JPH0648741A - Production of iron sulfide for removing mercury - Google Patents
Production of iron sulfide for removing mercuryInfo
- Publication number
- JPH0648741A JPH0648741A JP4204014A JP20401492A JPH0648741A JP H0648741 A JPH0648741 A JP H0648741A JP 4204014 A JP4204014 A JP 4204014A JP 20401492 A JP20401492 A JP 20401492A JP H0648741 A JPH0648741 A JP H0648741A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- hydrogen sulfide
- iron
- sulfide
- content
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、各種工場および廃棄物
焼却場その他より発生する排ガスおよび排水中の水銀除
去剤として使用できる硫化鉄の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing iron sulfide which can be used as a mercury removing agent in exhaust gas and waste water generated from various factories, waste incinerators and the like.
【０００２】[0002]
【従来の技術】水中の水銀を除去する公知の方法として
は、（１）硫化ナトリウムを添加する硫化物法、（２）
水銀キレート樹脂法等がある。また、気体中の水銀を除
去する方法としては、（１）薬液洗浄法、（２）凝集分
離法、（３）乾式吸着法など数多く知られている。ま
た、特願平２−１７４５１９号においては、重金属除去
剤として、硫化水素、硫化ナトリウム、硫化水素ナトリ
ウム、ポリ硫化水素、ポリ硫化ナトリウム、汚泥消化ガ
ス、粗コークスガスなど硫化水素を含むガスを用いて鉄
化合物を硫化した硫化鉄が有効であると提案している。
しかし、これらの硫化剤の中で硫化水素ガスを含有する
粗コークス炉ガスを使用する場合は、当該ガス中に含有
する炭化水素分、タール分、灰分等の影響により担体で
ある水酸化鉄の多孔質表面が覆われ、その結果硫化不十
分であるだけでなく硫化鉄となってからの除去性能が低
下するという問題点があった。Known methods for removing mercury in water include (1) a sulfide method in which sodium sulfide is added, and (2)
There is a mercury chelate resin method. Many known methods for removing mercury in a gas include (1) chemical cleaning method, (2) coagulation separation method, and (3) dry adsorption method. Further, in Japanese Patent Application No. 2-174519, a gas containing hydrogen sulfide such as hydrogen sulfide, sodium sulfide, sodium hydrogen sulfide, polyhydrogen sulfide, sodium polysulfide, sludge digestion gas, and crude coke gas is used as a heavy metal removing agent. It has been proposed that iron sulfide obtained by sulfurizing an iron compound is effective.
However, when a crude coke oven gas containing hydrogen sulfide gas is used among these sulfiding agents, the content of iron hydroxide, which is a carrier, is affected by the hydrocarbon content, tar content, ash content, etc. contained in the gas. There is a problem that the porous surface is covered and, as a result, not only insufficient sulfide but also the removal performance after becoming iron sulfide deteriorates.
【０００３】[0003]
【発明が解決しようとする課題】水銀の除去性の高い硫
化物とするには、硫化物自体は多孔質で比表面積が大き
く、かつ圧潰強度が大きい程よい。この点について多孔
質でかつ比表面積が大きい担体である水酸化鉄に硫化水
素ガスを含有する粗コークス炉ガスを使用し多孔質水酸
化鉄を硫化させるような方法では、当該ガス中に含有さ
れる炭化水素分、タール分、灰分等の影響により、担体
である水酸化鉄の多孔質表面が覆われ、その結果水銀除
去性能が低下するという問題があった。In order to obtain a sulfide having a high mercury removability, it is better that the sulfide itself is porous, has a large specific surface area, and has a high crush strength. In this regard, porous iron hydroxide, which is porous and has a large specific surface area, is sulfided by using a crude coke oven gas containing hydrogen sulfide gas in iron hydroxide, which is contained in the gas. There is a problem that the porous surface of iron hydroxide as a carrier is covered by the influence of hydrocarbons, tars, ash, etc., which results in a decrease in mercury removal performance.
