CN102815825A - Treatment process method of waste water containing hexavalent chromium - Google Patents
Treatment process method of waste water containing hexavalent chromium Download PDFInfo
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- CN102815825A CN102815825A CN2011101509388A CN201110150938A CN102815825A CN 102815825 A CN102815825 A CN 102815825A CN 2011101509388 A CN2011101509388 A CN 2011101509388A CN 201110150938 A CN201110150938 A CN 201110150938A CN 102815825 A CN102815825 A CN 102815825A
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Abstract
The invention relates to the field of heavy metal recovery and treatment, and discloses a process method for treating waste water containing hexavalent chromium. The method comprises the steps that: solid impurities are removed from the waste water containing hexavalent chromium; the waste water containing hexavalent chromium is injected into an absorption exchange column loaded with a heavy metal absorption material; hexavalent chromium is absorbed and enriched on the surface of the heavy metal absorption material; water processed by using the absorption exchange column is discharged; when heavy metal enriched on the surface of the heavy metal absorption material reaches a predetermined extent, dilute sulfuric acid is added, such that surface chromium ions of the heavy metal absorption material are desorbed into the dilute sulfuric acid, and an desorption solution is obtained; the desorption solution is added into an electro deposition apparatus; and electro deposition is carried out, such that solid chromium is obtained.
Description
Technical field
The present invention relates to field of waste water treatment, design a kind of treatment process method that contains hexavalent chromium wastewater especially.
Background technology
Develop rapidly along with socioeconomic, the quantity discharged of trade effluent increases year by year.Heavy metal wastewater thereby occupies sizable ratio in trade effluent, the waste water of heavy metal ion such as, chromium nickeliferous as all producing in many commercial runs such as plating, metallurgy, chemical industry, electronics, mine, copper, lead, cadmium.With regard to non-ferrous metal industry; About 700,000,000 tons of non-ferrous metals industry waste water year blowdown flow rate; Wherein five kinds of non-ferrous metal waste discharges such as copper, lead, zinc, aluminium, nickel account for more than 80%, have the waste water more than 2.7 hundred million tons to enter environment after the treated reuse approximately, pollute.According to statistics, national 27 trunk rivers, most of by severe contamination, contain phenol in some river, mercury generally surpasses the index several times, and even tens of times, many fish prodss of abounding with the river of fishes and shrimps are descended significantly.Water pollution has been aggravated the geographic water source of water shortage in north china tensity.South has also caused the severe contamination of water quality because a large amount of factory does not have the discharging heavy metal wastewater thereby of restraining, causes the pollution of the water of the Yangtze valley.
In recent years; Of common occurrence about the heavy metal contamination incident: 2008; 5 arsenic contamination incidents such as Guizhou Dushan County, Chenxi County, Hunan, Guangxi Hechi, Yunnan Yang Zonghai, big Shahe, Henan have taken place in China in succession; Since in August, 2009, taken place again that Fengxiang, Shaanxi children blood lead exceeds standard, liuyang hunan cadmium pollution and Linyi, Shandong arsenic contamination incident.
Because heavy metal can not decompose and destroy, be prone to participate in the circulation of food chain, and finally enrichment in vivo, destroying the normal physiological Metabolic activity, will constitute a serious threat to biological and HUMAN HEALTH.This shows; Improvement to heavy metal-containing waste water is very urgent; Country has also given great attention to this, and the each province has carried out the renovation about heavy metal contamination successively, at this crucial hour; The heavy metal-containing wastewater treatment technology of research, exploitation high efficiency, low cost alleviates heavy metal-containing waste water the pollution of environment is had important social, economy and Significance for Environment.
The method of wastewater treatment of Application and Development mainly contains chemical method, physico-chemical processes and biological process at present, comprises methods such as chemical precipitation, electrolysis, absorption exchange, membrane sepn, biofloculation, biological absorption, plant regulation.Specific as follows:
First chemical method: chemical method mainly comprises chemical precipitation method and electrolytic process, mainly is applicable to the processing that contains the higher concentration effluent containing heavy metal ions.
