CN106007423B - The method that electric plating sludge resource utilizes - Google Patents
The method that electric plating sludge resource utilizes Download PDFInfo
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- CN106007423B CN106007423B CN201610275847.XA CN201610275847A CN106007423B CN 106007423 B CN106007423 B CN 106007423B CN 201610275847 A CN201610275847 A CN 201610275847A CN 106007423 B CN106007423 B CN 106007423B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
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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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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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
- C02F2303/00—Specific treatment goals
- C02F2303/06—Sludge reduction, e.g. by lysis
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- 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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Treatment Of Sludge (AREA)
Abstract
The method that electric plating sludge resource utilizes, comprises the following steps：（1）Pretreatment：The heavy metal element in electroplating sludge is isolated with wet processing, in lime or lime stone and electroplating sludge, to obtain calcium sulphate dihydrate electroplating sludge waste residue as main component；（2）It is prepared by raw material：Substitute whole gypsum in raw meal proportioning, whole ferriferous raw materials with electroplating sludge waste residue or substitute part gypsum, part ferriferous raw material, production calcium sulphoaluminate or sulphur ferrous acid calcium clinker raw material are produced with lime stone, vanadine dispensing, grinding；（3）1250~1400 DEG C of 0.5~1h of roasting.The present invention is using electroplating sludge as containing polymetallic raw material, recycling recycling is implemented to electroplating sludge, produces two major class materials, i.e., corresponding metal and/or metal salt material and gypsum-based construction material, beneficial to the pollution problem for solving electroplating industry, develop beneficial to Implementing Circular Economy.
Description
Technical field
The present invention relates to environmental protection and waste utilization field more particularly to a kind of electric plating sludge resource Application ways.
Background technology
Electroplating industry is the current whole world three important basic processing industry of one of pollution industry and China greatly, and electric
The electroplating sludge that plating process generates, which is enriched nearly all element in electroplating wastewater, includes harmful heavy metal, in electroplating sludge often
Rule chemical composition mainly has:CaO、SO3 、Al2O3 、Fe2O3 、CuO 、NiO、ZnO、CdO、CrO、SiO2 、Na2O、MgO、
Co2O4 、SrO、Nb2O5 、ZrO2, PbO, HgO etc. and some anion, the heavy metals such as copper therein, nickel, chromium are mainly hydrogen-oxygen
Compound sediment.Mainly contain heavy metal compounds and its solubility salts such as chromium, iron, nickel, copper, zinc in most of electroplating sludges,
Have the characteristics that moisture content is high, heavy metal components are easy to migrate, be meta-alkalescence compounding substances, general pH value is 6.5~10, and moisture reaches
70~90%, dry basis ash content is burned up to 62~80%%（It decomposes）Volatile matter（It burns and loses）For CO2 、H2O and SO2Deng.Because containing a large amount of weights
Metal is listed in National Hazard waste.Currently, electroplating enterprise scale in China's is relatively small and product is more, the electroplating sludge base of generation
It is the mixing sludge of the ingredient containing various heavy in sheet, and the electroplating sludge generated every year exceedes 10,000,000 t.Most of plating at present
Sludge is simply simply stored up or landfill disposal, and environment is caused seriously to pollute, while also results in the waste of resource how
Recycling harmless treatment electroplating sludge is always the hot spot of association area.At present, both at home and abroad to the treatment technology of electroplating sludge
Path, method include：
1）Wet processing（Hydrometallurgy）Recycle valuable metal in electroplated mud（Waste landfills）Technology.
Wet processing（Hydrometallurgy）Valuable metal can be divided into leaching in recycling sludge and metal separates two big processes, leaching
Go out mainly to have bioleaching method, the acid-hatching of young eggs, alkaline leaching;Metal separation mainly has reduced separation method（It is reduced with iron plate or ferromanganese）、
Strike, chemical precipitation method, metal extraction method.
Its acid-hatching of young eggs is to add in sulfuric acid or the inorganic acids such as hydrochloric acid or nitric acid or inorganic acid and oxidant or organic acid to make sludge
Middle metal ion enters solution and becomes free state to separate and recover, and acid-hatching of young eggs research and application are more mature, dirty available for recycling
The various metals such as copper, nickel, chromium, titanium, zinc, lead, cadmium, manganese, iron, magnesium in mud.Acid-hatching of young eggs leaching efficiency is high, to gold such as copper, nickel, chromium
Category has very high leaching rate, and waste residue amount can generally reduce about 50% after acidleach.
Mainly using ammonia leaching process, ammonia leaching process is generally leached alkaline leaching using ammonia spirit or ammonium hydroxide-ammonia salt solution
Agent, ammonia have higher selectivity to Cu, Ni etc., stable complex compound can be generated with it, then by floatation, with aphthenic acids
Make extractant recycling cupro-nickel, and other metals or do not generate complex compound or only generate unstable complex compound, chromium, iron, aluminium enter
Ammonia leaching residue, waste residue amount can generally reduce 50~60% after ammonia leaching.
Bioleaching method is acted on using the production such as chemosynthetic autotroph thiobacillus ferrooxidans acid, enzymeization, by indissoluble in electroplating sludge
Heavy metal becomes free state from solid phase dissolution and enters liquid phase, then is recycled.Waste residue amount can generally be reduced about after bioleaching
50%。
Objectively, now all wet processings are only confined in the separation to valuable metal, still remain down the dirt of about half
Mud waste residue amount, still the waste residue containing heavy metal is now substantially directly thrown aside or is filled for these.
2）Thermochemical method（Pyrometallurgy）Recovery technology
Thermochemical method（Pyrometallurgy）Recovery technology mainly has smelting process, heat chemistry method for pretreating（Roast leaching method）, burn
Burn absorption method.
The heat chemistry recovery technology of electroplating sludge is conceived to recycling valuable metal therein especially noble metal.
