JPH1060449A - Purification of coke oven gas - Google Patents
Purification of coke oven gasInfo
- Publication number
- JPH1060449A JPH1060449A JP22149296A JP22149296A JPH1060449A JP H1060449 A JPH1060449 A JP H1060449A JP 22149296 A JP22149296 A JP 22149296A JP 22149296 A JP22149296 A JP 22149296A JP H1060449 A JPH1060449 A JP H1060449A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- liquid contact
- coke oven
- ammonia
- liquid
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、石炭を乾留してコ
ークスを製造する際副生するコークス炉ガス中に不純物
として含まれるアンモニア、硫化水素及びシアン化水素
の除去を目的としたガスの精製方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas purification method for removing ammonia, hydrogen sulfide and hydrogen cyanide contained as impurities in coke oven gas by-produced in producing coke by carbonizing coal. .
【０００２】[0002]
【従来の技術】石炭を乾留する際副生するコークス炉ガ
スはコールタールやべンゼン等の炭化水素の他に常温で
ガス体のアンモニアや硫化水素、シアン化水素等の酸性
ガスを含んでいるため、コークス炉ガスを燃料として使
用したり、水素ガス製造用の原料ガスとして使用するた
めには、これらの不純物を前もって除去しておく必要が
ある。この中でもアンモニアは古くから希硫酸で洗浄除
去し、副生硫安として回収されている。また、近年は環
境問題から硫化水素やシアン化水素の除去も要求される
ようになり、種々の脱硫方式が採用されている。2. Description of the Related Art Coke oven gas by-produced when carbonizing coal contains, in addition to hydrocarbons such as coal tar and benzene, gaseous ammonia, hydrogen sulfide, and acid gases such as hydrogen cyanide at room temperature, in addition to hydrocarbons such as coal tar and benzene. In order to use coke oven gas as a fuel or as a raw material gas for producing hydrogen gas, it is necessary to remove these impurities in advance. Among them, ammonia has long been washed and removed with dilute sulfuric acid and recovered as by-product ammonium sulfate. In recent years, removal of hydrogen sulfide and hydrogen cyanide has been required due to environmental problems, and various desulfurization methods have been adopted.
【０００３】しかしながら、この硫安は土壌が酸性にな
る等の理由から需要の減少に伴い価格が低迷し、原料と
して使用する硫酸の費用をもカバーできない状況になり
つつある。このため、硫安として回収することを止め、
アンモニア、硫化水素やシアン化水素の除去を、より効
果的に行ないたいとのニーズが高まってきている。[0003] However, the price of this ammonium sulfate has been stagnant due to a decrease in demand for reasons such as acidification of the soil, and it has become impossible to cover the cost of sulfuric acid used as a raw material. For this reason, we stopped collecting it as ammonium sulfate,
There is a growing need for more effective removal of ammonia, hydrogen sulfide and hydrogen cyanide.
【０００４】このニーズに応えることを目的として、例
えば図２に示すように水を用いてコークス炉ガス中のア
ンモニアを吸収除去する方式が提案されている。To meet this need, there has been proposed a system for absorbing and removing ammonia in coke oven gas using water, as shown in FIG. 2, for example.
【０００５】この方式では、アンモニア吸収塔３１でコ
ークス炉ガスと水を主とした吸収液３６とを気液接触さ
せれば、ガス中のアンモニアを十分に除去することは可
能であるが、硫化水素やシアン化水素はあまり除去でき
ないという欠点を有している。これは、コークス炉ガス
中に２〜３％存在する炭酸ガスの影響によるもので、吸
収液中のアンモニアが炭酸ガスと反応して、アンモニア
の大部分が炭酸アンモニウムとなり、酸性ガスと反応す
る遊離アンモニアの含有量が減少し、気液接触で吸収液
に吸収される硫化水素やシアン化水素量が少なくなるた
めと考えられている。したがって、アンモニア吸収塔で
硫化水素やシアン化水素の吸収量を増加させるために
は、循環吸収液量を増加させる必要がある。In this method, if the coke oven gas and the absorbent 36 mainly composed of water are brought into gas-liquid contact in the ammonia absorption tower 31, it is possible to sufficiently remove ammonia in the gas. There is a disadvantage that hydrogen and hydrogen cyanide cannot be removed so much. This is due to the effect of carbon dioxide present in the coke oven gas by 2 to 3%. The ammonia in the absorbing solution reacts with the carbon dioxide and most of the ammonia becomes ammonium carbonate, which reacts with the acid gas. It is considered that the content of ammonia decreases and the amount of hydrogen sulfide and hydrogen cyanide absorbed in the absorbing solution by gas-liquid contact decreases. Therefore, in order to increase the absorption amount of hydrogen sulfide and hydrogen cyanide in the ammonia absorption tower, it is necessary to increase the circulating absorption liquid amount.
