JP2013234925A - Cesium adsorbent - Google Patents
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- JP2013234925A JP2013234925A JP2012107681A JP2012107681A JP2013234925A JP 2013234925 A JP2013234925 A JP 2013234925A JP 2012107681 A JP2012107681 A JP 2012107681A JP 2012107681 A JP2012107681 A JP 2012107681A JP 2013234925 A JP2013234925 A JP 2013234925A
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- cesium
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- alkali metal
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- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 78
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003463 adsorbent Substances 0.000 title claims abstract description 49
- -1 cesium ions Chemical class 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 10
- 239000004111 Potassium silicate Substances 0.000 claims description 9
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical group [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 239000000378 calcium silicate Substances 0.000 claims description 8
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 8
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 8
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical group [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 6
- 229910001562 pearlite Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims 1
- 230000000274 adsorptive effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 23
- 238000010304 firing Methods 0.000 description 19
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 18
- 230000002285 radioactive effect Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 239000000356 contaminant Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000012857 radioactive material Substances 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 239000000428 dust Substances 0.000 description 7
- 239000010451 perlite Substances 0.000 description 7
- 235000019362 perlite Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000000941 radioactive substance Substances 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 230000002265 prevention Effects 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- GFZHEMRQPWLKAR-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);trihydrate Chemical compound O.O.O.[O-2].[O-2].[Al+3].[K+] GFZHEMRQPWLKAR-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000005332 obsidian Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- HCMVSLMENOCDCK-UHFFFAOYSA-N N#C[Fe](C#N)(C#N)(C#N)(C#N)C#N Chemical compound N#C[Fe](C#N)(C#N)(C#N)(C#N)C#N HCMVSLMENOCDCK-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000010849 combustible waste Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、セシウムイオンを吸着する吸着剤に関する。 The present invention relates to an adsorbent that adsorbs cesium ions.
原子力発電所の事故等が発生すると、高濃度の放射性物質（主に放射性セシウム）を含む原子炉汚染水が施設外に漏出したり、放射性物質が河川・海水・地下水あるいは大気中などへ拡散することにより、周辺環境に放射性物質で汚染された水・土壌・草木類等が大量に生じる恐れがある。また、これら放射能汚染物が雨水等により下水道に流入すると、放射性物質により汚染された下水汚泥、あるいはその下水汚泥を焼却減容化することで放射性物質が濃縮された焼却灰が生じる。さらに、放射性物質で汚染された草木類や塵芥などの可燃性廃棄物がゴミ焼却場などで焼却減容化されると、放射性物質が濃縮されたゴミ焼却灰が生じる。
放射能汚染物は人体に有害な放射線（ガンマ線など）を放出するため、これらの放射能汚染物に対しては適切に除去・保管等の処置を行い、放射線被爆による健康被害を防ぐ必要がある。特に汚染規模が大きく、広い地域に大量の放射能汚染物が発生した場合には、放射能汚染物の除染処理（放射能汚染物からの放射性物質の除去処理、放射能汚染物の保管など）に膨大な手間と時間と費用が必要になるため、放射能汚染物からの放射性物質の除去処理（セシウムイオンの吸着除去）、あるいは、保管時の放射性物質の拡散防止（雨水等によるセシウムイオンの拡散防止）を効率的かつ経済的に行うことができる技術が求められていた。
When a nuclear power plant accident occurs, reactor contaminated water containing high-concentration radioactive materials (mainly radioactive cesium) leaks out of the facility, or radioactive materials diffuse into rivers, seawater, groundwater, or the atmosphere. As a result, there is a risk that a large amount of water, soil, vegetation, etc. contaminated with radioactive materials may be generated in the surrounding environment. Moreover, when these radioactive contaminants flow into sewers by rainwater or the like, sewage sludge contaminated with radioactive substances, or incinerated ash enriched with radioactive substances by incineration and volume reduction of the sewage sludge is generated. Further, when combustible waste such as vegetation and dust contaminated with radioactive material is incinerated and reduced in a garbage incineration site, waste incinerated ash enriched with radioactive material is generated.