(1) chemical precipitation method: chemical precipitation method is in heavy metal-containing waste water, to add oxyhydroxide, sulfide, carbonated and phosphorylation thing etc.; Make the heavy metal ion that is dissolved state in the waste water change water-fast heavy metal compound into through chemical reaction; With separating throw out is removed through filtering from the aqueous solution, the different chemical precipitator method of precipitation agent are divided into neutralization precipitation method, sulphide precipitation, ferrite coprecipitation method again according to adding.The waste residue that sulphide precipitation produces in these three kinds of methods is less relatively, but the sulfide price is more expensive, the H of generation
2S gas also pollutes the environment.The ferrite precipitator method need heating in operating process, it is higher to consume energy, and can not reclaim useful metal separately.
Chemical precipitation method technology is simple, easy to operate, economical and practical, is one of method of a kind of main processing heavy metal wastewater thereby in the present industrial production.But owing to receive the influence of precipitation agent and envrionment conditions, go out water concentration and often do not reach emission standard, need be for further processing.After handling, chemical precipitation method can produce a large amount of heavy metal sewage sludges, disposal that must it is appropriate, otherwise can produce serious secondary pollution, be difficult to reach requirements of green environmental protection.The Cu that contains 0.1g/L like trade effluent
2+, Cd
2+, or Hg
2+Can produce the mud of 10 times, 9 times and 5 times heavy metallic salt content respectively; As handle the 1kg chromic salt, then can produce 6kg mud.When adopting lime to do precipitation agent, be not suitable for handling the waste water that wastewater flow rate is big, concentration of heavy metal ion is low.
(2) electrolytic process: electrolytic process is to utilize electrode and heavy metal ion generation electrochemical action and eliminate its toxic method.Electrolytic process mainly is applicable to the processing of higher concentration heavy metal wastewater thereby.Electrolytic process is a kind of treatment technology of comparative maturity, can reduce the growing amount of mud, and can reclaim metals such as Cu, Ag, Cd, has been applied to the improvement of waste water.It is big to adopt electrolytic process to handle heavy metal wastewater thereby current consumption, and cost of investment is higher, is not suitable for low concentration heavy metal water, generally electrolysis better economic benefit again after concentrating.
Second: physico-chemical processes: physico-chemical processes mainly comprises absorption method, absorption exchange process and membrane separation technique, is applicable to the processing that contains the low concentration effluent containing heavy metal ions.
(1) absorption method: absorption method comes down to rely on the adsorbent activity surface to the attraction of heavy metal ion and remove heavy metal ion.The sorbent material kind is a lot, and modal is gac.Gac can adsorb contents of many kinds of heavy metal ion simultaneously, and be characterized in: loading capacity is big, but valency is expensive, and work-ing life is short, must regenerate, and process cost is high.
In China, utilize abundant diatomite resource to work out and handle Cu
2+, Zn
2+Effect is sorbent material preferably, and Japan utilizes the natural zeolite resource, like the research of system adsorbent for heavy metal such as mordenite, clinoptilolite, wilkinite.The U.S. utilizes spent clay to prepare the patent of adsorbent for heavy metal.Natural resources prepares sorbent material, and raw material sources are wide, and is easy to manufacture, inexpensive, but sorbent material is short work-ing life, and the saturated back regeneration of heavy metal absorption difficulty is difficult to reclaim heavy metal resources.
(2) absorption exchange process: the absorption exchange process is carried out in the absorption interchanger; Be utilize heavy metal wastewater thereby when adsorbing exchange resin with the absorption exchange resin on the principle of certain group generation replacement(metathesis)reaction; Make that heavy metal concentration reduces gradually in the waste water, finally reach the purpose of removing heavy metal ion in the water.
Utilize the absorption exchange process not only can remove heavy metal ion in the water, and can be that heavy metal ion obtains enrichment and the final valuable metal that reclaims.But this method receives the influence of exchanger kind, output and cost.In the past few years, Chinese scholars has been launched number of research projects with regard to the development of adsorbing exchanger.Along with continuing to bring out of absorption exchanger, at the aspects such as recovery of electroplating wastewater advanced treatment, high-valency metal salt, the absorption exchange process more and more shows its advantage.