【０００６】また、この方式では、アンモニア吸収塔３
１で気液接触によりアンモニア、硫化水素、シアン化水
素及び炭酸ガスを吸収した吸収塔底液３７は、その全量
を水蒸気蒸留塔３３に送り、水蒸気蒸留法によってアン
モニア、硫化水素、シアン化水素及び炭酸ガスを含んだ
水蒸気４１と吸収液とに分離される。この水蒸気蒸留法
は、吸収液１トン当たり約０．１トンと多くの水蒸気を
必要とするため、省エネルギーの点よりアンモニア吸収
塔３１で気液接触用に使用する吸収液量はあまり多くす
ることができず、その量は通常コークス炉ガス１Ｎｍ3
当たり１リッター、多くても２リッターが限度とされて
いる。In this system, the ammonia absorption tower 3
The absorption tower bottom liquid 37 which has absorbed ammonia, hydrogen sulfide, hydrogen cyanide and carbon dioxide gas by gas-liquid contact in 1 sends the entire amount thereof to the steam distillation tower 33, and contains ammonia, hydrogen sulfide, hydrogen cyanide and carbon dioxide gas by the steam distillation method. Separated into water vapor 41 and an absorbent. Since this steam distillation method requires a large amount of steam of about 0.1 ton per ton of the absorbing solution, the amount of the absorbing solution used for gas-liquid contact in the ammonia absorption tower 31 should be too large from the viewpoint of energy saving. And the amount is usually 1 Nm 3 of coke oven gas.
It is limited to one liter, at most two liters.
【０００７】このような理由から、アンモニア吸収塔３
１では、コークス炉ガス中の硫化水素及びシアン化水素
の除去率が低いという結果を招いている。For these reasons, the ammonia absorption tower 3
No. 1 results in a low removal rate of hydrogen sulfide and hydrogen cyanide in the coke oven gas.
【０００８】次に、コークス炉ガスは下流側に設置され
た硫化水素吸収塔３２において、前記アンモニア吸収塔
３１で除去されずにガス中に残った硫化水素やシアン化
水素の除去のために、水酸化ナトリウム溶液等の吸収液
３８で洗浄される。しかし、この硫化水素吸収塔３２に
おいても、コークス炉ガス中の炭酸ガスの影響を受け
て、吸収液として補給された水酸化ナトリウムの大部分
は、炭酸ガスと反応して炭酸ナトリウムまたは重炭酸ナ
トリウムとなり、硫化水素やシアン化水素の吸収に寄与
する遊離のナトリウムの割合が低くなり、効率が悪いと
いう欠点を有している。Next, the coke oven gas is subjected to hydroxylation in a hydrogen sulfide absorption tower 32 installed downstream to remove hydrogen sulfide and hydrogen cyanide remaining in the gas without being removed by the ammonia absorption tower 31. It is washed with an absorbing solution 38 such as a sodium solution. However, also in the hydrogen sulfide absorption tower 32, most of the sodium hydroxide replenished as an absorbing solution under the influence of carbon dioxide in the coke oven gas reacts with carbon dioxide to produce sodium carbonate or sodium bicarbonate. And the ratio of free sodium that contributes to the absorption of hydrogen sulfide and hydrogen cyanide is low, resulting in poor efficiency.
【０００９】また、硫化水素吸収塔３２では、硫化水素
やシアン化水素の吸収能力を維持するために硫化ナトリ
ウムやシアン化ナトリウムの濃度を一定に保つよう、吸
収液の一部を吸収排液３９として系外に排出している。
しかし、この吸収排液中には硫化ナトリウムやシアン化
ナトリウムが存在するために、環境汚染上問題のない物
質にしてからでないと放流できない。この処理の一例と
して、この吸収排液を燃焼ガスを用いて焼却する方法が
あるが、燃焼炉の煉瓦が吸収液中のナトリウム分により
損傷し、炉の寿命が短くなるという問題がある等、この
排液処理も容易ではない。In the hydrogen sulfide absorption tower 32, a part of the absorbing solution is used as an absorbing and draining solution 39 so as to maintain the concentration of sodium sulfide and sodium cyanide constant in order to maintain the absorbing ability of hydrogen sulfide and hydrogen cyanide. Discharging to the outside.
However, since sodium sulfide and sodium cyanide are present in the absorbed and discharged liquid, it cannot be discharged unless a substance having no problem in environmental pollution is used. As an example of this treatment, there is a method of incinerating the absorbed waste liquid using a combustion gas.However, there is a problem that bricks of a combustion furnace are damaged by sodium content in the absorbing liquid and the life of the furnace is shortened. This drainage process is also not easy.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、石炭を乾留
してコークスを製造する際に副生するコークス炉ガス中
に含まれるアンモニア、硫化水素、シアン化水素を効率
よく除去するコークス炉ガスの精製方法を提供するもの
である。SUMMARY OF THE INVENTION The present invention relates to a method for purifying a coke oven gas for efficiently removing ammonia, hydrogen sulfide, and hydrogen cyanide contained in a coke oven gas produced as a coke by carbonizing coal to produce coke. It provides a method.
