JP4470216B2 - Treatment method for fluorine-containing solid waste - Google Patents
Treatment method for fluorine-containing solid waste Download PDFInfo
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- JP4470216B2 JP4470216B2 JP2001138847A JP2001138847A JP4470216B2 JP 4470216 B2 JP4470216 B2 JP 4470216B2 JP 2001138847 A JP2001138847 A JP 2001138847A JP 2001138847 A JP2001138847 A JP 2001138847A JP 4470216 B2 JP4470216 B2 JP 4470216B2
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- fluorine
- solid waste
- containing solid
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Description
【０００１】
【発明の属する技術分野】
本発明は、フッ素含有固体廃棄物の処理方法に関する。さらに詳しくは、本発明は、フッ素含有固体廃棄物を、容易かつ効率的に、しかも、安全に処理して、処理物からのフッ素の溶出を防止することができるフッ素含有固体廃棄物の処理方法に関する。
【０００２】
【従来の技術】
フッ酸製造工程の副産物の石こう、フッ素含有排水処理に際して発生する汚泥、フッ素汚染土壌、フッ素を含有する産業廃棄物などのフッ素含有固体廃棄物は、埋立処分するにあたっては、フッ素の溶出を防止する処理を施すことが望ましい。従来、フッ素含有廃水の処理方法は数多く提案されているが、フッ素含有固体廃棄物の処理方法についての提案は少ない。
例えば、特開２０００−２４７６９４号公報には、鉄鋼スラグ中に含有されるフッ素の溶出を効果的に抑制し得る鉄鋼スラグの安定化処理法として、鉄鋼スラグ融体にアルミニウム化合物を添加し、凝固過程において安定なＣａＯ−Ａｌ2Ｏ3−Ｆ系化合物をスラグ中に析出させるとともに、添加スラグの雨水や地下水などへの溶解に際して、鉄鋼スラグから溶出するカルシウムイオン及びアルミニウムイオンを用いて、鉄鋼スラグから溶出するフッ素を捕捉する方法が提案されている。
このように、フッ素を含有する特定の固体廃棄物の処理方法については、いくつかの提案がなされているが、一般的なフッ素含有固体廃棄物に汎用的に適用し得る処理方法は、まだ見いだされていない。
【０００３】
【発明が解決しようとする課題】
本発明は、フッ素含有固体廃棄物を、容易かつ効率的に、しかも、安全に処理して、処理物からのフッ素の溶出を防止することができるフッ素含有固体廃棄物の処理方法を提供することを目的としてなされたものである。
【０００４】
【課題を解決するための手段】
本発明者は、上記の課題を解決すべく鋭意研究を重ねた結果、フッ素含有固体廃棄物に、リン酸化合物及びカルシウム化合物を添加して混練することにより、フッ素を安定なフルオロアパタイトとして固定化し、溶出を防止し得ることを見いだし、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、フッ素含有固体廃棄物に、リン酸化合物及びカルシウム化合物を添加して混練して処理し、処理したフッ素含有固体廃棄物からのフッ素の溶出を防止することを特徴とするフッ素含有固体廃棄物の処理方法を提供するものである。
【０００５】
【発明の実施の形態】
本発明方法を適用することができるフッ素含有固体廃棄物に特に制限はなく、例えば、半導体製造業、金属精錬業、金属表面処理業、窯業などの工場排水処理の際に発生する汚泥、都市ゴミ焼却排ガスの洗煙水の処理の際に発生する汚泥、フッ素により汚染された土壌、フッ素樹脂やフッ素ゴムなどの廃棄物、鉄鋼スラグ、フッ化物ガラスの廃棄物などを挙げることができる。
本発明方法に用いるリン酸化合物としては、例えば、正リン酸、次亜リン酸、メタ亜リン酸、ピロ亜リン酸、正亜リン酸、次リン酸、メタリン酸、ピロリン酸、三リン酸、縮合リン酸などのリン酸類、リン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、リン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウムなどのリン酸塩類などを挙げることができる。これらの中で、正リン酸（Ｈ3ＰＯ4）、リン酸二水素ナトリウム（ＮａＨ2ＰＯ4）、リン酸水素二ナトリウム（Ｎａ2ＨＰＯ4）及び縮合リン酸を特に好適に使用することができる。本発明方法において、リン酸化合物の添加量に特に制限はなく、固体廃棄物のフッ素含有量などに応じて適宜選択することができるが、通常はフッ素含有固体廃棄物１００重量部に対して、０.５〜２０重量部であることが好ましく、２〜１５重量部であることがより好ましい。
本発明方法に用いるカルシウム化合物としては、例えば、酸化カルシウム、水酸化カルシウム、塩化カルシウム、臭化カルシウム、次亜塩素酸カルシウム、塩素酸カルシウム、過塩素酸カルシウム、リン酸二水素カルシウム、次亜リン酸カルシウム、亜リン酸カルシウム、硝酸カルシウムなどを挙げることができる。これらの中で、水酸化カルシウム及び塩化カルシウムを特に好適に用いることができる。本発明方法において、カルシウム化合物の添加量に特に制限はなく、固体廃棄物のフッ素含有量などに応じて適宜選択することができるが、通常はフッ素含有固体廃棄物１００重量部に対して、０.５〜２０重量部であることが好ましく、２〜１５重量部であることがより好ましい。