Radioactive contaminants emit radiation (gamma rays, etc.) that is harmful to the human body. Therefore, it is necessary to appropriately remove and store these radioactive contaminants to prevent health damage from radiation exposure. . In particular, when the scale of contamination is large and a large amount of radioactive contaminants are generated in a wide area, decontamination of radioactive contaminants (removal of radioactive contaminants from radioactive contaminants, storage of radioactive contaminants, etc.) ) Requires enormous effort, time and money, so removal of radioactive materials from radioactive contaminants (adsorption removal of cesium ions) or prevention of diffusion of radioactive materials during storage (cesium ions due to rainwater, etc.) Therefore, there is a need for a technology that can efficiently and economically prevent the diffusion of
従来、セシウムイオンの除去方法としては、例えば、ウラン水溶液中のセシウムイオンをゼオライトで吸着分離する方法（特許文献１）、ヘキサシアノ鉄でセシウムイオンを吸着分離する方法（特許文献２）、脱窒菌又はセシウム蓄積菌でセシウムイオンを吸着除去する方法（特許文献３）等が報告されている。また、ゼオライトについては、フライアッシュや鋳物廃砂を原料として合成ゼオライトを製造する方法（特許文献４、５）等が報告されている。また、放射能汚染物保管時の放射性物質の拡散防止方法として、ゼオライトを含む核種吸着セメント組成物で放射能汚染物を固化して放射性物質の拡散を防止する方法（特許文献６）等が報告されている。 Conventionally, as a method for removing cesium ions, for example, a method of adsorbing and separating cesium ions in a uranium aqueous solution with zeolite (Patent Document 1), a method of adsorbing and separating cesium ions with hexacyanoiron (Patent Document 2), denitrifying bacteria, or A method of adsorbing and removing cesium ions with cesium-accumulating bacteria (Patent Document 3) has been reported. Moreover, about zeolite, the method (patent documents 4, 5) etc. which manufacture a synthetic zeolite from fly ash and casting waste sand as a raw material are reported. Further, as a method for preventing the diffusion of radioactive substances during storage of radioactive contaminants, a method for preventing the diffusion of radioactive substances by solidifying radioactive contaminants with a radionuclide adsorbing cement composition containing zeolite (Patent Document 6), etc. has been reported. Has been.
しかしながら、これら従来の技術では、セシウムイオンの吸着除去性能が低い、高価なセシウム吸着剤を使用する必要がある、廃棄物原料を使用した吸着剤（合成ゼオライト）であるが水熱合成に手間と時間がかかるため製造コストが高くなる、放射性物質の拡散を防止するための放射能汚染物の固化処理に手間がかかる等の問題があり、大量の放射能汚染物を効率的かつ経済的に処理・保管するための技術としては不十分であった。
従って、本発明の課題は、セシウムイオンに対する吸着性能が高く、低コストで簡便に製造することができ、セシウムイオンの除去処理やセシウムイオンの拡散防止を効率的かつ経済性に行うことを可能にするセシウム吸着剤を提供することにある。
However, in these conventional techniques, it is necessary to use an expensive cesium adsorbent with low cesium ion adsorption removal performance, but it is an adsorbent (synthetic zeolite) using waste materials, but it takes time and effort to hydrothermal synthesis. There are problems such as time-consuming manufacturing costs increase, solidification of radioactive contaminants to prevent the diffusion of radioactive materials, and a large amount of radioactive contaminants can be processed efficiently and economically.・ It was insufficient as a technology for storage.
Therefore, the problem of the present invention is that the adsorption performance for cesium ions is high, and can be easily produced at low cost, and it is possible to efficiently and economically perform cesium ion removal treatment and cesium ion diffusion prevention. It is to provide a cesium adsorbent.
本発明者は、上記課題解決のため検討を重ねた結果、難水溶性珪酸質粉末、アルカリ金属珪酸塩、アルミン酸カリウムおよび水を含有する混合物を焼成することで、セシウムイオンに対する吸着性能がゼオライトに比べて顕著に優れる吸着剤が得られることを見出し、本発明を完成した。 As a result of repeated studies to solve the above problems, the present inventors have calcined a mixture containing a hardly water-soluble siliceous powder, an alkali metal silicate, potassium aluminate, and water, so that the adsorption performance for cesium ions is zeolite. As a result, it was found that an adsorbent remarkably superior to that of the present invention was obtained, and the present invention was completed.
すなわち、本発明は、次の［１］〜［５］に係るものである。
［１］難水溶性珪酸質粉末、アルカリ金属珪酸塩、アルカリ金属アルミン酸塩および水を含有する混合物の焼成物からなるセシウム吸着剤。
［２］難水溶性珪酸質粉末が、パーライト発泡体の製造時に生じる珪酸質廃棄物、珪酸カルシウムボードを製造・加工する際に生じる珪酸カルシウム廃棄物、及びフライアッシュから選ばれる１種以上である［１］の吸着剤。
［３］アルカリ金属珪酸塩が珪酸カリウムである［１］または［２］の吸着剤。
［４］アルカリ金属アルミン酸塩がアルミン酸カリウムである［１］〜［３］のいずれかの吸着剤。
［５］前記混合物の含水率が１０〜７０質量％であり、該混合物の焼成温度が２００〜８００℃である［１］〜［４］のいずれかの吸着剤。
That is, the present invention relates to the following [1] to [5].
[1] A cesium adsorbent comprising a fired product of a mixture containing a slightly water-soluble siliceous powder, an alkali metal silicate, an alkali metal aluminate and water.
