CN103553256B - Recycling treatment process for chlorohydric acid pickling liquid waste - Google Patents
Recycling treatment process for chlorohydric acid pickling liquid waste Download PDFInfo
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- CN103553256B CN103553256B CN201310537848.3A CN201310537848A CN103553256B CN 103553256 B CN103553256 B CN 103553256B CN 201310537848 A CN201310537848 A CN 201310537848A CN 103553256 B CN103553256 B CN 103553256B
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Abstract
The invention discloses a recycling treatment process for chlorohydric acid pickling liquid waste. The process comprises the following steps: adjusting the acidity of CaCO3 of the chlorohydric acid pickling liquid waste to 99.65-124.56g/L; adding ferrous chloride so as to enable ferrite to be in a saturation condition; heating to the bubble point, then feeding the mixture into a rectifying tower and separating, wherein the pressure in the rectifying tower is 61.05-67.50Kpa; recovering a 10-15% diluted hydrochloric acid liquid and ferrous chloride crystals. Through reasonable parameter control and decompressing and rectifying processes, hydrochloric acid liquor applicable to acid pickling steel pieces as well as a coagulant capable of being used for sewage and wastewater treatment or a chemical raw material ferrous chloride can be recovered just by means of materials generated in the steel piece acid pickling process without spending other raw materials, so that the cost is greatly saved. The process is process-investment-saving, low in energy consumption and easy for mastering of operation, and can be continuously operated or intermittently operated in batches, thereby realizing automatically controlled operation.
Description
Technical field
The present invention relates to a kind of hydrochloric acid pickling waste liquor recycling treatment process, be mainly applicable to the recycling of medium and small shaped steel enterprise hydrochloric acid pickling waste liquor.
Background technology
Steel part needs to use sulfuric acid or hydrochloric acid to remove steel surface iron scale before galvanizing.Compared with sulfuric acid washing, chlorohydric acid pickling speed is fast, surface quality of steel is good, therefore, many steel enterprises select hydrochloric acid to carry out pickling, and in washing lotion, concentration of hydrochloric acid reduces gradually with acid cleaning process, ferrous ion content increases gradually, pickling speed slows down, and pickling effect is affected, and the hydrochloric acid that must more renew is to maintain suitable pickling speed.Chlorohydric acid pickling produce containing free hydrochloric acid weight ratio be 5% ~ 7%, the hydrochloric acid pickler of iron-holder 100 ~ 140g/L is hydrochloric acid pickling waste liquor, domestic Iron And Steel Industry is often produced 1t steel and is about produced 60kg spent pickle liquor, nearly 1,000,000 cubes of annual spent pickle liquor quantity discharged.The spent acid of pH≤2 is listed in " National Hazard refuse register " by China, and strict restriction has been done to ferric remains discharge, if the total iron emission limit set of Zhejiang Province's provincial standard " pickling waste waters discharges total concentration of iron limit value " (DB33/844-2011) strict regulation is at 2-10mg/L, Taihu Lake basin is performed to the special standard of 2mg/L.
Spent pickle liquor treatment process conventional at present has traditional moderate water-cut stage and application technology as the second resource.Moderate water-cut stage is current domestic process spent acid solution most popular method, and the hydrochloric acid in the alkaline matters such as the method alkali, lime and in spent acid, makes ferrous ion precipitate simultaneously.This method needs to consume a large amount of industrial chemicals such as alkali, lime, and running cost is high; In spent acid, hydrochloric acid and ferrous salt can not get recycling, and a large amount of waste residues of generation also can cause secondary pollution to environment, and this method is suitable only for the very low poaching wastewater process of pickling finishing operation acid content.
Spent pickle liquor resource technology mainly contains one-step calcinations, ion exchange method, membrane separation process, extraction process, chemical transformation, distillation method etc.
Roasting method has spray roasting and fluiddized-bed roasting two kinds of methods: spray roasting is sprayed into by roasting oven top after spent acid preheating being concentrated, the direct combustion heating of coal gas in stove, furnace body temperature is at about 670 DEG C, the tail gas obtained containing hydrogenchloride once absorbs through packing tower and obtains hydrochloric acid, obtains the oxide particle of iron at the bottom of stoving oven; Fluiddized-bed roasting method is the fluidized-bed sprayed into after spent acid solution preheating being concentrated containing ferric oxide fluidizing medium, and coal gas is direct combustion heating at the bottom of bed, and the hydrogen chloride tail gas that roasting obtains under 850 ~ 950 DEG C of conditions once absorbs through bubble-plate column and obtains hydrochloric acid.Roasting method by large iron and steel enterprise industrial applications, but this method front-end investment is large, equipment and processing requirement strict, medium-sized and small enterprises are difficult to bear.In addition, the iron oxide dust that the absorption of hydrogenchloride furnace gas not exclusively causes hydrogen chloride in tail gas discharge beyond standards and roasting to produce all can cause secondary pollution.
