CN106241960B - A kind of processing method of acid heavy metal wastewater - Google Patents
A kind of processing method of acid heavy metal wastewater Download PDFInfo
- Publication number
- CN106241960B CN106241960B CN201610788301.4A CN201610788301A CN106241960B CN 106241960 B CN106241960 B CN 106241960B CN 201610788301 A CN201610788301 A CN 201610788301A CN 106241960 B CN106241960 B CN 106241960B
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- heavy metal
- water
- acid
- processing method
- electrodeposition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention provides a kind of processing methods of acid heavy metal wastewater, first pass through microfiltration membranes and are pre-processed, and when the acid content in waste water is less than 2wt%, are concentrated using industrial special film II or industrial special film III, the dope by gained containing heavy metal carries out electrodeposition；Sodium polydithio-dipropyl sulfonate is added in electrolytic deposition process into electrolyte, the concentration of sodium polydithio-dipropyl sulfonate is 0.045~0.1kg/m3, the circular flow of electrodeposition system is 10~80m3/h.The present invention can carry out high efficiente callback to the low-concentration heavy metal in acid heavy metal, while substantially improve the quality of discharge waste water, and environmental protection, efficient, the period is short, easy to operate.
Description
Technical field
The present invention relates to wastewater treatments, more particularly to a kind of processing method of acid heavy metal wastewater.
Background technique
In environment and human health field, heavy metal refer mainly to mercury (Hg), cadmium (Cd), lead (Pb), chromium (Cr), arsenic (As),
The heavy metals such as copper (Cu), zinc (Zn), cobalt (Co), nickel (Ni).The industries such as mining, metallurgy, chemical industry are main artificial dirts in water body
Dye source, excessive enrichment of the heavy metal in food chain can cause very big harm to natural environment and human health.Chemical method is
The main method of processing heavy metal-containing waste water, principle are made in waste water by chemical reaction in dissolved state both at home and abroad at present
Heavy metal is changed into heavy metal compound not soluble in water, by filtering and separation removes sediment from aqueous solution, including
Neutralization precipitation method, sulphide precipitation, ferrite coprecipitation.In the prior art using the supernatant obtained after chemical precipitation method
Liquid, the direct emission after mechanical filter, this method can make the concentration of heavy metal in waste water drop to national emission request substantially.
Because adding the raw more heavy metal sewage sludge of medicament fecund when usual chemical Treatment, and Heavy Metals in Sludge usually recycles
Difficulty is big, cost recovery is high, and sludge is fed directly to landfill yard landfill disposal after filters pressing, causes the waste of heavy metal resources.
The recycling of heavy metal may be implemented in electrolysis method, it is the effect by anode and cathode plate to heavy metal in waste water,
Make heavy metal ion obtain electronics to be precipitated in cathode, to recycle heavy metal.But usual electrolysis method recycling heavy metal requires waste water
Middle heavy metal concentration is high (general 5g/L or more).Waste water for low concentration (5g/L or less) containing heavy metal can not Direct Electrolysis time
Receive heavy metal.
Summary of the invention
The purpose of the present invention is to provide a kind of high efficiente callback can be carried out to the low-concentration heavy metal in acid heavy metal,
The quality of discharge waste water is substantially improved simultaneously, and environmental protection, efficient, the period is short, the processing side of acid heavy metal wastewater easy to operate
Method.
Technical program of the present invention lies in providing a kind of processing method of acid heavy metal wastewater, microfiltration membranes progress is first passed through
Pretreatment is concentrated, by gained when the acid content in waste water is less than 2wt% using industrial special film II or industrial special film III
Dope containing heavy metal carries out electrodeposition；Sodium polydithio-dipropyl sulfonate, poly- two sulphur dipropyl are added in electrolytic deposition process into electrolyte
The concentration of alkyl sulfonic acid sodium is 0.045~0.1kg/m3, the circular flow of electrodeposition system is 10~80m3/h。
The present invention further comprises following preferred technical solution:
In preferred scheme, when the acid content in waste water is greater than 2wt%, waste water after pretreatment first passes through extraordinary work
The processing of industry film I obtains the mixing dope containing acid and heavy metal, reuses industrial special film II or industrial special film III is concentrated.
By carrying out above-mentioned processing, can not only recycle to obtain heavy metal, moreover it is possible to while recycling acid therein.
It is preferred that first passing through most of bulky grain suspended matter in pretreatment removing waste water, indissoluble inorganic matter, colloid in advance and having
Machine object.
In preferred scheme, the current density in electrolytic deposition process is 100~500A/m2, anode is lead-calcium-tin alloy, cathode
For titanium.