Its smelting process is mainly for the purpose of recycling copper, nickel.Smelting process is using coal, coke as fuel and reducing substances, iron ore
Stone, Copper Ores, lime stone etc. are auxiliary material.During sludge of the melting based on copper, 1300 DEG C of furnace temperature or more, the copper melted out is known as ice
Copper;During sludge of the melting based on nickel, for furnace temperature at 1455 DEG C or more, the nickel melted out is known as thick nickel.
It roasts leaching method and extracts product of roasting using the impurity in high-temperature roasting pretreating sludge, then with media such as acid, water
In valuable metal.Such as F á bio use-two step of sulfidation roasting when handling the electroplating sludge containing Au, Ag, Cu and Zn
Lixiviation process separate precious metal.Sludge and vulcanizing agent quality are mixed in 1.0: 0.44 ratio, and 90min, calcining are roasted at 550 DEG C
Ag, Cu and Zn are obtained after going out 15min with water logging, leached mud is leached to obtain Au, waste landfills again with sodium thiosulfate.Also it is useful
Pyrite waste material is made to roast after acidifying raw material is mixed with electroplating sludge, and then product of roasting is carried out with deionized water at room temperature
Leaching separation recycling zinc, nickel, copper, waste residue are thrown aside.
It is that first electroplating sludge is pre-processed through burning to burn absorption method, reduces volume and quality, improves heavy metal in slag
Mass fraction.Reduction furnace process is nickeliferous, electroplating sludge of copper using burning by such as Xiang Changyou, under high temperature and reducing condition,
Nickel, Cu oxide are reduced to nickel, copper alloy, chromium, iron reduction enter in clinker, then use alkaline medium oxygen to the chromium in clinker
Change roast method, recycle sodium dichromate, waste residue is thrown aside.
Thermochemical method high energy consumption, investment is big, and processing procedure easily causes secondary pollution, and still has a large amount of waste residues that need to throw aside.
3）Electroplating sludge stabilizing surface treatment
So far, the technological treatment of electroplating sludge still neither one economy, domestic and international common method are to cure landfill
Method.
Before landfill stabilization is carried out to electroplating sludge, it is necessary to first it be carried out to cure stable processing.Cured method has
Cementitious matter cures and thermalization chemosetting.
Cementitious matter, which cures the stable common curing agent of processing, cement, lime, flyash, multiplicity reactivation industrial residue（Soil
Earth curing agent）, pitch, glass, waterglass, phosphoric acid and salt etc., wherein, cement is one of most commonly seen curing agent, there is research
The cement for proving to add in 4~5 times of amounts in electroplating sludge can obtain preferable intensity and relatively optimal stablizing effect.Cement is consolidated
Though change method is widely used, it there is also take up a large area, heavy metal long-time stability cannot be guaranteed etc. and lack in firming body
Point.There is researcher to add in xanthates, chelating agent etc. in ordinary cement to handle heavy metal sewage sludge, to reduce heavy metal therefore
Leaching rate, but the organic matters such as xanthates, chelating agent and pitch or even cured phosphate etc. be all difficult to be subjected to microorganism and
The biochemical action of root system of plant.
Due to additional or mix cementitious matter to cure stable method objectively very unsatisfactory, in recent years, in electroplating sludge
It has developed before final disposal and it is pre-processed with thermochemical treatment technology, thermalization chemosetting stabilization technique is in electroplating sludge
Innoxious aspect show certain advantage.Such as Cheng is by the mixture of electroplating sludge and clay respectively at 900 DEG C
After thermal curing 4h in 1100 DEG C of electric furnace, the valence state of wherein chromium is analyzed, is found through 900 DEG C of thermal curings processing
In mixture, chromium (VI) has overwhelming superiority, and in the mixture through 1100 DEG C of thermal curing processing, chromium is then mainly with chromium (III)
In the presence of.Electroplating sludge toxicity can be reduced with sufficiently high temperature.Ahmet etc. adds in Boratex and sodium metasilicate in electroplating sludge
It is uniformly mixed, first after precalcining, is divided into the sintering curing not at 850,900 and 950 DEG C, i.e., simultaneously in 900 DEG C of revolving burner
The molar ratio that two kinds of additives adjust acidic oxide and basic anhydride is added in, toxicity is leached the results show that at 950 DEG C
Best solidification effect is obtained during high oxide molar ratio.
Today, heat chemistry curing process electroplating sludge technology have become an important research side of electroplating sludge disposal field
To.But first the research of this technology at present still needs go deep into, and second energy consumption is excessively high, it is larger to invest and there are obvious secondary
Secondly pollution, wastes available resources, does not meet recycling economy development theory.
4）Materialized technology
The materialized technology of electroplating sludge refers to produce construction material or other materials using electroplating sludge for raw material or auxiliary material
The method of material.Mainly include electroplating sludge for producing portland cement and firing ceramics or glaze and brickmaking.
Ract is with the experiment of electroplating sludge part substitution cement raw material production portland cement, it is believed that adds in chromium in the feed
Mass fraction be 2% electroplating sludge in the case of, cement sintering process can be also normally carried out, and chromium in sintered product
Residual rate is up to 99.9%.
The experiment such as Magalhaes is mixed with electroplating sludge with clay mixture potting porcelain, with electroplating sludge with seabeach sludge
Baking ceramsite；The experiment such as Myrine V. fires red ceramic with oily pollution diatomite and electroplating sludge and cullet mixture；
The experiment such as Yuanyuan Tang is with water treatment plant's sludge of copper-contained electroplating sludge and rich aluminium firing ceramics material at high temperature；Also
There is researcher with high leaded electroplating sludge trial-production glaze；Nie Xinmiao etc. then tests utilization with a small amount of electroplating sludge and clay mixing system
Brick.