【００１１】[0011]
【課題を解決するための手段】前記の課題を解決するた
めに、本発明は、石炭を乾留してコークスを製造する際
副生するコークス炉ガスの精製方法において、第１気液
接触塔にて、前記コークス炉ガスと吸収液とを気液接触
させ、該吸収液に前記コークス炉ガス中の硫化水素とシ
アン化水素とを吸収せしめ、該吸収液を酸化槽にて微細
な空気と接触させてチオ硫酸、硫酸、ロダンの各アンモ
ニウム塩に酸化して該吸収液の吸収能力を回復させた
後、前記の第１気液接触塔へ循環使用すると共に、前記
第１気液接触塔において、硫化水素とシアン化水素の除
去されたコークス炉ガスを第２気液接触塔に導入し、水
を吸収液として気液接触し、該吸収液に該コークス炉ガ
ス中に残存するアンモニアを吸収せしめ、該アンモニア
を吸収した吸収液を水蒸気蒸留塔にてアンモニア蒸気と
して吸収液より分離せしめた後、前記第２気液接触塔へ
循環使用することを特徴とするコークス炉ガスの精製方
法である。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a method for purifying coke oven gas produced as a by-product when carbonizing coal to produce coke. The coke oven gas and the absorbent were brought into gas-liquid contact, and the absorbent was allowed to absorb hydrogen sulfide and hydrogen cyanide in the coke oven gas, and the absorbent was brought into contact with fine air in an oxidation tank. After being oxidized to ammonium salts of thiosulfuric acid, sulfuric acid, and rhodan to recover the absorption capacity of the absorbing solution, the solution is circulated to the first gas-liquid contact tower, and sulfided in the first gas-liquid contact tower. The coke oven gas from which hydrogen and hydrogen cyanide have been removed is introduced into the second gas-liquid contact tower, which is brought into gas-liquid contact with water as an absorbing solution, and the absorbing solution absorbs the ammonia remaining in the coke oven gas. Absorbed liquid absorbed After allowed to separate from the absorbing liquid as ammonia vapor in the vapor distillation column, a method for purifying coke-oven gas, characterized in that recycled to the second gas-liquid contact tower.
【００１２】[0012]
【発明の実施の形態】本発明は上記課題を解決するため
に、図１に示すようにコークス炉ガスの精製工程の上流
側に脱硫・脱シアン工程を、下流側に脱アンモニア工程
を設置する。脱硫・脱シアン工程は第１気液接触塔２と
酸化槽４とで構成される。コークス炉ガスは第１気液接
触塔２の下部に送入され、塔内を上昇する間に上部から
落下してきた吸収液と接触して、下記に示すような反応
によってアンモニア、硫化水素、シアン化水素及び炭酸
ガスが吸収される。BEST MODE FOR CARRYING OUT THE INVENTION In order to solve the above-mentioned problems, according to the present invention, as shown in FIG. 1, a desulfurization / de-cyanation step is provided upstream of a coke oven gas purification step, and a deammonification step is provided downstream. . The desulfurization / de-cyanation step includes the first gas-liquid contact tower 2 and the oxidation tank 4. The coke oven gas is fed into the lower part of the first gas-liquid contact tower 2, and comes into contact with the absorbing liquid that has fallen from the upper part while ascending in the tower, and reacts with ammonia, hydrogen sulfide, hydrogen cyanide by the following reaction. And carbon dioxide gas is absorbed.
【００１３】ＮＨ3＋Ｈ2Ｏ→ＮＨ4ＯＨ Ｈ2Ｓ＋ＮＨ4ＯＨ→ＮＨ4ＨＳ＋Ｈ2Ｏ ＨＣＮ＋ＮＨ4ＯＨ→ＮＨ4ＣＮ＋Ｈ2Ｏ ２ＮＨ4ＯＨ＋ＣＯ2→（ＮＨ4）2ＣＯ3＋Ｈ2Ｏ この反応生成物は、吸収液中では下記に示すように解離
して蒸気圧を呈するので、これら生成物の濃度が高くな
るほど、アンモニア、硫化水素及びシアン化水素の吸収
能力が低下する。NH 3 + H 2 O → NH 4 OH H 2 S + NH 4 OH → NH 4 HS + H 2 O HCN + NH 4 OH → NH 4 CN + H 2 O 2NH 4 OH + CO 2 → (NH 4 ) 2 CO 3 + H 2 O Since the substance dissociates in the absorbing solution to exhibit a vapor pressure as shown below, as the concentration of these products increases, the ability to absorb ammonia, hydrogen sulfide, and hydrogen cyanide decreases.
