CN104341080A - Method for removing and recovering Zn in sludge - Google Patents
Method for removing and recovering Zn in sludge Download PDFInfo
- Publication number
- CN104341080A CN104341080A CN201310317634.5A CN201310317634A CN104341080A CN 104341080 A CN104341080 A CN 104341080A CN 201310317634 A CN201310317634 A CN 201310317634A CN 104341080 A CN104341080 A CN 104341080A
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- Prior art keywords
- mud
- zinc
- solution
- acetic acid
- sample
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of sewage sludge treatment, and specifically relates to a method for effectively removing and recovering Zn in sludge. According to the method, H2O2 and an acetic acid solution are adopted to carry out constant temperature oscillation leaching on a sample to be treated at a room temperature, such that the acetic acid and the zinc in the sample to be treated are complexed, and then the zinc is leached out and is removed from the sample to be treated so as to be recovered. With the method of the present invention, the zinc recovery rate is 98%; the heavy metal Zn content in the treated sludge achieves the national city sludge agricultural standard, the recovered zinc is the precious metal resource, and finally the waste liquid achieves the national sewage sludge discharge secondary standard; and the method meets the circular economy and green environmental protection requirements, the resource recycling of the waste is achieved, and the good development utilization space is provided.
Description
Technical field
The invention belongs to Sewage Sludge Treatment Techniques field, relate to the Zn in a kind of effective removal mud specifically and the method reclaimed.
Background technology
Along with social economy is fast-developing and the improving constantly of the level of urbanization, the quantity discharged of industrial sewage and sanitary sewage increases day by day, and sludge of sewage treatment plant output sharply increases.According to relevant statistics, the dewatered sludge total amount that the current U.S. accumulates is more than 1,000 ten thousand tons/year, and European Countries adds up 6,600,000 tons/year, and Japan is about 2,400,000 tons/year.The Eleventh Five-Year Plan period, the sewage disposal industry of China is developed rapidly, and sewage treatment capacity and processing rate increase rapidly, also brings increasing sharply of sludge yield simultaneously.By the end of the end of the year in 2010, national urban wastewater treatment amount will reach 343 billion cubic meters, and dewatered sludge year, generation was close to 2,200 ten thousand tons, put into operation successively along with in the 2000 Duo Zuo sewage works built, and year mud total generation in the whole nation will break through 3,000 ten thousand tons very soon.Display is analyzed according to the Chinese network of rivers " 2011 Chinese specific resistance to filtration Market Report ", the mud that wastewater treatment in China factory produces, 80% is had not dealt carefully with, mud is arbitrarily stacked caused pollution and is highlighted with pollution problem again, especially in China's part one line big city, even there is the serious situation in " mud besieged city ", cause the extensive concern of various circles of society.
Municipal sludge (Sewage Sludge), according to " urban wastewater treatment firm specific resistance to filtration and pollution prevention technique policy (trying) " relevant regulations that 2009 promulgate, refer to the semi-solid state or solid matter that produce in sewage treatment process, its be produce in city domestic sewage and During Industrial Wastewater Treatment Process solid waste [
3].The process of municipal sludge is a global difficult problem, the mishandling secondary pollution easily causing the wasting of resources and environment.From technical standpoint analysis, mud is a kind of complicated component, unstable Biological resources; But compare with general solid waste, municipal sludge has that calorific value is little, perishable, organic content is high, the features such as N, P, K and other micronutrient levelss enrich, if through reasonably disposing and processing, usually can be recycled, be administered on farmland, both can improve soil quality, can fertility be improved again, realize the various value such as resource, environment and society.As far back as nineteen ninety-five, World Water environmental organization (Water Environment Federation, WEF) sewage sludge is renamed as biosolids (Biosolid), this change shows the understanding trend resource to mud, and mud is considered to a kind of secondary resource being rich in utilizability.Therefore, when disposing sludge, resource utilization is one of cardinal principle first considered.
Recycling sludge utilizes namely by various physics, chemistry and method and the technique such as biological, to improve moiety and the some properties of mud, make valuable component in mud, or directly or restructuring or be converted into other form of energy and be recovered utilization, eliminate secondary pollution simultaneously.Its mode disposed mainly comprises at present: landfill, throwing sea and Land_use change.