Secondly, the materialized technical research of recycling of electroplating sludge, which also has, magnetizes iron（Ferrite method）Technology, Composting skill
Art, catalysis material technology etc..
Magnetization iron technology therein is that iron hydroxide in electroplating sludge etc. is become compound iron oxygen using appropriate technology
Body, then the iron ion in electroplating sludge and other metal ions will be bound on ferroso-ferric oxide lattice lattice point, so as to
Achieve the purpose that eliminate heavy metal pollution, ferrite cured product again can further commercialization, such as the dry method of Jia Jin equality researchs
With wet method Ferrite method technique.The technology is still in experiment, and still have a large amount of sewage sludge waste slags that must handle.
Composting technology：It is to be studied with chromium containing electroplating Sludge Composting, but China's electroplating sludge toxicity is larger, ingredient is multiple
It is miscellaneous, still there are certain difficulty and risk using the electroplating sludge after compost treatment is agricultural；In addition composting cycle is long, program is complicated,
Also limit the research and application of electroplating sludge Composting treatment.
Catalysis material technology：I.e. by the use of the metal in electroplating sludge as catalyst material.Jia Zhang etc. are carried out
Using electroplating sludge as catalysis and the experiment of reaction material removal greenhouse gases sulfur hexafluoride (SF6), electroplated at 600 DEG C dirty
Mud is 1.10mmol/g to the removal capacity of SF6, while generates SO2、SiF4And a small amount of HF.
Although it is above-mentioned for produce portland cement, ceramics, brick materialized technology can limitedly using small part it is suitable
The sludge of ingredient is as raw material, but it is all the SO that must be limited in raw material to produce portland cement, ceramics, the ingredient requirement of brick3
Content, i.e., containing SO3High sewage sludge waste slag（Calcium sulphate content is high）Because seriously affecting production status and product quality objectively not
It preferably or cannot use, SO in exhaust gas can also be significantly increased2Concentration.
In conclusion although the hot spot that the recycling of electroplating sludge is always studied both at home and abroad, many scientific research institutions
And enterprise has carried out substantial amounts of research to the recycling of valuable metal in electroplated mud and harmless resource utilization processing, but it is more
In laboratory stage or exemplary, though have the wet processing of relative maturity（Hydrometallurgy）And heat chemistry（Pyrometallurgy）Have
Valency metal recovery technology, but comprehensively in the technology of recycling valuable metal in electroplated mud there are still of high cost, it is complicated for operation,
The problems such as recycled product purity is not high, and treating capacity is small, of high cost, the ultimate process problem or secondary all there are sewage sludge waste slag
Pollution problem, causes the electroplating industry pollution problem of one of global three major source of pollution cannot solve always, for this purpose, there is an urgent need to
One kind can using electroplating sludge as raw material, not only using existing maturation method, can economically extract most of valuable metal, but also
Resourcebility utilizes the recycling new method of all components of electroplating sludge.
The content of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of electric plating sludge resource profit
Method using electroplating sludge as a kind of available raw material, provides a kind of safety, simple, economic and can be fully utilize
The method that electroplating sludge ingredient produces metal/metal salt material with practical value and gypsum base material.
The present invention, which solves the above problems, to be adopted the technical scheme that, a kind of electric plating sludge resource Application way will be electroplated
Sludge is converted into two big material component of metal/metal salt material and gypsum base material, and calcium sulphoaluminate clinker is produced with electroplating sludge
Or sulphur ferrous acid calcium clinker, it mainly includes the following steps that：
（1）Pretreatment（Separating beavy metal）：With wet method（It is metallurgical）Technique isolates the heavy metal element in electroplating sludge, with
In lime or lime stone and electroplating sludge, calcium sulphate dihydrate is obtained as main component（Butt sulfate dihydrate calcium content>51wt%）Electricity
Plate sewage sludge waste slag；
The wet method（It is metallurgical）Technique is the well known ripe sulfuric acid to leach method separating technology and biological treatment applied
Separating technology, in lime or lime stone and electroplating sludge, the heavy metal element isolated in electroplating sludge pretreatment is by known
Technique corresponding metal salt or metal is made；
（2）It is prepared by raw material：By step（1）The electroplating sludge waste residue using calcium sulphate dihydrate as main mineral constituent of gained is made
For one of primary raw material of production calcium sulphoaluminate clinker or sulphur ferrous acid calcium clinker, i.e., substituted with electroplating sludge waste residue in raw meal proportioning
Whole gypsum and ferriferous raw material or substitute part gypsum and ferriferous raw material（When waste residue amount is inadequate）, pressed with lime stone, vanadine etc.
The proportioning process dispensing of well known production calcium sulphoaluminate clinker or sulphur ferrous acid calcium clinker, grinding produce production calcium sulphoaluminate or sulphur iron
Sour calcium clinker raw material；（The parameters such as chemical composition prepared by raw material are all the prior arts）
（3）It is prepared by clinker：By step（2）The raw material of gained are by the well known life for producing calcium sulphoaluminate or sulphur ferrous acid calcium clinker
Production. art roasts 0.5~1h in 1250~1400 DEG C, produces calcium sulphoaluminate or sulphur ferrous acid calcium clinker.
The present invention is the characteristics of dihydrate gypsum, submember are iron hydroxides for the main component of electroplating sludge waste residue,
And this exactly produces calcium sulphoaluminate or the necessary essential mineral raw material-calcium sulfate of sulphur ferrous acid calcium clinker and ferriferous raw material（Three oxygen
Change two iron）And it is subject to recycling, and by means of calcium sulphoaluminate or the high-temperature thermodynamics condition of sulphur ferrous acid calcium clinker production with material
In sial root ball lattice melt stabilizing heavy metal ion admittedly.