[2] The poorly water-soluble siliceous powder is at least one selected from siliceous waste produced during production of pearlite foam, calcium silicate waste produced during production and processing of calcium silicate board, and fly ash. [1] Adsorbent.
[3] The adsorbent according to [1] or [2], wherein the alkali metal silicate is potassium silicate.
[4] The adsorbent according to any one of [1] to [3], wherein the alkali metal aluminate is potassium aluminate.
[5] The adsorbent according to any one of [1] to [4], wherein the water content of the mixture is 10 to 70% by mass, and the firing temperature of the mixture is 200 to 800 ° C.
本発明のセシウム吸着剤は、天然ゼオライトに比べセシウムイオンの吸着性能が高く、さらには、産業廃棄物として発生する難水溶性珪酸質粉末を原料に使用して経済的に製造できる吸着剤である。放射能汚染物からの放射性セシウムの除去処理、あるいは、放射能汚染物保管時の放射性物質（セシウムイオン）の拡散防止への適用が期待できる吸着剤である。 The cesium adsorbent of the present invention has higher cesium ion adsorption performance than natural zeolite, and is an adsorbent that can be economically produced using raw water-soluble siliceous powder generated as industrial waste. . It is an adsorbent that can be expected to be applied to remove radioactive cesium from radioactive contaminants or to prevent diffusion of radioactive substances (cesium ions) during storage of radioactive contaminants.
本発明のセシウム吸着剤は、（Ａ）難水溶性珪酸質粉末、（Ｂ）アルカリ金属珪酸塩、（Ｃ）アルカリ金属アルミン酸塩および（Ｄ）水を含有する混合物の焼成物からなるものであり、当該焼成物は例えば当該成分（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）を含有する混合物を焼成することにより得られる。 The cesium adsorbent of the present invention comprises (A) a hardly water-soluble siliceous powder, (B) an alkali metal silicate, (C) an alkali metal aluminate, and (D) a fired mixture of water. Yes, the fired product is obtained, for example, by firing a mixture containing the components (A), (B), (C), and (D).
本発明のセシウム吸着剤に用いる（Ａ）難水溶性珪酸質粉末としては、水に対する溶解度が１００mg／Ｌ未満の珪酸を主成分とする粉末であればよく、珪酸を主成分とする種々の天然物、合成物及び廃棄物が用いられる。ここで珪酸を主成分とするとは、珪酸又は難水溶性珪酸塩を６０質量％以上含有することをいい、好ましくは８０質量％以上含有することをいう。なお、アルカリ金属珪酸塩は、水に可溶であるから、（Ａ）難水溶性珪酸塩には含まれない。 The (A) sparingly water-soluble siliceous powder used in the cesium adsorbent of the present invention may be any powder having a solubility in water of less than 100 mg / L as a main component, and various natural compounds mainly composed of silicic acid. Products, composites and wastes are used. Here, “having silicic acid as a main component” means that 60 mass% or more, preferably 80 mass% or more of silicic acid or a hardly water-soluble silicate is contained. In addition, since alkali metal silicate is soluble in water, it is not contained in (A) poorly water-soluble silicate.
（Ａ）難水溶性珪酸質粉末の具体例としては、黒曜石、真珠岩、松脂岩、珪藻土、珪酸塩白土、火山シラス、フライアッシュ、珪酸カルシウム、黒曜石や真珠岩を高温で熱処理してできる人工発泡体（パーライト発泡体）などが挙げられる。廃棄物資源の有効活用および製造コスト低減の観点から、パーライト発泡体の製造時に生じる珪酸質廃棄物（パーライト発泡体ダスト等）、珪酸カルシウムボードを製造・加工する際に生じる珪酸カルシウム廃棄物（珪酸カルシウムボードの切削粉等）、フライアッシュが特に好適に使用できる。これらの珪酸質粉末は、１種又は２種以上を組み合わせて使用することができる。 (A) Specific examples of sparingly water-soluble siliceous powders include obsidian, pearlite, pine stone, diatomaceous earth, silicate white clay, volcanic shirasu, fly ash, calcium silicate, obsidian, and pearlite that are heat-treated at high temperatures. Examples thereof include a foam (perlite foam). From the viewpoint of effective utilization of waste resources and reduction of manufacturing costs, siliceous waste (perlite foam dust, etc.) generated during the manufacture of pearlite foam, calcium silicate waste (silicic acid) generated during manufacture and processing of calcium silicate boards Calcium board cutting powder and the like) and fly ash can be used particularly preferably. These siliceous powders can be used alone or in combination of two or more.
