CN109160776B - Comprehensive treatment method of arsenic-containing tailings - Google Patents
Comprehensive treatment method of arsenic-containing tailings Download PDFInfo
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- CN109160776B CN109160776B CN201811105186.1A CN201811105186A CN109160776B CN 109160776 B CN109160776 B CN 109160776B CN 201811105186 A CN201811105186 A CN 201811105186A CN 109160776 B CN109160776 B CN 109160776B
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0263—Hardening promoted by a rise in temperature
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00775—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes the composition being used as waste barriers or the like, e.g. compositions used for waste disposal purposes only, but not containing the waste itself
Abstract
The invention provides a comprehensive treatment method of arsenic-containing tailings, which belongs to the field of mine waste residue treatment and specifically comprises the steps of sedimentation, wheel milling, digestion, repeated wheel milling, maintenance and backfilling, wherein in the sedimentation step, multifunctional water-soluble high polymer and coagulant are adopted to carry out sedimentation treatment on the arsenic-containing tailings; the weight ratio of the arsenic-containing tailings, the multifunctional water-soluble high polymer and the coagulant is 8-11: 7-8: 0.6. The comprehensive treatment method of arsenic-containing tailings provided by the invention has the advantages of simplified and mature process, high sedimentation rate, large heavy metal capture amount, reduced loss and cost, construction in four seasons, less reagent consumption, large and continuous treatment amount, no capacity increase, small shrinkage, excellent compressive strength, no arsenic toxicity, good freeze-thaw resistance and heat resistance, and economic and environmental benefits.
Description
Technical Field
The invention belongs to the field of mine waste residue treatment, and particularly relates to a comprehensive treatment method of arsenic-containing tailings.
Background
Arsenic is commonly called metalloid, has extremely strong toxicity and carcinogenic effect, and is listed as the first place of environmental pollution by the world health organization. It can enter the environment through natural action and artificial activities. In nature, generally, non-ferrous metal minerals contain arsenic, which coexists with metals such as tin, copper, lead, and nickel, and exists in the form of arsenate minerals, sulfides, and sulfur arsenides. With the gradual reduction of the high-quality nonferrous metal ores, ores with high impurity element content and high arsenic content are gradually mined, and the yield of arsenic-containing tailings is continuously increased. In the ore treatment stage, a large amount of arsenic still remains in the tailings under the influence of factors such as technology, transportation and the like, and arsenic-containing slag is formed. Arsenic released by mining activities has threatened human health through soil and food chain approaches, and the problem is more prominent particularly in southwest areas where mining activities are intensive.
For a long time, most of arsenic-containing tailings after mining in mines are treated by a stockpiling and storing method, so that secondary pollution is caused to the environment, potential resource waste is caused, the arsenic-containing tailings form the most main environmental pollution source of nonferrous metallurgy enterprises in China, and the environment around the enterprises is seriously polluted. With the expansion of gold development scale and the extension of mining history, the accumulation amount of tailings is increased year by year, the granularity of tailings minerals is very fine, the argillization phenomenon is serious, the mineral composition is complex, the tailings contain a certain amount of cyanide and partial residual medicament, and the arsenic-containing tailings mainly pollute the environment through three ways of atmosphere, water and solid. The pollution to the water environment is mainly caused by that the soluble arsenate in the water environment is dissolved by flushing the water and continuously migrates along with surface water to cause water pollution; the pollution to the atmosphere is mainly carried out through the weathering process of the arsenic waste residue or the dissipation of arsenic-containing gas generated by wetting; solid pollution of arsenic tailings includes pollution of land by stacking of waste rocks and landslide, debris flow, etc. caused by improper stacking of arsenic waste rocks, causing a wide range of pollution, and plants enrich excessive arsenic poisoning by absorbing nutrients in soil, and humans and livestock are poisoned by ingesting excessive arsenic through direct contact or food chain route. It can be seen that cyanide and metal ions remaining in tailings are leached, diffused and lost, which seriously threatens the nearby ecological environment, and a large amount of capital needs to be invested for building and maintaining and managing the tailings yard, so that the reduction, harmless and recycling treatment of gold mine tailings becomes an important measure for comprehensive utilization of gold mine resources and environmental protection.
Regarding the comprehensive utilization of gold mine tailings in China at present, the recovery and utilization of valuable metal elements such as gold, silver, copper, lead and the like in the tailings are reported and researched relatively, arsenic is a relatively common element in gold ores, and because the demand for arsenic in the world is relatively small, a large amount of arsenic in common mineral products is remained in tailings slags after mining of other metal elements, so that the arsenic content in the slags is generally higher, arsenic and compounds thereof are toxic heavy metals, and if the arsenic and the compounds are not treated, the environment is polluted, and the living environment of animals and plants and human beings is seriously damaged. The gold tailings are solid or powdery wastes which are discharged after mining and sorting ores and are not utilized, or ore materials discharged after gold concentrate is extracted by adopting a cyaniding gold extraction method, an alkali dissolution method and the like. The gold tailings are mainly made of SiO2、CaO、A12O3And a certain amount of Fe2O3And MgO. From the aspects of environmental protection and resource utilization, the gold tailings are utilized to change waste into valuable, the harm is turned into the benefit, and the exploitation of various comprehensive utilization ways of the gold tailings is an inevitable choice for the continuous development of mines.