Further, electroplating sludge is converted into metal/metal salt material and stone by a kind of electric plating sludge resource Application way
Two big material component of cream base material, produces manufacture of cement adjustable solidification agent with electroplating sludge, mainly includes the following steps that：
（1）Pretreatment（Separating beavy metal）：With wet method（It is metallurgical）Technique isolates the heavy metal element in electroplating sludge, with
In lime or lime stone and electroplating sludge, calcium sulphate dihydrate is obtained as main component（Butt sulfate dihydrate calcium content>51wt%）Electricity
Plate sewage sludge waste slag；
The wet method（It is metallurgical）Technique is the well known ripe sulfuric acid to leach method separating technology and biological treatment applied
Separating technology, in lime or lime stone and electroplating sludge, the heavy metal element isolated in electroplating sludge pretreatment is by known
Technique corresponding metal salt or metal is made；
（2）It is prepared by adjustable solidification agent：By step（1）Gained using calcium sulphate dihydrate as the electroplating sludge waste residue of main mineral constituent
As the manufacture of cement primary raw material of gypsum adjustable solidification agent, amount of colorant, reinforcing agent/enhanced type grinding aids, curing agent are incorporated,
It is electroplating sludge waste residue 80~97.5 in mass ratio:Colorant 1~10:Reinforcing agent or enhanced type grinding aids 0.5~5:Curing agent 1
~10 ratio is uniformly mixed（The sum of each component is 100）, block or rodlike or bulk goods is shaped to, it is dry to be given birth to get cement
Production gypsum adjustable solidification agent；Or in each component after mixing, first cure drying, then be crushed to the block grain object that grain size is less than 50mm
Material is to get manufacture of cement gypsum adjustable solidification agent.
The colorant is the substance that can cover or mitigate red iron hydroxide/di-iron trioxide tinting strength, tinting power in waste residue, excellent
Select at least one of waste active carbon, graphite, coke fines etc..The reinforcing agent or enhanced type grinding aids enhance for commercially available cement
The compound of agent or enhanced type grinding aids, preferably alcohol ether and hydramine.The curing agent for commercially available curing agent for example cement, lime,
At least one of the plaster of paris, activation waste residue powder, phosphoric acid, hydrophosphate etc..
The present invention needs substantial amounts of dihydrate gypsum as adjustable solidification agent for manufacture of cement（Account for the 5% of cement quality）, and it is electric
The main component of plating sewage sludge waste slag is dihydrate gypsum and iron hydroxide, is eliminated using colorant or mitigation iron hydroxide/tri- aoxidize
Two iron eliminate iron hydroxide/di-iron trioxide to the adverse effect of cement color using cement intensifier or enhanced type grinding aids
To the adverse effect of strength of cement, making it easier to manufacture of cement Wiring technology as block grain material using curing agent stable curing waste residue should
With.
Further, electroplating sludge is converted into metal/metal salt material and stone by a kind of electric plating sludge resource Application way
Two big material component of cream base material, produces high strength gypsum with electroplating sludge, mainly includes the following steps that：
（1）Pretreatment（Separating beavy metal）：With wet method（It is metallurgical）Technique isolates the heavy metal element in electroplating sludge, with
In lime or lime stone and electroplating sludge, calcium sulphate dihydrate is obtained as main component（Butt sulfate dihydrate calcium content>60wt%）Electricity
Plate sewage sludge waste slag；
The wet method（It is metallurgical）Technique is the well known ripe sulfuric acid to leach method separating technology and biological treatment applied
Separating technology, in lime or lime stone and electroplating sludge, the heavy metal element isolated in electroplating sludge pretreatment is by known
Technique corresponding metal salt or metal is made；
（2）Gypsum purifies：By step（1）The electroplating sludge waste residue using calcium sulphate dihydrate as main mineral constituent of gained is beaten
Slurry by well known acid purification, cleans technique, and hydrochloric acid or sulfuric acid is added to separate, purify the colorings such as acid-solubility iron hydroxide/iron oxide
Mineral obtain the dihydrate gypsum of purifying；
Waterproofing agent or iron chloride or sulfuric acid iron product is made by well known technique in the iron chloride or ferrum sulfuricum oxydatum solutum isolated.
（3）It is prepared by high strength gypsum：In step（2）In the purifying dihydrate gypsum of gained, addition is equivalent to purifying dihydrate gypsum
The crystal modifier of quality 0.05-1%, by well known damp and hot（Steam pressure or boiling）Technique is at a temperature of 128 DEG C~190 DEG C, damp and hot place
1~8h is managed, obtains the high strength gypsum of alpha-semi water plaster stone crystal form mineral；By alpha-semi water plaster stone obtained by humid heat treatment in 105 DEG C~180 DEG C
Dry, grinding, obtains high strength gypsum powder/super strong gypsum powder.
Change semi-hydrated gypsum crystallization shape characteristic of the crystal modifier used in well known damp and hot technique alpha-semi water plaster stone
Commercially available organic/inorganic compound such as at least one of succinic acid, tartaric acid, citric acid, melamine, polycarboxylate etc..
The present invention is that dihydrate gypsum, submember are to be easy to the molten hydroxide of acid for the main component of electroplating sludge waste residue
The characteristics of iron, and iron chloride and ferric sulfate are valuable raw materials, and process purification gypsum is cleaned by means of ripe acid purification, utilize public affairs
The ripe damp and hot technique known is converted into the high strength gypsum powder of high added value by gypsum is purified.
Beneficial effects of the present invention：
1）Using electroplating sludge as containing polymetallic raw material, recycling recycling is implemented to electroplating sludge, produces two
Major class material, i.e., corresponding metal and/or metal salt material and gypsum-based construction material are asked beneficial to the pollution for solving electroplating industry
Topic develops beneficial to Implementing Circular Economy.
