JPH0533173A - Treatment of waste hydrochloric acid and treating device - Google Patents
Treatment of waste hydrochloric acid and treating deviceInfo
- Publication number
- JPH0533173A JPH0533173A JP3214471A JP21447191A JPH0533173A JP H0533173 A JPH0533173 A JP H0533173A JP 3214471 A JP3214471 A JP 3214471A JP 21447191 A JP21447191 A JP 21447191A JP H0533173 A JPH0533173 A JP H0533173A
- Authority
- JP
- Japan
- Prior art keywords
- hydrochloric acid
- waste hydrochloric
- roasting
- waste
- concentration
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、鋼材酸洗装置から排出
される鉄分含有廃塩酸の焙焼方式による処理方法および
処理装置の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for treating iron-containing waste hydrochloric acid discharged from a steel pickling apparatus by a roasting method.
【０００２】[0002]
【従来の技術】鋼材酸洗ラインにおける酸洗装置の浴槽
から排出される鉄分含有廃塩酸〔遊離塩酸（Ｆ．ＨＣ
ｌ）濃度 約４０〜８０ｇ／ｌ，鉄分（塩化第一鉄，Ｆ
ｅＣｌ2 ）濃度 約７０〜１５０ｇ／ｌ〕は、酸化焙焼
に付され、酸化鉄（Ｆｅ2 Ｏ3 ）とＨＣｌガスを生成す
る。酸化鉄はフェライト原料等として回収され、他方Ｈ
Ｃｌ等を含む焙焼炉ガスは水と接触する塩酸回収処理に
付され、回収された塩酸は、酸洗装置の浴槽に還流され
る。2. Description of the Related Art Waste iron-containing hydrochloric acid (free hydrochloric acid (F.HC) discharged from a bath of a pickling device in a steel material pickling line
l) Concentration about 40-80 g / l, iron content (ferrous chloride, F
The eCl 2 ) concentration of about 70 to 150 g / l] is subjected to oxidative roasting to produce iron oxide (Fe 2 O 3 ) and HCl gas. Iron oxide is recovered as a ferrite raw material, while H
The roasting furnace gas containing Cl or the like is subjected to a hydrochloric acid recovery treatment in contact with water, and the recovered hydrochloric acid is refluxed in the bath of the pickling device.
【０００３】図２は、焙焼方式による従来の廃塩酸処理
系を示している。２は、酸洗装置ａから排出される廃塩
酸を濃縮する廃塩酸濃縮塔、３は廃塩酸焙焼炉、４は塩
酸回収塔である。酸洗装置ａから排出され、廃酸送給路
ｌ1 を通って廃塩酸濃縮塔２内に導入された鉄分含有廃
塩酸は、その濃縮塔２内において、焙焼炉３から送給さ
れたＨＣｌを含有する高温の焙焼炉ガスとの向流接触に
より加熱されて蒸発濃縮する。焙焼炉ガス中に含まれて
いるＨＣｌの一部および酸化鉄の一部は廃塩酸中に吸収
溶解される。濃縮された廃塩酸（Ｆ．ＨＣｌ濃度約６０
〜１１０ｇ／ｌ，鉄分濃度 約９０〜１９０ｇ／ｌ）は
経路ｌ3 を介して焙焼炉３に圧送される。廃塩酸を、焙
焼炉３に送給するに先立って濃縮処理するのは、焙焼炉
３の負荷を軽減して、燃料消費量や処理系全体の運転電
力を節減し、また塩酸回収塔４にもちこまれる酸化鉄の
量を少くするためである。FIG. 2 shows a conventional waste hydrochloric acid treatment system using a roasting method. 2 is a waste hydrochloric acid concentration tower for concentrating the waste hydrochloric acid discharged from the pickling apparatus a, 3 is a waste hydrochloric acid roasting furnace, and 4 is a hydrochloric acid recovery tower. The iron-containing waste hydrochloric acid discharged from the pickling apparatus a and introduced into the waste hydrochloric acid concentrating tower 2 through the waste acid feeding path l 1 was fed from the roasting furnace 3 in the concentrating tower 2. It is heated by countercurrent contact with a hot roasting furnace gas containing HCl to evaporate and concentrate. Part of HCl and part of iron oxide contained in the roasting furnace gas are absorbed and dissolved in waste hydrochloric acid. Concentrated waste hydrochloric acid (F.HCl concentration about 60
˜110 g / l, iron concentration about 90-190 g / l) is pressure-fed to the roasting furnace 3 via the path l 3 . Concentrating the waste hydrochloric acid prior to sending it to the roasting furnace 3 reduces the load on the roasting furnace 3, reduces the fuel consumption and the operating power of the entire processing system, and reduces the hydrochloric acid recovery tower. This is to reduce the amount of iron oxide contained in 4.