難水溶性珪酸質粉末のかさ密度は、セシウムイオン吸着能の点から、０．８ｇ／ｃｍ3以下が好ましく、０．５ｇ／ｃｍ3以下がより好ましい。また、難水溶性珪酸質粉末の粒度はセシウムイオン吸着能の点から、０.６ｍｍ以下が好ましく、０.３ｍｍ以下がより好ましい。 The bulk density of the sparingly water-soluble siliceous powder, in terms of cesium ion adsorption capacity is preferably 0.8 g / cm 3 or less, 0.5 g / cm 3 or less is more preferable. Further, the particle size of the slightly water-soluble siliceous powder is preferably 0.6 mm or less, more preferably 0.3 mm or less, from the viewpoint of cesium ion adsorption ability.
本発明のセシウム吸着剤に用いる（Ｂ）アルカリ金属珪酸塩としては、珪酸ナトリウム、珪酸カリウム、珪酸リチウムが挙げられる。珪酸ナトリウムとしては、水溶液状の１号珪酸ナトリウム、２号珪酸ナトリウム、３号珪酸ナトリウムなど、あるいは粉末状のメタ珪酸ナトリウムの1種または２種などが使用できる。また、珪酸カリウムとしては水溶液状の１号珪酸カリウムまたは２号珪酸カリウムなどが使用できる。これらアルカリ金属珪酸塩のなかでは、珪酸ナトリウムまたは珪酸カリウムが比較的安価であるため好ましく、珪酸カリウムを用いるとセシウムイオンの吸着性能が向上するため特に好ましい。 Examples of the (B) alkali metal silicate used in the cesium adsorbent of the present invention include sodium silicate, potassium silicate, and lithium silicate. As sodium silicate, aqueous solution No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, etc., or one or two kinds of powdered sodium metasilicate can be used. Moreover, as potassium silicate, aqueous No. 1 potassium silicate or No. 2 potassium silicate can be used. Among these alkali metal silicates, sodium silicate or potassium silicate is preferable because it is relatively inexpensive, and potassium silicate is particularly preferable because the adsorption performance of cesium ions is improved.
本発明のセシウム吸着剤に用いる（Ｃ）アルカリ金属アルミン酸塩としては、アルミン酸ナトリウム、アルミン酸カリウム、アルミン酸リチウムが挙げられる。アルミン酸ナトリウムとしては水溶液状または粉末状のいずれも使用できる。また、アルミン酸カリウムとしては水溶液状または粉末状（アルミン酸カリウム三水和物）のいずれも使用できる。これらアルカリ金属アルミン酸塩のなかでは、アルミン酸ナトリウムまたはアルミン酸カリウムが比較的安価であるため好ましく、アルミン酸カリウムを用いるとセシウムイオンの吸着性能が向上するため特に好ましい。 Examples of the (C) alkali metal aluminate used in the cesium adsorbent of the present invention include sodium aluminate, potassium aluminate, and lithium aluminate. As the sodium aluminate, either an aqueous solution or a powder can be used. As potassium aluminate, either aqueous solution or powder (potassium aluminate trihydrate) can be used. Among these alkali metal aluminates, sodium aluminate or potassium aluminate is preferable because it is relatively inexpensive, and potassium aluminate is particularly preferable because it improves the adsorption performance of cesium ions.
本発明のセシウム吸着剤は、例えば前述した難水溶性珪酸質粉末とアルカリ金属珪酸塩とアルカリ金属アルミン酸塩と水を混合した後、該混合物を焼成して得られる。該混合物において、アルカリ金属珪酸塩とアルカリ金属アルミン酸塩の配合割合は、セシウムイオン吸着能の点から、アルカリ金属珪酸塩１００重量部に対してアルカリ金属アルミン酸塩を５〜６０重量部配合するのが好ましく、１０〜３０重量部配合するのがより好ましい。
また、該混合物において、アルカリ金属珪酸塩とアルカリ金属アルミン酸塩は、セシウムイオン吸着能及び経済性の点から、その合計量が難水溶性珪酸質粉末１００重量部に対して１０〜１００重量部となるように配合するのが好ましく、３０〜７０重量部がより好ましい。
The cesium adsorbent of the present invention can be obtained, for example, by mixing the above-mentioned poorly water-soluble siliceous powder, alkali metal silicate, alkali metal aluminate, and water and then firing the mixture. In the mixture, the mixing ratio of the alkali metal silicate and the alkali metal aluminate is 5-60 parts by weight of the alkali metal aluminate with respect to 100 parts by weight of the alkali metal silicate in terms of cesium ion adsorption ability. Of these, 10 to 30 parts by weight are more preferable.
In the mixture, the total amount of alkali metal silicate and alkali metal aluminate is 10 to 100 parts by weight with respect to 100 parts by weight of the slightly water-soluble siliceous powder from the viewpoint of cesium ion adsorption ability and economy. It is preferable to mix | blend so that it may become, and 30-70 weight part is more preferable.
