CN102616743A - Treatment recycling process of hydrochloric acid liquid waste produced in rare metals extraction process - Google Patents
Treatment recycling process of hydrochloric acid liquid waste produced in rare metals extraction process Download PDFInfo
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- CN102616743A CN102616743A CN2012100873954A CN201210087395A CN102616743A CN 102616743 A CN102616743 A CN 102616743A CN 2012100873954 A CN2012100873954 A CN 2012100873954A CN 201210087395 A CN201210087395 A CN 201210087395A CN 102616743 A CN102616743 A CN 102616743A
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Abstract
The invention discloses a treatment recycling process of hydrochloric acid liquid waste produced in a rare metals extraction process, which belongs to the technical field of hydrochloric acid liquid waste treatment. The treatment recycling process adopts a multiple-effect evaporation mode to achieve evaporation of the hydrochloric acid liquid waste, greatly saves heat energy, achieves extraction recycling of products, simultaneously guarantees reduction of production cost, achieves recycling utilization of heavy metal elements in the hydrochloric acid liquid waste and solves the problem of environmental protection.
Description
Technical field
The present invention relates to the processing technology field of hydrochloride waste, particularly relate to the processing reuse technology of the hydrochloride waste that produces in a kind of rare metal leaching process.
Background technology
At present, the common employing of hydrochloride waste added the processing of alkali neutralisation, promptly in spent acid solution, add alkaline matter; Improve its pH value, acid solution obtains neutral makes heavy metal ion wherein combine deposition with hydroxide radical simultaneously, carries out solid-liquid separation again and removes; Direct discharging of waste water, waste residue are directly carried out landfill.This method is simple; Therefore accepted by a lot of blowdown enterprise; But the spent acid solution of precious resources such as hydrochloric acid that this method will contain and heavy metal ion discharges as after the waste treatment, has caused resource to waste significantly, and the earth of simultaneously people being depended on for existence has caused greatly harm; Especially wherein the permanent environmental protection harm that causes of heavy metal can reach the protection environment far away and reclaim the purpose of resource.And owing to just need the 1mol hydroxide ion with the 1mol hydrogen ion in every; Add in these abraum salt acid and contain ferrous ion; And to these ferrous ion depositions be removed; Need a large amount of alkali again, the consumption that therefore will handle these spent pickle liquor alkali will very huge, and adopt when adding the alkali neutralisation and handling hydrochloride waste easily because of the deficiency of adding medicament or excessive and cause secondary pollution.
And, mainly contain following several method at present in the prior art for the sour recovery of abraum salt:
1, high-temperature roasting method.High-temperature roasting method is that spent acid oxygenolysis under hot conditions is become ferrous salt, and with water evaporation, the red stone that obtains and the method for regenerating acid.This method treatment capacity is big, and the salt acid recovering rate is more thorough, but investment is big, and running cost is high, requires level of management high, only is fit to large-scale enterprise and uses.
2, ion exchange method.Ion exchange method is to utilize some ion exchange resin from spent acid solution, to absorb acid solution and the function of getting rid of metal-salt realizes acid and the isolating a kind of method of salt.But the advantage of this method is a normal temperature to be handled, and energy consumption is low, and technical process is short, but the concentration of recovery hydrochloric acid is on the low side, and the recovery is relatively poor, needs to add more concentrated hydrochloric acid and just can reuse.
3, electrolysis dialysis.Electrolysis dialysis ratio juris is to make spent acid get into the diffusion dialysis device, utilizes the selection perviousness and the molecular sieve effect of ion-exchange membrane, makes free acid constantly get into water mutually by spent acid, thereby obtains reclaiming.Raffinate gets into electrolyzer, under electric field action, makes iron ion be reduced into pure iron, and cl ions and hydrogen ion recombine are hydrochloric acid.This method has a thing equipment simple, and the recovery is higher, but power consumption is bigger.
