JP2599655B2 - Method and apparatus for treating waste hydrochloric acid - Google Patents
Method and apparatus for treating waste hydrochloric acidInfo
- Publication number
- JP2599655B2 JP2599655B2 JP3214471A JP21447191A JP2599655B2 JP 2599655 B2 JP2599655 B2 JP 2599655B2 JP 3214471 A JP3214471 A JP 3214471A JP 21447191 A JP21447191 A JP 21447191A JP 2599655 B2 JP2599655 B2 JP 2599655B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrochloric acid
- waste hydrochloric
- waste
- roasting
- concentrating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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)
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 for treating iron-containing waste hydrochloric acid discharged from a steel pickling apparatus by a roasting method and an improvement of the treatment apparatus.
【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 Iron-containing waste hydrochloric acid [free hydrochloric acid (F. HC) discharged from a bath of a pickling apparatus in a steel pickling line.
l) Concentration about 40-80 g / l, iron (ferrous chloride, F
eCl 2) concentration of about 70~150g / l] is subjected to oxidation roasting, to produce iron oxide (Fe 2 O 3) and HCl gas. Iron oxide is recovered as a ferrite raw material, etc.
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 returned to the bath of the pickling apparatus.
【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. Reference numeral 2 denotes a waste hydrochloric acid concentrating tower for concentrating waste hydrochloric acid discharged from the pickling apparatus a, 3 denotes a waste hydrochloric acid roasting furnace, and 4 denotes 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 feed line l 1 was supplied 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 the HCl and part of the iron oxide contained in the roasting furnace gas are absorbed and dissolved in the waste hydrochloric acid. Concentrated waste hydrochloric acid (F.HCl concentration about 60
１１０110 g / l, iron concentration about 90-190 g / l) is fed to the roasting furnace 3 via a path l 3 . The concentration of the waste hydrochloric acid prior to being sent to the roasting furnace 3 is performed by reducing the load on the roasting furnace 3 to reduce the fuel consumption and the operating power of the entire processing system, and to reduce the hydrochloric acid recovery tower. This is because the amount of iron oxide carried into the sample No. 4 is reduced.
【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。[0004] The waste hydrochloric acid 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. by blowing air, and an amount of oxygen sufficient to cause an oxidation reaction of iron (FeCl 2 ) in waste hydrochloric acid (formation of Fe 2 O 3 and HCl) is present, and The pressure is adjusted to a slight negative pressure. Waste hydrochloric sprayed from the furnace top is being roasted to produce iron oxide and HCl, iron oxide is discharged recovered from the furnace bottom, the roaster gases containing the other such as HCl, via path l 4 Waste 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 is cooled and sent to the hydrochloric acid recovery tower 4 from the concentration tower 2 through the path 15 together with the evaporated component of the waste hydrochloric acid. .
【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。[0005] The roasting furnace gas sent to the hydrochloric acid recovery tower 4 comes into contact with water 41 sprayed from the top thereof to absorb HCl and be recovered as hydrochloric acid. The recovered hydrochloric acid passes through a path 17. It is refluxed to the pickling device a. Exhaust gas after the recovery of hydrochloric acid (NOx,
SOx, CO 2, etc.) are introduced into the abatement tower 5 via a path 16 and subjected to abatement treatment, and then discharged to the atmosphere 51. All of the gas components in the processing system are circulated 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 scale and processing capacity of the waste hydrochloric acid treatment apparatus are determined and constructed in accordance with the processing capacity of the steel pickling apparatus a.
In actual operation, the amount of waste hydrochloric acid discharged from the pickling apparatus is greatly affected by the operation of the pickling line. For example, during pickling treatment of hardly pickled steel, waste hydrochloric acid having a relatively low Fe concentration is used. Due to the large amount of discharge, the treatment capacity of waste hydrochloric acid often becomes 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。[0007] As the amount of waste hydrochloric acid discharged increases, the amount of fuel and air blown into the roasting furnace must be correspondingly increased. However, in the roasting furnace, the oxidation reaction of iron (FeCl 2 ) in the waste hydrochloric acid needs to be sufficiently performed.
It is maintained in an oxygen-rich state and its thermal efficiency is low, so the burden on fuel costs increases greatly.In addition, the amount of fuel and air blown up and the amount of waste hydrochloric acid to be roasted increase, resulting in the production in a roasting furnace. The gas amount is significantly increased, and the accompanying increase in the load on the blower and the increase in power consumption are unavoidable.
