CN102531139A - Method for removing and recycling chrome from acid chromate wastewater in one step - Google Patents
Method for removing and recycling chrome from acid chromate wastewater in one step Download PDFInfo
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Abstract
The invention relates to a method for removing and recycling chrome from acid chromate wastewater in one step, which comprises the steps that: (1) phase-forming salt and polymer are added into acid chromate wastewater for forming two aqueous phases; (2) a yellow polymer phase which carries hexavalent chromium is obtained after separation and is placed, under the action of light or/and the outside environment, an aqueous phase layer is separated out from the lower layer of the yellow polymer phase, phase separation is carried out, and accordingly, trivalent chromium is recycled from the wastewater. Compared with the prior art, the invention has the advantages that: (1) the acid and alkali consumption problem does not exist, organic solvent is not needed to be added as well, so the cost is reduced; (2) the method is simple to operate and has less energy consumption, and industrial production is easy to realize; and (3) the method does not adopt the organic solvent, is green and non-toxic, and the damage to a human body of an operator and the pollution to the environment can be reduced to the maximum extent.
Description
Technical field
The present invention relates to environmental improvement and metals resources and recycle the field, relate to a kind of method of from acidic chromium-containing wastewater, removing and reclaim chromium.
Background technology
Chromate waste water is mainly derived from industrial pollution, particularly electroplating industry.Because the chromium combined plating has advantages such as hardness height, heat-resisting, wear-resisting, corrosion-resistant, light and beauty, application surface is quite wide.And the source of waste electroplating liquor containing chromium is generally plating piece cleaning and electroplating effluent etc.Wherein, the plating piece rinse water is the main source of waste electroplating liquor containing chromium, almost accounts for more than 80% of chromate waste water quantity discharged.
Pollution of chromium all has serious harm to ecotope and HUMAN HEALTH, and sexavalent chrome is than trivalent chromium toxicity bigger (big approximately 100 times).Sexavalent chrome is the property swallowed poisonous substance/imbedibility utmost point poisonous substance, and skin exposure possibly cause sensitivity; More possibly cause the heredity genetic flaw, sucking maybe be carcinogenic, and environment is had lasting danger.But these are chromic characteristics, and chromium metal, trivalent or tetravalence chromium do not have these toxicity.Sexavalent chrome is easy to be absorbed by the body, and it can invade human body through digestion, respiratory tract, skin and mucous membrane.Report is arranged, hoarse, nasal mucosa atrophy in various degree arranged when containing the chromic trioxide of different concns in the breathe air, also can make perforation of nasal septum and bronchiectasis etc. when serious.When digestive tube is invaded, can cause vomiting, abdomen is painful., skin can produce dermatitis and eczema when invading.Harm is maximum is long-term or short term contact or carcinogenic danger is arranged when sucking.
Chromate waste water is acknowledged as one of the most serious public hazards of harm environment, wherein is mainly sexavalent chrome, therefore, the separating treatment of chromate waste water is studied particularly important.
For a long time, people adopt chemical method, physico-chemical processes and biochemical process that pollution of chromium is administered.Wherein, chemical precipitation method and ion exchange method are two kinds of technology commonly used that industrial wastewater containing chromium is handled.Yet so far, still there are various deficiencies in the treatment technology of various chromate waste waters, and low like the advanced treatment efficient of lower concentration, step is tediously long, and acid and alkali consumption is big, and running cost is higher, and these all remain to be improved.
Treatment of chromium containing wastewater generally adopts " two step method " both at home and abroad at present.Under acidic conditions, utilize SO
2, NaHSO
3, FeSO
4Deng reductive agent, hexavalent chrome reduction is become trivalent chromium.The pH value that adds alkali raising waste water then makes it to generate chromium hydroxide precipitation, removes by filter then.CN 1050709A discloses the recovery method of chromium in a kind of chromium plating wastewater.This method mainly is in chrome-plating bath, to place the plastic wire liner, in waste water, adds sulfurous acid and makes hexavalent chrome reduction become trivalent chromium, and then add ammoniacal liquor; Contain the chromium deposition with trivalent chromium reaction generation, up to deposition fully, separate at last; Water purification closed circulation after the separation is reused for rinsing, and the chromium deposition water that contains after separating repeatedly cleans; Remove ammonium ion and sulfate ion, obtain the pure article of chromium cpd, be recycled and reused for chrome-plated process again.Because reduction reaction is generally carried out (general requirement pH＜4 are controlled pH=2.5～3 usually) under acidic conditions, and sedimentary best pH is 8.5～10.0; But the pH value of chromate waste water is generally 3.5～6.5; Therefore this method at first need add acid during the first step and regulates acidity to reducing acidity, when second step, adds alkali sedimentation trivalent chromium more then, and this process acid and alkali consumption is big; Step is tediously long, and is consuming time.