【００１４】[0014]
【化１】 このため、第１気液接触塔２の塔底に溜まった塔底液１
２を気泡式の酸化槽４に送り、塔底液中の硫化水素アン
モニウムとシアン化アンモニウムを、機械的に微細化さ
れた空気１８にて酸化し、下記に示すようにチオ硫酸ア
ンモニウム、硫酸アンモニウム及びロダンアンモニウム
に変化させる。酸化されて、硫化水素アンモニウムとシ
アン化アンモニウムが無くなり、吸収能力を回復した吸
収液１１は、第１気液接触塔２の塔頂に送られ、再度吸
収液として循環使用される。Embedded image Therefore, the bottom liquid 1 collected at the bottom of the first gas-liquid contact tower 2
2 is sent to a bubble-type oxidation tank 4, where ammonium hydrogen sulfide and ammonium cyanide in the bottom liquid are oxidized by mechanically finely divided air 18 and, as shown below, ammonium thiosulfate, ammonium sulfate and rodane Change to ammonium. The absorbing solution 11 which has been oxidized to remove the ammonium hydrogen sulfide and ammonium cyanide and has recovered the absorption capacity is sent to the top of the first gas-liquid contact tower 2, and is again circulated and used as the absorbing solution.
【００１５】この吸収能力の回復方法は、吸収液中に機
械的に微細化された空気を吹み、吸収液中に懸濁させる
ことによって、懸濁空気中の酸素によって酸化反応を行
わせる方法であるため、吸収液を容易に安価でしかも大
量に処理することが可能である。したがって、コークス
炉ガス中に含まれている硫化水素及びシアン化水素除去
用の吸収液として、コークス炉ガスｌＮｍ3当たり１５
〜４０リッター、好ましくは２０〜３０リッターと大量
の液量を使用することができるので、コークス炉ガス中
の炭酸ガスによる吸収性能の低下を補うことができ、高
い硫化水素及びシアン化水素の除去率を確保することが
できる。[0015] The method of recovering the absorption capacity is a method in which air that is mechanically finely divided is blown into the absorbing solution and suspended in the absorbing solution to cause an oxidation reaction by oxygen in the suspended air. Therefore, it is possible to easily and inexpensively treat the absorption liquid in large quantities. Therefore, as an absorbing solution for removing hydrogen sulfide and hydrogen cyanide contained in the coke oven gas, 15 g / lNm 3 of the coke oven gas is used.
Since it is possible to use a large amount of liquid of up to 40 liters, preferably 20 to 30 liters, it is possible to compensate for a decrease in absorption performance due to carbon dioxide in coke oven gas, and to achieve a high hydrogen sulfide and hydrogen cyanide removal rate. Can be secured.
【００１６】 ２ＮＨ4ＨＳ＋２Ｏ2→（ＮＨ4）2Ｓ2Ｏ3＋Ｈ2Ｏ ＮＨ4ＨＳ＋ＮＨ4ＯＨ＋２Ｏ2→（ＮＨ4）2ＳＯ4＋Ｈ2
Ｏ ＮＨ4ＣＮ＋ＮＨ4ＨＳ＋１／２Ｏ2→ＮＨ4ＳＣＮ＋ＮＨ
4ＯＨ 本発明は、吸収・酸化反応を繰り返し行なわせながら吸
収液を循環使用するため、吸収液中のチオ硫酸アンモニ
ウム、硫酸アンモニウム及びロダンアンモニウムの濃度
が高くなるので、定期的に吸収液の一部を系外に排出し
て、これらの濃度を一定に保つ必要がある。この抜き取
った吸収排液１５は、そのまま又は濃縮された後、酸化
窒素の発生を抑制した還元・酸化二段燃焼炉７ａにて焼
却され、二酸化硫黄が除去された後、大気中に放散され
る。2NH 4 HS + 2O 2 → (NH 4 ) 2 S 2 O 3 + H 2 O NH 4 HS + NH 4 OH + 2O 2 → (NH 4 ) 2 SO 4 + H 2
O NH 4 CN + NH 4 HS + 1 / 2O 2 → NH 4 SCN + NH
4 OH In the present invention, since the absorption solution is circulated and used while repeating the absorption / oxidation reaction, the concentration of ammonium thiosulfate, ammonium sulfate, and rhodan ammonium in the absorption solution becomes high. It is necessary to discharge these outside the system and keep these concentrations constant. The withdrawn and discharged effluent 15 is directly or concentrated, and then incinerated in a reduction / oxidation two-stage combustion furnace 7a in which generation of nitrogen oxide is suppressed, and after being removed from sulfur dioxide, is released into the atmosphere. .
