフロックを形成させイオンを除去する方法に比し、有害陰イオン回収処理の際の極端な環境条件の変動等によって網目構造が破壊される虞が少ない。また、高分子凝集剤のキレーションによって形成されるフロックは大きさがばらついているから、濾別等簡便な手段での溶液・フロック分離が困難である。これに対し、有機高分子ゲルを用いる方法によるときは、高分子網目構造は予定された大きさに揃えられて作られているから、濾別等簡便な手段での溶液・フロック分離が可能である。（４）素材を適切に選択すれば吸着した有害陰イオンを放出させることができ、砒酸、亜砒酸、クロム酸等金属酸化物放出後の有機高分子ゲルは、濾別等簡便な手段での溶液・フロック分離によって再利用も可能である。 In the present invention, the reason why the polymer gel is used as the adsorbent is that it has the following advantages in adsorbing and collecting harmful leaking harmful anions even at a low concentration. (1) Compared to ordinary ion exchange resins, organic polymer gels have a higher density of functional groups that contribute to ion adsorption. Therefore, the rate at which harmful anions encounter ionic functional groups is higher, and harmful anions. High adsorption efficiency. (2) Zeolite well known as an anion adsorbing material is A m B n O 2n · CH 2 O (A = Na, Ca, K, rarely Ba, Sr, B = Si + Al (Si: Al> 1 ), C = indeterminate), but contains a large amount of elements with a large atomic weight, so the weight of the adsorbent per unit weight of adsorbent is small. On the other hand, the organic polymer gel is composed of only light elements such as C, H, O, and N, so that the adsorbed substance weight per adsorbent unit weight is larger than that of zeolite and the like. Therefore, handling is easy and the transportation cost can be reduced. (3) The organic polymer gel in which a network is formed by a covalent bond has a relatively stable network structure against changes in the external environment. Therefore, the network structure is less likely to be destroyed due to changes in extreme environmental conditions during harmful anion recovery treatment, compared to the method of removing ions by forming flocs using the chelating ability of the polymer flocculant. . In addition, since the flocs formed by the chelation of the polymer flocculant vary in size, it is difficult to separate the solution and floc by simple means such as filtration. On the other hand, when the method using an organic polymer gel is used, the polymer network structure is made in a predetermined size, so that solution / floc separation can be performed by simple means such as filtration. is there. (4) Adsorbed harmful anions can be released if the material is selected appropriately. Organic polymer gels after release of metal oxides such as arsenic acid, arsenous acid, and chromic acid can be obtained by simple means such as filtration. -Reusable by floc separation.
本発明の有害陰イオン吸着有機高分子ゲルの網目構造を、模式的に図１に示す。本発明の有害陰イオン吸着有機高分子ゲルは、図１に示すように、架橋による三次元網目構造をもっている。網目を形成する主鎖は、主としてビニル基の重合体からなっている。イオン吸着に寄与する官能基は、主鎖から派生する側鎖末端の正の電荷をもつイオン性官能基である。 The network structure of the harmful anion-adsorbing organic polymer gel of the present invention is schematically shown in FIG. As shown in FIG. 1, the harmful anion-adsorbing organic polymer gel of the present invention has a three-dimensional network structure formed by crosslinking. The main chain forming the network is mainly composed of a vinyl group polymer. The functional group contributing to ion adsorption is an ionic functional group having a positive charge at the end of the side chain derived from the main chain.
本発明の有害陰イオン吸着有機高分子ゲルの原料は、アクリルアミド／ジメチルアミノエチルアクリレート塩化メチル重合体およびジメチルアミノエチルアクリレート塩化メチル重合体である。これらの物質は、下水処理の際の汚泥除去剤として広く使用されており、安全である。前記物質以外にも、カチオン性高分子凝集剤として使用されている物質を用いて有害陰イオン吸着高分子ゲルを製造することもできる。同様な物質としてキチンやキトサン等があるが、これらに比し上記原料によるときは、有害陰イオン吸着有機高分子ゲルを安価に製造することができる。 The raw materials for the harmful anion-adsorbing organic polymer gel of the present invention are acrylamide / dimethylaminoethyl acrylate methyl chloride polymer and dimethylaminoethyl acrylate methyl chloride polymer. These substances are widely used as a sludge remover during sewage treatment and are safe. In addition to the above substances, harmful anion adsorbing polymer gels can also be produced using substances used as cationic polymer flocculants. There are chitin and chitosan as similar substances, but when using the above raw materials, harmful anion-adsorbing organic polymer gels can be produced at low cost.
