JP2015182057A - Treating method of combustion ash and utilization of the same - Google Patents
Treating method of combustion ash and utilization of the same Download PDFInfo
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- 238000002485 combustion reaction Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000011737 fluorine Substances 0.000 claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 44
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 41
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052796 boron Inorganic materials 0.000 claims abstract description 41
- 239000011669 selenium Substances 0.000 claims abstract description 41
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004568 cement Substances 0.000 claims abstract description 31
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 29
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 27
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 27
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 27
- 239000011575 calcium Substances 0.000 claims abstract description 26
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 20
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 20
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002956 ash Substances 0.000 claims description 98
- 238000010828 elution Methods 0.000 claims description 44
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 43
- 239000010883 coal ash Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000007922 dissolution test Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002689 soil Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000003245 coal Substances 0.000 description 15
- 239000011400 blast furnace cement Substances 0.000 description 13
- 239000004033 plastic Substances 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 239000011398 Portland cement Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- -1 black liquor Substances 0.000 description 4
- 150000004688 heptahydrates Chemical class 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001653 ettringite Inorganic materials 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000010801 sewage sludge Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- 241000237503 Pectinidae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229940103272 aluminum potassium sulfate Drugs 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
本発明は、燃焼灰の処理に関する。本発明により、含まれるフッ素、ホウ素、セレンおよび六価クロムの溶出量を基準値以下に抑えた固化体が製造できる。本発明により処理された燃焼灰処理物は、融雪剤等として有用である。 The present invention relates to treatment of combustion ash. According to the present invention, it is possible to produce a solidified body in which the amount of elution of contained fluorine, boron, selenium and hexavalent chromium is suppressed to a reference value or less. The processed combustion ash treated by the present invention is useful as a snow melting agent or the like.
フッ素、ホウ素、セレンおよび六価クロムはいずれも第２種特定有害物質（重金属類）として指定されており、環境基準が定められている。火力発電所からの石炭燃焼灰（石炭灰）には、元来石炭が含有していたこれらの物質が含まれている。フッ素やホウ素はまた、家庭ゴミ焼却灰、下水汚泥焼却灰、各種産業廃棄物などの燃焼灰の中にも含まれている。 Fluorine, boron, selenium, and hexavalent chromium are all designated as Type 2 specified hazardous substances (heavy metals), and environmental standards are established. Coal-burning ash (coal ash) from thermal power plants contains these substances originally contained in coal. Fluorine and boron are also contained in combustion ash such as household waste incineration ash, sewage sludge incineration ash, and various industrial wastes.
燃焼灰の多くは土壌改良材や埋戻し材として利用されるので、雨などで有害物質が溶出して環境を汚染しないように適切に処理する必要がある。燃焼灰からの溶出を抑えるための方法として、溶融固化、セメント固化、キレート処理等が提案されているが、セメントを利用した処理は、原料が入手しやすく、比較的安価で操作が容易であるというメリットがある。例えば、特許文献１は、ペーパースラッジを焼却処理した際に発生する焼却灰に、水および／または温水、生石灰並びに石炭灰を加え、常温から９８℃までの温度で混合して粒状に造粒した成形体を養生した後、水熱固化反応を利用して固化体とすることを提案する。また、特許文献２は、石炭灰などの有害物を含有する廃棄物に、セメントおよび石灰を添加し混合し、該混合工程により得られる混合物を水熱処理することを提案する。さらに特許文献３は、木質系バイオマスの焼却灰およびペーパースラッジ焼却灰を含んでいてもよいバイオマス焼却灰５０〜１００重量部に、硫酸第一鉄１〜１０重量部、水２０〜８０重量部を混練し、固化体とすることによる処理方法を提案する。 Most of the combustion ash is used as a soil conditioner and backfill material, so it is necessary to treat it appropriately so that harmful substances are not eluted by rain and other substances. Melt solidification, cement solidification, chelation treatment, and the like have been proposed as methods for suppressing elution from combustion ash, but the treatment using cement is easy to obtain due to the availability of raw materials and relatively easy operation. There is a merit. For example, in Patent Document 1, water and / or hot water, quicklime and coal ash are added to incinerated ash generated when paper sludge is incinerated, and the mixture is granulated by mixing at a temperature from room temperature to 98 ° C. After curing the molded body, it is proposed to use a hydrothermal solidification reaction to obtain a solidified body. Moreover, patent document 2 proposes adding cement and lime to the waste containing harmful substances, such as coal ash, and mixing, and hydrothermally treating the mixture obtained by this mixing process. Furthermore, Patent Document 3 describes that 1 to 10 parts by weight of ferrous sulfate and 20 to 80 parts by weight of water are added to 50 to 100 parts by weight of biomass incineration ash which may contain incineration ash of woody biomass and paper sludge incineration ash. The processing method by kneading and making into a solidified body is proposed.
従来のセメントを用いる燃焼灰の処理方法においては、水分量が重視され、燃焼灰に対して比較的多い量の水が使用されてきた。そのため養生に数日要していた。
本発明が課題とするのは、燃焼灰からのフッ素、ホウ素、セレンおよび六価クロムを土壌環境基準値以下となるように処理するための、より短時間で処理できる効果的な方法を提供することである。また、そのような処理方法により得られた燃焼灰処理物の有効な利用方法を提供することである。
In conventional methods for treating combustion ash using cement, the amount of water is regarded as important, and a relatively large amount of water has been used for the combustion ash. Therefore, it took several days for curing.
An object of the present invention is to provide an effective method for treating fluorine, boron, selenium, and hexavalent chromium from combustion ash so as to be below the soil environment standard value in a shorter time. That is. Moreover, it is providing the effective utilization method of the combustion ash processed material obtained by such a processing method.