【０００４】焙焼炉３に圧送された廃塩酸は、炉頂より
炉内に噴霧される。焙焼炉４内は、燃料および空気３１
の吹込みにより約７００〜７５０℃に保持され、また廃
塩酸中の鉄分（ＦｅＣｌ2 ）の酸化反応（Ｆｅ2 Ｏ3 と
ＨＣｌの生成）を行なわせるに充分な量の酸素が存在
し、かつ若干の負圧となるように調節されている。炉頂
から噴霧される廃塩酸は、焙焼されて酸化鉄とＨＣｌを
生成し、酸化鉄は炉底から排出回収され、他方ＨＣｌ等
を含む焙焼炉ガスは、経路ｌ4 を介して廃塩酸濃縮塔２
に送給され、前記のように廃塩酸との熱交換により廃塩
酸を蒸発濃縮させ、自身は冷却され廃塩酸の蒸発成分と
共に濃縮塔２から経路ｌ5 を通って塩酸回収塔４に送り
込まれる。The waste hydrochloric acid pressure-fed to the roasting furnace 3 is sprayed into the furnace from the furnace top. In the roasting furnace 4, fuel and air 31
Is maintained at about 700 to 750 ° C., and there is sufficient oxygen to cause the oxidation reaction of iron (FeCl 2 ) in waste hydrochloric acid (formation of Fe 2 O 3 and HCl), and It is adjusted so as to have a slight negative pressure. The waste hydrochloric acid sprayed from the furnace top is roasted to produce iron oxide and HCl, and the iron oxide is discharged and recovered from the furnace bottom, while the roasting furnace gas containing HCl and the like is discharged via the path l 4. Hydrochloric acid concentration tower 2
The waste hydrochloric acid is evaporated and concentrated by heat exchange with the waste hydrochloric acid as described above, and itself is cooled and sent together with the evaporation component of the waste hydrochloric acid from the concentration tower 2 to the hydrochloric acid recovery tower 4 through the route l 5. .
【０００５】塩酸回収塔４に送り込まれた焙焼炉ガス
は、その頂部から散布される水４１と接触してＨＣｌが
吸収され塩酸として回収され、回収された塩酸は、経路
ｌ7 を通って酸洗装置ａに還流される。塩酸が回収され
た後の排ガス（焙焼炉内での燃焼生成物であるＮＯｘ，
ＳＯｘ，ＣＯ2 等を含む）は、経路ｌ6 を介して除害塔
５に導入され、除害処理された後、大気放出５１され
る。上記処理系におけるガス成分の系内流通は、すべて
塩酸回収塔４の後側に設置したブロアーＢの吸引により
行なわれる。The roasting furnace gas sent to the hydrochloric acid recovery tower 4 comes into contact with water 41 sprayed from the top of the roasting furnace gas to absorb HCl, and is recovered as hydrochloric acid. The recovered hydrochloric acid passes through a path l 7. It is refluxed to the pickling device a. Exhaust gas after hydrochloric acid is recovered (NOx which is a combustion product in the roasting furnace,
(Including SOx, CO 2 and the like) is introduced into the abatement tower 5 via a route 16 and subjected to an abatement treatment, and then released into the atmosphere 51. The gas components in the processing system are distributed in the system by suction of a blower B installed on the rear side of the hydrochloric acid recovery tower 4.
【０００６】[0006]
【発明が解決しようとする課題】上記廃塩酸処理装置
は、鋼材酸洗装置ａの処理能力に対応してその規模・処
理能力が決定され建設されることは言うまでもないが、
実際の操業では、酸洗ラインの操業内容により酸洗装置
から排出される廃塩酸の排出量が大きく左右され、例え
ば難酸洗鋼材の酸洗処理時には、比較的Ｆｅ分濃度の低
い廃塩酸が多量に排出されるため、廃塩酸の処理能力に
不足をきたすことがしばしばある。Needless to say, the above-mentioned waste hydrochloric acid treatment apparatus is constructed by determining the scale and treatment capacity in accordance with the treatment capacity of the steel material pickling apparatus a.
In the actual operation, the amount of waste hydrochloric acid discharged from the pickling equipment greatly depends on the operation content of the pickling line. For example, during pickling of difficult-to-pickle steel, waste hydrochloric acid with a relatively low Fe content concentration Since a large amount is discharged, the treatment capacity of waste hydrochloric acid is often insufficient.
【０００７】廃塩酸の排出量が増加すると、それに対応
して、焙焼炉の燃料および空気の吹込み量を増加しなけ
ればならない。しかるに、焙焼炉では、廃塩酸中の鉄分
（ＦｅＣｌ2 ）の酸化反応を充分に行なわせる必要上、
酸素リッチの状態に保持され、熱効率が低いため、燃料
コストの負担増が大きく、しかもその燃料・空気の吹込
み量の増加と廃塩酸の焙焼処理量の増加により、焙焼炉
での生成ガス量が著しく増大し、それに伴うブロアーの
負荷の増大と電力消費の増大を免れない。As the discharge of waste hydrochloric acid increases, the amount of fuel and air blown into the roasting furnace must be correspondingly increased. However, in the roasting furnace, it is necessary to sufficiently carry out the oxidation reaction of iron (FeCl 2 ) in the waste hydrochloric acid.
Since it is kept in an oxygen-rich state and its thermal efficiency is low, the burden of fuel cost is large, and the increase in the amount of fuel / air blown in and the amount of waste hydrochloric acid to be roasted are generated in the roasting furnace. The amount of gas increases remarkably, which inevitably increases the load on the blower and the power consumption.