In addition, the electrolytic reduction processing waste water containing chrome is to utilize iron plate to make anode, and dissolved ferric iron generates ferrous ion in electrolytic process, and under acidic conditions, ferrous ion is reduced into trivalent chromic ion with hexavalent chromium.Owing to separate out hydrogen on the negative electrode, wastewater pH is risen gradually simultaneously, be neutral at last, at this moment Cr
3+, Fe
3+All separate out, reach the purpose of purification of waste water with precipitation of hydroxide.CN 86106414B discloses a kind of method of electrolytic method for treating wastewater containing vanadium and chromium.This method comprises: waste water carries out electrolysis after prereduction is dissolved in acid.The iron cathode electrochemical dissolving produces ferrous ion hexavalent chrome reduction is become trivalent chromium, and cathodic reaction is reduced into the tetravalence vanadium with the pentavalent vanadium, ironic hydroxide absorption pentavalent vanadium, and last chromium, vanadium and iron precipitate with hydroxide form, obtain Cr
6+＜0.5, the deposition of the water purification of V＜0.4 mg/litre and enrichment vanadium, chromium.Problems such as electrolytic process exists energy consumption high, and step is many, is mixed with a large amount of ironic hydroxides in the mud, and utility value is low.
Other method for removing chromium also has ion exchange method and microbial bacteria reduction method.Ion exchange method only is confined to slightly acidic or neutral environment, only is fit to handle the Cr (VI) of lower concentration.And the use of microbial bacteria reduction method is also used under slightly acidic or neutral environment mostly, and industrial applications has certain distance.To sum up, although the method for dechromisation has multiplely from waste water, still there are problems such as step is long, acid and alkali consumption is big.Generally do not adopt the solvent extration dechromisation in the acidic solution, major cause is directly from acidic solution, to remove sexavalent chrome, can make the extraction agent sex change because of chromic strong oxidizing property in the acidic solution, reduces its work-ing life.
The double water-phase solvent extraction technology is used for the separation and the purification of biologics because its water cut is big, mass transfer is fast and green high-efficient more.And the typical double-aqueous phase system that makes up by water-soluble polymers such as polyoxyethylene glycol; Because the oxygen of ether-oxygen bond has lone-pair electron, has electronegativity, easily through electrostatic interaction absorption hydrogen ion; Thereby has positive polarity, then through solvation mechanism complexing metal complex anion.The pH of waste electroplating liquor containing chromium is generally 3.5～6.5, the nearly neutral water solution system of this slightly acidic, and this double water-phase technology that is very suitable for directly adopting us to develop, thus make sexavalent chrome transfer to polymer phase.It is yellow that the chromic polymer phase of load is, and the chromic polymer phase of load separated the back place.Discover, place a couple of days after, divides in the bottom of polymer phase and to have jade-green one deck, and that polymer phase becomes is colourless.Reason is that under the effect in the light and the external world, the sexavalent chrome that loads in the polymer phase is reduced into trivalent chromium, separates out from the bottom of polymkeric substance.The applicant has invented the method (application number 201110336246.2) that a kind of photoreduction coupling liquid-liquid-liquid three phase extraction removed and reclaimed chromium early stage.This invention adds inorganic strong electrolyte salt, water soluble polymer through in the aqueous solution that contains Cr (VI), regulates aqueous pH values; Add organic solvent then; Thorough mixing, leave standstill or centrifugal phase-splitting, obtain the liquid-liquid-liquid three-phase system, above-mentioned solution is placed under the illumination; Cr (VI) is reduced into Cr (III) and all transfers to phase, will go up Cr (III) back extraction of phase load at last and reclaim.But this method has adopted organic solvent, has certain toxicity, and cost is higher, is unfavorable for suitability for industrialized production.
All there is complicated operation in prior art, the energy consumption height/reagent consumption is big, cost is high, operation has problems such as toxicity, contaminate environment.Based on above prior art, present method proposes to adopt double water-phase technology single stage method to remove the sexavalent chrome in the acidic solution, does not have the problem of acid and alkali consumption, does not adopt organic solvent, does not also have the problem of extraction agent sex change.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide single stage method from acidic chromium-containing wastewater, to remove and reclaim the method for chromium, and this method operation is more simple, green, and less energy consumption is easy to realize industriallization.