石炭灰は元来水分量が少ないものであるので、できるだけ水を加えない状態で扱いたいという思いがあった。本発明者らは鋭意検討した結果、セレンの溶出を抑えるためには、燃焼灰に対してセメントを多く用いることが重要であるが、セメントのみでは溶出を抑えることが難しいことが分かった。特にフッ素やセレンの溶出を抑えるためにはｐＨにも配慮すべきことを見出し、本発明を完成した。本発明は、以下を提供する。 Since coal ash originally has a low water content, there was a desire to handle it with as little water as possible. As a result of intensive studies, the present inventors have found that it is important to use a large amount of cement with respect to combustion ash in order to suppress selenium elution, but it is difficult to suppress elution only with cement. In particular, in order to suppress elution of fluorine and selenium, it was found that pH should be taken into consideration, and the present invention was completed. The present invention provides the following.
［１］ 燃焼灰と、セメント、カルシウム源、アルミニウム源、硫酸第一鉄および水とを、燃焼灰１００質量部に対して、セメントが１〜２０質量部、カルシウム源が消石灰換算で１〜２０質量部、アルミニウム源が硫酸アルミニウム換算で０．５〜１５質量部、硫酸第一鉄が０．５〜１０質量部、水が１質量部以上３０質量部未満となる割合で混合して反応させる工程を含む、燃焼灰処理物の製造方法。
［２］ 燃焼灰処理物が、平成１５年環境省告示第１８号に基づく溶出試験方法によって含まれるフッ素、ホウ素、セレンおよび六価クロムについて溶出させた場合に、フッ素の溶出量が０．８ｍｇ／Ｌ以下、ホウ素の溶出量が１ｍｇ／Ｌ以下、セレンの溶出量が０．０１ｍｇ／Ｌ、および六価クロムの溶出量が０．０５ｍｇ／Ｌ以下である、［１］に記載の製造方法。
［３］ 燃焼灰が石炭灰である、１または２に記載の製造方法。
[1] Combustion ash, cement, calcium source, aluminum source, ferrous sulfate and water, 1 to 20 parts by mass of cement and 1 to 20 in terms of slaked lime in terms of calcium source with respect to 100 parts by mass of combustion ash Part by mass, the aluminum source is mixed in a proportion of 0.5 to 15 parts by mass in terms of aluminum sulfate, ferrous sulfate is 0.5 to 10 parts by mass, and water is mixed in a proportion of 1 to 30 parts by mass. The manufacturing method of a combustion ash processed material including a process.
[2] When the processed ash is eluted from fluorine, boron, selenium and hexavalent chromium contained by the dissolution test method based on the Ministry of the Environment Notification No. 18 of 2003, the amount of fluorine eluted is 0.8 mg. / L or less, the boron elution amount is 1 mg / L or less, the selenium elution amount is 0.01 mg / L, and the hexavalent chromium elution amount is 0.05 mg / L or less. .
[3] The production method according to 1 or 2, wherein the combustion ash is coal ash.
［４］ 燃焼灰処理物が、融雪剤として使用されるものである、［１］〜［３］のいずれか１項に記載の製造方法。
［５］ 燃焼灰処理物が、水分３〜１５質量％、原料燃焼灰１００質量部に対して硫酸第一鉄を０．５〜１０質量部含むものである、４に記載の製造方法。
［６］ 水分量３〜１５質量％、原料石炭灰１００質量部に対して硫酸第一鉄を０．５〜１５質量部含む、粉状石炭灰処理物。
[4] The production method according to any one of [1] to [3], wherein the burned ash product is used as a snow melting agent.
[5] The production method according to 4, wherein the combustion ash-treated product contains 0.5 to 10 parts by mass of ferrous sulfate with respect to 3 to 15% by mass of water and 100 parts by mass of raw material combustion ash.
[6] Processed powdery coal ash containing 3 to 15% by mass of water and 0.5 to 15 parts by mass of ferrous sulfate with respect to 100 parts by mass of raw material coal ash.
［７］ 融雪剤である、６に記載の粉状石炭灰処理物。
［８］ 平成１５年環境省告示第１８号に基づく溶出試験方法によって含まれるフッ素、ホウ素、セレンおよび六価クロムについて溶出させた場合に、フッ素の溶出量が０．８ｍｇ／Ｌ以下、ホウ素の溶出量が１ｍｇ／Ｌ以下、セレンの溶出量が０．０１ｍｇ／Ｌ、および六価クロムの溶出量が０．０５ｍｇ／Ｌ以下である、６または７に記載の粉状石炭灰処理物。
[7] The processed powdered coal ash according to 6, which is a snow melting agent.
[8] When eluting fluorine, boron, selenium and hexavalent chromium contained by the dissolution test method based on the Ministry of the Environment Notification No. 18 of 2003, the amount of fluorine eluted is 0.8 mg / L or less. The processed coal ash product according to 6 or 7, wherein the elution amount is 1 mg / L or less, the selenium elution amount is 0.01 mg / L, and the hexavalent chromium elution amount is 0.05 mg / L or less.
本発明により、燃焼灰からのフッ素、ホウ素、セレンおよび六価クロムの溶出を抑えるための処理を、短い時間で完了することができる。 According to the present invention, the treatment for suppressing elution of fluorine, boron, selenium and hexavalent chromium from combustion ash can be completed in a short time.
本発明により、燃焼灰処理物からの平成１５年環境省告示第１８号に基づく溶出試験方法により溶出するフッ素、ホウ素、セレンおよび六価クロムの溶出量を、環境基準以下とすることができる。 According to the present invention, the elution amount of fluorine, boron, selenium and hexavalent chromium eluted from the burned ash treated product by the dissolution test method based on the Ministry of the Environment Notification No. 18 of 2003 can be reduced to the environmental standard or less.
本発明の方法により得られた燃焼灰処理物は、融雪剤として有効に利用することができる。 The processed combustion ash obtained by the method of the present invention can be effectively used as a snow melting agent.
以下、本発明を具体的に説明する。なお、本発明に関し、数値範囲を「Ｘ〜Ｙ」で表した際は、その範囲は、両端のＸおよびＹを含んでいる。 Hereinafter, the present invention will be specifically described. In the present invention, when the numerical range is represented by “X to Y”, the range includes X and Y at both ends.