In the prior art, for example, CN104668266B discloses a harmless treatment method for arsenic-containing hazardous waste residues, wherein arsenic is recovered by a flotation process after an arsenide in arsenic-containing slurry is activated, so as to achieve harmless treatment of waste residues, however, although the arsenic content in gold tailings is relatively high, the requirements for the process and equipment for arsenic recovery are high, and the tailing treatment cost is high.
Disclosure of Invention
The invention aims to provide a comprehensive treatment method of arsenic-containing tailings, which has the advantages of high sedimentation rate, large heavy metal capture amount, less loss and cost, capability of being constructed in four seasons, less reagent dosage, large treatment capacity and continuity, can be used for preparing filling materials which are not compatibilized, have small shrinkage, excellent compressive strength, no arsenic toxicity and good freeze-thaw resistance and heat resistance, and has economic and environmental benefits.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a comprehensive treatment method of arsenic-containing tailings comprises the steps of sedimentation, wheel milling, digestion, repeated wheel milling, maintenance and backfilling, wherein the sedimentation step adopts a multifunctional water-soluble high polymer and a coagulant to carry out sedimentation treatment on the arsenic-containing tailings; the weight ratio of the arsenic-containing tailings, the multifunctional water-soluble high polymer and the coagulant is 8-11: 7-8: 0.6. The pretreatment method can fix arsenic metal ions or other inorganic matters and organic matters, form an insoluble or low-soluble mixture to weaken the toxicity of heavy metals, and control the oxidation-reduction potential of the heavy metals, so that toxic and harmful gases and soluble substances in hazardous wastes are treated, and the toxicity of the heavy metals is also weakened. Arsenic in gold tailings is mainly calcium salt (Ca)3(AsO4)2) Iron salt (FeAsO)4、Fe4As2O11) The multifunctional water-soluble high-molecular polymer is adopted to change the surface properties of particles in the hazardous waste, particularly the potential, the viscosity, the turbidity and the suspension degree, the particles are condensed due to the reduction of the electrokinetic potential on the surfaces of the particles, the molecular chains of the water-soluble high-molecular polymer are fixed on the surfaces of different particles, polymer bridges are formed among the particles to ensure that the particles form a group to settle, and polar group particles on the molecules of the water-soluble high-molecular polymer adsorb heavy metals in the hazardous waste, so that the heavy metal ions are fixed in the precipitate, and the subsequent further immobilization operation is facilitated.The addition of the coagulant improves the sedimentation effect, enhances the capturing and adsorbing capacity of the water-soluble heavy metal ions, converts the water-soluble heavy metal ions into an inactive form, increases the sedimentation rate and the capturing amount, and gains the flocculation sedimentation effect of a high molecular compound.
The gold tailings are tailings discharged from mines during the mining of gold concentrates or gold tailings accumulated in a tailing pond after the tailings are recleaning, or ore materials discharged after the gold concentrates are extracted by adopting a cyaniding gold extraction method, an alkali dissolution method and the like. The gold tailings contain heavy metal ions and other substances such as SiO2、Al2O3、CaO、MgO、K2O、Na2O、Fe2O3The content of (A) is also higher.
SiO contained in the gold tailings is activated through chemical activation and physical activation technologies2、CaO、A12O3The effective components are processed into silicate and aluminate with curing effect and calcium carbonate containing active components is generated, and the filling material with the characteristics of high strength and early strength is obtained by utilizing the displayed gelling property of the calcium carbonate. The consolidation agent is matched with other components in the formula for use, so that the traditional cement can be replaced, the generated hydrated silicate and hydrated aluminate are used for filling pores and capillary holes in the material, the pore structure is improved, the compactness of the filling material is improved, and the breaking strength, the compressive strength and the freeze-thaw resistance durability are excellent. The heavy metal in the gold tailings is solidified in the crystal lattice of the heavy metal stabilizer by utilizing the ionic reaction and the chelation of the heavy metal stabilizer, the oxidation-reduction potential of the heavy metal is controlled, the existing heavy metals such As Cu, Ag, As and the like have insolubility, a stable metal compound which cannot be leached under the normal environment is generated, radioactive gas is not generated, and meanwhile pathogens, viruses, malodorous gases and organic humus in the tailings and dangerous wastes are eliminated.
