CN102531139B - 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 removing and reclaiming chromium from acidic chromium-containing wastewater.
Background technology
Chromate waste water is mainly derived from industrial pollution, particularly electroplating industry.Because the chromium combined plating has the advantages such as hardness is high, heat-resisting, wear-resisting, corrosion-resistant, bright and beautiful, 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 has serious harm to ecotope and HUMAN HEALTH, and sexavalent chrome is than trivalent chromium toxicity larger (approximately large 100 times).Sexavalent chrome is the property swallowed poisonous substance/imbedibility utmost point poisonous substance, and skin contact may cause sensitivity; More may cause the heredity genetic flaw, sucking may 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 by digestion, respiratory tract, skin and mucous membrane.Report is arranged, in various degree hoarse, Atrophic nasal mucosas are arranged when containing the chromic trioxide of different concns in breathe air, also can make perforation of nasal septum and bronchiectasis etc. when serious.Can cause vomiting when digestive tube is invaded, abdomen pain.When invading, skin can produce dermatitis and eczema.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 processed.Yet so far, still there are various deficiencies in the treatment technology of various chromate waste waters, and is as low in the advanced treatment efficient of lower concentration, and step is tediously long, and acid and alkali consumption is large, and running cost is higher, and these are to be improved and raising all.
Treatment of chromium containing wastewater generally adopts " two step method " both at home and abroad at present.Utilize SO under acidic conditions
2, NaHSO
3, FeSO
4Deng reductive agent, hexavalent chrome reduction is become trivalent chromium.Then the pH value that adds alkali raising waste water makes it to generate chromium hydroxide precipitation, then removes by filter.CN 1050709A discloses a kind of recovery method of chromium from waste solution for electroplating chromium.The method is mainly to place the plastic wire liner in chrome-plating bath, add sulfurous acid to make hexavalent chrome reduction become trivalent chromium in waste water, and then add ammoniacal liquor, contain the chromium precipitation with trivalent chromium reaction generation, until precipitation fully, separate at last, the water purification closed circulation after separation is reused for rinsing, and the chromium precipitation water that contains after separating repeatedly cleans, remove ammonium ion and sulfate ion, obtain the chromium cpd sterling, then be recycled and reused for chrome-plated process.Because reduction reaction is generally carried out (general requirement pH＜4 under acidic conditions, usually control pH=2.5～3), and the best pH of precipitation is 8.5～10.0, but the pH value of chromate waste water is generally 3.5～6.5, therefore at first the method needs acid adding to regulate acidity to reducing acidity during the first step, then adds alkali sedimentation trivalent chromium when second step again, and this process acid and alkali consumption is large, 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 separating out hydrogen on negative electrode, make wastewater pH increase gradually simultaneously, be at last neutral, at this moment Cr
3+, Fe
3+All separate out with precipitation of hydroxide, reach the purpose of purification of waste water.CN 86106414B discloses a kind of method of electrolytic method for treating wastewater containing vanadium and chromium.The method comprises: waste water carries out electrolysis after the molten prereduction of 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+The precipitation of the water purification of＜0.5, V＜0.4 mg/litre and Vanadium Concentrationin, chromium.The problems such as electrolytic process exists energy consumption high, and step is many, is mixed with a large amount of ironic hydroxides in 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 process 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 the problems such as step is long, acid and alkali consumption is large.Generally do not adopt the solvent extration dechromisation in acidic solution, major cause is directly to remove sexavalent chrome from acidic solution, can make the extraction agent sex change because of chromic strong oxidizing property in acidic solution, reduces its work-ing life.
The double water-phase solvent extraction technology is large due to its water content, mass transfer fast and green high-efficient, and is multiplex in separation and the purification of biological product.And the typical double-aqueous phase system that is built by water-soluble polymers such as polyoxyethylene glycol, with lone-pair electron, have electronegativity due to the oxygen of ether-oxygen bond, easily adsorb hydrogen ion by electrostatic interaction, thereby has positive polarity, then by solvation mechanism complexing metal complex anion.The pH of waste electroplating liquor containing chromium is generally 3.5～6.5, and the water solution system that this slightly acidic is near neutral is very suitable for this Two-phase system of directly adopting us to develop, thereby makes sexavalent chrome transfer to polymer phase.It is yellow that the chromic polymer phase of load is, and places after the chromic polymer phase of load is separated.Research finds, after placing a couple of days, divide 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 light and the external world, the sexavalent chrome that loads in polymer phase is reduced into trivalent chromium, separates out from the bottom of polymkeric substance.The applicant has invented a kind of method (application number 201110336246.2) that photoreduction coupling liquid-liquid-liquid three phase extraction removed and reclaimed chromium early stage.This invention is by in the aqueous solution that contains Cr (VI), add inorganic strong electrolyte salt, water soluble polymer, regulate aqueous pH values, then add organic solvent, fully mixing, standing or centrifugal phase-splitting, obtain Liquid-Liquid-Liquid Systems, and mentioned solution is placed under illumination, Cr (VI) is reduced into Cr (III) and all transfers to phase, at last Cr (III) back extraction of upper phase load is reclaimed.But the method has adopted organic solvent, has certain toxicity, and cost is higher, is unfavorable for suitability for industrialized production.
