JP2000282273A - Treatment of waste hydrochloric acid - Google Patents
Treatment of waste hydrochloric acidInfo
- Publication number
- JP2000282273A JP2000282273A JP11090172A JP9017299A JP2000282273A JP 2000282273 A JP2000282273 A JP 2000282273A JP 11090172 A JP11090172 A JP 11090172A JP 9017299 A JP9017299 A JP 9017299A JP 2000282273 A JP2000282273 A JP 2000282273A
- Authority
- JP
- Japan
- Prior art keywords
- hydrochloric acid
- evaporator
- waste hydrochloric
- steam
- treating waste
- 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
Links
Landscapes
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、鋼線製造工場、鋼
板製造工場、メッキ工場などにおいて、鋼線、鋼板、鋼
製品などの洗浄工程で発生する高濃度鉄分含有廃塩酸の
処理方法に関する。さらに詳しくは、本発明は、蒸発缶
を用いて、従来はその殆どが産業廃棄物としてそのまま
処理されていた廃塩酸中に残存する塩酸および鉄塩を回
収することにより、その再利用をはかるとともに、廃棄
残分の減容化を行う廃塩酸の再生処理方法、および蒸発
缶内での濃縮液中鉄塩の固化を防止することにより、蒸
発缶を安定して運転し、かつ必要時にはその運転を円滑
に停止する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating high concentration iron-containing waste hydrochloric acid generated in a washing process of steel wires, steel plates, steel products, etc. in a steel wire manufacturing plant, a steel plate manufacturing plant, a plating plant and the like. More specifically, the present invention uses an evaporator to recover hydrochloric acid and iron salt remaining in waste hydrochloric acid, which has been mostly treated as industrial waste, and thereby to reuse it. A method for regenerating waste hydrochloric acid to reduce the volume of waste residue and preventing solidification of iron salts in the concentrated liquid in the evaporator to stably operate the evaporator and, when necessary, to operate the evaporator To a smooth stop.
【0002】[0002]
【従来の技術】例えば、特開昭59-26184号公報における
図面に示されている従来の蒸気圧縮式蒸発装置は、下部
に原液の溜室を備えた密閉型の蒸発器内の上部に多数本
の伝熱管を設け、該各伝熱管の外側面に、原液ポンプに
よって送られて来る原液を散布器にて散布することによ
り蒸発させ、この蒸発により発生した蒸気をブロワー圧
縮機で圧縮して昇温し、この昇温した蒸気をダクトを介
して、前記各伝熱管内に供給することにより、各伝熱管
の外側面に散布されている原液を加熱・蒸発させるとと
もに、前記各伝熱管内から空気等の非凝縮性ガスを真空
ポンプなどの真空発生手段にて抽出することにより、前
記蒸発器内を大気圧以下の減圧状態に保持している。2. Description of the Related Art For example, a conventional vapor compression type evaporator shown in the drawings of Japanese Patent Application Laid-Open No. 59-26184 discloses a large number of evaporators in a closed type evaporator having a stock solution chamber at the bottom. The heat transfer pipes are provided, and on the outer surface of each of the heat transfer pipes, the undiluted solution sent by the undiluted solution pump is sprayed by a sprayer to evaporate, and the steam generated by the evaporation is compressed by a blower compressor. The temperature is increased, and the heated vapor is supplied into each of the heat transfer tubes through a duct, thereby heating and evaporating the stock solution sprayed on the outer surface of each of the heat transfer tubes, and By extracting a non-condensable gas such as air from the evaporator by a vacuum generating means such as a vacuum pump, the inside of the evaporator is maintained at a reduced pressure below the atmospheric pressure.
【0003】しかしながら、この形式の蒸気圧縮式蒸発
装置には、以下の様な問題点がある。 イ.ブロワー圧縮機本体の圧縮効率が低く、単位原液量
を圧縮するための必要電力量が大きくなり、運転経費が
高くなり、設備も大きくなる。 ロ.原液は、散布器を介して、各伝熱管の外表面に散布
されるので、液分散不良から生じる熱交換器伝熱係数の
低下がある。 ハ.特に、多量の鉄分などを含有する廃塩酸の処理に際
して、液の濃縮倍率上昇または連続運転に伴い、液分散
器ノズル部分でのスラッジによる詰まりおよび分散不
良、各伝熱管外表面の汚れ、液比重または粘度の上昇な
どによる伝熱係数の低下に対し、有効に対処することが
できない。However, this type of vapor compression type evaporator has the following problems. I. The compression efficiency of the blower compressor body is low, the amount of power required to compress the unit stock solution increases, the operating cost increases, and the equipment increases. B. Since the undiluted solution is sprayed on the outer surface of each heat transfer tube via the sprayer, there is a reduction in the heat transfer coefficient of the heat exchanger caused by poor liquid dispersion. C. In particular, in the treatment of waste hydrochloric acid containing a large amount of iron, clogging and poor dispersion due to sludge at the nozzle of the liquid disperser, dirt on the outer surface of each heat transfer tube, specific gravity of the liquid due to the increase in the concentration ratio of the liquid or continuous operation. Alternatively, it is not possible to effectively cope with a decrease in heat transfer coefficient due to an increase in viscosity or the like.
【0004】また、各管の外表面付着スケールの除去
は、液が分散されているため、伝熱管外面に対する液流
速が遅いことなどから、困難となる場合が多い。In addition, it is often difficult to remove scale attached to the outer surface of each tube because the liquid is dispersed and the liquid flow velocity to the outer surface of the heat transfer tube is slow.
【0005】さらに、濃縮液中の鉄濃度が上昇すると、
鉄塩の固化による蒸発装置の安定した運転が困難となる
場合もある。 ニ.上記ロおよびハの結果、濃縮処理は、常に単位断面
積当たりの蒸発量が低い状態で行わざるを得ない。従っ
て、単位時間当たりの蒸発量を増大させるためには、伝
熱面積を増大させるか、或いはブロワー圧縮機として圧
縮比の高いものを使用しなければならないため、装置が
大型化するとともに、運転経費が嵩むという問題があ
る。 ホ.特に、廃塩酸を処理対象とする場合には、蒸気が高
濃度の塩酸を含むので、圧縮機本体などの材質の選択に
大きな制約を受ける。この様な装置の材質上の制約か
ら、原液中に残存する有用な塩酸を回収することができ
ないし、濃縮残分の十分な減容化もできない。Further, when the iron concentration in the concentrate increases,
In some cases, stable operation of the evaporator may be difficult due to solidification of the iron salt. D. As a result of the above (b) and (c), the concentration process must always be performed in a state where the evaporation amount per unit sectional area is low. Therefore, in order to increase the amount of evaporation per unit time, the heat transfer area must be increased, or a blower compressor having a high compression ratio must be used. However, there is a problem that the bulk increases. E. In particular, when treating waste hydrochloric acid, since steam contains high-concentration hydrochloric acid, selection of a material of the compressor body or the like is greatly restricted. Due to such restrictions on the material of the apparatus, useful hydrochloric acid remaining in the stock solution cannot be recovered, and the volume of the concentrated residue cannot be reduced sufficiently.
【0006】[0006]
【発明が解決しようとする課題】従って、本発明は、加
熱管を備えた加熱装置である蒸発缶を用いて廃塩酸の処
理を行うに際し、装置の小型化による設備費と運転経費
の節減を達成し、濃縮液中の固化鉄分(スラッジ)による
配管類および機器類の目詰まりおよび伝熱係数の低下な
どを抑制しつつ、廃塩酸からの塩酸および鉄塩の回収を
効率よく行うとともに、濃縮残分の高度の減容化を達成
し、さらに必要時には、装置を定常運転状態から円滑に
停止することを主な目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention reduces the equipment cost and operating cost due to downsizing of the apparatus when treating waste hydrochloric acid using an evaporator, which is a heating apparatus having a heating tube. Achieve efficient collection of hydrochloric acid and iron salts from waste hydrochloric acid while suppressing clogging of piping and equipment and a decrease in heat transfer coefficient due to solidified iron (sludge) in the concentrated solution The main purpose is to achieve volume reduction of the remaining altitude and, when necessary, to smoothly stop the device from a steady operation state.
【0007】[0007]
【課題を解決するための手段】本発明者は、上記の様な
技術の現状に鑑みて鋭意研究を重ねた結果、廃塩酸を導
入する蒸発缶内温度を110〜120℃に調節保持するか、廃
塩酸原液量に対する蒸発液量を調節するか、あるいは蒸
発缶内温度の調節と蒸発液量の調節とを併せて行うこと
により、蒸発缶内濃縮液中の鉄塩濃度を300g/l以下に抑
制する場合には、蒸発缶内での閉塞、伝熱係数の低下な
どの装置運転上の問題点が大幅に軽減されることを見出
した。Means for Solving the Problems The present inventor has conducted intensive studies in view of the state of the art as described above, and as a result, has determined whether the temperature in the evaporator for introducing waste hydrochloric acid is adjusted to 110 to 120 ° C. and maintained. By adjusting the amount of evaporant with respect to the amount of waste hydrochloric acid stock solution, or by adjusting the temperature in the evaporator and the amount of evaporate together, the iron salt concentration in the concentrated solution in the evaporator is 300 g / l or less. It has been found that, in the case where the temperature is controlled to be as low as possible, problems in the operation of the apparatus such as blockage in the evaporator and a decrease in the heat transfer coefficient are greatly reduced.
【0008】さらに、蒸発缶の運転停止時には、蒸発缶
内濃縮液中の鉄濃度を200g/l以下に低下させることによ
り、鉄塩の固化を防止して、装置の運転再開を円滑に行
いうることを見出した。Further, when the operation of the evaporator is stopped, the concentration of iron in the concentrated liquid in the evaporator is reduced to 200 g / l or less, thereby preventing solidification of iron salts and smoothly restarting the operation of the apparatus. I found that.
【0009】さらにまた、蒸発缶外に抜き出した濃縮液
を希釈して鉄濃度を200g/l以下に制御する場合には、配
管類での目詰まり、常温条件下の濃縮液貯槽における鉄
塩の析出などを防止しうるとともに、有用な塩酸の回収
と濃縮残分の十分な減容化を安定して達成できること
も、見出した。Further, when the concentration of the concentrated solution withdrawn out of the evaporator is diluted to control the iron concentration to 200 g / l or less, clogging in piping or the like, iron salts in the concentrated solution storage tank at normal temperature conditions may be removed. It has also been found that precipitation can be prevented, and useful hydrochloric acid can be recovered and a sufficient volume reduction of the concentrated residue can be stably achieved.