【０００８】また、酸洗装置ａからの廃塩酸の排出量の
増大により廃塩酸処理系の処理能力が不足するような場
合、その緩和・解消策として、廃塩酸の蒸発濃縮の熱源
として焙焼炉３から廃塩酸濃縮塔２内に供給される焙焼
炉ガスの温度を高くして廃塩酸の濃縮率を高めることが
考えられるが、焙焼炉ガスの温度を高くするには、焙焼
炉内の燃料および空気の吹込み量を多くしなければなら
ず、前述したように燃料コストおよび電力消費の多大の
負担増を余儀なくされる。When the amount of waste hydrochloric acid discharged from the pickling device a is increased and the treatment capacity of the waste hydrochloric acid treatment system becomes insufficient, as a measure to alleviate or eliminate it, roasting is performed as a heat source for evaporating and concentrating the waste hydrochloric acid. It is conceivable to increase the temperature of the roasting furnace gas supplied from the furnace 3 into the waste hydrochloric acid concentrating tower 2 to increase the concentration rate of the waste hydrochloric acid. It is necessary to increase the amount of fuel and air blown into the furnace, and as described above, the burden of fuel cost and electric power consumption is inevitably increased.
【０００９】廃塩酸の濃縮率を高める他の手段として、
例えば電気透析法を使用することも考えられるが、電気
透析では処理液に汚染のないことが要求されるので、酸
洗鋼材に付着していた油類や塵埃等が混濁している廃塩
酸の濃縮処理に適用することは困難である。As another means for increasing the concentration rate of waste hydrochloric acid,
For example, it may be possible to use the electrodialysis method, but in electrodialysis, the treatment liquid is required to be free of contamination, so the waste hydrochloric acid that is turbid with oil and dust adhering to the pickled steel material It is difficult to apply to concentration treatment.
【００１０】なお、廃塩酸の処理能力の不足を解消する
ために廃塩酸処理ラインを改造しようとすれば、多大の
費用と時間を必要とし、かつ改造期間中は廃塩酸処理操
業の制約ないしはその中断を余儀なくされる。本発明
は、廃塩酸処理に関する上記問題を解決するための改良
され処理方法および装置を提供しようとするものであ
る。If the waste hydrochloric acid treatment line is to be modified in order to eliminate the lack of waste hydrochloric acid treatment capacity, a great deal of cost and time are required, and the waste hydrochloric acid treatment operation is restricted during the modification period. You have to be interrupted. The present invention seeks to provide an improved treatment method and apparatus for overcoming the above problems associated with waste hydrochloric acid treatment.
【００１１】[0011]
【課題を解決するための手段】本発明は、鋼材酸洗装置
から排出される鉄分含有廃塩酸を蒸発濃縮する工程、濃
縮した廃塩酸を酸化焙焼して鉄分（塩化第一鉄）を酸化
鉄とＨＣｌに分解する焙焼工程、焙焼により生成したＨ
Ｃｌ等を含有する焙焼炉ガスを水と接触させて塩酸を回
収する工程を有し、前記廃塩酸の蒸発濃縮は、焙焼工程
で生成する焙焼炉ガスを熱源として廃塩酸と接触させる
ことにより行う焙焼式廃塩酸処理方法において、前記鋼
材酸洗装置から排出される廃塩酸を、前記焙焼炉ガスを
熱源とする蒸発濃縮工程に先立って、その熱源以外の熱
源による間接加熱により蒸発濃縮する予備濃縮処理を行
うと共に、予備濃縮により廃塩酸から発生する蒸気成分
を、凝縮水として回収し、これを前記塩酸回収工程にお
ける塩酸回収水の一部として使用することを特徴として
いる。According to the present invention, a step of evaporating and concentrating iron-containing waste hydrochloric acid discharged from a steel pickling apparatus, oxidizing concentrated iron chloride (ferrous chloride) by oxidizing and roasting the waste hydrochloric acid. Roasting step of decomposing into iron and HCl, H produced by roasting
The method has a step of recovering hydrochloric acid by bringing a roasting furnace gas containing Cl or the like into contact with water, and evaporating and concentrating the waste hydrochloric acid causes the roasting furnace gas generated in the roasting step to contact with the waste hydrochloric acid. In the roasting type waste hydrochloric acid treatment method performed by, the waste hydrochloric acid discharged from the steel material pickling device is subjected to indirect heating by a heat source other than the heat source before the evaporative concentration step using the roasting furnace gas as a heat source. The method is characterized by performing a preconcentration process of evaporative concentration, collecting the vapor component generated from the waste hydrochloric acid by preconcentration as condensed water, and using this as a part of the hydrochloric acid recovered water in the hydrochloric acid recovery step.
【００１２】本発明の廃塩酸処理方法は、鋼材酸洗装置
と、焙焼方式の廃塩酸処理系における廃塩酸濃縮塔とを
結ぶ廃塩酸送給路に、廃塩酸を蒸発濃縮する間接加熱装
置を備えた予備濃縮器を設けると共に、予備濃縮器内の
廃塩酸から発生する蒸発成分を、凝縮して前記塩酸回収
塔における塩酸回収水の一部とするための凝縮器を設け
た廃塩酸処理装置において実施することができる。The waste hydrochloric acid treating method of the present invention is an indirect heating device for evaporating and concentrating waste hydrochloric acid in a waste hydrochloric acid feed line connecting a steel material pickling device and a waste hydrochloric acid concentration tower in a roasting type waste hydrochloric acid treating system. A waste hydrochloric acid treatment provided with a pre-concentrator equipped with a condenser for condensing an evaporation component generated from waste hydrochloric acid in the pre-concentrator to form a part of the hydrochloric acid recovered water in the hydrochloric acid recovery tower. It can be implemented in a device.