本発明に用いられる燃焼灰は、特に制限されないが、本発明により、フッ素、ホウ素、セレンおよび六価クロムの溶出を効果的に抑えることができるので、これらの物質が比較的多く含まれている燃焼灰に対して、本発明を特に有効に活用できる。本発明に使用される燃焼灰の例として、石炭ボイラーからの石炭燃焼灰（石炭灰）が挙げられる。それ以外に、木材ペレット、樹皮などのバイオマス固形化燃料、ＲＰＦ、ＲＤＦなどの廃棄物固形化燃料、廃紙、廃タイヤ、黒液、製紙スラッジ、活性汚泥、脱水下水汚泥などの廃棄物系バイオマスを燃焼した際の排ガスを電気集塵機やバグフィルターなどで処理して得られる灰、ガス化した際に発生する灰、農業系バイオマスを燃焼させて得られる草木灰が挙げられる。これらのうち、特にフッ素、ホウ素、セレンおよび六価クロムが一定以上含まれており、それらの溶出を抑える要請が高いという観点からは、本発明の好ましい態様の一つにおいては、石炭灰が用いられる。本発明に用いられる燃焼灰は、複数の燃料または廃棄物を燃焼させて得られた灰であってもよく、また複数の燃焼灰を混合して、本発明に用いることもできる。 The combustion ash used in the present invention is not particularly limited. However, according to the present invention, elution of fluorine, boron, selenium and hexavalent chromium can be effectively suppressed, so that these substances are contained in a relatively large amount. The present invention can be used particularly effectively for combustion ash. Examples of the combustion ash used in the present invention include coal combustion ash (coal ash) from a coal boiler. Other than this, biomass biomass such as wood pellets and bark, waste solid fuel such as RPF and RDF, waste biomass such as waste paper, waste tire, black liquor, paper sludge, activated sludge, dehydrated sewage sludge Examples include ash obtained by treating exhaust gas when burning with an electric dust collector or a bag filter, ash generated when gasified, and plant ash obtained by burning agricultural biomass. Among these, from the viewpoint that fluorine, boron, selenium and hexavalent chromium are contained in a certain amount or more and there is a high demand for suppressing their elution, coal ash is used in one of the preferred embodiments of the present invention. It is done. The combustion ash used in the present invention may be ash obtained by burning a plurality of fuels or wastes, or a plurality of combustion ash may be mixed and used in the present invention.
〔セメント〕
本発明では、燃焼灰の処理に際し、セメントを用いる。本発明に使用できるセメントの例として、ポルトランドセメント（普通ポルトランドセメント、早強ポルトランドセメント、超早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント、耐硫酸塩ポルトランドセメントを含む。）、混合セメント（高炉セメント（Ａ、Ｂ、Ｃ種）、フライアッシュセメント（Ａ、Ｂ、Ｃ種）、シリカセメント（Ａ、Ｂ、Ｃ種））が挙げられる。高炉セメント（高炉スラグをポルトランドセメントに均一に混合したもの）を用いることが好ましい。高炉セメントは、高炉スラグとポルトランドセメントとの配合率によってＡ種、Ｂ種、Ｃ種に分類されるが、いずれも好適に本発明に用いることができる。また、本発明においては、セメントは、一種または二種以上用いることができる。
〔cement〕
In the present invention, cement is used in the treatment of combustion ash. Examples of cements that can be used in the present invention include Portland cement (including ordinary Portland cement, early-strength Portland cement, ultra-high-strength Portland cement, medium heat Portland cement, low heat Portland cement, sulfate-resistant Portland cement), mixed cement ( Blast furnace cement (A, B, C type), fly ash cement (A, B, C type), silica cement (A, B, C type)) may be mentioned. Blast furnace cement (a mixture of blast furnace slag uniformly mixed with Portland cement) is preferably used. Blast furnace cement is classified into A type, B type, and C type according to the blending ratio of blast furnace slag and Portland cement, and any of them can be suitably used in the present invention. In the present invention, one or more cements can be used.
本発明に用いられるセメントの量（二種以上用いる場合は、それらの総量）は、燃焼灰１００質量部に対して、０．１〜１００質量部とすることができ、０．５〜５０質量部が好ましく、１〜２０質量部がより好ましい。この範囲より少ない質量比では、フッ素，ホウ素，セレンおよび六価クロムの固定化が十分できず、またこの範囲を越える場合には、処理物の絶対量が増え、コストも増加するので実際的ではないからである。 The amount of cement used in the present invention (when two or more types are used, the total amount thereof) can be 0.1 to 100 parts by mass with respect to 100 parts by mass of combustion ash, and 0.5 to 50 parts by mass. Part is preferable, and 1 to 20 parts by mass is more preferable. If the mass ratio is less than this range, the fluorine, boron, selenium and hexavalent chromium cannot be fixed sufficiently, and if it exceeds this range, the absolute amount of the processed material increases and the cost also increases. Because there is no.
〔カルシウム源〕
本発明では、燃焼灰の処理に際し、カルシウム源を用いる。本発明でカルシウム源というときは、カルシウム単体またはカルシウム化合物を指す。例としては、消石灰（Ｃａ（ＯＨ）２）、生石灰（ＣａＯ）、炭酸カルシウム（ＣａＣＯ３）、ドロマイト、帆立貝、ペーパースラッジまたは古紙粕等のカルシウム源を焼成することにより得られる石灰が挙げられる。本発明においては、カルシウム源は、一種または二種以上用いることができる。カルシウム源は、燃焼灰中のフッ素、ホウ素、セレンおよび六価クロムあるいはそれらの化合物を結晶構造に取り込むことができ、フッ素、ホウ素、セレンおよび六価クロムの溶出抑制に寄与すると考えられる。
[Calcium source]
In the present invention, a calcium source is used in the treatment of combustion ash. In the present invention, the calcium source refers to a simple substance of calcium or a calcium compound. Examples include lime obtained by firing a calcium source such as slaked lime (Ca (OH) 2 ), quick lime (CaO), calcium carbonate (CaCO 3 ), dolomite, scallops, paper sludge or waste paper candy. In the present invention, one or two or more calcium sources can be used. The calcium source can incorporate fluorine, boron, selenium and hexavalent chromium or their compounds in the combustion ash into the crystal structure, and is considered to contribute to suppression of elution of fluorine, boron, selenium and hexavalent chromium.
