JP2002326819A - Iron sulfide, its production method, iron sulfide composition, heavy metal treatment agent and treatment method using the same - Google Patents

Iron sulfide, its production method, iron sulfide composition, heavy metal treatment agent and treatment method using the same

Info

Publication number
JP2002326819A
JP2002326819A JP2002012550A JP2002012550A JP2002326819A JP 2002326819 A JP2002326819 A JP 2002326819A JP 2002012550 A JP2002012550 A JP 2002012550A JP 2002012550 A JP2002012550 A JP 2002012550A JP 2002326819 A JP2002326819 A JP 2002326819A
Authority
JP
Japan
Prior art keywords
iron sulfide
iron
alkaline earth
earth metal
heavy metals
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.)
Granted
Application number
JP2002012550A
Other languages
Japanese (ja)
Other versions
JP4178794B2 (en
Inventor
Hajime Funakoshi
肇 船越
Mitsuru Takahashi
満 高橋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Tosoh Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tosoh Corp filed Critical Tosoh Corp
Priority to JP2002012550A priority Critical patent/JP4178794B2/en
Publication of JP2002326819A publication Critical patent/JP2002326819A/en
Application granted granted Critical
Publication of JP4178794B2 publication Critical patent/JP4178794B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Removal Of Specific Substances (AREA)
  • Compounds Of Iron (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a new iron sulfide and iron sulfide composition excellent in durability and treatment capability of heavy metals, to provide a method which synthesizes these new iron sulfides and to provide a method which treats heavy metals contained in ashes, soil and waste water and so on and renders it harmless by using the heavy metal treatment agent containing the iron sulfide as an active element and this treatment agent. SOLUTION: The iron sulfide excellent in durability having a maquinawate structure shown by Fe.Mx .Ny .Sz as an essential component of constituting element (in the formula, M shows an alkaline earth metal, N shows an alkali metal, x, y and z show mol ratio, 0.01<=x<=0.5, y<=0.2, 0.7<=z<=1.4), this production method, the iron sulfide composition and the heavy metal treatment agent whose active ingredient is this iron sulfide and the treatment method using it are used.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明が属する技術分野】本発明は、耐久性に優れた新
規な硫化鉄、その製造方法、これを含む硫化鉄組成物、
この新規な硫化鉄を有効成分とする重金属類処理剤、及
びこの重金属類処理剤を用いた各種重金属類を含む廃棄
物の無害化処理方法に関する。The present invention relates to a novel iron sulfide having excellent durability, a method for producing the same, an iron sulfide composition containing the same,
The present invention relates to a novel agent for treating heavy metals containing iron sulfide as an active ingredient, and a method for detoxifying waste containing various heavy metals using the agent for treating heavy metals.

【０００２】[0002]

【従来の技術】Ｒｅｖｉｅｗｓ ｏｆ Ｐｕｒｅ ａｎ
ｄ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ，２０巻，１
７５〜２０６頁（１９７０年）には、硫化鉄の構造が示
されており、一般に知られている工業用硫化鉄や鉄粉と
硫黄を融解して作られる硫化鉄はピロータイト構造であ
り、また、鉄（ＩＩ）イオンを含んだ溶液と硫黄イオン
を含んだ溶液を混合することにより生成する硫化鉄はマ
キナワイト構造であることが開示されている。2. Description of the Related Art Reviews of Pure an
d Applied Chemistry, Volume 20, 1
On pages 75 to 206 (1970), the structure of iron sulfide is shown, and generally known industrial iron sulfide and iron sulfide produced by melting iron powder and sulfur have a pyrrhotite structure, Further, it is disclosed that iron sulfide formed by mixing a solution containing iron (II) ions and a solution containing sulfur ions has a makinawite structure.

【０００３】硫化鉄を用いて各種重金属類を含んだ廃棄
物を無害化処理することは広く知られており、例えば、
特公昭４９−４３４７２号公報、特開昭４７−３１８０
６号公報、特開昭５０−１３２９４号公報、特開昭５０
−９６０５３号公報、特開昭５２−１２６６８５号公
報、特開昭６０−２２７８８１号公報等に工業用硫化鉄
（ピロータイト構造）等を用いて水溶液中のＰｂ、Ｃ
ｄ、Ｃｒ、Ｈｇ、Ａｓ等の有害な重金属類を処理する方
法が開示されている。It is widely known that iron sulfide is used to detoxify waste containing various heavy metals.
JP-B-49-43472, JP-A-47-3180
No. 6, JP-A-50-13294, JP-A-50-13294
No. 96053, JP-A-52-126885, JP-A-60-227881, etc., by using industrial iron sulfide (pyroite structure) or the like, Pb and C in an aqueous solution.
A method for treating harmful heavy metals such as d, Cr, Hg, and As is disclosed.

【０００４】また、鉄（ＩＩ）イオンを含んだ溶液と硫
黄イオンを含んだ溶液を混合して調製した硫化鉄（マキ
ナワイト構造）を用いて重金属類を処理することも公知
であり、この方法で得られた硫化鉄は工業用硫化鉄より
も重金属類を処理する能力が高いことが知られている。
例えば、特開昭４８−１１２９１号公報、特開昭４９−
３１１５２号公報、特開昭５２−１１３５５９号公報、
特開昭５２−１４８４７３号公報、特開昭５３−１０２
２７３号公報等に、鉄（ＩＩ）イオンを含んだ溶液と硫
黄イオンを含んだ溶液、あるいはこれらの溶液を混合し
て得られた硫化鉄を用いて有害な重金属類を処理する方
法が開示されている。It is also known to treat heavy metals with iron sulfide (makinawite structure) prepared by mixing a solution containing iron (II) ions and a solution containing sulfur ions. It is known that the obtained iron sulfide has a higher ability to treat heavy metals than industrial iron sulfide.
For example, JP-A-48-11291, JP-A-49-11291
No. 31152, JP-A-52-113559,
JP-A-52-148473, JP-A-53-102
No. 273 discloses a method for treating harmful heavy metals using a solution containing iron (II) ions and a solution containing sulfur ions, or iron sulfide obtained by mixing these solutions. ing.

【０００５】しかし、マキナワイト構造の硫化鉄は非常
に酸化されやすく、空気中の水分及び酸素と反応してイ
オウと水酸化鉄（ＩＩＩ）に分解し、重金属類を処理す
る能力が容易に低下してしまう。そのため従来は、鉄
（ＩＩ）イオンを含んだ溶液と硫黄イオンを含んだ溶液
を混合し硫化鉄を含んだスラリーを調製し、スラリーの
まま直ちに廃水のような被処理物と混合して使用するこ
とが通例であった。通常、硫黄イオンを含んだ溶液は価
格および工業的な入手のしやすさから硫化ナトリウムま
たは水硫化ナトリウム水溶液を用いるが、その有害性、
腐食性、悪臭等のため化学の知識を有した熟練者が操作
を行なう必要があり、一般的な取り扱いは困難であっ
た。さらにスラリーで用いる場合、一定の流動性を持た
せるために硫化鉄の濃度を高くすることは困難であり、
例えば工場で硫化鉄スラリーを製造した場合、輸送コス
トが多大なものとなり、また、廃水処理等に用いる場合
は問題が生じないものの、例えば高濃度の重金属類を含
んだ飛灰や土壌を処理するために多量の硫化鉄を添加し
た場合、被処理物の含水量が高くなりすぎ、そのあとの
ハンドリングが困難となる等の課題があった。However, iron sulfide having a mackinawite structure is very easily oxidized, reacts with moisture and oxygen in the air to decompose into sulfur and iron (III) hydroxide, and the ability to treat heavy metals easily decreases. Would. Therefore, conventionally, a solution containing iron (II) ions and a solution containing sulfur ions are mixed to prepare a slurry containing iron sulfide, and the slurry is used as it is immediately mixed with an object to be treated such as wastewater. That was customary. Normally, sodium sulfide or sodium bisulfide aqueous solution is used for the solution containing sulfur ions because of its price and industrial availability.
The operation must be performed by a skilled person having knowledge of chemistry due to corrosiveness and odor, and general handling is difficult. Further, when used in a slurry, it is difficult to increase the concentration of iron sulfide in order to have a certain fluidity,
For example, when iron sulfide slurry is manufactured at a factory, transportation costs become large, and when used for wastewater treatment, etc., there is no problem, but for example, fly ash and soil containing high concentration heavy metals are treated. Therefore, when a large amount of iron sulfide is added, there is a problem that the water content of the object to be treated becomes too high, and subsequent handling becomes difficult.

【０００６】一方、スラリーを濾過、乾燥してマキナワ
イト構造硫化鉄粉末を調製する場合、酸化を防ぐため、
不活性雰囲気下で操作を行なうか酸化防止剤を加える必
要があった。得られた硫化鉄粉末は酸化劣化を起こさな
いように、酸素および水分が透過しない容器に保存する
か、酸化防止のための還元剤を加える必要があった。還
元剤を加えても、酸化劣化されやすさを根本的に解決し
たわけでなく、還元剤が消費された時点で硫化鉄の酸化
が始まるために保存安定性は極めて低いものであった。On the other hand, in the case of preparing a makinawite-structured iron sulfide powder by filtering and drying the slurry, in order to prevent oxidation,
It was necessary to operate under an inert atmosphere or to add an antioxidant. The obtained iron sulfide powder had to be stored in a container impervious to oxygen and moisture or had to be added with a reducing agent for preventing oxidation so as not to cause oxidative deterioration. The addition of the reducing agent did not fundamentally solve the susceptibility to oxidative degradation, and the storage stability was extremely low because the oxidation of iron sulfide started when the reducing agent was consumed.

【０００７】[0007]

【発明が解決しようとする課題】本発明の目的は、上記
記載の背景において、耐久性に優れ、重金属類の処理特
性が優れた新規な硫化鉄、この新規な硫化鉄を含む硫化
鉄組成物及びこれらを合成する方法を提供することにあ
る。さらに、その硫化鉄を有効成分として含む重金属類
処理剤、及びこの処理剤を用いて、灰、土壌、廃水等に
含まれる重金属類を処理し無害化する方法を提供するこ
とも本発明の目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel iron sulfide having excellent durability and excellent heavy metal treatment properties, and an iron sulfide composition containing the novel iron sulfide. And a method for synthesizing them. Another object of the present invention is to provide a treating agent for heavy metals containing the iron sulfide as an active ingredient, and a method for treating and rendering harmless heavy metals contained in ash, soil, wastewater and the like using the treating agent. And

【０００８】[0008]

【課題を解決するための手段】本発明者らは上記課題、
すなわち従来の合成硫化鉄は重金属の処理活性が高いも
のの耐久性に劣る欠点を持っているため、これを解決す
るために鋭意検討した結果、硫化鉄中にアルカリ土類金
属を一定量以上取り込ませ、構成元素の必須成分とし
て、Ｆｅ・Ｍx・Ｎy・Ｓz（式中、Ｍはアルカリ土類金
属、Ｎはアルカリ金属、ｘ、ｙ及びｚはモル比であり、
０．０１＜ｘ≦０．５、ｙ≦０．２、０．７≦ｚ≦１．
４を示す。）で表される新規な組成の硫化鉄とすること
により耐久性を飛躍的に向上させることができることを
見出し、また、そのような硫化鉄は、２価の鉄塩の水溶
液と硫黄イオンを含む水溶液とアルカリ土類成分を混合
し、かつ、混合後のスラリーｐＨを７．０以上とするこ
とにより得られることを見出した。さらに、この新規な
硫化鉄を有効成分として含む重金属類処理剤は、従来の
合成硫化鉄やピロータイト構造の硫化鉄よりも各種重金
属類の処理特性が飛躍的に優れていることを見出し、本
発明を完成させるに至った。Means for Solving the Problems The present inventors have solved the above problems,
That is, the conventional synthetic iron sulfide has a high heavy metal treatment activity but has a disadvantage of poor durability, and as a result of intensive studies to solve this, as a result, the alkaline sulfide metal was incorporated into the iron sulfide in a certain amount or more. , as an essential component of the constituting elements in Fe · M x · N y · S z ( wherein, M is alkaline earth metal, N represents an alkali metal, x, y and z are molar ratios,
0.01 <x ≦ 0.5, y ≦ 0.2, 0.7 ≦ z ≦ 1.
4 is shown. )), The durability can be drastically improved by using a novel composition of iron sulfide, and such an iron sulfide contains an aqueous solution of a divalent iron salt and sulfur ions. It has been found that an aqueous solution can be obtained by mixing an aqueous solution with an alkaline earth component and adjusting the pH of the slurry after mixing to 7.0 or more. In addition, they found that the novel heavy metal treatment agent containing iron sulfide as an active ingredient has dramatically superior processing characteristics for various heavy metals compared to conventional synthetic iron sulfide and iron sulfide having a pyrrhotite structure. The invention has been completed.

【０００９】以下、本発明について詳細に説明する。Hereinafter, the present invention will be described in detail.

【００１０】本発明の硫化鉄は、構成元素の必須成分と
して、Ｆｅ・Ｍx・Ｎy・Ｓz（式中、Ｍはアルカリ土類
金属、Ｎはアルカリ金属、ｘ、ｙ及びｚはモル比であ
り、０．０１＜ｘ≦０．５、ｙ≦０．１、０．７≦ｚ≦
１．４を示す。）であることが必須である。[0010] the iron sulfide of the invention, as an essential component of the constituting elements in Fe · M x · N y · S z ( wherein, M is alkaline earth metal, N represents an alkali metal, x, y and z are mole Ratio, 0.01 <x ≦ 0.5, y ≦ 0.1, 0.7 ≦ z ≦
1.4 is shown. ) Is essential.

【００１１】一般に硫化鉄の鉄と硫黄のモル比は不定比
性があることが知られており、そのモル比１前後で任意
の値を取りうる。本発明の硫化鉄もこれまでのマキナワ
イト構造の硫化鉄と同様、鉄に対する硫黄のモル比ｚは
０．７以上１．４以下の値を示す。より安定性の高いマ
キナワイト構造とする為には、０．８以上１．０以下が
好ましい。In general, it is known that the molar ratio of iron to sulfur in iron sulfide is non-stoichiometric, and the molar ratio can take an arbitrary value around 1. The iron sulfide of the present invention also has a molar ratio z of sulfur to iron of 0.7 or more and 1.4 or less, similarly to the iron sulfide of the conventional mackinawite structure. In order to obtain a more stable Mackinawite structure, the ratio is preferably 0.8 or more and 1.0 or less.

【００１２】本発明の硫化鉄におけるアルカリ土類金属
の量は、鉄に対するモル比ｘで表し、ｘが０．０１＜ｘ
≦０．５の範囲である。モル比ｘが０．０１以下の場合
には耐久性の向上は望めず、一方、ｘが０．５を超える
場合には得られる安定化の向上効果は、この範囲内のも
のに比較し少ない。The amount of alkaline earth metal in the iron sulfide of the present invention is represented by a molar ratio x to iron, where x is 0.01 <x
≦ 0.5. When the molar ratio x is 0.01 or less, improvement in durability cannot be expected. On the other hand, when x exceeds 0.5, the obtained stabilization improving effect is less than that in the range. .