有害陰イオン吸着有機高分子ゲルの製造方法として、原料にγ線を照射して重合させる方法もあるが、Ｎ，Ｎ’−メチレンビスアクリルアミド等の架橋剤を用いてラジカル重合によって製造することもできる。 As a method for producing the harmful anion-adsorbing organic polymer gel, there is a method of polymerizing by irradiating the raw material with γ rays, but it can also be produced by radical polymerization using a crosslinking agent such as N, N′-methylenebisacrylamide. it can.
表１に示す濃度と割合のアクリルアミド（１５mol％）／ジメチルアミノエチルアクリレート塩化メチル（８５mol％）共重合体（カチオン性の側鎖を有する：Ａ）と、アクリルアミド（Ｂ）の混合水溶液をγ線照射（５０ｋＧｙ）による重合を行った。これによって、カチオン性の側鎖を有する有機高分子ゲルを得た。 A mixed aqueous solution of acrylamide (15 mol%) / dimethylaminoethyl acrylate methyl chloride (85 mol%) copolymer (having a cationic side chain: A) and acrylamide (B) in the concentrations and proportions shown in Table 1 is γ-rayed. Polymerization by irradiation (50 kGy) was performed. Thereby, an organic polymer gel having a cationic side chain was obtained.
表１に示す各試料の定量（０.５ｃｍ×０.５ｃｍ×１ｃｍ）を切り出し、未反応物の洗浄・除去のために、純水中に２４時間浸漬した。洗浄した試料群を、検査セル中のクロム酸水溶液（それぞれ１０ｍＭのＣｒＯ３水溶液２０ｍｌ）中に２４時間浸漬した。 A fixed amount (0.5 cm × 0.5 cm × 1 cm) of each sample shown in Table 1 was cut out and immersed in pure water for 24 hours for washing and removing unreacted substances. The cleaned sample group was immersed for 24 hours in a chromic acid aqueous solution (20 ml of 10 mM CrO 3 aqueous solution each) in the inspection cell.
クロム酸イオンを吸着した試料群を取り出し、残液中のクロム酸イオン濃度を、原子吸光法によって測定した。残液中のクロム酸イオン濃度に残液の容積を乗ずることによって、クロム酸の重量を算出した。算出された残液中のクロム酸重量を、試料群を投入する前の検査セル中のクロム酸重量から差し引いて有機高分子ゲルに吸着したクロム酸重量を算出した。 A sample group adsorbing chromate ions was taken out, and the chromate ion concentration in the residual liquid was measured by atomic absorption method. The weight of chromic acid was calculated by multiplying the chromate ion concentration in the residual liquid by the volume of the residual liquid. The calculated weight of chromic acid in the residual liquid was subtracted from the weight of chromic acid in the test cell before the sample group was added to calculate the weight of chromic acid adsorbed on the organic polymer gel.
表２に示す濃度と割合のジメチルアミノエチルメタクリレート塩化メチル（カチオン性の側鎖を有するＣ）とアクリルアミド（Ｂ）の混合水溶液にγ線照射による重合を行うことによって、カチオン性の側鎖を有する有機高分子ゲルを製造した。 Dimethylaminoethyl methacrylate methyl chloride (C having a cationic side chain) and acrylamide (B) in concentrations and proportions shown in Table 2 are polymerized by γ-ray irradiation to have a cationic side chain. An organic polymer gel was produced.
表２に示す各試料の定量（０.５ｃｍ×０.５ｃｍ×１ｃｍ）を切り出し、未反応物の洗浄・除去のために、純水中に２４時間浸漬した。洗浄した試料群を、検査セル中のクロム酸水溶液（それぞれ１０ｍＭのＣｒＯ３水溶液２０ｍｌ）中に２４時間浸漬した。 A fixed amount (0.5 cm × 0.5 cm × 1 cm) of each sample shown in Table 2 was cut out and immersed in pure water for 24 hours for washing and removing unreacted substances. The cleaned sample group was immersed for 24 hours in a chromic acid aqueous solution (20 ml of 10 mM CrO 3 aqueous solution each) in the inspection cell.