In developed countries such as America and Europes, the ratio that the mud of Land_use change accounts for mud production is more and more high.Add up according to German statistics bureau, current German sewage work produces sludge quantity and is about 2,200,000 tons (dry-matteies), and wherein nearly 60% for agricultural and land reclamation, and the agricultural use rate of Spruce from Northern Germany mud is especially up to 90%.Compared with other two kinds of processing modes, no matter be from technology or economically, sludge landfill characteristics all has sizable advantage
[9].
But, containing heavy metal element in mud, limit the utilization of mud on soil.Gasco etc. point out after Hispanic municipal sludge composition and agricultural analytical research, should pay close attention to the impact of heavy metal; Singh etc. point out, use the corn field of different ratios mud, cause the increase of heavy metal in soil and corn; The accumulation situation of heavy metal in the wheat of planting in soil after Pakistani Jamali etc. analyze and utilize improving sludge, points out that in heavy metal content in wheat grain and mud, exchangeable species heavy metal content is pole clear-cut correlation; Li Qiong etc. are pointed out by field test, and in high dosage applying sludge soil, the heavy metal content such as Zn obviously increases; Smith research finds that the content of heavy metal in plant materials is mostly relevant to the content using available heavy metals in compost soil, and Comparatively speaking, it is the highest that the content of Zn in soil used by compost, and activity is comparatively strong, is the most easily absorbed by plants.
Therefore, need before mud soil to process accordingly, to reduce its ecological risk.Zinc etc. are valuable metals resources simultaneously, if recycling, will turn waste into wealth.Therefore, Heavy Metals in Sludge is removed with reclaiming is a kind of technological method meeting recycling economy and environment protection requirement.
Summary of the invention
The object of the invention is that providing a kind of removes the Zn in mud and the method reclaimed.
For achieving the above object, the technical solution used in the present invention is:
Remove the Zn in mud and the method reclaimed, adopt H
2o
2treat the leaching of processing sample constant temperature oscillation with acetic acid solution in room temperature, make zinc complexing in acetic acid and pending sample, and then it can remove by Leaching Zinc from pending sample, and be reclaimed.
By above-mentioned through H
2o
2carry out solid-liquid separation with sample pending after acetic acid drip washing, collection liquid portion and mud leach liquor add ferric iron and ferrous solution under room temperature, and are 8-9 at pH, Fe in mud leach liquor
3+/ M
2+=10-20(is M wherein
2+for the general designation that the divalent ion of mud leach liquor is total) under condition, to make in leacheate ferrite co-precipitation and then zinc is able to recycling.
Described pending sample mud, H
2o
2be 1:(1.5-2.5 with the solid-liquid/liquid mass volume ratio of acetic acid solution): (35-65), best proportion is 1:2:50,25-30 DEG C, pH is 3-4, and with constant temperature oscillation leaching 4-6h under 150-250rpm rotating speed.
Described hydrogen peroxide add-on is the 1.8-2.5%(volume ratio of acetic acid solution add-on).
The volumetric molar concentration of acetic acid is 2-3mol/L; .
Described mud leach liquor adds ferric iron and ferrous solution at 25-35 DEG C, and add lime milk solution adjust pH be 8-9, make Fe in leacheate
3+/ M
2+=10-20, and then constant temperature oscillation reacts 1-2h under 150-250rpm rotating speed, thus zinc in ferrite co-precipitation in leacheate is able to recycling.
Described ferric iron strength of solution is 0.05-0.15mol/L, and ferrous solution concentration is 0.04-0.06mol/L, pH is 8-9; Described ferric iron solution is FeCl
3, ferrous solution is FeSO
4.
Adopt the inventive method zinc leaching clearance more than 99.5%, the rate of recovery of zinc reaches 98%.In treated mud, Zn reaches national municipal sludge agricultural standards, and the waste liquid reclaimed after zinc reaches national sewage sludge discharge secondary standard.
Know-why of the present invention: the present invention utilize acetic acid can with zinc generation complex reaction, Leaching Zinc from solid sludges; H
2o
2can produce the free radicals such as activity hydroxy in reaction system, react with iron ion generation fenton-type reagent in the iron oxide in mud or solution, zinc is removed in coupling; Fe is added in leach liquor
2+and Fe
3+generate precipitation of hydroxide, then throw out kinetics, gradate as ferrite, in leach liquor, ion to be removed occupies part Fe
2+position, mix equably in ferrite lattice, define special ferrite.