【００１３】本発明の組成のアルカリ土類金属を含有し
た硫化鉄は、調製時にアルカリ土類金属を加える順によ
り、異なるＸＲＤを示す。即ち、２価鉄塩と硫黄イオン
を含む水溶液を混合後、アルカリ土類金属成分を加えｐ
Ｈ７以上とした場合には、マキナワイト構造に帰属され
るＸＲＤを示し、アルカリ土類金属成分の共存下に２価
鉄塩と硫黄イオンを含む水溶液を混合しｐＨ７以上とし
た場合には、後述の変性マキナワイト構造を示す。本発
明者らは、いずれの場合においても、本発明の組成範囲
内においては、アルカリ土類金属成分に由来するピーク
が見られず、また、この範囲において耐久性の向上効果
が極めて大きい事を見出したものである。さらに、この
組成範囲を超えたアルカリ土類金属成分を加えた場合に
は、アルカリ土類金属成分の化合物に帰属されるピーク
が観測されるようになり、耐久性の向上効果は、それ以
下の組成のものとほぼ同等となる。但し、アルカリ土類
金属の種類により、この効果を認める最適範囲は若干異
なり、マグネシウムでは、０．０４≦ｘ≦０．５、カル
シウムでは、０．０３≦ｘ≦０．４、ストロンチウムで
は、０．０２≦ｘ≦０．３、更に、バリウムでは０．０
１≦ｘ≦０．２である。The alkaline earth metal-containing iron sulfide of the composition of the present invention exhibits different XRD depending on the order in which the alkaline earth metal is added during preparation. That is, after mixing an aqueous solution containing a ferrous salt and sulfur ions, an alkaline earth metal component is added and p
When it is H7 or more, it shows the XRD attributed to the mackinawite structure, and when an aqueous solution containing a ferrous salt and a sulfur ion is mixed in the presence of an alkaline earth metal component to make the pH 7 or more, 1 shows a modified mackinawite structure. The present inventors show that in any case, within the composition range of the present invention, no peak derived from the alkaline earth metal component is observed, and that the effect of improving the durability in this range is extremely large. It was found. Furthermore, when an alkaline earth metal component exceeding this composition range is added, a peak attributed to the compound of the alkaline earth metal component comes to be observed, and the effect of improving durability is less than that. It is almost equivalent to the composition. However, the optimum range for recognizing this effect is slightly different depending on the type of the alkaline earth metal, and is 0.04 ≦ x ≦ 0.5 for magnesium, 0.03 ≦ x ≦ 0.4 for calcium, and 0 for strontium. .02 ≦ x ≦ 0.3, and further, for barium, 0.0
1 ≦ x ≦ 0.2.

【００１４】本発明では、アルカリ土類金属の種類とし
て、上記した４つの元素を任意に組合せて複数種用いる
ことも可能である。なお、本発明において最も好ましい
アルカリ土類金属は上記した４つの元素のなかで、カル
シウムおよびマグネシウムである。カルシウムおよびマ
グネシウムは硫化鉄中に取り込まれやすいだけでなく、
工業的に入手が容易で、ストロンチウムのように高価で
なく、また、バリウムのように毒性が問題となることも
ない。In the present invention, it is also possible to use a plurality of kinds of alkaline earth metals by arbitrarily combining the above four elements. In the present invention, the most preferred alkaline earth metals are calcium and magnesium among the above four elements. Calcium and magnesium are not only easily incorporated into iron sulfide,
It is readily available industrially, is not as expensive as strontium, and does not pose toxicity problems like barium.

【００１５】本発明の硫化鉄におけるアルカリ金属の量
において、鉄に対するモル比であるｙはこれまで知られ
ていたマキナワイト構造を有する硫化鉄の場合よりも上
限が低く、０．２以下であることが必須である。アルカ
リ金属の量が０．２よりも大きい場合、本発明の目的で
ある耐久性に優れた硫化鉄を得ることは困難となり、ア
ルカリ金属の量が少ないほど耐久性の向上が期待でき、
より好ましくはアルカリ金属の量が０．１以下である。
尚、本発明の硫化鉄においては、アルカリ金属を全く含
まない場合も含まれ、例えば原料としてアルカリ金属を
含まないものにより製造したり、アルカリ金属分を洗浄
等により除去することでｙが０となるような硫化鉄が得
られうる。アルカリ金属の種類は用いる原料により異な
るため一概には言えないが、例えば硫黄イオンの原料と
して工業的に入手が容易な硫化ナトリウムや水硫化ナト
リウムをを用いた場合、上記組成式のＮはナトリウムと
なる。In the amount of alkali metal in the iron sulfide of the present invention, the upper limit of the molar ratio y to iron is lower than that of iron sulfide having a makinawite structure which has been known so far, and is 0.2 or less. Is required. When the amount of the alkali metal is larger than 0.2, it is difficult to obtain iron sulfide having excellent durability, which is the object of the present invention, and improvement in durability can be expected as the amount of the alkali metal is small,
More preferably, the amount of alkali metal is 0.1 or less.
Incidentally, the iron sulfide of the present invention includes a case where no alkali metal is contained at all, and for example, y is set to 0 by manufacturing a material containing no alkali metal as a raw material or removing an alkali metal component by washing or the like. Thus, iron sulfide can be obtained. Since the type of alkali metal differs depending on the raw material used, it cannot be said unconditionally.For example, when sodium sulfide or sodium hydrosulfide, which is industrially easily available, is used as a raw material for sulfur ions, N in the above composition formula is sodium and Become.

【００１６】本発明では、耐久性について温度、相対湿
度を変化させ評価を行った。従来の合成法によるマキナ
ワイト構造の硫化鉄は夏場の気温（〜３０℃）と相対湿
度（〜７０％）では１日で分解が進行し、ＸＲＤにおい
てＳのピークが観察され始め、７日で完全に分解し、マ
キナワイト構造に帰属できるピークは消失する。さら
に、５０℃、相対湿度７０％の条件では１日で完全に分
解し、マキナワイト構造に帰属できるピークが消失す
る。これに対し本発明の硫化鉄は更に厳しい７０℃、相
対湿度７０％の条件で１日の耐久処理を行なった場合で
も、その残存率は５０％以上（分解率が５０％未満）で
あり、極めて耐久性が向上していることで特徴づけられ
る。In the present invention, the durability was evaluated by changing the temperature and the relative humidity. Decomposition of the iron sulfide having a makinawite structure by a conventional synthetic method progresses in one day at summer temperature (up to 30 ° C.) and relative humidity (up to 70%), and a peak of S starts to be observed in XRD, and complete in seven days. And the peak attributable to the mackinawite structure disappears. Further, under the conditions of 50 ° C. and 70% relative humidity, the compound is completely decomposed in one day, and the peak attributed to the mackinawite structure disappears. On the other hand, the iron sulfide of the present invention has a residual rate of 50% or more (decomposition rate is less than 50%) even when subjected to one-day durability treatment at 70 ° C. and 70% relative humidity. It is characterized by extremely improved durability.

【００１７】アルカリ土類金属を添加することにより、
耐久性が向上する原因は明らかではないが、硫化鉄中に
アルカリ土類金属が取り込まれ硫化鉄の表面に酸化分解
を妨げる層が形成されるか、あるいはアルカリ土類金属
が酸化分解の進行を妨げているためと推定される。By adding an alkaline earth metal,
It is not clear why the durability is improved, but the alkaline earth metal is incorporated into the iron sulfide and a layer that prevents oxidative decomposition is formed on the surface of the iron sulfide, or the alkaline earth metal progresses oxidative decomposition. Presumed to be preventing.

【００１８】また、硫化鉄中に取り込まれるアルカリ土
類金属は、硫化鉄中の鉄と置換して取り込まれるのでは
なく、アルカリ土類金属の水酸化物、または酸化物の形
で取り込まれているものと推定される。The alkaline earth metal incorporated in the iron sulfide is not replaced by the iron in the iron sulfide but is incorporated in the form of a hydroxide or oxide of the alkaline earth metal. It is estimated that there is.

【００１９】尚、本発明でいうマキナワイト構造とは、
ＪＣＰＤＳカード（ＰｏｗｄｅｒＤｉｆｆｒａｃｔｉｏ
ｎ Ｆｉｌｅ）の１５−３７に示され、そのＸＲＤ回折
パターンは、以下の表１の通りである。In the present invention, the "makinawite structure"
JCPDS card (PowerDiffraction)
n File) 15-37, and its XRD diffraction pattern is as shown in Table 1 below.

【００２０】[0020]

【表１】 また、本明細書にいう変性マキナワイト構造とは、上記
表１に示されるマキナワイト構造のＸＲＤの回折パター
ンにおいて、００１面の面間隔が５．０３Å以上５．５
３Å以下とｃ軸方向に広がり、この００１面からのピー
ク強度を１００とした場合、他のｈｋｌ面からの回折ピ
ークの強度比がすべて２０以下であることにより特徴づ
けられる構造を意味する。[Table 1] In addition, the modified makinawite structure referred to in the present specification means that in the XRD diffraction pattern of the makinawite structure shown in Table 1 above, the plane spacing of the 001 plane is 5.03 ° or more and 5.5 or more.
It spreads in the c-axis direction at 3 ° or less, and when the peak intensity from this 001 plane is set to 100, it means a structure characterized by the fact that the intensity ratio of diffraction peaks from other hkl planes is all 20 or less.

【００２１】変性マキナワイト構造となる原因は明らか
ではないが、硫化鉄が生成する際にアルカリ土類金属成
分が存在していた場合、硫化鉄中へアルカリ土類金属
が、ｃ軸すなわち鉄原子層とイオウ原子層の間隔を広
げ、かつ、ａ軸及びｂ軸すなわち鉄原子及びイオウ原子
の並びの乱れを生じさせるように取り込まれるためと推
定される。Although the cause of the modified makinawite structure is not clear, when an alkaline earth metal component is present when iron sulfide is formed, the alkaline earth metal is introduced into the iron sulfide by the c-axis, that is, the iron atomic layer. It is presumed that the distance between the silicon atom and the sulfur atom layer is widened, and that the atoms are incorporated so as to cause disorder in the arrangement of the a-axis and the b-axis, that is, the arrangement of iron atoms and sulfur atoms.

【００２２】上記した変性マキナワイト構造の硫化鉄の
検討を行なった結果、変性マキナワイト構造の硫化鉄
は、これを水に分散し、酢酸のような弱酸を添加した
後、濾過洗浄を行なうことにより、アルカリ土類金属の
一部が溶出し、ＸＲＤ回折パターンがマキナワイト構造
に可逆的に変化することを見出した。従って、本発明の
変性マキナワイト構造とは、これまで知られていたマキ
ナワイト構造の特殊形態であると考えられる。As a result of examining the above-mentioned iron sulfide having the modified makinawite structure, the iron sulfide having the modified makinawite structure was dispersed in water, added with a weak acid such as acetic acid, and then filtered and washed. It was found that a part of the alkaline earth metal was eluted and the XRD diffraction pattern reversibly changed to a mackinawite structure. Therefore, it is considered that the modified makinawite structure of the present invention is a special form of the known makinawite structure.

【００２３】次に本発明の硫化鉄の製造方法について詳
細に説明する。Next, the method for producing iron sulfide of the present invention will be described in detail.

【００２４】本発明の方法は、２価の鉄塩の水溶液と硫
黄イオンを含む水溶液とアルカリ土類金属成分を混合
し、かつ、混合後のスラリーｐＨを７．０以上とするこ
とにより、耐久性に優れたマキナワイト構造の硫化鉄を
得るものである。In the method of the present invention, the aqueous solution of a divalent iron salt, the aqueous solution containing sulfur ions, and the alkaline earth metal component are mixed, and the pH of the slurry after mixing is adjusted to 7.0 or more. An iron sulfide having a makinawite structure having excellent properties is obtained.

【００２５】本発明の方法では、上記した３つの成分の
混合順序は適宜選択することができ、２価の鉄塩の水溶
液と硫黄イオンを含む水溶液を混合した後にアルカリ土
類金属成分を混合してもよく、また、２価の鉄塩の水溶
液とアルカリ土類金属成分を混合しその後硫黄イオンを
含む水溶液と混合しても良く、また、硫黄イオンを含む
水溶液とアルカリ土類金属成分を混合し、２価の鉄塩の
水溶液を混合しても良く、生産プロセス上最適な方法を
選択することができる。本発明者が更に、上記した混合
方法において、２価の鉄塩の水溶液と硫黄イオンを含む
水溶液を混合し硫化鉄が生成する際にアルカリ土類金属
が存在した場合は、生成するマキナワイト構造の硫化鉄
は変性マキナワイト構造となることを見出した。In the method of the present invention, the mixing order of the above three components can be appropriately selected. An aqueous solution of a divalent iron salt and an aqueous solution containing sulfur ions are mixed, and then the alkaline earth metal component is mixed. Alternatively, an aqueous solution of a divalent iron salt and an alkaline earth metal component may be mixed and then mixed with an aqueous solution containing sulfur ions, or an aqueous solution containing sulfur ions and an alkaline earth metal component may be mixed. Alternatively, an aqueous solution of a divalent iron salt may be mixed, and an optimal method can be selected in terms of a production process. The inventor further proposes that, in the above-described mixing method, when an alkaline earth metal is present when iron sulfide is generated by mixing an aqueous solution of a divalent iron salt and an aqueous solution containing sulfur ions, a makinawite structure to be generated is formed. It has been found that iron sulfide has a modified mackinawite structure.

【００２６】本発明の方法において用いられる２価の鉄
塩の水溶液は、水溶性の２価の鉄塩であれば特に限定さ
れず、具体的には塩化鉄（ＩＩ）、硝酸鉄（ＩＩ）、硫
酸鉄（ＩＩ）酢酸鉄（ＩＩ）等を例示することができ
る。この中で、塩化鉄（ＩＩ）が工業的に入手が容易で
安価なために最も好ましく、また、鉄屑等を塩酸で溶解
した溶液や、鉄板を塩酸で洗浄した後の廃液等も好まし
く用いることができる。一方、硫酸鉄（ＩＩ）は、アル
カリ土類金属成分がＣａ、Ｓｒ、Ｂａの場合はこれらと
難溶性の塩を作りやすいため、原料の混合を注意深くゆ
っくり行なわなければならず好ましいものではないが、
アルカリ土類金属成分がＭｇの場合は好適に用いること
ができる。The aqueous solution of a divalent iron salt used in the method of the present invention is not particularly limited as long as it is a water-soluble divalent iron salt. Specifically, iron (II) chloride, iron (II) nitrate , Iron (II) sulfate and iron (II) acetate. Among these, iron (II) chloride is most preferable because it is industrially easily available and inexpensive, and a solution obtained by dissolving iron scraps and the like with hydrochloric acid and a waste liquid after washing an iron plate with hydrochloric acid are also preferably used. be able to. On the other hand, when the alkaline earth metal component is Ca, Sr, or Ba, iron (II) sulfate is liable to form a sparingly soluble salt with these components. ,
When the alkaline earth metal component is Mg, it can be suitably used.

【００２７】用いられる２価の鉄塩の水溶液の濃度は特
に限定されないが、濃度が薄すぎると反応槽の容積が大
きくなり、さらに濾過を行なうスラリーの量が増大する
ため工業的に不利となることがある。逆に濃度が濃すぎ
ると、温度の変動による塩の析出等のトラブルが生じ易
くなり、また、生成するスラリーの粘度が高くなりハン
ドリングや均一な混合が困難になることがある。従って
具体的な２価の鉄塩の濃度としては、Ｆｅとして１〜２
５ｗｔ％、より好ましくは３〜２０ｗｔ％の範囲を例示
することができる。The concentration of the aqueous solution of the divalent iron salt used is not particularly limited, but if the concentration is too low, the volume of the reaction tank becomes large, and the amount of slurry to be filtered increases, which is industrially disadvantageous. Sometimes. Conversely, if the concentration is too high, problems such as salt precipitation due to temperature fluctuations are likely to occur, and the viscosity of the resulting slurry will increase, making handling and uniform mixing difficult. Therefore, the specific concentration of the divalent iron salt is 1 to 2 as Fe.
A range of 5 wt%, more preferably 3 to 20 wt% can be exemplified.

【００２８】本発明の方法において用いられる硫黄イオ
ンを含む溶液は、硫黄イオンを含むものであれば特に限
定されず、アルカリ金属塩の硫化物や水硫化物、アンモ
ニウム塩の硫化物や水硫化物、アルカリ土類金属の硫化
物や水硫化物を水に溶解したものであればすべて好適に
用いることができる。この中でも硫化ナトリウムや水硫
化ナトリウムが、工業的に入手が容易で安価なために最
も好ましく、また、石油の脱硫工程で得られる硫化水素
を水酸化ナトリウム等のアルカリ水溶液に吸収させた溶
液も好ましく用いることができる。The solution containing sulfur ions used in the method of the present invention is not particularly limited as long as the solution contains sulfur ions, and the sulfide or hydrosulfide of an alkali metal salt, the sulfide or hydrosulfide of an ammonium salt is used. Any one obtained by dissolving a sulfide or a hydrosulfide of an alkaline earth metal in water can be suitably used. Among them, sodium sulfide and sodium hydrosulfide are most preferable because they are industrially easily available and inexpensive, and a solution in which hydrogen sulfide obtained in a petroleum desulfurization step is absorbed in an aqueous alkali solution such as sodium hydroxide is also preferable. Can be used.