クロム酸イオンを吸着した試料群を取り出し、残液中のクロム酸イオン濃度を、原子吸光法によって測定した。残液中のクロム酸イオン濃度に残液の容積を乗ずることによって、クロム酸の重量を算出した。算出された残液中のクロム酸重量を、試料群を投入する前の検査セル中のクロム酸重量から差し引いて有機高分子ゲルに吸着したクロム酸重量を算出した。 A sample group adsorbing chromate ions was taken out, and the chromate ion concentration in the residual liquid was measured by atomic absorption method. The weight of chromic acid was calculated by multiplying the chromate ion concentration in the residual liquid by the volume of the residual liquid. The weight of chromic acid adsorbed to the organic polymer gel was calculated by subtracting the calculated weight of chromic acid in the residual liquid from the weight of chromic acid in the test cell before introducing the sample group.
実施例１および実施例２における有害陰イオン吸着有機高分子ゲルのクロム酸イオン吸着特性を、図２に示す。図２において、□試料１とあるは、実施例１における試料について、また◆試料２とあるは、実施例２における試料についてのものである。図２において、１.４Ｍゲル、２.１Ｍゲル、２.８Ｍゲル、および４.２Ｍゲルは、実施例１においては［Ａ＋Ｂ］の、実施例２においては［Ｃ＋Ｂ］の濃度で製造したゲルを示す。図２のグラフの横軸は、実施例１における試料についてはＡと（Ａ＋Ｂ）の、実施例２における試料についてはＣと（Ｃ＋Ｂ）のモル比を表している。
The chromate ion adsorption characteristics of the harmful anion adsorption organic polymer gel in Example 1 and Example 2 are shown in FIG. In FIG. 2, □ Sample 1 is for the sample in Example 1, and ◆
図２から明らかなように、有機高分子ゲル中の側鎖にカチオン性の側鎖を有するＡ（アクリルアミド（１５mol％）／ジメチルアミノエチルアクリレート塩化メチル（８５mol％）共重合体）やＣ（ジメチルアミノエチルアクリレート塩化メチル）の割合が増すと共にクロム酸の吸着量が増加している。このように、カチオン性の側鎖を有する有機高分子ゲルは高い有害陰イオン吸着性能を有する。 As is clear from FIG. 2, A (acrylamide (15 mol%) / dimethylaminoethyl acrylate methyl chloride (85 mol%) copolymer) having a cationic side chain in the side chain in the organic polymer gel and C (dimethyl). As the proportion of aminoethyl acrylate methyl chloride) increases, the adsorption amount of chromic acid increases. Thus, the organic polymer gel having a cationic side chain has high harmful anion adsorption performance.
本発明の有害陰イオン吸着有機高分子ゲルは、環境中の、微量であっても人体に有害な陰イオンの吸着処理剤として有効に利用することができる。具体的には、環境中に存在する有害な多価陰イオンである砒酸、亜砒酸、クロム酸、重クロム酸、セレン酸、亜セレン酸、硼酸、および燐酸等の除去に有効である。而して、先に述べた、廃棄物の最終処分場における環境汚染防止のほか、湖沼、海洋における燐酸の増加による富栄養化による環境汚染防止、めっき廃液中の六価クロム除去、休廃止鉱山からの砒素漏洩による地質汚染防止、セレン、硼素による土壌・地下水汚染防止等広範囲に応用することができる。 The harmful anion-adsorbing organic polymer gel of the present invention can be effectively used as an anion adsorption treatment agent harmful to the human body even in trace amounts in the environment. Specifically, it is effective in removing harmful polyvalent anions present in the environment, such as arsenic acid, arsenous acid, chromic acid, dichromic acid, selenic acid, selenous acid, boric acid, and phosphoric acid. Thus, in addition to preventing environmental pollution at the final disposal site for waste as described above, prevention of environmental pollution by eutrophication due to increase of phosphoric acid in lakes and marine areas, removal of hexavalent chromium from plating waste liquid, suspended mine It can be applied in a wide range such as prevention of geological contamination due to arsenic leakage from the soil, and prevention of soil and groundwater contamination by selenium and boron.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| EXPY | Cancellation because of completion of term |