前記混合物において、（Ｄ）水の配合割合は、難水溶性珪酸質粉末とアルカリ金属珪酸塩とアルカリ金属アルミン酸塩の合計１００重量部に対して、３０〜１５０重量部となるように配合するのが好ましく、６０〜１００重量部がより好ましい。水の配合割合が少なすぎると難水溶性珪酸質粉末とアルカリ金属珪酸塩とアルカリ金属アルミン酸塩を均一に混合することができなかったり、多すぎると混合後の混合物が分離するなどして、吸着剤の製造に支障が生じる場合があるため好ましくない。なお、水溶液状のアルカリ金属珪酸塩を用いる場合は、その水分量は水の配合量に含めるものとする。 In the mixture, (D) the mixing ratio of water is 30 to 150 parts by weight with respect to a total of 100 parts by weight of the slightly water-soluble siliceous powder, the alkali metal silicate, and the alkali metal aluminate. Of these, 60 to 100 parts by weight are more preferable. If the blending ratio of water is too small, the slightly water-soluble siliceous powder, the alkali metal silicate and the alkali metal aluminate cannot be mixed uniformly, or if it is too much, the mixture after mixing will be separated. This is not preferable because the production of the adsorbent may be hindered. In addition, when using aqueous alkali metal silicate, the moisture content shall be included in the compounding quantity of water.
本発明のセシウム吸着剤の製造において、難水溶性珪酸質粉末とアルカリ金属珪酸塩とアルカリ金属アルミン酸塩および水の混合方法は特に限定されず、ホバート式モルタルミキサー、パン型ミキサー、強制二軸ミキサーなどの一般的なミキサーを用いて混合することができる。 In the production of the cesium adsorbent of the present invention, the method of mixing the poorly water-soluble siliceous powder, the alkali metal silicate, the alkali metal aluminate and water is not particularly limited, and the Hobart mortar mixer, pan mixer, forced biaxial It can mix using common mixers, such as a mixer.
本発明では、前記混合物を未乾燥の状態で焼成してセシウム吸着剤を製造するのが好ましい。焼成時の該混合物の含水率は１０質量％以上が好ましく、１０〜７０質量％がより好ましく、２０〜４０質量％がさらに好ましい。含水率が低すぎるとセシウムイオンに対する吸着性能が大幅に低下するため好ましくなく、含水率が高すぎると焼成時間が長くなり効率的・経済的な製造が困難となる恐れがある。そのため、該混合物は含水率が１０質量％以上、さらに１０〜７０質量％の範囲に収まるように調整した後に焼成するのが好ましい。例えば、該混合物が含水率の高いスラリー状の混合物である場合は、型枠等に流し込んで一定期間養生し、変形しない程度まで固化した後に型枠等から取り外し、含水率が７０質量％以下になるまで乾燥させてから焼成するのが好ましい。また、該混合物が含水率の低い粉粒状である場合は、ロールプレス等で圧縮成形してから焼成するのが好ましい。焼成時の該混合物の形状は特に限定されないが、混合物の形状（厚み）が大きすぎると均質な焼成物が得られ難くなる恐れがあるため、混合物の厚みは３０ｍｍ以下程度にすることが望ましい。 In the present invention, it is preferable to produce the cesium adsorbent by firing the mixture in an undried state. The water content of the mixture during firing is preferably 10% by mass or more, more preferably 10 to 70% by mass, and further preferably 20 to 40% by mass. If the moisture content is too low, the adsorption performance for cesium ions is greatly reduced, which is not preferable. If the moisture content is too high, the firing time becomes long, and efficient and economical production may be difficult. Therefore, the mixture is preferably fired after adjusting the moisture content to be within the range of 10% by mass or more, and further within the range of 10 to 70% by mass. For example, if the mixture is a slurry-like mixture having a high water content, it is poured into a mold or the like, cured for a certain period of time, solidified to the extent that it does not deform, and then removed from the mold or the like, so that the moisture content is 70% by mass or less. It is preferable to dry it until it is fired. Further, when the mixture is in the form of powder having a low water content, it is preferably fired after being compression-molded by a roll press or the like. The shape of the mixture at the time of firing is not particularly limited. However, if the shape (thickness) of the mixture is too large, it may be difficult to obtain a homogeneous fired product. Therefore, the thickness of the mixture is preferably about 30 mm or less.