【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 processing capacity of the waste hydrochloric acid treatment system becomes insufficient due to an increase in the amount of waste hydrochloric acid discharged from the pickling apparatus a, as a measure to alleviate or eliminate the problem, roasting is performed as a heat source for evaporating and condensing 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. The amount of fuel and air to be blown into the furnace must be increased, and as described above, the fuel cost and the power consumption must be greatly 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 of waste hydrochloric acid,
For example, it is conceivable to use an electrodialysis method.However, since electrodialysis requires that the treatment solution be free from contamination, waste hydrochloric acid in which oils and dust attached to the pickling steel are turbid is used. It is difficult to apply to the concentration process.
【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。[0010] If the waste hydrochloric acid treatment line is to be remodeled in order to solve the shortage of the waste hydrochloric acid treatment capacity, a great deal of cost and time are required. Forced to suspend. The present invention seeks to provide an improved treatment method and apparatus for solving the above-mentioned problems relating to the treatment of waste hydrochloric acid.
【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。SUMMARY OF THE INVENTION The present invention provides a process for evaporating and concentrating iron-containing waste hydrochloric acid discharged from a steel pickling apparatus, and oxidizing and roasting the concentrated waste hydrochloric acid to oxidize iron (ferrous chloride). A roasting step in which iron and HCl are decomposed, H generated by roasting
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 by bringing the roasting furnace gas generated in the roasting step into contact with waste hydrochloric acid as a heat source. In the roasting type waste hydrochloric acid treatment method performed by the above, the waste hydrochloric acid discharged from the steel pickling apparatus, prior to the evaporative concentration step using the roasting furnace gas as a heat source, by indirect heating by a heat source other than the heat source. A preconcentration process of evaporating and concentrating is performed, and a vapor component generated from waste hydrochloric acid by the preconcentration is recovered as condensed water, which is used 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。A waste hydrochloric acid treatment method according to the present invention is directed to an indirect heating device for evaporating and concentrating waste hydrochloric acid in a waste hydrochloric acid supply path connecting a steel pickling apparatus and a waste hydrochloric acid concentration tower in a roasting waste hydrochloric acid treatment system. Waste water treatment with a pre-concentrator provided with a condenser for condensing the evaporative component generated from the waste hydrochloric acid in the pre-concentrator and making it a part of the hydrochloric acid recovery water in the hydrochloric acid recovery tower It can be implemented in an apparatus.
【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, prior to introducing waste hydrochloric acid discharged from a steel pickling apparatus into a roasting type waste hydrochloric acid treatment system,
That is, prior to the evaporation and concentration treatment 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 preconcentration treatment of waste hydrochloric acid is performed by indirect heating, the reduced amount of waste hydrochloric acid due to the evaporation and concentration directly reduces the load on the roasting furnace 3 and only reduces the fuel consumption of the roasting furnace. Instead, due to the reduction in the amount of gas generated in the system and the effect of reducing the load on the blower, the capacity of treating waste hydrochloric acid increases corresponding to the concentration rate in the preconcentration.
【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, in the above preconcentration treatment,
Needless to say, a fuel for evaporative concentration is required, but when compared with the increase in fuel consumption when the combustion in the roasting furnace 3 is enhanced, the roasting furnace can oxidize iron (FeCl 2 ). In order to carry out the reaction, it is necessary to maintain an oxygen-rich atmosphere, so that combustion with low thermal efficiency is inevitable, whereas in the pre-concentration process, there is no such restriction, and heat supply with high thermal efficiency is possible. Yes, that means less fuel consumption.