本発明に用いられるカルシウム源の量（二種以上用いる場合はそれらの総量）は、燃焼灰１００質量部に対して、カルシウム源として消石灰を用いる場合は、０．１〜１００質量部とすることができ、０．５〜５０質量部が好ましく、１〜２０質量部がより好ましい。この範囲より少ない質量比では、フッ素およびホウ素の固定化が十分できず、またこの範囲を越える場合には、処理物の絶対量が増え、コストも増加するので実際的ではないからである。カルシウム源として消石灰以外のものを用いる場合は、等量のカルシウムを含む消石灰（Ｃａ（ＯＨ）２、７４．０９２７ｇ／ｍｏｌ）に換算した量が、燃焼灰１００質量部に対して、０．１〜１００質量部となるようにする。好ましくは０．５〜５０質量部となるように、より好ましくは１〜２０質量部となるようにする。例えば、生石灰（ＣａＯ、モル質量５６．０７７４ｇ／ｍｏｌ）を用いる場合は、燃焼灰１００質量部に対し０．１３２〜１３２質量部（消石灰換算で０．１〜１００質量部）用いることができる。本発明者らの検討によると、セメントを用いるだけでは、フッ素、ホウ素、セレンおよび六価クロムの溶出を効果的に抑えることが難しかった。これらの溶出を抑えるためにはｐＨも重要であり、セメントのほかカルシウム源を適量用いることが重要であると考えられる。 When using slaked lime as a calcium source, the amount of calcium source used in the present invention (the total amount of two or more when used) is 0.1 to 100 parts by mass when using slaked lime as a calcium source. 0.5-50 mass parts is preferable, and 1-20 mass parts is more preferable. This is because if the mass ratio is less than this range, the fluorine and boron cannot be fixed sufficiently, and if it exceeds this range, the absolute amount of the treated product increases and the cost also increases, which is not practical. When using something other than slaked lime as the calcium source, the amount converted to slaked lime (Ca (OH) 2 , 74.0927 g / mol) containing an equal amount of calcium is 0.1% with respect to 100 parts by mass of combustion ash. ˜100 parts by mass. The amount is preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass. For example, when using quicklime (CaO, molar mass 56.0774 g / mol), 0.132-132 mass parts (0.1-100 mass parts in conversion of slaked lime) can be used with respect to 100 mass parts of combustion ash. According to the study by the present inventors, it was difficult to effectively suppress elution of fluorine, boron, selenium and hexavalent chromium only by using cement. In order to suppress these elutions, pH is also important, and it is considered important to use an appropriate amount of calcium source in addition to cement.
〔アルミニウム源〕
本発明では、燃焼灰の処理に際し、アルミニウム源を用いる。本発明でアルミニウム源というときは、アルミニウム単体またはアルミニウム化合物を指す。例として、無水硫酸アルミニウム、硫酸アルミニウム１４〜１８水和物、硫酸アルミニウム１２水和物、硫酸アルミニウムカリウム１２水和物、硫酸アルミニウムナトリウム１２水和物、硫酸アンモニウムアルミニウム１２水和物が挙げられる。それ以外に、酸化アルミニウム、ボーキサイト、ミョウバンなどが挙げられる。無水硫酸アルミニウムまたは硫酸アルミニウム１４〜１８水和物を用いることが好ましい。なお、フッ素を固定化するために重要な、後述するエトリンガイトの生成には硫酸根が必要である。硫酸根は、硫酸鉄等からも供給されるが、硫酸アルミニウムを使用することが効果的である。経済的な観点からは、硫酸アルミニウムの水和物を用いることが好ましい。本発明においては、アルミニウム源は一種または二種以上用いることができる。
[Aluminum source]
In the present invention, an aluminum source is used for the treatment of combustion ash. In the present invention, the term “aluminum source” refers to an aluminum simple substance or an aluminum compound. Examples include anhydrous aluminum sulfate, aluminum sulfate 14-18 hydrate, aluminum sulfate 12 hydrate, aluminum potassium sulfate 12 hydrate, aluminum sodium sulfate 12 hydrate, and ammonium aluminum sulfate 12 hydrate. Other examples include aluminum oxide, bauxite, and alum. It is preferable to use anhydrous aluminum sulfate or aluminum sulfate 14-18 hydrate. In addition, a sulfate group is necessary for the production of ettringite, which will be described later, which is important for immobilizing fluorine. The sulfate radical is also supplied from iron sulfate or the like, but it is effective to use aluminum sulfate. From an economical viewpoint, it is preferable to use a hydrate of aluminum sulfate. In the present invention, one or more aluminum sources can be used.
本発明に用いられるアルミニウム源の量（二種以上用いる場合はそれらの総量）は、燃焼灰１００質量部に対して、アルミニウム源として硫酸アルミニウム（無水物）を用いる場合は、０．０５〜１５０質量部とすることができる。０．１〜５０質量部が好ましく、０．５〜１５質量部がより好ましい。アルミニウム源としてそれ以外のものを用いる場合は、等量のアルミニウムを含む硫酸アルミニウム無水物（Ａｌ２（ＳＯ４）３、３４２．１４ｇ／ｍｏｌ）に換算した量が、燃焼灰１００質量部に対して、０．０５〜１５０質量部となるようにする。好ましくは０．１〜５０質量部となるように、より好ましくは０．５〜１５質量部となるようにする。 The amount of the aluminum source used in the present invention (when two or more types are used, the total amount thereof) is 0.05 to 150 when aluminum sulfate (anhydride) is used as the aluminum source with respect to 100 parts by mass of combustion ash. It can be a mass part. 0.1-50 mass parts is preferable, and 0.5-15 mass parts is more preferable. When other than that is used as the aluminum source, the amount converted to aluminum sulfate anhydride (Al2 (SO4) 3, 342.14 g / mol) containing an equal amount of aluminum is 100 parts by mass of combustion ash, The amount is 0.05 to 150 parts by mass. Preferably it is 0.1-50 mass parts, More preferably, it is 0.5-15 mass parts.
