CN103553256A - 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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- CN103553256A CN103553256A CN201310537848.3A CN201310537848A CN103553256A CN 103553256 A CN103553256 A CN 103553256A CN 201310537848 A CN201310537848 A CN 201310537848A CN 103553256 A CN103553256 A CN 103553256A
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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 that medium and small shaped steel is looked forward to hydrochloric acid pickling waste liquor.
Background technology
Steel part needs to remove steel surface iron scale with sulfuric acid or hydrochloric acid before galvanizing.Compare with sulfuric acid washing, chlorohydric acid pickling speed is fast, surface quality of steel is good, therefore, many steel are looked forward to selecting 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, every productions of domestic Iron And Steel Industry 1t steel approximately produce 60kg spent pickle liquor, spent pickle liquor quantity discharged is nearly 1,000,000 cubes every year.China has listed the spent acid of pH≤2 in the Hazardous Waste List > > of < < country, and residual iron discharge has been done to strict restriction, as Zhejiang Province's provincial standard < < pickling waste waters discharges the total iron emission limit set of total concentration of iron limit value > > (DB33/844-2011) strict regulation at 2-10mg/L, for Taihu Lake basin, carry out the special standard of 2mg/L.
Conventional spent pickle liquor treatment process has traditional neutralization precipitation method and application technology as the second resource at present.Neutralization precipitation method is current domestic processing spent acid solution most popular method, and the hydrochloric acid for the method in the alkaline matter such as alkali, lime and in spent acid makes ferrous ion precipitation simultaneously.This method need to consume the industrial chemicals such as a large amount of 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 only suitable for processing in the very low poaching wastewater of pickling finishing operation acid content.
Spent pickle liquor resource technology mainly contains direct roasting method, ion exchange method, membrane separation process, extraction process, chemical transformation, distillation method etc.
Roasting method has spray roasting and two kinds of methods of fluiddized-bed roasting: spray roasting is by roasting oven top, to be sprayed into after spent acid preheating is concentrated, the direct combustion heating of coal gas in stove, furnace body temperature is 670 ℃ of left and right, the tail gas that obtains containing hydrogenchloride once absorbs and obtains hydrochloric acid through packing tower, obtains the oxide particle of iron at the bottom of stoving oven; Fluiddized-bed roasting method is to spray into the fluidized-bed containing ferric oxide fluidizing medium after spent acid solution preheating is concentrated, and coal gas is direct combustion heating at the bottom of bed, and the hydrogen chloride tail gas that roasting obtains under 850～950 ℃ of conditions once absorbs and obtains hydrochloric acid through bubble-plate column.Roasting method is by large-scale 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 are subject to the restriction of high density iron level, easily cause resin and film to pollute; Extraction process is had relatively high expectations 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, need to consume chlorine, to add iron trichloride unmarketable because iron trichloride transforms, and seldom adopts now.
Ferrous sulfate method need be replaced iron protochloride with sulfuric acid and be produced ferrous sulfate, because ferrous sulfate crystallization temperature is low, need 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, under constant pressure, be heated to boiling, liquid is constantly vaporized, the steam producing reclaims as dilute hydrochloric acid after condensation, the recyclable iron protochloride of still liquid crystallisation by cooling, its advantage is neither to consume the various raw materials such as chlorine, sulfuric acid, alkali, lime, can reclaim hydrochloric acid and ferrous salt again, there is the advantages such as equipment is simple, processing cost is low, but when hydrochloric acid pickling waste liquor is distilled, can run into hydrochloric acid-water azeotrope obstacle, 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 larger, 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 looks forward to providing 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 the interim equalizing tank that the salt picking acid pond that fills hydrochloric acid pickling waste liquor is processed as hydrochloric acid pickling waste liquor recycling, in this interim equalizing tank, regulate the acidity of hydrochloric acid pickling waste liquor, by the CaCO of this hydrochloric acid pickling waste liquor
3acidity is adjusted into 99.65～124.56g/L, then in interim equalizing tank, add iron protochloride make hydrochloric acid pickling waste liquor in the ferrous salt state that reaches capacity, through chemical pump pump, carry successively by interchanger interior conduit I, preheater is warming up to hydrochloric acid pickling waste liquor to enter rectifying tower opening for feed after bubble point by column plate, to flow in still kettle from top to bottom, solution in still kettle heats vaporization again through reboiler, the steam that arrives rectifying tower top vapour outlet passes through successively through interchanger interior conduit II, condenser I is condensed into liquid, wherein partially liq returns to 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 can I in parallel through Y-tube order, in service sink, the dilute hydrochloric acid solution that the steam of rectifying tower bottom vapour outlet is recycled through interchanger interior conduit III, the condensation of condenser II successively, this dilute hydrochloric acid solution is in pipeline order enters two withdrawing can II in parallel, salt picking acid pond, raffinate in still kettle flows into crystallization kettle crystallisation by cooling and obtains iron protochloride crystal, vacuum state in rectifying tower maintains by connecting empty pump, and its pressure is 61.05Kpa～67.50Kpa.