【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。[0015] Looking at the amount of gas generated in the system,
When increasing the evaporation rate of waste hydrochloric acid in the waste hydrochloric acid concentrating tower 2, an increase in the amount of fuel / air 31 blown to raise the temperature of the roasting product gas of the roasting furnace 3, which is the heat source, and the accompanying roasting. In contrast to the increase in the amount of gas produced by burning, the preconcentration treatment does not have such disadvantages, and the blower load due to the reduction in the amount of waste hydrochloric acid to be roasted and the amount of gas produced by roasting is reduced according to the concentration rate. Is obtained. Since the load power of the blower B for sucking the gas in the system has a relationship proportional to the cube of the increase rate of the amount of gas in the system, the effect of reducing the amount of gas generated by the preconcentration and reducing the amount of gas generated in the system 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。In the preconcentration process, the evaporative components generated from the waste hydrochloric acid (which vary depending on the F.HCl concentration and the iron concentration of the waste hydrochloric acid, but contain about 1 to 5% HCl) are condensed and recovered with hydrochloric acid. There is no loss of hydrochloric acid as it is used as absorption water for
【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。FIG. 1 shows a waste hydrochloric acid treatment system according to the present invention. The processing system portion surrounded by a broken line is the same as that of the conventional system shown in FIG. 2, and the same portions are denoted by the same reference numerals. In the figure, reference numeral 1 denotes a pre-concentrator for waste hydrochloric acid, and reference numeral 6 denotes a condenser for recovering evaporated components of waste hydrochloric acid generated in the pre-concentrator 1 as coagulated 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, and a steel pickling device a, the sheet path l 1 feed waste hydrochloric connecting the concentrating tower 2 processing system b, the path l 2
Is installed through. A part or all of the waste hydrochloric acid discharged from the pickling apparatus a is partially or entirely changed by the opening and closing operation of the valve V of the waste hydrochloric acid supply passage l 1 , and a part or the whole of the waste hydrochloric acid is supplied to the preconcentrator 1.
Without passing through the pre-concentrator 1 and sent to the concentration tower 2 of the processing system b. The opening and closing operation of the valve V is appropriately performed according to the discharge flow rate of the waste hydrochloric acid from the pickling apparatus a. The pre-concentrator 1 has an indirect heating device 11 that uses an external heat source independent of the processing system b as a heat source, unlike the concentrating tower 2 in the processing system b. The heat source is not limited, and may be, for example, steam, combustion gas, or resistance heat.
【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 pre-concentrator 1 is heated under a reduced pressure by a heating device 11 to a suitable temperature (for example, 60 to 70).
℃) and concentrated by evaporation. Needless to say, the concentration ratio is appropriately set according to the original concentration of the waste hydrochloric acid. However, at a normal concentration of the waste hydrochloric acid, the concentration is increased by about 10 to 15%. HCl about 70-10
0 g / l, Fe concentration, about 80 to 120 g / l, is preferably introduced into the concentration tower 2 as primary concentrated waste hydrochloric acid.
【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 the preconcentration treatment in the preconcentrator 1 is performed by the roasting furnace fed from the roasting furnace 3 as described with reference to FIG. After evaporative concentration by direct contact with gas, the roasting furnace 3
Is roasted and oxidized and roasted, and the generated iron oxide is separated and recovered as a ferrite raw material or the like. On the other hand, the roasting furnace gas containing HCl is heat-exchanged with waste hydrochloric acid in the concentration tower 2 and then transferred to the hydrochloric acid recovery tower 4. It is introduced and subjected to hydrochloric acid recovery treatment. The exhaust gas after the recovery of hydrochloric acid is treated in the abatement tower 5 and released to the atmosphere, which is not different from that in FIG.
【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 evaporated component generated from the waste hydrochloric acid in the preconcentrator 1 contains a small amount of HCl. The concentration of the HCl component is determined by the F.C. Although it depends on the concentration of HCl and iron (FeCl 2 ), it is usually about 1 to
It is about 5%. The evaporated component is introduced into the condenser 6 through the path 18 and cooled by the cooling device 61 to be collected as flocculated water. Recovered condensed water is supplied to the hydrochloric acid recovery column 4 via the path l 9, is used as 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)
It is refluxed in pickling tanks in the pickling device a via path l 7.
During the reflux to the pickling tank, the concentration is adjusted if necessary.