In preferred scheme, the temperature in electrolytic deposition process is 20~30 DEG C.
In preferred scheme, the special industrial film I is for separating ion and water.
In preferred scheme, the special industrial film II is used for divalent ion and 1 valence ion.
In preferred scheme, the special industrial film III is used for trivalent ion and divalent ion.
In preferred scheme, the electrode distance in the electrolytic deposition process is 3-6cm.
In preferred scheme, the heavy metal is copper or/and nickel.
In preferred scheme, the number of the circulation is 4-6 times.
In preferred scheme, it is filtered in the preprocessing process using microfiltration membranes.
In preferred scheme, the concentration of the heavy metal is 0.01g/L~5g/L.
The concentration of the heavy metal is more preferably 0.01g/L~1g/L.
The special industrial film I, special industrial film II, special industrial film III can enumerate the SIMS film of HWA company, model
Respectively WDK, WGH, WAPE.
HWA refers to HWA TECHNOLOGY (HK) CO LTD..
Technique in treatment process of the invention is preferred are as follows: waste water is introduced into microfiltration membrane system and removes oil removal, then passes through
Intermediate water tank enters special industrial membranous system, and clear water is produced according to water quality situation outlet or reuse, and concentrated water enters in concentrated water case, dense
Water selects circulating filtration number according to water quality situation, reaches the concentrated water that electrodeposition water inlet requires and enters electrodeposition system circulation water tank；?
Electrodeposition additive is added in cyclic water tank, and circulates waste water constantly in Winning cell, when metal concentration is low in Winning cell
When electrodeposition efficiency value, terminate electrodeposition；Waste liquid is back to the first step in Winning cell and cyclic water tank, into subsequent cycle.
By the cooperation of above-mentioned technique, the acquisition of beneficial effects of the present invention can be further ensured, carry out industrialized
Concrete application.
The heavy metal concentration reached in the concentrated water that electrodeposition water inlet requires is preferably 5g/L or more.
When metal concentration is lower than electrodeposition efficiency value in Winning cell, the metal concentration is preferably shorter than 0.1g/L.
Beneficial effects of the present invention
The present invention is for for multi-stage reverse osmosis is contained in acid heavy metal wastewater treatment process, process is multiple in the prior art
Miscellaneous, process flow is long, and time cost is high, and the status of water pollution is aggravated during recycling heavy metal, provides one
Kind process efficiency is high, it might even be possible to entire work flow operation is completed within 2h.The low concentration weight for being 0.01g/L~5g/L to concentration
Metal can play good recovering effect, and the operating time is shorter, more efficient, and valuable metal recovery efficiency is up to 95% or more
Acid heavy metal wastewater processing method.In specific experimentation, the present invention by pretreatment plus feature industrial membrane and
The combination of electrolytic deposition process, and stringent restriction is carried out to processing step and parameter, obtain the beneficial of extraordinary synergy
Effect.Wherein, 95% or more has been reached to the rate of recovery of copper and mickel.Have the effect of very excellent recycling heavy metal, and
Treated that waste water is substantially clear water for discharge, can be with direct emission.Significantly reduce environmental pressure.Moreover, this hair
Bright to recycle to obtain acid and heavy metal simultaneously, this is that existing method cannot achieve at all.
Detailed description of the invention
Fig. 1 is an example of the schematic diagram for the treatment of process process of the invention.
Specific embodiment
Embodiment 1:
Certain 1m3The waste water of sulfur acid and heavy metal copper, sulfuric acid concentration 4% (mass ratio), copper ion concentration 1g/L.
Using the microfiltration membranes in the aperture 5um to waste water filtering, remove the suspended matter in waste water.
1m after filtering3Waste water retains sulfuric acid and heavy metal by special industrial film I, for the concentration for improving nickel in concentrated water
Multiple, concentrated water are passed through membranous system, membranous system pressure 2.0MPa, internal circulating load 25m by circulating pump again3/ h divides after recycling 5 times
It separates out 200L and contains sour dope.Sulfuric acid concentration is 20% (mass ratio), cupric 4.9g/L in dope.Clear water 800L, sulfur acid
0.01mol/L, cupric 0.025g/L.
200L dope is entering special industrial film II and special industrial film III, and the film is for separating copper ion and acid, equally
Using multi-cycle separation mode, membranous system pressure 2.0MPa, internal circulating load 25m3/ h isolates 42L dope after recycling 5 times.Dope
Middle copper ion concentration 22.1g/L, pH=2.In permeate 158L, copper ion concentration 0.2g/L, acid concentration 3.035mol/L.It should
The acid of stage permeate can be used for recycling.