【0010】すなわち、本発明は、下記の廃塩酸の処理
方法を提供するものである。 1.蒸発缶を使用する廃塩酸の処理方法において、
(1)廃塩酸原液を蒸発缶内に導入する工程、(2)蒸
気を供給し、蒸発缶内の液を間接的に加熱して、蒸発さ
せる工程、(3)蒸発缶内で発生した蒸気を冷却器で冷
却し、これを塩酸水溶液として回収する工程、(4)蒸
発缶内での加熱・蒸発に利用した蒸気の凝縮液を回収す
る工程、(5)蒸発缶内温度および/または廃塩酸原液
量に対する蒸留液量の割合を調整することにより、蒸発
缶内濃縮液中の鉄濃度を300g/l以下に制御する工程、
(6)蒸発缶内の液面高さに対応して濃縮液を抜き出
し、濃縮液貯槽に送る工程、(7)発缶外に抜き出した
濃縮液を希釈することにより、その鉄濃度を200g/l以下
に制御する工程、および(8)(a)蒸発缶内温度および
/または廃塩酸原液量に対する蒸留液量の割合を調整す
るか、および/または(b)廃塩酸原液に代えて希釈液を
供給することにより、蒸発缶内濃縮液中鉄濃度を200g/l
以下とした後、廃塩酸の処理を停止する工程を備えたこ
とを特徴とする廃塩酸の処理方法。 2.工程(5)における蒸発缶内温度が、110〜120℃で
ある上記項1に記載の廃塩酸の処理方法。 3.工程(7)において、蒸発缶からの濃縮液の抜き出
しを80〜100℃の加熱条件下に行った後、濃縮液を希釈
する上記項1に記載の廃塩酸の処理方法。 4.蒸発缶内下部および/または濃縮液抜き出しライン
に外部から蒸気および/または空気を間欠的に導入する
ことにより、鉄塩の固化を抑制する上記項1に記載の廃
塩酸の処理方法。 5.工程(7)において、希釈液として、工程(4)か
らの凝縮液および/または廃塩酸原液および/または水
を使用する上記項3に記載の廃塩酸の処理方法。 6.蒸発缶が、加熱管を備えた蒸気加熱型装置である上
記項1に記載の廃塩酸の処理方法。 7.蒸発缶が、カランドリア型蒸発缶、縦型多管式熱交
換器蒸発缶あるいは横型多管式熱交換器蒸発缶である上
記項6に記載の廃塩酸の処理方法。 8.加熱・蒸発用熱源が、ボイラーで発生する蒸気およ
び/またはコジェネレーション設備で発生する蒸気であ
る上記項1に記載の廃塩酸の処理方法。 9.加熱・蒸発用熱源が、加熱熱媒および/または高温
燃焼排ガスおよび/または電気である上記項1に記載の
廃塩酸の処理方法。 10.加熱・蒸発用熱源が、高温・高圧蒸気を減圧弁で
減圧した蒸気である上記項1、3、4、6、7または8
に記載の廃塩酸の処理方法。 11.加熱・蒸発用熱源が、低温・低圧蒸気を圧縮機で
圧縮・昇温した蒸気である上記項1、3、4、6、7ま
たは8に記載の廃塩酸の処理方法。 12.圧縮機が、スクリュー型圧縮機である上記項11
に記載の廃塩酸の処理方法。 13.スクリュー型圧縮機のモーター回転数をインバー
ター装置により制御する上記項12に記載の廃塩酸の処
理方法。 14.蒸発缶内および/または再濃縮装置内および/ま
たは晶析装置内で発生する蒸気量(回収塩酸水溶液量)
に対応してスクリュー型圧縮機のモーター回転数を制御
する上記項12または13に記載の廃塩酸の処理方法。 15.蒸発缶内温度に対応してスクリュー型圧縮機のモ
ーター回転数を制御する上記項12または13に記載の
廃塩酸の処理方法。 16.複数個の圧縮機が設けられている上記項11に記
載の廃塩酸の処理方法。 17.工程(7)において、蒸発缶内の塔底液をポンプ
で抜き取り、廃塩酸原液の導入ラインへ循環する上記項
1に記載の廃塩酸の処理方法。 18.加熱・蒸発用熱源として使用した蒸気の凝縮液を
ボイラー給水として使用する上記項1に記載の廃塩酸の
処理方法。 19.蒸発缶内液面の上方空間部にデミスターを設けた
上記項1に記載の廃塩酸の処理方法。 20.加熱側の蒸気ラインに、蒸発缶内の非凝縮性気体
の自動的排出を定期的に行うための電磁弁を設けた上記
項1に記載の廃塩酸の処理方法。 21.スタートアップ時または長期運転時に蒸発缶内伝
熱管の汚れによる蒸発量の低下に対応するために、補助
熱源を蒸発缶内底部へ導入する上記項1に記載の廃塩酸
の処理方法。 22.スタートアップ時または長期運転時に蒸発缶内伝
熱管の汚れによる蒸発量の低下に対応するために、補助
熱源を圧縮機出口ラインへ導入する上記項11に記載の
廃塩酸の処理方法。 23.補助熱源が蒸気である上記項21または22に記
載の廃塩酸の処理方法。 24.蒸発缶内伝熱管の汚れによる伝熱係数の低下が生
じた場合に、運転中に廃塩酸原液の供給を一時的に中断
し、水を供給することにより、汚れを洗浄・除去する上
記項1に記載の廃塩酸の処理方法。 25.工程(6)において、液面高さを示す信号に対応
して濃縮液を塔底から抜き出す上記項1に記載の廃塩酸
処理方法。 26.工程(6)において、蒸発缶内の液面に相当する
位置で、蒸発缶底部と連通するオーバーフロー管から濃
縮液を抜き出す上記項1に記載の廃塩酸の処理方法。 27.工程(3)において、蒸発缶内で発生する蒸気を
冷却・凝縮させて塩酸として回収した後、鉄鋼製品の表
面処理に使用する上記項1に記載の廃塩酸の処理方法。 28.回分式および/または連続式の鉄鋼製品処理槽か
ら廃塩酸原液を連続的に抜き出し、処理する上記項1に
記載の廃塩酸の処理方法。 29.蒸発缶外に取り出した濃縮液を再濃縮装置または
晶析装置において間接的に加熱し、蒸発させた後、生成
する蒸気を工程(3)で得られた蒸気と併せて塩酸水溶
液として回収するとともに、残余を塩化鉄を主成分とす
る固体状物として回収する上記項1に記載の廃塩酸の処
理方法。That is, the present invention provides the following method for treating waste hydrochloric acid. 1. In the method for treating waste hydrochloric acid using an evaporator,
(1) a step of introducing a waste hydrochloric acid stock solution into an evaporator, (2) a step of supplying steam and indirectly heating and evaporating the liquid in the evaporator, and (3) a steam generated in the evaporator. Is cooled by a cooler and recovered as an aqueous hydrochloric acid solution, (4) a step of recovering a condensate of steam used for heating and evaporation in the evaporator, (5) a temperature and / or waste in the evaporator A step of controlling the concentration of iron in the concentrated solution in the evaporator to 300 g / l or less by adjusting the ratio of the amount of the distillate to the amount of the hydrochloric acid stock solution,
(6) A step of extracting the concentrated liquid corresponding to the liquid level in the evaporator and sending it to the concentrated liquid storage tank. (7) Diluting the concentrated liquid extracted outside the canister to reduce the iron concentration to 200 g / (8) (a) adjusting the temperature in the evaporator and / or the ratio of the amount of the distillate to the amount of the waste hydrochloric acid stock solution, and / or (b) diluting the waste hydrochloric acid stock solution instead of the waste hydrochloric acid stock solution. To reduce the iron concentration in the concentrated liquid in the evaporator to 200 g / l.
A method for treating waste hydrochloric acid, comprising a step of stopping the treatment of waste hydrochloric acid after the following. 2. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein the temperature in the evaporator in the step (5) is 110 to 120 ° C. 3. 2. The method for treating waste hydrochloric acid according to item 1, wherein in step (7), the concentrated liquid is extracted from the evaporator under heating conditions of 80 to 100 ° C., and then the concentrated liquid is diluted. 4. 2. The method for treating waste hydrochloric acid according to the above item 1, wherein the solidification of the iron salt is suppressed by intermittently introducing steam and / or air from the outside into the lower portion inside the evaporator and / or the concentrated liquid extracting line. 5. Item 4. The method for treating waste hydrochloric acid according to Item 3, wherein in Step (7), the condensate from Step (4) and / or the waste hydrochloric acid stock solution and / or water are used as the diluent. 6. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein the evaporator is a steam heating type device provided with a heating tube. 7. Item 7. The method for treating waste hydrochloric acid according to Item 6, wherein the evaporator is a calandria evaporator, a vertical multitubular heat exchanger evaporator, or a horizontal multitubular heat exchanger evaporator. 8. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein the heat source for heating / evaporation is steam generated in a boiler and / or steam generated in a cogeneration facility. 9. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein the heat source for heating / evaporation is a heating heat medium and / or a high-temperature combustion exhaust gas and / or electricity. 10. Item 1, 3, 4, 6, 7, or 8 wherein the heat source for heating / evaporation is steam obtained by reducing high-temperature / high-pressure steam by a pressure reducing valve.
3. The method for treating waste hydrochloric acid according to 1.). 11. Item 9. The method for treating waste hydrochloric acid according to Item 1, 3, 4, 6, 6, 7 or 8, wherein the heat source for heating / evaporation is steam obtained by compressing and raising the temperature of low-temperature / low-pressure steam with a compressor. 12. Item 11. wherein the compressor is a screw compressor.
3. The method for treating waste hydrochloric acid according to 1.). 13. Item 13. The method for treating waste hydrochloric acid according to Item 12, wherein the motor rotation speed of the screw compressor is controlled by an inverter device. 14. Amount of steam generated in the evaporator and / or in the re-concentrator and / or in the crystallizer (recovered hydrochloric acid aqueous solution)
Item 14. The method for treating waste hydrochloric acid according to Item 12 or 13, wherein the number of revolutions of the motor of the screw compressor is controlled in accordance with the above. 15. Item 14. The method for treating waste hydrochloric acid according to Item 12 or 13, wherein the number of revolutions of the motor of the screw compressor is controlled in accordance with the temperature in the evaporator. 16. Item 12. The method for treating waste hydrochloric acid according to Item 11, wherein a plurality of compressors are provided. 17. 3. The method for treating waste hydrochloric acid according to the above item 1, wherein in the step (7), the bottom liquid in the evaporator is withdrawn by a pump and circulated to a line for introducing a waste hydrochloric acid stock solution. 18. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein the condensate of steam used as a heat source for heating and evaporating is used as boiler feed water. 19. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein a demister is provided in a space above the liquid level in the evaporator. 20. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein a solenoid valve for periodically periodically discharging the non-condensable gas in the evaporator is provided in the steam line on the heating side. 21. Item 2. The method for treating waste hydrochloric acid according to the above item 1, wherein an auxiliary heat source is introduced into the bottom of the evaporator to cope with a decrease in the amount of evaporation due to contamination of the heat transfer tube in the evaporator during start-up or long-term operation. 22. Item 12. The method for treating waste hydrochloric acid according to Item 11, wherein an auxiliary heat source is introduced into the compressor outlet line in order to cope with a decrease in the amount of evaporation due to contamination of the heat transfer tube in the evaporator during startup or long-term operation. 23. Item 23. The method for treating waste hydrochloric acid according to Item 21 or 22, wherein the auxiliary heat source is steam. 24. In the case where the heat transfer coefficient is reduced due to the contamination of the heat transfer tube in the evaporator, the supply of the waste hydrochloric acid stock solution is temporarily interrupted during operation and the water is supplied to wash and remove the contamination. 3. The method for treating waste hydrochloric acid according to 1.). 25. 2. The waste hydrochloric acid treatment method according to the above item 1, wherein in the step (6), the concentrated liquid is extracted from the bottom of the column in response to the signal indicating the liquid level. 26. 2. The method for treating waste hydrochloric acid according to the above item 1, wherein in the step (6), the concentrated liquid is extracted from the overflow pipe communicating with the bottom of the evaporator at a position corresponding to the liquid level in the evaporator. 27. 2. The method for treating waste hydrochloric acid according to the above item 1, wherein in the step (3), the steam generated in the evaporator is cooled and condensed and recovered as hydrochloric acid, and then used for surface treatment of a steel product. 28. Item 2. The method for treating waste hydrochloric acid according to Item 1, wherein the waste hydrochloric acid stock solution is continuously extracted from a batch type and / or continuous type steel product treatment tank and treated. 29. The concentrated liquid taken out of the evaporator is heated indirectly in a re-concentrator or crystallizer to evaporate, and the generated vapor is recovered as an aqueous hydrochloric acid solution together with the vapor obtained in the step (3). Item 1. The method for treating waste hydrochloric acid according to Item 1, wherein the residue is recovered as a solid containing iron chloride as a main component.