Ion exchange method and membrane separation process, by the restriction of high density iron level, easily cause resin and fouling membrane; Extraction process requires higher to extraction agent preparation, extractant regeneration etc., and recovery hydrochloric acid is directly used in pickling procedure may affect quality product due to residual extraction agent.
Chemical transformation is that free hydrochloric acid and iron protochloride are all converted into iron trichloride or ferrous sulfate, needs to consume chlorine, to add iron trichloride unmarketable, seldom adopt now because iron trichloride transforms.
Ferrous sulfate method need produce ferrous sulfate with sulfate substitution iron protochloride, because ferrous sulfate crystallization temperature is low, needs to add a set of ice maker system, and investment is large and working cost is higher.
Distillation method is that spent pickle liquor is squeezed into still kettle, be heated to boiling under a constant, liquid is constantly vaporized, the steam produced reclaims as dilute hydrochloric acid after condensation, the recyclable iron protochloride of still liquid crystallisation by cooling, its advantage neither consumes the various raw materials such as chlorine, sulfuric acid, alkali, lime, hydrochloric acid and ferrous salt can be reclaimed again, there is the advantages such as equipment is simple, processing cost is low, but when hydrochloric acid pickling waste liquor is distilled, hydrochloric acid-water azeotrope obstacle can be run into, cause reclaiming concentration of hydrochloric acid not high, reclaim not thorough.For solving hydrochloric acid-water azeotrope problem, CN103288232A adopts distillation with adding salts technology, add calcium chloride, magnesium chloride to change the vapor liquid equilibrium curve of hydrochloric acid-water, improve distilling effect, improve and reclaim concentration of hydrochloric acid, still raffinate can be used for preparing compound coagulant, but this method adopts atmosphere intermission distillation, energy consumption is comparatively large, and productivity is low; Additional calcium chloride, magnesium chloride cause working cost to increase.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, for medium and small shaped steel enterprise provides a kind of hydrochloric acid pickling waste liquor recycling treatment process.
A kind of hydrochloric acid pickling waste liquor recycling treatment process of the present invention, it is characterized in that filling the interim equalizing tank of salt picking acid pond as the process of hydrochloric acid pickling waste liquor recycling of hydrochloric acid pickling waste liquor, the acidity of hydrochloric acid pickling waste liquor is regulated, by the CaCO of this hydrochloric acid pickling waste liquor in this interim equalizing tank
3acidity is adjusted to 99.65 ~ 124.56g/L, then in interim equalizing tank, add iron protochloride makes ferrous salt in hydrochloric acid pickling waste liquor reach capacity state, carry successively by inner tube of heat exchanger road I through chemical pump pump, preheater enters rectifying tower opening for feed and passes through in column plate inflow still kettle after making hydrochloric acid pickling waste liquor be warming up to bubble point, solution in still kettle is again heat vaporized through reboiler, the steam arriving rectifying tower top vapour outlet passes through successively through inner tube of heat exchanger road II, condenser I is condensed into liquid, wherein partially liq returns rectifying tower column plate at the highest level through Y-tube by rectifying tower column plate import at the highest level, all the other liquid enter two withdrawing cans I in parallel through Y-tube order, in service sink, the steam of rectifying tower lower steam outlet is successively through dilute hydrochloric acid solution that inner tube of heat exchanger road III, condenser II condensation are recycled, this dilute hydrochloric acid solution enters in two withdrawing cans II in parallel, salt picking acid pond through pipeline order, raffinate in still kettle flows into crystallization kettle crystallisation by cooling and obtains iron protochloride crystal, vacuum state in rectifying tower is by connecting empty pump to maintain, and its pressure is 61.05Kpa ~ 67.50Kpa.