(3) membrane separation technique: membrane separation technique is to utilize a kind of special semi-permeable membranes, under the effect of ambient pressure, does not change on the basis of chemical form in the solution, and solvent is separated with solute or spissated method, comprises electrodialysis and diaphragm electrolysis.Contain Cu
2+, Ni
2+, Zn
2+, Cr
6+Deng the metals ion waste water electrodialysis process that all suits to use, existing suite of equipment.Reverse osmosis method is used to plate Zn, Ni, Cr rinse water and mixture-metal wastewater treatment on a large scale.Adopt reverse osmosis method to handle electroplating wastewater, treated water can reuse, realizes closed cycle.The problems such as all having run into polarization of electrode, fouling and corrosion but these two kinds of methods are in operation.
The the 3rd: biological process: biological treatment is to utilize the microbial metabolism effect, makes organic pollutant and inorganic micro-nutrients in the waste water be converted into stable, harmless material.
(1) bio-flocculation process: bio-flocculation process is the metabolite that utilizes mikrobe or microorganisms, carries out a kind of method for separating polluted particles of flocculation sediment.Develop mikrobe at present totally 17 kinds in bacterium, mould, actinomycetes, yeast and algae etc. are arranged with throwing out.Have 12 kinds that wherein heavy metal had throwing out.With the mikrobe flocculence handle the waste water safe ready nontoxic, do not produce secondary pollution, flocculating effect is good, and microorganism growth fast, be easy to realize characteristics such as industriallization.In addition, mikrobe can be through genetic engineering, tame or construct bacterial strain with specific function.Therefore the mikrobe flocculence has vast potential for future development.But biological flocculant also has disadvantage, and is high like production cost, and the living body biological flocculation agent is preserved difficulty etc.And biological process can fluctuation occur with the changes of seasons living weight, influences effluent quality.When heavy metal concentration is higher, can causing of having poisons, thereby limits its application.
(2) phytoremediation technology: the plant that in phytoremediation technology, can utilize is a lot, and phycophyta, herbage, xylophyta or the like are arranged.Its principal feature is that heavy metal is had very strong resistance to poison and accumulation ability, and the different sorts plant has the differing absorption accumulation ability to different heavy metals, and its resistance to poison also has nothing in common with each other.But governance efficiency is lower when adopting phytoremediation technology to handle heavy metal wastewater thereby, and can not administer the soil of heavily contaminated.
Following table is the treatment effect deck watch of present each heavy metal species treatment process.
Table one: heavy metal wastewater thereby is administered technology relatively
In sum, though the heavy metal in the waste water can administered and reclaim to chemical method, physico-chemical processes, biochemical process, the whole bag of tricks cuts both ways and can select suitable method to handle heavy metal wastewater thereby according to the character of waste water.
Summary of the invention
The embodiment of the invention first purpose is: the treatment process that contains hexavalent chromium wastewater method is provided, and the hypertoxic sexavalent chrome element that it can effectively be removed wherein helps heavy metal and recycles, and improves environmental protection.
A kind of treatment process method that contains hexavalent chromium wastewater that the embodiment of the invention provides comprises:
Removal contains the solid impurity of hexavalent chromium wastewater;
The said hexavalent chromium wastewater that contains is injected the absorption exchange column that the heavy metal sorbing material is housed, and said sexavalent chrome is adsorbed the surface that is enriched in said heavy metal sorbing material, efflux through the water behind the said absorption exchange column,
Wherein said heavy metal sorbing material is: being rigid backbone with silica gel, is chelating polymer with the complex polyelectrolyte particle polyetherimide, carries out coupling grafted material at normal temperatures;
When being enriched in said heavy metal sorbing material surface metal and reaching predetermined extent, inject dilute sulphuric acid, the surperficial chromium ion that is enriched in said heavy metal sorbing material is separated to be drawn onto in the said dilute sulphuric acid, obtains stripping liquid;
Said stripping liquid is injected electrodeposition apparatus, and galvanic deposit obtains solid chromium.