【0011】[0011]
【発明の実施の形態】本発明の処理対象となる廃塩酸原
液が、濃縮条件下に発泡を生じる可能性がある成分(界
面活性剤など)を含んでいる場合には、あらかじめシリ
コーン系などの公知の消泡剤を添加してもよい。消泡剤
の添加量は、発泡性成分の含有量などを考慮して定めれ
ば良く、特に限定されるものではないが、通常30〜500m
g/l程度である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS When the waste hydrochloric acid stock solution to be treated according to the present invention contains a component (such as a surfactant) that may cause foaming under concentrated conditions, a silicone-based material such as a silicone-based solution is used in advance. A known antifoaming agent may be added. The addition amount of the defoaming agent may be determined in consideration of the content of the foaming component, and is not particularly limited, but is usually 30 to 500 m.
It is about g / l.
【0012】本発明方法で使用する蒸発缶としては、カ
ランドリア型蒸発缶、縦型多管式熱交換器蒸発缶、横型
多管式熱交換器蒸発缶などの加熱管を備えた加熱方式蒸
発缶が挙げられる。As the evaporator used in the method of the present invention, a heating evaporator equipped with a heating tube such as a calandria evaporator, a vertical multitubular heat exchanger evaporator, a horizontal multitubular heat exchanger evaporator, etc. Is mentioned.
【0013】本発明方法においては、鉄塩の固化による
機器/配管などの閉塞を防止して、装置を安定して運転
するために、蒸発缶内の濃縮液中の鉄濃度を300g/l以下
に保持する。この鉄濃度調整は、蒸発缶内温度を110〜1
20℃程度、より好ましくは110〜115℃程度に調整するこ
とにより、あるいは廃塩酸原液量に対する蒸発液量の割
合を調整することにより、あるいは蒸発缶内温度および
蒸発液量の割合を調整することにより、行うことができ
る。In the method of the present invention, the iron concentration in the concentrated solution in the evaporator is set to 300 g / l or less in order to prevent equipment / pipe or the like from being clogged due to solidification of the iron salt and to operate the apparatus stably. To hold. This iron concentration adjustment is performed by setting the temperature inside the evaporator to 110 to 1
By adjusting the temperature to about 20 ° C., more preferably about 110 to 115 ° C., or by adjusting the ratio of the amount of evaporant to the amount of waste hydrochloric acid stock solution, or by adjusting the temperature in the evaporator and the ratio of the amount of evaporant Can be performed.
【0014】蒸発缶における加熱・蒸発用熱源として
は、ガスだきボイラーからの蒸気、コジェネレーション
設備で発生する蒸気、種々の場所で発生する低温・低圧
蒸気を圧縮機で圧縮・昇圧した蒸気、高温・高圧の蒸気
を減圧した蒸気、加熱した熱媒体、高温燃焼排ガス、電
気などが利用される。以下においては、蒸気を以て蒸発
缶における加熱・蒸発用熱源を代表させる。The heat source for heating / evaporating in the evaporator includes steam from a gas-fired boiler, steam generated in a cogeneration facility, low-temperature / low-pressure steam generated in various places, compressed / pressurized by a compressor, and high-temperature. -High-pressure steam reduced in pressure, heated heat medium, high-temperature combustion exhaust gas, electricity, etc. are used. In the following, the heat source for heating and evaporating in the evaporator is represented by steam.
【0015】蒸発缶(以下「カランドリア型蒸発缶」を
もって代表させる)においては、従来技術で生じていた
伝熱管外側への液分散不良などによる伝熱係数の低下を
防ぐために、カランドリア型蒸発缶(以下単に「カラン
ドリア」ということもある)内液面から伝熱管上部まで
の液深さの上方から15〜50%程度の位置に液を導入する
ことが好ましい。これにより、液は、伝熱管内に常時保
持された状態で、伝熱管外の蒸気により加熱・蒸発され
る。従来の液供給方法では、発泡を促進することがあ
り、その結果濃縮処理が不能となることがあった。しか
るに、本発明方法では、前記の液の分散による流速の低
下ならびに発泡促進などの問題は、解消される。In the evaporator (hereinafter referred to as "calandria evaporator"), a calandria evaporator (hereinafter referred to as "calandria evaporator") is used in order to prevent a decrease in heat transfer coefficient due to poor liquid dispersion to the outside of the heat transfer tube caused by the prior art. The liquid is preferably introduced at a position of about 15 to 50% from above the liquid depth from the inner liquid level to the upper part of the heat transfer tube. Thus, the liquid is heated and evaporated by the steam outside the heat transfer tube while being constantly held in the heat transfer tube. In the conventional liquid supply method, foaming may be promoted, and as a result, concentration processing may not be performed. However, in the method of the present invention, the above-mentioned problems such as a decrease in the flow rate due to the dispersion of the liquid and promotion of foaming are eliminated.
【0016】さらに、塩酸および水の蒸気が蒸発缶を出
る前流側(蒸発缶内液面の上方空間部)に充填物、フィル
ター、たれ壁など(デミスター)を配置することによ
り、原液飛沫あるいは缶内液飛沫の蒸気側への同伴混入
を防止することができる。Further, by disposing a filler, a filter, a dripping wall, etc. (demister) on the upstream side (space above the liquid level in the evaporator) before the vapor of hydrochloric acid and water leaves the evaporator, undiluted liquid or It is possible to prevent entrainment of liquid droplets in the can on the vapor side.
【0017】また、必要に応じ、カランドリア内塔底液
をポンプで抜き出し、原液導入位置へ循環することによ
り、伝熱管内の液流速を増大させて、伝熱係数を上げる
ことができる。If necessary, the bottom liquid in the calandria is withdrawn by a pump and circulated to the undiluted liquid introduction position, so that the liquid flow velocity in the heat transfer tube can be increased and the heat transfer coefficient can be increased.
【0018】伝熱管外の蒸気は、伝熱管内の液を加熱
し、蒸発させた後、凝縮する。本発明においては、蒸発
缶内伝熱管外の蒸気の凝縮液面高さを一定に制御するた
めに、スチームトラップあるいは凝縮液槽を設けること
により、圧縮蒸気の系外への排出による損失を防いでい
る。凝縮液は、スチームトラップあるいは凝縮液槽を経
て系外に排出される。この凝縮液は、ボイラー給水とし
て、あるいは蒸発缶塔底部から抜き出された濃縮液中の
鉄濃度を200g/l以下として、濃縮液の固化を防止するた
めの希釈水などとして、再利用することができる。The vapor outside the heat transfer tube heats the liquid inside the heat transfer tube, evaporates, and then condenses. In the present invention, a steam trap or a condensate tank is provided in order to keep the condensate level of the vapor outside the heat transfer tube in the evaporator constant, thereby preventing loss due to discharge of the compressed vapor out of the system. In. The condensate is discharged out of the system via a steam trap or a condensate tank. This condensate can be reused as boiler feed water or as diluting water to prevent solidification of the concentrate by reducing the iron concentration in the concentrate extracted from the bottom of the evaporator to 200 g / l or less. Can be.
【0019】圧縮機の効率、消費電力などに影響を与え
るカランドリア内の空気などの非凝縮性ガスは、伝熱管
外側の蒸気ラインに設けた電磁弁の開閉により、カラン
ドリア外へ排出される。排出ガスは、ガス中の成分に対
応して、必要ならば、活性炭吸着などにより所定成分を
除去した後、或いは濃縮液タンク内の液にバブリングさ
せて所定成分を吸収除去した後、大気中に放出される。
電磁弁の開閉は、カランドリア内圧力と連動させる方
法、任意のタイマー設定などにより、自動的に行われ
る。Non-condensable gas such as air in calandria that affects the efficiency and power consumption of the compressor is discharged out of calandria by opening and closing a solenoid valve provided in a steam line outside the heat transfer tube. Exhaust gas is released into the atmosphere after removal of a predetermined component by activated carbon adsorption or the like, if necessary, or after bubbling the liquid in the concentrated solution tank to absorb and remove the predetermined component, in accordance with the components in the gas. Released.
The opening and closing of the solenoid valve is automatically performed by a method linked to the pressure in the calandria, an arbitrary timer setting, and the like.
【0020】濃縮液は、濃縮器内の液面計からの信号を
受けて、塔底部から制御弁を通しておよび/または蒸発
缶内の液面に相当する位置で蒸発缶底部と連通するオー
バーフロー管から、排出される。本発明においては、好
ましくは80〜100℃程度の加熱条件下に蒸発缶から濃縮
液を抜き出し、これを希釈して、その鉄濃度を200g/l以
下とする。The concentrated liquid is supplied with a signal from a liquid level gauge in the concentrator, through a control valve from the bottom of the column and / or from an overflow pipe communicating with the bottom of the evaporator at a position corresponding to the liquid level in the evaporator. Is discharged. In the present invention, the concentrated liquid is extracted from the evaporator under a heating condition of preferably about 80 to 100 ° C., and the concentrated liquid is diluted to make its iron concentration 200 g / l or less.
【0021】廃塩酸処理操作を停止する場合には、蒸発
缶内温度を109〜113℃程度(より好ましくは110〜112℃
程度)に調整するか、および/または廃塩酸原液量に対
する蒸留液量の割合を調整する(すなわち、蒸留液量を
減少させる)か、および/または廃塩酸原液に代えて希
釈液(蒸発缶で得られた蒸気の凝縮水、廃塩酸原液およ
び水の少なくとも1種)を供給することにより、蒸発缶
内濃縮液中の鉄濃度を200g/l以下とする。When the waste hydrochloric acid treatment operation is stopped, the temperature in the evaporator is set to about 109 to 113 ° C. (more preferably, 110 to 112 ° C.).
Degree) and / or adjust the ratio of the amount of distillate to the amount of waste hydrochloric acid stock solution (that is, reduce the amount of distillate solution), and / or dilute the waste hydrochloric acid stock solution (with an evaporator). By supplying the condensed water of the obtained steam, at least one of the undiluted hydrochloric acid solution and water), the iron concentration in the concentrated liquid in the evaporator is adjusted to 200 g / l or less.
【0022】蒸発缶から抜き出された濃縮液を再度濃縮
させて、その鉄濃度を350g/l以上、より好ましくは400g
/l以上とすることにより、濃縮液中の残余の塩酸をほぼ
全量塩酸水として回収するとともに、塩化鉄を主成分と
する固体状生成物を分離することができる。この固体状
生成物からは、有用な塩化鉄を回収することができる。The concentrated liquid extracted from the evaporator is concentrated again to have an iron concentration of 350 g / l or more, more preferably 400 g / l.
By setting the concentration to / l or more, almost all of the residual hydrochloric acid in the concentrated liquid is recovered as aqueous hydrochloric acid, and a solid product containing iron chloride as a main component can be separated. From this solid product, useful iron chloride can be recovered.
【0023】カランドリア内の運転圧力が減圧系である
場合には、伝熱管外側の蒸気ラインに設けた電磁弁の後
流側にこの電磁弁の開閉と連動する真空ポンプを設け
る。When the operating pressure in the calandria is a pressure reducing system, a vacuum pump is provided on the downstream side of the solenoid valve provided in the steam line outside the heat transfer tube in conjunction with opening and closing of the solenoid valve.
【0024】必要ならば、スタートアップ時の装置全体
の昇温のために、或いは長期運転後の予熱器やカランド
リア伝熱管の汚れによる蒸発量の低下に応じて、補助熱
源(ガスだきボイラーからの蒸気、コジェネレーション
設備で発生する蒸気、低温・低圧蒸気を圧縮機で圧縮・
昇圧した蒸気など)を、カランドリア内底部または圧縮
器出口ラインへ導入する。If necessary, an auxiliary heat source (vapor from a gas-fired boiler) can be used to raise the temperature of the entire system at startup, or to reduce the amount of evaporation due to contamination of the preheater or calandria heat transfer tube after long-term operation. , Steam generated by cogeneration equipment, low-temperature, low-pressure steam
Pressurized steam) is introduced into the calandria inner bottom or compressor outlet line.