【００１３】[0013]
【作用】本発明は、鋼材酸洗装置から排出される廃塩酸
を、焙焼方式の廃塩酸処理系内に導入するに先立って、
すなわち焙焼炉３から供給される高温の焙焼炉ガスを熱
源とする廃塩酸濃縮塔２内での蒸発濃縮処理に先行し
て、廃塩酸処理系内の熱源とは別の熱源を使用する間接
加熱により廃塩酸の予備濃縮処理を行うこととしている
ので、その蒸発濃縮による廃塩酸の容量減少分が、その
まま焙焼炉３の負荷の軽減となり、焙焼炉の燃料消費が
節減されるだけでなく、系内のガス生成量の減少とブロ
アーの負荷の軽減効果により、予備濃縮での濃縮率に対
応して廃塩酸処理能力が増大する。According to the present invention, the waste hydrochloric acid discharged from the steel pickling apparatus is introduced into the roasting type waste hydrochloric acid treatment system prior to introduction.
That is, prior to the evaporative concentration process in the waste hydrochloric acid concentration tower 2 using the high temperature roasting furnace gas supplied from the roasting furnace 3 as a heat source, a heat source different from the heat source in the waste hydrochloric acid treatment system is used. Since the pre-concentration process of waste hydrochloric acid is performed by indirect heating, the volume reduction of the waste hydrochloric acid due to the evaporative concentration directly reduces the load on the roasting furnace 3 and saves fuel consumption of the roasting furnace. Instead, the waste hydrochloric acid treatment capacity increases corresponding to the concentration rate in the preconcentration due to the effect of reducing the gas generation amount in the system and the effect of reducing the load of the blower.
【００１４】すなわち、上記予備濃縮処理においても、
蒸発濃縮のための燃料を必要とすることはいうまでもな
いが、これを焙焼炉３の燃焼を強化する場合の燃料消費
の増加と比較すると、焙焼炉では鉄分（ＦｅＣｌ2 ）の
酸化反応を遂行させるために、酸素リッチの雰囲気を保
持する必要上、熱効率の低い燃焼を余儀なくされるのに
対し、上記予備濃縮処理ではそのような制約はなく、高
い熱効率での給熱が可能であり、それだけ燃料使用量が
少くて済むのである。That is, even in the above preconcentration treatment,
Needless to say, a fuel for evaporating and concentrating is required, but when this is compared with the increase in fuel consumption when the combustion in the roasting furnace 3 is strengthened, iron (FeCl 2 ) oxidation in the roasting furnace is performed. In order to carry out the reaction, it is necessary to maintain an oxygen-rich atmosphere, and combustion with low thermal efficiency is inevitable. On the other hand, there is no such restriction in the preconcentration process, and heat supply with high thermal efficiency is possible. Yes, it requires less fuel.
【００１５】また、系内のガス生成量についてみると、
廃塩酸濃縮塔２において廃塩酸の蒸発濃縮率を高める場
合は、その熱源である焙焼炉３の焙焼生成ガスを高温化
するための燃料・空気３１の吹込み量の増加とそれ伴う
焙焼生成ガス量の増加に帰結するのに対し、予備濃縮処
理ではそのような不都合はなく、その濃縮率に応じて廃
塩酸の焙焼処理量の減少・焙焼生成ガス量の減少による
ブロアー負荷の軽減効果が得られる。系内ガスを吸引す
るブロアーＢの負荷電力は系内ガス量の増加率の３乗に
比例する関係にあるので、上記予備濃縮による系内ガス
生成量の減少によるブロアー電力の節減効果は大であ
る。Looking at the amount of gas produced in the system,
When the evaporation concentration rate of waste hydrochloric acid in the waste hydrochloric acid concentration tower 2 is increased, the amount of fuel / air 31 blown in to raise the temperature of the roasting product gas of the roasting furnace 3 which is the heat source is increased, and While the result is an increase in the amount of gas produced by baking, there is no such inconvenience in the pre-concentration process, and the blower load due to a decrease in the amount of roasting treatment of waste hydrochloric acid and a decrease in the amount of gas produced by baking according to the concentration rate. The effect of reducing is obtained. Since the load power of the blower B that sucks in the system gas is proportional to the cube of the increase rate of the system gas amount, the effect of saving the blower power by the reduction of the system gas production amount by the above preconcentration is large. is there.
【００１６】なお、予備濃縮処理において廃塩酸から発
生する蒸発成分（廃塩酸のＦ．ＨＣｌ濃度および鉄分濃
度により異なるが、約１〜５％のＨＣｌを含む）は、凝
縮されたうえ、塩酸回収のための吸収水として使用され
るので、塩酸分の損失はない。Evaporative components generated from waste hydrochloric acid in the pre-concentration treatment (containing about 1 to 5% HCl, which varies depending on the F.HCl concentration and iron concentration of the waste hydrochloric acid) are condensed and then recovered. Since it is used as absorbed water for, there is no loss of hydrochloric acid content.
【００１７】[0017]
【実施例】図１は、本発明の廃塩酸処理系を示してい
る。破線で囲まれた処理系部分は、前記図２に示した従
来のそれと同一であり、同じ部分には同じ符号を付して
いる。図中、１は廃塩酸の予備濃縮器であり、６は、予
備濃縮器１で発生する廃塩酸の蒸発成分を凝集水として
回収するための凝縮器である。EXAMPLE FIG. 1 shows a waste hydrochloric acid treatment system of the present invention. The processing system part surrounded by a broken line is the same as the conventional one shown in FIG. 2, and the same parts are denoted by the same reference numerals. In the figure, 1 is a waste hydrochloric acid pre-concentrator, and 6 is a condenser for collecting the evaporated components of the waste hydrochloric acid generated in the pre-concentrator 1 as condensed water.