Prior art all exist complicated operation, energy consumption high/reagent consumption is large, cost is high, operation has the problems such as toxicity, contaminate environment.Based on above prior art, present method proposes to adopt the sexavalent chrome in Two-phase system single stage method removal 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
For the deficiencies in the prior art, one of purpose of the present invention is to provide single stage method to remove and reclaim the method for chromium from acidic chromium-containing wastewater, and the method operation is more simple, green, and less energy consumption is easy to realize industrialization.
Chromium was removed and reclaimed to described single stage method from acidic chromium-containing wastewater method comprises:
(1) add into phase salt and polymkeric substance in acidic chromium-containing wastewater, after becoming phase salt and polymer dissolution, namely form double water-phase, this process has realized the transfer of sexavalent chrome to polymer phase simultaneously, and other negatively charged ion that coexists still is retained in salt phase under water;
(2) separate and to obtain load chromic yellow polymer phase is arranged, place, make polymer phase lower floor separate out aqueous phase layer, be separated, thereby the trivalent chromium in waste water is reclaimed.
Preferably, the isolated polymer phase of step (2) is reusable.
Layering described in step (2) refers to that polymer phase lower floor separates out absinthe-green aqueous phase layer, and this absinthe-green aqueous phase layer is actual is trivalent chromium solutions.
Preferably, make polymer phase lower floor separate out aqueous phase layer by light or/and external influence is realized described in step (2).
Preferably, described chromate waste water pH value is below 7, such as 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, particularly preferably pH is 1～6, exceed this Acidity Range, chromium descends to the rate of transform of polymer phase.
Preferably, chromate waste water of the present invention, both comprised the chromate waste water that electroplating industry produces, also comprise other chromate waste waters, in described chromate waste water, hexavalent chromium concentration is 1～400mg/L, such as: 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., 20～350mg/L more preferably, be particularly preferably 50～300mg/L, the chromium solution of higher concentration, percentage extraction descends.
Preferably, described polymkeric substance is water-soluble polymers, comprises the polyethers superpolymer, as 50-HB-170, and 5-HB-5100,50-HB-5100 etc.; The polyoxyethylene glycol of different molecular weight, as PEG2000, PEG10000 etc., segmented copolymer, as PEO-PPO blend series, PEO-PPO-PEO block series, polyethylene glycol-propylene glycol-monobutyl ether series etc. are particularly preferably polyoxyethylene glycol or/and block polymer, for example EOPO (PEP-101).
Preferably, described one-tenth phase salt is vitriol, phosphoric acid salt, hydrosulfate, hydrophosphate, dihydrogen phosphate, such as: sodium sulfate, vitriolate of tartar, ammonium sulfate, sodium pyrosulfate, sal enixum, ammonium phosphate, sodium phosphate, potassiumphosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC etc., more preferably vitriol, be particularly preferably ammonium sulfate, sodium sulfate.
Preferably, becoming the mass percent concentration of phase salt in described double water-phase is 5%～80%, more preferably 8%～70%, be particularly preferably 10%～60%.
Preferably, in described double water-phase, the mass percent concentration of polymkeric substance is 5%～80%, more preferably 8%～70%, be particularly preferably 10%～60%.
Preferably, described in step (2), be at least 2 days storage period, such as: 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 particularly preferably at least 3 days.
Described light be lamp or/and the natural light that artificial light sends or/and artificial light.
Described external influence can be heating, illumination, airbath, ultrasonic etc.
Chromate waste water of the present invention allows other metal ion that exists with cationic form coexist and do not disturb.
Compared with prior art, the method for removing from acidic chromium-containing wastewater and reclaiming chromium of the present invention it is advantageous that:
(1) there is not the acid and alkali consumption problem, do not need to 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 as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered 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 on polymkeric substance mutually standing 3 days, phase-splitting, the lower mutually chromic rate of recovery is 86%.
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.With on polymkeric substance standing 4 days under fluorescent light mutually, phase-splitting, the lower mutually chromic rate of recovery is 92%.
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 on polymkeric substance under 40 ℃ standing 2 days, phase-splitting, the lower mutually chromic rate of recovery is 86%.
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.With on polymkeric substance standing 2 days under fluorescent light mutually, phase-splitting, the lower mutually chromic rate of recovery is 85%.
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.With on polymkeric substance standing 2.5 days under fluorescent light mutually, phase-splitting, the lower mutually chromic rate of recovery is 89%.
The comparative example
Adopt the applicant first to file (application number 201110336246.2) as a comparison embodiment compare.