2）Select ripe wet method（It is metallurgical）Sulfuric acid to leach method and the pretreatment separation plating of bioleaching method in technique is dirty
Heavy metal in mud, and neutralized with lime or lime stone, recycling overwhelming majority valuable metal or heavy metal that first can be inexpensive
Corresponding metal or metal salt material are produced, and is easily obtained the metal of higher degree or metal salt material or raw material；Second may be used
Easily obtain the sewage sludge waste slag using dihydrate gypsum as essential mineral, you can the gypsum base resource utilized.Electroless plating sewage sludge waste slag
Discharge completely eliminates environmental pollution and the hidden danger of waste residue, beneficial to environmental protection.
3）With（It pre-processes separating obtained）Gypsum base sewage sludge waste slag is ultra-fine for raw material production gypsum base new material-gypsum
Filler and/or anhydrite cementitious material and/or water resistant and water resistant drop resistance building gypsum plaster（And product）And/or high strength gypsum powder
（And product）And/or calcium sulphoaluminate, sulphur ferrous acid calcium clinker and/or modified cement adjustable solidification agent, economical production construction is supplied, can both be saved
Substantial amounts of natural resources are saved, and are protected beneficial to air and soil and water resources.
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Electroplating sludge used in experiment is derived from the electroplating sludge of certain industrial park Electronics Factory and electroplating enterprise stockpiling, all experiments
Carry out in laboratory conditions.
Plastics products for building toxicity detection according to《Hazardous waste judging standard leaching characteristic identification》（GB/T5085.3-
2007）、《Solid waste Leaching leaching method sulfonitric method》（HJ/T299-2007)、《Hazardous waste authentication technique is advised
Model》 (HJ/T298-2007) 、《Radioactive material radionuclides limitation》(GB6566-2010).
Land plaster according to《Building gypsum ordinary test condition》（GB/T17669.1-1999）；Setting time measure according to
GB/T17669.4-1999, ruggedness test method is according to GB/T17669.3-1999 and GB/T17671-1999；Expansion rate is examined
Method is according to Ajax/T313-1996.
Embodiment 1
The electroplating sludge that certain Electronics Factory stores up is taken to carry out recycling, butt ingredient is analyzed through ICP-AES（%）For【Cu】
11.47、【Fe】25.31、【Mn】0.59、【S】3.52、【Sn】0.032、【Mg】1.11、【Na】0.32、【K】0.02、【P】0.12、
【Al】0.08、【Ca】9.41、【Ti】0.19、【Cr】0.008、【Co】0.003、【Ni】0.008、【Zn】0.003、【Ag】0.001、
【Ba】0.14、【Pb】0.002。
Electroplating sludge is converted into copper sulphate, sulfuric acid iron material and gypsum base material according to the following steps, with electroplating sludge system
Manufacture of cement adjustable solidification agent：
（1）Pretreatment（Separate valuable heavy metal）：With（It is well known）Hydrometallurgy biological treatment technique isolates plating
Heavy metal element in sludge, in lime and electroplating sludge, to obtain calcium sulphate dihydrate as main component（Butt calcium sulphate dihydrate contains
Measure 80.12wt%）Electroplating sludge waste residue；
Electroplating sludge is using the thiobacillus ferrooxidans tamed（Thiobacillus ferrooxidans, Thiobacillus thioxidans）It is separated in pretreatment
Copper sulphate, sulfuric acid iron material is made by well known wet processing in valuable heavy metal copper, the ferro element gone out；
（2）It is prepared by adjustable solidification agent：By step（1）Gained using calcium sulphate dihydrate as the electroplating sludge waste residue of main mineral constituent
As the manufacture of cement primary raw material of gypsum adjustable solidification agent, coke fines is selected to make colorant, commercially available alcohol amine compound is selected to increase
Strong type grinding aid selects commercially available building gypsum plaster to make curing agent.
It is electroplating sludge waste residue 84.4 in mass ratio:Colorant 5:Enhanced type grinding aids 0.6:Curing agent（Building gypsum plaster）
10 ratio is uniformly mixed, and is shaped to diameter 12mm rod-like materials, dry, obtains manufacture of cement adjustable solidification agent.
This tune, which is doubted agent and sent to certain novel dry-process rotary kiln enterprise laboratory, substitutes natural dihydrate gypsum to make small mill contrast test
（Unified grinding amount 5kg, 25 minutes time, adjustable solidification agent or the natural gypsum 5%）, feedback result：1）To cement color without unfavorable shadow
It rings；2）Specific surface area improves 13%, and grindability is good, can save grinding energy；3）Strength of cement improves 2.7MPa for 3 days, improves within 28 days
5.7MPa。
Toxicity characteristic leaching procedure：Cement test block in 28 days using the natural gypsum and this adjustable solidification agent is crushed and carries out toxicity leaching pair
Than experiment, Cu2+、Mn2+、T-Cr、Cd2+、Ni2+、Zn2+、Pb2+And As2+、Hg+It does not detect.Illustrate the weight in electroplating sludge waste residue
Metallic element is able to completeness stable curing.
Radionuclide work amount：Adjustable solidification agent 0.19.