【0025】本発明においては、加熱源としての蒸気が
蒸発缶内の廃塩酸原液を加熱・蒸発させるに必要な温度
・圧力を有する場合には、そのままあるいは減圧して使
用する。低温・低圧蒸気を使用する場合には、圧縮機に
より、圧縮・昇圧した後、使用する。圧縮機としては、
特に限定されるものではないが、従来の濃縮技術では用
いられたことがなかったスクリュー型圧縮機であること
が好ましい。スクリュー型圧縮機は、次の様な特性を備
えている。 a.低速回転時から高圧力・高効率運転が可能である。 b.高い応答性を持っている。 c.小型、コンパクトで据え付けが容易である。 d.発生蒸気量に対応して、スクリュー型圧縮機のモー
ター回転数を制御することができる。In the present invention, when the steam as a heating source has a temperature and a pressure necessary to heat and evaporate the waste hydrochloric acid stock solution in the evaporator, the steam is used as it is or under reduced pressure. When using low-temperature, low-pressure steam, it is used after being compressed and pressurized by a compressor. As a compressor,
Although not particularly limited, it is preferable that the screw type compressor has not been used in the conventional concentration technology. The screw compressor has the following characteristics. a. High pressure and high efficiency operation is possible from low speed rotation. b. Has high responsiveness. c. Small, compact and easy to install. d. The motor rotation speed of the screw compressor can be controlled according to the amount of generated steam.
【0026】この様なスクリュー型圧縮機は、通常アル
ミニウム合金製のケーシング部に一対の雄、雌シリンダ
ーを内蔵する構造を有している。以下においては、スク
リュー型圧縮機を使用する実施態様について説明を行
う。Such a screw type compressor has a structure in which a pair of male and female cylinders is usually built in a casing part made of aluminum alloy. In the following, an embodiment using a screw compressor will be described.
【0027】上記の様な構造を有し、且つ効果を発揮す
るスクリュー型圧縮機を使用する場合には、従来の圧縮
機を使用する場合に比して、設備費および運転費が大幅
に安価となる。When a screw-type compressor having the above-mentioned structure and exerting its effects is used, the equipment and operation costs are significantly lower than when a conventional compressor is used. Becomes
【0028】本発明で使用するスクリュー型圧縮機は、
一例として、最大吐出圧力として160KPa、最高許容吐出
温度として160℃、最大吸気量として760m3/hr(空気換
算)、圧縮比として約2.3という高い特性を発揮するこ
とができる。The screw type compressor used in the present invention comprises:
As an example, high characteristics such as a maximum discharge pressure of 160 KPa, a maximum allowable discharge temperature of 160 ° C., a maximum intake amount of 760 m 3 / hr (in terms of air), and a compression ratio of about 2.3 can be exhibited.
【0029】従来の圧縮機としてのルーツブロワーでの
圧縮比限界が約1.8程度で、全断熱効率が約45〜60%で
あるのに対し、スクリュー型圧縮機は、圧縮比1.5で全
断熱効率約65%、圧縮比2〜2.3で約70%と高い性能を発
揮することができる。The compression ratio limit of a conventional roots blower as a compressor is about 1.8, and the total adiabatic efficiency is about 45 to 60%, whereas the screw type compressor has a total adiabatic efficiency of about 1.5 at a compression ratio of 1.5. High performance of about 65% and about 70% with a compression ratio of 2 to 2.3 can be achieved.
【0030】スクリュー型圧縮機のローターは、熱膨張
を少なくし、必要クリアランスを小さくするために、好
ましくは、膨張係数の少ないアルミニウム合金を用い、
ローターの表面にフッ素樹脂(たとえば、デュポン社か
ら商標名「テフロン」として市販されている)系コーテ
ィング材を塗布する。圧縮機は、必要蒸気量に応じて、
複数個設けることができる。The rotor of the screw compressor is preferably made of an aluminum alloy having a small expansion coefficient in order to reduce the thermal expansion and the required clearance.
A fluororesin (for example, commercially available from DuPont under the trade name “Teflon”)-based coating material is applied to the surface of the rotor. Depending on the required amount of steam, the compressor
A plurality can be provided.
【0031】従来、必要蒸気量に対応して、低温・低圧
の蒸気を圧縮機により吸引および吐出させて、蒸発缶
(以下「濃縮器」ということがある)内での蒸発を効率
よく行わせることは、圧縮機の制御上困難であった。本
発明で使用するスクリュー型圧縮機においては、圧縮機
の駆動源として高速回転型の誘導電動機からなるモータ
ーを使用し、このモーターの回転数制御機構としてイン
バーター装置を用いる。すなわち、冷却器後流側に設け
た流量計および/または蒸発缶内温度を測定する温度計
により、蒸気発生量および/または温度を検出し、この
入力信号を調節計に送り、この調節計からの出力信号を
インバーターに入力して、蒸気発生量が一定となる様に
するか、或いは蒸気発生量に対応してモーターの回転数
を増減することができる。その結果、装置全体が簡略化
され、始動時などにおける制御も容易となる。Conventionally, low-temperature and low-pressure steam is sucked and discharged by a compressor in accordance with the required amount of steam, so that evaporation in an evaporator (hereinafter sometimes referred to as "concentrator") is efficiently performed. It was difficult to control the compressor. In the screw compressor used in the present invention, a motor composed of a high-speed rotation type induction motor is used as a driving source of the compressor, and an inverter device is used as a rotation speed control mechanism of the motor. That is, the amount of steam generation and / or the temperature is detected by a flow meter provided on the downstream side of the cooler and / or a thermometer for measuring the temperature inside the evaporator, and this input signal is sent to the controller. Is output to an inverter so that the amount of generated steam is constant, or the number of revolutions of the motor can be increased or decreased in accordance with the amount of generated steam. As a result, the entire apparatus is simplified, and control at the time of starting or the like becomes easy.
【0032】また、圧縮機前流側の蒸気ラインにおいて
は、保温および/またはヒーターによる加熱により、圧
縮機入口側での蒸気の凝縮を防止することができる。In the steam line upstream of the compressor, condensation of steam at the compressor inlet side can be prevented by keeping the temperature and / or heating with a heater.
【0033】本発明においては、装置の小型化とコスト
低減を目的として、原液の予熱のためにプレート型熱交
換器を用いることもできる。この予熱器および原液導入
ライン内の圧力を蒸発缶内圧力よりも高くすることによ
り、予熱器内での気泡生成による伝熱係数の低下を防ぐ
ため、予熱器出口(例えばカランドリア型蒸発缶などの
蒸発缶入口)側に背圧弁を設けることもできる。In the present invention, a plate-type heat exchanger may be used for preheating the undiluted solution for the purpose of reducing the size and cost of the apparatus. By setting the pressure in the preheater and the stock solution introduction line higher than the pressure in the evaporator, the preheater outlet (e.g., calandria evaporator, etc.) A back pressure valve may be provided on the side of the evaporator inlet).
【0034】以下図面を参照しつつ、本発明をさらに詳
細に説明する。なお、以下においては、廃塩酸の濃縮に
ついて説明するが、本発明は、その作動原理上、その他
の廃酸、廃アルカリ液、廃水、さらには液状食品などの
濃縮にも適用できることはいうまでもない。Hereinafter, the present invention will be described in more detail with reference to the drawings. In the following, the concentration of waste hydrochloric acid will be described, but it is needless to say that the present invention can be applied to the concentration of other waste acids, waste alkaline liquids, waste water, and even liquid foods on the principle of operation. Absent.
【0035】図1は、本発明による廃塩酸の濃縮処理の
一例を示すフローシートである。濃縮すべき廃塩酸は、
タンク1から、ライン2を経て、ポンプ3において所定
圧力まで昇圧された後、ライン4から濃縮器(カランド
リア型蒸発缶)12へ導入される。図示はしないが、必
要ならば、ポンプ3の前流側にストレーナーを設け、後
流側に流量計を設けることができる。廃塩酸は、濃縮器
12内の液面から伝熱管上部までの液深さの15〜50%の
位置(液面から下方に向けての位置)で濃縮器に導入さ
れる。FIG. 1 is a flow sheet showing an example of the treatment for concentrating waste hydrochloric acid according to the present invention. The waste hydrochloric acid to be concentrated is
After the pressure is increased from the tank 1 to a predetermined pressure in the pump 3 through the line 2, it is introduced into the concentrator (calandria evaporator) 12 from the line 4. Although not shown, if necessary, a strainer can be provided on the upstream side of the pump 3 and a flow meter can be provided on the downstream side. The waste hydrochloric acid is introduced into the concentrator at a position of 15 to 50% of the liquid depth from the liquid level in the concentrator 12 to the upper part of the heat transfer tube (position downward from the liquid level).
【0036】伝熱缶内での廃塩酸の加熱は、通常廃塩酸
の発生源である鋼線製造/加工工場、鋼板製造/加工工
場、メッキ工場などで発生する回収蒸気(ボイラーで発
生する蒸気、コジェネレーション設備で発生する蒸気、
廃熱回収により発生する蒸気など)により行う。The heating of waste hydrochloric acid in the heat transfer can is carried out by recovering steam (steam generated by a boiler) generated in a steel wire manufacturing / processing plant, a steel plate manufacturing / processing plant, a plating plant, etc., which are sources of waste hydrochloric acid. , Steam generated in cogeneration facilities,
(E.g., steam generated by waste heat recovery).
【0037】この際、利用すべき蒸気が低温・低圧(110
℃以下/0.15MPa以下程度)である場合には、圧縮機で予
め圧縮・昇温を行う。すなわち、この蒸気をライン6を
経て圧縮機7に供給し、ここで圧縮・昇温した後、ライ
ン9および10を経て、濃縮器12の伝熱管外側に供給
し、伝熱管内の液を加熱し、蒸発させる。高温・高圧の
蒸気が得られる場合には、この蒸気をそのままライン9
および10を経て、濃縮器に供給する。この様な操作に
より、伝熱管外の蒸気自体は、凝縮・液化する。凝縮液
は、濃縮器12内の伝熱管の下部に接続されたライン1
8からスチームトラップ19を経て、ライン20から排
出される。この凝縮液は、必要に応じ、ボイラー5への
給水用水として、あるいはライン24から抜き出される
濃縮液の固化防止用希釈水などとして、再利用される。
さらに、この凝縮水は、再利用に先立って、ポンプ3の
出口側のライン4に設けた予熱器(図示せず)におい
て、原液の予熱源として利用することができる。At this time, the steam to be used is a low temperature / low pressure (110
(° C. or less / about 0.15 MPa or less), compression and temperature increase are performed in advance by a compressor. That is, this vapor is supplied to the compressor 7 through the line 6, where it is compressed and heated, and then supplied to the outside of the heat transfer tube of the concentrator 12 through lines 9 and 10, thereby heating the liquid in the heat transfer tube. And evaporate. When high-temperature and high-pressure steam is obtained, this steam is directly transferred to line 9
And 10 to feed the concentrator. By such an operation, the steam itself outside the heat transfer tube is condensed and liquefied. The condensate is supplied to the line 1 connected to the lower part of the heat transfer tube in the concentrator 12.
From 8, the steam is discharged from the line 20 through the steam trap 19. This condensate is reused as necessary for supplying water to the boiler 5 or as diluting water for preventing solidification of the concentrated liquid extracted from the line 24.
Further, this condensed water can be used as a preheat source of the stock solution in a preheater (not shown) provided in the line 4 on the outlet side of the pump 3 before reuse.
【0038】低温・低圧の蒸気圧縮機7としては、先述
の通り、アルミニウム合金製ケーシング内に一対の雄お
よび雌ローターを内蔵した形式のスクリュー型圧縮機を
使用することが好ましい。As described above, as the low-temperature and low-pressure steam compressor 7, it is preferable to use a screw-type compressor in which a pair of male and female rotors are built in an aluminum alloy casing.