【００１７】第１気液接触塔２で硫化水素及びシアン化
水素を除去されたコークス炉ガス中には、なおアンモニ
アが第１気液接触塔２に送入される前の濃度の４０〜６
０％程度が残っているので、第１気液接触塔２の下流側
に設置された脱アンモニア工程で、残存アンモニアの除
去が行なわれる。In the coke oven gas from which hydrogen sulfide and hydrogen cyanide have been removed in the first gas-liquid contact tower 2, ammonia still has a concentration of 40 to 6 before being sent to the first gas-liquid contact tower 2.
Since about 0% remains, the remaining ammonia is removed in a deammonification step installed downstream of the first gas-liquid contact tower 2.
【００１８】この脱アンモニア工程は第２気液接触塔
３、水蒸気蒸留塔５、熱交換器８及び冷却器９で構成さ
れている。コークス炉ガスは第２気液接触塔３の下部に
送入され、塔内を上昇する間に上部から落下してきた水
と気液接触して、アンモニアの大部分と炭酸ガスの一部
が吸収される。This deammonification step comprises a second gas-liquid contact tower 3, a steam distillation tower 5, a heat exchanger 8 and a cooler 9. The coke oven gas is sent to the lower part of the second gas-liquid contact tower 3, and comes into gas-liquid contact with the water that has fallen from the upper part while rising in the tower, so that most of the ammonia and part of the carbon dioxide gas are absorbed. Is done.
【００１９】このアンモニアおよび炭酸ガスを含んだ第
２気液接触塔の塔底液１４は、水蒸気蒸留塔５に送ら
れ、アンモニアと炭酸ガスを含んだ水蒸気と吸収水とに
分離される。第２気液接触塔３の塔底液１４中のアンモ
ニアと炭酸ガスが反応してできた炭酸アンモニウムは、
硫化水素アンモニウム等と異なり、約５８°Ｃでアンモ
ニアと炭酸ガスに分解し気化するので、水蒸気蒸留法で
容易に水から分離することができ、アンモニアの含有量
の少ない吸収水を得ることができる。水蒸気蒸留塔５の
塔底液１３は水蒸気蒸留塔５に送入する第２気液接触塔
の塔底液１４と熱交換した後冷却器９で冷却されて、第
２気液接触塔３の頂部に送られ循環使用される。The bottom liquid 14 of the second gas-liquid contact tower containing ammonia and carbon dioxide gas is sent to the steam distillation tower 5 and separated into water vapor containing ammonia and carbon dioxide gas and absorbed water. The ammonium carbonate formed by the reaction of ammonia and carbon dioxide in the bottom liquid 14 of the second gas-liquid contact tower 3 is:
Unlike ammonium hydrogen sulfide, etc., it decomposes into ammonia and carbon dioxide gas at about 58 ° C and evaporates, so it can be easily separated from water by steam distillation, and absorbed water with a low ammonia content can be obtained. . The bottom liquid 13 of the steam distillation tower 5 exchanges heat with the bottom liquid 14 of the second gas-liquid contact tower fed into the steam distillation tower 5 and is then cooled by the cooler 9. It is sent to the top and used for circulation.
【００２０】前記第１気液接触塔２において、コークス
炉ガスは既に約半量のアンモニアが除去されているの
で、第２気液接触塔３でのアンモニアの除去量が少なく
て済む上に、第２気液接触塔８ではアンモニア含有量の
少ない吸収水と気液接触させるので、アンモニアの除去
効率が良くなる。このため、第２気液接触塔３の循環水
量は通常コークス炉ガス１Ｎｍ3当たり０．５〜１リッ
ターと少なくてよい，なお、このアンモニアの吸収は温
度が低いほど効率がよいので、通常は４０°Ｃ以下、好
ましくは３５°Ｃ以下で運転される。In the first gas-liquid contact tower 2, since about half of the ammonia has already been removed from the coke oven gas, the amount of ammonia removed in the second gas-liquid contact tower 3 can be reduced, Since the gas-liquid contact tower 8 is brought into gas-liquid contact with absorbed water having a small ammonia content, the efficiency of removing ammonia is improved. For this reason, the amount of circulating water in the second gas-liquid contact tower 3 may be as small as 0.5 to 1 liter per 1 Nm 3 of the coke oven gas. Note that the lower the temperature, the better the efficiency of the absorption of ammonia. It is operated below 40 ° C, preferably below 35 ° C.
【００２１】水蒸気蒸留塔５で分離されたアンモニアと
炭酸ガスを含んだ水蒸気１６は、酸化窒素の発生を抑制
した還元・酸化二段燃焼炉７ｂにて焼却された後、大気
中に放散される。The steam 16 containing ammonia and carbon dioxide gas separated in the steam distillation tower 5 is incinerated in a reduction / oxidation two-stage combustion furnace 7b in which generation of nitrogen oxide is suppressed, and then is released into the atmosphere. .