前記混合物の焼成においては、セシウムイオン吸着能の点から、焼成温度を２００〜８００℃とするのが好ましく、３００〜５００℃がより好ましい。焼成時間は概ね５〜３０分程度で良く、前記混合物の含水率が高い場合や焼成温度が低い場合には焼成時間を長めに設定する。本発明のセシウム吸着剤は、前記混合物の含水率を２０〜４０質量％に調整して、３００〜５００℃の温度で焼成すると、２０分程度の短い焼成時間で吸着性能の高いセシウム吸着剤が得られるため、製造コスト（エネルギーコスト）低減の面から特に好ましい。焼成設備は特に限定されないが、焼成温度の管理が容易で簡便に使用できることから、電気炉や外熱式キルン等の焼成設備が好ましい。 In firing the mixture, the firing temperature is preferably 200 to 800 ° C, more preferably 300 to 500 ° C, from the viewpoint of cesium ion adsorption ability. The firing time may be approximately 5 to 30 minutes, and when the water content of the mixture is high or the firing temperature is low, the firing time is set longer. The cesium adsorbent of the present invention is a cesium adsorbent with high adsorption performance in a short baking time of about 20 minutes when the moisture content of the mixture is adjusted to 20 to 40% by mass and baking is performed at a temperature of 300 to 500 ° C. Since it is obtained, it is particularly preferable from the viewpoint of reducing the manufacturing cost (energy cost). The firing equipment is not particularly limited, but firing equipment such as an electric furnace or an external heating kiln is preferable because the firing temperature can be easily controlled and used easily.
本発明のセシウム吸着剤としては、セシウムイオン吸着能の点から、前記焼成物の粒度を粒径０．０５〜５ｍｍになるように調整して用いることが好ましく、粒径０.１〜３ｍｍが特に好ましい。本発明において、粒度の調整方法は特に限定されず、一般的な粉砕機器を用いて焼成物を粉砕した後にふるい等を用いて所定の粒度に調整することができる。粉砕機器として、回転刃で固形物を切断粉砕するミル式粉砕機や粉砕刃の反復運動で固形物を粉砕するジョークラッシャーを用いると０．０５ｍｍ以下の微粉の発生を少なくすることができるため特に好ましい。 The cesium adsorbent of the present invention is preferably used by adjusting the particle size of the fired product so that the particle size is 0.05 to 5 mm from the viewpoint of cesium ion adsorption ability. Particularly preferred. In the present invention, the method for adjusting the particle size is not particularly limited, and the baked product can be pulverized using a general pulverizer and then adjusted to a predetermined particle size using a sieve or the like. Especially when using a mill-type pulverizer that cuts and pulverizes solids with a rotary blade or a jaw crusher that pulverizes solids by repeated movement of the pulverizing blade, the generation of fine powder of 0.05 mm or less can be reduced. preferable.
本発明のセシウム吸着剤の使用量は、用途（セシウム含有物からのセシウムイオンの吸着除去、セシウム含有物からのセシウムイオンの拡散防止）あるいはセシウム含有物中のセシウムイオン濃度や吸着処理時間等によって異なるが、セシウムイオンの吸着除去に使用する場合は、セシウム含有物中のセシウムイオン濃度の５０〜３００倍程度の使用量（例えば、セシウム含有水のセシウムイオン濃度が１０ｍｇ／Ｌの場合は、本発明のセシウム吸着剤を０.５〜３ｇ／Ｌ使用する）で十分な吸着効果を発揮する。 The amount of the cesium adsorbent of the present invention depends on the application (adsorption removal of cesium ions from cesium-containing materials, prevention of diffusion of cesium ions from cesium-containing materials) or the concentration of cesium ions in the cesium-containing materials and the adsorption treatment time. Although it is different, when used for adsorption removal of cesium ions, the amount used is about 50 to 300 times the concentration of cesium ions in the cesium-containing material (for example, when the concentration of cesium ions in cesium-containing water is 10 mg / L, Adequate adsorption effect is exhibited by using 0.5 to 3 g / L of the inventive cesium adsorbent.
本発明のセシウム吸着剤の使用方法は特に限定されず、例えば、セシウム含有水からセシウムイオンを吸着除去する場合は、一般的に排水の凝集沈殿処理などで使用される凝集沈殿槽、攪拌ミキサー、吸引ろ過機、フィルタープレス等の装置を用いて、排水とセシウム吸着剤との混合および固液分離（セシウムイオンを吸着した吸着剤の除去）を行うことができる。また、本発明のセシウム吸着剤をセシウム含有物の保管（セシウムイオンの拡散防止）に用いる場合は、セシウム吸着剤を充填した透水性の袋やシート等をセシウム含有物の周囲に設置することで、雨水などによりセシウム含有物から溶出するセシウムイオンを吸着剤に捕捉させて周囲への拡散を防止することができる。 The method of using the cesium adsorbent of the present invention is not particularly limited. For example, when cesium ions are adsorbed and removed from cesium-containing water, a coagulation sedimentation tank, a stirring mixer, and the like generally used in coagulation sedimentation treatment of wastewater, Using a device such as a suction filter or a filter press, mixing of the waste water and the cesium adsorbent and solid-liquid separation (removal of the adsorbent adsorbing cesium ions) can be performed. In addition, when the cesium adsorbent of the present invention is used for storage of cesium-containing materials (preventing diffusion of cesium ions), a water-permeable bag or sheet filled with the cesium adsorbent is installed around the cesium-containing materials. In addition, the cesium ions eluted from the cesium-containing material by rainwater or the like can be captured by the adsorbent to prevent diffusion to the surroundings.