〔硫酸第一鉄〕
本発明では、燃焼灰の処理に際し、硫酸第一鉄を用いる。本発明に用いられる硫酸第一鉄の量は、燃焼灰１００質量部に対して、アルミニウム源として硫酸アルミニウムを用いる場合は、０．０５〜１００質量部とすることができ、０．１〜５０質量部が好ましく、０．５〜１０質量部がより好ましい。
[Ferrous sulfate]
In the present invention, ferrous sulfate is used for the treatment of combustion ash. The amount of ferrous sulfate used in the present invention can be 0.05 to 100 parts by mass when aluminum sulfate is used as the aluminum source with respect to 100 parts by mass of combustion ash. A mass part is preferable and 0.5-10 mass part is more preferable.
本発明においては、セメント、カルシウム、アルミニウムおよび硫酸第一鉄に水を添加して混合すると、エトリンガイト（３ＣａＯ・Ａｌ２Ｏ３・３ＣａＳＯ４・３２Ｈ２Ｏ）が生成し、それによってフッ素、ホウ素等の有害成分の溶出が抑制することができると考えられる。 In the present invention, when water is added to and mixed with cement, calcium, aluminum, and ferrous sulfate, ettringite (3CaO · Al 2 O 3 · 3CaSO 4 · 32H 2 O) is generated, thereby fluorine, boron, etc. It is considered that elution of harmful components can be suppressed.
〔水の存在〕
本発明においては、燃焼灰の処理に際し、水の存在下で、セメント、カルシウム源、アルミニウム源、硫酸第一鉄を混合する。
[Presence of water]
In the present invention, cement, a calcium source, an aluminum source, and ferrous sulfate are mixed in the presence of water when treating the combustion ash.
本発明に用いられる水の量は、適宜とすることができるが、本発明の特徴の一つは、水の量を比較的少なく用いていることである。水の量の上限値は、例えば３０質量部未満であり、好ましくは２６質量部未満であり、より好ましくは２０質量部未満であり、さらに好ましくは１５質量部未満である。これより多いと、反応のために必要な時間が長くなるからである。 The amount of water used in the present invention can be set appropriately, but one of the features of the present invention is that the amount of water is relatively small. The upper limit of the amount of water is, for example, less than 30 parts by mass, preferably less than 26 parts by mass, more preferably less than 20 parts by mass, and even more preferably less than 15 parts by mass. This is because if it is more than this, the time required for the reaction becomes longer.
本発明に用いられる水の量の下限値は、燃焼灰、セメント、カルシウム源、アルミニウム源、硫酸第一鉄を所定の割合で混合したものの全体に行き渡る量であれば、特に制限はない。燃焼灰１００質量部に対して、例えば０．１質量部以上であり、好ましくは０．２質量部以上であり、より好ましくは０．５質量部以上であり、さらに好ましくは１質量部以上である。 The lower limit value of the amount of water used in the present invention is not particularly limited as long as it is an amount that reaches the entire mixture of combustion ash, cement, calcium source, aluminum source, and ferrous sulfate in a predetermined ratio. For example, it is 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more with respect to 100 parts by mass of combustion ash. is there.
〔反応〕
本発明では、上述の燃焼灰と、セメント、カルシウム源、アルミニウム源、硫酸第一鉄および水とを均一に混合し、反応させる。原料として水溶性の化合物（例えば、硫酸アルミニウム）を用いる場合は、その化合物を所定の量の水に溶解して、混合することができる。また、水または水溶液は、噴霧等の手段により、その他の材料に均一に行き渡るようにしてもよい。セメント、カルシウム源、アルミニウム源、硫酸第一鉄および水を混合するために、適切な攪拌手段を用いてもよい。反応中には、臭気等はほとんど発生しない。
〔reaction〕
In the present invention, the above-mentioned combustion ash, cement, calcium source, aluminum source, ferrous sulfate and water are uniformly mixed and reacted. When a water-soluble compound (for example, aluminum sulfate) is used as a raw material, the compound can be dissolved in a predetermined amount of water and mixed. Further, the water or the aqueous solution may be uniformly distributed to other materials by means such as spraying. Any suitable stirring means may be used to mix the cement, calcium source, aluminum source, ferrous sulfate and water. During the reaction, almost no odor is generated.
上述のように混合すると、数時間で反応が終了する。反応のために加熱する必要はなく、反応は環境温度（例えば、２５℃）で進行させることができる。反応時間は、２時間以上とすることができ、３時間とすることが好ましい。このように処理することで、燃焼灰は、
平成１５年環境省告示第１８号に基づく溶出試験方法によって含まれるフッ素、ホウ素、セレンおよび六価クロムについて溶出させた場合に、フッ素の溶出量が０．８ｍｇ／Ｌ以下、ホウ素の溶出量が１ｍｇ／Ｌ以下、セレンの溶出量が０．０１ｍｇ／Ｌ、および六価クロムの溶出量が０．０５ｍｇ／Ｌ以下である処理物となる。
When mixed as described above, the reaction is completed within a few hours. There is no need to heat for the reaction, and the reaction can proceed at ambient temperature (eg, 25 ° C.). The reaction time can be 2 hours or more, and preferably 3 hours. By processing in this way, combustion ash is
When eluting fluorine, boron, selenium and hexavalent chromium contained by the dissolution test method based on Notification No. 18 of the Ministry of the Environment in 2003, the amount of fluorine eluted is 0.8 mg / L or less, and the amount of boron eluted is The processed product is 1 mg / L or less, the selenium elution amount is 0.01 mg / L, and the hexavalent chromium elution amount is 0.05 mg / L or less.
