JP2916969B2 - Method for preventing deterioration of sulfur-containing minerals - Google Patents
Method for preventing deterioration of sulfur-containing mineralsInfo
- Publication number
- JP2916969B2 JP2916969B2 JP23225892A JP23225892A JP2916969B2 JP 2916969 B2 JP2916969 B2 JP 2916969B2 JP 23225892 A JP23225892 A JP 23225892A JP 23225892 A JP23225892 A JP 23225892A JP 2916969 B2 JP2916969 B2 JP 2916969B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfur
- deterioration
- containing mineral
- preventing
- nickel compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、含硫鉱物の劣化防止方
法に関し、更に詳細には、廃鉱山等におけるチオバチル
ス（Thiobacillus)属硫黄酸化細菌による含硫鉱物の劣
化を防止し、且つ硫酸の発生を防止するための含硫鉱物
の劣化防止方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing the deterioration of sulfur-containing minerals, and more particularly to a method for preventing the deterioration of sulfur-containing minerals caused by sulfur oxidizing bacteria belonging to the genus Thiobacillus in waste mines and the like. The present invention relates to a method for preventing deterioration of sulfur-containing minerals for preventing generation.
【０００２】[0002]
【従来の技術】従来、廃鉱山においては、酸性の浸出水
が流出し、自然破壊、農水産業の被害、コンクリート構
造物の劣化等を引き起こしており、このような酸性浸出
水の流出を防止することが検討されている。このような
酸性流出水は、一般的に廃鉱山における白鉄鉱、黄鉄鉱
等の含硫鉱物が、採鉱により酸化的雰囲気下に暴され、
廃鉱山中の雨水等に存在するチオバチルス属の硫黄酸化
細菌によって酸化され硫酸を生成することが原因である
ことが知られている。2. Description of the Related Art Conventionally, in an abandoned mine, acidic leachate has flowed out, causing natural destruction, damage to agriculture and fisheries industries, deterioration of concrete structures, and the like. That is being considered. Such acidic effluents are generally exposed to sulfur-containing minerals such as pyrite and pyrite in abandoned mines under oxidizing atmosphere by mining,
It is known that this is caused by sulfuric acid being oxidized by sulfur oxidizing bacteria of the genus Thiobacillus present in rainwater or the like in a waste mine.
【０００３】そこで従来よりこのような廃鉱山において
は、酸性雰囲気下に暴露された含硫鉱物に流入あるいは
浸透する水の量を減じたり、このような廃鉱山から流出
する水を、石灰等で中和、沈澱物を除去した後流出させ
る方法等が採用されている。[0003] Conventionally, in such a waste mine, the amount of water flowing into or penetrating into the sulfur-containing mineral exposed to an acidic atmosphere is reduced, or the water flowing out of the waste mine is reduced by lime or the like. A method of neutralizing and removing the precipitate and then flowing it out is employed.
【０００４】しかしながら、含硫鉱物に流入あるいは浸
透する水の量を減ずる方法は、ほとんど効果がなく、ま
た流出水を中和する方法では、含硫鉱物の劣化原因であ
るチオバチルス属の硫黄酸化細菌自体を防菌又は殺菌す
るのではないので、該中和処理は、継続的に行う必要が
あり、従って多額の費用を要し、更には中和の際に析出
する重金属を継続的に廃棄するためのヤード等を設置し
連続的に管理しなければならないという欠点がある。[0004] However, the method of reducing the amount of water flowing into or penetrating the sulfur-containing mineral has almost no effect, and the method of neutralizing the effluent requires sulfur oxidizing bacteria belonging to the genus Thiobacillus, which is a cause of deterioration of the sulfur-containing mineral. Since it does not sterilize or sterilize itself, the neutralization process must be performed continuously, which is costly, and furthermore, continuously discards heavy metals deposited during neutralization. There is a drawback that yards and the like must be installed and managed continuously.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、効率
的に、且つ容易に含硫鉱物の劣化を防止し、廃鉱山等に
おける硫酸の発生を防ぐことができる含硫鉱物の劣化防
止方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently and easily preventing the deterioration of sulfur-containing minerals and preventing the generation of sulfuric acid in waste mines and the like. Is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明によれば、チオバ
チルス属の硫黄酸化細菌による含硫鉱物の劣化を防止す
る方法であって、含硫鉱物にニッケル化合物含有物を接
触させることを特徴とする含硫鉱物の劣化防止方法が提
供される。According to the present invention, there is provided a method for preventing the deterioration of a sulfur-containing mineral by sulfur-oxidizing bacteria of the genus Thiobacillus, comprising contacting the sulfur-containing mineral with a nickel compound-containing substance. To provide a method for preventing deterioration of sulfur-containing minerals.