Therefore, to above problem, press for a kind of new recovery technology of research; It is low to invest energy consumption on the one hand; The cost of investment is low, and the amount of the hydrochloric acid that reclaims on the other hand is big, not only can solve the treatment and disposal problem of a large amount of hydrochloride wastes; But also fundamentally solve the problem of environmental protection, also can produce simultaneously and reclaim the economic benefit that resource is brought.
Summary of the invention
The technical problem that the present invention mainly solves provides the processing reuse technology of the hydrochloride waste that produces in a kind of rare metal leaching process; Can handle the acid of a large amount of abraum salt of reuse, simultaneously wherein heavy metal element also carried out reuse, energy consumption is low; Cost of investment is low, meets environmental protection requirement.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: the processing reuse technology of the hydrochloride waste that produces in a kind of rare metal leaching process is provided, comprises:
(1) hydrochloride waste in the spent acid storage tank is filtered through strainer tube, import multiple-effect heating evaporation system, multiple-effect evaporation: each effect vapo(u)rization system is made up of a heating chamber and an evaporator room; During each is imitated; Abraum salt acid circulates in heating chamber and evaporation therebetween; The low concentration of salt acid waste liquid successively through one imitate, two imitate, triple effect following current evaporation back concentrated liquid concentrator; Use the hydrochloride waste heating of living steam to an effect heating chamber, hydrochloride waste absorbs heat after an effect evaporator room evaporates, and secondary steam is imitated in generation one; One effect secondary steam is to the acid heating of two effect heating chambers, and the acid heat absorption of two effects produces two effect secondary steams after two effect evaporator rooms evaporate; Two imitate the acid heating of secondary steam to the triple effect heating chamber, and the acid heat absorption of triple effect is after absorb heat after the evaporation of triple effect evaporation chamber;
(2) steam that produces through multi-effect evaporation system is sent into condensing surface through mixing duct and is carried out condensation, squeezes into reuse acid storage tank through vacuum pump and stores; The liquid phase that produces through multi-effect evaporation system adopts extraction agent extraction 3-4 time, is extracted into the heavy metal element of 90-95%, reclaims for use.
In preferred embodiment of the present invention, also comprise:
(3) remaining liquid phase is taked thermal crystalline technology; The control vaporization temperature is 100-110 ℃; Azeotropic hydrochloric acid in the double evaporation-cooling concentrating waste acid, the hydrochloric acid vapour of generation are sent into condensing surface through mixing duct once more and are carried out condensation, squeeze into reuse acid storage tank through vacuum pump and store; Remaining liquid concentrator is delivered to centrifugal filter through recycle pump, carries out spinning, obtains the iron protochloride crystal, and mother liquor is back to the spent acid storage tank after the spinning.
(4) iron protochloride that obtains is burned at 800-900 ℃, obtain red stone and hydrochloric acid flue gas; This hydrochloric acid flue gas adopts the reuse Hydrogen chloride in the reuse acid storage tank to carry out multistage absorption, finally obtains the hydrochloric acid that concentration is 20%-36%.
In preferred embodiment of the present invention, the order of magnitude of imitating in the multi-effect evaporation system described in the step (1) is more than three grades.
In preferred embodiment of the present invention, the pressure position 0.4-0.8Mpa of described living steam.
The invention has the beneficial effects as follows:
1, the present invention adopts the mode of multiple-effect evaporation to realize the evaporation to hydrochloride waste, has practiced thrift heat energy greatly, in the reduction that realizes having guaranteed when product refines recovery production cost.
2, the present invention had both realized the recycling to the heavy metal element in the hydrochloride waste, had solved the problem of environmental protection again.
3, the processing reuse technology of hydrochloride waste of the present invention can fully reclaim a large amount of hydrochloric acid and red stone; Do not produce waste in the whole process; Really realized the recycle of hydrochloride waste, had that technological operation is simple, energy consumption is low, cost of investment is low, an environmental protection and improved advantages such as economic benefit.
Embodiment
Set forth in detail in the face of preferred embodiment of the present invention down, thereby protection scope of the present invention is made more explicit defining so that advantage of the present invention and characteristic can be easier to it will be appreciated by those skilled in the art that.