In order to achieve the technical purpose, the comprehensive treatment method of the arsenic-containing tailings comprises the following steps:
and (3) settling: adding a high molecular compound and a coagulant into arsenic-containing tailings according to a weight ratio, feeding the arsenic-containing tailings into a concentration tank, stirring the arsenic-containing tailings for 35 to 45 minutes under the condition that the stirring intensity is 165 to 175r/min, and carrying out in-situ processingThe working pressure is 5-9 kg/cm2Performing filter pressing for 35-45 min under the condition of (1), and controlling the water content of a filter cake to be 16-20% to obtain concentrated ore pulp;
wheel milling: feeding the concentrated ore pulp into a wheel mill, adding 10-18 parts of industrial waste residues, 0.5-2.5 parts of F14 exciting agent and 0.5-5 parts of heavy metal stabilizing agent, grinding and mixing for 5-15 min to obtain a mixture, wherein the mixture is subjected to the grinding pressure of the wheel mill in the wheel mill, the heavy metal stabilizing agent can solidify heavy metals in gold tailings in the crystal lattices of the heavy metal stabilizing agent while the heavy metal stabilizing agent is mechanically activated, the oxidation-reduction potential of the heavy metals is controlled, so that the heavy metals have insolubility, and original calcium, silicon, aluminum ions and the like in the material are converted into oxide ions through mechanical action, so that the oxide ions can be excited by the exciting agent, the material is compacted to reduce the volume, the volume density of the final filler is greatly improved, the capacity is not increased, and the performance of the filler is improved;
digestion: feeding the mixture into a continuous digestion bin for material digestion, wherein the digestion temperature is 40-70 ℃, and the digestion time is 2-4 hours, so as to obtain a digestion material, wherein the digestion function is mainly to promote an exciting agent to activate and modify active mineral components contained in waste residues and tailings, and then to improve plasticity, and the third is to eliminate the influence of f-CaO, f-Mgo and other unstable factors;
and (3) repeating wheel milling: adding 5-15 parts of a consolidation agent, 0.03-0.3 part of a water reducing agent and 0.04-0.2 part of a cementing material into the digestion material, and then sending the digestion material into a wheel mill for repeated grinding and mixing for 5-15 min to obtain the filling material, wherein the water content of the mixture of the raw materials is controlled to be 10-17%, active components of the consolidation agent penetrate into phase boundary curves of basic particles of the digestion material in the wheel mill to excite the internal activity of the material, and the active components of the digestion material are subjected to dilution and dispersion effects by utilizing the super-superposition effect generated by multi-component compounding to form a polycrystalline aggregate, so that the filling material has the characteristics of early strength and high strength;
and (5) maintenance: placing the filling material into a curing room, and naturally pre-curing for 36-60 h when the indoor temperature is higher than 10 ℃; introducing hot air at the temperature of less than 10 ℃, and precuring for 4-10 h at the temperature of 50-70 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is increased to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 174-194 ℃, and the pressure is controlled to be 0.8-1.3 MPa; then keeping the temperature for 6-8 h, cooling to 60-80 ℃, maintaining the filling material, so that the consolidation agent, the cementing material and the water have proper hardening conditions in the maintenance stage, the strength of the filling material can be continuously increased along with the hardening degree, the coagulation of the filling material is facilitated, and the compressive strength is improved;
backfilling: and (4) the filling materials are conveyed through a pipeline or are piled to a tailing pond in a dumping mode.
Preferably, the stirring in the sedimentation step can be operated continuously or intermittently, and clear liquid obtained by pressure filtration can be directly discharged or returned to the process for recycling without influencing the process index.
Preferably, the industrial waste residue used in the wheel milling step is at least one of fly ash, blast furnace slag, slag of metal smelting plants, red mud, volcanic ash or other materials with volcanic ash activity.
Preferably, the consolidating agent in the repeated wheel milling step is a hydraulic cementing material.
Preferably, the cementing material in the repeated wheel grinding step is a synthetic high molecular polymer. The gold tailings are treated by arsenic solidification to obtain a digestion material, a cementing material is added into the digestion material to strengthen the cementing effect, so that the gold tailings are coagulated into a whole with certain strength, and the strength of the filling material can be strengthened after the gold tailings are coagulated, so that the surrounding rock can be effectively and safely supported.
Preferably, the filling material also comprises 0-5 wt% of an auxiliary material, and the auxiliary material is an additive with water-resistant, quick-setting, antifreezing, expanding or anti-seepage effects. The addition of auxiliary material can improve the performance of the filling material, regulate and gain the strength grade and the working performance of the filling material, thereby greatly prolonging the service life and greatly improving the effect of the filling material.
Preferably, the arsenic leaching concentration of the filler obtained after the arsenic-containing tailings are subjected to comprehensive treatment is less than 2.5 mg/L. The arsenic ion concentration in the leaching solution reaches the national discharge and landfill standard, the leaching solution belongs to general solid waste, harmful pollutants are changed into substances with low solubility, low toxicity and low fluidity, the harm of the waste is reduced, and the environmental pollution can not be caused after the landfill.
The invention discloses a comprehensive treatment method of tailings containing arsenic, which comprises the steps of carrying out heavy metal immobilization on gold tailings, piling the tailings to a tailing pond, not increasing the capacity, having low leaching toxicity, directly burying a mine goaf, taking local materials and utilizing wastes, avoiding the cost of producing filling material crushed stones by collection, crushing, transportation and the like, obviously reducing the production cost and the pollution discharge cost, solving the problem of environmental pollution puzzling the tailing area, timely treating the goaf, not causing large ground pressure activity, and having good economic, social and environmental benefits.
The invention has the beneficial effects that:
1) the comprehensive treatment method of the arsenic-containing tailings provided by the invention has the advantages that the process is simplified and mature, arsenic ions are fully converted into forms with low solubility, low toxicity and low fluidity from soluble forms and gaseous forms and are fixed in the filling material, so that the filling material has the advantages of no toxicity, good freeze-thaw resistance and heat resistance and no secondary pollution, the reduction and the recycling are realized, and the economic and environmental benefits are realized;
2) according to the invention, the heavy metal ions in the gold tailings are solidified in the internal crystal lattices of the filling material by using the macromolecular compound, the coagulant, the excitant, the stabilizer, the consolidating agent and the cementing material, and the filling material with stable and low leaching toxicity is generated without capacity increase and large shrinkage during hardening;
3) the method has the advantages of less dosage of various added reagents, stable treatment effect, cost saving, simple process flow, easily controlled parameters, stable and efficient system operation, flexible and adjustable tailing treatment proportion, large treatment capacity, continuous operation and easy operation and management;
4) in the invention, after the gold tailings are subjected to heavy metal immobilization comprehensive treatment, the tailings are piled in the tailing pond, the capacity is not increased, the compressive strength is excellent, the production cost and the pollution discharge cost are reduced, the secondary pollution problem of tailing piling is avoided, and the method is suitable for harmless treatment of arsenic-polluted soil and tailings of related mines.