【０００７】以下本発明を更に詳細に説明する。Hereinafter, the present invention will be described in more detail.
【０００８】本発明の劣化防止方法では、例えばＮｉ、
ＮｉＯ、ＮｉＣＯ3、ＮｉＣｌ2、Ｎｉ（ＣｌＯ3）2、Ｎ
ｉ（ＣｌＯ4）2、Ｎｉ（ＩＯ3）2、ＮｉＰｒ2（ＮＯ3）
12、ＮｉＳＯ4、Ｎｉ（ＯＨ）2、ニッケルジメチルグリ
オキシム、ニケロセン等のニッケル化合物を、水溶液、
水分散液、水懸濁液或いはセメント等との混合物等とし
たニッケル化合物含有物を、チオバチルス属の硫黄酸化
細菌による劣化を防止しようとする含硫鉱物に接触させ
ることにより実施することができる。In the method for preventing deterioration according to the present invention, for example, Ni,
NiO, NiCO 3 , NiCl 2 , Ni (ClO 3 ) 2 , N
i (ClO 4 ) 2 , Ni (IO 3 ) 2 , NiPr 2 (NO 3 )
12 , an aqueous solution of a nickel compound such as NiSO 4 , Ni (OH) 2 , nickel dimethylglyoxime, nickelocene,
The method can be carried out by bringing a nickel compound-containing substance, such as an aqueous dispersion, an aqueous suspension, or a mixture with cement or the like, into contact with a sulfur-containing mineral whose deterioration is to be prevented by a sulfur-oxidizing bacterium of the genus Thiobacillus.
【０００９】前記ニッケル化合物含有物は、該含硫鉱物
がチオバチルス属の硫黄酸化細菌により劣化する際に生
ずる硫酸と反応して硫酸塩を形成し、硫黄酸化細菌を防
菌及び／又は殺菌する成分であって、使用に際しては、
ニッケル化合物含有物中のニッケル化合物を微粉末形状
として用いるのが好ましく、特に平均粒径０．００１〜
０．１ｍｍの微粉末であるのが好ましい。また前記ニッ
ケル化合物含有物を含硫鉱物と接触させる際の量は、ニ
ッケル化合物含有物中のニッケル化合物が、含硫鉱物１
００重量部に対して、０．０１〜２０重量部、特に０．
１〜２重量部となるように接触させるのが好ましい。前
記接触量が０．０１重量部未満の場合には、硫黄酸化細
菌に対する防菌及び殺菌効果を長時間保持することが困
難であり、含硫鉱物の劣化防止効果が十分でなく、また
２０重量部を超える場合には、含硫鉱物の劣化防止効果
の更なる向上が期待できないにもかかわらず、コストが
増大するので好ましくない。The nickel compound-containing substance reacts with sulfuric acid generated when the sulfur-containing mineral is degraded by sulfur-oxidizing bacteria belonging to the genus Thiobacillus to form a sulfate, thereby preventing and / or sterilizing the sulfur-oxidizing bacteria. And when using,
It is preferable to use the nickel compound in the nickel compound-containing material in the form of a fine powder, particularly the average particle diameter is 0.001 to
It is preferably a fine powder of 0.1 mm. When the nickel compound-containing material is brought into contact with the sulfur-containing mineral, the amount of the nickel compound in the nickel compound-containing material is determined by the amount of the sulfur-containing mineral 1
0.01 to 20 parts by weight, especially 0.1 to 100 parts by weight.
It is preferable to make contact so as to become 1 to 2 parts by weight. When the contact amount is less than 0.01 part by weight, it is difficult to maintain the antibacterial and bactericidal effects against sulfur oxidizing bacteria for a long time, the effect of preventing the sulfur-containing mineral from being deteriorated is insufficient, and the weight of 20 wt. If the amount exceeds the limit, the cost is increased, although the effect of preventing the sulfur-containing mineral from being deteriorated cannot be expected to be further improved.