Chromium was removed and reclaimed to said single stage method from acidic chromium-containing wastewater method comprises:
(1) in acidic chromium-containing wastewater, add into phase salt and polymkeric substance, treat into phase salt and polymer dissolution after, promptly form double water-phase, this process has realized the transfer of sexavalent chrome to polymer phase simultaneously, and the coexistence other negatively charged ion still be retained in salt phase under water;
(2) separation obtains load has chromic yellow polymer phase, places, and makes polymer phase lower floor separate out aqueous phase layer, is separated, thereby the trivalent chromium in the waste water is reclaimed.
Preferably, the isolated polymer phase of step (2) is reusable.
Layering described in the step (2) is meant that polymer phase lower floor separates out absinthe-green aqueous phase layer, and this absinthe-green aqueous phase layer is actual to be trivalent chromium solutions.
Preferably, make described in the step (2) polymer phase lower floor separate out aqueous phase layer through light or/and external influence realize.
Preferably; Said chromate waste water pH value is below 7; For example pH=7, pH=6.99, pH=6.95, pH=6.9, pH=6.5, pH=6.1, pH=6, pH=5.95, pH=5.9, pH=4, pH=2, pH=1.1, pH=1, pH=0.9, pH=0.5, pH=0.1 etc., further preferred pH is below 6, preferred especially pH is 1～6; Exceed this acidity scope, chromium descends to the rate of transform of polymer phase.
Preferably; Chromate waste water of the present invention had both comprised the chromate waste water that electroplating industry produces, and also comprised other chromate waste waters; Hexavalent chromium concentration is 1～400mg/L in the said chromate waste water; For example: 1.1mg/L, 1.2mg/L, 1.5mg/L, 10mg/L, 11mg/L, 30mg/L, 40mg/L, 100mg/L, 200mg/L, 300mg/L, 360mg/L, 390mg/L, 395mg/L, 398mg/L, 399mg/L etc., further be preferably 20～350mg/L, be preferably 50～300mg/L especially; The chromium solution of higher concentration, percentage extraction descends.
Preferably, said polymkeric substance is a water-soluble polymers, comprises the polyethers superpolymer, like 50-HB-170, and 5-HB-5100,50-HB-5100 etc.; Different molecular weight polyethylene glycol; Like PEG2000, PEG10000 etc., segmented copolymer; Like PEO-PPO blend series; PEO-PPO-PEO block series, polyethylene glycol-Ucar 35-monobutyl ether series etc. are preferably polyoxyethylene glycol especially or/and block polymer, for example EOPO (PEP-101).
Preferably; Said one-tenth phase salt is vitriol, phosphoric acid salt, hydrosulfate, hydrophosphate, dihydrogen phosphate; For example: sodium sulfate, vitriolate of tartar, ammonium sulfate, sodium pyrosulfate, sal enixum, ammonium phosphate, sodium phosphate, potassiumphosphate, Sodium phosphate, dibasic, SODIUM PHOSPHATE, MONOBASIC etc.; Further be preferably vitriol, be preferably ammonium sulfate, sodium sulfate especially.
Preferably, becoming the mass percent concentration of phase salt in the said double water-phase is 5%～80%, further is preferably 8%～70%, is preferably 10%～60% especially.
Preferably, the mass percent concentration of polymkeric substance is 5%～80% in the said double water-phase, further is preferably 8%～70%, is preferably 10%～60% especially.
Preferably; Be at least 2 days storage period described in the step (2); For example: 2.05 days, 2.1 days, 2.15 days, 2.2 days, 2.9 days, 2.95 days, 2.99 days, 3 days, 3.1 days, 3.5 days, 4 days, 10 days etc., further preferably at least 2.5 days, be preferably at least 3 days especially.
Said light be lamp or/and the natural light that artificial light sends or/and artificial light.
Said external influence can be heating, illumination, airbath, ultrasonic etc.
Chromate waste water of the present invention allows other metals ion that exists with cationic form coexistence and does not disturb.
Compared with prior art, the method for from acidic chromium-containing wastewater, removing and reclaim chromium according to the invention it is advantageous that:
(1) there is not the acid and alkali consumption problem, need do not add organic solvent yet, reduced cost;
(2) simple to operate, less energy consumption is easy to realize suitability for industrialized production;
(3) do not adopt organic reagent, green non-poisonous, can at utmost reduce to the infringement of operator's health with to the pollution of environment.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
Get the 15mL industrial wastewater containing chromium, wherein, Cr (IV) concentration is 200mg/L, and acidity is pH 3.5, is mixed with Cu
2+And Fe
3+In the foreign metal ion, add 3g ammonium sulfate and 3g Macrogol 2000, after the whirlpool dissolving mixes, phase-splitting, polymer phase is 90% to chromic percentage extraction.With leaving standstill mutually on the polymkeric substance 3 days, phase-splitting, the mutually chromic recovery is 86% down.