【００２９】用いられる硫黄イオンを含む溶液の濃度は
特に限定されないが、２価の鉄塩の水溶液の濃度と同様
の理由である。具体的な硫黄イオンの濃度としては、Ｓ
として１〜１５ｗｔ％、より好ましくは２〜１０ｗｔ％
の範囲を例示することができる。The concentration of the solution containing sulfur ions to be used is not particularly limited, but for the same reason as the concentration of the aqueous solution of a divalent iron salt. As a specific sulfur ion concentration, S
1 to 15 wt%, more preferably 2 to 10 wt%
Can be exemplified.

【００３０】アルカリ土類金属成分は水溶性のものであ
れば特に限定されず、また、炭酸塩のように水溶性を示
さないものであっても酸性溶液に溶解するものも使用が
可能である。具体的なアルカリ土類金属成分としてはア
ルカリ土類金属の塩化物やカルボン酸塩、硝酸塩、水酸
化物、硫化物を例示することができる。The alkaline earth metal component is not particularly limited as long as it is water-soluble. In addition, even if it does not show water-solubility such as carbonate, it is possible to use one which dissolves in an acidic solution. . Specific examples of alkaline earth metal components include chlorides, carboxylate salts, nitrates, hydroxides, and sulfides of alkaline earth metals.

【００３１】２価の鉄塩の水溶液と硫黄イオンを含む水
溶液との混合割合は特に限定されないが、硫黄イオンが
多すぎた場合、原料コストが高くなるだけでなく、未反
応の硫黄イオンが母液中に残存し廃水処理が必要となる
ことがある。逆に少なすぎた場合は過剰の鉄分が水酸化
鉄として沈澱し、硫化鉄と水酸化物の混合物が得られ、
硫化鉄の特性の低下は生じないものの、水酸化鉄の重量
分だけ硫化鉄が希釈され見かけの特性が低下する。従っ
て、ＦｅとＳのモル比は、１：０．７〜１．８、さらに
好ましくは１：０．８〜１．５の範囲になるように混合
することが好ましい。The mixing ratio of the aqueous solution of a divalent iron salt and the aqueous solution containing sulfur ions is not particularly limited. However, if the amount of sulfur ions is too large, not only does the raw material cost increase, but also unreacted sulfur ions are removed from the mother liquor. It may remain inside and require wastewater treatment. Conversely, if too little, the excess iron will precipitate as iron hydroxide, resulting in a mixture of iron sulfide and hydroxide,
Although the characteristics of the iron sulfide do not deteriorate, the iron sulfide is diluted by the weight of the iron hydroxide, and the apparent characteristics deteriorate. Therefore, it is preferable to mix Fe and S in a molar ratio of 1: 0.7 to 1.8, more preferably 1: 0.8 to 1.5.

【００３２】２価の鉄塩の水溶液とアルカリ土類金属成
分の混合割合はアルカリ土類金属の種類により異なる
が、アルカリ土類金属の量が少ないと本発明の耐久性に
優れたマキナワイト構造を有する硫化鉄は得られない。
従って、アルカリ土類金属成分がマグネシウム（Ｍｇ）
の場合ＦｅとＭｇのモル比が、１：０．０４以上となる
ように混合することが好ましく、アルカリ土類金属成分
がカルシウム（Ｃａ）の場合ＦｅとＣａのモル比が、
１：０．０３以上なるように混合することが好ましく、
アルカリ土類金属成分がストロンチウム（Ｓｒ）の場合
ＦｅとＳｒのモル比が、１：０．０２以上となるように
混合することが好ましく、アルカリ土類金属成分がバリ
ウム（Ｂａ）の場合ＦｅとＢａのモル比が、１：０．０
１以上となるように混合することが好ましい。The mixing ratio of the aqueous solution of the divalent iron salt and the alkaline earth metal component varies depending on the type of the alkaline earth metal. If the amount of the alkaline earth metal is small, the durable makinawite structure of the present invention can be obtained. No iron sulfide can be obtained.
Therefore, when the alkaline earth metal component is magnesium (Mg)
In the case of, it is preferable that the molar ratio of Fe and Mg is 1: 0.04 or more. When the alkaline earth metal component is calcium (Ca), the molar ratio of Fe and Ca is
1: It is preferable to mix them so as to be 0.03 or more,
When the alkaline earth metal component is strontium (Sr), it is preferable to mix them so that the molar ratio of Fe and Sr is 1: 0.02 or more. When the alkaline earth metal component is barium (Ba), it is preferable to mix Fe and Sr. When the molar ratio of Ba is 1: 0.0
It is preferable to mix them so as to be at least one.

【００３３】混合操作は特に限定されず、化学工学で知
られている半回分式方法または連続式を用いることがで
きる。The mixing operation is not particularly limited, and a semi-batch method or a continuous method known in chemical engineering can be used.

【００３４】混合時の温度は特に限定されず、冷却及び
加熱する必要はなく、例えば１０〜６０℃の温度を例示
することができる。The temperature at the time of mixing is not particularly limited, and there is no need to cool and heat. For example, a temperature of 10 to 60 ° C. can be exemplified.

【００３５】混合時の撹拌は特に限定されず、生成する
硫化鉄を含んだスラリーの滞留が生じないような撹拌強
度であれば特に問題はない。The stirring at the time of mixing is not particularly limited, and there is no particular problem as long as the stirring intensity is such that the generated slurry containing iron sulfide does not stay.

【００３６】原料の混合速度は特に限定されないが、混
合があまり遅いと生産性が低下することがあり、速すぎ
ると局部的な滞留や粘度の上昇が起きる可能性がある。
従って、例えば半回分式の場合１〜２４０分で、より好
ましくは３〜１２０分ですべての原料が混ざるような添
加速度を選択すればよく、また連続法では原料の供給速
度を平均滞留時間が１０〜２４０分、より好ましくは１
５〜１２０分となるようにすればよい。The mixing speed of the raw materials is not particularly limited, but if the mixing is too slow, the productivity may decrease, and if the mixing is too fast, local stagnation and an increase in viscosity may occur.
Therefore, for example, in the case of a semi-batch system, the addition rate may be selected so that all the raw materials are mixed in 1 to 240 minutes, more preferably in 3 to 120 minutes. 10 to 240 minutes, more preferably 1
What is necessary is just to make it 5-120 minutes.

【００３７】以上のように、混合操作が終了した時点で
本発明の硫化鉄を含むスラリーが得られる。本発明で
は、混合操作終了時のスラリーｐＨが７．０以上となっ
ていることが必須である。スラリーｐＨを７．０以上と
するために混合終了後にアルカリ源を添加してもよい
が、予めアルカリ源を硫黄イオンを含む水溶液に添加し
ておくことがより好ましい。アルカリ源は特に限定され
ず、アルカリ金属の水酸化物、アルカリ土類金属の水酸
化物等を例示でき、具体的には水酸化ナトリウム、水酸
化カリウム、水酸化カルシウム、水酸化バリウム等を例
示できる。スラリーｐＨが７．０未満の場合、アルカリ
土類金属が硫化鉄内に取り込まれず本発明の硫化鉄は得
られない。スラリーｐＨは高いほど好ましく、８．０以
上、より好ましくは１０．０以上、さらに好ましくは１
２．０前後とすることがよい。As described above, when the mixing operation is completed, the slurry containing the iron sulfide of the present invention is obtained. In the present invention, it is essential that the slurry pH at the end of the mixing operation is 7.0 or more. Although an alkali source may be added after the completion of mixing to make the slurry pH 7.0 or more, it is more preferable to add the alkali source to an aqueous solution containing sulfur ions in advance. The alkali source is not particularly limited, and examples thereof include hydroxides of alkali metals and hydroxides of alkaline earth metals. Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. it can. When the slurry pH is less than 7.0, the alkaline earth metal is not taken into the iron sulfide, and the iron sulfide of the present invention cannot be obtained. The slurry pH is preferably as high as possible, more preferably 8.0 or more, more preferably 10.0 or more, and still more preferably 1 or more.
It is good to be around 2.0.

【００３８】また、原料の混合が終了した後、生成した
スラリー全体を均一にするために、そのまま撹拌を継続
し、熟成を行なってもよい。熟成時間は特に限定され
ず、例えば０〜３００分の時間を例示することができ
る。Further, after the mixing of the raw materials is completed, stirring may be continued and aging may be performed in order to make the entire slurry formed uniform. The aging time is not particularly limited, and may be, for example, a time of 0 to 300 minutes.

【００３９】以上の方法で本発明の硫化鉄を含んだスラ
リーが得られる。このスラリーをそのまま重金属類の処
理に用いてもよいが、輸送コストが多大なものとなり、
また、高濃度の重金属類を含んだ飛灰や土壌を処理する
ために多量の硫化鉄を添加する場合、被処理物の含水量
が高くなりすぎ、そのあとのハンドリングが困難となる
可能性がある。そのため、通常は濾過・洗浄を行なった
後、乾燥を行ない硫化鉄の粉末とする。The slurry containing the iron sulfide of the present invention can be obtained by the above method. This slurry may be used as it is for the treatment of heavy metals, but the transportation cost becomes enormous,
In addition, if a large amount of iron sulfide is added to treat fly ash or soil containing high concentrations of heavy metals, the water content of the material to be treated may be too high and handling after that may be difficult. is there. Therefore, usually, after filtration and washing, drying is performed to obtain iron sulfide powder.

【００４０】このときの濾過・洗浄の方法としては公知
の方法を用いることができるが、濾過・洗浄が不十分で
あると、硫化鉄中に残存するアルカリ金属のため耐久性
に優れた硫化鉄を得ることは困難となる。従って、濾過
・洗浄条件は、濾過・洗浄後に得られる硫化鉄中の鉄と
アルカリ金属のモル比が、鉄のモル比を１とした場合、
アルカリ金属の値が０．２以下、より好ましくは０．１
以下となるような条件とすることが必要である。As a method of filtration and washing at this time, a known method can be used. However, if filtration and washing are insufficient, the alkali sulfide remaining in the iron sulfide has a high durability. It will be difficult to obtain. Therefore, the filtration and washing conditions are as follows: when the molar ratio of iron to alkali metal in the iron sulfide obtained after filtration and washing is 1, and the molar ratio of iron is 1,
Alkali metal value is 0.2 or less, more preferably 0.1
It is necessary to satisfy the following conditions.

【００４１】乾燥は従来知られているどのような方法で
行なっても良いが、硫化鉄の酸化を防ぐために、不活性
雰囲気ガス中での乾燥あるいは真空乾燥がより好ましく
用いることができる。Drying may be carried out by any conventionally known method, but in order to prevent oxidation of iron sulfide, drying in an inert atmosphere gas or vacuum drying can be more preferably used.

【００４２】以上の方法で本発明の硫化鉄を得ることが
できる。The iron sulfide of the present invention can be obtained by the above method.

【００４３】本発明者らは更に検討を加えた結果、本発
明の組成の硫化鉄に各種のアルカリ土類金属化合物を加
えることにより、本発明の目的の一つである重金属類の
処理剤としてより好適に用いることができる硫化鉄組成
物が得られることを見出した。この硫化鉄組成物は、本
発明の組成の硫化鉄を調製し、これに別途添加して混合
する、例えばボールミル等で機械的に混合するなどして
調製するか、或いは本発明の組成の硫化鉄の範囲を超え
たアルカリ土類金属成分を過剰に使用して調製すること
も可能である。The present inventors have further studied and found that by adding various alkaline earth metal compounds to the iron sulfide having the composition of the present invention, it can be used as a treating agent for heavy metals which is one of the objects of the present invention. It has been found that an iron sulfide composition that can be used more preferably can be obtained. This iron sulfide composition is prepared by preparing the iron sulfide of the composition of the present invention and separately adding and mixing the iron sulfide, for example, mechanically mixing with a ball mill or the like, or preparing the iron sulfide of the present invention. It is also possible to prepare using an excess of alkaline earth metal component beyond the range of iron.

【００４４】添加或いは過剰に使用するアルカリ土類金
属化合物としては、アルカリ土類の水酸化物、カルボン
酸塩、リン酸塩、亜硫酸塩、硫酸塩、炭酸塩等が例示で
きる。更に詳しくは、水酸化マグネシウム、水酸化カル
シウム、水酸化ストロンチウム、水酸化バリウム、酢
酸、ぎ酸、しゅう酸、クエン酸、ステアリン酸などの対
応するアルカリ土類金属塩、また、例えば、リン酸水素
カルシウム等のリン酸、ポリリン酸の対応するアルカリ
土類金属塩、炭酸マグネシウム、炭酸カルシウムなどの
アルカリ土類金属の炭酸塩、硫酸マグネシウム、硫酸カ
ルシウム、硫酸バリウムなどのアルカリ土類金属の硫酸
塩、更には、酸化防止機能などを有する亜硫酸、アスコ
ルビン酸などのアルカリ土類金属塩などが例示できる。Examples of the alkaline earth metal compound to be added or used in excess include hydroxide, carboxylate, phosphate, sulfite, sulfate, carbonate and the like of alkaline earth. More specifically, corresponding alkaline earth metal salts such as magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, acetic acid, formic acid, oxalic acid, citric acid, stearic acid, and, for example, hydrogen phosphate Phosphoric acid such as calcium, corresponding alkaline earth metal salt of polyphosphoric acid, magnesium carbonate, carbonate of alkaline earth metal such as calcium carbonate, sulfate of alkaline earth metal such as magnesium sulfate, calcium sulfate, barium sulfate, Further, examples thereof include alkaline earth metal salts such as sulfurous acid and ascorbic acid having an antioxidant function.

【００４５】これらのアルカリ土類金属化合物は本発明
の硫化鉄の耐久性を低下させることがなく、また、その
種類に応じて、硫化鉄の担体効果による重金属処理活性
向上作用、耐久性の向上作用、重金属類の処理時の補助
剤、ハンドリンク性の向上、等の作用を有しており、目
的により１種以上複数種のアルカリ土類金属塩を本発明
の硫化鉄に添加して用いることもできる。例えば、酸性
の飛灰を処理する場合、アルカリ剤を補助剤として添加
することが好ましく、その場合、本発明の硫化鉄とアル
カリ土類の水酸化物の混合物が好適に用いることがで
き、また、多量の６価クロムのような酸化成分が大量に
含まれている場合は、本発明の硫化鉄と亜硫酸塩の混合
物が好適に用いることができる。また、本発明の硫化鉄
は耐久性に優れているが、本発明者らはアルカリ土類の
カルボン酸塩、とくに酢酸塩を加えることによりその耐
久性は更に向上することを見出しており、過酷な保存条
件が考えられるときにはこれらを添加することができ
る。These alkaline earth metal compounds do not reduce the durability of the iron sulfide of the present invention and, depending on the type, improve the activity of heavy metal treatment by the carrier effect of iron sulfide and improve the durability. It has an action, an auxiliary agent in the treatment of heavy metals, an improvement in hand linkability, etc., and is used by adding one or more kinds of alkaline earth metal salts to the iron sulfide of the present invention depending on the purpose. You can also. For example, when treating acidic fly ash, it is preferable to add an alkaline agent as an auxiliary agent, in which case, a mixture of the iron sulfide of the present invention and an alkaline earth hydroxide can be suitably used, When a large amount of an oxidizing component such as hexavalent chromium is contained, the mixture of iron sulfide and sulfite of the present invention can be suitably used. Further, the iron sulfide of the present invention has excellent durability, but the present inventors have found that the durability is further improved by adding an alkaline earth carboxylate, particularly an acetate, and severe These can be added when suitable storage conditions are considered.

【００４６】これらのアルカリ土類金属化合物の添加量
は特に限定されず、目的に応じて変化し、例えば本発明
の硫化鉄１００重量部に対し０．１〜１００重量部添加
することができる。The amount of the alkaline earth metal compound to be added is not particularly limited, and varies depending on the purpose. For example, 0.1 to 100 parts by weight can be added to 100 parts by weight of the iron sulfide of the present invention.

【００４７】本発明の硫化鉄および硫化鉄組成物は、極
めて耐久性に優れ、これを有効成分とする「重金属類処
理剤」として用いた場合、きわめて高い性能を発揮す
る。以下、本発明の重金属類処理剤について、その詳細
を説明する。The iron sulfide and the iron sulfide composition of the present invention are extremely excellent in durability, and exhibit extremely high performance when used as a "heavy metal treating agent" containing this as an active ingredient. Hereinafter, the heavy metal treating agent of the present invention will be described in detail.