For economizing on resources, described will fill the interim equalizing tank adjustment acidity of salt picking acid pond as the process of hydrochloric acid pickling waste liquor recycling of hydrochloric acid pickling waste liquor, add water and regulate its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank when preferably the acidity of hydrochloric acid pickling waste liquor is higher in interim equalizing tank
3acidity is adjusted to 99.65g/L ~ 124.56g/L; Or the hydrochloric acid pickling waste liquor adding concentration of hydrochloric acid when the acidity of hydrochloric acid pickling waste liquor is lower in interim equalizing tank higher than the concentration of hydrochloric acid of the hydrochloric acid pickling waste liquor in this interim equalizing tank regulates its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank
3acidity is adjusted to 99.65g/L ~ 124.56g/L.
Described a kind of hydrochloric acid pickling waste liquor recycling treatment process, the dilute hydrochloric acid concentration of recovery is 10% ~ 15%, and described percentage ratio is hydrochloric acid massfraction.The dilute hydrochloric acid concentration reclaimed is suitable for being re-used as hydrochloric acid pickler and utilizes.
Principle of work of the present invention and technical process are:
In the pickling operating mode of steel part, usually multiple salt picking acid pond is provided with side by side, after one of them salt picking acid pond process steel part, when hydrochloric acid soln in its pond has been hydrochloric acid pickling waste liquor (chlorohydric acid pickling produce containing free hydrochloric acid weight ratio be 5% ~ 7%, the hydrochloric acid pickler of iron-holder 100 ~ 140g/L is hydrochloric acid pickling waste liquor), pickling steel part in the salt picking acid pond that another fills suitable steel part pickling concentration again, the concentration of hydrochloric acid of suitable steel part pickling is usually 10% ~ 20% (weight).
The present invention will be that the salt picking acid pond of hydrochloric acid pickling waste liquor is as interim equalizing tank in its pond after pickling steel part, the acidity of this hydrochloric acid pickling waste liquor is regulated in this pond, by regulating the suitable acidity of hydrochloric acid pickling waste liquor, add iron protochloride and reach that ferrous salt is saturated, preheating reaches bubble point temperature, enter rectifying tower rectification under vacuum, the salting-out effect utilizing ferrous salt to produce changes the vapor liquid equilibrium curve of hydrochloric acid-water, efficiently solves the problem that hydrochloric acid-water constant boiling solution is difficult to be separated.Have three pipelines in interchanger, two ends, inner tube of heat exchanger road I are connected with chemical pump, preheater respectively by pipe connecting, and the liquid that chemical pump is carried from interim acidity adjustment pond pump enters rectifying tower by interchanger, preheater successively; Two ends, inner tube of heat exchanger road II export with overhead vapours respectively by pipe connecting, condenser I is connected, make the steam of arrival tower top return rectifying tower by interchanger, condenser I condensation rear section successively, remainder order enters withdrawing can I, service sink (service sink is the pond with the steel part surface of water cleaning after chlorohydric acid pickling); III two ends, inner tube of heat exchanger road export with rectifying tower lower steam respectively by pipe connecting, condenser II is connected recovery and obtains dilute hydrochloric acid, and therefore, in interchanger, the material of three pipelines does not interfere with each other.The acidity that the present invention regulates is suitable for, ferrous salt hydrochloric acid pickling waste liquor that is saturated and that reach bubble point temperature passes through chemical pump, preheater enters rectifying tower, by column plate stage trapping, wherein relatively light in mixed gas vaporous water has more volatility than hydrogen chloride gas, thus, the gas arriving tower top is hydrochloric few vaporous water, through inner tube of heat exchanger road II, the liquid portion that condenser I becomes containing pole dilute hydrochloric acid returns rectifying tower, remainder order enters withdrawing can I, service sink mixes with the water in service sink, the water behind steel part surface is cleaned in service sink, alkaline cleaning can reach the requirement of related industries wastewater discharge standard and discharge according to a conventional method, thus do not pollute the environment.The hydrochloric acid liquid order that the hydrogen chloride gas that volatility is little relative to vaporous water in rectifying tower can export through rectifying tower lower steam, pipeline III in interchanger, condenser II become recovery enters withdrawing can II, salt picking acid pond, pickling steel part is mixed for the hydrochloric acid pickler in salt picking acid pond, thus, in hydrochloric acid pickling waste liquor, most of hydrochloric acid obtains recycling.The solution of ferrous chloride that rectifier bottoms flows out becomes the iron protochloride byproduct of recovery through crystallization kettle crystallization.In the iron protochloride reclaimed, part can add in interim equalizing tank ferrous salt in hydrochloric acid pickling waste liquor is reached capacity state, and part oven drying at low temperature, as byproduct, can be used for coagulating agent or the industrial chemicals of sewage disposal.The reboiler of still kettle outer wall heats again makes still liquid vaporize, and can obtain the steam of rising to maintain the carrying out of rectifying.