【０００６】
本発明方法において、フッ素含有固体廃棄物へのリン酸化合物とカルシウム化合物の添加順序に特に制限はなく、リン酸化合物とカルシウム化合物のいずれを先に添加することもでき、あるいは、両者を同時に又は交互に添加することもできる。また、混練が困難な場合には、必要に応じて、フッ素含有固体廃棄物に水を添加することができる。水の添加量は、フッ素含有固体廃棄物１００重量部に対して、５〜３０重量部であることが好ましい。水の添加量によって、処理後のフッ素溶出防止効果に差は生じないので、水の添加量は、作業性などの面から任意に設定することができる。
本発明方法において、リン酸化合物とカルシウム化合物を添加したフッ素含有固体廃棄物の混練方法に特に制限はなく、フッ素含有固体廃棄物の性状や量などに応じて適宜選択することができ、例えば、コンクリートミキサなどを用いて閉鎖空間で混練することができ、あるいは、油圧ショベルなどを用いて開放空間で混練することもできる。
本発明方法において、フッ素含有固体廃棄物にリン酸化合物とカルシウム化合物を添加して混練することにより、フッ素の溶出を防止し得る機構は、フッ素含有固体廃棄物中のフッ素が、リン酸化合物及びカルシウム化合物と反応し、安定なフルオロアパタイトとして固定化されるためであると推定される。
【０００７】
【実施例】
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
実施例１
フッ酸製造工程で副産物として発生するフッ素を含有する石こうの処理を行った。
このフッ素含有石こう５０ｇを容量５００mLのポリプロピレン製ビーカーに採り、水５.０ｇ、正リン酸１.５ｇ、水酸化カルシウム１.５ｇを添加し、充分に混ざるようにスパーテルで５分間混練した。この処理物について、環境庁告示１３号試験に準じて、溶出試験を行った。
容量２５０mLのポリエチレン製広口びんに、処理物２０ｇと純水２００mLを入れて密栓し、振盪回数２００回／分、振盪幅４.５cmに調整した振盪機に取り付け、常温で６時間連続して振盪した。次いで、びんの中の水をろ過し、ろ液のフッ化物イオンの濃度を、ＪＩＳ Ｋ ０１０２ ３４.２ イオン電極法にしたがって測定した。フッ素の溶出量は、１.５mg／Ｌであった。
実施例２
正リン酸と水酸化カルシウムの添加量をそれぞれ２.５ｇとした以外は、実施例１と同様にして、試験を行った。フッ素の溶出量は、０.９mg／Ｌであった。
実施例３
正リン酸と水酸化カルシウムの添加量をそれぞれ５.０ｇとした以外は、実施例１と同様にして、試験を行った。フッ素の溶出量は、０.５mg／Ｌであった。
比較例１
正リン酸と水酸化カルシウムを添加しない以外は、実施例１と同様にして、試験を行った。フッ素の溶出量は、４.２mg／Ｌであった。
【０００８】
【表１】
第１表に見られるように、正リン酸と水酸化カルシウムを添加しない比較例１では、フッ素が４.２mg／Ｌ溶出するのに対して、正リン酸と水酸化カルシウムを添加した実施例１〜３では、フッ素の溶出量が減少し、かつ、正リン酸と水酸化カルシウムの添加量が多いほどフッ素の溶出量が少なくなることから、正リン酸と水酸化カルシウムの添加によりフッ素が固定化され、溶出が防止されることが分かる。
【００１０】
【発明の効果】
本発明のフッ素含有固体廃棄物の処理方法によれば、廃棄物にリン酸化合物とカルシウム化合物を添加して混練するという簡単な操作により、フッ素含有固体廃棄物を、容易かつ効率的に、しかも、安全に処理して、処理物からのフッ素の溶出を防止することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for treating fluorine-containing solid waste. More specifically, the present invention relates to a method for treating fluorine-containing solid waste, which can treat fluorine-containing solid waste easily, efficiently and safely and prevent elution of fluorine from the treated product. About.
[0002]
[Prior art]
Fluorine-containing solid waste, such as gypsum, a by-product of the hydrofluoric acid production process, sludge generated during treatment of fluorine-containing wastewater, fluorine-contaminated soil, and industrial waste containing fluorine, is prevented from elution of fluorine during landfill disposal. It is desirable to perform processing. Conventionally, many treatment methods for fluorine-containing wastewater have been proposed, but there are few proposals for treatment methods for fluorine-containing solid waste.