【００４８】本発明の重金属類処理剤では、その処理が
可能な重金属類とは具体的な元素として、Ｐｂ、Ｃｄ、
Ｃｒ、Ｈｇ、Ａｓ、Ｓｅ、Ｃｕ、Ｎｉ、Ｓｂ、Ｍｏを示
すことができる。もちろん、本発明の処理剤では上記し
た重金属類をそれぞれ単独に処理するだけでなく、これ
らの内の任意の複数の元素が含まれたものを処理する場
合においても処理が可能である。In the agent for treating heavy metals of the present invention, the heavy metals that can be treated include Pb, Cd,
Cr, Hg, As, Se, Cu, Ni, Sb, and Mo can be shown. Needless to say, the treatment agent of the present invention can treat not only the heavy metals described above individually but also those containing arbitrary plural elements among them.

【００４９】本発明の重金属類処理剤は、重金属類を含
んだごみ焼却灰や飛灰の処理に極めて有効である。ごみ
焼却灰や飛灰中には、各種ごみに含まれていた重金属類
が濃縮されている。特に飛灰や溶融飛灰において顕著で
あり、溶融飛灰の中にはパーセントオーダーで鉛のよう
な重金属が含まれているものも数多く、無害化処理が必
要とされる。飛灰や溶融飛灰は焼却炉の構造や運転方法
の違いにより、アルカリ性飛灰、中性飛灰、アルカリ性
溶融飛灰、中性溶融飛灰等の種類があり、また、焼却す
るごみの種類によって含まれる重金属類の種類と含有量
は大きく異なっていることが知られているが、本発明の
重金属類処理剤はどのような種類の飛灰にも用いること
ができる。これらごみ焼却灰や飛灰に対し、本発明の重
金属類処理剤と水を添加し混練する。The agent for treating heavy metals of the present invention is extremely effective for treating incineration ash and fly ash containing heavy metals. Heavy metals contained in various types of waste are concentrated in the waste incineration ash and fly ash. This is particularly remarkable in fly ash and molten fly ash, and many of the molten fly ash contain heavy metals such as lead in the order of percent, and require detoxification treatment. Fly ash and molten fly ash are classified into alkaline fly ash, neutral fly ash, alkaline molten fly ash, neutral molten fly ash, etc., depending on the incinerator structure and operating method. It is known that the type and content of heavy metals contained in the ash vary greatly, but the heavy metal treating agent of the present invention can be used for any kind of fly ash. The heavy metal treating agent of the present invention and water are added to these waste incineration ash and fly ash and kneaded.

【００５０】本発明の重金属類処理剤の添加量は、ごみ
焼却灰や飛灰に含まれる重金属類の種類と総量により異
なるため一概に規定できず、ごみ焼却灰や飛灰の量に対
して、０．１〜５０ｗｔ％、好ましくは０．５〜３０ｗ
ｔ％を例示することができ、さらに、予めごみ焼却灰や
飛灰をサンプリングしてラボテストで最小添加量を求
め、ごみ焼却灰や飛灰に含まれる重金属類の量の変動を
考慮して最適添加量を求めておくことが好ましい。ま
た、仮に過剰添加を行なっても、例えば水銀（Ｈｇ）が
多硫化物となり可溶性となるような現象は生じず、問題
はない。The amount of the heavy metal treating agent of the present invention cannot be specified unconditionally because it differs depending on the type and total amount of heavy metals contained in the incineration ash and fly ash. , 0.1 to 50 wt%, preferably 0.5 to 30 w
t%, and furthermore, sampling waste incineration ash and fly ash in advance to determine the minimum addition amount in a lab test, and taking into account fluctuations in the amount of heavy metals contained in waste incineration ash and fly ash It is preferable to determine the amount of addition. Even if excessive addition is performed, for example, a phenomenon that mercury (Hg) becomes polysulfide and becomes soluble does not occur, and there is no problem.

【００５１】水の添加量はごみ焼却灰や飛灰の性質によ
り異なるが、通常、ごみ焼却灰や飛灰の量に対して、１
０〜４０ｗｔ％を例示することができる。混練の方法、
時間は特に限定されず従来から知られている方法を用い
ることができ、可溶性の重金属類は不溶性の硫化物また
は鉄塩となり処理が行われる。The amount of water added depends on the nature of the incineration ash and fly ash.
0 to 40 wt% can be exemplified. Kneading method,
The time is not particularly limited, and a conventionally known method can be used, and the soluble heavy metals are converted into insoluble sulfides or iron salts, and the treatment is performed.

【００５２】また、本発明の重金属類処理剤は、重金属
類を含んだ土壌の処理にも有効である。重金属類を含ん
だ土壌に対して、重金属類処理剤を、さらに必要に応じ
て、水を添加し、混練する。The agent for treating heavy metals of the present invention is also effective for treating soil containing heavy metals. A heavy metal treating agent is further added to the soil containing heavy metals, if necessary, and kneaded.

【００５３】本発明の重金属類処理剤の添加量は、土壌
に含まれる重金属類の総量により異なるため一概に規定
できず、処理すべき土壌の量に対して０．１〜２０ｗｔ
％を例示することができ、さらに、予め土壌をサンプリ
ングしてラボテストで最小添加量を求め、安全を見込ん
で若干過剰量を添加することが好ましい。土壌に含まれ
る水分が少ない場合は、土壌の種類によっても異なる
が、必要に応じて水を添加し、土壌に含まれる水分の量
が通常１０〜６０ｗｔ％となるようにする。混練の方
法、時間は特に限定されず従来から知られている方法を
用いることができ、可溶性の重金属類は不溶性の硫化物
または鉄塩となり処理が行われる。The amount of the heavy metal treating agent of the present invention varies depending on the total amount of heavy metals contained in the soil and cannot be specified unconditionally.
%. Further, it is preferable to sample the soil in advance and determine the minimum addition amount by a lab test, and add a slight excess in view of safety. When the water content in the soil is low, it depends on the type of the soil, but water is added as necessary so that the water content in the soil is usually 10 to 60 wt%. The method and time of kneading are not particularly limited, and a conventionally known method can be used, and the soluble heavy metals are converted into insoluble sulfides or iron salts, and the treatment is performed.

【００５４】さらに、本発明の重金属類処理剤を用い、
重金属類を含んだ廃水の処理も可能である。重金属類を
含んだ廃水に対して、重金属類処理剤を添加し混合す
る。重金属類処理剤の添加量は、廃水に含まれる重金属
類の総量により異なるため一概に規定できず、予め廃水
をサンプリングしてラボテストで最小添加量を求め、安
全を見込んで若干過剰量を添加することが好ましい。こ
の時に、廃水のｐＨが低いと硫化鉄が分解し硫化水素の
生成の可能性があるため、廃水のｐＨを前もって調整し
ておくことが好ましく、その場合には廃水のｐＨは３．
０以上、より好ましくは６．０以上となるようにする。
混合の方法、時間は特に限定されず従来から知られてい
る方法を用いることができ、廃水中の重金属類は不溶性
の硫化物または鉄塩となり処理が行われる。また、通
常、凝集沈澱処理の際に使用される無機系凝集沈澱剤、
例えば塩化第２鉄、ポリ塩化アルミニウム、硫酸バンド
等を併用し、あるいは凝集速度を速める高分子凝集剤等
を併用することも可能である。Further, using the heavy metal treating agent of the present invention,
It is also possible to treat wastewater containing heavy metals. A heavy metal treating agent is added to and mixed with wastewater containing heavy metals. The addition amount of heavy metal treatment agent cannot be unconditionally specified because it differs depending on the total amount of heavy metals contained in wastewater.Sampling wastewater in advance and finding the minimum addition amount in a lab test, and adding a slight excess in anticipation of safety Is preferred. At this time, if the pH of the wastewater is low, iron sulfide may be decomposed and hydrogen sulfide may be generated. Therefore, it is preferable to adjust the pH of the wastewater in advance.
0 or more, more preferably 6.0 or more.
The method and time for mixing are not particularly limited, and a conventionally known method can be used. The heavy metals in the wastewater are converted into insoluble sulfides or iron salts, and the treatment is performed. In addition, usually, an inorganic coagulant / precipitant used in the coagulation / precipitation treatment,
For example, ferric chloride, polyaluminum chloride, a sulfuric acid band, or the like can be used in combination, or a polymer coagulant for increasing the coagulation rate can be used in combination.

【００５５】[0055]

【実施例】以下、実施例において本発明をさらに詳細に
説明する。しかし、本発明はこれら実施例のみに限定さ
れるものではない。尚、実施例における各測定方法は以
下の通りである。The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to only these examples. In addition, each measuring method in an Example is as follows.

【００５６】（１）化学組成の測定方法 Ｆｅ、Ｓ、Ｃａ、Ｓｒ、Ｂａは、蛍光Ｘ線分析装置（日
本電子社製、型式ＪＳＸ−３２００）を用いて測定し
た。また、Ｎａ、Ｍｇ、Ｆｅは試料を塩酸で溶解した
後、ＩＣＰ発光分析装置（パーキンエルマー社製、型
式：ｏｐｔｉｍａ ３０００）を用いて測定した。測定
後、鉄を基準としてアルカリ土類金属元素、アルカリ金
属元素、硫黄のモル比を求めた。(1) Method for Measuring Chemical Composition Fe, S, Ca, Sr, and Ba were measured using a fluorescent X-ray analyzer (Model JSX-3200, manufactured by JEOL Ltd.). Na, Mg, and Fe were measured using an ICP emission spectrometer (Perkin Elmer, model: optima 3000) after dissolving the sample with hydrochloric acid. After the measurement, the molar ratio of alkaline earth metal element, alkali metal element, and sulfur was determined based on iron.

【００５７】（２）結晶構造の測定方法 Ｘ線回折装置（マックサイエンス社製、型式：ＭＸＰ−
３、Ｃｕターゲット）を用い測定した。(2) Method of measuring crystal structure X-ray diffractometer (manufactured by Mac Science, Model: MXP-
3, Cu target).

【００５８】（３）硫化鉄の残存率 耐久処理前の硫化鉄のメインピーク強度をＩ１、耐久処
理後の硫化鉄のメインピーク強度をＩ２として、硫化鉄
残存率（％）＝Ｉ２／Ｉ１×１００ として計算した。(3) Residual rate of iron sulfide Assuming that the main peak intensity of the iron sulfide before the durability treatment is I1 and the main peak intensity of the iron sulfide after the durability treatment is I2, the residual rate of iron sulfide (%) = I2 / I1 × Calculated as 100.

【００５９】実施例１ 実効内容積７５０ｍＬのステンレス製連続反応容器を２
５℃に保ち、攪拌しながら塩化鉄（ＩＩ）水溶液（０．
５ｍｏｌ／Ｌ）と硫化ナトリウム水溶液（１．０ｍｏｌ
／Ｌ）をそれぞれ５００ｍｌ／ｈ、２５０ｍｌ／ｈで連
続的に添加し、硫化鉄スラリーを調製した。Example 1 A continuous stainless steel reaction vessel having an effective internal volume of 750 mL
An aqueous solution of iron (II) chloride (0.
5 mol / L) and aqueous sodium sulfide solution (1.0 mol
/ L) were continuously added at 500 ml / h and 250 ml / h, respectively, to prepare an iron sulfide slurry.

【００６０】得られた硫化鉄スラリーのうち１０００ｍ
ｌを内容積２Ｌのガラス製反応容器に入れ、攪拌しなが
ら塩化カルシウム８３ｍｍｏｌを添加し、さらに４８％
ＮａＯＨ水溶液を加え、スラリーｐＨを１２．８とし
た。このまま６０分攪拌を継続し熟成を行なった。熟成
後得られたスラリーを濾過・洗浄した後、乾燥し、粉砕
を行ない硫化鉄粉末を得た。得られた硫化鉄粉末は、Ｘ
線回折の結果マキナワイト構造であった。このときのＸ
線回折のチャートを図１及び図２に示す。また組成分析
の結果、各成分のモル比は、Ｆｅ・Ｃａ0.22・Ｎａ
0.016・Ｓ1.00であった。1000 m of the obtained iron sulfide slurry
was placed in a glass reaction vessel having an internal volume of 2 L, and 83 mmol of calcium chloride was added thereto with stirring.
An aqueous NaOH solution was added to adjust the slurry pH to 12.8. Stirring was continued for 60 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder is X
As a result of a line diffraction, it was a makinawite structure. X at this time
The charts of the line diffraction are shown in FIGS. As a result of the composition analysis, the molar ratio of each component was Fe.Ca 0.22.Na
It was 0.016 · S 1.00 .

【００６１】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末はＸ線回折の結果マキナ
ワイト構造であり、硫化鉄の分解生成物である硫黄、お
よび酸化鉄（ＩＩＩ）のピークは観察されなかった。こ
のときのＸ線回折のチャートを図１に示す。耐久処理前
後におけるメインピークの強度比をもとに硫化鉄の残存
率を計算した結果、８５％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction, the powder after the durability treatment had a mackinawite structure, and no peaks of sulfur, which is a decomposition product of iron sulfide, and iron (III) oxide were observed. FIG. 1 shows a chart of X-ray diffraction at this time. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 85%.

【００６２】実施例２ スラリーｐＨを１１．７とした以外、実施例１と全く同
じ操作を行ない硫化鉄粉末を得た。得られた硫化鉄粉末
は、Ｘ線回折の結果マキナワイト構造であった。このと
きのＸ線回折のチャートを図２に示す。また組成分析の
結果、各成分のモル比は、Ｆｅ・Ｃａ0.073・Ｎａ0.032
・Ｓ0.99であった。Example 2 The same operation as in Example 1 was carried out except that the slurry pH was changed to 11.7, to obtain iron sulfide powder. The obtained iron sulfide powder had a Mackinawite structure as a result of X-ray diffraction. A chart of the X-ray diffraction at this time is shown in FIG. As a result of the composition analysis, the molar ratio of each component was Fe.Ca 0.073.Na 0.032.
-S was 0.99 .

【００６３】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末はＸ線回折の結果マキナ
ワイト構造であり、硫化鉄の分解生成物である硫黄のピ
ークがわずかに観察された。耐久処理前後におけるメイ
ンピークの強度比をもとに硫化鉄の残存率を計算した結
果、７１％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction, the powder after the durability treatment had a mackinawite structure, and a slight peak of sulfur, which was a decomposition product of iron sulfide, was observed. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 71%.

【００６４】実施例３ スラリーｐＨを１０．３とした以外、実施例１と全く同
じ操作を行ない硫化鉄粉末を得た。得られた硫化鉄粉末
は、Ｘ線回折の結果マキナワイト構造であった。このと
きのＸ線回折のチャートを図２に示す。また組成分析の
結果、各成分のモル比は、Ｆｅ・Ｃａ0.035・Ｎａ0.077
・Ｓ0.99であった。Example 3 The same operation as in Example 1 was performed except that the slurry pH was changed to 10.3, to obtain iron sulfide powder. The obtained iron sulfide powder had a Mackinawite structure as a result of X-ray diffraction. A chart of the X-ray diffraction at this time is shown in FIG. Further, as a result of composition analysis, the molar proportions of the respective components, Fe · Ca 0.035 · Na 0.077
-S was 0.99 .

【００６５】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末はＸ線回折の結果、マキ
ナワイト構造硫化鉄以外に分解生成物である硫黄に帰属
できるピークが観察された。耐久処理前後におけるメイ
ンピークの強度比をもとに硫化鉄の残存率を計算した結
果、５３％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction of the powder after the durability treatment, a peak attributable to sulfur, which is a decomposition product, was observed other than the iron sulfide having the makinawite structure. The residual ratio of iron sulfide calculated based on the intensity ratio of the main peak before and after the durability treatment was 53%.

【００６６】実施例４ 添加した塩化カルシウムの量を２２０ｍｍｏｌ、スラリ
ーｐＨを１２．６とした以外、実施例１と全く同じ操作
を行ない硫化鉄粉末を得た。得られた硫化鉄粉末は、Ｘ
線回折の結果、マキナワイト構造の硫化鉄以外に水酸化
カルシウムのピークが観察された。組成分析の結果、各
成分のモル比は、Ｆｅ・Ｃａ0.43・Ｎａ 0.004・Ｓ0.98
であった。Example 4 The amount of calcium chloride added was 220 mmol,
Exactly the same operation as in Example 1 except that the pH was changed to 12.6
To obtain iron sulfide powder. The obtained iron sulfide powder is X
As a result of X-ray diffraction, hydroxylation other than iron sulfide having a makinawite structure
A calcium peak was observed. As a result of the composition analysis,
The molar ratio of the components is Fe.Ca0.43・ Na 0.004・ S0.98
Met.