The present invention is by large quantity research and test, and the acidity adjustment parameter of the hydrochloric acid pickling waste liquor of acquisition is by the CaCO of hydrochloric acid pickling waste liquor
3acidity is adjusted to 99.65g/L ~ 124.56g/L, and drop into that iron protochloride makes that spent pickle liquor ferrous salt is saturated, vacuum pressure parameter (tower internal pressure 61.05Kpa ~ 67.50Kpa), reasonably technical process, the HCl recovery product of suitable steel part pickling and industrial iron protochloride product can be recovered to.The CaCO of hydrochloric acid pickling waste liquor
3acidity is lower than 99.65g/L, and its concentration of hydrochloric acid reclaimed is lower, can not be used for pickling steel part, the CaCO of hydrochloric acid pickling waste liquor
3acidity is higher than 124.56g/L, and in the mixing steam of rectifying tower bottom, the hydrogen chloride gas scale of construction is excessive and vaporous water that is that can not be condensed absorbs completely, and cause HCl recovery rate to reduce, both all can not reach the object of the recycling process of waste liquid; And passing through the control of parameter of the present invention, the concentration of hydrochloric acid of recovery is 10% ~ 15%, and this concentration is the hydrochloric acid acid strength of suitable steel part pickling, and the concentration of hydrochloric acid of recovery is too high or mistake is rare is all not suitable for steel part pickling.Therefore, compared with prior art, beneficial effect of the present invention has:
1, the present invention is by large quantity research and test, the vacuum pressure parameter obtain the acidity adjustment parameter of rational hydrochloric acid pickling waste liquor, maintaining in tower, by these state modulator and ferrous salt is saturated, preheating reaches bubble point, rectification under vacuum technical process reasonable coordination, only utilize the material produced in steel part acid cleaning process, do not need to spend other raw material can effectively be recovered to the hydrochloric acid soln being suitable for steel part pickling, and can be used for coagulating agent or the industrial chemicals iron protochloride of stain disease process, greatly save cost.
The concentration of hydrochloric acid that the present invention reclaims is 10% ~ 15%, is the hydrochloric acid acid strength of suitable steel part pickling, and the concentration of hydrochloric acid of recovery is too high or mistake is rare is all not suitable for steel part pickling, neither wastes resource, in turn saves the energy.
The salting-out effect that the byproduct iron protochloride that the present invention only utilizes the present invention to reclaim produces can change the vapor liquid equilibrium curve of hydrochloric acid-water, effective solution hydrochloric acid-water constant boiling solution is difficult to the problem be separated, do not need to add other raw material of cost, utilize the acidity of water or hydrochloric acid pickling waste liquor and adjustable hydrochloric acid pickling waste liquor, also greatly save cost.
2, the salt picking acid pond filling hydrochloric acid pickling waste liquor is provided to rectifying tower the raw material treating that recycling treatment utilizes by the present invention after interim equalizing tank adjustment acidity, both investment cost can be reduced, also continuously-running or batch intermittent operation, realize auto-controll operation, its rational technology is ingenious, wide adaptability.
3, the whole technology investment of the present invention is economized, energy consumption is low, easy and simple to handle, be easy to grasp.Used unit such as the equipment such as interchanger, preheater, rectifying tower, condenser, chemical pump, vacuum pump can select existing relevant device on market according to production scale of enterprise, simple installation.
4, the present invention has good economic benefit and environmental benefit, is suitable for the recycling of middle and small scale hydrochloric acid pickling waste liquor.
Accompanying drawing explanation
Fig. 1 is hydrochloric acid pickling waste liquor recycling treatment process schema of the present invention.
Fig. 2 is hydrochloric acid pickling waste liquor recycling treatment process equipment therefor schematic diagram of the present invention.