42L cupric concentrate enters electrodeposition system circulation slot, and 2g sodium polydithio-dipropyl sulfonate is added in electric effusion, is adopted
Use 20m3The internal circulating load of/h, 200A/m2Current density, lead-calcium-tin alloy anode, Ti cathode, electrodeposition 1.2h in the case where 25 DEG C
Afterwards, 0.97kg copper is obtained on cathode plate, copper concentration is 0.2g/L in circulating slot.
In the present embodiment, the rate of recovery of copper is 97%, and whole process operates about 2.3h.
Embodiment 2:
Certain 1m3Nickeliferous waste water, pH=2, nickel ion concentration 0.2g/L.
Using the microfiltration membranes in the aperture 5um to waste water filtering, remove the suspended matter in waste water.
Filtered waste water enters III system of special industrial film II and special industrial film, in special industrial film II and extraordinary work
Nickel ion is largely trapped in concentrated water under the retention of industry film III, and fraction enters clear water, for the concentration for improving nickel in concentrated water
Multiple, concentrated water are passed through membranous system, membranous system pressure 2.0MPa, internal circulating load 25m by circulating pump again3/h.It is recycled by 5 times
Afterwards, concentrate 38L is obtained, concentrate nickel concentration is 5.2g/L, and 26 times of cycles of concentration, clear water yield is 962L, 0.0025g/L.
The nickeliferous concentrate of 38L enters electrodeposition system circulation slot, and 2g sodium polydithio-dipropyl sulfonate is added in electric effusion, is adopted
Use 20m3The internal circulating load of/h, 200A/m2Current density, lead-calcium-tin alloy anode, Ti cathode, electrodeposition 1.2h in the case where 25 DEG C
Afterwards, 0.19kg nickel is obtained on cathode plate, nickel concentration is 0.2g/L in circulating slot.
In the present embodiment, the rate of recovery of nickel is 95%, and whole process operates about 2h.
Comparative example 1:
Certain 1m3Nickeliferous waste water, pH=2, nickel ion concentration 0.5g/L.
Using the microfiltration membranes in the aperture 5um to waste water filtering, remove the suspended matter in waste water.
Filtered waste water enters nanofiltration membrane system, which is 1~2nm, can molecular cut off 150~
500 or so.Membranous system pressure 2.0MPa, internal circulating load 25m3/ h obtains concentrate 96L after 5 circulations, in concentrate
Nickel concentration is 2g/L, cycles of concentration 4, clear water yield, nickel 0.35g/L in clear water.
The nickeliferous concentrate of 96L enters electrodeposition system circulation slot, 5g electrodeposition additive is added in electric effusion, using 20m3/h
Internal circulating load, 200A/m2Current density, lead-calcium-tin alloy anode, Ti cathode, in the case where 25 DEG C after electrodeposition 1.2h, in yin
0.18kg nickel is obtained on pole plate, nickel concentration is 0.125g/L in circulating slot.
In this comparative example, the rate of recovery of nickel is 36%, and whole process operates about 2h.Under same operating condition, recovery efficiency
It is decreased obviously.
Comparative example 2
When 38L concentrate enters electrodeposition system, in addition to not adding sodium polydithio-dipropyl sulfonate, remaining is according to embodiment 2
It is operated, as a result cathode plate obtains nickel 0.15kg, the rate of recovery 75%.
Comparative example 3
When 38L concentrate enters electrodeposition system, except circular flow is 2m3Outside/h, remaining is operated according to embodiment 2,
As a result cathode plate obtains nickel 0.17kg, the rate of recovery 85%.
Comparative example 4
When 38L concentrate enters electrodeposition system, except current density is 50A/m2Outside, remaining is operated according to embodiment 2,
As a result cathode plate obtains nickel 0.16kg, the rate of recovery 80%.
Comparative example 5
When 38L concentrate enters electrodeposition system, in addition to operation temperature is 10 DEG C, remaining is operated according to embodiment 2, knot
Fruit cathode plate obtains nickel 0.17kg, the rate of recovery 85%.
Claims (9)
1. a kind of processing method of acid heavy metal wastewater, which is characterized in that first pass through microfiltration membranes and pre-processed, when in waste water
Acid content when being less than 2wt%, be concentrated using industrial special film II or industrial special film III, the dope by gained containing heavy metal into
Row electrodeposition；Sodium polydithio-dipropyl sulfonate is added in electrolytic deposition process into electrolyte, the concentration of sodium polydithio-dipropyl sulfonate is
0.045~0.1kg/m3, the circular flow of electrodeposition system is 10~80m3/h；Current density in electrolytic deposition process is 100~
500A/m2, anode is lead-calcium-tin alloy, and cathode is titanium.