【００６７】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末はＸ線回折の結果、マキ
ナワイト構造の硫化鉄以外に水酸化カルシウムおよび炭
酸カルシウムのピークが観察された。耐久処理前後にお
けるメインピークの強度比をもとに硫化鉄の残存率を計
算した結果、８７％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction of the powder after the durability treatment, peaks of calcium hydroxide and calcium carbonate were observed in addition to the iron sulfide having the makinawite structure. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 87%.

【００６８】比較例１ 実施例１と同様の方法で連続的に調製した硫化鉄スラリ
ーを濾過・洗浄した後、乾燥し、粉砕を行ない硫化鉄粉
末を得た。得られた硫化鉄粉末は、Ｘ線回折の結果マキ
ナワイト構造であった。このときのＸ線回折のチャート
を図３に示す。また組成分析の結果、各成分のモル比
は、Ｆｅ・Ｎａ0.22・Ｓ0.99であった。Comparative Example 1 An iron sulfide slurry continuously prepared in the same manner as in Example 1 was filtered, washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder had a Mackinawite structure as a result of X-ray diffraction. FIG. 3 shows a chart of X-ray diffraction at this time. Further, as a result of composition analysis, the molar ratio of each component was Fe · Na 0.22 · S 0.99.

【００６９】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末はＸ線回折の結果、硫化
鉄の分解生成物である硫黄と酸化鉄（ＩＩＩ）の混合物
であり、硫化鉄に帰属できるピークは観察されなかっ
た。このときのＸ線回折のチャートを図３に示す。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction, the powder after the durability treatment was a mixture of sulfur, which is a decomposition product of iron sulfide, and iron (III) oxide, and no peak attributed to iron sulfide was observed. FIG. 3 shows a chart of X-ray diffraction at this time.

【００７０】比較例２ 比較例１で調製した硫化鉄粉末３０ｇに水酸化カルシウ
ム４ｇを加え、ボールミルで３０分混合し、硫化鉄と水
酸化カルシウムの混合組成物を調製した。この組成物
は、Ｘ線回折の結果マキナワイト構造の硫化鉄と水酸化
カルシウムの混合物であった。また組成分析の結果、各
成分のモル比は、Ｆｅ・Ｃａ0.19・Ｎａ0. 22・Ｓ0.99で
あった。Comparative Example 2 4 g of calcium hydroxide was added to 30 g of the iron sulfide powder prepared in Comparative Example 1 and mixed by a ball mill for 30 minutes to prepare a mixed composition of iron sulfide and calcium hydroxide. As a result of X-ray diffraction, this composition was a mixture of iron sulfide having a mackinawite structure and calcium hydroxide. Further, as a result of composition analysis, the molar ratio of each component was Fe · Ca 0.19 · Na 0. 22 · S 0.99.

【００７１】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末はＸ線回折の結果、硫化
鉄の分解生成物である硫黄と酸化鉄（ＩＩＩ）および水
酸化カルシウムと炭酸カルシウムの混合物であり、硫化
鉄に帰属できるピークは観察されなかった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction, the powder after the durability treatment was a mixture of sulfur and iron oxide (III), which are decomposition products of iron sulfide, and calcium hydroxide and calcium carbonate, and no peak attributed to iron sulfide was observed. .

【００７２】比較例３ 塊状の市販試薬硫化鉄（ＩＩ）を粉砕し硫化鉄粉末を得
た。得られた硫化鉄粉末は、Ｘ線回折の結果ピロータイ
ト構造であった。このときのＸ線回折のチャートを図４
に示す。Comparative Example 3 A massive commercial reagent iron (II) sulfide was pulverized to obtain iron sulfide powder. The obtained iron sulfide powder had a pyrotite structure as a result of X-ray diffraction. The X-ray diffraction chart at this time is shown in FIG.
Shown in

【００７３】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末は、Ｘ線回折の結果１ピ
ロータイト構造と、硫化鉄の分解生成物である硫黄に帰
属できるピークが観察された。このときのＸ線回折のチ
ャートを図４に示す。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction of the powder after the durability treatment, a 1-pilotite structure and a peak attributed to sulfur, which is a decomposition product of iron sulfide, were observed. The X-ray diffraction chart at this time is shown in FIG.

【００７４】実施例１、比較例１、２、３の結果より、
本発明における硫化鉄は、従来知られていた合成硫化鉄
より耐久性が大きく向上しており、しかも、添加したカ
ルシウムは単なる混合物ではなく、硫化鉄内に取り込ま
れていると判断できる。実施例１〜４の結果より、スラ
リーｐＨが高いほどカルシウムが硫化鉄に取り込まれや
すくなり、取り込まれるカルシウムの量が多いほど硫化
鉄の安定性が向上することがわかる。さらに、アルカリ
土類金属が硫化鉄に取り込まれる量には上限があり、カ
ルシウムの場合では０．４前後であると推定でき、それ
以上のカルシウムを導入しようとした場合、水酸化カル
シウムとの混合組成物となることがわかる。以上のこと
より、アルカリ土類金属がカルシウムの場合、鉄に対し
てカルシウムのモル比が０．０３〜０．４の領域で本発
明の耐久性が向上した硫化鉄が得られると判断できる。
また、図２において、実施例１で得られた硫化鉄の回折
ピークが実施例２、３で得られたものよりも低角度側に
シフトしており、硫化鉄にカルシウムが多く取り込まれ
たためと考えられる。From the results of Example 1 and Comparative Examples 1, 2, and 3,
The durability of the iron sulfide in the present invention is greatly improved compared to conventionally known synthetic iron sulfide, and it can be determined that the added calcium is not a mere mixture but is incorporated in the iron sulfide. The results of Examples 1 to 4 show that the higher the slurry pH, the easier calcium is taken into iron sulfide, and the larger the amount of calcium taken in, the better the stability of iron sulfide. Furthermore, there is an upper limit to the amount of alkaline earth metal that can be incorporated into iron sulfide. In the case of calcium, it can be estimated to be around 0.4. It turns out that it becomes a composition. From the above, it can be determined that when the alkaline earth metal is calcium, iron sulfide with improved durability of the present invention can be obtained in a region where the molar ratio of calcium to iron is 0.03 to 0.4.
Further, in FIG. 2, the diffraction peak of iron sulfide obtained in Example 1 was shifted to a lower angle side than those obtained in Examples 2 and 3, and more calcium was incorporated into iron sulfide. Conceivable.

【００７５】実施例５ 実施例１と同様の方法で連続的に調製した硫化鉄スラリ
ーのうち１０００ｍｌを内容積２Ｌのガラス製反応容器
に入れ、攪拌しながら塩化バリウム８３ｍｍｏｌを添加
し、さらに４８％ＮａＯＨ水溶液を加え、スラリーｐＨ
を１３．０とした。このまま６０分攪拌を継続し熟成を
行なった。熟成後得られたスラリーを濾過・洗浄した
後、乾燥し、粉砕を行ない硫化鉄粉末を得た。得られた
硫化鉄粉末は、Ｘ線回折の結果マキナワイト構造であっ
た。このときのＸ線回折のチャートを図５に示す。また
組成分析の結果、各成分のモル比は、Ｆｅ・Ｂａ0.078
・Ｎａ0.014・Ｓ0.96であった。Example 5 1000 ml of the iron sulfide slurry continuously prepared in the same manner as in Example 1 was placed in a glass reaction vessel having an internal volume of 2 L, and 83 mmol of barium chloride was added thereto with stirring, followed by 48% NaOH aqueous solution is added and slurry pH
Was set to 13.0. Stirring was continued for 60 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder had a Mackinawite structure as a result of X-ray diffraction. A chart of the X-ray diffraction at this time is shown in FIG. As a result of composition analysis, the molar ratio of each component was Fe.Ba 0.078
-It was Na 0.014 * S 0.96 .

【００７６】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末はマキナワイト構造であ
り、硫化鉄の分解生成物である硫黄、および酸化鉄（Ｉ
ＩＩ）のピークは観察されなかった。このときのＸ線回
折のチャートを図５に示す。耐久処理前後におけるメイ
ンピークの強度比をもとに硫化鉄の残存率を計算した結
果、９３％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. The powder after the durability treatment has a mackinawite structure, and sulfur, which is a decomposition product of iron sulfide, and iron oxide (I
No peak of II) was observed. A chart of the X-ray diffraction at this time is shown in FIG. The residual ratio of iron sulfide calculated based on the intensity ratio of the main peak before and after the durability treatment was 93%.

【００７７】実施例６ 実施例１と同様の方法で連続的に調製した硫化鉄スラリ
ーのうち１０００ｍｌを内容積２Ｌのガラス製反応容器
に入れ、攪拌しながら塩化ストロンチウム６６ｍｍｏｌ
を添加し、さらに４８％ＮａＯＨ水溶液を加え、スラリ
ーｐＨを１３．１とした。このまま６０分攪拌を継続し
熟成を行なった。熟成後得られたスラリーを濾過・洗浄
した後、乾燥し、粉砕を行ない硫化鉄粉末を得た。得ら
れた硫化鉄粉末は、Ｘ線回折の結果マキナワイト構造で
あった。また組成分析の結果、各成分のモル比は、Ｆｅ
・Ｓｒ0.095・Ｎａ0.023・Ｓ0.98であった。Example 6 1000 ml of the iron sulfide slurry continuously prepared in the same manner as in Example 1 was placed in a glass reactor having an internal volume of 2 L, and strontium chloride (66 mmol) was stirred.
Was added, and a 48% aqueous NaOH solution was further added to adjust the slurry pH to 13.1. Stirring was continued for 60 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder had a Mackinawite structure as a result of X-ray diffraction. As a result of composition analysis, the molar ratio of each component was Fe
-It was Sr 0.095 * Na 0.023 * S 0.98 .

【００７８】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末は、Ｘ線回折の結果マキ
ナワイト構造であり、硫黄、および酸化鉄（ＩＩＩ）の
ピークは観察されなかった。耐久処理前後におけるメイ
ンピークの強度比をもとに硫化鉄の残存率を計算した結
果、８８％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. The powder after the durability treatment had a mackinawite structure as a result of X-ray diffraction, and no sulfur or iron (III) oxide peak was observed. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 88%.

【００７９】実施例７ 実施例１と同様の方法で連続的に調製した硫化鉄スラリ
ーのうち１０００ｍｌを内容積２Ｌのガラス製反応容器
に入れ、攪拌しながら塩化マグネシウム１３０ｍｍｏｌ
を添加し、さらに４８％ＮａＯＨ水溶液を加え、スラリ
ーｐＨを１２．９とした。このまま６０分攪拌を継続し
熟成を行なった。熟成後得られたスラリーを濾過・洗浄
した後、乾燥し、粉砕を行ない硫化鉄粉末を得た。得ら
れた硫化鉄粉末は、Ｘ線回折の結果マキナワイト構造で
あった。また組成分析の結果、各成分のモル比は、Ｆｅ
・Ｍｇ0.37・Ｎａ0.068・Ｓ0.95であった。Example 7 1000 ml of the iron sulfide slurry continuously prepared in the same manner as in Example 1 was placed in a glass reactor having an internal volume of 2 L, and stirred with 130 mmol of magnesium chloride.
Was added, and a 48% aqueous NaOH solution was further added to adjust the slurry pH to 12.9. Stirring was continued for 60 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder had a Mackinawite structure as a result of X-ray diffraction. As a result of composition analysis, the molar ratio of each component was Fe
· Mg was 0.37 · Na 0.068 · S 0.95.

【００８０】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末は、Ｘ線回折の結果マキ
ナワイト構造であり、硫化鉄の分解生成物である硫黄に
帰属できるピークがわずかに観察された。耐久処理前後
におけるメインピークの強度比をもとに硫化鉄の残存率
を計算した結果、７２％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. As a result of X-ray diffraction, the powder after the durability treatment had a mackinawite structure, and a slight peak attributable to sulfur, which is a decomposition product of iron sulfide, was slightly observed. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 72%.

【００８１】実施例５〜７の結果より、カルシウム以外
のアルカリ土類金属にも合成硫化鉄の耐久性を向上する
作用があることがわかる。From the results of Examples 5 to 7, it can be seen that alkaline earth metals other than calcium have an effect of improving the durability of synthetic iron sulfide.

【００８２】実施例８ 内容積２リットルのガラス製反応容器に市販試薬の水硫
化ナトリウム４８０ｍｍｏｌ、水酸化ナトリウム７２０
ｍｍｏｌ、水１０００ｇを入れ撹拌・溶解しながらウォ
ーターバスを用い２５℃に保った。この溶液に、水６０
０ｇに塩化鉄（ＩＩ）４８０ｍｍｏｌ、塩化カルシウム
１２０ｍｍｏｌを溶解した溶液を４０分かけて添加し
た。添加終了後のスラリーのｐＨは、１２．３であっ
た。このまま３０分撹拌を継続し熟成を行なった。熟成
後得られたスラリーを濾過・洗浄した後、乾燥し、粉砕
を行ない硫化鉄粉末を得た。得られた硫化鉄粉末は、Ｘ
線回折の結果１７〜１８°付近にブロードなピークを持
った、変性マキナワイト構造であった。このときのＸ線
回折のチャートを図６及び図８に示す。また組成分析の
結果、各成分のモル比は、Ｆｅ・Ｃａ0.16・Ｎａ0.006
・Ｓ0.90であった。Example 8 A commercially available reagent (480 mmol) of sodium hydrosulfide and 720 mL of sodium hydroxide were placed in a glass reactor having an internal volume of 2 liters.
mmol and 1000 g of water were added, and the mixture was kept at 25 ° C. using a water bath while stirring and dissolving. To this solution is added water 60
A solution in which 480 mmol of iron (II) chloride and 120 mmol of calcium chloride were dissolved in 0 g was added over 40 minutes. The pH of the slurry after the addition was 12.3. Stirring was continued for 30 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder is X
As a result of the line diffraction, it was a modified mackinawite structure having a broad peak around 17 to 18 °. The X-ray diffraction charts at this time are shown in FIGS. Further, as a result of composition analysis, the molar proportions of the respective components, Fe · Ca 0.16 · Na 0.006
S was 0.90 .

【００８３】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末は、Ｘ線回折の結果１７
〜１８°付近にブロードなピークを持った変性マキナワ
イト構造であり、硫化鉄の分解生成物である硫黄、およ
び酸化鉄（ＩＩＩ）のピークは観察されなかった。この
ときのＸ線回折のチャートを図６に示す。耐久処理前後
におけるメインピークの強度比をもとに硫化鉄の残存率
を計算した結果、９１％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. The powder after the endurance treatment was analyzed by X-ray diffraction.
It has a modified makinawite structure having a broad peak around １８18 °, and no peak of sulfur, which is a decomposition product of iron sulfide, and iron (III) oxide was observed. FIG. 6 shows a chart of the X-ray diffraction at this time. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 91%.

【００８４】また、得られた硫化鉄粉末の一部を用い
て、夏場から秋にかけて３ヶ月の室内保存試験を行なっ
た。保存試験後の粉末は、Ｘ線回折の結果変性マキナワ
イト構造であり、硫化鉄の分解生成物である硫黄、およ
び酸化鉄（ＩＩＩ）のピークは観察されなかった。A part of the obtained iron sulfide powder was subjected to a three-month indoor storage test from summer to autumn. The powder after the storage test had a modified mackinawite structure as a result of X-ray diffraction, and no peaks of sulfur, which is a decomposition product of iron sulfide, and iron (III) oxide were not observed.