【０００４】したがって、これらの問題点を回避するべ
く方法として、市販されている硫化水素ガスを使用する
方法がある。この方法によれば、水銀の除去性能は良好
ではあるが、市販硫化水素ガスが高価であるということ
と併せて排ガスの精製処理設備も必要となり経済的でな
いという問題点があった。Therefore, as a method for avoiding these problems, there is a method using commercially available hydrogen sulfide gas. According to this method, although the performance of removing mercury is good, there is a problem in that a commercially available hydrogen sulfide gas is expensive and an exhaust gas refining treatment facility is also required, which is not economical.
【０００５】さらに、具体的に説明すると図１に示すよ
うに、石炭を乾留するコークス炉１より発生する粗コー
クス炉ガス２は、ガス冷却器３に導入され約４０℃まで
冷却され回収装置４に供給される。この粗コークス炉ガ
ス４を予め１〜１０ｍ／ｍφで多孔質に成型した水酸化
鉄を充填した硫化器５に供給し水酸化鉄を硫化させ硫化
鉄としていた。More specifically, as shown in FIG. 1, a crude coke oven gas 2 generated from a coke oven 1 for carbonizing coal is introduced into a gas cooler 3 and cooled to about 40 ° C., and a recovery device 4 is provided. Is supplied to. This crude coke oven gas 4 was supplied to a sulfidizer 5 filled with iron hydroxide formed in advance at a porous rate of 1 to 10 m / mφ, and the iron hydroxide was sulfided into iron sulfide.
【０００６】この方法では、図３に示すように、例えば
原水中の水銀濃度が１０００〜２０００μｇ／ｌの時、
通常品の水銀キレート樹脂で処理した処理水の水銀濃度
１００〜３００μｇ／ｌと比べ処理水中の水銀濃度３〜
１０μｇ／ｌと低く、初期除去性能は良好でありかつ強
度も１５０〜２００ｇであり、水中における強度性能も
良好である。しかしながら除去剤担体である水酸化鉄の
多孔質表面が粗コークス炉ガス中の炭化水素分、タール
分および灰分等に覆われることにより除去寿命が短くな
るという問題点を生じ経済的でなかった。In this method, as shown in FIG. 3, for example, when the mercury concentration in the raw water is 1000 to 2000 μg / l,
Compared with the mercury concentration of treated water treated with regular mercury chelate resin, which is 100-300 μg / l, the mercury concentration in treated water is 3-
It is as low as 10 μg / l, the initial removal performance is good, and the strength is 150 to 200 g, and the strength performance in water is also good. However, since the porous surface of iron hydroxide, which is the carrier for the removing agent, is covered with the hydrocarbon content, tar content, ash content, etc. in the crude coke oven gas, the removal life is shortened, which is not economical.
【０００７】したがって、本発明は、上述するような問
題点に着目し、安価でかつ水銀の除去性能が高い硫化鉄
を得る方法を提供することを目的とする。Therefore, an object of the present invention is to provide a method for obtaining iron sulfide which is inexpensive and has a high mercury removing performance, focusing on the above-mentioned problems.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明は、水
酸化鉄に硫化水素ガスを含むガスより硫化水素ガス分の
みを選択的に吸収・精製・濃縮した後、水酸化鉄に接触
反応をせさることを特徴とする水銀除去用硫化鉄の製造
方法を提供するものである。硫化水素ガスを含むガスと
しては、粗コークス炉ガスを用いるのが経済上好適であ
る。That is, according to the present invention, after selectively absorbing, purifying, and concentrating only a hydrogen sulfide gas component from a gas containing hydrogen sulfide gas in iron hydroxide, the contact reaction with iron hydroxide is performed. The present invention provides a method for producing iron sulfide for mercury removal, which is characterized in that It is economically preferable to use a crude coke oven gas as the gas containing hydrogen sulfide gas.
【０００９】[0009]
【作用】以下に本発明をさらに詳細に説明する。本発明
者等は、鋭意研究を重ねた結果、水銀の除去性能が良
く、かつ水中での強度も有する水銀除去用硫化鉄の製造
方法を見い出した。粗コークス炉ガスを工場用および都
市ガス用エネルギーとして使用する時、事前に当該ガス
中のアンモニア分、揮発油分、硫黄分等を除去回収して
いる。この回収設備を図２に示す。本発明においてはこ
の回収設備の硫黄回収装置を利用する。The present invention will be described in more detail below. As a result of intensive studies, the present inventors have found a method for producing iron sulfide for mercury removal, which has good mercury removal performance and strength in water. When the crude coke oven gas is used as energy for factories and town gas, the ammonia content, volatile oil content, sulfur content, etc. in the gas are removed and collected in advance. This recovery equipment is shown in FIG. In the present invention, the sulfur recovery device of this recovery facility is used.