【００１０】本発明の劣化防止方法において、含硫鉱物
にニッケル化合物含有物を接触させるには、例えば、ニ
ッケル化合物含有物が、溶液、分散液又は懸濁液等の溶
液状である場合には、廃鉱山の廃抗にニッケル化合物含
有物を流入或いは廃鉱山自体に散布し、含硫鉱物をニッ
ケル化合物含有物で浸漬する方法又は含硫鉱物中に注入
する方法等により行うことができ、またニッケル化合物
含有物を公知のグラウト工法等により、含硫鉱物中に注
入する方法等により行うことができる。更に、２液性グ
ラウトには、ＮｉＣｌ2水溶液と、炭酸、重炭酸ナトリ
ウム、炭酸ナトリウム又はこれらの混合物との水溶液或
いは懸濁液を用いて、接触沈澱させる方法等を行うこと
もできる。In the method for preventing deterioration according to the present invention, the nickel compound-containing substance is brought into contact with the sulfur-containing mineral, for example, when the nickel compound-containing substance is in the form of a solution such as a solution, a dispersion or a suspension. The method can be carried out by injecting a nickel compound-containing material into the waste mine or spraying it on the waste mine itself, and immersing the sulfur-containing mineral with the nickel compound-containing material or injecting the sulfur-containing mineral into the sulfur-containing mineral. The method can be carried out by injecting the nickel compound-containing material into the sulfur-containing mineral by a known grouting method or the like. Further, for the two-part grout, a method of contact precipitation using an aqueous solution or suspension of NiCl 2 aqueous solution and carbonic acid, sodium bicarbonate, sodium carbonate or a mixture thereof can also be performed.
【００１１】本発明の劣化防止方法において、前記含硫
鉱物に接触させたニッケル化合物含有物は、炭酸水、重
炭酸ナトリウム、炭酸ナトリウム、炭酸カルシウム等に
より中和沈澱させることにより回収することができる。
この際本発明の劣化防止方法が、チオバチルス属の硫黄
酸化細菌自体を防菌及び殺菌することにより含硫鉱物の
劣化を防止するので、前記接触処理を継続的に行う必要
がなく、従って前記中和沈澱も連続的に行う必要がな
く、単に含硫鉱物からの流出液を連続的に中和処理する
従来の方法に比して低コストで行うことができる。In the method for preventing deterioration according to the present invention, the nickel compound-containing substance brought into contact with the sulfur-containing mineral can be recovered by neutralization and precipitation with carbonated water, sodium bicarbonate, sodium carbonate, calcium carbonate and the like. .
At this time, since the deterioration prevention method of the present invention prevents deterioration of the sulfur-containing mineral by preventing and sterilizing the sulfur-oxidizing bacteria of the genus Thiobacillus itself, it is not necessary to continuously perform the contact treatment. The precipitation does not need to be performed continuously, and can be performed at a lower cost than a conventional method in which the effluent from the sulfur-containing mineral is simply neutralized continuously.
【００１２】[0012]
【発明の効果】本発明の含硫鉱物の劣化防止方法では、
単にニッケル化合物含有物を、含硫鉱物に接触させるの
みで、チオバチルス属の硫黄酸化細菌による含硫鉱物の
劣化を有効に防止することができるので、特に廃鉱山等
における含硫鉱物の劣化防止及びそれに伴う硫酸の発生
を、従来の方法に比して容易に、且つ低コストで防止す
ることができる。更に本発明の方法では、含硫鉱物の劣
化の原因であるチオバチルス属の硫黄酸化細菌自体を防
菌及び殺菌するので、一度の処理により長期間にわたり
含硫鉱物の劣化を防止することができる。According to the method for preventing sulfur-containing mineral deterioration of the present invention,
By simply contacting the nickel compound-containing substance with the sulfur-containing mineral, it is possible to effectively prevent the degradation of the sulfur-containing mineral caused by sulfur-oxidizing bacteria of the genus Thiobacillus, and thus to prevent the degradation of the sulfur-containing mineral particularly in a waste mine and the like. The accompanying generation of sulfuric acid can be prevented more easily and at lower cost than in the conventional method. Furthermore, in the method of the present invention, sulfur-oxidizing bacteria belonging to the genus Thiobacillus, which cause deterioration of sulfur-containing minerals, are sterilized and sterilized, so that a single treatment can prevent deterioration of sulfur-containing minerals for a long period of time.
【００１３】[0013]
【実施例】以下、本発明を実施例に基づき更に詳細に説
明するが、本発明はこれらに限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
【００１４】[0014]
【実施例１】直径１０ｃｍ、高さ１ｃｍのガラス製シャ
ーレ６個に、１リットルあたりの組成が、(NH4)2SO4 2
g、KNO3 3g、MgCl2・6H2O 0.5g、CaCl2・6H2O 0.25g、FeS
O4・7H2O 0.01g、Na2MoO4・2H2O 0.3mg、Na2S2O3・5H2O 0.