【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。According to the present invention, for example, a processing capacity of 5000 l / H
r applied to the treatment system b and discharged from the pickling apparatus a
Concentrating 00 l / Hr of waste hydrochloric acid to 4500 l / Hr by pre-concentrating the pre-concentrator 1 at, for example, a concentration rate of 10% increases the processing capacity by an amount corresponding to the reduction of 500 l / Hr. Is equivalent to Waste hydrochloric acid discharged from the pickling apparatus a at a flow rate of 5000 l / Hr (for example, 70 g / l of F.HCl and 100 g /
l) was subjected to a pre-concentration treatment at a concentration ratio of 10% to obtain 4500 l
/ Hr as waste hydrochloric acid and supply it into the treatment system b, the overall fuel consumption is about 25 Nm 3 / Hr
(Natural gas) and power consumption can save 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。After the primary concentration by the pre-concentrator 1 and the secondary concentration treatment in the concentration tower 2, if the concentration of the waste hydrochloric acid fed from the concentration tower 2 to the roasting furnace 3 becomes too high,
Since iron (FeCl 2 ) is crystallized from the waste hydrochloric acid and causes troubles in the apparatus (for example, clogging of a pipeline), the concentration treatment in the preconcentrator 1 is performed by using the waste hydrochloric acid discharged from the concentration tower 2. Is F. HCl about 100g /
It is preferable to adjust the l and Fe contents so as not to exceed about 150 g / l. However, an increase in the amount of waste hydrochloric acid discharged from the pickling apparatus a and an insufficiency of the processing capacity of the processing system b are mainly caused by the pickling of the hard-to-pick steel material. Since the concentration of the waste hydrochloric acid is relatively low, there is almost no restriction on the execution of the preconcentration treatment in practical operation, and the enrichment rate in the preconcentration treatment is generally 10 to 15% under the normal operating conditions. If it is set in the range, the effect of the 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。According to the present invention, the effect of the preconcentration of waste hydrochloric acid is to significantly reduce fuel and electric power costs in the treatment of waste hydrochloric acid (recovery of iron oxide, recovery and reflux of hydrochloric acid), and to increase the processing capacity. Is obtained. In addition, the preconcentration treatment does not require a major modification of the existing treatment equipment, and only takes a simple measure of attaching a preconcentrator to the waste hydrochloric acid feed line between the existing equipment and the pickling equipment. It can be carried out in a practical way.
【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 Preconcentrator, 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 pickling apparatus, and oxidizing and roasting the concentrated waste hydrochloric acid to decompose iron (ferrous chloride) into iron oxide and HCl. A step of recovering hydrochloric acid by bringing a roasting furnace gas containing HCl or the like generated by roasting into contact with water, and evaporating and concentrating the waste hydrochloric acid by roasting the roasting furnace gas generated in the roasting step. In the 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 pickling apparatus is subjected to the heat source prior to the evaporative concentration step using the roasting furnace gas as a heat source. Pre-concentration by evaporating and concentrating by indirect heating with a heat source other than the above, and recovering the vapor component generated from the waste hydrochloric acid by the pre-concentration as condensed water, which is used as a part of the hydrochloric acid recovered water in the hydrochloric acid recovery step 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 concentrating tower for evaporating and concentrating iron-containing waste hydrochloric acid discharged from a steel pickling apparatus, and a concentrated waste hydrochloric acid derived from the waste hydrochloric acid concentrating tower is oxidized and roasted to iron (ferrous chloride). A waste-hydrochloric acid roasting furnace for decomposing the waste gas into iron oxide and HCl; a hydrochloric acid recovery tower for recovering hydrochloric acid by bringing HCl-containing roasting furnace gas generated 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 concentrating tower, and after a heat exchange by direct contact with waste hydrochloric acid as a heat source for evaporating and condensing the waste hydrochloric acid, introduced into the hydrochloric acid recovery tower, A pre-concentrator equipped with an indirect heating device for evaporating and concentrating waste hydrochloric acid is provided in the waste hydrochloric acid feed line connecting the steel pickling equipment and the waste hydrochloric acid concentrating tower, and evaporative components generated from waste hydrochloric acid in the pre-concentrator. A waste hydrochloric acid treatment apparatus, wherein a condenser is provided for condensing water into a part of the hydrochloric acid recovered 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 JPH0533173A (en) | 1993-02-09 |
| JP2599655B2 true 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) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5500098A (en) * | 1993-08-05 | 1996-03-19 | Eco-Tec Limited | Process for regeneration of volatile acids |
| CN103391897B (en) | 2010-12-24 | 2016-05-18 | 昭荣化学工业株式会社 | The manufacture method of double oxide and manufacturing installation |
| 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 |
| 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 |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4816119U (en) * | 1971-07-08 | 1973-02-23 | ||
| JPS6242781A (en) * | 1985-08-14 | 1987-02-24 | 関東自動車工業株式会社 | Heat pump type steam washing apparatus and its operation |
-
1991
- 1991-07-30 JP JP3214471A patent/JP2599655B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH0533173A (en) | 1993-02-09 |
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| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19961022 |