本発明により得られる燃焼灰処理物中の水分量は３〜１５質量％とすることができる。また原料石炭灰１００質量部に対して硫酸第一鉄を０．０５〜１５０質量部、好ましくは０．１〜５０質量部、さらに好ましくは０．５〜１５質量部、含むものでありうる。なお、本発明で燃焼灰処理物中の水分量を質量％で表す場合は、特に示した場合を除き、燃焼灰処理物全体を１００質量部としている。具体的には、水分量３〜１５質量％とは、例えば、燃焼灰処理物１００ｇある場合、水分３〜１５ｇおよび固形分が９７ｇ〜８５からなるという意味である。水分は常法により測定することができる。例えば、燃焼灰処理物を適量計量し（２〜３ｇ）、送風乾燥機内（１０５℃）にて３時間乾燥させ、重量の変化により算出することによる。
本発明により得られる燃焼灰処理物は、典型的には粉状であるが、顆粒上、固化体状、多孔質状等とすることができる。
The amount of water in the processed ash product obtained by the present invention can be 3 to 15% by mass. Moreover, 0.05-150 mass parts of ferrous sulfate with respect to 100 mass parts of raw material coal ash, Preferably it is 0.1-50 mass parts, More preferably, it may contain 0.5-15 mass parts. In addition, when the moisture content in a combustion ash processed material is represented by the mass% by this invention, the whole combustion ash processed material is 100 mass parts except the case where it showed especially. Specifically, the moisture content of 3 to 15% by mass means that, for example, when there are 100 g of the processed combustion ash, the moisture content is 3 to 15 g and the solid content is 97 to 85 g. Moisture can be measured by conventional methods. For example, by measuring an appropriate amount of the processed ash product (2 to 3 g), drying it in an air dryer (105 ° C.) for 3 hours, and calculating the weight change.
The burned ash product obtained by the present invention is typically in the form of powder, but may be in the form of a granule, a solidified body, a porous body, or the like.
本発明により得られた燃焼灰処理物は、融雪剤、土壌改良材、草地改良材、埋め戻し材、盛土等、種々の用途に利用することができる。特に石炭灰から得られた水分量３〜１５質量％である燃焼灰処理物は、黒色であり、かつ水分を含むために飛散がある程度抑えられ、取り扱いが容易であるとの利点から、融雪剤として使用するのに特に優れている。
以下、本発明を、実施例を例に説明するが、本発明の範囲は、これらの実施例によっては制限されない。
The burned ash product obtained by the present invention can be used for various applications such as a snow melting agent, a soil improving material, a grassland improving material, a backfilling material, and embankment. In particular, the processed ash product obtained from coal ash and having a moisture content of 3 to 15% by mass is black, and since it contains moisture, the scattering is suppressed to some extent, and the snow melting agent is easy to handle. Especially good to use as.
EXAMPLES Hereinafter, although an Example demonstrates this invention, the scope of the present invention is not restrict | limited by these Examples.
〔溶出試験方法〕
平成１５年環境省告示第１８号に順じて行なった。すなわち、試料を、非金属製である目開き２ｍｍの篩を通過させたもの５０ｇを、１，０００ｍＬの蓋つきのポリエチレン容器に取り、純水（ｐＨ５．８〜６．３）を５００ｍＬ加えて試料液を調整した。この試料液を、常温、大気圧下で、産廃溶出振とう機（タイテック社製）を用いて６時間連続振とうした（振とう幅４〜５ｃｍ、振動数２００回／分）。ついで、振とう後の試料液を、３０分間静置した後、毎分約３，０００回転で２０分間遠心分離した。上澄み液を孔径０．４５μｍのメンブレンフィルターでろ過し、ろ液を取り、定量に必要な量を計り取り、これを検液とした。
[Dissolution test method]
In accordance with the Ministry of the Environment Notification No. 18 in 2003. That is, 50 g of a sample that has been passed through a non-metallic sieve with an opening of 2 mm is placed in a 1,000 mL polyethylene container with a lid, and 500 mL of pure water (pH 5.8 to 6.3) is added to the sample. The liquid was adjusted. This sample solution was shaken continuously for 6 hours at room temperature and atmospheric pressure using an industrial waste elution shaker (manufactured by Taitec Corporation) (shaking width: 4 to 5 cm, vibration frequency: 200 times / min). Next, the sample solution after shaking was allowed to stand for 30 minutes, and then centrifuged at about 3,000 rpm for 20 minutes. The supernatant was filtered through a membrane filter having a pore size of 0.45 μm, the filtrate was taken, the amount required for quantification was measured, and this was used as a test solution.
（フッ素の測定）
検液をイオンクロマトグラフ（ＩＣＳ−２０００／ＤＩＯＮＥＸ社製）で定量した（ＪＩＳ Ｋ ０１０２の３４．２、水質環境基準告示付表６）。
(Measurement of fluorine)
The test solution was quantified with an ion chromatograph (ICS-2000 / DIONEX) (JIS K 0102 34.2, Attached Table 6 for Water Quality Standards).
（ホウ素の測定）
検液をＩＣＰ発光分析（ＣＩＲＯＳ−１２０／ＳＰＥＣＴＲＯ社製）で定量した（ＪＩＳ Ｋ ０１０２の３４．２）。
(Measurement of boron)
The test solution was quantified by ICP emission analysis (CIROS-120 / SPECTRO) (JIS K 0102 34.2).
（セレンの測定）
検液をＩＣＰ発光分析法で定量した（ＪＩＳ Ｋ ０１０２の５４．４）。
(Measurement of selenium)
The test solution was quantified by ICP emission spectrometry (JIS K 0102 54.4).