【００１０】図２に示すように、Ｃガス脱硫塔６におい
て粗コークス炉ガス２中の硫化水素ガス分をアンモニア
水７で吸収し、その後硫化水素ガス吸収液８をストリッ
パーへ供給し、スチームを用いてストリッピングを行な
うと、塔頂より精製濃縮した硫化水素ガス１０が流出し
てくる。このガス１０を用いて、硫化器１１において経
済的に１〜１０ｍ／ｍφで多孔質に成型した水酸化鉄を
硫化させ硫化鉄とすることができる。１２は硫黄製造装
置である。As shown in FIG. 2, the hydrogen sulfide gas content in the crude coke oven gas 2 is absorbed by the ammonia water 7 in the C gas desulfurization tower 6, and then the hydrogen sulfide gas absorption liquid 8 is supplied to the stripper to generate steam. When stripping is performed using the hydrogen sulfide gas 10, the purified and concentrated hydrogen sulfide gas 10 flows out from the top of the column. Using this gas 10, it is possible to economically sulphate the porous iron hydroxide of 1 to 10 m / m? 12 is a sulfur manufacturing apparatus.
【００１１】この方法によると硫化器へ供給する当該精
製濃縮硫化水素ガスは、大過剰を供給したとしてもオフ
ガスは排ガス処理設備を設置することなく０．５kg/mm2
Ｇの低圧側精製濃縮硫化水素ガスラインに戻し、従来の
硫黄製造装置で処理することが可能である。その結果、
実施例に示すように、粗コークス炉ガスを用いた硫化鉄
と性能比較をすると、処理水中の水銀濃度も低くかつ除
去寿命も長く、併せて強度も１５０〜２００ｇと同レベ
ルであり、経済的にかつ高性能な水銀除去剤を製造する
ことが可能となった。According to this method, even if a large excess of the purified concentrated hydrogen sulfide gas to be supplied to the sulfidizer is used, the off gas is 0.5 kg / mm 2 without installing an exhaust gas treatment facility.
It is possible to return to the low-pressure side purified concentrated hydrogen sulfide gas line of G and process it with a conventional sulfur manufacturing apparatus. as a result,
As shown in the examples, when the performance is compared with iron sulfide using a crude coke oven gas, the mercury concentration in the treated water is low, the removal life is long, and the strength is the same level of 150 to 200 g, which is economical. It has become possible to produce a highly efficient mercury remover.
【００１２】また、硫化剤として使用する精製濃縮硫化
水素ガスは、当該法のように粗コークス炉ガスに限定す
るものではなく、他のガス等にも適用できる。Further, the purified concentrated hydrogen sulfide gas used as the sulfiding agent is not limited to the crude coke oven gas as in the above method, but can be applied to other gases.
【００１３】なお、下記の実施例では排水中の水銀除去
性能について説明をするが、本発明により得られた硫化
鉄は、排水中の水銀除去に限るものではなく他の重金属
の除去についても利用が可能である。Although the following examples explain the performance of removing mercury in wastewater, the iron sulfide obtained by the present invention is not limited to the removal of mercury in wastewater, but can be used for the removal of other heavy metals. Is possible.