Embodiment 2
The electroplating sludge that certain Electronics Factory stores up is taken to carry out recycling, butt ingredient is analyzed through ICP-AES（%）For【Cu】
11.47、【Fe】25.31、【Mn】0.59、【S】3.52、【Sn】0.032、【Mg】1.11、【Na】0.32、【K】0.02、【P】0.12、
【Al】0.08、【Ca】9.41、【Ti】0.19、【Cr】0.008、【Co】0.003、【Ni】0.008、【Zn】0.003、【Ag】0.001、
【Ba】0.14、【Pb】0.002。
Electroplating sludge is converted into copper sulphate, sulfuric acid iron material and gypsum base material according to the following steps, with electroplating sludge system
Manufacture of cement adjustable solidification agent：
（1）Pretreatment（Separate valuable heavy metal）：With（It is well known）Hydrometallurgy biological treatment technique isolates plating
Heavy metal element in sludge, in lime and electroplating sludge, to obtain calcium sulphate dihydrate as main component（Butt calcium sulphate dihydrate contains
Measure 80.72wt%）Electroplating sludge waste residue；
Electroplating sludge is using the thiobacillus ferrooxidans tamed（Thiobacillus ferrooxidans, Thiobacillus thioxidans）It is separated in pretreatment
Copper sulphate, sulfuric acid iron material is made by well known wet processing in valuable heavy metal copper, the ferro element gone out；
（2）It is prepared by adjustable solidification agent：By step（1）Gained using calcium sulphate dihydrate as the electroplating sludge waste residue of main mineral constituent
As the manufacture of cement primary raw material of gypsum adjustable solidification agent, coke fines is selected to make colorant, select commercially available alcohol ether and hydramine
Compound enhanced type grinding aids select commercially available building gypsum plaster to make curing agent.
It is electroplating sludge waste residue 85.5 in mass ratio:Colorant 5:Enhanced type grinding aids 0.5:Curing agent（Building gypsum plaster）
9 ratio is uniformly mixed, and is shaped to diameter 12mm rod-like materials, dry, obtains manufacture of cement adjustable solidification agent.
This tune, which is doubted agent and sent to certain novel dry-process rotary kiln enterprise laboratory, substitutes natural dihydrate gypsum to make small mill contrast test
（Unified grinding amount 5kg, 25 minutes time, adjustable solidification agent or the natural gypsum 5%）, feedback result：1）To cement color without unfavorable shadow
It rings；2）Specific surface area improves 13%, and grindability is good, can save grinding energy；3）Strength of cement improves 2.2MPa for 3 days, improves within 28 days
6.1MPa。
Toxicity characteristic leaching procedure：Cement test block in 28 days using the natural gypsum and this adjustable solidification agent is crushed and carries out toxicity leaching pair
Than experiment, Cu2+, Mn2+, T-Cr, Cd2+, Ni2+, Zn2+, Pb2+ and As2+, Hg+ are not detected.Illustrate electroplating sludge waste residue
In heavy metal element be able to completeness stable curing.
Radionuclide work amount：Adjustable solidification agent 0.19.
Embodiment 3
The electroplating sludge that certain electroplating enterprise is stored up is taken to carry out recycling, butt ingredient is analyzed through ICP-AES（%）For
【Cu】13.32、【Fe】28.51、【Mn】0.87、【S】2.94、【Sn】0.081、【Mg】0.61、【Na】1.24、【K】0.04、【P】
0.37、【Al】0.89、【Ca】1.95、【Ti】0.05、【Cr】0.016、【Co】0.004、【Ni】0.017、【Zn】0.042、【Ag】
0.002、【Ba】0.37、【Pb】0.001, another Au6.12g/t.Electroplating sludge is converted into metal material and gypsum according to the following steps
Sill is produced calcium sulphoaluminate clinker and sulphur ferrous acid calcium clinker with electroplating sludge, is mainly included the following steps that：
（1）Pretreatment（Separating beavy metal）：With（It is well known）Hydrometallurgical processes isolate the heavy metal in electroplating sludge
Element, in lime and electroplating sludge, to obtain calcium sulphate dihydrate as main component（Butt sulfate dihydrate calcium content 83.71wt%）'s
Electroplating sludge waste residue；
Gold, copper are obtained through refining with well known thiourea gold extraction, sulfuric acid to leach electrodeposition process for copper respectively in pretreatment；
（2）It is prepared by raw material：By step（1）The electroplating sludge waste residue using calcium sulphate dihydrate as main mineral constituent of gained is made
To produce one of primary raw material of calcium sulphoaluminate clinker and sulphur ferrous acid calcium clinker, i.e., substituted with electroplating sludge waste residue in raw meal proportioning
Whole gypsum and ferriferous raw material, press（It is well known）The dispensings such as the dispensing requirements and lime stone, vanadine of production calcium sulphoaluminate clinker,
Grinding produces production calcium sulphoaluminate clinker raw material A；Or it presses（It is well known）Produce the dispensing requirements and lime of sulphur ferrous acid calcium clinker
The dispensings such as stone, vanadine, iron powder, grinding produce production sulphur ferrous acid calcium clinker raw material B；
（3）It is prepared by clinker：By step（2）Raw material A, the raw material B of gained are pressed respectively（It is well known）Produce calcium sulphoaluminate, sulphur iron
The technological requirement of sour calcium clinker roasts 0.6h in 1300 DEG C, and calcium sulphoaluminate clinker and sulphur ferrous acid calcium clinker is made in chilling respectively.It presses
Setting time is measured according to GB/T1346-2001, measures intensity by GB/T17671-1999, calcium sulphoaluminate obtained by the present embodiment is ripe
Expect 89 minutes presetting periods, 1 day resistance to compression 34.3MPa, anti-folding 6.1MPa, 3 days resistance to compression 45.7MPa, anti-folding 6.8MPa, resistance to compression in 28 days
63.8MPa, anti-folding 8.7MPa；93 minutes ferrous acid calcium clinker presetting periods of sulphur obtained by the present embodiment, final setting time 112 minutes, 1 day
Resistance to compression 33.9MPa, anti-folding 6.3MPa, 3 days resistance to compression 46.8MPa, anti-folding 7.1MPa, 28 days resistance to compression 67.8MPa, anti-folding 9.2MPa.
Toxicity characteristic leaching procedure：Leaching test, Cu are crushed to the sample that cures for 28 days of calcium sulphoaluminate clinker and sulphur ferrous acid calcium clinker2 +、Mn2+、T-Cr、Cd2+、Ni2+、Zn2+、Pb2+And As2+、Hg+It does not detect.Illustrate that the heavy metal element in electroplating sludge waste residue obtains
With completeness stable curing.