【0039】濃縮器12内で発生した塩酸および水の蒸
気は、ライン13を経て、冷却水ライン15を備えた冷
却器14で冷却され、凝縮した後、ライン16を経て、
蒸留液タンク17に溜められる。この様に再生された塩
酸水溶液は、鉄鋼製品の表面処理に再度使用することが
できる。The vapor of hydrochloric acid and water generated in the concentrator 12 is cooled by a cooler 14 having a cooling water line 15 through a line 13 and condensed.
It is stored in the distillate tank 17. The aqueous hydrochloric acid solution thus regenerated can be used again for surface treatment of steel products.
【0040】濃縮器12の上部空間には、充填物、フィ
ルター、たれ壁などのデミスター(「26」として示す)
を配設することにより、原液飛沫あるいは缶内液飛沫の
上記への同伴混入を防止することができる。In the upper space of the concentrator 12, a demister (shown as "26") such as a filler, a filter, and a falling wall is provided.
By disposing the above, the entrainment of the undiluted liquid droplets or the liquid droplets in the can into the above can be prevented.
【0041】圧縮機7の効率および消費電力などに影響
を与える濃縮器12内の空気などの非凝縮性ガスは、伝
熱管外側の蒸気ライン21に設けた電磁弁22の開閉に
より蒸発缶外へ排出される。この電磁弁22の開閉は、
濃縮器12内圧力と連動させることにより行ってもよ
く、或いはタイマー設定により自動的に行ってもよい。
必要ならば、排出ガスを活性炭などによる吸着処理に供
したり、或いは濃縮液タンク25内の液中にバブリング
させる。A non-condensable gas such as air in the concentrator 12 which affects the efficiency and power consumption of the compressor 7 is discharged to the outside of the evaporator by opening and closing a solenoid valve 22 provided in a steam line 21 outside the heat transfer tube. Is discharged. The opening and closing of this solenoid valve 22
It may be performed in conjunction with the pressure in the concentrator 12, or may be performed automatically by setting a timer.
If necessary, the exhaust gas is subjected to an adsorption treatment using activated carbon or the like, or is bubbled in the liquid in the concentrated liquid tank 25.
【0042】濃縮器12内に蓄積する濃縮液は、濃縮器
12内の液面計(図示せず)からの信号により、濃縮器
12の底部からのライン24および制御弁(図示せず)
を通じて、再濃縮槽(晶析槽)132に送られ、ここで間
接加熱される。濃縮液から発生する残存塩酸の蒸気は、
ライン133からライン13に送られて、先述の塩酸と
水の蒸気と混合され、冷却器14で冷却され、塩酸水の
一部として回収される。再濃縮槽132で生成する塩化
鉄を主成分とする固体成分は、ライン134を経て塩化
鉄槽25に溜められる。あるいは、濃縮液は、制御弁を
用いることなく、蒸発缶内の液面に相当する位置におい
て、濃縮器12の底部に連通するオーバーフロー管(図
示せず)から抜き出すことも可能である。The concentrate accumulated in the concentrator 12 is supplied to a line 24 from the bottom of the concentrator 12 and a control valve (not shown) by a signal from a liquid level gauge (not shown) in the concentrator 12.
Through the re-concentration tank (crystallization tank) 132, where it is indirectly heated. The residual hydrochloric acid vapor generated from the concentrated liquid is
The water is sent from the line 133 to the line 13, mixed with the above-described hydrochloric acid and water vapor, cooled by the cooler 14, and collected as a part of the hydrochloric acid water. The solid component mainly composed of iron chloride generated in the re-concentration tank 132 is stored in the iron chloride tank 25 via the line 134. Alternatively, the concentrated liquid can be extracted from an overflow pipe (not shown) communicating with the bottom of the concentrator 12 at a position corresponding to the liquid level in the evaporator without using a control valve.
【0043】また、必要に応じて、濃縮器12内の液を
液抜き出しライン24から循環ポンプ(図示せず)によ
り抜き出し、原液ライン4へ循環することにより、伝熱
管内の液流速を増大させ、伝熱係数を上げることができ
る濃縮器12内の運転圧力が減圧系である場合には、電
磁弁22の後流側に電磁弁22の開閉と連動する真空ポ
ンプ(図示せず)を設ける。減圧系で運転する場合に
は、ライン20上に凝縮液ポンプ(図示せず)を設け、
ライン24上に濃縮液ポンプ(図示せず)を設ける必要
がある。Further, if necessary, the liquid in the concentrator 12 is withdrawn from the liquid withdrawing line 24 by a circulation pump (not shown) and circulated to the raw liquid line 4 to increase the liquid flow rate in the heat transfer tube. When the operating pressure in the concentrator 12 capable of increasing the heat transfer coefficient is a pressure reducing system, a vacuum pump (not shown) is provided on the downstream side of the solenoid valve 22 in conjunction with opening and closing of the solenoid valve 22. . When operating in a reduced pressure system, a condensate pump (not shown) is provided on the line 20,
A concentrate pump (not shown) must be provided on line 24.
【0044】また、必要に応じ、スタートアップ時の加
熱・昇温のために、あるいは長期運転後に濃縮器12の
伝熱管などの汚れによる蒸発量の低下に応じて、補助熱
源として、各種の蒸気源(例えばボイラー5)からの蒸気
をライン6、圧縮機7、ライン9および10を経て、あ
るいはライン6、バイパスライン8、ライン9および1
0を経て、ライン11から導入する。As necessary, various steam sources may be used as auxiliary heat sources for heating and raising the temperature during start-up or for reducing the amount of evaporation due to contamination of the heat transfer tubes of the concentrator 12 after long-term operation. (Eg, boiler 5) via line 6, compressor 7, lines 9 and 10 or line 6, bypass line 8, lines 9 and 1
Introduce from line 11 via 0.
【0045】なお、濃縮器12の伝熱管などの汚れとそ
れに伴う伝熱係数の低下を生じた場合には、運転中に廃
塩酸の供給を一時的に中断し、工業用水を供給すること
により、汚れを洗浄・除去することができる。When contamination of the heat transfer tube of the concentrator 12 and the resulting decrease in the heat transfer coefficient occur, the supply of waste hydrochloric acid is temporarily interrupted during operation and industrial water is supplied. And dirt can be washed and removed.
【0046】図2は、本発明による廃塩酸の濃縮処理の
他の一例を示すフローシートである。図2において、図
1と同機能の構成要素は、図1と同じ番号で示してあ
り、その機能については、説明を省略することがある。FIG. 2 is a flow sheet showing another example of the treatment for concentrating waste hydrochloric acid according to the present invention. 2, components having the same functions as those in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and descriptions of the functions may be omitted.
【0047】濃縮すべき廃塩酸原液は、図1におけると
同様に、タンク1から、ライン2を経て、廃液ポンプ3
において所定圧力まで昇圧された後、ライン4からライ
ン105を経て蒸発缶12(この場合、横型熱交換器タ
イプの蒸発缶)の伝熱管の上側(上部)の分散器126
に導入される。図示はしないが、必要ならば、ポンプ3
の前流側にストレーナーを設け、後流側に流量計を設け
ることができる。分散器126は、伝熱管に対して廃塩
酸を均一に分散ないし滴下させる構造となっている。As in FIG. 1, a waste hydrochloric acid stock solution to be concentrated is supplied from a tank 1 through a line 2 to a waste liquid pump 3.
After the pressure is increased to a predetermined pressure in the above, the disperser 126 on the upper side (upper part) of the heat transfer tube of the evaporator 12 (in this case, the horizontal heat exchanger type evaporator) via the line 4 to the line 105
Will be introduced. Although not shown, if necessary, pump 3
Can be provided with a strainer on the upstream side and a flow meter on the downstream side. The disperser 126 has a structure in which the waste hydrochloric acid is uniformly dispersed or dropped on the heat transfer tube.
【0048】蒸発缶12内で発生した塩酸および水の蒸
気は、ラシッヒリングなどの充填物および/または活性
炭などの濾過材を充填した充填部128およびライン1
3を経て冷却器14において冷却・凝縮された後、ライ
ン16を経て蒸留液タンク17に溜められる。The vapor of hydrochloric acid and water generated in the evaporator 12 is supplied to a filling section 128 filled with a filler such as a Raschig ring and / or a filtering material such as activated carbon and a line 1.
After being cooled and condensed in the cooler 14 through 3, it is stored in the distillate tank 17 through the line 16.
【0049】蒸発缶内での廃塩酸の加熱は、例えば、コ
ジェネレーション設備におけるボイラー106で発生す
る低圧蒸気(1kg/cm2G程度)を利用して行う。すなわ
ち、この蒸気をライン107、108を経て圧縮機10
9に供給し、ここで圧縮・昇温した後、ライン110を
経て、蒸発缶12の伝熱管127の内側に供給し、伝熱
管127外の液を加熱し、蒸発させる。これにより、伝
熱管内の蒸気自体は、凝縮・液化する。この凝縮液は、
蒸発缶12内の伝熱管の下部に接続されたライン118
から凝縮液槽119に溜められる。The heating of the waste hydrochloric acid in the evaporator is performed, for example, using low-pressure steam (about 1 kg / cm 2 G) generated in the boiler 106 in the cogeneration facility. That is, this steam is passed through the lines 107 and 108 to the compressor 10
9, where it is compressed and heated, and then supplied via line 110 to the inside of the heat transfer tube 127 of the evaporator 12 to heat and evaporate the liquid outside the heat transfer tube 127. Thereby, the steam itself in the heat transfer tube is condensed and liquefied. This condensate is
A line 118 connected to the lower part of the heat transfer tube in the evaporator 12
From the condensate tank 119.
【0050】圧縮機109としては、先述の通り、アル
ミニウム合金製ケーシング内にアルミニウム合金製の一
対の雄および雌ローターを内蔵した形式のスクリュー型
圧縮機を使用することが好ましい。As described above, as the compressor 109, it is preferable to use a screw-type compressor in which a pair of male and female rotors made of an aluminum alloy are built in an aluminum alloy casing.
【0051】未凝縮蒸気の系外への排出による損失を防
ぐため、凝縮液槽119での液面は、蒸発缶12から凝
縮液槽119への凝縮液取り出しライン118の位置よ
りも高くなるように制御する。凝縮液槽119の気相部
は、ライン120を経て、圧縮前流側の蒸発缶12に接
続されている。凝縮液は、必要に応じ、ボイラー106
への給水用水として、あるいは濃縮液の固化防止用希釈
水などとして、ライン121から抜き出され、再利用さ
れる。さらに、この凝縮液は、再利用に先立って、ポン
プ3の出口側のライン4に設けた予熱器(図示せず)に
おいて、原液の予熱源として利用することができる。In order to prevent loss due to discharge of uncondensed vapor to the outside of the system, the liquid level in the condensate tank 119 is higher than the position of the condensate take-out line 118 from the evaporator 12 to the condensate tank 119. To control. The gas phase portion of the condensate tank 119 is connected to the evaporator 12 on the upstream side of the compression via a line 120. The condensate is supplied to the boiler 106 if necessary.
The water is withdrawn from the line 121 and reused as water for supplying water to the water or as diluting water for preventing solidification of the concentrated liquid. Further, this condensate can be used as a preheat source of the stock solution in a preheater (not shown) provided in the line 4 on the outlet side of the pump 3 before reuse.
【0052】蒸発缶12の上部空間には、デミスター1
28を配設することにより、原液飛沫あるいは缶内液飛
沫の蒸気への同伴混入を防止することができる。The demister 1 is located in the upper space of the evaporator 12.
By arranging 28, it is possible to prevent entrainment of the undiluted liquid or liquid in the can into the vapor.