【００１８】予備濃縮器１は、鋼材酸洗装置ａと、処理
系ｂの濃縮塔２とを結ぶ廃塩酸送給路ｌ1 に、経路ｌ2
を介して設置されている。酸洗装置ａから排出される廃
塩酸は、廃塩酸送給路ｌ1 のバルブＶの開閉操作による
流路切換えにより、その一部または全量が予備濃縮器１
に導入され、あるいは予備濃縮器１を経由することな
く、処理系ｂの濃縮塔２に送給される。そのバルブＶの
開閉操作は、酸洗装置ａからの廃塩酸の排出流量に応じ
て適宜行なわれる。予備濃縮器１は、処理系ｂ内の濃縮
塔２と異なり、処理系ｂとは独立した外部熱源を熱源と
する間接加熱装置１１を帯有している。その熱源に制限
はなく、例えば蒸気、燃焼ガス、あるいは抵抗発熱など
であってよい。The preconcentrator 1 is provided with a path l 2 in a waste hydrochloric acid feed path l 1 connecting the steel material pickling apparatus a and the concentration tower 2 of the treatment system b.
Is installed through. A part or all of the waste hydrochloric acid discharged from the pickling device a is switched by opening / closing the valve V of the waste hydrochloric acid supply path l 1 so that a part or all of the waste hydrochloric acid is discharged from the preconcentrator
Or is fed to the concentration tower 2 of the processing system b without passing through the preconcentrator 1. The opening / closing operation of the valve V is appropriately performed according to the discharge flow rate of the waste hydrochloric acid from the pickling device a. The pre-concentrator 1 has an indirect heating device 11 that uses an external heat source as a heat source, which is independent from the treatment system b, unlike the concentration tower 2 in the treatment system b. The heat source is not limited and may be, for example, steam, combustion gas, or resistance heating.
【００１９】予備濃縮器１に導入された廃塩酸は、減圧
下に加熱装置１１により適当な温度（例えば６０〜７０
℃）に加熱され蒸発濃縮される。その濃縮率は、廃塩酸
のもとの濃度に応じて適宜設定されることは言うまでも
ないが、通常の廃塩酸濃度では、約１０〜１５％程度の
濃縮率の蒸発濃縮を行って、Ｆ．ＨＣｌ 約７０〜１０
０ｇ／ｌ，Ｆｅ分濃度 約８０〜１２０ｇ／ｌ程度の一
次濃縮廃塩酸として濃縮塔２に導入するようにするとよ
い。The waste hydrochloric acid introduced into the preconcentrator 1 is heated under reduced pressure by the heating device 11 to an appropriate temperature (for example, 60 to 70).
It is heated to (.degree. C.) and concentrated by evaporation. Needless to say, the concentration rate is appropriately set according to the original concentration of the waste hydrochloric acid, but with the normal concentration of the waste hydrochloric acid, evaporation concentration is performed at a concentration rate of about 10 to 15%, and F.I. HCl about 70-10
It is advisable to introduce it into the concentration tower 2 as primary concentrated waste hydrochloric acid having a concentration of 0 g / l and a Fe content of about 80 to 120 g / l.
【００２０】予備濃縮器１での予備濃縮処理をうけて濃
縮塔２に導入された後の廃塩酸の処理は、前記図２につ
いて説明したとおり、焙焼炉３から送給される焙焼炉ガ
スとの直接々触による蒸発濃縮をうけたのち、焙焼炉３
に圧送されて酸化焙焼され、生成した酸化鉄はフェライ
ト原料等として分離回収される一方、ＨＣｌを含む焙焼
炉ガスは、濃縮塔２で廃塩酸と熱交換したのち、塩酸回
収塔４に導入されて塩酸回収処理に付される。塩酸回収
後の排ガスは除害塔５で処理されたうえ大気放出される
ことも、図２におけるそれと異ならない。The treatment of the waste hydrochloric acid after being introduced into the concentration tower 2 after undergoing the pre-concentration treatment in the pre-concentrator 1 is carried out by the roasting furnace fed from the roasting furnace 3 as described with reference to FIG. After undergoing evaporative concentration by direct contact with gas, roasting furnace 3
The iron oxide thus produced is sent by pressure to and oxidized and roasted and separated and recovered as a ferrite raw material, and the roasting furnace gas containing HCl is heat-exchanged with waste hydrochloric acid in the concentrating tower 2 and then fed to the hydrochloric acid recovery tower 4. It is introduced and subjected to hydrochloric acid recovery processing. It is no different from that in FIG. 2 that the exhaust gas after the hydrochloric acid recovery is treated in the detoxification tower 5 and then released into the atmosphere.