The processing reuse technology of the hydrochloride waste that produces in a kind of rare metal leaching process comprises:
(1) hydrochloride waste in the spent acid storage tank is filtered through strainer tube, import multiple-effect heating evaporation system, multiple-effect evaporation: each effect vapo(u)rization system is made up of a heating chamber and an evaporator room; During each is imitated; Abraum salt acid circulates in heating chamber and evaporation therebetween; The low concentration of salt acid waste liquid successively through one imitate, two imitate, triple effect following current evaporation back concentrated liquid concentrator; Use the hydrochloride waste heating of living steam to an effect heating chamber, hydrochloride waste absorbs heat after an effect evaporator room evaporates, and secondary steam is imitated in generation one; One effect secondary steam is to the acid heating of two effect heating chambers, and the acid heat absorption of two effects produces two effect secondary steams after two effect evaporator rooms evaporate; Two imitate the acid heating of secondary steam to the triple effect heating chamber, and the acid heat absorption of triple effect is after absorb heat after the evaporation of triple effect evaporation chamber;
(2) steam that produces through multi-effect evaporation system is sent into condensing surface through mixing duct and is carried out condensation, squeezes into reuse acid storage tank through vacuum pump and stores; The liquid phase that produces through multi-effect evaporation system adopts extraction agent extraction 3-4 time, is extracted into the heavy metal element of 90-95%, reclaims for use.
Further; Also comprise: (3) remaining liquid phase is taked thermal crystalline technology; The control vaporization temperature is 100-110 ℃; Azeotropic hydrochloric acid in the double evaporation-cooling concentrating waste acid, the hydrochloric acid vapour of generation are sent into condensing surface through mixing duct once more and are carried out condensation, squeeze into reuse acid storage tank through vacuum pump and store; Remaining liquid concentrator is delivered to centrifugal filter through recycle pump, carries out spinning, obtains the iron protochloride crystal, and mother liquor is back to the spent acid storage tank after the spinning; (4) iron protochloride that obtains is burned at 800-900 ℃, obtain red stone and hydrochloric acid flue gas; This hydrochloric acid flue gas adopts the reuse Hydrogen chloride in the reuse acid storage tank to carry out multistage absorption, finally obtains the hydrochloric acid that concentration is 20%-36%.
The order of magnitude of wherein, imitating in the multi-effect evaporation system described in the step (1) is more than three grades.
The pressure position 0.4-0.8Mpa of described living steam.
The above is merely embodiments of the invention; Be not so limit claim of the present invention; Every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (4)
1. the processing reuse technology of the hydrochloride waste that produces in the rare metal leaching process is characterized in that, comprising:
(1) hydrochloride waste in the spent acid storage tank is filtered through strainer tube, import multiple-effect heating evaporation system, multiple-effect evaporation: each effect vapo(u)rization system is made up of a heating chamber and an evaporator room; During each is imitated; Abraum salt acid circulates in heating chamber and evaporation therebetween; The low concentration of salt acid waste liquid successively through one imitate, two imitate, triple effect following current evaporation back concentrated liquid concentrator; Use the hydrochloride waste heating of living steam to an effect heating chamber, hydrochloride waste absorbs heat after an effect evaporator room evaporates, and secondary steam is imitated in generation one; One effect secondary steam is to the acid heating of two effect heating chambers, and the acid heat absorption of two effects produces two effect secondary steams after two effect evaporator rooms evaporate; Two imitate the acid heating of secondary steam to the triple effect heating chamber, and the acid heat absorption of triple effect is after absorb heat after the evaporation of triple effect evaporation chamber;
(2) steam that produces through multi-effect evaporation system is sent into condensing surface through mixing duct and is carried out condensation, squeezes into reuse acid storage tank through vacuum pump and stores; The liquid phase that produces through multi-effect evaporation system adopts extraction agent extraction 3-4 time, is extracted into the heavy metal element of 90-95%, reclaims for use.