5gである硫黄酸化細菌培養用の寒天培地を４０ｍｌづつ
入れた。次いでシャーレ２個毎に、それぞれ２００メッ
シュ以下の白鉄鉱、黄鉄鉱微粉末を５ｇ投入し、また残
りの２個のシャーレには何も入れず、３組のシャーレを
用意した。次にそれぞれの組の一方に２００メッシュ以
下のニッケル粉末０．１ｇを添加した後、それぞれのシ
ャーレに市販の硫黄酸化細菌（Thiobacillus thiooxida
ns)を106cells/cm2植種し、３５℃の培養器中で１週間
培養した。１週間後の硫黄酸化細菌数及びｐＨを測定し
た。その結果を表１に示す。[Example 1] The composition per liter was (NH 4 ) 2 SO 4 2 in 6 glass dishes having a diameter of 10 cm and a height of 1 cm.
g, KNO 3 3g, MgCl 2・ 6H 2 O 0.5g, CaCl 2・ 6H 2 O 0.25g, FeS
O 4 · 7H 2 O 0.01g, Na 2 MoO 4 · 2H 2 O 0.3mg, Na 2 S 2 O 3 · 5H 2 O 0.
An agar medium for culturing 5 g of sulfur oxidizing bacteria was added in 40 ml portions. Then, for each two petri dishes, 5 g of a fine powder of hematite and pyrite having a mesh size of 200 mesh or less was charged, and nothing was put in the remaining two petri dishes to prepare three sets of petri dishes. Next, after adding 0.1 g of nickel powder of 200 mesh or less to one of the sets, commercially available sulfur-oxidizing bacteria (Thiobacillus thiooxida) were added to each dish.
ns) was inoculated at 10 6 cells / cm 2 and cultured in an incubator at 35 ° C. for 1 week. One week later, the number and pH of sulfur-oxidizing bacteria were measured. Table 1 shows the results.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【実施例２〜６】ニッケル粉末の代わりに、ＮｉＯ（実
施例２）、ＮｉＣＯ3（実施例３）、ＮｉＣｌ2（実施例
４）、ＮｉＳＯ4（実施例５）又はＮｉ（ＯＨ）2（実施
例６）を用いた以外は実施例１と同様に培養を行い、１
週間後のｐＨを測定した。その結果を表２に示す。Examples 2 to 6 Instead of nickel powder, NiO (Example 2), NiCO 3 (Example 3), NiCl 2 (Example 4), NiSO 4 (Example 5) or Ni (OH) 2 ( Culture was performed in the same manner as in Example 1 except that Example 6) was used.
Weekly pH was measured. Table 2 shows the results.
【００１７】表２の結果より実施例２〜６はいずれもｐ
Ｈが中性付近であったので、硫黄細菌の菌数が減少した
ことがわかる。According to the results shown in Table 2, in Examples 2 to 6,
Since H was near neutral, it was found that the number of sulfur bacteria decreased.
【００１８】[0018]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) A01N 59/16 C22B 23/04 ＣＡ（ＳＴＮ) ＷＰＩ／Ｌ（ＱＵＥＳＴＥＬ)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) A01N 59/16 C22B 23/04 CA (STN) WPI / L (QUESTEL)
Claims (1)
硫鉱物の劣化を防止する方法であって、含硫鉱物にニッ
ケル化合物含有物を接触させることを特徴とする含硫鉱
物の劣化防止方法。1. A method for preventing deterioration of a sulfur-containing mineral caused by sulfur-oxidizing bacteria belonging to the genus Thiobacillus, comprising contacting a sulfur-containing mineral with a nickel compound-containing substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23225892A JP2916969B2 (en) | 1992-08-31 | 1992-08-31 | Method for preventing deterioration of sulfur-containing minerals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23225892A JP2916969B2 (en) | 1992-08-31 | 1992-08-31 | Method for preventing deterioration of sulfur-containing minerals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0672815A JPH0672815A (en) | 1994-03-15 |
| JP2916969B2 true JP2916969B2 (en) | 1999-07-05 |
Family
ID=16936451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23225892A Expired - Fee Related JP2916969B2 (en) | 1992-08-31 | 1992-08-31 | Method for preventing deterioration of sulfur-containing minerals |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2916969B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6224658B1 (en) | 1997-07-14 | 2001-05-01 | Hazama Corporation | Thiobacillus thiooxidansgrowth inhibitor, cement composition, and cement structure |
-
1992
- 1992-08-31 JP JP23225892A patent/JP2916969B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672815A (en) | 1994-03-15 |
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