The invention adopts the technical scheme to provide the comprehensive treatment method of the arsenic-containing tailings, overcomes the defects of the prior art, and has reasonable design and convenient operation.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments:
a comprehensive treatment method of arsenic-containing tailings comprises the steps of sedimentation, wheel milling, digestion, repeated wheel milling, maintenance and backfilling, wherein the sedimentation step adopts a multifunctional water-soluble high polymer and a coagulant to carry out sedimentation treatment on the arsenic-containing tailings; the weight ratio of the arsenic-containing tailings, the multifunctional water-soluble high polymer and the coagulant is 8-11: 7-8: 0.6.
The multifunctional water-soluble high molecular polymer comprises polyacrylamide, polyacrylic acid, alkali-added hydrolysate of polyacrylamide, acrylamide graft copolymer and the like. The pretreatment method can fix arsenic metal ions or other inorganic matters and organic matters, form an insoluble or low-soluble mixture to weaken the toxicity of heavy metals, and control the oxidation-reduction potential of the heavy metals, so that toxic and harmful gases and soluble substances in hazardous wastes are treated, and the toxicity of the heavy metals is also weakened. Arsenic in gold tailings is mainly calcium salt (Ca)3(AsO4)2) Iron salt (FeAsO)4、Fe4As2O11) The multifunctional water-soluble high-molecular polymer is adopted to change the surface properties of particles in the hazardous waste, particularly the potential, the viscosity, the turbidity and the suspension degree, the particles are condensed due to the reduction of the electrokinetic potential on the surfaces of the particles, the molecular chains of the water-soluble high-molecular polymer are fixed on the surfaces of different particles, polymer bridges are formed among the particles to ensure that the particles form a group to settle, and polar group particles on the molecules of the water-soluble high-molecular polymer adsorb heavy metals in the hazardous waste, so that the heavy metal ions are fixed in the precipitate, and the subsequent further immobilization operation is facilitated.
In order to achieve the best technical scheme, the coagulant contains dimethylacetamide and p-aminobenzoic acid, wherein the weight ratio of dimethylacetamide to p-aminobenzoic acid is 7-9: 4. The addition of the coagulant gains the flocculation sedimentation effect of a macromolecular compound, and utilizes the thermal stability and the ultraviolet oxidation resistance of the coagulant in the sedimentation process to reduce the temperature sensitivity of the macromolecular compound, inhibit the macromolecular compound from generating free radicals, avoid the macromolecular compound from degrading, improve the sedimentation effect, can be constructed in four seasons, reduce the loss and the cost, simultaneously utilize mechanical shearing to ensure that the amido bond and the carboxyl functional group are in bridging connection to form a more extended linear long chain, increase the molecular chain and fully expose the effective active group of the carboxyl, enhance the catching and adsorbing capacity of water-soluble heavy metal ions, convert the water-soluble heavy metal ions into an inactive form, increase the sedimentation rate and the catching capacity, and ensure that the process is carried out efficiently, massively and continuously.
The gold tailings are tailings discharged from mines during the mining of gold concentrates or gold tailings accumulated in a tailing pond after the tailings are recleaning, or ore materials discharged after the gold concentrates are extracted by adopting a cyaniding gold extraction method, an alkali dissolution method and the like. The gold tailings contain heavy metal ions and other substances such as SiO2、Al2O3、CaO、MgO、K2O、Na2O、Fe2O3The content of (A) is also higher.
SiO contained in the gold tailings is activated through chemical activation and physical activation technologies2、CaO、A12O3The effective components are processed into silicate and aluminate with curing effect and calcium carbonate containing active components is generated, and the filling material with the characteristics of high strength and early strength is obtained by utilizing the displayed gelling property of the calcium carbonate. The consolidation agent is matched with other components in the formula for use, so that the traditional cement can be replaced, the generated hydrated silicate and hydrated aluminate are used for filling pores and capillary holes in the material, the pore structure is improved, the compactness of the filling material is improved, and the breaking strength, the compressive strength and the freeze-thaw resistance durability are excellent. The heavy metal in the gold tailings is solidified in the crystal lattice of the heavy metal stabilizer by utilizing the ion reaction and the chelation of the heavy metal stabilizer, the oxidation-reduction potential of the heavy metal is controlled, so that the existing heavy metals such As Cu, Ag, As and the like have insolubility, and the heavy metals are generated stably and cannot be generated under the normal environmentThe leached metal compound does not produce radioactive gas, and can kill pathogens, viruses, malodorous gas and organic humus in tailings and dangerous waste.