【００２２】なお、このようにして得られた脱硫・脱シ
アン工程の吸収排液１５と、脱アンモニア工程の炭酸ガ
スを含んだ水蒸気１６は、一つの炉で焼却することも可
能である。It is also possible to incinerate the thus obtained absorption wastewater 15 in the desulfurization / cyanation step and steam 16 containing carbon dioxide gas in the deammonia step in a single furnace.
【００２３】また、焼却排ガス中の二酸化硫黄の除去
は、湿式法としては、水酸化マグネシウムのスラリーに
て洗浄して放流する方法や、水酸化カルシウムのスラリ
ーにて洗浄し、石膏として回収する方法があり、乾式法
としては、排ガス中に消石灰の粉末を吹き込みガス中の
二酸化硫黄と反応させた後、バグフィルターにて回収す
る方法等がある。どの方式を採用するかは、本設備を設
置する地域の環境条件や原料条件によって決定される。The removal of sulfur dioxide from the incineration exhaust gas can be carried out by a wet method including washing with magnesium hydroxide slurry and discharging it, or washing with calcium hydroxide slurry and collecting as gypsum. As a dry method, there is a method in which slaked lime powder is blown into an exhaust gas to react with sulfur dioxide in a gas, and then collected by a bag filter. Which method is adopted depends on the environmental conditions and raw material conditions in the area where this facility is installed.
【００２４】[0024]
実施例１ 図１に示す本発明の方法と同じ機能を有する小型実験機
を用いて、コークス炉ガスを３５°Ｃで、時間当たり１
０Ｎｍ3処理した結果（コークス炉ガス中の不純物量）
を表１に示す。なお、第１気液接触塔に使用した吸収液
量は、時間当り３００リッター、第２気液接触塔に使用
した吸収液量は、時間当り１０リッターであった。ま
た、各塔の循環液の組成は表２及び表３のとおりであっ
た。Example 1 Using a small experimental machine having the same function as the method of the present invention shown in FIG.
Result of 0Nm 3 treatment (impurity amount in coke oven gas)
Are shown in Table 1. The amount of the absorbent used for the first gas-liquid contact tower was 300 liters per hour, and the amount of the absorbent used for the second gas-liquid contact tower was 10 liters per hour. The composition of the circulating liquid in each column was as shown in Tables 2 and 3.
【００２５】表１及び表２に示すとおり、酸化槽におい
て第１気液接触塔底液中に存在した硫化水素イオンとシ
アンイオンが酸化され、吸収能力が回復しているので、
第１気液接触塔では硫化水素及びシアン化水素が十分に
除去されている。また、表３に示すとおり、水蒸気蒸留
塔底液はアンモニアが十分に除去されているので、第２
気液接触塔ではコークス炉ガス中のアンモニアの除去も
完全に行なわれている。As shown in Tables 1 and 2, hydrogen sulfide ions and cyan ions present in the bottom liquid of the first gas-liquid contact tower were oxidized in the oxidation tank, and the absorption capacity was restored.
In the first gas-liquid contact tower, hydrogen sulfide and hydrogen cyanide are sufficiently removed. Further, as shown in Table 3, the ammonia in the bottom liquid of the steam distillation column was sufficiently removed.
In the gas-liquid contact tower, ammonia in the coke oven gas is completely removed.
【００２６】[0026]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 実施例２ 実施例１と同じ実験機を用い、コークス炉ガス中のアン
モニアの濃度を変え、その他の条件は実施例１と同一の
条件で実験を行なった結果（コークス炉ガス中の不純物
量及び各塔の循環液の組成）を表４、表５及び表６に示
す。[Table 3] Example 2 An experiment was performed using the same experimental machine as in Example 1 except that the concentration of ammonia in the coke oven gas was changed, and the other conditions were the same as those in Example 1 (results of impurities in the coke oven gas and The composition of the circulating liquid in each column is shown in Tables 4, 5 and 6.
【００２７】表４及び表５に示すとおり、酸化槽におい
て第１気液接触塔底液中に存在した硫化水素イオンとシ
アンイオンが酸化され、吸収能力が回復しているので、
第１気液接触塔では硫化水素及びシアン化水素が十分に
除去されている。また、表６に示すとおり、水蒸気蒸留
塔底液はアンモニアが十分に除去されているので、第２
気液接触塔ではコークス炉ガス中のアンモニアの除去も
完全に行なわれている。As shown in Tables 4 and 5, hydrogen sulfide ions and cyan ions present in the bottom liquid of the first gas-liquid contact tower were oxidized in the oxidation tank, and the absorption capacity was restored.
In the first gas-liquid contact tower, hydrogen sulfide and hydrogen cyanide are sufficiently removed. Further, as shown in Table 6, since the ammonia in the bottom liquid of the steam distillation column was sufficiently removed, the second liquid was removed.