【００２１】他方、前記予備濃縮器１において廃塩酸か
ら発生する蒸発成分は、若干量のＨＣｌを含有してい
る。そのＨＣｌ分の濃度は、廃塩酸のＦ．ＨＣｌおよび
鉄分（ＦｅＣｌ2 ）の濃度により異なるが、通常約１〜
５％程度である。その蒸発成分は経路ｌ8 を通って凝縮
器６内に導入され、冷却装置６１により冷却されて凝集
水として回収される。回収された凝集水は経路ｌ9 を介
して塩酸回収塔４に供給され、塩酸回収水の一部として
使用される。こうして塩酸回収塔４で回収された塩酸
（例えば、Ｆ．ＨＣｌ濃度 約１５０〜１８０ｇ／ｌ）
は経路ｌ7 を介して酸洗装置ａの酸洗槽に還流される。
酸洗槽に還流される途中において、必要に応じ濃度調整
が施こされる。On the other hand, the evaporation component generated from the waste hydrochloric acid in the preconcentrator 1 contains a slight amount of HCl. The concentration of the HCl component is F. Depending on the concentration of HCl and iron (FeCl 2 ), it is usually about 1 to
It is about 5%. The vaporized component is introduced into the condenser 6 through the path l 8 , cooled by the cooling device 61 and collected as condensed water. The recovered condensed water is supplied to the hydrochloric acid recovery tower 4 via the route l 9 and used as a part of the hydrochloric acid recovered water. The hydrochloric acid thus recovered in the hydrochloric acid recovery tower 4 (for example, F.HCl concentration of about 150 to 180 g / l)
Is refluxed to the pickling tank of the pickling device a via a path l 7 .
The concentration is adjusted as necessary during the reflux into the pickling tank.
【００２２】本発明を例えば処理能力５０００ ｌ／Ｈ
ｒの処理系ｂに適用し、酸洗装置ａから排出される５０
００ ｌ／Ｈｒの廃塩酸を、予備濃縮器１で例えば濃縮
率１０％の予備濃縮を施して４５００ ｌ／Ｈｒに濃縮
することは、その減量５００ｌ／Ｈｒに相当する分だけ
処理能力が増大したと等価である。また、その酸洗装置
ａから流量５０００ ｌ／Ｈｒで排出される廃塩酸（例
えば、Ｆ．ＨＣｌ ７０ｇ／ｌ，Ｆｅ分 １００ｇ／
ｌ）に濃縮率１０％の予備濃縮処理を施し４５００ ｌ
／Ｈｒの廃塩酸としたうえで処理系ｂ内に供給した場合
において、全体として燃料消費は約２５Ｎｍ3 ／Ｈｒ
（天然ガス）および電力消費は約４６ＫＷの節減効果を
得ることができる。The present invention can be applied, for example, to a processing capacity of 5000 l / H.
50 applied to the treatment system b of r and discharged from the pickling apparatus a 50
Concentration of 00 l / Hr of waste hydrochloric acid in the preconcentrator 1 to 4500 l / Hr by preconcentration with a concentration rate of 10%, for example, increased the treatment capacity by the amount corresponding to the reduction of 500 l / Hr. Is equivalent to Further, waste hydrochloric acid discharged from the pickling device a at a flow rate of 5000 l / Hr (for example, F.HCl 70 g / l, Fe content 100 g /
l500) was subjected to a pre-concentration treatment with a concentration rate of 10%
When the waste hydrochloric acid of / Hr is supplied into the processing system b, the fuel consumption is about 25 Nm 3 / Hr as a whole.
(Natural gas) and power consumption can get a saving effect of about 46 KW.
【００２３】なお、予備濃縮器１による一次濃縮と、濃
縮塔２での二次濃縮処理をうけたうえ、濃縮塔２から焙
焼炉３に送給される廃塩酸の濃度があまり高くなると、
その廃塩酸から鉄分（ＦｅＣｌ2 ）が晶出し、装置上の
トラブル（例えば、管路の詰まり）を生じる原因となる
ので、予備濃縮器１における濃縮処理は、濃縮塔２から
導出される廃塩酸の濃度が、Ｆ．ＨＣｌ 約１００ｇ／
ｌ，Ｆｅ分 約１５０ｇ／ｌを越えない程度に調節する
のがよい。もっとも、酸洗装置ａからの廃塩酸の排出量
が増大し、処理系ｂの処理能力の不足をきたすのは主と
して、難酸洗鋼材の酸洗処理が行なわれる場合であっ
て、そのときの廃塩酸は比較的低濃度であるので、実操
業上予備濃縮処理の実施に制限が加えられることは殆ん
どなく、また通常の操業条件では、予備濃縮処理におけ
る濃縮率を概ね１０〜１５％の範囲に設定すれば、上記
トラブルを生じることなく予備濃縮による効果を確保す
ることができる。If the concentration of waste hydrochloric acid fed from the concentration tower 2 to the roasting furnace 3 becomes too high after the primary concentration by the preconcentrator 1 and the secondary concentration treatment by the concentration tower 2,
Iron (FeCl 2 ) is crystallized from the waste hydrochloric acid, which causes a trouble on the apparatus (for example, clogging of the pipeline). Therefore, the concentration treatment in the preconcentrator 1 is performed by the waste hydrochloric acid discharged from the concentration tower 2. The concentration of F. HCl about 100 g /
It is preferable to adjust the l, Fe content so as not to exceed about 150 g / l. However, the amount of waste hydrochloric acid discharged from the pickling apparatus a increases, and the treatment capacity of the treatment system b is insufficient mainly when the pickling treatment of the difficult-to-pickle steel material is performed. Since the concentration of waste hydrochloric acid is relatively low, there is almost no limit to the implementation of the preconcentration treatment in actual operation, and under normal operating conditions, the concentration rate in the preconcentration treatment is approximately 10 to 15%. If the range is set to, the effect of preconcentration can be secured without causing the above trouble.
