JPH0253115B2 - - Google Patents
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- Publication number
- JPH0253115B2 JPH0253115B2 JP59050355A JP5035584A JPH0253115B2 JP H0253115 B2 JPH0253115 B2 JP H0253115B2 JP 59050355 A JP59050355 A JP 59050355A JP 5035584 A JP5035584 A JP 5035584A JP H0253115 B2 JPH0253115 B2 JP H0253115B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- vapor
- desulfurization waste
- evaporator
- coke oven
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Industrial Gases (AREA)
- Treating Waste Gases (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Description
技術分野
この発明は、コークス炉ガスの湿式脱硫工程か
ら排出される脱硫廃液の濃縮方法に関する。
技術背景
コークス炉ガス中には、硫化水素、シアン化水
素、アンモニア等の有害成分が含有されており、
燃料として利用するため、これら有害成分の除去
処理が行なわれている。
例えば、コークス炉ガス中の硫化水素、シアン
化水素を、触媒を含むアルカリ吸収液で吸収せし
め、吸収後の吸収液を空気酸化して触媒を酸化再
生せしめると共に、遊離硫黄とロダン塩、チオ硫
酸塩等として分離除去するコークス炉ガスの湿式
脱硫、脱シアン方法が知られている。
上記コークス炉ガスの湿式脱硫工程において、
ロダン塩、チオ硫酸塩、遊離硫黄等が吸収液中に
蓄積すると、脱硫、脱シアン効率が低下するばか
りでなく、循環系において遊離硫黄による閉塞ト
ラブルが発生し、連続運転が不可能となる。この
ため、循環吸収液中の遊離硫黄をフイルタープレ
スで分離すると共に、吸収液の一部を脱硫廃液と
して抜出すか、あるいは循環吸収液を遠心分離し
て高濃度遊離硫黄含有の脱硫廃液として抜出し、
新しく触媒を含む吸収液を補給している。
このようにして排出される硫黄ケーキ、脱硫廃
液の処理方法としては、燃焼処理して硫酸を回収
するか、あるいは石膏を回収し、処理後のガスを
無害化せしめる方法が行なわれている。
上記脱硫廃液の燃焼処理に際しては、補助燃料
を用いて燃焼せしめるのであるが、それに先立ち
脱硫廃液を濃縮するのが補助燃料を低減せしめる
ことができ有利である。しかし、従来の脱硫廃液
の濃縮方法は、スチームを用いて加熱濃縮し、濃
縮により発生したベーパーは、冷却水を用いて冷
却、凝縮されていた。このため、濃縮のための処
理コストが高価となる。また、前記高濃度遊離硫
黄を含有する脱硫廃液の場合には、濃縮部でのス
ケール発生により濃縮が不可能であるなどの欠点
がある。
この対策として、上記硫黄ケーキを分離した脱
硫廃液を濃縮することなく、再び硫黄ケーキと混
合したのち、燃焼炉の火炎に直線噴射し燃焼せし
める方法が提案されており、濃縮工程を省略でき
る利点を有するが、補助燃料の点から満足すべき
ものではない。
この発明者らは、先に上記脱硫廃液濃縮のため
の処理コストを大巾に低減せしめることができる
と共に、前記高濃度遊離硫黄含有脱硫廃液の濃縮
を可能としたコークス炉ガス湿式脱硫廃液の濃縮
方法としてコークス炉ガスの湿式脱硫工程から排
出される脱硫廃液を燃焼処理するに先立つて濃縮
するに際し、脱硫廃液を濃縮液及び、又は凝縮水
と熱交換させて予熱したのち蒸発缶に供給し、濃
縮により発生したベーパーを圧縮昇圧した加熱蒸
気により常圧又は減圧下で濃縮することを特徴と
するコークス炉ガス湿式脱硫廃液の濃縮方法（特
願昭57−193029、特開昭59−82986号公報参照）
を提案した。
これによつて、従来、冷却水を用いて冷却、凝
縮されていた脱硫廃液濃縮時に発生するベーパー
の保有する熱を有効利用して脱硫廃液を加熱濃縮
するので、従来の蒸気加熱に比べ大巾に濃縮コス
トを低減せしめることができ、又、とつおう面を
もつたヒーテイングエレメント群内蔵の蒸発缶を
使用し、ヒーテイングエレメント表面に脱硫廃液
を流下せしめることによりスケールの生成が抑制
され、高濃度遊離硫黄含有脱硫廃液の濃縮が可能
となる優れた発明である。
発明の目的
上記コークス炉ガス湿式脱硫廃液の濃縮方法は
優れてはいるが、コークス炉ガスの湿式脱硫廃液
中には、コークス炉ガス中に含有されるアンモニ
アと二酸化炭素が溶解し、その反応によつて生成
した炭酸アンモニウムが含有されており、蒸発缶
で加熱濃縮時、炭酸アンモニウムが分解してベー
パー中に混入し、該ベーパーを圧縮昇圧して加熱
源として使用しても、アンモニア、二酸化炭素が
凝縮することなく排出ベーパー中に残留する。こ
のため、排出ベーパー処理に先立つて冷却する
と、排出ベーパー中に残留したアンモニアと二酸
化炭素が反応して炭酸アンモニウムが析出し、排
出ベーパー抜出系を閉塞せしめて長期の連続運転
が困難である。
この発明は、かかる欠点の排除を目的とするも
のであり、この発明者らの種々試験研究の結果、
蒸発缶からの非凝縮ベーパー抜出系に洗浄塔を設
け、入口ガス温度管理をして該ベーパーを水洗浄
することによつて、アンモニア、二酸化炭素を溶
解せしめ、炭酸アンモニウム水溶液とすることに
より長期連続運転が可能となることを究明し、こ
の発明を完成せしめたのである。
発明の構成
この発明は、コークス炉ガスの湿式脱硫工程か
ら排出される脱硫廃液を予熱したのち蒸発缶に供
給し、常圧又は減圧下、前記脱硫廃液を蒸発缶の
上部よりヒーテイングエレメント表面に流下せし
めつつ、濃縮により発生したベーパーを圧縮昇圧
した加熱蒸気により濃縮するに際し、加熱に使用
した加熱蒸気の非凝縮ベーパー抜出し系に洗浄塔
を設けて水洗浄し、該非凝縮ベーパー中のアンモ
ニア、二酸化炭素を水に溶解せしめたのち、無害