【００８５】実施例９ 内容積２リットルのガラス製反応容器に市販試薬の水硫
化ナトリウム４８０ｍｍｏｌ、水酸化ナトリウム７２０
ｍｍｏｌ、水１０００ｇを入れ撹拌・溶解しながらウォ
ーターバスを用い２５℃に保った。この溶液に、水６０
０ｇに塩化鉄（ＩＩ）４８０ｍｍｏｌ、塩化バリウム１
２０ｍｍｏｌを溶解した溶液を４０分かけて添加した。
添加終了後のスラリーのｐＨは、１２．６であった。こ
のまま３０分撹拌を継続し熟成を行なった。熟成後得ら
れたスラリーを濾過・洗浄した後、乾燥し、粉砕を行な
い硫化鉄粉末を得た。得られた硫化鉄粉末は、Ｘ線回折
の結果１７〜１８°付近にブロードなピークを持った、
変性マキナワイト構造であった。このときのＸ線回折の
チャートを図７に示す。また組成分析の結果、各成分の
モル比は、Ｆｅ・Ｂａ0.083・Ｎａ0.028・Ｓ0.88であっ
た。Example 9 A commercially available reagent of sodium hydrosulfide 480 mmol and sodium hydroxide 720 were placed in a glass reactor having an internal volume of 2 liters.
mmol and 1000 g of water were added, and the mixture was kept at 25 ° C. using a water bath while stirring and dissolving. To this solution is added water 60
480 mmol of iron (II) chloride and 1 barium chloride in 0 g
A solution in which 20 mmol was dissolved was added over 40 minutes.
The pH of the slurry after the completion of the addition was 12.6. Stirring was continued for 30 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder had a broad peak around 17 to 18 ° as a result of X-ray diffraction.
It had a modified mackinawite structure. FIG. 7 shows a chart of X-ray diffraction at this time. Further, as a result of composition analysis, the molar ratio of each component was Fe · Ba 0.083 · Na 0.028 · S 0.88.

【００８６】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末は、Ｘ線回折の結果１７
〜１８°付近にブロードなピークを持った変性マキナワ
イト構造であり、硫化鉄の分解生成物である硫黄に帰属
できるピークがわずかに観察された。このときのＸ線回
折のチャートを図７に示す。耐久処理前後におけるメイ
ンピークの強度比をもとに硫化鉄の残存率を計算した結
果、８７％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. The powder after the endurance treatment was analyzed by X-ray diffraction.
It has a modified makinawite structure having a broad peak around １８18 °, and a slight peak attributable to sulfur, which is a decomposition product of iron sulfide, was observed. FIG. 7 shows a chart of X-ray diffraction at this time. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 87%.

【００８７】実施例１０ 内容積２リットルのガラス製反応容器に市販試薬の水硫
化ナトリウム４８０ｍｍｏｌ、水酸化ナトリウム７２０
ｍｍｏｌ、水１０００ｇを入れ撹拌・溶解しながらウォ
ーターバスを用い２５℃に保った。この溶液に、水６０
０ｇに塩化鉄（ＩＩ）４８０ｍｍｏｌ、塩化ストロンチ
ウム１２０ｍｍｏｌを溶解した溶液を４０分かけて添加
した。添加終了後のスラリーのｐＨは、１２．４であっ
た。このまま３０分撹拌を継続し熟成を行なった。熟成
後得られたスラリーを濾過・洗浄した後、乾燥し、粉砕
を行ない硫化鉄粉末を得た。得られた硫化鉄粉末は、Ｘ
線回折の結果１７〜１８°付近にブロードなピークを持
った、変性マキナワイト構造であった。また組成分析の
結果、各成分のモル比は、Ｆｅ・Ｓｒ0.097・Ｎａ0 .019
・Ｓ0.92であった。Example 10 A commercially available reagent (480 mmol) of sodium bisulfide and 720 mL of sodium hydroxide were placed in a glass reactor having an internal volume of 2 liters.
mmol and 1000 g of water were added, and the mixture was kept at 25 ° C. using a water bath while stirring and dissolving. To this solution is added water 60
A solution in which 480 mmol of iron (II) chloride and 120 mmol of strontium chloride were dissolved in 0 g was added over 40 minutes. The pH of the slurry after the completion of the addition was 12.4. Stirring was continued for 30 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder is X
As a result of the line diffraction, it was a modified mackinawite structure having a broad peak around 17 to 18 °. Further, as a result of composition analysis, the molar proportions of the respective components, Fe · Sr 0.097 · Na 0 .019
S was 0.92 .

【００８８】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末は、Ｘ線回折の結果１７
〜１８°付近にブロードなピークを持った変性マキナワ
イト構造であり、硫化鉄の分解生成物である硫黄、およ
び酸化鉄（ＩＩＩ）のピークは観察されなかった。耐久
処理前後におけるメインピークの強度比をもとに硫化鉄
の残存率を計算した結果、９３％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. The powder after the endurance treatment was analyzed by X-ray diffraction.
It has a modified makinawite structure having a broad peak around １８18 °, and no peak of sulfur, which is a decomposition product of iron sulfide, and iron (III) oxide was observed. The residual ratio of iron sulfide calculated based on the intensity ratio of the main peak before and after the durability treatment was 93%.

【００８９】実施例１１ 内容積２リットルのガラス製反応容器に市販試薬の水硫
化ナトリウム４２０ｍｍｏｌ、水酸化ナトリウム７８０
ｍｍｏｌ、水１０００ｇを入れ撹拌・溶解しながらウォ
ーターバスを用い２５℃に保った。この溶液に、水６０
０ｇに硫酸鉄（ＩＩ）４２０ｍｍｏｌ、硫酸マグネシウ
ム１８０ｍｍｏｌを溶解した溶液を４０分かけて添加し
た。添加終了後のスラリーのｐＨは、１０．５であっ
た。このまま３０分撹拌を継続し熟成を行なった。熟成
後得られたスラリーを濾過・洗浄した後、乾燥し、粉砕
を行ない硫化鉄粉末を得た。得られた硫化鉄粉末は、Ｘ
線回折の結果１７〜１８°付近にブロードなピークを持
った、変性マキナワイト構造であった。また組成分析の
結果、各成分のモル比は、Ｆｅ・Ｍｇ0.37・Ｎａ0.07 9
・Ｓ0.94であった。Example 11 A commercially available reagent (420 mmol) of sodium hydrosulfide and sodium hydroxide (780) were placed in a glass reactor having an internal volume of 2 liters.
mmol and 1000 g of water were added, and the mixture was kept at 25 ° C. using a water bath while stirring and dissolving. To this solution is added water 60
A solution in which 420 mmol of iron (II) sulfate and 180 mmol of magnesium sulfate were dissolved in 0 g was added over 40 minutes. The pH of the slurry after the addition was 10.5. Stirring was continued for 30 minutes for aging. The slurry obtained after aging was filtered and washed, dried, and pulverized to obtain iron sulfide powder. The obtained iron sulfide powder is X
As a result of the line diffraction, it was a modified mackinawite structure having a broad peak around 17 to 18 °. The results of the composition analysis, the molar proportions of the respective components, Fe · Mg 0.37 · Na 0.07 9
-S was 0.94 .

【００９０】次に、得られた硫化鉄粉末の一部を７０
℃、相対湿度７０％の恒温恒湿機に入れ、１日耐久処理
を行なった。耐久処理後の粉末は、Ｘ線回折の結果１７
〜１８°付近にブロードなピークを持った変性マキナワ
イト構造以外に、硫化鉄の分解生成物である硫黄に帰属
できるピークがわずかに観察された。耐久処理前後にお
けるメインピークの強度比をもとに硫化鉄の残存率を計
算した結果、７８％であった。Next, a part of the obtained iron sulfide powder was
The sample was placed in a thermo-hygrostat at 70 ° C. and a relative humidity of 70%, and subjected to durability treatment for one day. The powder after the endurance treatment was analyzed by X-ray diffraction.
In addition to the modified makinawite structure having a broad peak around １８18 °, a slight peak attributable to sulfur, which is a decomposition product of iron sulfide, was observed. As a result of calculating the residual ratio of iron sulfide based on the intensity ratio of the main peak before and after the durability treatment, it was 78%.

【００９１】実施例８〜１１の結果により、アルカリ土
類金属成分の存在下で、２価の鉄塩の水溶液と硫黄イオ
ンを含む水溶液を混合した場合には、変性マキナワイト
構造の硫化鉄が得られることがわかる。According to the results of Examples 8 to 11, when an aqueous solution of a divalent iron salt and an aqueous solution containing sulfur ions were mixed in the presence of an alkaline earth metal component, iron sulfide having a modified mackinawite structure was obtained. It is understood that it is possible.

【００９２】実施例１２ 用いる水硫化ナトリウムの量を４２０ｍｍｏｌ水酸化ナ
トリウムの量を７８０ｍｍｏｌ、塩化鉄（ＩＩ）の量を
４２０ｍｍｏｌ、塩化カルシウムの量を１８０ｍｍｏｌ
として実施例８と同じ操作を行なった。Example 12 The amount of sodium hydrosulfide used was 420 mmol, the amount of sodium hydroxide was 780 mmol, the amount of iron (II) chloride was 420 mmol, and the amount of calcium chloride was 180 mmol.
The same operation as in Example 8 was performed.

【００９３】添加終了後のスラリーｐＨは１２．６、得
られた粉末は変性マキナワイト構造の硫化鉄、各成分の
モル比はＦｅ・Ｃａ0.28・Ｎａ0.002・Ｓ0.88であっ
た。このときのＸ線回折のチャートを図８に示す。ま
た、耐久処理後の粉末は変性マキナワイト構造の硫化鉄
であり、硫化鉄の残存率は８８％であった。[0093] The slurry pH after completion of the addition 12.6, iron sulfide of the resulting powder modified Makinawaito structure, the molar ratio of each component was Fe · Ca 0.28 · Na 0.002 · S 0.88. FIG. 8 shows a chart of the X-ray diffraction at this time. Further, the powder after the durability treatment was iron sulfide having a modified mackinawite structure, and the residual ratio of iron sulfide was 88%.

【００９４】実施例１３ 用いる水硫化ナトリウムの量を３６０ｍｍｏｌ水酸化ナ
トリウムの量を８４０ｍｍｏｌ、塩化鉄（ＩＩ）の量を
３６０ｍｍｏｌ、塩化カルシウムの量を２４０ｍｍｏｌ
として実施例８と同じ操作を行なった。Example 13 The amount of sodium hydrosulfide used was 360 mmol, the amount of sodium hydroxide was 840 mmol, the amount of iron (II) chloride was 360 mmol, and the amount of calcium chloride was 240 mmol.
The same operation as in Example 8 was performed.

【００９５】添加終了後のスラリーｐＨは１２．５、得
られた粉末は変性マキナワイト構造の硫化鉄でありトレ
ース量の水酸化カルシウムのピークが観察され、各成分
のモル比はＦｅ・Ｃａ0.39・Ｎａ0.001・Ｓ0.91であっ
た。このときのＸ線回折のチャートを図８に示す。ま
た、耐久処理後の粉末は変性マキナワイト構造の硫化鉄
であり、トレース量の水酸化カルシウムと炭酸カルシウ
ムのピークが観察され、硫化鉄の残存率は９３％であっ
た。The pH of the slurry after the addition was 12.5, and the obtained powder was iron sulfide having a modified mackinawite structure. A trace of calcium hydroxide was observed in the trace amount, and the molar ratio of each component was Fe.Ca 0.39. Na 0.001 · S 0.91 . FIG. 8 shows a chart of the X-ray diffraction at this time. In addition, the powder after the durability treatment was iron sulfide having a modified mackinawite structure, peaks of trace amounts of calcium hydroxide and calcium carbonate were observed, and the residual ratio of iron sulfide was 93%.

【００９６】実施例１４ 用いる水硫化ナトリウムの量を３００ｍｍｏｌ水酸化ナ
トリウムの量を９００ｍｍｏｌ、塩化鉄（ＩＩ）の量を
３００ｍｍｏｌ、塩化カルシウムの量を３００ｍｍｏｌ
として実施例８と同じ操作を行なった。Example 14 The amount of sodium hydrosulfide used was 300 mmol, the amount of sodium hydroxide was 900 mmol, the amount of iron (II) chloride was 300 mmol, and the amount of calcium chloride was 300 mmol.
The same operation as in Example 8 was performed.

【００９７】添加終了後のスラリーｐＨは１２．５、得
られた粉末は変性マキナワイト構造の硫化鉄と水酸化カ
ルシウムの混合物であった。各成分のモル比はＦｅ・Ｃ
ａ0. 66・Ｎａ0.001・Ｓ0.88であった。このときのＸ線
回折のチャートを図８に示す。また、耐久処理後の粉末
は変性マキナワイト構造の硫化鉄と水酸化カルシウムと
炭酸カルシウムの混合物であり、硫化鉄の残存率は９３
％であった。The pH of the slurry after the addition was 12.5, and the obtained powder was a mixture of iron sulfide and calcium hydroxide having a modified mackinawite structure. The molar ratio of each component is Fe
was a 0. 66 · Na 0.001 · S 0.88. FIG. 8 shows a chart of the X-ray diffraction at this time. The powder after the durability treatment was a mixture of iron sulfide having a modified mackinawite structure, calcium hydroxide and calcium carbonate, and the residual ratio of iron sulfide was 93%.
%Met.

【００９８】実施例１５ 用いる水硫化ナトリウムの量を５４０ｍｍｏｌ水酸化ナ
トリウムの量を６６０ｍｍｏｌ、塩化鉄（ＩＩ）の量を
２７０ｍｍｏｌ、塩化カルシウムの量を６０ｍｍｏｌと
して実施例８と同じ操作を行なった。Example 15 The same operation as in Example 8 was performed except that the amount of sodium hydrosulfide used was 540 mmol, the amount of sodium hydroxide was 660 mmol, the amount of iron (II) chloride was 270 mmol, and the amount of calcium chloride was 60 mmol.

【００９９】添加終了後のスラリーｐＨは１１．１、得
られた粉末は変性マキナワイト構造の硫化鉄であり、各
成分のモル比はＦｅ・Ｃａ0.038・Ｎａ0.089・Ｓ0.85で
あった。このときのＸ線回折のチャートを図８に示す。
また、耐久処理後の粉末は変性マキナワイト構造の硫化
鉄とその分解生成物の硫黄の混合物であり、硫化鉄の残
存率は５６％であった。[0099] The slurry pH after completion of the addition 11.1, powder obtained is iron sulfide modified Makinawaito structure, the molar ratio of each component was Fe · Ca 0.038 · Na 0.089 · S 0.85. FIG. 8 shows a chart of the X-ray diffraction at this time.
The powder after the durability treatment was a mixture of iron sulfide having a modified mackinawite structure and sulfur as a decomposition product thereof, and the residual ratio of iron sulfide was 56%.

【０１００】比較例４ 用いる水硫化ナトリウムの量を６００ｍｍｏｌ水酸化ナ
トリウムの量を６００ｍｍｏｌ、塩化鉄（ＩＩ）の量を
６００ｍｍｏｌ、塩化カルシウムの量を１０ｍｍｏｌと
して実施例５と同じ操作を行なった。Comparative Example 4 The same operation as in Example 5 was performed except that the amount of sodium hydrosulfide used was 600 mmol, the amount of sodium hydroxide was 600 mmol, the amount of iron (II) chloride was 600 mmol, and the amount of calcium chloride was 10 mmol.

【０１０１】添加終了後のスラリーｐＨは６．８、得ら
れた粉末はマキナワイト構造の硫化鉄であり、各成分の
モル比はＦｅ・Ｃａ0.008・Ｎａ0.14・Ｓ0.94であっ
た。また、耐久処理後の粉末は硫化鉄の分解生成物であ
る硫黄と酸化鉄（ＩＩ）の混合物であり、硫化鉄に帰属
できるピークは観察されなかった。[0102] The slurry pH after completion of the addition 6.8, the resulting powder is iron sulfide Makinawaito structure, the molar ratio of each component was Fe · Ca 0.008 · Na 0.14 · S 0.94. The powder after the durability treatment was a mixture of sulfur, which is a decomposition product of iron sulfide, and iron (II), and no peak attributed to iron sulfide was observed.

【０１０２】実施例１〜５、１２〜１５の結果より、マ
キナワイト構造の硫化鉄より、変性マキナワイト構造で
あるほうがより耐久性が向上していると考えられる。ま
た、比較例４の結果より、添加終了後のスラリーｐＨが
７未満の場合、カルシウムの存在下で硫化鉄を調製して
も、カルシウムが取り込まれず、耐久性が向上しないこ
とがわかる。From the results of Examples 1 to 5 and 12 to 15, it is considered that the modified makinawite structure has higher durability than the iron sulfide having the makinawite structure. In addition, the results of Comparative Example 4 show that when the pH of the slurry after completion of the addition is less than 7, even if iron sulfide is prepared in the presence of calcium, calcium is not taken in and the durability is not improved.

【０１０３】次に本発明の硫化鉄を用いて重金属類の処
理を行なった結果を示す。Next, the results of treating heavy metals using the iron sulfide of the present invention will be described.