【００２４】[0024]
【発明の効果】本発明によれば、廃塩酸の予備濃縮の効
果として廃塩酸の処理（酸化鉄の回収，塩酸の回収還
流）における燃料・電力コストの節減、および処理能力
の増強に大きな効果が得られる。また、その予備濃縮処
理は、既設の処理装置の大幅な改造を必要とせず、既設
の装置と酸洗装置との間の廃塩酸送給路に予備濃縮器を
付設する簡単な措置を施すだけで実施することができ実
用性にもすぐれている。EFFECTS OF THE INVENTION According to the present invention, as a result of the pre-concentration of waste hydrochloric acid, there is a great effect on the reduction of fuel / electricity cost in the treatment of waste hydrochloric acid (recovery of iron oxide, recovery / reflux of hydrochloric acid) and the enhancement of the treatment capacity. Is obtained. In addition, the pre-concentration process does not require a major modification of the existing treatment equipment, and only a simple measure is required to attach a pre-concentrator to the waste hydrochloric acid feed line between the existing equipment and the pickling equipment. It can be carried out in and has excellent practicability.
【図１】本発明の廃塩酸処理系を示すフローチャートで
ある。FIG. 1 is a flowchart showing a waste hydrochloric acid treatment system of the present invention.
【図２】従来の廃塩酸処理系を示すフローチャートであ
る。FIG. 2 is a flowchart showing a conventional waste hydrochloric acid treatment system.
１ 予備濃縮器，２ 濃縮塔，３ 焙焼炉，３１ 燃料
・空気，４ 塩酸回収塔，４１ 塩酸吸収水，５ 除害
塔，６ 凝縮器，ａ 酸洗装置，ｖ バルブ，Ｂブロア
ー。1 pre-concentrator, 2 concentration tower, 3 roasting furnace, 31 fuel / air, 4 hydrochloric acid recovery tower, 41 hydrochloric acid absorption water, 5 detoxification tower, 6 condenser, a pickling device, v valve, B blower.
Claims (2)
塩酸を蒸発濃縮する工程、 濃縮した廃塩酸を酸化焙焼して鉄分（塩化第一鉄）を酸
化鉄とＨＣｌに分解する焙焼工程、 焙焼により生成したＨＣｌ等を含有する焙焼炉ガスを水
と接触させて塩酸を回収する工程を有し、 前記廃塩酸の蒸発濃縮は、焙焼工程で生成する焙焼炉ガ
スを熱源として廃塩酸と接触させることにより行なう焙
焼式廃塩酸処理方法において、 前記鋼材酸洗装置から排出される廃塩酸を、前記焙焼炉
ガスを熱源とする蒸発濃縮工程に先立って、その熱源以
外の熱源による間接加熱により蒸発濃縮する予備濃縮処
理を行うと共に、 予備濃縮により廃塩酸から発生する蒸気成分を、凝縮水
として回収し、これを前記塩酸回収工程における塩酸回
収水の一部として使用することを特徴とする廃塩酸の処
理方法。1. A step of evaporating and concentrating iron-containing waste hydrochloric acid discharged from a steel material pickling apparatus, and roasting in which concentrated waste hydrochloric acid is oxidized and roasted to decompose iron (ferrous chloride) into iron oxide and HCl. And a step of contacting a roasting furnace gas containing HCl or the like generated by roasting with water to recover hydrochloric acid. The evaporative concentration of the waste hydrochloric acid is performed by roasting the roasting furnace gas generated in the roasting step. In a roasting type waste hydrochloric acid treatment method performed by contacting with waste hydrochloric acid as a heat source, the waste hydrochloric acid discharged from the steel material pickling device is heated before the evaporative concentration step using the roasting furnace gas as a heat source. In addition to performing a pre-concentration process that evaporates and concentrates by indirect heating with a heat source other than the above, the vapor component generated from waste hydrochloric acid by pre-concentration is recovered as condensed water and used as a part of the hydrochloric acid recovered water in the hydrochloric acid recovery process. To do Method of processing waste hydrochloric characterized by.