The advantage that the present invention has:
1. the present invention utilizes the heavy metal zinc in the acetic acid solution removal sludge of sewage treatment plant being added with hydrogen peroxide, then adopts and improves ferrite coprecipitation method, make neutralizing agent, from the acetic acid-H of mud with lime milk solution
2o
2zinc is reclaimed in leach liquor.Utilize the inventive method heavy metal Zn clearance and the rate of recovery high,
Simple to operate, treated mud reaches national municipal sludge agricultural standards, and the zinc of recovery is valuable metals resources, and last waste liquid reaches national sewage sludge discharge secondary standard.This method meets recycling economy and environment protection requirement, and the resource achieving waste follows ring profit, with there being good development utilization space again.
2. the present invention utilize easily degraded, lower-cost acetic acid adds hydrogen peroxide, effectively removes Zn in mud.Utilize organic monoacid to remove Heavy Metals in Sludge under the condition not destroying sludge structure, efficient leaching removal heavy metal, has good development prospect.
3. the present invention adopts the zinc improved in ferrite coprecipitation method recovery mud leach liquor, and reaction can be carried out at normal temperatures, and the reaction times is short, and consumption of energy obviously declines; Need not air be passed into, simplify technical process; Make neutralizing agent with lime milk solution, solve ferrite coprecipitation method NaOH and make neutralizing agent cost high problem, economic benefit and obvious environment benefit.
4. adopt removing method zinc leaching clearance more than 95% of the present invention, the rate of recovery of zinc reaches 98%.Treated mud reaches national municipal sludge agricultural standards, and the waste liquid reclaimed after zinc reaches national sewage sludge discharge secondary standard.
5. method provided by the invention, simple to operate, economical and practical, safe and reliable.Reaction is at room temperature carried out, and without the need to foreign aid's heating, adds mineral acid compare with the chemical extraction technology of other solvents with other tradition, cost-saving, and operation can not produce electrodeless acid and produce industrial accident.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention removal provided and the process flow sheet reclaiming Zn in mud.
Embodiment
The quantitative analysis of the mud adopted in following embodiment, mud gathers, process and zinc total amount, chemical form measure: handled mud is sewage treatment plant residual active sludge, mud from place after sewage work gathers in the cool natural air drying, grind, sieve, be placed in electric oven, dry 3 hours at 105 DEG C of temperature, to constant weight, then move in moisture eliminator stand-by.Adopt HNO
3-HClO
4-HF clears up, and atomic absorption spectrophotometry measures; Analyze the metamorphosis of Zn with Tessier continuous extraction method, use ICP-MS determination data.In mud, the total amount of zinc is 2171mg/Kg, seriously exceedes country " in agricultural sludge pollutant catabolic gene standard " (GB4284-88); The form of zinc consists of: water-soluble exchangeable species 26.0mg/Kg, accounts for 1.20% of total amount; Carbonate combined 20.8mg/Kg, accounts for 0.96% of total amount; Iron and manganese oxides combined 77.9mg/Kg, accounts for 3.59% of total amount; Sulfide and combination state 1333mg/Kg, account for 61.41% of total amount, residual form 712.9mg/Kg, account for 32.84% of total amount.
Processing mode as shown in Figure 1,
Embodiment 1
1. the mud sample accurately taking 0.5g joins in 100mL Erlenmeyer flask, add the hydrogen peroxide of acetic acid solution 24.5ml and 0.5ml of 2.0mol/L again, mix, and adopt concentration to be that NaOH or the HCl solution tune pH of 0.1mol/L is to 4, it is 25 DEG C in temperature, constant temperature oscillation leaching 4h under 200pm rotating speed, centrifugal solid-liquid is separated.
2. get mud leach liquor 10mL and be placed in 100mL Erlenmeyer flask, add the certain density FeSO of 2mL
4solution and the certain density FeCl of 2ml
3solution, makes FeCl
3and FeSO
4in reaction system, starting point concentration is respectively 0.05mol/L and 0.05mol/L; Fe
3+/ M
2+=10, adjust pH of mixed to be constant temperature oscillation reaction 1h under 9,250rpm rotating speed with the lime milk solution of 0.8mol/L, centrifugal solid-liquid is separated.
3, in mud, the clearance of zinc is 98.8%, and the rate of recovery of drenching zinc in fluid is 97.9%.(zinc clearance is (x) by formula x=(M
0c
0-MC)/M
0c
0calculate, M in formula
0and C
0be respectively the quality and zinc concentration that add mud; V and C is respectively quality and the zinc concentration of the rear mud of real reaction.Zinc recovery (y) is by formula y=(V
0c
0-VC)/V
0c
0calculate, V in formula
0and C
0be respectively the volume and zinc concentration that add leach liquor; V and C is respectively volume and the zinc concentration of the rear leach liquor of real reaction.)