【０１０４】実施例１６ 鉛を２４００ｐｐｍ、クロムを１６０ｐｐｍ、水銀を
２．１ｐｐｍ含有するアルカリ性飛灰を用い、重金属類
の処理特性の検討を行なった。アルカリ性飛灰１００重
量部に対し、水３０重量部、および実施例、比較例で調
製した硫化鉄を加え、混練し重金属処理を行なった。得
られた処理飛灰に対し、環境庁告示第１３号溶出試験
（１９７３年）を行ない、その結果を表２に示した。Example 16 Using alkaline fly ash containing 2400 ppm of lead, 160 ppm of chromium, and 2.1 ppm of mercury, treatment characteristics of heavy metals were examined. To 100 parts by weight of alkaline fly ash, 30 parts by weight of water and iron sulfide prepared in Examples and Comparative Examples were added, kneaded and subjected to heavy metal treatment. The obtained treated fly ash was subjected to a 13th dissolution test (1973) notified by the Environment Agency, and the results are shown in Table 2.

【０１０５】[0105]

【表２】 表２の結果から明らかなように、実施例で得た硫化鉄
は、耐久処理前の重金属類の処理特性はマキナワイト型
の硫化鉄とほぼ同等であり、比較例で得たピロータイト
型の硫化鉄よりはるかに優れていることがわかる。さら
に、従来のマキナワイト型の硫化鉄は、７０℃、相対湿
度７０％で１日耐久処理を行なった場合、重金属類の処
理特性が劣化してしまうのに対し、本発明における硫化
鉄は耐久処理後も重金属類の処理特性を維持しているこ
とがわかる。[Table 2] As is evident from the results in Table 2, the iron sulfide obtained in the examples had almost the same treatment characteristics as heavy iron sulfides before the durability treatment, and the pitrotite type sulfide obtained in the comparative example had the same treatment characteristics as the makinawite type iron sulfide. It turns out that it is much better than iron. Furthermore, conventional mackinawite-type iron sulfide deteriorates the processing characteristics of heavy metals when subjected to a durability treatment at 70 ° C. and a relative humidity of 70% for one day, whereas iron sulfide in the present invention has a durability treatment. It can be seen that the processing characteristics of heavy metals are maintained afterwards.

【０１０６】実施例１７ 鉛を１９００ｐｐｍ、クロムを１１００ｐｐｍ、カドミ
ウムを１００ｐｐｍ含有する中性飛灰を用い、重金属類
の処理特性の検討を行なった。中性飛灰１００重量部に
対し、水３０重量部、および実施例、比較例で調製した
硫化鉄を加え、混練し重金属処理を行なった。得られた
処理飛灰に対し、環境庁告示第１３号溶出試験（１９７
３年）を行ない、その結果を表３に示した。Example 17 Using neutral fly ash containing 1900 ppm of lead, 1100 ppm of chromium, and 100 ppm of cadmium, the treatment characteristics of heavy metals were examined. To 100 parts by weight of neutral fly ash, 30 parts by weight of water and iron sulfide prepared in Examples and Comparative Examples were added, kneaded and subjected to heavy metal treatment. The obtained fly ash was subjected to a 13th dissolution test (197
3 years), and the results are shown in Table 3 .

【０１０７】[0107]

【表３】 表３の結果から明らかなように、実施例８及び９で得た
硫化鉄は、中性飛灰に含まれる重金属類の処理も可能で
あり、さらに比較例１で得た従来の合成硫化鉄とほぼ同
等の初期特性を持ち、しかもはるかに耐久性が優れてい
ることがわかる。[Table 3] As is clear from the results in Table 3, the iron sulfide obtained in Examples 8 and 9 can also treat heavy metals contained in neutral fly ash, and the conventional synthetic iron sulfide obtained in Comparative Example 1 It can be seen that it has almost the same initial characteristics as that of, and has much more excellent durability.

【０１０８】実施例１８ 鉛を７７００ｐｐｍ、カドミウムを４７０ｐｐｍ、６価
クロムを１８００ｐｐｍ、ヒ素を９６ｐｐｍ、セレンを
２２００ｐｐｍ含有するモデル汚染土壌（含水量５０
％）を用い、重金属類の処理特性の検討を行なった。土
壌１００重量部に対し、実施例、比較例で調製した硫化
鉄を加え、混練し重金属処理を行なった。得られた土壌
に対し、環境庁告示第４６号による溶出試験（１９９１
年）を行ない、その結果を表４及び表５に示した。Example 18 A model contaminated soil containing 7700 ppm of lead, 470 ppm of cadmium, 1800 ppm of hexavalent chromium, 96 ppm of arsenic, and 2200 ppm of selenium (water content: 50
%), The processing characteristics of heavy metals were examined. Iron sulfide prepared in Examples and Comparative Examples was added to 100 parts by weight of soil, kneaded, and treated with heavy metals. The obtained soil was subjected to a dissolution test according to the Environment Agency Notification No. 46 (1991).
Year), and the results are shown in Tables 4 and 5.

【０１０９】[0109]

【表４】 [Table 4]

【表５】 表４及び５の結果から明らかなように、実施例１、８で
得た硫化鉄は、土壌に含まれる重金属類の処理も可能で
あり、比較例１で得たマキナワイト型の硫化鉄とほぼ同
等の初期特性を持ち、さらにマキナワイト型の硫化鉄よ
りもはるかに耐久性が優れていることがわかる。[Table 5] As is clear from the results of Tables 4 and 5, the iron sulfide obtained in Examples 1 and 8 can also treat heavy metals contained in soil, and is substantially the same as the makinawite-type iron sulfide obtained in Comparative Example 1. It can be seen that they have the same initial properties and are much more durable than the Makinawite-type iron sulfide.

【０１１０】実施例１９ 鉛１０ｐｐｍを含む溶液、カドミニウム１０ｐｐｍ含む
溶液、水銀１ｐｐｍを含む溶液、六価クロム１０ｐｐｍ
を含む溶液、砒素１０ｐｐｍを含む溶液、セレン１０ｐ
ｐｍを含む溶液の６種類のモデル排水に対し、実施例１
および８で調製した硫化鉄を０．２重量部添加し、硫化
鉄による重金属類の処理特性の検討を行なった。モデル
排水に硫化鉄を加えた後、３０分混合し、ガラス濾紙
（アドバンテック東洋製ＧＳ−２５）で濾過後、濾液中
に含まれている各成分の量を測定した。その結果を表６
に示した。Example 19 A solution containing 10 ppm of lead, a solution containing 10 ppm of cadmium, a solution containing 1 ppm of mercury, and 10 ppm of hexavalent chromium
Solution, arsenic 10ppm solution, selenium 10p
Example 1 for six types of model drainage of a solution containing pm
0.2 parts by weight of the iron sulfide prepared in Steps 8 and 8 were added, and the treatment characteristics of heavy metals with iron sulfide were examined. After iron sulfide was added to the model wastewater, the mixture was mixed for 30 minutes, filtered through a glass filter paper (GS-25 manufactured by Advantech Toyo), and the amount of each component contained in the filtrate was measured. Table 6 shows the results.
It was shown to.

【０１１１】[0111]

【表６】 表６の結果から明らかなように、本発明における硫化鉄
は、排水中の重金属類の処理も可能である。[Table 6] As is clear from the results in Table 6, the iron sulfide of the present invention can also treat heavy metals in wastewater.

【０１１２】[0112]

【発明の効果】本発明によれば、以下の効果を奏する。 １）本発明の硫化鉄は、従来知られていなかった新規な
組成のマキナワイト構造を有し、重金属類の処理特性が
優れると共に、その耐久性も優れている。 ２）本発明の製造方法は、この優れた硫化鉄を容易に製
造することができる。 ３）本発明の重金属類処理剤は、この優れた硫化鉄を有
効成分として含むものであり、この処理剤を用いること
で、灰、土壌、廃水等に含まれる重金属類を処理し無害
化できる。According to the present invention, the following effects can be obtained. 1) The iron sulfide of the present invention has a mackinawite structure having a novel composition which has not been known so far, and has excellent treatment properties for heavy metals and excellent durability. 2) The manufacturing method of the present invention can easily manufacture this excellent iron sulfide. 3) The agent for treating heavy metals of the present invention contains this excellent iron sulfide as an active ingredient. By using this treating agent, heavy metals contained in ash, soil, wastewater, etc. can be treated and made harmless. .

【図面の簡単な説明】[Brief description of the drawings]

【図１】実施例１で調製した硫化鉄粉末、およびそれを
７０℃、相対湿度７０％で１日耐久処理を行なった後の
Ｘ線回折の結果を示す。Ｘ軸（横軸）は回折角２θ（単
位は、ｄｅｇｒｅｅ）を示し、Ｙ軸（縦軸）はＸ線の強
度（単位はｃｐｓ）を示す。FIG. 1 shows the results of X-ray diffraction after iron sulfide powder prepared in Example 1 and its durability treatment at 70 ° C. and 70% relative humidity for 1 day. The X axis (horizontal axis) indicates the diffraction angle 2θ (unit is degree), and the Y axis (vertical axis) indicates the X-ray intensity (unit is cps).

【図２】実施例１、実施例２、実施例３で調製した硫化
鉄粉末のＸ線回折の結果を示す。Ｘ軸（横軸）は回折角
２θ（単位は、ｄｅｇｒｅｅ）を示し、Ｙ軸（縦軸）は
Ｘ線の強度（単位はｃｐｓ）を示す。FIG. 2 shows the results of X-ray diffraction of the iron sulfide powders prepared in Examples 1, 2 and 3. The X axis (horizontal axis) indicates the diffraction angle 2θ (unit is degree), and the Y axis (vertical axis) indicates the X-ray intensity (unit is cps).

【図３】比較例１で調製した硫化鉄粉末、およびそれを
７０℃、相対湿度７０％で１日耐久処理を行なった後の
Ｘ線回折の結果を示す。Ｘ軸（横軸）は回折角２θ（単
位は、ｄｅｇｒｅｅ）を示し、Ｙ軸（縦軸）はＸ線の強
度（単位はｃｐｓ）を示す。FIG. 3 shows the results of X-ray diffraction after the iron sulfide powder prepared in Comparative Example 1 and its durability treatment at 70 ° C. and 70% relative humidity for one day. The X axis (horizontal axis) indicates the diffraction angle 2θ (unit is degree), and the Y axis (vertical axis) indicates the X-ray intensity (unit is cps).

【図４】比較例３で調製した硫化鉄粉末、およびそれを
７０℃、相対湿度７０％で１日耐久処理を行なった後の
Ｘ線回折の結果を示す。Ｘ軸（横軸）は回折角２θ（単
位は、ｄｅｇｒｅｅ）を示し、Ｙ軸（縦軸）はＸ線の強
度（単位はｃｐｓ）を示す。FIG. 4 shows the results of X-ray diffraction after the iron sulfide powder prepared in Comparative Example 3 and its durability treatment at 70 ° C. and 70% relative humidity for one day. The X axis (horizontal axis) indicates the diffraction angle 2θ (unit is degree), and the Y axis (vertical axis) indicates the X-ray intensity (unit is cps).

【図５】実施例５で調製した硫化鉄粉末、およびそれを
７０℃、相対湿度７０％で１日耐久処理を行なった後の
Ｘ線回折の結果を示す。Ｘ軸（横軸）は回折角２θ（単
位は、ｄｅｇｒｅｅ）を示し、Ｙ軸（縦軸）はＸ線の強
度（単位はｃｐｓ）を示す。FIG. 5 shows the results of X-ray diffraction after iron sulfide powder prepared in Example 5 and its durability treatment at 70 ° C. and 70% relative humidity for one day. The X axis (horizontal axis) indicates the diffraction angle 2θ (unit is degree), and the Y axis (vertical axis) indicates the X-ray intensity (unit is cps).

【図６】実施例８で調製した硫化鉄粉末、およびそれを
７０℃、相対湿度７０％で１日耐久処理を行なった後の
Ｘ線回折の結果を示す。Ｘ軸（横軸）は回折角２θ（単
位は、ｄｅｇｒｅｅ）を示し、Ｙ軸（縦軸）はＸ線の強
度（単位はｃｐｓ）を示す。FIG. 6 shows the results of X-ray diffraction after the iron sulfide powder prepared in Example 8 and its durability treatment at 70 ° C. and 70% relative humidity for one day. The X axis (horizontal axis) indicates the diffraction angle 2θ (unit is degree), and the Y axis (vertical axis) indicates the X-ray intensity (unit is cps).

【図７】実施例９で調製した硫化鉄粉末、およびそれを
７０℃、相対湿度７０％で１日耐久処理を行なった後の
Ｘ線回折の結果を示す。Ｘ軸（横軸）は回折角２θ（単
位は、ｄｅｇｒｅｅ）を示し、Ｙ軸（縦軸）はＸ線の強
度（単位はｃｐｓ）を示す。FIG. 7 shows the results of X-ray diffraction after iron sulfide powder prepared in Example 9 and its durability treatment at 70 ° C. and 70% relative humidity for 1 day. The X axis (horizontal axis) indicates the diffraction angle 2θ (unit is degrees), and the Y axis (vertical axis) indicates the X-ray intensity (unit is cps).

【図８】実施例８、実施例１２、実施例１３、実施例１
４、実施例１５で調製した硫化鉄粉末のＸ線回折の結果
を示す。Ｘ軸（横軸）は回折角２θ（単位は、ｄｅｇｒ
ｅｅ）を示し、Ｙ軸（縦軸）はＸ線の強度（単位はｃｐ
ｓ）を示す。FIG. 8 is a diagram illustrating an eighth embodiment, a twelfth embodiment, a thirteenth embodiment, and a first embodiment.
4 shows the results of X-ray diffraction of the iron sulfide powder prepared in Example 15. X axis (horizontal axis) is diffraction angle 2θ (unit is degr
ee), and the Y-axis (vertical axis) represents the intensity of X-rays (unit is cp).
s).

【符号の説明】[Explanation of symbols]

１：実施例１で調製した硫化鉄粉末のＸ線回折パターン ２：実施例１で調製した硫化鉄粉末を耐久処理した後の
Ｘ線回折パターン ３：実施例１で調製した硫化鉄粉末のＸ線回折パターン ４：実施例２で調製した硫化鉄粉末のＸ線回折パターン ５：実施例３で調製した硫化鉄粉末のＸ線回折パターン ６：比較例１で調製した硫化鉄粉末のＸ線回折パターン ７：比較例１で調製した硫化鉄粉末を耐久処理した後の
Ｘ線回折パターン ８：比較例３で調製した硫化鉄粉末のＸ線回折パターン ９：比較例３で調製した硫化鉄粉末を耐久処理した後の
Ｘ線回折パターン １０：実施例５で調製した硫化鉄粉末のＸ線回折パター
ン １１：実施例５で調製した硫化鉄粉末を耐久処理した後
のＸ線回折パターン １２：実施例８で調製した硫化鉄粉末のＸ線回折パター
ン １３：実施例８で調製した硫化鉄粉末を耐久処理した後
のＸ線回折パターン １４：実施例９で調製した硫化鉄粉末のＸ線回折パター
ン １５：実施例９で調製した硫化鉄粉末を耐久処理した後
のＸ線回折パター １６：実施例１４で調製した硫化鉄粉末のＸ線回折パタ
ーン １７：実施例１３で調製した硫化鉄粉末のＸ線回折パタ
ーン １８：実施例１２で調製した硫化鉄粉末のＸ線回折パタ
ーン １９：実施例８で調製した硫化鉄粉末のＸ線回折パター
ン ２０：実施例１５で調製した硫化鉄粉末のＸ線回折パタ
ーン1: X-ray diffraction pattern of iron sulfide powder prepared in Example 1 2: X-ray diffraction pattern of iron sulfide powder prepared in Example 1 after durable treatment 3: X of iron sulfide powder prepared in Example 1 X-ray diffraction pattern 4: X-ray diffraction pattern of iron sulfide powder prepared in Example 2 5: X-ray diffraction pattern of iron sulfide powder prepared in Example 3 6: X-ray diffraction of iron sulfide powder prepared in Comparative Example 1 Pattern 7: X-ray diffraction pattern of iron sulfide powder prepared in Comparative Example 1 after durable treatment 8: X-ray diffraction pattern of iron sulfide powder prepared in Comparative Example 3 9: Iron sulfide powder prepared in Comparative Example 3 X-ray diffraction pattern after endurance treatment 10: X-ray diffraction pattern of iron sulfide powder prepared in Example 5 11: X-ray diffraction pattern after endurance treatment of iron sulfide powder prepared in Example 5 12: Example X-ray of iron sulfide powder prepared in 8 Folding pattern 13: X-ray diffraction pattern of iron sulfide powder prepared in Example 8 after endurance treatment 14: X-ray diffraction pattern of iron sulfide powder prepared in Example 9 15: Iron sulfide powder prepared in Example 9 X-ray diffraction pattern of iron sulfide powder prepared in Example 14 16: X-ray diffraction pattern of iron sulfide powder prepared in Example 13 18: Prepared in Example 12 X-ray diffraction pattern of iron sulfide powder 19: X-ray diffraction pattern of iron sulfide powder prepared in Example 8 20: X-ray diffraction pattern of iron sulfide powder prepared in Example 15