Embodiment 2
Get the 90g industrial wastewater containing chromium, wherein, Cr (IV) concentration is 1mg/L, and acidity is pH 6, is mixed with Cu
2+And Fe
3+In the foreign metal ion, add 5g sodium sulfate and 5g polyethers 50-HB-170, after the whirlpool dissolving mixes, phase-splitting, polymer phase is 95% to chromic percentage extraction.Phase on the polymkeric substance was left standstill 4 days under fluorescent light, phase-splitting, the mutually chromic recovery is 92% down.
Embodiment 3
Get the 15g industrial wastewater containing chromium, wherein, Cr (IV) concentration is 400mg/L, and acidity is pH 1, is mixed with Cu
2+And Fe
3+In the foreign metal ion, add 5g sodium phosphate and 80g Macrogol 2000, after the whirlpool dissolving mixes, phase-splitting, polymer phase is 90% to chromic percentage extraction.With under 40 ℃, leaving standstill 2 days on the polymkeric substance, phase-splitting, the mutually chromic recovery is 86% down.
Embodiment 4
Get the 20g industrial wastewater containing chromium, wherein, Cr (IV) concentration is 300mg/L, and acidity is pH 7, is mixed with Cu
2+And Fe
3+In the foreign metal ion, add 20g sal enixum and 60g Macrogol 2000, after the whirlpool dissolving mixes, phase-splitting, polymer phase is 92% to chromic percentage extraction.Phase on the polymkeric substance was left standstill 2 days under fluorescent light, phase-splitting, the mutually chromic recovery is 85% down.
Embodiment 5
Get the 15g industrial wastewater containing chromium, wherein, Cr (IV) concentration is 20mg/L, and acidity is pH 6.2, is mixed with Cu
2+And Fe
3+In the foreign metal ion, add 80g sodium pyrosulfate and 5g Macrogol 2000, after the whirlpool dissolving mixes, phase-splitting, polymer phase is 93% to chromic percentage extraction.Phase on the polymkeric substance was left standstill 2.5 days under fluorescent light, phase-splitting, the mutually chromic recovery is 89% down.
The comparative example
Adopt the applicant first to file (application number 201110336246.2) as a comparison embodiment compare.
Containing Cr (VI) toward 20mL is that 4000 polyoxyethylene glycol dissolves with 5g ammonium sulfate for adding the 1.5g weight-average molecular weight in the solution of 100mg/L; Transfer pH=6 with sulfuric acid and sodium hydroxide; Then add 3.3mL 30% (v/v) di-(2-ethylhexyl)phosphoric acid ester/normal hexane mixed organic solvents; Behind the vibration 5min, centrifugal 10min under rotating speed 3000rpm condition forms the liquid-liquid-liquid three-phase system this moment.Cr (VI) percentage extraction of phase in polyoxyethylene glycol reaches 90.5%, under sunshine behind the irradiation 30min, in Cr (VI) in mutually thoroughly be reduced into Cr (III) and all transfer to phase, the Cr of last phase load (III) is with the dilution heat of sulfuric acid back extraction recovery of pH=2.5.
Through embodiment of the invention 1-5 and comparative example are compared and can know, the present invention compares with the comparative example, and the recovery is more or less the same; But operate more simple; And need not regulate pH, also not adopt organic solvent, not only reduce cost but also prevented murder by poisoning operator's health.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. single stage method removes and reclaims the method for chromium from acidic chromium-containing wastewater, comprising:
(1) in acidic chromium-containing wastewater, adds into phase salt and polymkeric substance, form double water-phase;
(2) separation obtains load has chromic yellow polymer phase, places, and makes polymer phase lower floor separate out aqueous phase layer, is separated, thereby the trivalent chromium in the waste water is reclaimed.
2. the method for claim 1 is characterized in that, the isolated polymer phase of step (2) is preferably reused;
Preferably, make described in the step (2) polymer phase lower floor separate out aqueous phase layer through light or/and external influence realize.
3. according to claim 1 or claim 2 method is characterized in that said chromate waste water pH value is preferably below 7, and further preferred pH is below 6, and preferred especially pH is 1～6.
4. like each described method of claim 1-3, it is characterized in that hexavalent chromium concentration is preferably 1～400mg/L in the said chromate waste water, further be preferably 20～350mg/L, be preferably 50～300mg/L especially.