In order to achieve the technical purpose, the comprehensive treatment method of the arsenic-containing tailings comprises the following steps:
and (3) settling: adding a high molecular compound and a coagulant into arsenic-containing tailings according to a weight ratio, feeding the arsenic-containing tailings into a concentration tank, stirring the arsenic-containing tailings for 35 to 45 minutes under the condition that the stirring intensity is 165 to 175r/min, and then, working at a pressure of 5 to 9kg/cm2Performing filter pressing for 35-45 min under the condition of (1), and controlling the water content of a filter cake to be 16-20% to obtain concentrated ore pulp;
wheel milling: feeding the concentrated ore pulp into a wheel mill, adding 10-18 parts of industrial waste residues, 0.5-2.5 parts of F14 exciting agent and 0.5-5 parts of heavy metal stabilizing agent, grinding and mixing for 5-15 min to obtain a mixture, wherein the mixture is subjected to the grinding pressure of the wheel mill in the wheel mill, the heavy metal stabilizing agent can solidify heavy metals in gold tailings in the crystal lattices of the heavy metal stabilizing agent while the heavy metal stabilizing agent is mechanically activated, the oxidation-reduction potential of the heavy metals is controlled, so that the heavy metals have insolubility, and original calcium, silicon, aluminum ions and the like in the material are converted into oxide ions through mechanical action, so that the oxide ions can be excited by the exciting agent, the material is compacted to reduce the volume, the volume density of the final filler is greatly improved, the capacity is not increased, and the performance of the filler is improved;
digestion: feeding the mixture into a continuous digestion bin for material digestion, wherein the digestion temperature is 40-70 ℃, and the digestion time is 2-4 hours, so as to obtain a digestion material, wherein the digestion function is mainly to promote an exciting agent to activate and modify active mineral components contained in waste residues and tailings, and then to improve plasticity, and the third is to eliminate the influence of f-CaO, f-Mgo and other unstable factors;
and (3) repeating wheel milling: adding 5-15 parts of a consolidation agent, 0.03-0.3 part of a water reducing agent and 0.04-0.2 part of a cementing material into the digestion material, and then sending the digestion material into a wheel mill for repeated grinding and mixing for 5-15 min to obtain the filling material, wherein the water content of the mixture of the raw materials is controlled to be 10-17%, active components of the consolidation agent penetrate into phase boundary curves of basic particles of the digestion material in the wheel mill to excite the internal activity of the material, and the active components of the digestion material are subjected to dilution and dispersion effects by utilizing the super-superposition effect generated by multi-component compounding to form a polycrystalline aggregate, so that the filling material has the characteristics of early strength and high strength;
and (5) maintenance: placing the filling material into a curing room, and naturally pre-curing for 36-60 h when the indoor temperature is higher than 10 ℃; introducing hot air at the temperature of less than 10 ℃, and precuring for 4-10 h at the temperature of 50-70 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is increased to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 174-194 ℃, and the pressure is controlled to be 0.8-1.3 MPa; then keeping the temperature for 6-8 h, cooling to 60-80 ℃, maintaining the filling material, so that the consolidation agent, the cementing material and the water have proper hardening conditions in the maintenance stage, the strength of the filling material can be continuously increased along with the hardening degree, the coagulation of the filling material is facilitated, and the compressive strength is improved;
backfilling: and (4) the filling materials are conveyed through a pipeline or are piled to a tailing pond in a dumping mode.
The stirring in the settling step can be continuous or intermittent operation, and clear liquid obtained by filter pressing can be directly discharged or returned to the process for recycling without influencing the process index.
The industrial waste residue used in the wheel milling step is at least one of fly ash, blast furnace slag, slag of metal smelting plants, red mud, volcanic ash or other materials with volcanic ash activity.
The consolidation agent in the repeated wheel milling step is a hydraulic cementing material.
The binder in the repeated wheel milling step comprises a synthetic high molecular polymer. The gold tailings are treated by arsenic solidification to obtain a digestion material, a cementing material is added into the digestion material to strengthen the cementing effect, so that the gold tailings are coagulated into a whole with certain strength, and the strength of the filling material can be strengthened after the gold tailings are coagulated, so that the surrounding rock can be effectively and safely supported.
The filling material also comprises 0-5 wt% of an auxiliary material, wherein the auxiliary material is an additive with the functions of resisting water, accelerating setting, preventing freezing, expanding or preventing seepage. The addition of auxiliary material can improve the performance of the filling material, regulate and gain the strength grade and the working performance of the filling material, thereby greatly prolonging the service life and greatly improving the effect of the filling material.
The stabilizer is heptasodium diethylenetriamine pentamethylene phosphonic acid, and the water reducing agent is a polycarboxylic acid high-performance water reducing agent or a naphthalene high-performance water reducing agent, a melamine high-performance water reducing agent, an amino sulfonate high-performance water reducing agent or an aliphatic high-performance water reducing agent.
The arsenic leaching concentration of the filling material obtained after the arsenic-containing tailings are subjected to comprehensive treatment is less than 2.5 mg/L. The arsenic ion concentration in the leaching solution reaches the national discharge and landfill standard, the leaching solution belongs to general solid waste, harmful pollutants are changed into substances with low solubility, low toxicity and low fluidity, the harm of the waste is reduced, and the environmental pollution can not be caused after the landfill.
Example 1:
the arsenic tailings of a certain gold mine are subjected to toxicity leaching detection, the pollutants in the leachate exceed the standard, the pH is 6, the As is 30.87Mg/L, the Al is 23.28Mg/L, the Ca is 19.75Mg/L, the Fe is 3.55Mg/L, the Mg is 11.36Mg/L, the Pb is 5.97Mg/L, other substances are trace or not detected, and the toxicity leaching result is dangerous waste.