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０２Ｆ 1/58 Ｃ０２Ｆ 1/62 Ｄ 1/62 Ｅ Ｚ Ｂ０９Ｂ 3/00 ３０４Ｇ ３０４Ｋ Ｆターム(参考） 2E191 BA02 BB00 BB01 BC01 BD11 4D004 AA36 AA37 AA41 AB03 CA15 CA34 CC03 4D038 AA08 AB65 AB67 AB68 AB69 AB70 AB71 AB72 AB73 AB74 BB17 4G002 AA06 AA08 AA12 AB02 AD04 AE05 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C02F 1/58 C02F 1/62 D 1/62 EZ B09B 3/00 304G 304K F-term (Reference) 2E191 BA02 BB00 BB01 BC01 BD11 4D004 AA36 AA37 AA41 AB03 CA15 CA34 CC03 4D038 AA08 AB65 AB67 AB68 AB69 AB70 AB71 AB72 AB73 AB74 BB17 4G002 AA06 AA08 AA12 AB02 AD04 AE05

Claims (16)

【特許請求の範囲】[Claims] 【請求項１】構成元素の必須成分として、Ｆｅ・Ｍx・
Ｎy・Ｓz（式中、Ｍはアルカリ土類金属、Ｎはアルカリ
金属、ｘ、ｙ及びｚはモル比であり、０．０１＜ｘ≦
０．５、ｙ≦０．２、０．７≦ｚ≦１．４を示す。）で
表されるマキナワイト構造を有する耐久性に優れた硫化
鉄。As an essential component of claim 1] constituent elements, Fe · M x ·
N y · S z (where M is an alkaline earth metal, N is an alkali metal, x, y and z are molar ratios, and 0.01 <x ≦
0.5, y ≦ 0.2, 0.7 ≦ z ≦ 1.4. Durable iron sulfide having a makinawite structure represented by). 【請求項２】請求項１記載のマキナワイト構造におい
て、ＸＲＤの回折パターンが、００１面の面間隔が５．
０３Å以上５．５３Å以下とｃ軸方向に広がり、この０
０１面からのピーク強度を１００とした場合、他のｈｋ
ｌ面からの回折ピークの強度比がすべて２０以下の変性
マキナワイト構造である耐久性に優れた硫化鉄。2. The makinawite structure according to claim 1, wherein the XRD diffraction pattern has a 001 plane spacing of 5.
Spread in the c-axis direction from 03 ° to 5.53 °,
When the peak intensity from the 01 plane is 100, other hk
Iron sulfide excellent in durability, having a modified Mackinawite structure in which the intensity ratios of diffraction peaks from the l-plane are all 20 or less. 【請求項３】２価の鉄塩の水溶液と硫黄イオンを含む水
溶液とアルカリ土類金属成分を混合し、かつ、混合後の
スラリーｐＨを７．０以上とすることを特徴とする請求
項１記載の硫化鉄の製造方法。3. An aqueous solution of a divalent iron salt, an aqueous solution containing sulfur ions, and an alkaline earth metal component, and the pH of the slurry after mixing is adjusted to 7.0 or more. The method for producing iron sulfide described above. 【請求項４】アルカリ土類金属がカルシウム（Ｃａ）お
よび／またはマグネシウム（Ｍｇ）であることを特徴と
する請求項３記載の硫化鉄の製造方法。4. The method for producing iron sulfide according to claim 3, wherein the alkaline earth metal is calcium (Ca) and / or magnesium (Mg). 【請求項５】アルカリ土類金属成分の存在下で、２価の
鉄塩の水溶液と硫黄イオンを含む水溶液を混合してスラ
リーを生成させ、かつ混合後のスラリーｐＨを７．０以
上とすることを特徴とする請求項２記載の硫化鉄の製造
方法。5. A slurry is produced by mixing an aqueous solution of a divalent iron salt and an aqueous solution containing sulfur ions in the presence of an alkaline earth metal component, and adjusting the pH of the slurry after mixing to 7.0 or more. 3. The method for producing iron sulfide according to claim 2, wherein: 【請求項６】アルカリ土類金属がカルシウム（Ｃａ）お
よび／またはマグネシウム（Ｍｇ）であることを特徴と
する請求項５記載の硫化鉄の製造方法。6. The method for producing iron sulfide according to claim 5, wherein the alkaline earth metal is calcium (Ca) and / or magnesium (Mg). 【請求項７】請求項１又は請求項２記載の硫化鉄と、ア
ルカリ土類金属化合物とを含んでなる硫化鉄組成物。7. An iron sulfide composition comprising the iron sulfide according to claim 1 and an alkaline earth metal compound. 【請求項８】アルカリ土類金属化合物が、アルカリ土類
金属の水酸化物、カルボン酸塩、リン酸塩及び亜硫酸塩
からなる群より選ばれる１種以上の化合物である請求項
７記載の硫化鉄組成物。8. The sulfide according to claim 7, wherein the alkaline earth metal compound is at least one compound selected from the group consisting of an alkaline earth metal hydroxide, carboxylate, phosphate and sulfite. Iron composition. 【請求項９】請求項１又は請求項２記載の硫化鉄を有効
成分とする重金属類処理剤。9. A heavy metal treating agent comprising the iron sulfide according to claim 1 or 2 as an active ingredient. 【請求項１０】請求項７又は請求項８記載の硫化鉄組成
物を有効成分とする重金属類処理剤。10. A heavy metal treating agent comprising the iron sulfide composition according to claim 7 or 8 as an active ingredient. 【請求項１１】重金属類を含むごみ焼却灰、飛灰又は溶
融飛灰のいずれかに、請求項９又は請求項１０記載の重
金属類処理剤を添加し、混練することを特徴とする無害
化処理方法。11. A detoxifying method comprising adding the heavy metal treating agent according to claim 9 to any of incineration ash, fly ash or molten fly ash containing heavy metals and kneading them. Processing method. 【請求項１２】重金属類処理剤に加えさらに水を添加
し、混練することを特徴とする請求項１１記載の無害化
処理方法。12. The detoxifying method according to claim 11, wherein water is further added to the heavy metal treating agent, followed by kneading. 【請求項１３】重金属類を含む土壌に、請求項９又は請
求項１０記載の重金属類処理剤を添加し、混練すること
を特徴とする無害化処理方法。13. A detoxification method comprising adding the heavy metal treating agent according to claim 9 to a soil containing heavy metals and kneading the mixture. 【請求項１４】重金属類処理剤に加えさらに水を添加
し、混練することを特徴とする請求項１３記載の無害化
処理方法。14. The detoxification treatment method according to claim 13, wherein water is further added to the heavy metal treating agent, followed by kneading. 【請求項１５】重金属類を含む廃水に、請求項９又は請
求項１０記載の重金属類処理剤を添加し、混合すること
を特徴とする無害化処理方法。15. A detoxification method comprising adding the heavy metal treating agent according to claim 9 or 10 to waste water containing heavy metals and mixing. 【請求項１６】重金属類が、Ｐｂ、Ｃｄ、Ｈｇ、Ｚｎ、
Ｃｕ、Ｎｉ、Ｃｒ、Ａｓ、Ｓｅ、Ｓｂ及びＭｏの群より
選択される１種以上の元素である請求項１１〜１５のい
ずれかに記載の無害化処理方法。16. The method according to claim 16, wherein the heavy metals are Pb, Cd, Hg, Zn,
The detoxification method according to any one of claims 11 to 15, wherein the method is one or more elements selected from the group consisting of Cu, Ni, Cr, As, Se, Sb, and Mo.
JP2002012550A 2001-01-26 2002-01-22 Iron sulfide, method for producing the same, iron sulfide composition, treatment agent for heavy metals, and treatment method using the same Expired - Fee Related JP4178794B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002012550A JP4178794B2 (en) 2001-01-26 2002-01-22 Iron sulfide, method for producing the same, iron sulfide composition, treatment agent for heavy metals, and treatment method using the same

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2001019022 2001-01-26
JP2001-19022 2001-03-01
JP2001056658 2001-03-01
JP2001-56658 2001-03-01
JP2002012550A JP4178794B2 (en) 2001-01-26 2002-01-22 Iron sulfide, method for producing the same, iron sulfide composition, treatment agent for heavy metals, and treatment method using the same

Publications (2)

Publication Number Publication Date
JP2002326819A true JP2002326819A (en) 2002-11-12
JP4178794B2 JP4178794B2 (en) 2008-11-12

Family

ID=27345828

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2002012550A Expired - Fee Related JP4178794B2 (en) 2001-01-26 2002-01-22 Iron sulfide, method for producing the same, iron sulfide composition, treatment agent for heavy metals, and treatment method using the same

Country Status (1)

Country Link
JP (1) JP4178794B2 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005279405A (en) * 2004-03-29 2005-10-13 Cosmo Oil Co Ltd Method for removing nitrogen in wastewater
JP2006160542A (en) * 2004-12-03 2006-06-22 Tosoh Corp Iron sulfide particle-containing solution, its production method, and heavy metal treatment agent as well as treatment method using the same
JP2007063026A (en) * 2005-06-28 2007-03-15 Tosoh Corp Iron sulfide particle-containing solution, method for producing the same, heavy metal treating agent using the same and method for treating heavy metal
JP2007125536A (en) * 2005-01-31 2007-05-24 Egs:Kk Immobilizing agent and method for harmful component
WO2007074776A1 (en) * 2005-12-28 2007-07-05 Osaka University Method for purification of substances contaminated with organic chemicals
JP2008169449A (en) * 2007-01-15 2008-07-24 Dowa Metals & Mining Co Ltd Method for purifying arsenic solution
CN108975410A (en) * 2018-08-27 2018-12-11 合肥学院 One kind extracting high-purity AlFeO from flyash3The method of powder
WO2020013037A1 (en) * 2018-07-09 2020-01-16 シチズン時計株式会社 Hexavalent chromium treatment agent, method for treating contaminants containing hexavalent chromium, and method for treating bone meal containing hexavalent chromium
CN115432799A (en) * 2022-08-29 2022-12-06 山东大学 Nitrogen-sulfur synergistically modified micron zero-valent iron material and preparation method and application thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4523786B2 (en) * 2004-03-29 2010-08-11 コスモ石油株式会社 How to remove nitrogen from wastewater
JP2005279405A (en) * 2004-03-29 2005-10-13 Cosmo Oil Co Ltd Method for removing nitrogen in wastewater
JP2006160542A (en) * 2004-12-03 2006-06-22 Tosoh Corp Iron sulfide particle-containing solution, its production method, and heavy metal treatment agent as well as treatment method using the same
JP2007125536A (en) * 2005-01-31 2007-05-24 Egs:Kk Immobilizing agent and method for harmful component
JP2007063026A (en) * 2005-06-28 2007-03-15 Tosoh Corp Iron sulfide particle-containing solution, method for producing the same, heavy metal treating agent using the same and method for treating heavy metal
US9309164B2 (en) 2005-12-28 2016-04-12 Osaka University Method for purification of substances contaminated with organic chemicals
JP5403531B2 (en) * 2005-12-28 2014-01-29 国立大学法人大阪大学 Purification method for contaminated substances containing organic chemicals
WO2007074776A1 (en) * 2005-12-28 2007-07-05 Osaka University Method for purification of substances contaminated with organic chemicals
JP2008169449A (en) * 2007-01-15 2008-07-24 Dowa Metals & Mining Co Ltd Method for purifying arsenic solution
WO2020013037A1 (en) * 2018-07-09 2020-01-16 シチズン時計株式会社 Hexavalent chromium treatment agent, method for treating contaminants containing hexavalent chromium, and method for treating bone meal containing hexavalent chromium
CN112088198A (en) * 2018-07-09 2020-12-15 西铁城时计株式会社 6-valent chromium treating agent, method for treating pollutant containing 6-valent chromium and method for treating bone ash containing 6-valent chromium
JPWO2020013037A1 (en) * 2018-07-09 2021-08-05 シチズン時計株式会社 Hexavalent chromium treatment agent, treatment method of pollutants containing hexavalent chromium, and treatment method of bone powder containing hexavalent chromium
JP7264895B2 (en) 2018-07-09 2023-04-25 シチズン時計株式会社 Hexavalent chromium treatment agent, method for treating contaminants containing hexavalent chromium, and method for treating bone meal containing hexavalent chromium
CN112088198B (en) * 2018-07-09 2023-10-03 西铁城时计株式会社 Treatment agent for 6-valent chromium, method for treating pollutant containing 6-valent chromium, and method for treating bone ash containing 6-valent chromium
CN108975410A (en) * 2018-08-27 2018-12-11 合肥学院 One kind extracting high-purity AlFeO from flyash3The method of powder
CN108975410B (en) * 2018-08-27 2020-07-21 合肥学院 High-purity AlFeO extracted from fly ash3Method for producing powder
CN115432799A (en) * 2022-08-29 2022-12-06 山东大学 Nitrogen-sulfur synergistically modified micron zero-valent iron material and preparation method and application thereof
CN115432799B (en) * 2022-08-29 2023-10-13 山东大学 Nitrogen-sulfur synergistic modified micrometer zero-valent iron material and preparation method and application thereof

Also Published As

Publication number Publication date
JP4178794B2 (en) 2008-11-12

Similar Documents

Publication Publication Date Title
US6682713B2 (en) Iron sulfides, processes for producing the same, iron sulfide mixture, heavy metal treating agent, and method of treating with the agent
US8092764B2 (en) Method of processing non-ferrous smelting intermediate containing arsenic
AU2013227632B2 (en) Method for separating rhenium and arsenic, and method for purification of rhenium
JP4178794B2 (en) Iron sulfide, method for producing the same, iron sulfide composition, treatment agent for heavy metals, and treatment method using the same
CN113060754B (en) Doped cuprous dechlorinating agent and preparation method and application thereof
JP7372691B2 (en) How to obtain scorodite with a high arsenic content from an acidic solution with a high sulfuric acid content
TW201605511A (en) Agent for treating hazardous materials
US3819051A (en) Process for treating wastes containing chromates and/or complex iron cyanides
JP2005097431A (en) Iron sulfide composition, its production method, heavy metals-treatment agent and treatment method using the same
Kim et al. Li+ extraction reactions with spinel-type LiM0. 5Mn1. 5O4 (M= Ti, Fe) and their electronic structures
JP3294181B2 (en) Method for producing calcium arsenate
CN115403224A (en) Treatment method of acidic arsenic-containing industrial wastewater
US5173157A (en) Method for processing residual fixing-baths
CN110606512B (en) Method for stabilizing arsenic-calcium slag
CN108191031B (en) Sulfur-free arsenical chalcanthite and application thereof in purifying trivalent arsenic wastewater
JP3802264B2 (en) Detoxification method for soil contaminated with arsenic
JPH0780479A (en) Treatment of organic compound-containing waste liquid
JP2718221B2 (en) Treatment method for arsenic-containing sulfuric acid wastewater
JPH0268192A (en) Harmful heavy metal trapping agent for waste water or industrial waste
KR100482204B1 (en) Waste water treatment agent and a method for treating waste water using it
JP3171605B2 (en) Industrial waste liquid treatment method
JPH0866687A (en) Treatment of waste liquid incorporating borofluoride compound
JPS5939369B2 (en) How to treat chromium-containing powder
JP4604203B2 (en) Treatment method for waste liquid containing heavy metals
JP4537118B2 (en) Treatment method for dilute arsenic-containing waste liquid

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20041202

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20070524

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20080507

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20080626

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20080805

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20080818

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110905

Year of fee payment: 3

LAPS Cancellation because of no payment of annual fees