塩酸を蒸発濃縮する廃塩酸濃縮塔、 廃塩酸濃縮塔から導出される濃縮廃塩酸を酸化焙焼して
鉄分（塩化第一鉄）を酸化鉄とＨＣｌに分解する廃塩酸
焙焼炉、 廃塩酸焙焼炉内で生成したＨＣｌ含有焙焼炉ガスを水と
接触させて塩酸を回収する塩酸回収塔、を有し、 前記廃塩酸焙焼炉で生成したＨＣｌ含有焙焼炉ガスは、
廃塩酸濃縮塔内に導入され、廃塩酸の蒸発濃縮のための
熱源として廃塩酸との直接々触による熱交換の後、前記
塩酸回収塔に導入される焙焼式廃塩酸処理装置におい
て、 前記鋼材酸洗装置と廃塩酸濃縮塔とを結ぶ廃塩酸送給路
に、廃塩酸を蒸発濃縮する間接加熱装置を備えた予備濃
縮器を設けると共に、 予備濃縮器内の廃塩酸から発生する蒸発成分を、凝縮し
て前記塩酸回収塔における塩酸回収水の一部とするため
の凝縮器を設けたことを特徴とする廃塩酸処理装置。2. A waste hydrochloric acid concentration tower for evaporating and concentrating iron-containing waste hydrochloric acid discharged from a steel pickling apparatus, and iron (ferrous chloride) obtained by oxidizing and roasting concentrated waste hydrochloric acid derived from the waste hydrochloric acid concentration tower. A waste hydrochloric acid roasting furnace for decomposing iron oxide into HCl and HCl; and a hydrochloric acid recovery tower for recovering hydrochloric acid by bringing the HCl-containing roasting furnace gas produced in the waste hydrochloric acid roasting furnace into contact with water. The HCl-containing roasting furnace gas generated in the roasting furnace is
In a roasting-type waste hydrochloric acid treatment apparatus which is introduced into the waste hydrochloric acid concentration tower and, after heat exchange by direct contact with the waste hydrochloric acid as a heat source for evaporative concentration of the waste hydrochloric acid, is introduced into the hydrochloric acid recovery tower, A preconcentrator equipped with an indirect heating device that evaporates and concentrates the waste hydrochloric acid is installed in the waste hydrochloric acid feed line that connects the steel material pickling device and the waste hydrochloric acid concentration tower, and the evaporative components generated from the waste hydrochloric acid in the preconcentrator Is provided with a condenser for condensing to form a part of the hydrochloric acid recovery water in the hydrochloric acid recovery tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3214471A JP2599655B2 (en) | 1991-07-30 | 1991-07-30 | Method and apparatus for treating waste hydrochloric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3214471A JP2599655B2 (en) | 1991-07-30 | 1991-07-30 | Method and apparatus for treating waste hydrochloric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0533173A true JPH0533173A (en) | 1993-02-09 |
| JP2599655B2 JP2599655B2 (en) | 1997-04-09 |
Family
ID=16656277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3214471A Expired - Lifetime JP2599655B2 (en) | 1991-07-30 | 1991-07-30 | Method and apparatus for treating waste hydrochloric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2599655B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004844A1 (en) * | 1993-08-05 | 1995-02-16 | Eco-Tec Limited | Process and apparatus for regeneration of volatile acids |
| CN103938218A (en) * | 2014-05-07 | 2014-07-23 | 苏州皇森机电科技有限公司 | Recovery device of stainless steel pickling waste liquid |
| CN104047009A (en) * | 2014-06-28 | 2014-09-17 | 南通久信石墨科技开发有限公司 | Recovery process device of ferrous chloride in steel pickling liquid |
| US9073760B2 (en) | 2010-12-24 | 2015-07-07 | Shoei Chemical Inc. | Manufacturing method and manufacturing device for multiple oxide |
| CN105439361A (en) * | 2016-01-06 | 2016-03-30 | 南宁汇安电工设备有限公司 | Method and device for waste hydrochloric acid evaporating separation and heat energy multi-time utilization |
| CN110723767A (en) * | 2019-10-28 | 2020-01-24 | 广东莞绿环保工程有限公司 | Low-temperature evaporation treatment and recovery method and device for iron-containing waste hydrochloric acid in steel plant |
| CN115215377A (en) * | 2022-06-08 | 2022-10-21 | 日照宝华新材料有限公司 | Production system and production process for producing iron oxide powder by self-circulation of waste acid |
| CN115417380A (en) * | 2022-08-17 | 2022-12-02 | 南通山剑防腐科技有限公司 | Hydrochloric acid concentrator for hydrochloric acid regeneration with hydrochloric acid gas recovery function |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995004844A1 (en) * | 1993-08-05 | 1995-02-16 | Eco-Tec Limited | Process and apparatus for regeneration of volatile acids |
| EP0714458A1 (en) * | 1993-08-05 | 1996-06-05 | Eco Tec | Process and apparatus for regeneration of volatile acids |
| US9073760B2 (en) | 2010-12-24 | 2015-07-07 | Shoei Chemical Inc. | Manufacturing method and manufacturing device for multiple oxide |
| CN103938218A (en) * | 2014-05-07 | 2014-07-23 | 苏州皇森机电科技有限公司 | Recovery device of stainless steel pickling waste liquid |
| CN104047009A (en) * | 2014-06-28 | 2014-09-17 | 南通久信石墨科技开发有限公司 | Recovery process device of ferrous chloride in steel pickling liquid |
| CN104047009B (en) * | 2014-06-28 | 2016-07-27 | 南通久信石墨科技开发有限公司 | The recovery process device of ferrous chloride in acid washing rolled steel liquid |
| CN105439361A (en) * | 2016-01-06 | 2016-03-30 | 南宁汇安电工设备有限公司 | Method and device for waste hydrochloric acid evaporating separation and heat energy multi-time utilization |
| CN110723767A (en) * | 2019-10-28 | 2020-01-24 | 广东莞绿环保工程有限公司 | Low-temperature evaporation treatment and recovery method and device for iron-containing waste hydrochloric acid in steel plant |
| CN115215377A (en) * | 2022-06-08 | 2022-10-21 | 日照宝华新材料有限公司 | Production system and production process for producing iron oxide powder by self-circulation of waste acid |
| CN115215377B (en) * | 2022-06-08 | 2024-02-06 | 日照宝华新材料有限公司 | Production system and production process for producing ferric oxide powder by self-circulation of waste acid |
| CN115417380A (en) * | 2022-08-17 | 2022-12-02 | 南通山剑防腐科技有限公司 | Hydrochloric acid concentrator for hydrochloric acid regeneration with hydrochloric acid gas recovery function |
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| JP2599655B2 (en) | 1997-04-09 |
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