The comprehensive treatment method of the arsenic-containing tailings comprises the following steps:
1) and (3) settling: adding a high molecular compound and a coagulant into arsenic-containing tailings according to the weight ratio of 8:7:0.6, feeding the arsenic-containing tailings into a concentration tank, continuously stirring the arsenic-containing tailings for 35min under the condition that the stirring intensity is 165r/min, and then, controlling the working pressure to be 5kg/cm2The filter cake is pressed and filtered for 35min, the water content of the filter cake is controlled to be 16 percent, concentrated ore pulp is obtained, the obtained clear liquid is returned to the process for recycling, and the weight ratio of dimethylacetamide to p-aminobenzoic acid in the coagulant is 7: 4;
2) wheel milling: feeding the concentrated ore pulp into a wheel mill, adding 10 parts of industrial waste residue, 0.7 part of F14 exciting agent and 0.9 part of heavy metal stabilizing agent, and grinding and mixing for 7min to obtain a mixture;
3) digestion: feeding the mixture into a continuous digestion bin for material digestion at the digestion temperature of 40 ℃ for 2 hours to obtain a digestion material;
4) and (3) repeating wheel milling: adding 5 parts of consolidation agent, 0.08 part of polycarboxylic acid water reducing agent and 0.04 part of resin into the digestion material, and then sending the digestion material into a wheel mill for repeated grinding and mixing for 7min to obtain a filling material, wherein the water content of the mixture of the raw materials is controlled at 10%;
5) and (5) maintenance: placing the filling material into a curing room, and naturally pre-curing for 38 hours when the indoor temperature is higher than 10 ℃; introducing hot air at a temperature lower than 10 ℃, and precuring for 4h at a temperature of 50 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is increased to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 175 ℃, and the pressure is controlled to be 0.8 MPa; then keeping the temperature for 6 hours, and cooling to 80 ℃;
6) backfilling: and (3) conveying the filling materials through a pipeline or piling the filling materials into a tailing pond in a dumping mode or filling the filling materials into a mined-out area of the mine.
The strength of the cured filling material is 16MPa, and the toxicity leaching detection is carried out on the filling material, and the results are as follows: as is 1.38Mg/L, Al is 0.55Mg/L, Ca is 0.75Mg/L, Fe is 0.65Mg/L, Mg is 0.36Mg/L, Pb is 0.37Mg/L, and other substances are trace or not detected, which indicates that after the tailings are comprehensively treated, the arsenide is fully fixed in the filling material, the filling material belongs to common solid waste, and the stacking treatment or the mine filling is feasible and safe.
Example 2:
a comprehensive treatment method of arsenic-containing tailings comprises the following further optimization steps:
1) and (3) settling: adding a high molecular compound and a coagulant into arsenic-containing tailings of a certain gold mine in example 1 according to the weight ratio of 9:7.5:0.6, feeding the mixture into a concentration tank, continuously stirring the mixture for 40min under the condition that the stirring intensity is 170r/min, and then, working at the working pressure of 7kg/cm2The filter cake is pressed and filtered for 45min, the water content of the filter cake is controlled to be 16 percent, concentrated ore pulp is obtained, the obtained clear liquid is returned to the process for recycling, and the weight ratio of dimethylacetamide to p-aminobenzoic acid in the coagulant is 7: 4;
2) wheel milling: feeding the concentrated ore pulp into a wheel mill, adding 10 parts of industrial waste residue, 0.7 part of F14 exciting agent and 0.9 part of heavy metal stabilizing agent, and grinding and mixing for 7min to obtain a mixture;
3) digestion: feeding the mixture into a continuous digestion bin for material digestion at the digestion temperature of 40 ℃ for 2 hours to obtain a digestion material;
4) and (3) repeating wheel milling: adding 3.5 parts of a consolidation agent, 0.08 part of a polycarboxylic acid water reducing agent and 0.03 part of a cementing agent into the digestion material, and then sending the digestion material into a wheel mill for repeated grinding and mixing for 7min to obtain the filling material, wherein the water content of the mixture of the raw materials is controlled to be 10%, the cementing agent comprises resin, polyamide-imide and polyimide, the weight ratio of the resin to the polyamide-imide to the polyimide is 3:0.5:0.4, the cementing agent can bond particles of the raw materials by virtue of the self-gelling property, reduce the inter-particle pores and increase the strength of a finished product, and meanwhile, the cementing agent is influenced by mechanical force activation in the wheel mill, so that a new arrangement and bridging are generated between activated amido bonds and imide rings (-CO-NH-CO-) in a polymer, thereby forming a cross-linked mesh structure with better pressure resistance effect and stronger adhesiveness, filling and blocking the inter-particle pores, and effectively reducing the usage amount of other materials with gelling property, the cost is reduced, the problem of large hardening shrinkage of a hydraulic cementing material during maintenance is avoided, and meanwhile, the electric coordination among ions and arsenic ions in tailings are mutually adsorbed to form a stable whole with balanced electrovalence, so that arsenide is fixed in the arsenic ions and is not leached out, the toxicity of the arsenide in the filling material is eliminated, and the freeze-thaw resistance and heat resistance are excellent;
5) and (5) maintenance: placing the filling material into a curing room, and naturally pre-curing for 38 hours when the indoor temperature is higher than 10 ℃; introducing hot air at a temperature lower than 10 ℃, and precuring for 5h at a temperature of 60 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is increased to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 175 ℃, and the pressure is controlled to be 0.8 MPa; then keeping the temperature for 7 hours, and cooling to 80 ℃;
6) backfilling: and (4) conveying the filling body through a pipeline or piling the filling body to a tailing pond in a dumping mode or filling the filling body to a mine goaf.