For economizing on resources, the interim equalizing tank that process as hydrochloric acid pickling waste liquor recycling in the described salt picking acid pond using filling hydrochloric acid pickling waste liquor regulates acidity, when preferably the acidity of hydrochloric acid pickling waste liquor is higher in interim equalizing tank, adds water to regulate its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank
3acidity is adjusted into 99.65g/L～124.56g/L; Or add the high hydrochloric acid pickling waste liquor of concentration of hydrochloric acid of concentration of hydrochloric acid hydrochloric acid pickling waste liquor in interim equalizing tank than this to regulate its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank when the acidity of hydrochloric acid pickling waste liquor is lower in interim equalizing tank
3acidity is adjusted into 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%, described percentage ratio is hydrochloric acid massfraction.The dilute hydrochloric acid concentration that reclaims is suitable is re-used as hydrochloric acid pickler utilization.
Principle of work of the present invention and technical process are:
In the pickling operating mode of steel part, conventionally be provided with side by side a plurality of salt picking acids pond, process after steel part in one of them salt picking acid pond, when the 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 another fills the salt picking acid pond of suitable steel part pickling concentration again, the concentration of hydrochloric acid of common suitable steel part pickling is 10%～20% (weight).
The present invention has been that the salt picking acid pond of hydrochloric acid pickling waste liquor is as interim equalizing tank in its pond after pickling steel part, in this pond, regulate the acidity of this hydrochloric acid pickling waste liquor, by regulate hydrochloric acid pickling waste liquor suitable acidity, add iron protochloride to reach that ferrous salt is saturated, preheating reaches bubble point temperature, enter rectifying tower rectification under vacuum, the salting-out effect of utilizing ferrous salt to produce has changed the vapor liquid equilibrium curve of hydrochloric acid-water, efficiently solves hydrochloric acid-water constant boiling solution and is difficult to separated problem.In interchanger, have three pipelines, interchanger interior conduit I two ends 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; Interchanger interior conduit II two ends are connected with overhead vapours outlet, condenser I by pipe connecting respectively, make the steam that arrives tower top by interchanger, condenser I condensation rear section, return to rectifying tower successively, remainder sequentially enters withdrawing can I, service sink (service sink is the pond that water cleans the steel part surface after chlorohydric acid pickling); Interchanger interior conduit III two ends are connected respectively recovery and obtain dilute hydrochloric acid with rectifying tower bottom vapour outlet, condenser II by pipe connecting, therefore, in interchanger, the material of three pipelines does not interfere with each other.The acidity that the present invention regulates is suitable, ferrous salt hydrochloric acid pickling waste liquor saturated and that reach bubble point temperature passes through chemical pump, preheater enters rectifying tower, by column plate stage trapping, wherein in mixed gas, relatively light vaporous water has more volatility than hydrogen chloride gas, thereby, the gas that arrives tower top is hydrochloric few vaporous water, through interchanger interior conduit II, the liquid portion that condenser I becomes containing utmost point dilute hydrochloric acid returns to rectifying tower, remainder sequentially enters withdrawing can I, service sink mixes with the water in service sink, in service sink, clean the water behind steel part surface, alkaline cleaning can reach the requirement of related industries wastewater discharge standard and discharge according to a conventional method, thereby do not pollute the environment.The hydrogen chloride gas that the relative vaporous water of volatility is little in rectifying tower can be in rectifying tower bottom vapour outlet, interchanger pipeline III, the condenser II hydrochloric acid liquid that becomes recovery sequentially enter withdrawing can II, salt picking acid pond, be mixed for pickling steel part with the hydrochloric acid pickler in salt picking acid pond, thereby most of hydrochloric acid has obtained recycling in hydrochloric acid pickling waste liquor.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 reclaiming, part can add and in interim equalizing tank, makes in hydrochloric acid pickling waste liquor the ferrous salt state that reaches capacity, and part oven drying at low temperature, as byproduct, can be used for coagulating agent or industrial chemicals that sewage disposal is used.The reboiler of still kettle outer wall heats again makes the vaporization of still liquid, 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 about to the CaCO of hydrochloric acid pickling waste liquor
3acidity is adjusted into 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, can be recovered to HCl recovery product that suitable steel part pickling uses and industrial iron protochloride product.The CaCO of hydrochloric acid pickling waste liquor
3acidity is lower than 99.65g/L, and the concentration of hydrochloric acid of its recovery is lower, can not be for pickling steel part, and the CaCO of hydrochloric acid pickling waste liquor