化処理することを要旨とする。
発明の作用
この発明の作用を、この発明の実施の一例を示
す系統図に基いて説明する。
コークス炉ガスの湿式脱硫廃液は、パイプ１に
よりタンク２に導入一時貯蔵したのち、パイプ３
により熱交換器５に導入され、蒸発缶６のヒーテ
イングエレメント１２内からパイプ８により抜き
出された凝縮水と熱交換して加熱され、パイプ９
により蒸発缶６に供給される。
蒸発缶６は、パイプ１０で導かれた蒸発ベーパ
ーをリサイクルして圧縮機１１で圧縮昇圧して加
熱蒸気として利用する形式で、二枚のとつおう面
をもつたヒーテイングエレメント１２群が配設さ
れており、ヒーテイングエレメント１２の内部に
は上記加熱蒸気が注入され、循環管路１３により
上部デイストリビユータ１４から落下する脱硫廃
液がヒーテイングエレメント１２の外面を流下す
ることにより熱交換が行なわれ、水分が蒸発して
濃縮される。蒸発缶６内で蒸発したベーパーはパ
イプ１０で導出され、圧縮機１１で圧縮昇圧して
加熱蒸気としてヒーテイングエレメント１２の内
部に注入される。ヒーテイングエレメント１２の
外面を流下した濃縮液はパイプ７により底部から
抜出され、図示しない燃焼炉へパイプ１５により
送出し燃焼処理される。又、熱交換器５で脱硫廃
液と熱交換した凝縮水はパイプ１６により後述の
洗浄工程へ送出される。なお、上記パイプ１０の
圧縮機１１より下流側にはパイプ４を接続して補
給用蒸気を送入する。
そして、ヒーテイングエレメント１２の内部で
凝縮しないアンモニア、二酸化炭素等を含有する
ベーパーは、ヒーテイングエレメント１２の上部
からパイプ１７を経て洗浄塔１８に装入され、循
環管路２０により塔上部から噴射される散水によ
り洗浄されNH3、CO2を除去したのち、真空ポン
プ１９により吸引されパイプ２３を経て処理工程
へ送られる。
上記循環管路２０は途中にポンプ２４とクーラ
ー２５を有し、又凝縮水のパイプ１６、補給水供
給管２２及び洗浄水の一部を抜き出し、ガス液処
理工程へ送出するための抜出管２１を設け、塔底
から取出した洗浄水を循環冷却して塔上部より散
水するように構成される。
洗浄塔１８で洗浄された後真空ポンプ１９によ
り吸引されるベーパーの吸引量は、蒸発缶６を常
圧で運転するか、減圧で運転するかによつて調整
され、水分蒸発温度を低くできる減圧運転の場合
には吸引量が多く、又水分蒸発温度が100℃の常
圧運転の場合には、吸引量を少なくすればよい。
実施例
第１表の「入口」に示す性状のコークス炉ガス
の湿式脱硫廃液を78℃に予熱したのち、蒸発缶に
供給し、濃縮により発生した88℃のベーパーを圧
縮昇圧して得た加熱蒸気を主熱源として減圧下循
環濃縮せしめ、第１表の「出口」に示す性状の濃
縮液を得た。
TECHNICAL FIELD This invention relates to a method for concentrating desulfurization waste liquid discharged from a wet desulfurization process of coke oven gas. Technical background Coke oven gas contains harmful components such as hydrogen sulfide, hydrogen cyanide, and ammonia.
In order to use it as a fuel, these harmful components are removed. For example, hydrogen sulfide and hydrogen cyanide in coke oven gas are absorbed by an alkaline absorption liquid containing a catalyst, and the absorbed absorption liquid is oxidized with air to oxidize and regenerate the catalyst, and free sulfur, rhodan salt, thiosulfate, etc. Wet desulfurization and decyanization methods are known for separating and removing coke oven gas. In the above wet desulfurization process of coke oven gas,
If rhodan salt, thiosulfate, free sulfur, etc. accumulate in the absorbent, not only will the desulfurization and decyanization efficiency decrease, but the free sulfur will cause blockage problems in the circulation system, making continuous operation impossible. For this reason, free sulfur in the circulating absorption liquid is separated by a filter press, and a part of the absorption liquid is extracted as desulfurization waste liquid, or the circulating absorption liquid is centrifuged and extracted as desulfurization waste liquid containing a high concentration of free sulfur. ,