Alternatively, when being enriched in said heavy metal sorbing material surface metal and reaching capacity, inject dilute sulphuric acid, the surperficial chromium ion that is enriched in said heavy metal sorbing material is separated to be drawn onto in the said dilute sulphuric acid, obtains stripping liquid.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, does not constitute to improper qualification of the present invention, in the accompanying drawings:
The treatment process method flow synoptic diagram of a kind of chromium quarrel that Fig. 1 provides for the embodiment of the invention 1;
Fig. 2 is Cr in the embodiment of the invention 1 test one
6+Concentration and clearance are with water outlet volume changing trend diagram;
Fig. 3 is Cr in the embodiment of the invention 1 test two
6+Concentration and clearance are with water outlet volume changing trend diagram.
Embodiment
To combine accompanying drawing and specific embodiment to specify the present invention below, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as to qualification of the present invention.
Embodiment 1:
A kind of treatment process method flow synoptic diagram that contains hexavalent chromium wastewater that Fig. 1 provides for present embodiment, referring to diagram, should; Flow process mainly may further comprise the steps:
Step 101: pre-treatment, remove the solid impurity in the chromyl waste water.
In this step, carry out waste water is carried out pre-treatment; Preprocessing means such as through filtration, deposition etc. is removed suspended substance and other solid impurities in the waste water; To avoid wherein impurity, improve the effect of subsequent processing steps to the influence of absorption exchange effect.
Step 102: absorption exchange.
The pretreated hexavalent chromium wastewater that contains is injected the absorption exchange column that the heavy metal sorbing material is housed; Containing hexavalent chromium wastewater at this flows through in the process of adsorbing exchange column; Sexavalent chrome is adsorbed the surface that is enriched in said heavy metal sorbing material; Water through behind the said absorption exchange column effluxes, and through experimental test, water outlet can qualified discharge or reuse.
The experimental study that adopts the heavy metal sorbing material to handle western light factory electroplating wastewater of chromium shows: material is fine to the treatment effect of chromium ion, and chromium ion concentration is less than 0.0083mg/L, much smaller than the electroplating wastewater emission standard 0.2mg/L of national regulation in the water outlet; Clearance to hexavalent chromium reaches 99.995%.
Adopt the heavy metal sorbing material to handle the Cr that contains of Huashan factory
6+Demonstration is ground in the experiment of waste water: material is to Cr
6+Clearance be respectively 99.98%, concentration C r in the water outlet
6+Be respectively 0.1721mg/L and 0.0121mg/L, same electroplating wastewater emission standard far below national regulation.
The absorption switching technology can be removed the heavy metal in the waste water; The concentration of heavy metal ion in the water outlet after concentration of heavy metal ion is handled far below chemical precipitation method in the water outlet after purifying; Through regeneration, solution after the reclaiming can be realized the recovery of heavy metal; Reduce the risk that heavy metal ion gets into environment, a large amount of mud that produce when also avoiding simultaneously adopting chemical precipitation method to handle heavy metal wastewater thereby.
Wherein said heavy metal sorbing material is: being rigid backbone with silica gel, is chelating polymer with the complex polyelectrolyte particle polyetherimide, carries out coupling grafted material at normal temperatures.
Step 103: separate adsorption desorption.
When being enriched in heavy metal sorbing material surface metal and reaching predetermined extent (preferably when it is saturated or when it is almost saturated); Inject dilute sulphuric acid; Under the effect of dilute sulphuric acid, the surperficial chromium ion that is enriched in the heavy metal sorbing material is separated adsorption desorption in dilute sulphuric acid, obtains stripping liquid; In stripping liquid, contain sexavalent chrome, wherein this stripping liquid can adopt the mode of using repeatedly.
Step 104: galvanic deposit.
Stripping liquid is injected electrodeposition apparatus, and galvanic deposit obtains solid chromium.
Because if contained chromium concentration is lower than the galvanic deposit requirement in waste water; Can't directly decomposite solid-state chromium, and can adopt the processing of absorption exchange in the present embodiment earlier, make the sexavalent chrome of the severe toxicity in the waste water be enriched in the surface of heavy metal sorbing material through galvanic deposit; Desorb is handled chromium desorption with enrichment in stripping liquid then; Thereby obtain the higher stripping liquid of chromium concn, again this stripping liquid is carried out electrodeposition process and obtain decompositing solid chromium, accomplish chromic recovery.