次に実施例を挙げて本発明をさらに詳細に説明する。 EXAMPLES Next, an Example is given and this invention is demonstrated still in detail.
（セシウム吸着剤の製造）
以下のＡ１〜Ｄの材料を表１に示す割合で配合し、ホバート式モルタルミキサーを用いて３分間混合して混合物を得た。該混合物を内寸１５×１５×１５ｍｍの型枠に入れて成形し、１日後に脱型してから４０℃の乾燥温度で一定時間乾燥し、その後、電気炉を用いて該混合物を焼成した。焼成後、焼成物を常温近傍まで炉外で自然冷却してからジョークラッシャーまたはミル式粉砕機を用いて粉砕し、ふるいを用いて所定の粒度に調整してセシウム吸着剤を得た。セシウム吸着剤の製造条件（使用した混合物Ｎｏ．、焼成前の混合物の含水率、焼成温度および焼成時間、粉砕・粒度調整した焼成物の粒度）を表２に示す。
(Manufacture of cesium adsorbent)
The following materials A1 to D were blended in the proportions shown in Table 1 and mixed for 3 minutes using a Hobart mortar mixer to obtain a mixture. The mixture was put into a mold having an inner size of 15 × 15 × 15 mm, molded after one day, and then dried at a drying temperature of 40 ° C. for a certain period of time. Thereafter, the mixture was baked using an electric furnace. . After firing, the fired product was naturally cooled outside the furnace to near room temperature, then ground using a jaw crusher or a mill grinder, and adjusted to a predetermined particle size using a sieve to obtain a cesium adsorbent. Table 2 shows the production conditions of the cesium adsorbent (the mixture No. used, the water content of the mixture before firing, the firing temperature and firing time, and the particle size of the fired product after pulverization and particle size adjustment).
（Ａ１）珪酸質粉末：パーライト発泡体ダスト（かさ密度０．４ｇ／ｃｍ3、粒径０．３ｍｍ以下）
（Ａ２）珪酸質粉末：パーライト発泡体ダスト（かさ密度０．４ｇ／ｃｍ3、粒径０．６ｍｍ以下）
（Ａ３）珪酸質粉末：パーライト発泡体ダスト（かさ密度０．４ｇ／ｃｍ3、粒径０．６〜０．８ｍｍ）
（Ａ４）珪酸質粉末：パーライト発泡体ダスト（かさ密度０．６ｇ／ｃｍ3、粒径０．３ｍｍ以下）
（Ａ５）珪酸質粉末：未発泡パーライトダスト（かさ密度０．９ｇ／ｃｍ3、粒径０．３ｍｍ以下）
（Ａ６）珪酸質粉末：珪酸カルシウムボード切削粉（かさ密度０．４ｇ／ｃｍ3、粒径０．３ｍｍ以下）
（Ａ７）珪酸質粉末：フライアッシュ市販品（かさ密度０．９ｇ／ｃｍ3、粒径０．０２ｍｍ以下）
(A1) Silicate powder: Perlite foam dust (bulk density 0.4 g / cm 3 , particle size 0.3 mm or less)
(A2) Silicate powder: Perlite foam dust (bulk density 0.4 g / cm 3 , particle size 0.6 mm or less)
(A3) Silicic powder: perlite foam dust (bulk density 0.4 g / cm 3 , particle size 0.6 to 0.8 mm)
(A4) Silicate powder: Perlite foam dust (bulk density 0.6 g / cm 3 , particle size 0.3 mm or less)
(A5) Siliceous powder: Unfoamed perlite dust (bulk density 0.9 g / cm 3 , particle size 0.3 mm or less)
(A6) Silicate powder: Calcium silicate board cutting powder (bulk density 0.4 g / cm 3 , particle size 0.3 mm or less)
(A7) Silicic powder: fly ash commercial product (bulk density 0.9 g / cm 3 , particle size 0.02 mm or less)
（Ｂ１）アルカリ金属珪酸塩：１号珪酸カリウム（富士化学社製、二酸化珪素２７．５〜２９％、酸化ナトリウム２１〜２３％）
（Ｂ２）アルカリ金属珪酸塩：１号珪酸ナトリウム（富士化学社製、二酸化珪素３５〜３８％、酸化ナトリウム１７〜１９％）
(B1) Alkali metal silicate: No. 1 potassium silicate (Fuji Chemical Co., Ltd., silicon dioxide 27.5-29%, sodium oxide 21-23%)
(B2) Alkali metal silicate: No. 1 sodium silicate (Fuji Chemical Co., Ltd., silicon dioxide 35-38%, sodium oxide 17-19%)
（Ｃ１）アルカリ金属アルミン酸塩：アルミン酸カリウム三水和物（関東化学社製試薬）
（Ｃ２）アルカリ金属アルミン酸塩：アルミン酸ナトリウム（関東化学社製試薬）
（Ｄ）水：蒸留水
(C1) Alkali metal aluminate: potassium aluminate trihydrate (reagent manufactured by Kanto Chemical Co., Inc.)