Embodiment 2
1. the mud sample accurately taking 0.5g joins in 100mL Erlenmeyer flask, add the hydrogen peroxide of acetic acid solution 24.5ml and 0.5ml of 2.0mol/L again, mix, and adopt concentration to be that NaOH or the HCl solution tune pH of 0.1mol/L is to 3, it is 25 DEG C in temperature, constant temperature oscillation leaching 4h under 200pm rotating speed, centrifugal solid-liquid is separated.
2. get mud leach liquor 10mL and be placed in 100mL Erlenmeyer flask, add the certain density FeSO of 2mL
4solution and the certain density FeCl of 2ml
3solution, makes FeCl
3and FeSO
4in reaction system, starting point concentration is respectively 0.15mol/L and 0.10mol/L; Fe
3+/ M
2+=20, adjust pH of mixed to be constant temperature oscillation reaction 1h under 9,200rpm rotating speed with the lime milk solution of 0.8mol/L, centrifugal solid-liquid is separated.
3, in mud, the clearance of zinc is 99.5%, and the rate of recovery of drenching zinc in fluid is 98%.(zinc clearance is (x) by formula x=(M
0c
0-MC)/M
0c
0calculate, M in formula
0and C
0be respectively the quality and zinc concentration that add mud; V and C is respectively quality and the zinc concentration of the rear mud of real reaction.Zinc recovery (y) is by formula y=(V
0c
0-VC)/V
0c
0calculate, V in formula
0and C
0be respectively the volume and zinc concentration that add leach liquor; V and C is respectively volume and the zinc concentration of the rear leach liquor of real reaction.)
Embodiment 3
1. the mud sample accurately taking 0.5g joins in 100mL Erlenmeyer flask, add the hydrogen peroxide of acetic acid solution 24.5ml and 0.5ml of 2.0mol/L again, mix, and adopt concentration to be that NaOH or the HCl solution tune pH of 0.1mol/L is to 3, it is 25 DEG C in temperature, constant temperature oscillation leaching 4h under 150pm rotating speed, centrifugal solid-liquid is separated.
2. get mud leach liquor 10mL and be placed in 100mL Erlenmeyer flask, add the certain density FeSO of 2mL
4solution and the certain density FeCl of 2ml
3solution, makes FeCl
3and FeSO
4in reaction system, starting point concentration is respectively 0.15mol/L and 0.05mol/L; Fe
3+/ M
2+=20, adjust pH of mixed to be constant temperature oscillation reaction 1h under 9,200rpm rotating speed with the lime milk solution of 0.8mol/L, centrifugal solid-liquid is separated.
3, in mud, the clearance of zinc is 99.3%, and the rate of recovery of drenching zinc in fluid is 97.6%.(zinc clearance is (x) by formula x=(M
0c
0-MC)/M
0c
0calculate, M in formula
0and C
0be respectively the quality and zinc concentration that add mud; V and C is respectively quality and the zinc concentration of the rear mud of real reaction.Zinc recovery (y) is by formula y=(V
0c
0-VC)/V
0c
0calculate, V in formula
0and C
0be respectively the volume and zinc concentration that add leach liquor; V and C is respectively volume and the zinc concentration of the rear leach liquor of real reaction.)
Embodiment 4
1. the mud sample accurately taking 0.5g joins in 100mL Erlenmeyer flask, add the hydrogen peroxide of acetic acid solution 24.5ml and 0.5ml of 2.0mol/L again, mix, and adopt concentration to be that NaOH or the HCl solution tune pH of 0.1mol/L is to 3, it is 30 DEG C in temperature, constant temperature oscillation leaching 4h under 200pm rotating speed, centrifugal solid-liquid is separated.
2. get mud leach liquor 10mL and be placed in 100mL Erlenmeyer flask, add the certain density FeSO of 2mL
4solution and the certain density FeCl of 2ml
3solution, makes FeCl
3and FeSO
4in reaction system, starting point concentration is respectively 0.15mol/L and 0.10mol/L; Fe
3+/ M
2+=20, adjust pH of mixed to be constant temperature oscillation reaction 1h under 9,200rpm rotating speed with the lime milk solution of 0.8mol/L, centrifugal solid-liquid is separated.