In the gas-liquid contact tower, ammonia in the coke oven gas is completely removed.
【００２８】[0028]
【表４】 [Table 4]
【表５】 [Table 5]
【表６】 [Table 6]
【００２９】[0029]
【発明の効果】本発明は、コークス炉ガス中に含まれて
いる不純物のアンモニア、硫化水素及びシアン化水素を
除去するにあたり、水に溶解した時にアルカリ性を呈す
るアンモニアと、酸性を呈する硫化水素、シアン化水素
及び炭酸ガスをお互いに反応させながら、しかもコーク
ス炉ガス中に存在する炭酸ガスの影響を十分考慮にいれ
た方法を採用することによって、アンモニア、硫化水素
及びシアン化水素を効率よく除去することを狙いとし
た、コークス炉ガスの精製方法である。According to the present invention, in removing impurities such as ammonia, hydrogen sulfide and hydrogen cyanide contained in coke oven gas, ammonia which exhibits alkalinity when dissolved in water, and hydrogen sulfide, hydrogen cyanide which exhibits acidity and The aim was to remove ammonia, hydrogen sulfide and hydrogen cyanide efficiently by adopting a method in which carbon dioxide gas reacts with each other and that takes into account the effects of carbon dioxide gas present in the coke oven gas. And a method of purifying coke oven gas.
【００３０】即ち、脱硫・脱シアン工程では大量の吸収
液の循環が可能であるため、第１気液接触塔において、
硫化水素及びシアン化水素を十分に除去することが可能
である。また、この第１気液接触塔において、アンモニ
アの約半量が除去されるので、第２気液接触塔でのアン
モニアの除去量が少なくて済む上に、第２気液接触塔底
液はアンモニアと炭酸ガスが主成分のため、水蒸気蒸留
塔でアンモニアの含有量の少ない循環液を造ることがで
きるので、脱アンモニア工程での循環水量が少なくて済
むという特長も兼ね備えている。That is, in the desulfurization / de-cyanation step, a large amount of the absorption liquid can be circulated.
Hydrogen sulfide and hydrogen cyanide can be sufficiently removed. Further, since about half of the ammonia is removed in the first gas-liquid contact tower, the amount of ammonia removed in the second gas-liquid contact tower can be reduced, and the bottom liquid of the second gas-liquid contact tower can be reduced. Because the main component is carbon dioxide and carbon dioxide, a circulating liquid having a small content of ammonia can be produced in the steam distillation column, so that it also has the advantage that the amount of circulating water in the deammonification step can be reduced.
【図１】 本発明によるコークス炉ガスの精製方法の工
程図である。FIG. 1 is a process diagram of a method for purifying a coke oven gas according to the present invention.
【図２】 従来のコークス炉ガス中のアンモニア吸収除
去の工程図である。FIG. 2 is a process diagram of a conventional method for absorbing and removing ammonia in coke oven gas.
１ コークス炉ガス ２ 第１気液接触塔 ３ 第２気液接触塔 ４ 酸化槽 ５ 水蒸気蒸留塔 ６ 脱硫塔 ７ａ，７ｂ 還元・酸化二段燃焼炉 ８ 熱交換器 ９ 冷却器 １１ Ｎｏ．１気液接触塔吸収液 １２ Ｎｏ．１気液接触塔底液 １３ Ｎｏ．２気液接触塔吸収水 １４ Ｎｏ．２気液接触塔底液 １５ 吸収排液 １６ アンモニア蒸気 １７ Ｎｏ．１気液接触塔補給水 １８ 空気 １９ 水蒸気 ２０ 水酸化マグネシウムスラリー ２１ 放流排液 ２２ 燃焼排ガス ３１ アンモニア吸収塔 ３２ 硫化水素吸収塔 ３３ 水蒸気蒸留塔 ３４ 熱交換器 ３５ 冷却器 ３６ アンモニア吸収塔吸収液 ３７ アンモニア吸収塔底液 ３８ 水酸化ナトリウム溶液 ３９ 硫化水素吸収塔排液 ４０ 補給新水 ４１ アンモニア、硫化水素、シアン混合蒸気 ４２ 水蒸気 Reference Signs List 1 coke oven gas 2 first gas-liquid contact tower 3 second gas-liquid contact tower 4 oxidation tank 5 steam distillation tower 6 desulfurization tower 7a, 7b reduction / oxidation two-stage combustion furnace 8 heat exchanger 9 cooler 11 1 Gas-liquid contact tower absorption liquid 12 No. 1 Gas-liquid contact tower bottom liquid 13 No. 2 Gas-liquid contact tower absorption water 14 No. 2 Gas-liquid contact tower bottom liquid 15 Absorbed waste liquid 16 Ammonia vapor 17 No. 1 Gas-liquid contact tower make-up water 18 Air 19 Steam 20 Magnesium hydroxide slurry 21 Discharge effluent 22 Combustion exhaust gas 31 Ammonia absorption tower 32 Hydrogen sulfide absorption tower 33 Steam distillation tower 34 Heat exchanger 35 Cooler 36 Ammonia absorption tower absorption liquid 37 Ammonia absorption tower bottom liquid 38 Sodium hydroxide solution 39 Hydrogen sulfide absorption tower effluent 40 Replenishment fresh water 41 Ammonia, hydrogen sulfide, cyanide mixed vapor 42 Steam