Mark in two figure and represent successively: 1-interim equalizing tank; 2-chemical pump; 3-interchanger; 4-preheater; 5-rectifying tower; 6-still kettle; 7-reboiler; 8-vacuum pump; 9-condenser I; 10-service sink; 11-condenser II; 12-salt picking acid pond; 13-galvanizing pond; 14-crystallization kettle; 15-rectifying tower lower steam exports; 16-inner tube of heat exchanger road I; 17-inner tube of heat exchanger road II; 18-inner tube of heat exchanger road III; 19-withdrawing can I; 20-withdrawing can II; 21-rectifying tower top vapour outlet; The column plate import at the highest level of 22-rectifying tower; 23-rectifying tower opening for feed.
Embodiment
See Fig. 2, the commercially available conventional components of equipment therefor in hydrochloric acid pickling waste liquor recycling treatment process flow process of the present invention, to be formed by connecting in the usual way, the connection wherein relating generally to each parts that connection, 2. rectifying tower top vapour stream that 1. hydrochloric acid pickling waste liquor enters each parts that rectifying tower relates to go out to relate to, the dilute hydrochloric acid solution 3. reclaimed are recovered to the connection of connection, the 4. vacuum pump of each parts that salt picking acid pond relates to, and the annexation of each parts is as follows:
1. hydrochloric acid pickling waste liquor enters the connection of each parts that rectifying tower relates to: chemical pump 2 suction side connects interim equalizing tank 1, water side connects inner tube of heat exchanger road I 16, the other end in inner tube of heat exchanger road I 16 connects preheater 4, and preheater 4 is connected by pipeline with rectifying tower opening for feed 22;
2. the rectifying tower top vapour stream connection of each parts that goes out to relate to: rectifying tower top vapour outlet 21 is connected with inner tube of heat exchanger road II 17 by pipeline, the other end in inner tube of heat exchanger road II 17 is connected with by the steam inlet of pipeline with condenser I9, two mouths of pipe of Y-tube respectively with the liquid outlet of condenser I9, rectifying tower column plate import 22 at the highest level connects, another mouth of pipe of Y-tube is connected with two withdrawing can I19 in parallel, the pipeline that the fluid inlet of two withdrawing can I19 is connected with liquid outlet is provided with valve respectively, the liquid outlet of two withdrawing can I19 is connected with service sink 10,
3. the dilute hydrochloric acid solution reclaimed is recovered to the connection of each parts that salt picking acid pond relates to: the pipeline that the outlet of rectifying tower lower steam 15 is connected with inner tube of heat exchanger road III18 by pipeline, the other end of inner tube of heat exchanger road III18 is connected with condenser II11 by pipeline, the liquid outlet of condenser II is connected with two withdrawing can II20 of parallel connection by pipeline, the fluid inlet of two withdrawing can II20 and liquid outlet connect is provided with valve respectively, and the liquid outlet of two withdrawing can II20 is connected with salt picking acid pond 12; Still kettle 6 exports and connects crystallization kettle 14 import;
4. the connection of vacuum pump: the inlet mouth of vacuum pump 8 is connected in parallel respectively by pipeline and condenser I9, condenser II11.
See Fig. 1, hydrochloric acid pickling waste liquor recycling treatment process of the present invention is:
The interim equalizing tank 1 of salt picking acid pond as the process of hydrochloric acid pickling waste liquor recycling of hydrochloric acid pickling waste liquor will be filled, in this interim equalizing tank 1, regulate the acidity of hydrochloric acid pickling waste liquor, add water when the acidity of hydrochloric acid pickling waste liquor is higher in interim equalizing tank 1 and regulate its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank 1
3acidity is adjusted to 99.65g/L ~ 124.56g/L; The hydrochloric acid pickling waste liquor adding concentration of hydrochloric acid when the acidity of hydrochloric acid pickling waste liquor is lower in interim equalizing tank 1 higher than the concentration of hydrochloric acid of the hydrochloric acid pickling waste liquor in this interim equalizing tank 1 regulates its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank 1
3acidity is adjusted to 99.65g/L ~ 124.56g/L.Then in interim equalizing tank 1, add iron protochloride makes ferrous salt in hydrochloric acid pickling waste liquor reach capacity state, carry successively by interchanger 3 interior conduit I 16 through chemical pump 2 pump, preheater 4 enters rectifying tower opening for feed 23 and passes through in column plate inflow still kettle 6 after making hydrochloric acid pickling waste liquor be warming up to bubble point, solution in still kettle 6 is again heat vaporized through reboiler 7, the steam arriving rectifying tower top vapour outlet 21 passes through successively through inner tube of heat exchanger road II 17, condenser I 9 is condensed into liquid, wherein partially liq returns rectifying tower column plate at the highest level through Y-tube by rectifying tower column plate import 22 at the highest level, rest part liquid enters two withdrawing cans I 19 in parallel through Y-tube order, in service sink 10, the steam of rectifying tower lower steam outlet 15 is successively through inner tube of heat exchanger road III(18), the dilute hydrochloric acid solution that condenser II 11 condensation is recycled, this dilute hydrochloric acid solution enters two withdrawing cans II 20 in parallel through pipeline order, in salt picking acid pond 12, two withdrawing cans II 20 can be connected with same salt picking acid pond 12, from can be connected with different salt picking acid ponds 12 respectively, raffinate in still kettle 6 flows into crystallization kettle 14 crystallisation by cooling and obtains iron protochloride crystal, vacuum state in rectifying tower 5 tower maintains by connecting vacuum pump 8, its pressure is maintained 61.05Kpa ~ 67.50Kpa.