Absorption fluid containing new catalyst is being replenished. As a method for treating the sulfur cake and desulfurization waste liquid discharged in this way, methods are used in which sulfuric acid is recovered by combustion treatment, or gypsum is recovered and the gas after treatment is rendered harmless. In the combustion treatment of the desulfurization waste liquid, auxiliary fuel is used for combustion, but it is advantageous to concentrate the desulfurization waste liquid prior to this, since this can reduce the amount of auxiliary fuel. However, in the conventional method of concentrating desulfurization waste liquid, steam is used to heat and concentrate, and the vapor generated by the concentration is cooled and condensed using cooling water. Therefore, the processing cost for concentration becomes high. Furthermore, in the case of desulfurization waste liquid containing a high concentration of free sulfur, there is a drawback that it is impossible to concentrate due to scale generation in the concentration section. As a countermeasure to this problem, a method has been proposed in which the desulfurization waste liquid from which the sulfur cake has been separated is mixed with the sulfur cake again without concentrating it, and then injected straight into the flame of a combustion furnace to combust it.This method has the advantage of omitting the concentration step. However, it is not satisfactory from the point of view of auxiliary fuel. The present inventors have previously discovered that the processing cost for concentrating the desulfurization waste liquid can be greatly reduced, and the coke oven gas wet desulfurization waste liquid can be concentrated, making it possible to concentrate the desulfurization waste liquid containing a high concentration of free sulfur. As a method, when concentrating the desulfurization waste liquid discharged from the wet desulfurization process of coke oven gas before combustion treatment, the desulfurization waste liquid is preheated by exchanging heat with the concentrated liquid and/or condensed water, and then supplied to the evaporator, A method for concentrating coke oven gas wet desulfurization waste liquid characterized by concentrating the vapor generated by condensation using compressed and pressurized heated steam (Japanese Patent Application No. 57-193029, Japanese Patent Application Laid-Open No. 59-82986) reference)
proposed. As a result, the desulfurization waste liquid is heated and concentrated by effectively utilizing the heat possessed by the vapor generated during concentration of the desulfurization waste liquid, which was conventionally cooled and condensed using cooling water. In addition, by using an evaporator with a built-in group of heating elements with a condensing surface and allowing the desulfurization waste liquid to flow down onto the surface of the heating element, scale formation can be