3, in mud, the clearance of zinc is 99.7%, and the rate of recovery of drenching zinc in fluid is 98.2%.(zinc clearance is (x) by formula x=(M
0c
0-MC)/M
0c
0calculate, M in formula
0and C
0be respectively the quality and zinc concentration that add mud; V and C is respectively quality and the zinc concentration of the rear mud of real reaction.Zinc recovery (y) is by formula y=(V
0c
0-VC)/V
0c
0calculate, V in formula
0and C
0be respectively the volume and zinc concentration that add leach liquor; V and C is respectively volume and the zinc concentration of the rear leach liquor of real reaction.)
Claims (7)
1. remove the Zn in mud and the method reclaimed, it is characterized in that: adopt H
2o
2treat the leaching of processing sample constant temperature oscillation with acetic acid solution in room temperature, make zinc complexing in acetic acid and pending sample, and then it can remove by Leaching Zinc from pending sample, and be reclaimed.
2., by the Zn in removal mud according to claim 1 and the method reclaimed, it is characterized in that: by above-mentioned through H
2o
2carry out solid-liquid separation with sample pending after acetic acid drip washing, collection liquid portion and mud leach liquor add ferric iron and ferrous solution under room temperature, and are 8-9 at pH, Fe in mud leach liquor
3+/ M
2+under=10-20 condition, to make in leacheate ferrite co-precipitation and then zinc is able to recycling.
3., by the Zn in removal mud according to claim 1 and the method reclaimed, it is characterized in that: described pending sample mud, H
2o
2be 1:(1.5-2.5 with the solid-liquid/liquid mass volume ratio of acetic acid solution): (35-65), 25-30 DEG C, pH is 3-4, and with constant temperature oscillation leaching 4-6h under 150-250rpm rotating speed.
4. by the Zn in removal mud according to claim 3 and the method reclaimed, it is characterized in that: described hydrogen peroxide add-on is the 1.8-2.5%(volume ratio of acetic acid solution add-on).
5., by the Zn in the removal mud described in claim 1,3 or 4 and the method reclaimed, it is characterized in that: the volumetric molar concentration of acetic acid is 2-3mol/L.
6. by the Zn in removal mud according to claim 2 and the method reclaimed, it is characterized in that: described mud leach liquor adds ferric iron and ferrous solution at 25-35 DEG C, and add lime milk solution and adjust pH to be 8-9, make Fe in leacheate
3+/ M
2+=10-20, and then constant temperature oscillation reacts 1-2h under 150-250rpm rotating speed, thus zinc in ferrite co-precipitation in leacheate is able to recycling.
7., by the Zn in the removal mud described in claim 2 or 6 and the method reclaimed, it is characterized in that: described ferric iron strength of solution is 0.05-0.15mol/L, ferrous solution concentration is 0.04-0.06mol/L, pH is 8-9; Described ferric iron solution is FeCl
3, ferrous solution is FeSO
4.
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CN201310317634.5A CN104341080A (en) | 2013-07-24 | 2013-07-24 | Method for removing and recovering Zn in sludge |
Applications Claiming Priority (1)
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---|---|---|---|
CN201310317634.5A CN104341080A (en) | 2013-07-24 | 2013-07-24 | Method for removing and recovering Zn in sludge |
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Family
ID=52497615
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109279751A (en) * | 2018-11-13 | 2019-01-29 | 天津城建大学 | A kind of preprocess method of excess sludge and application |
CN114920436A (en) * | 2022-06-28 | 2022-08-19 | 南京贝克特环保科技有限公司 | Method for chemically strengthening bioleaching treatment of anaerobic digestion sludge |
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2013
- 2013-07-24 CN CN201310317634.5A patent/CN104341080A/en active Pending
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US20050056598A1 (en) * | 2003-06-06 | 2005-03-17 | Chowdhury Ajit K. | Method for treating recalcitrant organic compounds |
CN102964015A (en) * | 2012-12-11 | 2013-03-13 | 湖南大学 | Method for removing heavy metals Zn and Cu in dredged river sediment |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109279751A (en) * | 2018-11-13 | 2019-01-29 | 天津城建大学 | A kind of preprocess method of excess sludge and application |
CN114920436A (en) * | 2022-06-28 | 2022-08-19 | 南京贝克特环保科技有限公司 | Method for chemically strengthening bioleaching treatment of anaerobic digestion sludge |
CN114920436B (en) * | 2022-06-28 | 2024-04-30 | 南京贝克特环保科技有限公司 | Method for performing bioleaching treatment on chemically-reinforced anaerobic digested sludge |
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Application publication date: 20150211 |