Radionuclide work amount is respectively 0.29,0.31.
Embodiment 4
Take certain electroplating enterprise store up electroplating sludge carry out recycling, through ICP-AES analyze electroplating sludge butt into
Point（%）For【Cu】9.79、【Fe】24.24、【Mn】0.61、【S】3.89、【Sn】1.03、【Mg】1.11、【Na】0.38、【K】
0.08、【P】0.11、【Al】0.27、【Ca】8.45、【Ti】0.11、【Cr】0.02、【Co】0.004、【Ni】0.005、【Zn】
0.045、【Ag】0.005、【Ba】0.29、【Pb】0.001.It is former that electroplating sludge is converted into copper sulphate, ferric sulfate according to the following steps
Material and gypsum base material, high strength gypsum is produced with electroplating sludge：
（1）Pretreatment（Separate valuable heavy metal）：With（It is well known）Sulfuric acid to leach method technique is isolated in electroplating sludge
Heavy metal element, in lime and electroplating sludge, to obtain calcium sulphate dihydrate as main component（Butt sulfate dihydrate calcium content
84.02wt%）Electroplating sludge waste residue；
Electroplating sludge pretreatment in isolate valuable heavy metal copper, ferro element by well known wet processing Sulphuric acid copper,
Sulfuric acid iron product；
（2）Gypsum purifies：By step（1）The electroplating sludge waste residue using calcium sulphate dihydrate as main mineral constituent of gained is beaten
Slurry by well known acid purification, cleans technique, adds the coloring mineral such as hydrochloric acid separation, purification acid-solubility iron hydroxide/iron oxide,
The dihydrate gypsum that must be purified；
Ferric trichloride waterproofing agent product is made by well known technique in the ferric chloride solution isolated.
（3）It is prepared by high strength gypsum：It is crystal modifier to select commercially available succinic acid and melamine, by step（2）The purifying two of gained
The addition of water gypsum accounts for the crystal modifier of purifying dihydrate gypsum quality 0.25%（Wherein succinic acid 0.1%, melamine 0.15%）By well known
It is damp and hot（Boiling）Technique is at a temperature of 170 DEG C, humid heat treatment 2h, obtains the high strength gypsum of α-semi-hydrated gypsum crystal form mineral；It will be damp and hot
Processing gained alpha-semi water plaster stone obtains high strength gypsum powder in 130 DEG C of dryings, grindings.
Gained high strength gypsum powder physical property is after testing：Presetting period 13 divides 26 seconds, and final setting time 26 divides 50 seconds, 2 it is small when
Resistance to compression 42.1MPa, anti-folding 8.0MPa, 28 days（Drying）Resistance to compression 56.7MPa, anti-folding 8.6MPa.
Toxicity characteristic leaching procedure：28 days are cured with sample and crushes progress toxicity characteristic leaching procedure Cu2+、Mn2+、T-Cr、Cd2+、Ni2+、
Zn2+、Pb2+And As2+、Hg+It does not detect.Illustrate that the heavy metal element in electroplating sludge waste residue is able to completeness stable curing.
Radionuclide work amount 0.11.
Embodiment 5
The electroplating sludge that certain Electronics Factory stores up is taken to carry out recycling, butt ingredient is analyzed through ICP-AES（%）For【Cu】
8.65、【Fe】23.31、【Mn】0.39、【S】3.68、【Sn】0.032、【Mg】1.01、【Na】0.37、【K】0.02、【P】0.12、
【Al】0.08、【Ca】9.41、【Ti】0.19、【Cr】0.008、【Co】0.003、【Ni】0.008、【Zn】0.003、【Ag】0.001、
【Ba】0.24、【Pb】0.001.Electroplating sludge is converted into copper sulphate, sulfuric acid iron material and gypsum base material according to the following steps, with
Electroplating sludge produces high strength gypsum powder：
（1）Pretreatment（Separate valuable heavy metal）：With（It is well known）Biological treatment（Thiobacillus ferrooxidans）Technique point
The heavy metal element in electroplating sludge is separated out, in lime and electroplating sludge, to obtain calcium sulphate dihydrate as main component（Two water of butt
Calcium sulphate content 82.77wt%）Electroplating sludge waste residue；
Electroplating sludge pretreatment in isolate valuable heavy metal copper, ferro element by well known wet processing Sulphuric acid copper,
Sulfuric acid iron product；
（2）Gypsum purifies：By step（1）The electroplating sludge waste residue using calcium sulphate dihydrate as main mineral constituent of gained is beaten
Slurry by well known acid purification, cleans technique, adds the coloring mineral such as hydrochloric acid separation, purification acid-solubility iron hydroxide/iron oxide,
The dihydrate gypsum that must be purified；
Ferric trichloride product is made by well known technique in the ferric chloride solution isolated.
（3）It is prepared by high strength gypsum：It is crystal modifier to select commercially available citric acid and polycarboxylate, by step（2）Gained it is pure
Change the crystal modifier that dihydrate gypsum addition accounts for purifying dihydrate gypsum quality 0.28%（Wherein citric acid 0.1%, polycarboxylate 0.18%）It presses
Well known is damp and hot（Boiling）Technique is at a temperature of 160 DEG C, humid heat treatment 2.5h, obtains the high-strength stone of alpha-semi water plaster stone crystal form mineral
Cream；By alpha-semi water plaster stone obtained by humid heat treatment in 130 DEG C of dryings, grindings, high strength gypsum powder is obtained.
Gained high strength gypsum powder physical property is after testing：Presetting period 15 divides 20 seconds, and final setting time 29 divides 50 seconds, 2 it is small when
Resistance to compression 47.8MPa, anti-folding 8.1MPa, 28 days（Drying）Resistance to compression 55.8MPa, anti-folding 8.7MPa.