3acidity is higher than 124.56g/L, and in the mixing steam of rectifying tower bottom, hydrogen chloride gas scale of construction vaporous water excessive and that can not be condensed absorbs completely, causes HCl recovery rate to reduce, and both all can not reach the object of the recycling processing of waste liquid; And by the control of parameter of the present invention, the concentration of hydrochloric acid of recovery is 10%～15%, 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 cross rare steel part pickling that is all not suitable for.Therefore, compared with prior art, beneficial effect of the present invention has:
1, the present invention is by large quantity research and test, obtain the vacuum pressure parameter that maintains in the acidity adjustment parameter, tower of rational hydrochloric acid pickling waste liquor, by these parameters, control and ferrous salt is saturated, preheating reaches bubble point, rectification under vacuum technical process reasonable coordination, only utilize the material producing in steel part acid cleaning process, do not need to spend other raw material and can effectively be recovered to the hydrochloric acid soln that is suitable for steel part pickling, and can be used for coagulating agent or the industrial chemicals iron protochloride of dirty wastewater treatment, greatly saved 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 cross rare steel part pickling that is all not suitable for, and neither wastes resource, has saved again the energy.
The present invention only utilizes salting-out effect that byproduct iron protochloride that the present invention reclaims produces can change the vapor liquid equilibrium curve of hydrochloric acid-water, effectively solve hydrochloric acid-water constant boiling solution and be difficult to separated problem, do not need to add other raw material of cost, utilizing water or hydrochloric acid pickling waste liquor is the acidity of adjustable hydrochloric acid pickling waste liquor, has also greatly saved cost.
2, the present invention regulates the backward rectifying tower of acidity that the raw material for the treatment of that recycling treatment is utilized is provided as interim equalizing tank in the salt picking acid pond that fills hydrochloric acid pickling waste liquor, both can reduce investment cost, also continuously-running or in batches intermittent operation, realize auto-controll operation, its technique is rationally 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 can be selected existing relevant device on market according to enterprise's industrial scale, simple installation as equipment such as interchanger, preheater, rectifying tower, condenser, chemical pump, vacuum pumps.
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.
In two figure, mark represents 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 bottom vapour outlet; 16-interchanger interior conduit I; 17-interchanger interior conduit II; 18-interchanger interior conduit 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
Referring to Fig. 2, commercially available conventional components for equipment therefor in hydrochloric acid pickling waste liquor recycling treatment process flow process of the present invention, be formed by connecting in the usual way, wherein relate generally to the connection of connection that 1. hydrochloric acid pickling waste liquor enters each parts that rectifying tower relates to, each parts that 2. rectifying tower top vapour stream goes out to relate to, the dilute hydrochloric acid solution 3. reclaiming is recovered to connection, the 4. connection of vacuum pump of each parts that salt picking acid pond relates to, 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 sides connect interim equalizing tank 1, water side connects interchanger interior conduit I 16, the other end of interchanger interior conduit I 16 connects preheater 4, and preheater 4 is connected by pipeline with rectifying tower opening for feed 22;
The connection of each parts that 2. rectifying tower top vapour stream goes out to relate to: rectifying tower top vapour outlet 21 is connected with interchanger interior conduit II 17 by pipeline, the other end of interchanger interior conduit II 17 with by pipeline, be connected with the steam inlet of 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, on the pipeline that the fluid inlet of two withdrawing can I19 is connected with liquid outlet, be provided with respectively valve, the liquid outlet of two withdrawing can I19 is connected with service sink 10,
3. the dilute hydrochloric acid solution reclaiming is recovered to the connection of each parts that salt picking acid pond relates to: rectifying tower bottom vapour outlet 15 by pipeline be connected with interchanger interior conduit III18, the other end of interchanger interior conduit III18 by pipeline be connected with condenser II11, the liquid outlet of condenser II is by being provided with respectively valve on the pipeline that pipeline is connected with two withdrawing can II20 of parallel connection, the fluid inlet of two withdrawing can II20 is connected with liquid outlet, the liquid outlet of two withdrawing can II20 is connected with salt picking acid pond 12; Still kettle 6 outlets connect crystallization kettle 14 imports;
4. the connection of vacuum pump: the inlet mouth of vacuum pump 8 is connected in parallel by pipeline and condenser I9, condenser II11 respectively.