2. the processing reuse technology of the hydrochloride waste that produces in the rare metal leaching process according to claim 1 is characterized in that, also comprises:
(3) remaining liquid phase is taked thermal crystalline technology; The control vaporization temperature is 100-110 ℃; Azeotropic hydrochloric acid in the double evaporation-cooling concentrating waste acid, the hydrochloric acid vapour of generation are sent into condensing surface through mixing duct once more and are carried out condensation, squeeze into reuse acid storage tank through vacuum pump and store; Remaining liquid concentrator is delivered to centrifugal filter through recycle pump, carries out spinning, obtains the iron protochloride crystal, and mother liquor is back to the spent acid storage tank after the spinning;
(4) iron protochloride that obtains is burned at 800-900 ℃, obtain red stone and hydrochloric acid flue gas; This hydrochloric acid flue gas adopts the reuse Hydrogen chloride in the reuse acid storage tank to carry out multistage absorption, finally obtains the hydrochloric acid that concentration is 20%-36%.
3. the processing reuse technology of the hydrochloride waste that produces in the rare metal leaching process according to claim 1 is characterized in that, the order of magnitude of imitating in the multi-effect evaporation system described in the step (1) is more than three grades.
4. the processing reuse technology of the hydrochloride waste that produces in the rare metal leaching process according to claim 1 is characterized in that, the pressure position 0.4-0.8Mpa of described living steam.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395746A (en) * | 2013-08-13 | 2013-11-20 | 安徽海华科技股份有限公司 | Method for purifying byproduct hydrochloric acid in 3, 4-dichloronitrobenzene production process |
| CN104986736A (en) * | 2015-07-16 | 2015-10-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recovering waste hydrochloric acid solution in hydrochloric acid method rutile preparation technology |
| CN105417828A (en) * | 2016-01-05 | 2016-03-23 | 中南大学 | Resource recycling method for heavy metal wastewater containing low-boiling-point acid and acid radicals of low-boiling-point acid |
| CN109502870A (en) * | 2018-12-31 | 2019-03-22 | 天津滨港电镀企业管理有限公司 | A kind of plating garden derusting waste hydrochloric acid triple effect evaporation processing system and pretreating process |
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| CN101307456A (en) * | 2007-04-25 | 2008-11-19 | 黄健 | Pickling waste acid regeneration process |
| CN101570316A (en) * | 2009-05-27 | 2009-11-04 | 无锡市星亿涂装环保设备有限公司 | Method and device for refining and recycling hydrochloric acid from hydrochloric acid pickling waste liquid |
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Patent Citations (4)
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| EP0595492A1 (en) * | 1992-10-30 | 1994-05-04 | Tioxide Group Services Limited | Treatment of waste containing metal chlorides |
| 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395746A (en) * | 2013-08-13 | 2013-11-20 | 安徽海华科技股份有限公司 | Method for purifying byproduct hydrochloric acid in 3, 4-dichloronitrobenzene production process |
| CN103395746B (en) * | 2013-08-13 | 2015-04-01 | 安徽海华科技股份有限公司 | Method for purifying byproduct hydrochloric acid in 3, 4-dichloronitrobenzene production process |
| CN104986736A (en) * | 2015-07-16 | 2015-10-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recovering waste hydrochloric acid solution in hydrochloric acid method rutile preparation technology |
| CN104986736B (en) * | 2015-07-16 | 2017-06-16 | 攀钢集团攀枝花钢铁研究院有限公司 | Hydrochloric acid method prepares the recovery method of abraum salt acid solution in rutile technique |
| CN105417828A (en) * | 2016-01-05 | 2016-03-23 | 中南大学 | Resource recycling method for heavy metal wastewater containing low-boiling-point acid and acid radicals of low-boiling-point acid |
| CN105417828B (en) * | 2016-01-05 | 2018-06-12 | 中南大学 | A kind of heavy metal wastewater thereby resource recycle method containing low boiling point acid and its acid group |
| CN109502870A (en) * | 2018-12-31 | 2019-03-22 | 天津滨港电镀企业管理有限公司 | A kind of plating garden derusting waste hydrochloric acid triple effect evaporation processing system and pretreating process |
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Application publication date: 20120801 |