【００１４】[0014]
【実施例】以下に本発明を実施例に基づいて具体的に説
明する。 （実施例）図２に示すように硫黄分回収装置中、Ｃガス
脱硫塔６において、下表１に示す粗コークス炉ガス２中
の硫化水素ガス分をアンモニア水７で吸収し、その後当
該吸収液８をストリッパー９へ供給し、塔底よりスチー
ムを吹き込みストリッピングを行なった。すると、塔頂
より精製濃縮した硫化水素ガス１０［組成：Ｈ2 Ｓ＝１
５〜４５vol%、Ｎ2 ＝１vol%、ＣＨ4 ＝０．０５vol%、
Ｃ2 Ｈ6 ＝０．０２vol%、ＣＯ2 ＝Balance 、ＮＨ3 ＝
０．２ｇ／Ｎｍ3 、ＨＣＮ＝０．２ｇ／Ｎｍ 3 、タール
分、灰分＝Trace 、温度：２０〜４０℃、圧力：１kg/m
m2Ｇ］が流出してきた。本発明によれば、当該硫化水素
ガスを１〜１０ｍ／ｍφで多孔質に成型した水酸化鉄を
充填した硫化器１１に供給することで粗コークス炉ガス
と比較し多孔質の表面を炭化水素分、タール分、灰分等
で覆うことなく、水酸化鉄を硫化鉄へと硫化させた。こ
の硫化鉄を内径５０ｍｍ、高さ５００ｍｍ、容積１Ｌの
容器に充填し、原水を５Ｌ／ｈｒで通水しながら原水中
の水銀を除去する試験を行なった。EXAMPLES The present invention will be specifically described below based on examples.
Reveal (Example) As shown in FIG. 2, C gas in a sulfur content recovery apparatus
In the desulfurization tower 6, in the crude coke oven gas 2 shown in Table 1 below
The hydrogen sulfide gas content of
The absorption liquid 8 is supplied to the stripper 9 and is fed from the bottom of the tower.
The strips were blown in and stripped. Then the tower top
More purified and concentrated hydrogen sulfide gas 10 [Composition: H2 S = 1
5 to 45 vol%, N2 = 1vol%, CHFour = 0.05vol%,
C2 H6 = 0.02vol%, CO2 = Balance, NH3 =
0.2 g / Nm3 , HCN = 0.2g / Nm 3 ,tar
Min, ash = Trace, temperature: 20-40 ° C, pressure: 1 kg / m
m2G] came out. According to the present invention, the hydrogen sulfide
Iron hydroxide formed by forming gas into porous form at 1-10 m / mφ
The crude coke oven gas is supplied by supplying it to the filled sulfidizer 11.
Hydrocarbon content, tar content, ash content, etc. on the porous surface compared to
Iron hydroxide was sulfided to iron sulfide without being covered with. This
Of iron sulfide with an inner diameter of 50 mm, a height of 500 mm and a volume of 1 L
Fill the container and pass the raw water at 5 L / hr while
A test was conducted to remove mercury.
【００１５】また、表１に示す粗コークス炉ガスおよび
市販のＨ2 Ｓガスを用いて同様にして硫化鉄を製造し
た。これらの硫化鉄およびキレート樹脂（ミヨシ油脂
（株）製、商品名：エポラスＺ−７）についても前述の
内径５０ｍｍ、高さ５００ｍｍの容器に充填して水銀除
去試験を行なった。その結果を図４にまとめて示す。Iron sulfide was produced in the same manner using the crude coke oven gas shown in Table 1 and a commercially available H 2 S gas. These iron sulfide and chelate resin (manufactured by Miyoshi Yushi Co., Ltd., trade name: Eporus Z-7) were also filled in the above-mentioned container having an inner diameter of 50 mm and a height of 500 mm to perform a mercury removal test. The results are summarized in Fig. 4.
【００１６】図４から明らかなように、高価なキレート
樹脂を用いても排水基準を満足できない。また高価な市
販のＨ2 Ｓガスを用いることなく、本発明によれば粗コ
ークス炉ガス精製するだけで排水基準を長期間に亙り維
持することができる硫化鉄を得ることができる。As is clear from FIG. 4, even if an expensive chelating resin is used, the drainage standard cannot be satisfied. Further, according to the present invention, iron sulfide capable of maintaining the drainage standard for a long period of time can be obtained only by purifying the crude coke oven gas without using expensive commercially available H 2 S gas.
【００１７】 [0017]
【００１８】[0018]
【発明の効果】以上、述べたように本発明を利用するこ
とにより安価でかつ高性能な水銀除去用硫化鉄の製造が
可能となった。As described above, the use of the present invention makes it possible to manufacture inexpensive and high-performance iron sulfide for mercury removal.
【図１】 従来の硫化鉄製造フロー図である。FIG. 1 is a conventional iron sulfide production flow chart.
【図２】 本発明の硫化鉄製造フロー図である。FIG. 2 is an iron sulfide production flow chart of the present invention.