（六価クロムの測定）
検液をジフェニルカルバジド吸光光度法で定量した（ＪＩＳ Ｋ ０１０２の６５．２．１）。
(Measurement of hexavalent chromium)
The test solution was quantified by diphenylcarbazide spectrophotometry (JIS K 0102 65.2.1).
［実施例１]
石炭ボイラの燃焼灰を２００ｇビニール袋に計量し、消石灰を９ｇ、高炉セメントＢ種を２０ｇ、硫酸第一鉄・七水和物を１１ｇ添加後に十分混合し、灰（絶乾）１００部に対して硫酸アルミニウムが３．５部、添加水が１０部となるように調整した硫酸アルミニウム水溶液を均一に噴霧後、よく混合し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Example 1]
Weigh coal fired ash in a 200g plastic bag, add 9g slaked lime, 20g blast furnace cement B, 11g ferrous sulfate heptahydrate and mix well. After spraying uniformly with an aluminum sulfate aqueous solution adjusted to 3.5 parts of aluminum sulfate and 10 parts of added water, mix well and leave at ambient temperature (about 20 ° C) for about 3 hours for combustion ash treatment I got a thing. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［実施例２］
石炭ボイラの燃焼灰を２００ｇビニール袋に計量し、消石灰を９ｇ、高炉セメントＢ種を２０ｇ、硫酸第一鉄・七水和物を２２ｇ添加後に十分混合し、灰（絶乾）１００部に対して硫酸アルミニウムが３．５部、添加水が１０部となるように調整した硫酸アルミニウム水溶液を均一に噴霧後、よく混合し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Example 2]
Coal boiler combustion ash is weighed into a 200g plastic bag, 9g of slaked lime, 20g of blast furnace cement B, 20g of ferrous sulfate and heptahydrate are added and mixed well to 100 parts of ash (absolutely dry) After spraying uniformly with an aluminum sulfate aqueous solution adjusted to 3.5 parts of aluminum sulfate and 10 parts of added water, mix well and leave at ambient temperature (about 20 ° C) for about 3 hours for combustion ash treatment I got a thing. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［実施例３］
石炭ボイラの燃焼灰を２００ｇビニール袋に計量し、消石灰を１２ｇ、高炉セメントＢ種を６ｇ、硫酸第一鉄・七水和物を１１ｇ添加後に十分攪拌し、灰（絶乾）１００部に対して硫酸アルミニウムが５部、添加水が１４部となるように調整した硫酸アルミニウム水溶液を均一に噴霧後、よく攪拌し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Example 3]
Weigh the coal boiler combustion ash in a 200g plastic bag, add 12g of slaked lime, 6g of blast furnace cement B, 11g of ferrous sulfate and heptahydrate, and stir well, to 100 parts of ash (absolutely dry) After spraying uniformly with an aluminum sulfate aqueous solution adjusted to 5 parts of aluminum sulfate and 14 parts of added water, stir well and leave at ambient temperature (about 20 ° C.) for about 3 hours. Obtained. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［実施例４］
石炭ボイラの燃焼灰を２００ｇビニール袋に計量し、消石灰を１２ｇ、高炉セメントＢ種を２０ｇ、硫酸第一鉄・七水和物を１１ｇ添加後に十分混合し、灰（絶乾）１００部に対して硫酸アルミニウムが５部、添加水が１４質量部となるように調整した硫酸アルミニウム水溶液を均一に噴霧し、水を２２ｇ加えよく混合し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Example 4]
Weigh coal fired ash in a 200g plastic bag, add 12g of slaked lime, 20g of Blast Furnace Cement B, and 11g of ferrous sulfate heptahydrate, and mix well. Then, uniformly spray an aluminum sulfate aqueous solution adjusted to 5 parts of aluminum sulfate and 14 parts by weight of added water, add 22 g of water, mix well, and leave at ambient temperature (about 20 ° C.) for about 3 hours. A combustion ash treatment product was obtained. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［実施例５］
石炭ボイラの燃焼灰を２００ｇビニール袋に計量し、消石灰を９ｇ、高炉セメントＢ種を２０ｇ、硫酸第一鉄・七水和物を２２ｇ添加後に十分混合し、灰（絶乾）１００部に対して硫酸アルミニウムが３．５部、添加水が１０部となるように調整した硫酸アルミニウム水溶液を均一に噴霧し、水を２２ｇ加え、よく混合し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Example 5]
Coal boiler combustion ash is weighed into a 200g plastic bag, 9g of slaked lime, 20g of blast furnace cement B, 20g of ferrous sulfate and heptahydrate are added and mixed well to 100 parts of ash (absolutely dry) Spray uniformly with an aqueous aluminum sulfate solution adjusted to 3.5 parts of aluminum sulfate and 10 parts of added water, add 22 g of water, mix well, and leave at ambient temperature (about 20 ° C.) for about 3 hours. As a result, a combustion ash treatment product was obtained. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［比較例１］
石炭ボイラから排出される燃焼灰のフッ素、ホウ素、セレンおよび、六価クロムの溶出量を求めた。その結果を表１に示す。
[Comparative Example 1]
The elution amounts of fluorine, boron, selenium and hexavalent chromium in combustion ash discharged from a coal boiler were determined. The results are shown in Table 1.
［比較例２］
石炭ボイラの燃焼灰を２００ｇビニール袋に計り取り、高炉セメントＢ種を６ｇ添加後に十分攪拌し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、上記の溶出法と測定法で分析し、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Comparative Example 2]
The combustion ash of the coal boiler was weighed into a 200 g plastic bag, 6 g of blast furnace cement B was added and sufficiently stirred, and left at ambient temperature (about 20 ° C.) for about 3 hours to obtain a processed ash product. Then, it analyzed by said elution method and measuring method, and calculated | required the elution amount of fluorine, boron, selenium, and hexavalent chromium. The results are shown in Table 1.