The strength of the cured filling material is 20MPa, and the toxicity leaching detection is carried out on the filling body, and the results are as follows: as is 0.48Mg/L, Al is 0.51Mg/L, Ca is 0.63Mg/L, Fe is 0.74Mg/L, Mg is 0.48Mg/L, Pb is 0.42Mg/L, other substances are trace or not detected, show that the arsenious substance is fully fixed after the tailings are comprehensively treated, in the process of preparing the filling material, polyamide imide and polyimide are added into the cementing material, the dosage of the cementing agent and the cementing material is reduced, the strength of the filling material is obviously improved compared with that in the embodiment 1, the compressive strength of the filling material is improved, the leaching concentration of the arsenious substance is obviously reduced, the filling material has a non-toxic effect, belongs to common solid waste, and the piling treatment or the filling of mines is feasible and safe.
Example 3:
the comprehensive treatment method of the arsenic-containing tailings comprises the following steps:
1) pretreatment: after adding a high molecular compound and a coagulant into arsenic-containing tailings of a certain gold mine in example 1 according to the weight ratio of 10.5:7.5:0, feeding the arsenic-containing tailings into a concentration tank, continuously stirring the arsenic-containing tailings for 35min under the condition that the stirring intensity is 175r/min, and then working at the working pressure of 9kg/cm2The filter cake is pressed and filtered for 35min, the water content of the filter cake is controlled to be 18 percent, concentrated ore pulp is obtained, and the obtained clear liquid is returned to the process for recycling;
2) wheel milling: feeding the concentrated ore pulp into a wheel mill, adding 10 parts of industrial waste residue, 0.7 part of F14 exciting agent and 0.9 part of heavy metal stabilizing agent, and grinding and mixing for 7min to obtain a mixture;
3) digestion: feeding the mixture into a continuous digestion bin for material digestion at the digestion temperature of 40 ℃ for 2 hours to obtain a digestion material;
4) and (3) repeating wheel milling: adding 5 parts of consolidation agent, 0.08 part of polycarboxylic acid water reducing agent and 0.04 part of resin into the digestion material, and then sending the digestion material into a wheel mill for repeated grinding and mixing for 7min to obtain a filling material, wherein the water content of the mixture of the raw materials is controlled at 10%;
5) and (5) maintenance: placing the filling material into a curing room, and naturally pre-curing for 45 hours when the indoor temperature is higher than 10 ℃; introducing hot air at the temperature of below 10 ℃, and precuring for 5 hours at the temperature of 65 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is raised to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 183 ℃, and the pressure is controlled to be 1.1 MPa; then keeping the temperature for 7.5h, and cooling to 70 ℃;
6) backfilling: and (4) conveying the filling body through a pipeline or piling the filling body to a tailing pond in a dumping mode or filling the filling body to a mine goaf.
The strength of the cured filler is 16MPa, and the toxicity leaching detection is carried out on the filler, and the results are as follows: as is 2.46Mg/L, Al is 0.43Mg/L, Ca is 0.69Mg/L, Fe is 0.58Mg/L, Mg is 0.56Mg/L, Pb is 0.47Mg/L, and other substances are trace or not detected, which indicates that the arsenic compound is fixed after the tailings are comprehensively treated, but because dimethylacetamide and para-aminobenzoic acid are not added in a coagulant, the leaching amount of arsenic ions is increased, the fixation is insufficient, the filling material belongs to common solid waste, and the filling material is feasible and safe for stacking treatment or filling mines.
Example 4:
the comprehensive treatment method of the arsenic-containing tailings comprises the following steps:
1) pretreatment: adding a high molecular compound and a coagulant into arsenic-containing tailings of a certain gold mine in example 1 according to the weight ratio of 11:8:0.6, feeding the arsenic-containing tailings into a concentration tank, continuously stirring the arsenic-containing tailings for 45min under the condition that the stirring intensity is 175r/min, and then, working at the working pressure of 7kg/cm2The filter cake is pressed and filtered for 35min, the water content of the filter cake is controlled to be 20 percent, concentrated ore pulp is obtained, the obtained clear liquid is returned to the process for recycling, and the weight ratio of dimethylacetamide to para aminobenzoic acid in the coagulant is 2: 1;
2) wheel milling: feeding the concentrated ore pulp into a wheel mill, adding 13 parts of industrial waste residue, 1.9 parts of F14 exciting agent and 2.3 parts of heavy metal stabilizing agent, and grinding and mixing for 12min to obtain a mixture;
3) digestion: feeding the mixture into a continuous digestion bin for material digestion at 55 ℃ for 2.5 hours to obtain a digestion material;
4) and (3) repeating wheel milling: adding 12 parts of consolidation agent, 0.26 part of polycarboxylic acid water reducing agent and 0.12 part of resin into the digestion material, and then sending the digestion material into an edge runner mill for repeated grinding and mixing for 12min to obtain a filling material, wherein the water content of the mixture of the raw materials is controlled at 16%;
5) and (5) maintenance: placing the filling material into a curing room, and naturally pre-curing for 48 hours when the indoor temperature is higher than 10 ℃; introducing hot air at the temperature of below 10 ℃, and precuring for 8 hours at the temperature of 65 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is increased to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 187 ℃, and the pressure is controlled to be 1.0 MPa; then keeping the temperature for 6.5h, and cooling to 80 ℃;
6) backfilling: and (4) conveying the filling body through a pipeline or piling the filling body to a tailing pond in a dumping mode or filling the filling body to a mine goaf.