The salt picking acid pond that namely failed for pickle solution former pickling pond is filled hydrochloric acid pickling waste liquor by the present invention is as interim equalizing tank 1 and regulate hydrochloric acid pickling waste liquor acidity to described Acidity Range, then in equalizing tank 1, add the iron protochloride of recovery, waste liquid ferrous salt is reached capacity state, carrying being entered after being heated to hydrochloric acid pickling waste liquor bubble point by interchanger 3, preheater 4 through chemical pump 2 pump is in the rectifying tower 5 of vacuum state, and now in rectifying tower, hydrochloric acid pickling waste liquor flows through column plate from top to bottom and flows in still kettle 6; Be located at still kettle 6) reboiler 7 of outer wall the liquid in still kettle 6 is heated again make its components vaporize after flow through column plate from bottom to top, gas, liquid two-phase are undertaken conducting heat and mass transfer by column plate.Because the volatility of water vapour in tower is larger than the volatility of hydrogenchloride, therefore, in the steam of tower top, hydrogen chloride content is few, thus, the liquid of condensation is that pole dilute hydrochloric acid enters in service sink, alkaline cleaning can reach the requirement of related industries wastewater discharge standard and discharge according to a conventional method, does not thus pollute the environment.The CaCO of hydrochloric acid pickling waste liquor is regulated in the present invention
3acidity is adjusted to 99.65g/L ~ 124.56g/L, in hydrochloric acid pickling waste liquor, ferrous salt reaches capacity state, liquid reaches bubble point and enters in rectifying tower 5 tower, under vacuum state pressure in rectifying tower 5 tower is maintained the condition of 61.05Kpa ~ 67.50Kpa, 15 steam flowed out are exported through interchanger 3 by rectifying tower lower steam, condenser II 11 condensation can be recycled to the dilute hydrochloric acid that concentration of hydrochloric acid is 10% ~ 15%, (described percentage ratio is massfraction), this concentration is the hydrochloric acid acid strength of suitable steel part pickling, the concentration of hydrochloric acid reclaimed is too high or mistake is rare is all not suitable for steel part pickling, therefore the inventive method both save energy, the object of the recycling process of hydrochloride waste can be reached again, cost is low, suitable especially medium-sized and small enterprises.In tower reactor, raffinate is supersaturation ferrous salt solution, recyclable iron protochloride byproduct after crystallization kettle 14 crystallisation by cooling.
Claims (2)
1. a hydrochloric acid pickling waste liquor recycling treatment process, it is characterized in that: will the interim equalizing tank (1) of salt picking acid pond as the process of hydrochloric acid pickling waste liquor recycling of hydrochloric acid pickling waste liquor be filled, the acidity of hydrochloric acid pickling waste liquor is regulated in this interim equalizing tank (1), add water in this interim equalizing tank (1) or add the concentration of hydrochloric acid hydrochloric acid pickling waste liquor higher than the concentration of hydrochloric acid of the hydrochloric acid pickling waste liquor in this interim equalizing tank (1) to regulate acidity, by the CaCO of this hydrochloric acid pickling waste liquor
3acidity is adjusted to 99.65 ~ 124.56g/L, then in interim equalizing tank (1), add iron protochloride makes ferrous salt in hydrochloric acid pickling waste liquor reach capacity state, carry successively by inner tube of heat exchanger road I (16) through chemical pump (2) pump, preheater (4) enters rectifying tower opening for feed (23) and passes through in column plate inflow still kettle (6) after making hydrochloric acid pickling waste liquor be warming up to bubble point, solution in still kettle (6) is again heat vaporized through reboiler (7), the steam arriving rectifying tower top vapour outlet (21) passes through successively through inner tube of heat exchanger road II (17), condenser I (9) is condensed into liquid, wherein partially liq returns rectifying tower column plate at the highest level through Y-tube by rectifying tower column plate import (22) at the highest level, all the other liquid are introduced into two withdrawing cans I (19) in parallel through another mouth of pipe of Y-tube, enter in service sink (10) again, the steam of rectifying tower lower steam outlet (15) is successively through inner tube of heat exchanger road
(18), the dilute hydrochloric acid solution that is recycled of condenser II (11) condensation, this dilute hydrochloric acid solution is introduced into two withdrawing cans II (20) in parallel through pipeline, enters in salt picking acid pond (12) again, raffinate in still kettle (6) flows into crystallization kettle (14) crystallisation by cooling and obtains iron protochloride crystal, vacuum state in rectifying tower (5) tower is maintained by the vacuum pump (8) connected, and its pressure is 61.05Kpa ~ 67.50 Kpa.