(C2) Alkali metal aluminate: sodium aluminate (reagent manufactured by Kanto Chemical Co., Inc.)
(D) Water: Distilled water
（セシウム含有水からのセシウムイオンの吸着除去試験）
関東化学社製のセシウム標準液（セシウムイオン濃度１０００ｍｇ／Ｌ）を使用してセシウムイオン濃度２０ｍｇ／Ｌのセシウム含有水を作成し、吸着除去試験の対象物とした。セシウム含有水１Ｌに対し、吸着剤として表２に示すセシウム吸着剤ならびに天然ゼオライト（北海道産モルデン沸石、粒度０．１５〜２．５ｍｍ）を所定量加え、攪拌機（回転数２００ｒ．ｐ．ｍ）で１０分間または３０分間混合した後に孔径０．４５μｍのメンブレンフィルターでろ過して検液とし、セシウムイオン濃度をＩＣＰ（ 高周波誘導結合プラズマ）質量分析法で測定してセシウムイオンの吸着量を算出した。セシウム含有水に対するセシウム吸着剤と天然ゼオライトの添加量およびセシウムイオンの吸着量を表３に示す。
(Adsorption removal test of cesium ions from cesium-containing water)
A cesium-containing water having a cesium ion concentration of 20 mg / L was prepared using a cesium standard solution (cesium ion concentration of 1000 mg / L) manufactured by Kanto Chemical Co., and used as an object for the adsorption removal test. A predetermined amount of cesium adsorbent shown in Table 2 and natural zeolite (Hokkaido mordenite, particle size 0.15 to 2.5 mm) as an adsorbent is added to 1 L of cesium-containing water, and a stirrer (rotation speed 200 rpm) After mixing for 10 minutes or 30 minutes, it was filtered through a membrane filter with a pore size of 0.45 μm to obtain a test solution, and the cesium ion concentration was measured by ICP (high frequency inductively coupled plasma) mass spectrometry to calculate the amount of adsorption of cesium ions . Table 3 shows the amount of cesium adsorbent and natural zeolite added to cesium-containing water and the amount of cesium ions adsorbed.
表３の結果より、本発明のセシウム吸着剤を用いてセシウム含有水のセシウムイオンを吸着処理したものは、天然ゼオライトあるいは本発明以外のセシウム吸着剤を用いて処理した場合に比べて、セシウムイオンの吸着量が多いことが分かる。また、本発明のセシウム吸着剤は少ない添加量でセシウムイオンを効果的に吸着しており、セシウムイオンの除去処理を経済的に行うことができる。さらに、本発明のセシウム吸着剤を用いて処理したものは、短時間でセシウムイオンを吸着することから、セシウムイオンの除去処理を効率的に実施できることが分かる。 From the results of Table 3, the cesium ion of the cesium-containing water adsorbed using the cesium adsorbent of the present invention is more cesium ion than the case of using natural zeolite or a cesium adsorbent other than the present invention. It can be seen that the amount of adsorbed is large. In addition, the cesium adsorbent of the present invention effectively adsorbs cesium ions with a small addition amount, and the cesium ion removal treatment can be performed economically. Furthermore, what was processed using the cesium adsorption agent of this invention adsorb | sucks a cesium ion in a short time, and it turns out that the removal process of a cesium ion can be implemented efficiently.
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| JP2014173847A (en) * | 2013-03-05 | 2014-09-22 | Toyokazutada Kk | Radioactive element adsorbent and radioactive element removal method, and processing method for adsorbent on which radioactive element is adsorbed |
| JP2015152464A (en) * | 2014-02-17 | 2015-08-24 | 積水化学工業株式会社 | Radiation shield body and radiation shield structure |
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| JPH04209750A (en) * | 1990-11-30 | 1992-07-31 | T T C:Kk | Production of high-strength steric formed body of special shape |
| JP2000119014A (en) * | 1998-08-12 | 2000-04-25 | Fuji Chem Ind Co Ltd | Amorphous calcium aluminosilicate compound oxide, its production and antacid |
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| JP2000119014A (en) * | 1998-08-12 | 2000-04-25 | Fuji Chem Ind Co Ltd | Amorphous calcium aluminosilicate compound oxide, its production and antacid |
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| JP2014173847A (en) * | 2013-03-05 | 2014-09-22 | Toyokazutada Kk | Radioactive element adsorbent and radioactive element removal method, and processing method for adsorbent on which radioactive element is adsorbed |
| JP2015152464A (en) * | 2014-02-17 | 2015-08-24 | 積水化学工業株式会社 | Radiation shield body and radiation shield structure |
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