5. like each described method of claim 1-4, it is characterized in that said polymkeric substance is preferably water-soluble polymers, comprise the polyethers superpolymer, like 50-HB-170,5-HB-5100,50-HB-5100 etc.; Different molecular weight polyethylene glycol; Like PEG2000, PEG10000 etc., segmented copolymer; Like PEO-PPO blend series; PEO-PPO-PEO block series, polyethylene glycol-Ucar 35-monobutyl ether series etc. are preferably polyoxyethylene glycol especially or/and block polymer, for example EOPO (PEP-101).
6. like each described method of claim 1-5, it is characterized in that said one-tenth phase salt is preferably vitriol, phosphoric acid salt, hydrosulfate, hydrophosphate, dihydrogen phosphate, further is preferably vitriol, is preferably ammonium sulfate, sodium sulfate especially.
7. like each described method of claim 1-6, it is characterized in that, become the mass percent concentration of phase salt to be preferably 5%～80% in the said double water-phase, further be preferably 8%～70%, be preferably 10%～60% especially.
8. like each described method of claim 1-7, it is characterized in that the mass percent concentration of polymkeric substance is preferably 5%～80% in the said double water-phase, further be preferably 8%～70%, be preferably 10%～60% especially.
9. like each described method of claim 1-8, it is characterized in that be at least 2 days storage period described in the step (2), further preferably at least 2.5 days, be preferably at least 3 days especially.
10. like each described method of claim 1-9, it is characterized in that said external influence is illumination, airbath, heating, ultrasonic etc.
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| CN104787952A (en) * | 2015-03-25 | 2015-07-22 | 湖南永清环保研究院有限责任公司 | Process for recovering chromium from hexavalent chromium-containing wastewater |
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| CN105986125A (en) * | 2016-02-24 | 2016-10-05 | 湖南永清环保研究院有限责任公司 | Technology for extracting and recycling chromium from hexavalent chromium containing waste water |
| CN106756123A (en) * | 2016-12-02 | 2017-05-31 | 燕山大学 | A kind of method of extraction water Molybdenum in Solution (VI) |
| CN106756125A (en) * | 2016-12-02 | 2017-05-31 | 燕山大学 | A kind of method of tungsten in extract and separate aqueous solution |
| CN106756116A (en) * | 2016-12-02 | 2017-05-31 | 燕山大学 | A kind of method of vanadium in extract and separate aqueous solution |
| CN107352709A (en) * | 2017-07-17 | 2017-11-17 | 北京矿冶研究总院 | Method for removing and recovering chromium by membrane filtration coupling photoreduction |
| CN107473310A (en) * | 2017-07-17 | 2017-12-15 | 北京矿冶研究总院 | Method for extracting, removing and recovering chromium by photoreduction coupling film |
| CN107352709B (en) * | 2017-07-17 | 2019-09-24 | 北京矿冶研究总院 | Method for removing and recovering chromium by membrane filtration coupling photoreduction |
| CN107540039B (en) * | 2017-10-11 | 2020-06-16 | 大连理工大学 | Biomass-based two-aqueous-phase construction and method for purifying harmful substances in salt solution |
| CN107540039A (en) * | 2017-10-11 | 2018-01-05 | 大连理工大学 | A kind of biomass-based aqueous two-phase structure and harmful substance purification method in saline solution |
| CN109574187A (en) * | 2018-12-26 | 2019-04-05 | 大连理工大学 | A kind of multi-stage nano gel photo-reduction co-precipitation recycling heavy metal ion method |
| WO2021044200A1 (en) * | 2019-09-06 | 2021-03-11 | Aperam | Method for recovering chromium contained in a bath for pickling metallic materials and facility for implementing same |
| CN114364826A (en) * | 2019-09-06 | 2022-04-15 | 艾普伦 | Method for recovering chromium contained in washing liquid for pickling metallic material and facility for carrying out the method |
| JP2022551811A (en) * | 2019-09-06 | 2022-12-14 | アペラム | Method and equipment for recovering chromium contained in bath for pickling metal materials |
| JP7453350B2 (en) | 2019-09-06 | 2024-03-19 | アペラム | Method for recovering chromium contained in a bath for pickling metal materials and equipment for its implementation |
| CN112011688A (en) * | 2020-08-21 | 2020-12-01 | 湖北振华化学股份有限公司 | Method for separating vanadium and chromium from chromium-containing polyvanadate |
| CN112011688B (en) * | 2020-08-21 | 2022-06-24 | 湖北振华化学股份有限公司 | Method for separating vanadium and chromium from chromium-containing polyvanadate |
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