Referring to Fig. 1, hydrochloric acid pickling waste liquor recycling treatment process of the present invention is:
The interim equalizing tank 1 that the salt picking acid pond that fills hydrochloric acid pickling waste liquor is processed as hydrochloric acid pickling waste liquor recycling, in the acidity of the interior adjusting hydrochloric acid pickling waste liquor of this interim equalizing tank 1, when the acidity of interim equalizing tank 1 interior hydrochloric acid pickling waste liquor is higher, add water to regulate its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank 1
3acidity is adjusted into 99.65g/L～124.56g/L; When the acidity of interim equalizing tank 1 interior hydrochloric acid pickling waste liquor is lower, add the high hydrochloric acid pickling waste liquor of concentration of hydrochloric acid of concentration of hydrochloric acid hydrochloric acid pickling waste liquor in interim equalizing tank 1 than this to regulate its acidity to make the CaCO of the hydrochloric acid pickling waste liquor in interim equalizing tank 1
3acidity is adjusted into 99.65g/L～124.56g/L.Then in interim equalizing tank 1, add iron protochloride make hydrochloric acid pickling waste liquor in the ferrous salt state that reaches capacity, through chemical pump 2 pumps, carry successively by interchanger 3 interior conduit I 16, preheater 4 is warming up to hydrochloric acid pickling waste liquor to enter rectifying tower opening for feed 23 after bubble point by column plate, to flow in still kettle 6 from top to bottom, solution in still kettle 6 heats vaporization again through reboiler 7, the steam that arrives rectifying tower top vapour outlet 21 passes through successively through interchanger interior conduit II 17, condenser I 9 is condensed into liquid, wherein partially liq returns to 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 can I 19 in parallel through Y-tube order, in service sink 10, the steam of rectifying tower bottom vapour outlet 15 is successively through interchanger interior conduit III(18), the dilute hydrochloric acid solution that 11 condensations of condenser II are recycled, this dilute hydrochloric acid solution enters two withdrawing can II 20 in parallel through pipeline order, in salt picking acid pond 12, two withdrawing can 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 towers maintains by connecting vacuum pump 8, its pressure is maintained 61.05Kpa～67.50Kpa.
The salt picking acid pond that the present invention fills the failed former pickling of pickle solution pond hydrochloric acid pickling waste liquor 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, make the waste liquid ferrous salt state that reaches capacity, through chemical pump 2 pumps, carry by interchanger 3, preheater 4 and after being heated to hydrochloric acid pickling waste liquor bubble point, entering in the rectifying tower 5 in vacuum state, now the hydrochloric acid pickling waste liquor column plate of flowing through from top to bottom flows in still kettle 6 in rectifying tower; Being located at still kettle 6) reboiler 7 of outer wall again heats the liquid in still kettle 6 and makes to flow through after its part vaporization column plate from bottom to top, and gas, liquid two-phase are conducted 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, thereby, the liquid of condensation is that utmost point 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, thereby does not pollute the environment.In the present invention, regulate the CaCO of hydrochloric acid pickling waste liquor
3acidity is adjusted into 99.65g/L～124.56g/L, the ferrous salt state that reaches capacity in hydrochloric acid pickling waste liquor, liquid reaches bubble point and enters in rectifying tower 5 towers, vacuum state pressure in rectifying tower 5 towers is maintained under the condition of 61.05Kpa～67.50Kpa, the steam being flowed out by rectifying tower bottom vapour outlet 15 is through interchanger 3, it is 10%～15% dilute hydrochloric acid that 11 condensations of condenser II can be recycled to concentration of hydrochloric acid, (described percentage ratio is massfraction), this concentration is the hydrochloric acid acid strength of suitable steel part pickling, the concentration of hydrochloric acid that reclaims is too high or cross rare steel part pickling that is all not suitable for, therefore both save energy of the inventive method, can reach again the object of the recycling processing of hydrochloride waste, 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 (3)
1. a hydrochloric acid pickling waste liquor recycling treatment process, is characterized in that:
The interim equalizing tank (1) that the salt picking acid pond that fills hydrochloric acid pickling waste liquor is processed as hydrochloric acid pickling waste liquor recycling, the acidity of adjusting hydrochloric acid pickling waste liquor in this interim equalizing tank (1), by the CaCO of this hydrochloric acid pickling waste liquor
3acidity is adjusted into 99.65～124.56g/L, then in interim equalizing tank (1), add iron protochloride make hydrochloric acid pickling waste liquor in the ferrous salt state that reaches capacity, through chemical pump (2) pump, carry successively by interchanger interior conduit I (16), preheater (4) is warming up to hydrochloric acid pickling waste liquor to enter rectifying tower opening for feed (23) after bubble point by column plate, to flow in still kettle (6) from top to bottom, solution in still kettle (6) heats vaporization again through reboiler (7), the steam that arrives rectifying tower top vapour outlet (21) passes through successively through interchanger interior conduit II (17), condenser I (9) is condensed into liquid, wherein partially liq returns to rectifying tower column plate at the highest level through Y-tube by rectifying tower column plate import at the highest level (22), all the other liquid enter two withdrawing can I (19) in parallel through Y-tube order, in service sink (10), the dilute hydrochloric acid solution that the steam of rectifying tower bottom vapour outlet (15) is recycled through interchanger interior conduit III (18), condenser II (11) condensation successively, this dilute hydrochloric acid solution is in pipeline order enters two withdrawing can II (20) in parallel, salt picking acid pond (12), 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 the vacuum pump (8) connecting, and its pressure is 61.05Kpa～67.50Kpa.
2. a kind of hydrochloric acid pickling waste liquor recycling treatment process according to claim 1, is characterized in that: it is in this interim equalizing tank (1), to add water or add the high hydrochloric acid pickling waste liquor of concentration of hydrochloric acid of concentration of hydrochloric acid hydrochloric acid pickling waste liquor in interim equalizing tank (1) than this to regulate acidity that the interim equalizing tank (1) that process as hydrochloric acid pickling waste liquor recycling in the described salt picking acid pond using filling hydrochloric acid pickling waste liquor regulates acidity.
3. a kind of hydrochloric acid pickling waste liquor recycling treatment process according to claim 1 and 2, is characterized in that: the dilute hydrochloric acid concentration of recovery is 10%～15%, and described percentage ratio is massfraction.
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| CN103819042A (en) * | 2014-03-19 | 2014-05-28 | 江苏星瑞化工工程科技有限公司 | Purification treatment method for hydrochloric acid waste liquid |
| CN104003490A (en) * | 2014-05-19 | 2014-08-27 | 上海大学 | Method for treating stainless steel acid pickling waste liquid and recovering metal with addition of [beta]-ferric fluoride trihydrate seed crystal |
| CN104860269A (en) * | 2015-04-14 | 2015-08-26 | 广东工业大学 | Method and device for recovering hydrochloric acid from industrial waste liquid |
| CN104944665A (en) * | 2015-06-19 | 2015-09-30 | 浙江大学 | Comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid |
| CN106430100A (en) * | 2016-10-19 | 2017-02-22 | 深圳泛科环保产业发展有限公司 | Continuous-production reduced pressure distillation device and process for recovering iron-containing waste acid liquid |
| CN106630398A (en) * | 2016-12-02 | 2017-05-10 | 国家海洋局天津海水淡化与综合利用研究所 | Method for treating high-salt organic wastewater |
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| CN103819042A (en) * | 2014-03-19 | 2014-05-28 | 江苏星瑞化工工程科技有限公司 | Purification treatment method for hydrochloric acid waste liquid |
| 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 |
| CN104003490A (en) * | 2014-05-19 | 2014-08-27 | 上海大学 | Method for treating stainless steel acid pickling waste liquid and recovering metal with addition of [beta]-ferric fluoride trihydrate seed crystal |
| CN104860269A (en) * | 2015-04-14 | 2015-08-26 | 广东工业大学 | Method and device for recovering hydrochloric acid from industrial waste liquid |
| 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 |
| CN104944665A (en) * | 2015-06-19 | 2015-09-30 | 浙江大学 | Comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid |
| CN106430100A (en) * | 2016-10-19 | 2017-02-22 | 深圳泛科环保产业发展有限公司 | Continuous-production reduced pressure distillation device and process for recovering iron-containing waste acid liquid |
| CN106630398A (en) * | 2016-12-02 | 2017-05-10 | 国家海洋局天津海水淡化与综合利用研究所 | Method for treating high-salt organic wastewater |
| 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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