【0053】圧縮機109の効率および消費電力などに
影響を与える蒸発缶12内の空気などの非凝縮性ガス
は、蒸気ライン22に設けた電磁弁23の開閉により蒸
発缶外へ排出される。この電磁弁23の開閉は、蒸発缶
12内圧力と連動させることにより行ってもよく、或い
はタイマー設定により自動的に行ってもよい。必要なら
ば、排出ガスを活性炭などによる吸着処理に供したり、
或いは濃縮液タンク25内の液中にバブリングさせる。A non-condensable gas such as air in the evaporator 12 which affects the efficiency and power consumption of the compressor 109 is discharged out of the evaporator by opening and closing a solenoid valve 23 provided in the vapor line 22. The opening and closing of the electromagnetic valve 23 may be performed in conjunction with the pressure in the evaporator 12 or may be automatically performed by setting a timer. If necessary, use the exhaust gas for adsorption treatment with activated carbon, etc.
Alternatively, bubbling is performed in the liquid in the concentrated liquid tank 25.
【0054】蒸発缶12内に蓄積する濃縮液は、蒸発缶
12内の液面計(図示せず)からの信号により、蒸発缶
12の底部からのライン129および制御弁(図示せ
ず)を通じて、再濃縮槽(晶析槽)132に送られ、ここ
で間接加熱される。濃縮液から発生する残存塩酸の蒸気
は、ライン133からライン13に送られて、先述の塩
酸と水の蒸気と混合され、冷却器14で冷却され、塩酸
水の一部として回収される。再濃縮槽132で生成する
塩化鉄を主成分とする固体成分は、ライン134を経て
塩化鉄槽25に貯められる。あるいは、濃縮液は、制御
弁を用いることなく、蒸発缶内の液面に相当する位置に
おいて、蒸発缶12の底部に連通するオーバーフロー管
(図示せず)から抜き出すことも可能である。The concentrated liquid accumulated in the evaporator 12 is supplied by a signal from a liquid level gauge (not shown) in the evaporator 12 through a line 129 from the bottom of the evaporator 12 and a control valve (not shown). Is sent to a re-concentration tank (crystallization tank) 132 where it is heated indirectly. The residual hydrochloric acid vapor generated from the concentrated liquid is sent from the line 133 to the line 13 and mixed with the aforementioned hydrochloric acid and water vapor, cooled by the cooler 14 and recovered as a part of the hydrochloric acid water. The solid component mainly composed of iron chloride generated in the re-concentration tank 132 is stored in the iron chloride tank 25 via the line 134. Alternatively, the concentrated liquid can be extracted from an overflow pipe (not shown) communicating with the bottom of the evaporator 12 at a position corresponding to the liquid level in the evaporator without using a control valve.
【0055】排出された濃縮液の固化を防止する必要が
ある場合には、水または前記ライン121からの凝縮水
をライン129内または凝縮液槽25内に供給し、濃縮
液を希釈すればよい。When it is necessary to prevent the discharged concentrated liquid from solidifying, water or condensed water from the line 121 may be supplied into the line 129 or the condensed liquid tank 25 to dilute the concentrated liquid. .
【0056】また、必要に応じて、蒸発缶12内の液を
液抜き出しライン129から循環ポンプ130により抜
き出し、原液ライン5へ循環することにより、伝熱管1
27外の液流速を増大させ、伝熱係数を上げることがで
きる蒸発缶器12内の運転圧力が減圧系である場合に
は、電磁弁23の後流側に電磁弁23の開閉と連動する
真空ポンプ(図示せず)を設ける。Further, if necessary, the liquid in the evaporator 12 is withdrawn from the liquid withdrawing line 129 by the circulation pump 130 and circulated to the undiluted liquid line 5 so that the heat transfer tube 1
When the operating pressure in the evaporator 12 that can increase the heat flow coefficient by increasing the liquid flow rate outside the system 27 is a pressure-reducing system, the opening and closing of the solenoid valve 23 is linked to the downstream side of the solenoid valve 23. A vacuum pump (not shown) is provided.
【0057】また、必要に応じ、スタートアップ時の加
熱・昇温のために、あるいは長期運転後に蒸発缶12の
伝熱管などの汚れによる蒸発量の低下に応じて、補助熱
源として、例えばガスだきボイラー106からの蒸気を
ライン107およびライン111から導入する。If necessary, for the purpose of heating / heating at start-up, or after a long-term operation, as the amount of evaporation due to contamination of the heat transfer tube of the evaporator 12 decreases, an auxiliary heat source such as a gas-fired boiler may be used. Steam from 106 is introduced from lines 107 and 111.
【0058】本発明は、各種の廃酸液、廃アルカリ液の
濃縮処理のみならず、各種の産業廃水、洗浄廃水、写真
現像液、定着液および洗浄廃水などの濃縮・減容化、原
液中の有用成分或いは不純物の蒸留分離、食品工業での
溶液(だし汁、ジュース、ミルクなど)の濃縮などの広
い分野で利用できる。本発明は、その他の分野でも利用
可能であり、ここに例示した分野での利用に限定される
ものではない。The present invention not only concentrates various kinds of waste acid solution and waste alkali solution, but also concentrates and reduces the volume of various kinds of industrial waste water, washing waste water, photographic developer, fixing solution, washing waste water, etc. It can be used in a wide range of fields such as separation of useful components or impurities by distillation and concentration of solutions (dashi, juice, milk, etc.) in the food industry. The present invention can be used in other fields, and is not limited to use in the fields exemplified here.
【0059】[0059]
【発明の効果】本発明方法によれば、以下の様な顕著な
効果が達成される。 (1)従来技術に比して、原液の濃縮プロセスが簡単で
あり、設備が小型化されるので、設備費、運転経費など
が低減される。 (2)連続的に安定した運転が可能である。 (3)例えば、コジェネレーション設備などで比較的多
量に発生するにもかかわらず、従来ほとんど利用されて
いなかった低圧蒸気を有効に利用することができる。 (4)廃塩酸中に残存する有用な塩酸をほぼ全量回収
し、例えば、鉄鋼製品の洗浄などに再利用することがで
きる。 (5)廃塩酸中の塩酸および水分が回収される結果、残
分は塩化鉄を主成分とする固体となるので、塩化鉄の再
利用も可能となり、さらに廃棄処理量を減容化すること
ができ、従来法に比して、廃棄コストを低減することが
できる。 (6)濃縮装置の運転中および停止中の装置内での鉄塩
の固化による閉塞を伴うことなく、装置の安定した維持
管理を行うことができる。 (7)鋼線、鋼板などの鉄鋼製品の回分式あるいは連続
式表面処理過程で発生する廃塩酸を適宜あるいは連続的
に抜き出して濃縮することにより、塩酸を連続的に回収
して、繰り返し利用することができる。従って、鉄鋼製
品の表面処理工程に本発明による廃塩酸処理工程を併設
する場合には、表面処理工程における塩酸濃度および純
度がほぼ一定に保持されるので、鉄鋼製品の表面処理を
一定時間で安定して行うことができ、防食剤を使用する
ことなく、高品質の処理製品が得られる。According to the method of the present invention, the following remarkable effects are achieved. (1) Compared with the prior art, the process of concentrating the undiluted solution is simpler and the equipment is downsized, so that equipment costs, operation costs, and the like are reduced. (2) Continuous and stable operation is possible. (3) For example, low-pressure steam, which has rarely been used in the past, can be effectively used, despite being generated in a relatively large amount in a cogeneration facility or the like. (4) Almost all useful hydrochloric acid remaining in waste hydrochloric acid can be recovered and reused, for example, for washing steel products. (5) As a result of the recovery of hydrochloric acid and water in the waste hydrochloric acid, the residue becomes a solid containing iron chloride as a main component, so that iron chloride can be reused and the volume of waste disposal can be further reduced. Thus, the disposal cost can be reduced as compared with the conventional method. (6) The apparatus can be stably maintained without clogging due to solidification of the iron salt in the apparatus during operation and when the concentration apparatus is stopped. (7) By extracting or concentrating waste hydrochloric acid generated during batch or continuous surface treatment of steel products such as steel wires and steel sheets as appropriate or continuously, the hydrochloric acid is continuously collected and repeatedly used. be able to. Therefore, when the waste hydrochloric acid treatment step according to the present invention is added to the surface treatment step of the steel product, the hydrochloric acid concentration and the purity in the surface treatment step are kept almost constant, and the surface treatment of the steel product is stabilized in a certain time. A high-quality treated product can be obtained without using an anticorrosive.
【0060】[0060]
【実施例】以下に実施例を示し、本発明の特徴とすると
ころをより一層明らかにする。 実施例1〜4 蒸留液を回収するための冷却器および蒸留液受器を備え
た容量1リットルのガラス製濃縮器(シリコーン油を熱媒
体とする)を用いて、鋼線製造工場(A社)で発生した数種
の廃塩酸(それぞれ0.5リットル)の処理を大気圧下に行
った。The following examples are provided to further clarify the features of the present invention. Examples 1 to 4 Using a 1-liter glass concentrator (using silicone oil as a heat medium) equipped with a condenser for collecting distillate and a distillate receiver, a steel wire manufacturing plant (Company A) ) Were treated under atmospheric pressure with several kinds of waste hydrochloric acid (each 0.5 liter).
【0061】廃塩酸の分析値および処理条件を表1に示
す。Table 1 shows the analytical values of waste hydrochloric acid and the treatment conditions.
【0062】[0062]
【表1】 [Table 1]
【0063】注:実施例4では、連続槽とバッチ槽に由
来する廃塩酸を等量混合して、処理した。Note: In Example 4, an equal amount of waste hydrochloric acid from the continuous tank and the batch tank was mixed and treated.
【0064】濃縮液中の鉄(Fe+2+Fe+3)濃度が約300g/l
となる様に、廃塩酸を蒸留液と濃縮液とに分離した。蒸
留液の分析結果と蒸留液および遊離HClの回収率を表2
に示す。The concentration of iron (Fe +2 + Fe +3 ) in the concentrate is about 300 g / l
Was separated into a distillate and a concentrate. Table 2 shows the analysis results of the distillate and the recoveries of the distillate and free HCl.
Shown in
【0065】[0065]
【表2】 [Table 2]
【0066】注:遊離HClとは、Fe+2+Fe+3などと不結
合状態の分子状のHClを意味する。Note: Free HCl means molecular HCl that is not bound to Fe +2 + Fe +3 or the like.
【0067】蒸留液回収率=蒸留液量/廃塩酸量×100 遊離HCl回収率=蒸留液量×蒸留液中遊離HCl/廃塩酸量×
廃塩酸中HCl 以上の結果から、廃塩酸中の鉄濃度が高く、遊離HCl濃
度が低い場合には、蒸留液中のHCl濃度が低く、HCl回収
率が低いことが明らかである。 実施例5〜8 メッキ処理工場(B社)で発生した廃塩酸を原液とし、且
つ試験温度を各濃縮条件に対応した温度とする以外は実
施例1〜4の手法に準じて、処理を行った。廃塩酸の分
析値および処理条件を表3に示し、蒸留液の分析結果と
蒸留液および遊離HClの回収率を表4に示す。Distillate recovery rate = distillate amount / waste hydrochloric acid amount × 100 Free HCl recovery rate = distillate amount × free HCl in distillate / waste hydrochloric acid amount ×
From the results above, it is clear that when the iron concentration in the waste hydrochloric acid is high and the free HCl concentration is low, the HCl concentration in the distillate is low and the HCl recovery is low. Examples 5 to 8 The treatment was performed according to the method of Examples 1 to 4, except that the waste hydrochloric acid generated in the plating plant (Company B) was used as a stock solution and the test temperature was adjusted to a temperature corresponding to each concentration condition. Was. Table 3 shows the analytical values of waste hydrochloric acid and treatment conditions, and Table 4 shows the analytical results of the distillate and the recoveries of the distillate and free HCl.