For example, JP 2000-247694 A discloses a method for stabilizing steel slag that can effectively suppress elution of fluorine contained in steel slag, by adding an aluminum compound to the steel slag melt, and solidifying it. In this process, a stable CaO—Al 2 O 3 —F-based compound is precipitated in slag, and at the time of dissolution of the added slag into rainwater or groundwater, using calcium ions and aluminum ions eluted from the steel slag, There has been proposed a method for capturing fluorine eluting from the substrate.
As described above, several proposals have been made for a method for treating a specific solid waste containing fluorine. However, a treatment method that can be generally applied to general fluorine-containing solid waste has not yet been found. Not.
[0003]
[Problems to be solved by the invention]
The present invention provides a method for treating fluorine-containing solid waste that can treat fluorine-containing solid waste easily, efficiently and safely and prevent elution of fluorine from the treated product. It was made for the purpose.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventor fixed and fixed fluorine as stable fluoroapatite by adding a phosphoric acid compound and a calcium compound to a fluorine-containing solid waste and kneading them. The inventors have found that elution can be prevented and have completed the present invention based on this finding.
That is, the present invention provides a fluorine-containing solid waste, which is prepared by adding a phosphoric acid compound and a calcium compound and kneading and treating the fluorine-containing solid waste to prevent elution of fluorine from the treated fluorine-containing solid waste. The present invention provides a method for treating contained solid waste.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
There are no particular restrictions on the fluorine-containing solid waste to which the method of the present invention can be applied. For example, sludge and municipal waste generated during factory wastewater treatment in the semiconductor manufacturing industry, metal refining industry, metal surface treatment industry, ceramic industry, etc. Examples include sludge generated during the treatment of smoking water of incineration exhaust gas, soil contaminated with fluorine, waste such as fluororesin and fluororubber, steel slag, and fluoride glass waste.