【図３】 従来法による水銀除去剤を用いて行なった水
銀除去処理の経時変化を示す図である。FIG. 3 is a diagram showing changes over time in mercury removal treatment performed using a conventional method for removing mercury.
【図４】 本発明法による硫化鉄、従来の水銀除去剤を
用いて行なった水銀除去処理の経時変化を示す図であ
る。FIG. 4 is a diagram showing changes over time in mercury removal treatment performed using iron sulfide according to the method of the present invention and a conventional mercury removing agent.
１ コークス炉 ２ 粗コークス炉
ガス ３ ガス冷却器 ４ 回収装置 ５ 硫化器 ６ Ｃガス脱硫塔 ７ アンモニア水 ８ 硫化水素ガス
吸収液 ９ ストリッパー １０ 精製濃縮硫化
水素ガス １１ 硫化器 １２ 硫黄製造装置1 Coke Oven 2 Crude Coke Oven Gas 3 Gas Cooler 4 Recovery Device 5 Sulfidator 6 C Gas Desulfurization Tower 7 Ammonia Water 8 Hydrogen Sulfide Gas Absorption Liquid 9 Stripper 10 Purified Concentrated Hydrogen Sulfide Gas 11 Sulfide 12 Sulfur Production Equipment
Claims (2)
化水素ガス分のみを選択的に吸収・精製・濃縮した後、
水酸化鉄に接触反応をせさることを特徴とする水銀除去
用硫化鉄の製造方法。1. After selectively absorbing, purifying and concentrating only a hydrogen sulfide gas component from a gas containing hydrogen sulfide gas in iron hydroxide,
A method for producing iron sulfide for mercury removal, which comprises subjecting iron hydroxide to a catalytic reaction.
スである請求項１に記載の水銀除去用硫化鉄の製造方
法。2. The method for producing iron sulfide for mercury removal according to claim 1, wherein the gas containing hydrogen sulfide gas is a crude coke oven gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4204014A JPH0648741A (en) | 1992-07-30 | 1992-07-30 | Production of iron sulfide for removing mercury |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4204014A JPH0648741A (en) | 1992-07-30 | 1992-07-30 | Production of iron sulfide for removing mercury |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0648741A true JPH0648741A (en) | 1994-02-22 |
Family
ID=16483344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4204014A Withdrawn JPH0648741A (en) | 1992-07-30 | 1992-07-30 | Production of iron sulfide for removing mercury |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0648741A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100834451B1 (en) * | 2007-03-22 | 2008-06-09 | 주식회사 코캣 | Mercury removal by sulfidated iron oxide |
| JP2008246432A (en) * | 2007-03-30 | 2008-10-16 | Kocat Inc | Mercury removing adsorbent using iron oxide subjected to sulfurization treatment and its manufacturing method |
| US7901486B2 (en) | 2008-10-02 | 2011-03-08 | Conocophillips Company | Removal of heavy metals from hydrocarbon gases |
| KR101110553B1 (en) * | 2004-12-22 | 2012-01-31 | 재단법인 포항산업과학연구원 | Removal method of hydrogen sulfide in coke oven gas |
| KR101429981B1 (en) * | 2006-11-03 | 2014-08-18 | 재단법인 포항산업과학연구원 | Exhaust gas treatment method |
-
1992
- 1992-07-30 JP JP4204014A patent/JPH0648741A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101110553B1 (en) * | 2004-12-22 | 2012-01-31 | 재단법인 포항산업과학연구원 | Removal method of hydrogen sulfide in coke oven gas |
| KR101429981B1 (en) * | 2006-11-03 | 2014-08-18 | 재단법인 포항산업과학연구원 | Exhaust gas treatment method |
| KR100834451B1 (en) * | 2007-03-22 | 2008-06-09 | 주식회사 코캣 | Mercury removal by sulfidated iron oxide |
| JP2008246432A (en) * | 2007-03-30 | 2008-10-16 | Kocat Inc | Mercury removing adsorbent using iron oxide subjected to sulfurization treatment and its manufacturing method |
| US7901486B2 (en) | 2008-10-02 | 2011-03-08 | Conocophillips Company | Removal of heavy metals from hydrocarbon gases |
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