2. a kind of hydrochloric acid pickling waste liquor recycling treatment process according to claim 1, is characterized in that: the dilute hydrochloric acid concentration of recovery is 10% ~ 15%, and described percentage ratio is massfraction.
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| CN103819042B (en) * | 2014-03-19 | 2016-06-08 | 江苏星瑞化工工程科技有限公司 | A kind of hydrochloride waste purifying treatment method |
| CN104003490B (en) * | 2014-05-19 | 2015-10-07 | 上海大学 | Utilize the method for adding β-three water ferric fluoride crystal seed process stainless steel acid-washing waste liquid Footwall drift |
| CN104860269B (en) * | 2015-04-14 | 2017-08-11 | 广东工业大学 | The recovery method and device of hydrochloric acid in industrial wastes |
| CN104944665B (en) * | 2015-06-19 | 2017-04-26 | 浙江大学 | Comprehensive resourceful treatment method for chlorohydric acid pickling waste liquid |
| CN106430100B (en) * | 2016-10-19 | 2019-04-16 | 深圳泛科环保产业发展有限公司 | A kind of ferrous waste acid liquid recycling continuous production vacuum distillation equipment and technique |
| CN106630398B (en) * | 2016-12-02 | 2019-07-16 | 自然资源部天津海水淡化与综合利用研究所 | A method of handling high salt organic waste water |
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| JPH0517160A (en) * | 1991-07-08 | 1993-01-26 | Asaka Riken Kogyo Kk | Recovery of hydrochloric acid and iron sulfate from waste liquor of ferrous chloride |
| JP2000264640A (en) * | 1999-03-17 | 2000-09-26 | Tsurumi Soda Co Ltd | Treatment of waste liquor of hydrochloric acid |
| CN1373243A (en) * | 2001-12-31 | 2002-10-09 | 南昌大学 | Process for treating waste pickling liquid of hydrochloric acid by negative-pressure external-circulation evaporation-concentrating crystallization method |
| CN201010528Y (en) * | 2007-03-06 | 2008-01-23 | 天津市聚鑫源水处理技术开发有限公司 | Processing system for recycling ferrous chloride crystal and hydrochloric acid from hydrochloric acid waste liquid |
| CN101665301A (en) * | 2008-09-05 | 2010-03-10 | 中国科学院生态环境研究中心 | Resource treatment method for hydrochloric acid pickling waste liquor |
| CN102690010A (en) * | 2011-03-24 | 2012-09-26 | 镇江市丹徒区江南热镀锌有限公司 | Resource integrated utilization and treatment method of hydrochloric acid pickling waste liquid |
| CN202072465U (en) * | 2011-05-24 | 2011-12-14 | 钱钧 | Pickling waste liquid recycling treatment device |
| CN202193614U (en) * | 2011-08-08 | 2012-04-18 | 常州化工设备有限公司 | Processing equipment for concentrating and recycling hydrochloric acid |
| CN102602890A (en) * | 2012-03-20 | 2012-07-25 | 恩典汇智(北京)投资管理有限公司 | Method and device for recycling useful substances from waste hydrochloric acid liquor |
| CN102660751B (en) * | 2012-04-28 | 2014-05-21 | 浙江大学 | Resourceful treating method and resourceful treating device for metal pickling effluent |
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| CN103553256A (en) | 2014-02-05 |
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