Examples of the phosphoric acid compound used in the method of the present invention include orthophosphoric acid, hypophosphorous acid, metaphosphorous acid, pyrophosphorous acid, orthophosphorous acid, hypophosphoric acid, metaphosphoric acid, pyrophosphoric acid, and triphosphoric acid. And phosphoric acids such as condensed phosphoric acid, phosphates such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, etc. be able to. Among these, orthophosphoric acid (H 3 PO 4 ), sodium dihydrogen phosphate (NaH 2 PO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ) and condensed phosphoric acid are particularly preferably used. it can. In the method of the present invention, the amount of the phosphoric acid compound added is not particularly limited and can be appropriately selected according to the fluorine content of the solid waste, etc. The amount is preferably 0.5 to 20 parts by weight, and more preferably 2 to 15 parts by weight.
Examples of the calcium compound used in the method of the present invention include calcium oxide, calcium hydroxide, calcium chloride, calcium bromide, calcium hypochlorite, calcium chlorate, calcium perchlorate, calcium dihydrogen phosphate, and calcium hypophosphite. , Calcium phosphite, calcium nitrate and the like. Among these, calcium hydroxide and calcium chloride can be particularly preferably used. In the method of the present invention, the addition amount of the calcium compound is not particularly limited and can be appropriately selected depending on the fluorine content of the solid waste, etc., but is usually 0 with respect to 100 parts by weight of the fluorine-containing solid waste. 0.5 to 20 parts by weight is preferable, and 2 to 15 parts by weight is more preferable.
[0006]
In the method of the present invention, the addition order of the phosphoric acid compound and the calcium compound to the fluorine-containing solid waste is not particularly limited, and either the phosphoric acid compound or the calcium compound can be added first, or both of them can be performed simultaneously or It can also be added alternately. If kneading is difficult, water can be added to the fluorine-containing solid waste as necessary. The amount of water added is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the fluorine-containing solid waste. Since there is no difference in the effect of preventing fluorine elution after the treatment depending on the amount of water added, the amount of water added can be arbitrarily set in terms of workability and the like.
In the method of the present invention, the method for kneading the fluorine-containing solid waste to which the phosphoric acid compound and the calcium compound are added is not particularly limited, and can be appropriately selected according to the properties and amount of the fluorine-containing solid waste. It can be kneaded in a closed space using a concrete mixer or the like, or can be kneaded in an open space using a hydraulic excavator or the like.
In the method of the present invention, by adding a phosphoric acid compound and a calcium compound to a fluorine-containing solid waste and kneading, the mechanism capable of preventing the elution of fluorine is that the fluorine in the fluorine-containing solid waste is a phosphoric acid compound and This is presumably because it reacts with the calcium compound and is immobilized as stable fluoroapatite.
[0007]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
The gypsum containing fluorine generated as a by-product in the hydrofluoric acid production process was treated.
50 g of this fluorine-containing gypsum was put into a polypropylene beaker having a capacity of 500 mL, and 5.0 g of water, 1.5 g of normal phosphoric acid, and 1.5 g of calcium hydroxide were added, and kneaded with a spatula for 5 minutes so as to be sufficiently mixed. The treated product was subjected to a dissolution test according to the Environmental Agency Notification No. 13 test.
Put the treated product 20g and pure water 200mL into a 250mL polyethylene jar and seal it, attach it to a shaker adjusted to 200 times / min and shake width 4.5cm, and shake continuously for 6 hours at room temperature. did. Subsequently, the water in the bottle was filtered, and the fluoride ion concentration in the filtrate was measured according to JIS K 0102 34.2 ion electrode method. The elution amount of fluorine was 1.5 mg / L.
Example 2
The test was conducted in the same manner as in Example 1 except that the addition amounts of orthophosphoric acid and calcium hydroxide were 2.5 g. The elution amount of fluorine was 0.9 mg / L.
Example 3
The test was performed in the same manner as in Example 1 except that the addition amounts of orthophosphoric acid and calcium hydroxide were 5.0 g. The elution amount of fluorine was 0.5 mg / L.
Comparative Example 1
The test was conducted in the same manner as in Example 1 except that normal phosphoric acid and calcium hydroxide were not added. The elution amount of fluorine was 4.2 mg / L.