In order to further specify the present embodiment scheme to Cr
6+Removal effect, further specify below in conjunction with experimental data:
Experiment one: the heavy metal sorbing material that adopts present embodiment is to containing the western light Cr of factory
6+Waste water is handled.
Experimental implementation:
Take by weighing the 88.64gGXA-1 material and adorn post, material is carried out pre-treatment with the 300ml deionized water;
Measure 1000ml and contain Cr
6+Waste water makes waste water flow through adsorption column with the 14.6ml/L flow, and time appearance was got in water outlet in per 2 minutes, and 4 minutes sample times, water sampling detects for 12 parts altogether.
Obtain the experimental result shown in the following table:
The present embodiment method is to Cr
6+Removal experiment effect synopsis one
Fig. 2 is Cr
6+Concentration and clearance are with water outlet volume changing trend diagram, and its left ordinate zou is: Cr
6+Clearance unit be %, right ordinate zou is Cr in the water outlet
6+Concentration, unit is mg/L.Wherein curve 201 is Cr in Fig. 1
6+Clearance, curve 202 is Cr in the water outlet
6+Concentration.
Can find out that by Fig. 2 the CX-1 material is very desirable to the adsorption effect of Cr6+, adsorption rate is mixed the plating pollutant emission standard (0.2mg/L) that effluent quality is much better than national regulation more than 99.98%.
The absorption exchange column that test two, employing present embodiment are equipped with the heavy metal sorbing material is to Cr in the Huashan factory waste water
6+Adsorption experiment
1. experimental procedure: adopt heavy metal sorbing material GX-1 material that Hua Shanchang is contained Cr
6+Waste water is handled.
1. take by weighing 95.52g heavy metal sorbing material GX-1 material and adorn post; With the flow velocity of 1.5m/h material is carried out pre-treatment with the 400ml deionized water; Once more material is carried out pre-treatment with 268ml ammoniacal liquor (1mol/L) with the flow velocity of 1.0m/h, use deionized water to regulate that pH value is about 7 in the adjustable column.
2. measure 1000ml waste water, make waste water flow through adsorption column with the flow of 14.6ml/min, the every 4min of water outlet gets time appearance, and be 4min each sample time, gets 8 parts of water sample detection altogether.
2. shown in experimental result and discussion see table:
Handle Cr in the Huashan factory waste water
6+The data results table
Fig. 3 is Cr
6+Concentration and clearance are with water outlet volume changing trend diagram, and its left ordinate zou is: Cr
6+Clearance unit be %, right ordinate zou is Cr in the water outlet
6+Concentration, unit is mg/L.Wherein curve 302 is Cr in Fig. 1
6+Clearance, curve 301 is Cr in the water outlet
6+Concentration.
Can find out that by Fig. 3 the CX-1 material is very desirable to the adsorption effect of Cr6+, adsorption rate is mixed the plating pollutant emission standard (0.2mg/L) that effluent quality is much better than national regulation more than 99.98%.
Experiment three: adopt heavy metal sorbing material GX-2 that western light factory is contained Gr
6+Waste water carries out adsorption experiment
Experimental implementation:
Take by weighing 135.93g heavy metal sorbing material GX-2 material and adorn post, use the 300ml deionized water, material is carried out pre-treatment with the 14.6ml/minL flow.Measure 300ml and contain Gr
6+Waste water, with the 14.6ml/min flow, through adsorption column, the every 80ml of water outlet gets time water sample, and water sampling is 4 parts altogether, send the analyzer room to detect.
The Cr that wherein this is contained chromium filtrating
6+The removal experimental data is as shown in the table:
The present embodiment method is to Cr
6+Removal experiment effect synopsis two
Can use the present embodiment method to containing the Cr of chromium filtrating by last table
6+Removal effect is fairly obvious, and clearance is all more than 99.995%.Cr
6+Go out the plating pollutant emission standard that water concentration has reached national regulation.