2. the processing method of acid heavy metal wastewater according to claim 1, which is characterized in that when the acid in waste water contains
When amount is greater than 2wt%, waste water after pretreatment first passes through the processing of special industrial film I, and it is dense to obtain the mixing containing acid and heavy metal
Liquid, reuses industrial special film II or industrial special film III is concentrated.
3. the processing method of acid heavy metal wastewater according to claim 1 or 2, which is characterized in that in electrolytic deposition process
Temperature is 20~30 DEG C.
4. the processing method of acid heavy metal wastewater according to claim 2, which is characterized in that the special industrial film
I, special industrial film II, special industrial film III are purchased from the SIMS film of HWA company, and model is respectively WDK, WGH, WAPE.
5. the processing method of acid heavy metal wastewater according to claim 1 or 2, which is characterized in that the special industrial
Film I is for separating ion and water；The special industrial film II is used for divalent ion and 1 valence ion；The special industrial film III is used for
Trivalent ion and divalent ion.
6. the processing method of acid heavy metal wastewater according to claim 3, which is characterized in that in the electrolytic deposition process
Electrode distance be 3~6cm.
7. the processing method of acid heavy metal wastewater according to claim 1 or 2, which is characterized in that the heavy metal is
Copper or/and nickel.
8. the processing method of acid heavy metal wastewater according to claim 1 or 2, which is characterized in that the heavy metal
Concentration is 0.01~5g/L.
9. the processing method of acid heavy metal wastewater according to claim 1 or 2, which is characterized in that in treatment process
Technique are as follows: waste water is introduced into microfiltration membrane system and removes oil removal, then enters special industrial membranous system, clear water root through intermediate water tank
It is produced according to water quality situation outlet or reuse, concentrated water enters in concentrated water case, and concentrated water selects circulating filtration number according to water quality situation, reaches
The concentrated water required to electrodeposition water inlet enters electrodeposition system circulation water tank；Electrodeposition additive is added in cyclic water tank, and makes waste water
It is constantly circulated in Winning cell, when metal concentration is lower than electrodeposition efficiency value in Winning cell, terminates electrodeposition；It Winning cell and follows
Waste liquid is back to the first step in ring water tank, into subsequent cycle.
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| CN201610788301.4A CN106241960B (en) | 2016-08-31 | 2016-08-31 | A kind of processing method of acid heavy metal wastewater |
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| CN201610788301.4A CN106241960B (en) | 2016-08-31 | 2016-08-31 | A kind of processing method of acid heavy metal wastewater |
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| CN107298509A (en) * | 2017-05-14 | 2017-10-27 | 安徽泛亚环保科技有限公司 | A kind of purification method of acid heavy metal wastewater |
| CN107129104A (en) * | 2017-05-14 | 2017-09-05 | 安徽泛亚环保科技有限公司 | A kind of processing method of the waste liquid containing heavy metal |
| CN109502824A (en) * | 2018-12-26 | 2019-03-22 | 北京大井易通科技发展有限公司 | A kind of anolyte recovery and processing system and method |
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| JP2006274397A (en) * | 2005-03-30 | 2006-10-12 | Nikko Kinzoku Kk | Purification method of zinc concentrate decoction |
| CN100488899C (en) * | 2007-02-01 | 2009-05-20 | 天津大学 | Diaphragm separation electrolyzing integrated treatment method for waste water containing heavy metal copper |
| CN101805083A (en) * | 2010-03-26 | 2010-08-18 | 南通市申海特种镀饰有限责任公司 | Process method for recycling precious metal from electroplating wastewater |
| KR20130040627A (en) * | 2011-10-14 | 2013-04-24 | 삼성전자주식회사 | Apparatus for producing reducing water by electrolysis |
| CN103510107B (en) * | 2013-09-24 | 2015-12-23 | 湖南凯天重金属污染治理工程有限公司 | A kind of method reclaiming copper from brown oxide waste liquid |
| CN105400959B (en) * | 2015-12-30 | 2019-03-19 | 清大国华环境集团股份有限公司 | Heavy metal and the method and apparatus of resource utilization in a kind of waste acid recovery |
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Effective date of registration: 20190828 Address after: 410100 Xingsha Avenue, Changsha Economic and Technological Development Zone, Changsha City, Hunan Province Co-patentee after: Hunan spaceflight kaytian water Co., Ltd. Patentee after: Aerospace Kay environmental Polytron Technologies Inc Address before: 410100 Changsha economic and Technological Development Zone, Hunan, Xingsha Road, No. 15, No. Patentee before: Aerospace Kay environmental Polytron Technologies Inc |