suppressed. This is an excellent invention that makes it possible to concentrate desulfurization waste liquid containing a high concentration of free sulfur. Purpose of the Invention Although the above method for concentrating coke oven gas wet desulfurization waste liquid is excellent, ammonia and carbon dioxide contained in coke oven gas are dissolved in the coke oven gas wet desulfurization waste liquid, and the reaction is affected. When concentrated by heating in an evaporator, ammonium carbonate decomposes and mixes into the vapor, and even if the vapor is compressed and pressurized and used as a heating source, ammonia and carbon dioxide are remains in the discharged vapor without condensing. Therefore, if the exhaust vapor is cooled prior to treatment, the ammonia and carbon dioxide remaining in the exhaust vapor will react and ammonium carbonate will precipitate, which will clog the exhaust vapor extraction system and make long-term continuous operation difficult. This invention aims to eliminate such drawbacks, and as a result of various test and research conducted by the inventors,
A cleaning tower is installed in the system for extracting non-condensed vapor from the evaporator, and by controlling the inlet gas temperature and washing the vapor with water, ammonia and carbon dioxide are dissolved to form an ammonium carbonate aqueous solution, which can be used for a long period of time. They discovered that continuous operation was possible and completed this invention. Structure of the Invention This invention preheats the desulfurization waste liquid discharged from the wet desulfurization process of coke oven gas and then supplies it to the evaporator, and the desulfurization waste liquid is applied to the surface of the heating element from the upper part of the evaporator under normal pressure or reduced pressure. When condensing the vapor generated by condensation using compressed and pressurized heated steam while letting it flow down, a cleaning tower is installed in the non-condensed vapor extraction system of the heated vapor used for heating, and the ammonia and dioxide in the non-condensed vapor are washed with water. The gist is to dissolve carbon in water and then detoxify it. Effects of the Invention The effects of the invention will be explained based on a system diagram showing an example of implementation of the invention. The wet desulfurization waste liquid of coke oven gas is introduced into tank 2 through pipe 1 and stored temporarily, and then is stored in tank 2 through pipe 3.
The condensed water is introduced into the heat exchanger 5 and heated by exchanging heat with the condensed water extracted from the heating element 12 of the evaporator 6 through the pipe 8.