Containing Cr (VI) toward 20mL is 4000 polyoxyethylene glycol and the dissolving of 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, after vibration 5min, centrifugal 10min under rotating speed 3000rpm condition forms Liquid-Liquid-Liquid Systems this moment.Cr (VI) percentage extraction of phase in polyoxyethylene glycol reaches 90.5%, shine 30min under sunlight after, middle Cr (VI) in mutually thoroughly is reduced into Cr (III) and all transfers to phase, and the Cr of upper phase load (III) reclaims with the dilution heat of sulfuric acid back extraction of pH=2.5.
By embodiment of the present invention 1-5 and comparative example are compared as can be known, the present invention compares with the comparative example, and the rate of recovery is more or less the same, but operate more simple, and need not regulate pH-value, also not adopt organic solvent, not only reduce cost but also prevented murder by poisoning to operator's health.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention is 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., within all dropping on protection scope of the present invention and open scope.
Claims (23)
1. the method for chromium is removed and reclaimed to single stage method from acidic chromium-containing wastewater, comprising:
(1) add into phase salt and polymkeric substance in acidic chromium-containing wastewater, form double water-phase;
(2) separate and to obtain load chromic yellow polymer phase is arranged, place, make polymer phase lower floor separate out aqueous phase layer, be separated, thereby the trivalent chromium in waste water is reclaimed;
Described chromate waste water pH value is below 7, and in described chromate waste water, hexavalent chromium concentration is 1～400mg/L, and described one-tenth phase salt is vitriol, phosphoric acid salt, and described polymkeric substance is water-soluble polymers; Becoming the mass percent concentration of phase salt in described double water-phase is 5%～80%; In described double water-phase, the mass percent concentration of polymkeric substance is 5%～80%.
2. the method for claim 1, is characterized in that, the isolated polymer phase of step (2) is reused.
3. the method for claim 1, is characterized in that, makes polymer phase lower floor separate out aqueous phase layer described in step (2) and realize by external influence, and described external influence is illumination, airbath, heating, ultrasonic.
4. method as claimed in claim 1 or 2, is characterized in that, described chromate waste water pH is below 6.
5. method as claimed in claim 4, is characterized in that, described chromate waste water pH is 1～6.
6. as the described method of claim 1-3 any one, it is characterized in that, in described chromate waste water, hexavalent chromium concentration is 20～350mg/L.
7. method as claimed in claim 6, is characterized in that, in described chromate waste water, hexavalent chromium concentration is 50～300mg/L.
8. as the described method of claim 1-4 any one, it is characterized in that, described polymkeric substance is the polyethers superpolymer, the polyoxyethylene glycol of different molecular weight, segmented copolymer.
9. method as claimed in claim 8, is characterized in that, described polyethers superpolymer is 50-HB-170,50-HB-5100.
10. method as claimed in claim 8, is characterized in that, the polyoxyethylene glycol of described different molecular weight is PEG2000, PEG10000.
11. method as claimed in claim 8 is characterized in that, described segmented copolymer is PEO-PPO blend series, PEO-PPO-PEO block series, polyethylene glycol-propylene glycol-monobutyl ether series.
12. method as claimed in claim 8 is characterized in that, described polymkeric substance is that polyoxyethylene glycol is or/and block polymer.
13. method as claimed in claim 8 is characterized in that, described polymkeric substance is PEP-101.
14. as the described method of claim 1-5 any one, it is characterized in that, described one-tenth phase salt is vitriol.
15. method as claimed in claim 14 is characterized in that, described vitriol is ammonium sulfate, sodium sulfate.
16. as the described method of claim 1-6 any one, it is characterized in that, becoming the mass percent concentration of phase salt in described double water-phase is 8%～70%.
17. method as claimed in claim 16 is characterized in that, becoming the mass percent concentration of phase salt in described double water-phase is 10%～60%.
18. as the described method of claim 1-7 any one, it is characterized in that, in described double water-phase, the mass percent concentration of polymkeric substance is 8%～70%.
19. method as claimed in claim 18 is characterized in that, in described double water-phase, the mass percent concentration of polymkeric substance is 10%～60%.
20. as the described method of claim 1-8 any one, it is characterized in that, described in step (2), be at least 2 days storage period.
21. method as claimed in claim 20 is characterized in that, at least 2.5 days storage periods described in step (2).
22. method as claimed in claim 21 is characterized in that, described in step (2), be in particular at least 3 days storage period.
23. the method for claim 1 is characterized in that, described one-tenth phase salt is: hydrosulfate, hydrophosphate, dihydrogen phosphate.
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| CN2012100075579A CN102531139B (en) | 2012-01-11 | 2012-01-11 | Method for removing and recycling chrome from acid chromate wastewater in one step |
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| CN2012100075579A CN102531139B (en) | 2012-01-11 | 2012-01-11 | Method for removing and recycling chrome from acid chromate wastewater in one step |
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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 |
| CN106756123B (en) * | 2016-12-02 | 2018-12-28 | 燕山大学 | A kind of method of extraction water Molybdenum in Solution (VI) |
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| 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 |
| 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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| RU2809020C2 (en) * | 2019-09-06 | 2023-12-05 | Аперам | Method for extraction of chrome contained in bath for etching metal materials and installation for its implementation |
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