【0068】[0068]
【表3】 [Table 3]
【0069】[0069]
【表4】 [Table 4]
【0070】濃縮液中の鉄濃度が387g/lの場合(実施例
8)には、塩酸を全量回収することができる。 実施例9 図1に示すフローに従って大気圧で本発明を実施した。
すなわち、鋼線製造工場(C社)で発生した廃塩酸(遊離HC
l=200g/l、Fe(Fe+2+Fe+3=88g/l)を使用して、連続的に
その処理を行い、蒸発缶内部温度と濃縮倍率との関係を
求めた。運転時の各機器における条件は、表5に示す通
りである。When the iron concentration in the concentrate is 387 g / l (Example 8), the entire amount of hydrochloric acid can be recovered. Example 9 The present invention was carried out at atmospheric pressure according to the flow shown in FIG.
In other words, waste hydrochloric acid (free HC) generated at a steel wire manufacturing plant (Company C)
The treatment was continuously performed using l = 200 g / l and Fe (Fe +2 + Fe +3 = 88 g / l), and the relationship between the evaporator internal temperature and the concentration ratio was determined. Table 5 shows the conditions for each device during operation.
【0071】[0071]
【表5】 [Table 5]
【0072】結果を表6に示す。Table 6 shows the results.
【0073】[0073]
【表6】 [Table 6]
【0074】表6に示す結果から明らかな様に、濃縮液
の温度または比重を測定することにより、原液中の鉄濃
度に対応して、濃縮倍率を決めることができる。As is clear from the results shown in Table 6, by measuring the temperature or specific gravity of the concentrated solution, the concentration ratio can be determined according to the iron concentration in the stock solution.
【0075】なお、各濃縮液を系外に取り出したとこ
ろ、常温/常圧下において、2.1倍濃縮時(鉄濃度185g/l)
には、濃縮液は固化しなかった。これに対し、3.5倍濃
縮時(鉄濃度307g/l)には濃縮液の約50%が、4倍濃縮時
(鉄濃度350g/l)には約90%が、5倍濃縮時(鉄濃度400g/
l)には約100%がそれぞれ固化し、結晶体として取り出
された。 実施例10〜11 図1に示すフローに従って大気圧で本発明を実施した。
すなわち、鋼線製造工場(d社)で発生した廃塩酸(連続槽
およびバッチ槽で発生した2種の廃塩酸の等量混合物)
を使用して、その処理を連続的に行った。運転時の各機
器における条件は、実施例9と同様である。廃塩酸の分
析値および濃縮倍率を表7に示す。When each concentrated solution was taken out of the system, it was concentrated at normal temperature / normal pressure by 2.1 times (iron concentration: 185 g / l).
In, the concentrate did not solidify. On the other hand, when concentrated 3.5 times (iron concentration 307 g / l), about 50% of the concentrated solution is concentrated 4 times.
(Iron concentration 350g / l) is about 90% when concentrated 5 times (iron concentration 400g / l
In l), about 100% of each was solidified and taken out as crystals. Examples 10 to 11 The present invention was carried out at atmospheric pressure according to the flow shown in FIG.
That is, waste hydrochloric acid generated in a steel wire manufacturing plant (Company d) (equivalent mixture of two types of waste hydrochloric acid generated in a continuous tank and a batch tank)
Was used to perform the treatment continuously. The conditions for each device during operation are the same as in Example 9. Table 7 shows the analysis value and the concentration ratio of the waste hydrochloric acid.
【0076】[0076]
【表7】 [Table 7]
【0077】濃縮液中の鉄(Fe+2+Fe+3)濃度が約300g/l
となる様に、廃塩酸を蒸留液と濃縮液とに分離した。蒸
留液および濃縮液の分析結果などを表8に示す。The concentration of iron (Fe +2 + Fe +3 ) in the concentrate is about 300 g / l
Was separated into a distillate and a concentrate. Table 8 shows the analysis results of the distillate and the concentrate.
【0078】[0078]
【表8】 [Table 8]
【0079】蒸発缶内濃縮液中の鉄濃度が約300g/lであ
る実施例10および11のいずれにおいても、安定した
長期濃縮処理が可能であった。In each of Examples 10 and 11 in which the concentration of iron in the concentrated liquid in the evaporator was about 300 g / l, stable long-term concentration treatment was possible.
【0080】また、蒸発缶外に取り出した濃縮液を再濃
縮槽(晶析装置)に送り、間接加熱してその鉄濃度を400g
/l以上とすることにより、実施例10および11のいず
れにおいても、濃縮液中の残余の塩酸をほぼ全量回収す
ることができ、また塩化鉄を主成分とする固体状物を回
収した。The concentrated solution taken out of the evaporator is sent to a re-concentration tank (crystallizer) and heated indirectly to reduce its iron concentration to 400 g.
By setting the ratio to / l or more, in each of Examples 10 and 11, almost all of the residual hydrochloric acid in the concentrated solution could be recovered, and a solid containing iron chloride as a main component was recovered.
【0081】さらに、廃塩酸の濃縮操作を停止した場合
にも、廃塩酸原液量に対する蒸留液量の割合を調整する
ことにより、すなわち濃縮倍率を3.4倍から2.3倍に低下
させることにより、蒸発缶内での鉄塩の固化を防止し、
蒸発缶の閉塞を防ぐことができた。 実施例12 カランドリア型蒸発缶を用い、実施例10の手法に準じ
て、減圧下にメッキ工場廃液(廃塩酸)の濃縮処理を行
った。処理条件を表9に示し、結果を表10に示す。Further, even when the operation of concentrating the waste hydrochloric acid is stopped, by adjusting the ratio of the amount of the distillate to the amount of the waste hydrochloric acid stock solution, that is, by reducing the concentration ratio from 3.4 times to 2.3 times, To prevent solidification of the iron salt within
Blockage of the evaporator could be prevented. Example 12 A plating plant waste liquid (waste hydrochloric acid) was concentrated under reduced pressure according to the method of Example 10 using a calandria evaporator. Table 9 shows the processing conditions, and Table 10 shows the results.
【0082】[0082]
【表9】 [Table 9]
【0083】[0083]
【表10】 [Table 10]
【0084】表9および表10に示す結果から明らかな
様に、減圧下での処理によっても、実施例10とほぼ同
様の廃液処理結果が得られている。 実施例13 カランドリア型蒸発缶を使用し、図1に示すフローに従
って大気圧下に112.5℃で本発明を実施した。すなわ
ち、鋼線製造工場(e社)で発生した廃塩酸(連続槽および
バッチ槽で発生した2種の廃塩酸の混合物)を使用し
て、その処理を連続的に(月曜日午前処理開始/金曜日
午後処理停止の繰り返し)行った。運転時の各機器にお
ける条件は、実施例9と同様である。As is evident from the results shown in Tables 9 and 10, almost the same waste liquid treatment results as in Example 10 were obtained by the treatment under reduced pressure. Example 13 The present invention was carried out at 112.5 ° C. under atmospheric pressure using a calandria evaporator according to the flow shown in FIG. That is, using a waste hydrochloric acid (a mixture of two kinds of waste hydrochloric acid generated in a continuous tank and a batch tank) generated in a steel wire manufacturing plant (company e), the processing is continuously performed (Monday morning processing start / Friday) In the afternoon, the processing was stopped repeatedly). The conditions for each device during operation are the same as in Example 9.
【0085】2種の廃塩酸それぞれと両者の混合物の分
析値/処理量を表11に示し、蒸留液の分析値/回収量と
濃縮液の分析値/回収量とをそれぞれ表12と13に示
す。The analytical values / processed amounts of each of the two kinds of waste hydrochloric acid and the mixture thereof are shown in Table 11, and the analytical values / recovered amounts of the distillate and the analyzed values / recovered amounts of the concentrated solution are shown in Tables 12 and 13, respectively. Show.
【0086】[0086]
【表11】 [Table 11]
【0087】[0087]
【表12】 [Table 12]
【0088】[0088]
【表13】 [Table 13]
【0089】その結果、鉄濃度80g/l、塩酸濃度126g/l
の廃塩酸を185リットル/hrの割合で処理して、濃度126g
/lの塩酸水溶液を135.4リットル/hrの割合で回収するこ
とができた。蒸留液回収率は73.2%であり、遊離塩酸回
収率は86.2%であった。As a result, an iron concentration of 80 g / l and a hydrochloric acid concentration of 126 g / l
The waste hydrochloric acid is treated at a rate of 185 liters / hr, and the concentration is 126 g.
/ l hydrochloric acid aqueous solution could be recovered at a rate of 135.4 l / hr. Distillate recovery was 73.2% and free hydrochloric acid recovery was 86.2%.
【0090】濃縮液の塩酸濃度は54.7g/l、鉄濃度は300
g/lであった。この濃縮液を鉄濃度が約400g/lとなるま
で加熱濃縮することにより、濃縮液中の塩酸をほぼ全量
回収するとともに、残余を塩化鉄を主成分とする固体状
物として回収した。The concentrated solution had a hydrochloric acid concentration of 54.7 g / l and an iron concentration of 300.
g / l. This concentrated solution was concentrated by heating until the iron concentration became about 400 g / l, thereby recovering almost all of the hydrochloric acid in the concentrated solution and the remainder as a solid containing iron chloride as a main component.
【0091】回収塩酸は、少量の新しい塩酸とともに連
続槽およびバッチ槽に循環して、鋼線処理に使用するこ
とができた。この場合、鋼線処理用塩酸の濃度および純
度はほぼ一定に保持されるので、常に安定した操作が行
われ、所定の時間で高品質の製品が得られた。鋼線処理
時に防食剤を使用する必要はなく、また廃棄処理量が大
幅に減少した。The recovered hydrochloric acid was circulated in a continuous tank and a batch tank together with a small amount of fresh hydrochloric acid, and could be used for steel wire processing. In this case, since the concentration and purity of the hydrochloric acid for steel wire treatment were kept almost constant, a stable operation was always performed, and a high-quality product was obtained in a predetermined time. There is no need to use anticorrosives when treating steel wire, and the amount of waste disposal has been greatly reduced.
【図1】本発明による廃水の濃縮処理の一例を示すフロ
ーシートである。FIG. 1 is a flow sheet showing an example of a wastewater concentration process according to the present invention.
【図2】本発明による廃水の濃縮処理の他の一例を示す
フローシートである。FIG. 2 is a flow sheet showing another example of the wastewater concentration treatment according to the present invention.