More than the technical scheme that the embodiment of the invention provided has been carried out detailed introduction; Used concrete example among this paper the principle and the embodiment of the embodiment of the invention are set forth, the explanation of above embodiment only is applicable to the principle that helps to understand the embodiment of the invention; Simultaneously, for one of ordinary skill in the art, according to the embodiment of the invention, the part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (2)
1. a treatment process method that contains hexavalent chromium wastewater is characterized in that, comprising:
Removal contains the solid impurity of hexavalent chromium wastewater;
The said hexavalent chromium wastewater that contains is injected the absorption exchange column that the heavy metal sorbing material is housed, and said sexavalent chrome is adsorbed the surface that is enriched in said heavy metal sorbing material, efflux through the water behind the said absorption exchange column,
Wherein said heavy metal sorbing material is: being rigid backbone with silica gel, is chelating polymer with the complex polyelectrolyte particle polyetherimide, carries out coupling grafted material at normal temperatures;
When being enriched in said heavy metal sorbing material surface metal and reaching predetermined extent, inject dilute sulphuric acid, the surperficial chromium ion that is enriched in said heavy metal sorbing material is separated to be drawn onto in the said dilute sulphuric acid, obtains stripping liquid;
Said stripping liquid is injected electrodeposition apparatus, and galvanic deposit obtains solid chromium.
2. the treatment process method that contains hexavalent chromium wastewater according to claim 1 is characterized in that,
When being enriched in said heavy metal sorbing material surface metal and reaching capacity, inject dilute sulphuric acid, the surperficial chromium ion that is enriched in said heavy metal sorbing material is separated to be drawn onto in the said dilute sulphuric acid, obtains stripping liquid.
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| CN2011101509388A CN102815825A (en) | 2011-06-08 | 2011-06-08 | Treatment process method of waste water containing hexavalent chromium |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178628A (en) * | 2013-05-28 | 2014-12-03 | 工信华鑫科技有限公司 | Novel wet-smelting technology |
| CN104925923A (en) * | 2015-05-29 | 2015-09-23 | 尹小波 | Method for treating wastewater containing hexavalent chromium |
| CN110064381A (en) * | 2019-04-30 | 2019-07-30 | 广州大学 | A kind of alginate complex microsphere and its preparation method and application of efficient removal contents of many kinds of heavy metal ion |
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| RU1836295C (en) * | 1991-04-30 | 1993-08-23 | Вера Васильевна Мясоедова | Method of recovering of nickel from drainage waters of electrochemical plants |
| CN101444541A (en) * | 2007-11-26 | 2009-06-03 | 中国中医科学院中药研究所 | Application of bonded silicagel composite material to removing heavy metals from tradition Chinese medicine extracting solution |
| CN101838064A (en) * | 2010-01-26 | 2010-09-22 | 中国环境科学研究院 | Method for recycling manganese ion in electrolytic manganese production tail end wastewater |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU1836295C (en) * | 1991-04-30 | 1993-08-23 | Вера Васильевна Мясоедова | Method of recovering of nickel from drainage waters of electrochemical plants |
| CN101444541A (en) * | 2007-11-26 | 2009-06-03 | 中国中医科学院中药研究所 | Application of bonded silicagel composite material to removing heavy metals from tradition Chinese medicine extracting solution |
| CN101838064A (en) * | 2010-01-26 | 2010-09-22 | 中国环境科学研究院 | Method for recycling manganese ion in electrolytic manganese production tail end wastewater |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178628A (en) * | 2013-05-28 | 2014-12-03 | 工信华鑫科技有限公司 | Novel wet-smelting technology |
| CN104925923A (en) * | 2015-05-29 | 2015-09-23 | 尹小波 | Method for treating wastewater containing hexavalent chromium |
| CN104925923B (en) * | 2015-05-29 | 2016-09-07 | 湖南中大建设工程检测技术有限公司 | A kind of method administered containing hexavalent chromium wastewater |
| CN110064381A (en) * | 2019-04-30 | 2019-07-30 | 广州大学 | A kind of alginate complex microsphere and its preparation method and application of efficient removal contents of many kinds of heavy metal ion |
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