is supplied to the evaporator 6. The evaporator 6 is of a type that recycles evaporated vapor led through a pipe 10, compresses and pressurizes it with a compressor 11, and uses it as heated steam, and is equipped with 12 groups of heating elements each having two interfacing surfaces. The heated steam is injected into the heating element 12, and the desulfurization waste liquid falling from the upper distributor 14 flows down the outer surface of the heating element 12 through the circulation pipe 13, thereby exchanging heat. The water is evaporated and concentrated. The vapor evaporated in the evaporator 6 is led out through a pipe 10, compressed and pressurized by a compressor 11, and injected into the heating element 12 as heated vapor. The concentrated liquid flowing down the outer surface of the heating element 12 is extracted from the bottom through a pipe 7, and sent through a pipe 15 to a combustion furnace (not shown) where it is burned. Further, the condensed water that has undergone heat exchange with the desulfurization waste liquid in the heat exchanger 5 is sent out through a pipe 16 to a cleaning process to be described later. Note that a pipe 4 is connected to the pipe 10 on the downstream side of the compressor 11 to supply replenishment steam. Vapor containing ammonia, carbon dioxide, etc. that is not condensed inside the heating element 12 is charged into the cleaning tower 18 from the upper part of the heating element 12 via the pipe 17, and is injected from the upper part of the tower through the circulation pipe 20. After being washed by water sprinkling to remove NH 3 and CO 2 , it is sucked by a vacuum pump 19 and sent to a treatment process via a pipe 23 . The circulation pipe 20 has a pump 24 and a cooler 25 along the way, and also has a condensed water pipe 16, a make-up water supply pipe 22, and an extraction pipe for extracting a part of the cleaning water and sending it to the gas liquid processing process. 21 is provided to circulate and cool the washing water taken out from the bottom of the tower and to spray it from the top of the tower. The amount of vapor sucked by the vacuum pump 19 after cleaning in the cleaning tower 18 is adjusted depending on whether the evaporator 6 is operated at normal pressure or at reduced pressure. In the case of operation, the amount of suction is large, and in the case of normal pressure operation where the water evaporation temperature is 100°C, the amount of suction may be reduced. Example Wet desulfurization waste liquid of coke oven gas having the properties shown in "Inlet" in Table 1 was preheated to 78°C, then supplied to the evaporator, and the 88°C vapor generated by concentration was compressed and pressurized. The mixture was circulated and concentrated under reduced pressure using steam as the main heat source to obtain a concentrated liquid having the properties shown in "Outlet" in Table 1.
【表】
そして、蒸発缶で凝縮しなかつた不凝縮ベーパ
ーは蒸発缶から抜き出し、この発明の実施により
洗浄塔に装入して洗浄処理した。
すなわち、第２表に性状を示した非凝縮ベーパ
ーは温度66℃、流量90.42Nm3／Hrで洗浄塔に装
入され、ここで第３表に性状を示す凝縮水を温度
29℃、供給量3.8m3／Hrで装入すると共に新水を
供給量0.5m3／Hrで補給し、第３表に性状を示す
散水として温度23℃、散水量17m3／Hrで噴射し
洗浄した。その結果、洗浄後のベーパーは第２表
に示すように、アンモニア、二酸化炭素はほとん
ど水に溶解し清浄化されていることがわかる。な
お、塔底から抜き出される冷却水は温度29℃、流
量17.5m3／Hrで、その性状は第３表に示すとお
りである。[Table] The non-condensable vapor that was not condensed in the evaporator was extracted from the evaporator and charged into a cleaning tower according to the present invention for cleaning treatment. That is, the non-condensed vapor whose properties are shown in Table 2 is charged into a cleaning tower at a temperature of 66°C and a flow rate of 90.42Nm 3 /Hr, and here the condensed water whose properties are shown in Table 3 is
The water was charged at 29°C with a supply rate of 3.8m 3 /Hr, and fresh water was replenished with a supply rate of 0.5m 3 /Hr, and the water spraying properties shown in Table 3 was injected at a temperature of 23°C with a water supply rate of 17m 3 /Hr. and washed. As a result, as shown in Table 2, it can be seen that most of the ammonia and carbon dioxide in the vapor after washing were dissolved in water, and the vapor was purified. The cooling water extracted from the bottom of the tower had a temperature of 29° C. and a flow rate of 17.5 m 3 /Hr, and its properties are as shown in Table 3.
【表】【table】
【表】
発明の効果
この発明は、コークス炉ガスの湿式脱硫工程か
ら排出される含硫黄脱硫廃液を蒸発缶で濃縮処理
する際、加熱に使用した加熱蒸気の非凝縮ベーパ
ーを処理する以前に水洗浄してベーパー中のアン
モニアと二酸化炭素を除去するため、排出ベーパ
ー系配管の炭酸アンモニウムの析出による閉塞を
防止することができ、装置の長期連続運転が可能
となり、工業上極めて有益である。[Table] Effects of the Invention This invention provides a method for concentrating sulfur-containing desulfurization waste liquid discharged from a wet desulfurization process of coke oven gas in an evaporator, before processing the non-condensed vapor of heated steam used for heating. Since the ammonia and carbon dioxide in the vapor are removed by cleaning, it is possible to prevent the discharge vapor system piping from clogging due to the precipitation of ammonium carbonate, making it possible to operate the device continuously for a long period of time, which is extremely useful industrially.