【符号の説明】 1…廃水タンク 3…廃水ポンプ 5、106…ボイラー 7、109…圧縮機 12…濃縮器 14…冷却器 15…冷却水ライン 17…蒸留液槽 19…スチームトラップ 22…電磁弁 25…濃縮液槽 26…充填物 111…補助熱源(蒸気)ライン 119…凝縮槽 126…分散器 127…伝熱管 128…デミスター 132…再濃縮槽(晶析装置)[Description of Signs] 1 ... Waste water tank 3 ... Waste water pump 5,106 ... Boiler 7,109 ... Compressor 12 ... Concentrator 14 ... Cooler 15 ... Cooling water line 17 ... Distillate tank 19 ... Steam trap 22 ... Solenoid valve 25: Concentrated liquid tank 26: Packing material 111: Auxiliary heat source (steam) line 119: Condensing tank 126: Disperser 127: Heat transfer tube 128: Demister 132: Reconcentrating tank (crystallizer)
───────────────────────────────────────────────────── 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 1/04 C02F 1/04 C C23G 3/00 C23G 3/00 B (72)発明者 佐藤 悦郎 大阪府大阪市中央区平野町四丁目1番2号 大阪瓦斯株式会社内 (72)発明者 山田 末和 大阪府大阪市中央区平野町四丁目1番2号 大阪瓦斯株式会社内 Fターム(参考) 4D034 AA11 AA19 BA01 CA12 4D076 BA04 CB04 CD25 CD33 DA04 DA05 DA22 DA25 DA28 DA37 EA04Z EA08Z EA12Z EA15Y EA20Z EA49 HA05 JA03 4G048 AA06 AB08 AE01 4K053 PA02 PA12 PA13 PA14 RA19 TA16 XA11 XA14 XA50 YA05 YA10 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C02F 1/04 C02F 1/04 C C23G 3/00 C23G 3/00 B (72) Inventor Etsuo Sato Osaka 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi Osaka Gas Co., Ltd. (72) Inventor Suewa Yamada 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Prefecture F-term (reference) 4D034 AA11 AA19 BA01 CA12 4D076 BA04 CB04 CD25 CD33 DA04 DA05 DA22 DA25 DA28 DA37 EA04Z EA08Z EA12Z EA15Y EA20Z EA49 HA05 JA03 4G048 AA06 AB08 AE01 4K053 PA02 PA12 PA13 PA14 RA19 TA16 XA11 XA10 YA50
Claims (29)
て、(1)廃塩酸原液を蒸発缶内に導入する工程、
(2)蒸気を供給し、蒸発缶内の液を間接的に加熱し
て、蒸発させる工程、(3)蒸発缶内で発生した蒸気を
冷却器で冷却し、これを塩酸水溶液として回収する工
程、(4)蒸発缶内での加熱・蒸発に利用した蒸気の凝
縮液を回収する工程、(5)蒸発缶内温度および/また
は廃塩酸原液量に対する蒸留液量の割合を調整すること
により、蒸発缶内濃縮液中の鉄濃度を300g/l以下に制御
する工程、(6)蒸発缶内の液面高さに対応して濃縮液
を抜き出し、濃縮液貯槽に送る工程、(7)発缶外に抜
き出した濃縮液を希釈することにより、その鉄濃度を20
0g/l以下に制御する工程、および(8)(a)蒸発缶内温
度および/または廃塩酸原液量に対する蒸留液量の割合
を調整するか、および/または(b)廃塩酸原液に代えて
希釈液を供給することにより、蒸発缶内濃縮液中鉄濃度
を200g/l以下とした後、廃塩酸の処理を停止する工程を
備えたことを特徴とする廃塩酸の処理方法。1. A method for treating waste hydrochloric acid using an evaporator, comprising: (1) introducing a waste hydrochloric acid stock solution into the evaporator;
(2) a step of supplying steam and indirectly heating and evaporating the liquid in the evaporator; and (3) a step of cooling the steam generated in the evaporator with a cooler and recovering it as an aqueous hydrochloric acid solution. (4) a step of recovering the condensate of the vapor used for heating and evaporation in the evaporator, (5) adjusting the temperature in the evaporator and / or the ratio of the amount of distillate to the amount of waste hydrochloric acid stock solution, (6) a step of controlling the iron concentration in the concentrated liquid in the evaporator to 300 g / l or less, (6) a step of extracting the concentrated liquid corresponding to the liquid level in the evaporator, and sending the concentrated liquid to a concentrated liquid storage tank; By diluting the concentrate extracted outside the can, its iron concentration can be reduced to 20%.
And (8) (a) adjusting the temperature in the evaporator and / or adjusting the ratio of the amount of the distillate to the amount of the waste hydrochloric acid stock solution, and / or (b) replacing the waste hydrochloric acid stock solution. A method for treating waste hydrochloric acid, comprising a step of stopping the treatment of waste hydrochloric acid after supplying the diluent to reduce the iron concentration in the concentrated solution in the evaporator to 200 g / l or less.
〜120℃である請求項1に記載の廃塩酸の処理方法。2. The temperature in the evaporator in step (5) is 110
The method for treating waste hydrochloric acid according to claim 1, wherein the temperature is -120 ° C.
の抜き出しを80〜100℃の加熱条件下に行った後、濃縮
液を希釈する請求項1に記載の廃塩酸の処理方法。3. The method for treating waste hydrochloric acid according to claim 1, wherein in the step (7), the concentrated liquid is extracted from the evaporator under heating conditions of 80 to 100 ° C., and then the concentrated liquid is diluted.
しラインに外部から蒸気および/または空気を間欠的に
導入することにより、鉄塩の固化を抑制する請求項1に
記載の廃塩酸の処理方法。4. The treatment of waste hydrochloric acid according to claim 1, wherein the solidification of the iron salt is suppressed by intermittently introducing steam and / or air from the outside into the lower part inside the evaporator and / or the concentrated liquid extraction line. Method.
(4)からの凝縮液および/または廃塩酸原液および/
または水を使用する請求項3に記載の廃塩酸の処理方
法。5. In step (7), the condensate from step (4) and / or the waste hydrochloric acid stock solution and / or
4. The method for treating waste hydrochloric acid according to claim 3, wherein water is used.
である請求項1に記載の廃塩酸の処理方法。6. The method for treating waste hydrochloric acid according to claim 1, wherein the evaporator is a steam heating type device provided with a heating tube.
管式熱交換器蒸発缶あるいは横型多管式熱交換器蒸発缶
である請求項6に記載の廃塩酸の処理方法。7. The method for treating waste hydrochloric acid according to claim 6, wherein the evaporator is a calandria evaporator, a vertical multitubular heat exchanger evaporator or a horizontal multitubular heat exchanger evaporator.
蒸気および/またはコジェネレーション設備で発生する
蒸気である請求項1に記載の廃塩酸の処理方法。8. The method for treating waste hydrochloric acid according to claim 1, wherein the heat source for heating and evaporating is steam generated in a boiler and / or steam generated in a cogeneration facility.
たは高温燃焼排ガスおよび/または電気である請求項1
に記載の廃塩酸の処理方法。9. The heating / evaporating heat source is a heating heat medium and / or high-temperature combustion exhaust gas and / or electricity.
3. The method for treating waste hydrochloric acid according to 1.).
減圧弁で減圧した蒸気である請求項1、3、4、6、7
または8に記載の廃塩酸の処理方法。10. The heating / evaporating heat source is a steam obtained by depressurizing high-temperature / high-pressure steam by a pressure reducing valve.
Or the method for treating waste hydrochloric acid according to 8.
圧縮機で圧縮・昇温した蒸気である請求項1、3、4、
6、7または8に記載の廃塩酸の処理方法。11. The heat source for heating and evaporating is steam obtained by compressing and raising the temperature of low-temperature and low-pressure steam by a compressor.
The method for treating waste hydrochloric acid according to 6, 7, or 8.
求項11に記載の廃塩酸の処理方法。12. The method for treating waste hydrochloric acid according to claim 11, wherein the compressor is a screw compressor.
インバーター装置により制御する請求項12に記載の廃
塩酸の処理方法。13. The method for treating waste hydrochloric acid according to claim 12, wherein the rotational speed of the motor of the screw compressor is controlled by an inverter device.
よび/または晶析装置内で発生する蒸気量(回収塩酸水
溶液量)に対応してスクリュー型圧縮機のモーター回転
数を制御する請求項12または13に記載の廃塩酸の処
理方法。14. The motor speed of the screw compressor is controlled in accordance with the amount of steam (amount of recovered hydrochloric acid solution) generated in the evaporator and / or in the reconcentrator and / or in the crystallization device. 14. The method for treating waste hydrochloric acid according to 12 or 13.
縮機のモーター回転数を制御する請求項12または13
に記載の廃塩酸の処理方法。15. A motor for controlling a screw type compressor according to the temperature in the evaporator.
3. The method for treating waste hydrochloric acid according to 1.).
11に記載の廃塩酸の処理方法。16. The method for treating waste hydrochloric acid according to claim 11, wherein a plurality of compressors are provided.
をポンプで抜き取り、廃塩酸原液の導入ラインへ循環す
る請求項1に記載の廃塩酸の処理方法。17. The method for treating waste hydrochloric acid according to claim 1, wherein in step (7), the bottom liquid in the evaporator is withdrawn by a pump and circulated to a line for introducing a waste hydrochloric acid stock solution.
凝縮液をボイラー給水として使用する請求項1に記載の
廃塩酸の処理方法。18. The method according to claim 1, wherein the condensate of steam used as a heat source for heating and evaporating is used as boiler feed water.
を設けた請求項1に記載の廃塩酸の処理方法。19. The method for treating waste hydrochloric acid according to claim 1, wherein a demister is provided in a space above the liquid level in the evaporator.
縮性気体の自動的排出を定期的に行うための電磁弁を設
けた請求項1に記載の廃塩酸の処理方法。20. The method for treating waste hydrochloric acid according to claim 1, wherein an electromagnetic valve for periodically discharging the non-condensable gas in the evaporator is provided in the steam line on the heating side.
発缶内伝熱管の汚れによる蒸発量の低下に対応するため
に、補助熱源を蒸発缶内底部へ導入する請求項1に記載
の廃塩酸の処理方法。21. The method for treating waste hydrochloric acid according to claim 1, wherein an auxiliary heat source is introduced into the bottom of the evaporator to cope with a decrease in the amount of evaporation due to contamination of the heat transfer tube in the evaporator during startup or during long-term operation. .
発缶内伝熱管の汚れによる蒸発量の低下に対応するため
に、補助熱源を圧縮機出口ラインへ導入する請求項11
に記載の廃塩酸の処理方法。22. An auxiliary heat source is introduced to a compressor outlet line at the time of start-up or long-term operation in order to cope with a decrease in the amount of evaporation due to contamination of the heat transfer tube in the evaporator.
3. The method for treating waste hydrochloric acid according to 1.).
22に記載の廃塩酸の処理方法。23. The method for treating waste hydrochloric acid according to claim 21, wherein the auxiliary heat source is steam.
低下が生じた場合に、運転中に廃塩酸原液の供給を一時
的に中断し、水を供給することにより、汚れを洗浄・除
去する請求項1に記載の廃塩酸の処理方法。24. When the heat transfer coefficient decreases due to contamination of the heat transfer tube in the evaporator, the supply of the waste hydrochloric acid stock solution is temporarily interrupted during operation and water is supplied to clean the contamination. The method for treating waste hydrochloric acid according to claim 1, which is removed.
号に対応して濃縮液を塔底から抜き出す請求項1に記載
の廃塩酸処理方法。25. The waste hydrochloric acid treatment method according to claim 1, wherein in step (6), the concentrated liquid is extracted from the bottom of the column in response to the signal indicating the liquid level.
相当する位置で、蒸発缶底部と連通するオーバーフロー
管から濃縮液を抜き出す請求項1に記載の廃塩酸の処理
方法。26. The method for treating waste hydrochloric acid according to claim 1, wherein in the step (6), the concentrated liquid is extracted from an overflow pipe communicating with the bottom of the evaporator at a position corresponding to the liquid level in the evaporator.
る蒸気を冷却・凝縮させて塩酸として回収した後、鉄鋼
製品の表面処理に使用する請求項1に記載の廃塩酸の処
理方法。27. The method according to claim 1, wherein in step (3), steam generated in the evaporator is cooled and condensed and recovered as hydrochloric acid, and then used for surface treatment of steel products.
処理槽から廃塩酸原液を連続的に抜き出し、処理する請
求項1に記載の廃塩酸の処理方法。28. The method for treating waste hydrochloric acid according to claim 1, wherein the waste hydrochloric acid stock solution is continuously extracted from the batch type and / or continuous type steel product treatment tank and treated.
置または晶析装置において間接的に加熱し、蒸発させた
後、生成する蒸気を工程(3)で得られた蒸気と併せて
塩酸水溶液として回収するとともに、残余を塩化鉄を主
成分とする固体状物として回収する請求項1に記載の廃
塩酸の処理方法。29. The condensate taken out of the evaporator is heated indirectly in a reconcentrator or crystallizer and evaporated, and the generated steam is combined with the steam obtained in the step (3) to obtain hydrochloric acid. 2. The method for treating waste hydrochloric acid according to claim 1, wherein the waste hydrochloric acid is recovered as an aqueous solution, and a residue is recovered as a solid substance containing iron chloride as a main component.
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