Toxicity characteristic leaching procedure：28 days are cured with sample and crushes progress toxicity characteristic leaching procedure Cu2+、Mn2+、T-Cr、Cd2+、Ni2+、
Zn2+、Pb2+And As2+、Hg+It does not detect.Illustrate that the heavy metal element in electroplating sludge waste residue is able to completeness stable curing.
Radionuclide work amount 0.10.
Claims (6)
1. the method that electric plating sludge resource utilizes, which is characterized in that including following several technical solutions：
Scheme one：Electroplating sludge is converted into two big material component of metal/metal salt material and gypsum base material, with electroplating sludge
Manufacture of cement adjustable solidification agent is produced, is mainly included the following steps that：
（1）Pretreatment：The heavy metal element in electroplating sludge is isolated with well known wet processing, is neutralized with lime or lime stone
Electroplating sludge obtains calcium sulphate dihydrate electroplating sludge waste residue as main component；Butt sulfate dihydrate in gained electroplating sludge waste residue
Calcium content>51wt%；
（2）It is prepared by adjustable solidification agent：By step（1）Gained using calcium sulphate dihydrate as main mineral constituent electroplating sludge waste residue as
The primary raw material of manufacture of cement gypsum adjustable solidification agent, supplying amount of colorant, reinforcing agent/enhanced type grinding aids, curing agent, by matter
Amount is than being electroplating sludge waste residue 80~97.5:Colorant 1~10:Reinforcing agent or enhanced type grinding aids 0.5~5:Curing agent 1~10
Ratio be uniformly mixed, be shaped to block or rodlike or bulk goods, it is dry to get manufacture of cement gypsum adjustable solidification agent；Or each
Component after mixing, first cures drying, then is crushed to block grain material of the grain size less than 50mm to get manufacture of cement gypsum
Adjustable solidification agent；
Or scheme two：Electroplating sludge is converted into two big material component of metal/metal salt material and gypsum base material, to electroplate dirt
It is clay to take high strength gypsum, it mainly includes the following steps that：
（1）Pretreatment：The heavy metal element in electroplating sludge is isolated with well known wet processing, is neutralized with lime or lime stone
Electroplating sludge obtains calcium sulphate dihydrate electroplating sludge waste residue as main component；Butt sulfate dihydrate in gained electroplating sludge waste residue
Calcium content>60wt%；
（2）Gypsum purifies：By step（1）The electroplating sludge waste residue using calcium sulphate dihydrate as main mineral constituent of gained is beaten,
By well known acid purification, technique is cleaned, hydrochloric acid or sulfuric acid is added to separate, purify acid-solubility iron hydroxide/iron oxide, obtains purifying
Dihydrate gypsum；
（3）It is prepared by high strength gypsum：In step（2）In the purifying dihydrate gypsum of gained, addition is equivalent to purifying dihydrate gypsum quality
The crystal modifier of 0.05-1% by well known damp and hot technique at a temperature of 128 DEG C~190 DEG C, 1~8h of humid heat treatment, obtains α-half water
The high strength gypsum of gypsum crystal form mineral；By alpha-semi water plaster stone obtained by humid heat treatment in 105 DEG C~180 DEG C dryings, grindings, obtain high-strength
Land plaster.
2. the method that electric plating sludge resource according to claim 1 utilizes, which is characterized in that two step of scheme（3）In,
The crystal modifier is at least one of succinic acid, tartaric acid, citric acid, melamine, polycarboxylate.
3. the method that electric plating sludge resource according to claim 1 utilizes, which is characterized in that one step of scheme（2）In,
The colorant is the substance that can cover or mitigate red iron hydroxide/di-iron trioxide tinting strength, tinting power in waste residue.
4. the method that electric plating sludge resource according to claim 3 utilizes, which is characterized in that the colorant is lived to be useless
At least one of property charcoal, graphite, coke fines.
5. the method that electric plating sludge resource according to claim 1 utilizes, which is characterized in that one step of scheme（2）In,
The reinforcing agent or enhanced type grinding aids are alcohol ether and the compound of hydramine.
6. the method that electric plating sludge resource according to claim 1 utilizes, which is characterized in that one step of scheme（2）In,
The curing agent is at least one of cement, lime, the plaster of paris, activation waste residue powder, phosphoric acid, hydrophosphate.
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| CN106630712B (en) * | 2016-11-29 | 2019-11-05 | 湖南埃格环保科技有限公司 | A kind of water resistant building gypsum plaster and preparation method thereof using the preparation of copper-contained sludge Bioleaching slag |
| CN107162151B (en) * | 2017-05-16 | 2021-05-14 | 华南理工大学 | Preparation for treating heavy metal elements in wastewater and preparation method thereof |
| CN107398165B (en) * | 2017-08-10 | 2020-10-20 | 上海博丹环境工程技术股份有限公司 | Desulfurization and denitrification process for boiler flue gas |
| CN108543517B (en) * | 2018-04-24 | 2020-09-29 | 中国科学院过程工程研究所 | Resource recovery method of red mud, product and application thereof |
| CN108275896B (en) * | 2018-05-02 | 2021-04-13 | 东北大学 | Method for preparing sulphoaluminate cement by utilizing cyanidation tailings |
| CN109896721A (en) * | 2019-04-03 | 2019-06-18 | 宝武集团环境资源科技有限公司 | A kind of processing method of stanniferous sludge |
| CN110357576A (en) * | 2019-08-12 | 2019-10-22 | 常州大学 | Blend the method that waterglass promotes the performance and heavy metals immobilization effect of clay brick |
| CN113145304B (en) * | 2021-04-26 | 2023-03-21 | 昆明理工大学 | Method for recovering copper, nickel, zinc, iron and chromium by combining in-situ reduction, vulcanization, floatation, magnetism and electricity of electroplating sludge |
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