[0008]
[Table 1]
As can be seen from Table 1, in Comparative Example 1 in which normal phosphoric acid and calcium hydroxide were not added, fluorine was eluted at 4.2 mg / L, whereas normal phosphoric acid and calcium hydroxide were added. 1 to 3, the elution amount of fluorine decreases, and the more the addition amount of normal phosphoric acid and calcium hydroxide, the smaller the elution amount of fluorine. It can be seen that it is immobilized and elution is prevented.
[0010]
【The invention's effect】
According to the method for treating fluorine-containing solid waste of the present invention, fluorine-containing solid waste can be easily and efficiently treated by a simple operation of adding a phosphoric acid compound and a calcium compound to the waste and kneading. It can be safely processed to prevent the elution of fluorine from the treated product.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2001138847A JP4470216B2 (en) | 2001-05-09 | 2001-05-09 | Treatment method for fluorine-containing solid waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001138847A JP4470216B2 (en) | 2001-05-09 | 2001-05-09 | Treatment method for fluorine-containing solid waste |
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| Publication Number | Publication Date |
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| JP2002331272A JP2002331272A (en) | 2002-11-19 |
| JP4470216B2 true JP4470216B2 (en) | 2010-06-02 |
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| JP2001138847A Expired - Fee Related JP4470216B2 (en) | 2001-05-09 | 2001-05-09 | Treatment method for fluorine-containing solid waste |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4540941B2 (en) * | 2003-04-03 | 2010-09-08 | 川崎重工業株式会社 | Waste stabilization treatment method |
| JP2006241429A (en) * | 2005-02-07 | 2006-09-14 | Fujita Corp | Soil-improving material and engineering method for improving soil |
| JP4540554B2 (en) * | 2005-06-09 | 2010-09-08 | オルガノ株式会社 | Treatment method of fluorine-contaminated soil |
| JP2007105722A (en) * | 2005-08-04 | 2007-04-26 | Kobelco Eco-Solutions Co Ltd | Detoxicating method for fluorine-contaminated soil |
| JP4818092B2 (en) * | 2006-07-28 | 2011-11-16 | 新日本製鐵株式会社 | Method for suppressing elution of fluorine in steelmaking slag |
| JP2008086911A (en) * | 2006-10-02 | 2008-04-17 | Kurita Water Ind Ltd | Civil engineering material and its manufacturing method |
| JP2008127270A (en) * | 2006-11-26 | 2008-06-05 | Jfe Steel Kk | Method of treatment of granulated blast furnace slag |
| JP5018041B2 (en) * | 2006-11-26 | 2012-09-05 | Ｊｆｅスチール株式会社 | Slag processing method |
| JP4717018B2 (en) * | 2007-01-16 | 2011-07-06 | 新日本製鐵株式会社 | Soil purification agent and method for producing soil purification agent |
| JP5098505B2 (en) * | 2007-08-10 | 2012-12-12 | Ｊｆｅスチール株式会社 | Steel slag treatment method |
| JP5088040B2 (en) * | 2007-08-10 | 2012-12-05 | Ｊｆｅスチール株式会社 | Processing method of granulated blast furnace slag |
| JP5171493B2 (en) * | 2007-09-10 | 2013-03-27 | 新日鐵住金株式会社 | Method for producing solid steelmaking slag |
| JP4788721B2 (en) * | 2008-02-13 | 2011-10-05 | 新日本製鐵株式会社 | Insolubilizer and insolubilization method of fluorine in steelmaking slag |
| JP4748608B2 (en) * | 2008-03-13 | 2011-08-17 | 独立行政法人国立高等専門学校機構 | Soil-solidifying agent and soil-solidifying method |
| CN111167830A (en) * | 2019-12-30 | 2020-05-19 | 兴化市永泰铝业有限公司 | Comprehensive treatment and utilization process of secondary aluminum ash |
| JP7016894B2 (en) * | 2020-01-20 | 2022-02-07 | 大和工業株式会社 | Method for insolubilizing fluorine contained in reduced slag |
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2001
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