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡 清爾 北九州市戸畑区大字中原46−59 日鐵プラ ント設計株式会社内 (72)発明者 白水 渡 北九州市戸畑区大字中原46−59 日鐵プラ ント設計株式会社内 (72)発明者 小林 純 室蘭市仲町12番地 新日本製鐵株式会社室 蘭製鐵所内 (72)発明者 山口 彰一 東海市東海町５−３ 新日本製鐵株式会社 名古屋製鐵所内 (72)発明者 田中 繁三 大分市大字西ノ洲１番地 新日本製鐵株式 会社大分製鐵所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiji Watari 46-59, Nakahara, Tobata-ku, Kitakyushu Nippon Steel Plant Design Co., Ltd. Plant Design Co., Ltd. (72) Inventor Jun Kobayashi 12 Nakamachi, Muroran City Nippon Steel Corporation Muroran Steel Works (72) Inventor Shoichi Yamaguchi 5-3 Tokaicho, Tokai City Nippon Steel Corporation Nagoya Inside the steelworks (72) Inventor: Shigeru Tanaka Oita Nishi-no-Shi, 1 Oita City Nippon Steel Corporation Oita Works
Claims (1)
生するコークス炉ガスの精製方法において、第１気液接
触塔にて、前記コークス炉ガスと吸収液とを気液接触さ
せ、該吸収液に前記コークス炉ガス中の硫化水素とシア
ン化水素とを吸収せしめ、該吸収液を酸化槽にて微細な
空気と接触させてチオ硫酸、硫酸、ロダンの各アンモニ
ウム塩に酸化して該吸収液の吸収能力を回復させた後、
前記の第１気液接触塔ヘ循環使用すると共に、前記第１
気液接触塔において、硫化水素とシアン化水素の除去さ
れたコークス炉ガスを第２気液接触塔に導入し、水を吸
収液として気液接触し、該吸収液に該コークス炉ガス中
に残存するアンモニアを吸収せしめ、該アンモニアを吸
収した吸収液を水蒸気蒸留塔にてアンモニア蒸気として
吸収液より分離せしめた後、前記第２気液接触塔へ循環
使用することを特徴とするコークス炉ガスの精製方法。In a method for purifying a coke oven gas by-produced when coke is produced by dry-distilling coal, the coke oven gas and the absorbent are brought into gas-liquid contact in a first gas-liquid contact tower. The absorption liquid absorbs hydrogen sulfide and hydrogen cyanide in the coke oven gas, and the absorption liquid is brought into contact with fine air in an oxidation tank to oxidize to thiosulfuric acid, sulfuric acid, and ammonium salt of rodane to form the absorption liquid. After restoring the absorption capacity of
While circulating and using the first gas-liquid contact tower,
In the gas-liquid contact tower, the coke oven gas from which hydrogen sulfide and hydrogen cyanide have been removed is introduced into the second gas-liquid contact tower, which is brought into gas-liquid contact with water as an absorbent, and remains in the coke oven gas with the absorbent. A method for purifying a coke oven gas, comprising: absorbing ammonia, separating the absorbing solution having absorbed the ammonia as ammonia vapor in a steam distillation column from the absorbing solution, and then circulating the ammonia gas to the second gas-liquid contact tower. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22149296A JPH1060449A (en) | 1996-08-22 | 1996-08-22 | Purification of coke oven gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22149296A JPH1060449A (en) | 1996-08-22 | 1996-08-22 | Purification of coke oven gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1060449A true JPH1060449A (en) | 1998-03-03 |
Family
ID=16767568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22149296A Pending JPH1060449A (en) | 1996-08-22 | 1996-08-22 | Purification of coke oven gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1060449A (en) |
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|---|---|---|---|---|
| KR20010001431A (en) * | 1999-06-04 | 2001-01-05 | 이구택 | A method for removing hydrogen sulfide in coke oven gas purification |
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| WO2004016717A1 (en) * | 2002-08-06 | 2004-02-26 | Mitsubishi Heavy Industries, Ltd. | Wet gas purification method and system for practicing the same |
| KR100405522B1 (en) * | 1998-12-18 | 2004-03-18 | 주식회사 포스코 | How to exclude carbon dioxide capture in coke gas purification |
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-
1996
- 1996-08-22 JP JP22149296A patent/JPH1060449A/en active Pending
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