第１図はこの発明の一実施例における装置の系
統図である。
１，３，４，７，８，９，１０，１５，１６，
１７，２３……パイプ、２……タンク、５……熱
交換器、６……蒸発缶、１１……圧縮機、１２…
…ヒーテイングエレメント、１３，２０……循環
管路、１４……上部デイストリビユータ、１８…
…洗浄塔、１９……真空ポンプ、２１……抜出
管、２２……補給水供給管、２４……ポンプ、２
５……クーラー。
FIG. 1 is a system diagram of an apparatus in an embodiment of the present invention. 1, 3, 4, 7, 8, 9, 10, 15, 16,
17, 23...pipe, 2...tank, 5...heat exchanger, 6...evaporator, 11...compressor, 12...
...Heating element, 13, 20...Circulation pipe, 14...Upper distributor, 18...
...Washing tower, 19...Vacuum pump, 21...Extraction pipe, 22...Makeup water supply pipe, 24...Pump, 2
5... Cooler.
Claims (1)
る脱硫廃液を予熱したのち蒸発缶に供給し、常圧
又は減圧下、前記脱硫廃液を蒸発缶の上部よりヒ
ーテイングエレメント表面に流下せしめつつ、濃
縮により発生したベーパーを圧縮昇圧した加熱蒸
気により濃縮するに際し、加熱に使用した加熱蒸
気の非凝縮ベーパー抜出し系に洗浄塔を設けて水
洗浄し、該非凝縮ベーパー中のアンモニア、二酸
化炭素を水に溶解せしめたのち、無害化処理する
ことを特徴とするコークス炉ガス湿式脱硫廃液の
濃縮方法。1 The desulfurization waste liquid discharged from the wet desulfurization process of coke oven gas is preheated and then supplied to the evaporator, and the desulfurization waste liquid is allowed to flow down from the upper part of the evaporator onto the surface of the heating element under normal pressure or reduced pressure, and is then concentrated. When concentrating the generated vapor using compressed and pressurized heated steam, a cleaning tower is installed in the non-condensed vapor extraction system of the heated vapor used for heating, and the ammonia and carbon dioxide in the non-condensed vapor are dissolved in water. A method for concentrating coke oven gas wet desulfurization waste liquid, which is characterized in that it is then subjected to detoxification treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59050355A JPS60193580A (en) | 1984-03-15 | 1984-03-15 | Method for concentrating waste liquid from wet desulfurization of coke-oven gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59050355A JPS60193580A (en) | 1984-03-15 | 1984-03-15 | Method for concentrating waste liquid from wet desulfurization of coke-oven gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60193580A JPS60193580A (en) | 1985-10-02 |
| JPH0253115B2 true JPH0253115B2 (en) | 1990-11-15 |
Family
ID=12856588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59050355A Granted JPS60193580A (en) | 1984-03-15 | 1984-03-15 | Method for concentrating waste liquid from wet desulfurization of coke-oven gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60193580A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2863807B2 (en) * | 1988-07-08 | 1999-03-03 | コニカ株式会社 | Processing equipment for photographic processing waste liquid |
| CN106000054A (en) * | 2016-07-13 | 2016-10-12 | 枣庄薛能天然气有限公司 | Coke oven flue ammonia water spraying and desulfurizing technology and device |
| CN107235597A (en) * | 2017-06-30 | 2017-10-10 | 山东国舜建设集团有限公司 | A kind of nonhomogen-ous nucleation crystallisation handles the method and system of desulfurization wastewater |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5715955A (en) * | 1980-07-02 | 1982-01-27 | Toray Industries | Fiber reinforced resin |
-
1984
- 1984-03-15 JP JP59050355A patent/JPS60193580A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60193580A (en) | 1985-10-02 |
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