［比較例３］
石炭ボイラの燃焼灰を２００ｇビニール袋に計り取り、消石灰を９ｇ、高炉セメントＢ種を２０ｇ添加後に十分攪拌し、灰（絶乾）１００部に対して硫酸アルミニウムが３．５部、添加水が１０部となるように調整した硫酸アルミニウム水溶液をスプレーで均一に噴霧後、よく攪拌し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Comparative Example 3]
Coal boiler combustion ash is weighed in a 200 g plastic bag, 9 g of slaked lime and 20 g of blast furnace cement B type are added and stirred well. 3.5 parts of aluminum sulfate and 100 parts of ash (absolutely dry) The aluminum sulfate aqueous solution adjusted to 10 parts was uniformly sprayed and then stirred well and left at ambient temperature (about 20 ° C.) for about 3 hours to obtain a burned ash treatment product. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［比較例４］
石炭ボイラの燃焼灰を２００ｇビニール袋に計り取り、消石灰を９ｇ、硫酸第一鉄・七水和物を１１ｇ添加後に十分攪拌し、灰（絶乾）１００部に対して硫酸アルミニウムが３．５部、添加水が１０部となるように調整した硫酸アルミニウム水溶液をスプレーで均一に噴霧後、よく攪拌し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Comparative Example 4]
Weigh the combustion ash of a coal boiler in a 200 g plastic bag, add 9 g of slaked lime and 11 g of ferrous sulfate heptahydrate, and stir well. The aqueous solution of aluminum sulfate adjusted to 10 parts by weight and the added water was uniformly sprayed and then stirred well, and left at ambient temperature (about 20 ° C.) for about 3 hours to obtain a combustion ash-treated product. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［比較例５］
石炭ボイラの燃焼灰を２００ｇビニール袋に計り取り、高炉セメントＢ種を２０ｇ、硫酸第一鉄・七水和物を１１ｇ添加後に十分攪拌し、水を１３ｇ加え、よく攪拌し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Comparative Example 5]
Weigh the combustion ash of a coal boiler in a 200 g plastic bag, add 20 g of blast furnace cement type B and 11 g of ferrous sulfate heptahydrate, stir well, add 13 g of water, stir well, (20 ° C.) for about 3 hours to obtain a combustion ash-treated product. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［比較例６］
石炭ボイラの燃焼灰を２００ｇビニール袋に計り取り、高炉セメントＢ種を２０ｇ、硫酸第一鉄・七水和物を２２ｇ添加後に十分攪拌し、水を１３ｇ加え、よく攪拌し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Comparative Example 6]
Weigh the combustion ash from a coal boiler in a 200 g plastic bag, add 20 g of Blast Furnace Cement B, 22 g of Ferrous Sulfate and Heptahydrate, stir well, add 13 g of water, stir well, (20 ° C.) for about 3 hours to obtain a combustion ash-treated product. Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
［比較例７］
石炭ボイラの燃焼灰を２００ｇビニール袋に計り取り、消石灰を９ｇ、高炉セメントＢ種を６ｇ添加後に十分攪拌し、環境温度（約２０℃）で約３時間放置し、燃焼灰処理物を得た。その後、フッ素、ホウ素、セレン、六価クロムの溶出量を求めた。その結果を表１に示す。
[Comparative Example 7]
Coal boiler combustion ash was weighed into a 200 g plastic bag, 9 g of slaked lime and 6 g of blast furnace cement B were added and stirred well, and left at ambient temperature (about 20 ° C.) for about 3 hours to obtain a processed ash product. . Thereafter, elution amounts of fluorine, boron, selenium and hexavalent chromium were determined. The results are shown in Table 1.
表１から分かるように、実施例１〜５では、石炭灰にセメント、消石灰、硫酸アルミニウム溶液および硫酸第一鉄を加えて混合するのみで、フッ素、ホウ素、セレンおよび六価クロムの溶出量が土壌汚染対策法の基準値を下回り、これら元素の不溶化を達成した。 As can be seen from Table 1, in Examples 1 to 5, only the cement, slaked lime, aluminum sulfate solution and ferrous sulfate are added to and mixed with coal ash, and the amount of elution of fluorine, boron, selenium and hexavalent chromium is increased. The insolubilization of these elements was achieved below the standard value of the Soil Contamination Countermeasures Law.
一方、比較例２のように石炭灰にセメントのみを混合した場合は石炭灰そのままよりも、フッ素、ホウ素、セレンの溶出量を減少できるが、規制値を超過している。また、比較例３〜７では、セメント、消石灰、硫酸アルミニウム、硫酸第一鉄のいずれかが存在しない場合には、フッ素、ホウ素、セレン、六価クロムの溶出量を同時に規制値以下にすることは不可能であった。 On the other hand, when only cement is mixed with coal ash as in Comparative Example 2, the elution amount of fluorine, boron, and selenium can be reduced as compared with the coal ash as it is, but it exceeds the regulation value. Moreover, in Comparative Examples 3-7, when any of cement, slaked lime, aluminum sulfate, and ferrous sulfate does not exist, the elution amount of fluorine, boron, selenium, and hexavalent chromium is simultaneously reduced to the regulation value or less. Was impossible.
以上のように、燃焼灰にセメント、消石灰、硫酸アルミニウム溶液および硫酸第一鉄を添加して混合処理を行い、燃焼灰中のフッ素、ホウ素、セレン、六価クロムの溶出抑制を同時に達成できた。土壌汚染対策法の規制値以下にすることができる本発明は、簡便で極めて有効な方法であることがわかる。 As described above, cement, slaked lime, aluminum sulfate solution and ferrous sulfate were added to the combustion ash and mixed to achieve the simultaneous suppression of elution of fluorine, boron, selenium and hexavalent chromium in the combustion ash. . It turns out that this invention which can be made into the regulation value or less of the soil pollution countermeasure method is a simple and extremely effective method.
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