The strength of the cured filler is 17MPa, and the toxicity leaching detection is carried out on the filler, and the results are as follows: as is 1.34Mg/L, Al is 0.84Mg/L, Ca is 0.87Mg/L, Fe is 0.47Mg/L, Mg is 0.24Mg/L, Pb is 0.42Mg/L, and other substances are trace or not detected, which indicates that the arsenious substance is fully fixed after the tailings are comprehensively treated, the filling material belongs to common solid waste, and the accumulation treatment or the filling of mines are feasible and safe.
Example 5:
the comprehensive treatment method of the arsenic-containing tailings comprises the following steps:
1) and (3) settling: after adding a high molecular compound and a coagulant into arsenic-containing tailings of a certain gold mine in example 1 according to the weight ratio of 8.5:7.5:0.6, feeding the arsenic-containing tailings into a concentration tank, continuously stirring the arsenic-containing tailings for 45min under the condition that the stirring intensity is 165r/min, and then working at the working pressure of 9kg/cm2The filter cake is pressed and filtered for 35min, the water content of the filter cake is controlled to be 17 percent, concentrated ore pulp is obtained, the obtained clear liquid is returned to the process for recycling, and the weight ratio of dimethylacetamide to p-aminobenzoic acid in the coagulant is 8.5: 4;
2) wheel milling: feeding the concentrated ore pulp into a wheel mill, adding 16 parts of industrial waste residue, 1.4 parts of F14 exciting agent and 3.4 parts of heavy metal stabilizing agent, and grinding and mixing for 10min to obtain a mixture;
3) digestion: feeding the mixture into a continuous digestion bin for material digestion at 55 ℃ for 2.5 hours to obtain a digestion material;
4) and (3) repeating wheel milling: adding 12 parts of consolidation agent, 0.26 part of polycarboxylic acid water reducing agent and 0.12 part of resin into the digestion material, then adding 2.4 wt% of silicate accelerating agent, feeding the mixture into an edge runner mill for repeated grinding and mixing for 12min to obtain the filling material, wherein the water content of the mixture of the raw materials is controlled at 16%;
5) and (5) maintenance: placing the filling material into a curing room, and naturally pre-curing for 52 hours when the indoor temperature is higher than 10 ℃; introducing hot air at a temperature lower than 10 ℃, and precuring for 9h at a temperature of 60 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is raised to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 192 ℃, and the pressure is controlled to be 1.2 MPa; then keeping the temperature for 7 hours, and cooling to 70 ℃;
6) backfilling: and (4) conveying the filling body through a pipeline or piling the filling body to a tailing pond in a dumping mode or filling the filling body to a mine goaf.
The strength of the cured filling material is 18MPa, and the toxicity leaching detection is carried out on the filling body, and the results are as follows: as is 1.28Mg/L, Al is 0.34Mg/L, Ca is 0.58Mg/L, Fe is 0.49Mg/L, Mg is 0.42Mg/L, Pb is 0.41Mg/L, other substances are trace or not detected, which indicates that the arsenical is fully fixed after the tailings are comprehensively treated, auxiliary materials are added in the process of preparing the filling material, the strength of the filling material can be improved, but the strength requirement of the prepared filling material is less than that of a common building material, so that little or no addition can be considered in the actual production to save the cost, the filling material belongs to common solid wastes, and the piling treatment or the mine filling are feasible and safe.
The multifunctional water-soluble high molecular polymer also comprises at least one of polyacrylamide, polyacrylic acid, alkali-added hydrolysate of the polyacrylamide, acrylamide graft copolymer, amphoteric polyacrylamide polymer, quaternized polyacrylamide or styrene sulfonate, lignosulfonate, acrylic acid, methacrylic acid and other copolymers; the weight ratio of the auxiliary materials contained in the filling material is not limited to 0-5%, and 0% or 0.1% or 0.2% or 0.3% or 0.4% … … or 4.8% or 4.9% or 5.0% is also included.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (5)
1. The comprehensive treatment method of the arsenic-containing tailings comprises the steps of sedimentation, wheel milling, digestion, repeated wheel milling, maintenance and backfilling, and is characterized in that: in the sedimentation step, a multifunctional water-soluble high-molecular polymer and a coagulant are adopted to carry out sedimentation treatment on the arsenic-containing tailings; the weight ratio of the arsenic-containing tailings, the multifunctional water-soluble high polymer and the coagulant is 8-11: 7-8: 0.6;
the multifunctional water-soluble high molecular polymer comprises polyacrylamide, polyacrylic acid, an alkali-added hydrolysate of the polyacrylamide, and an acrylamide grafted copolymer;
the coagulant contains dimethylacetamide and p-aminobenzoic acid, wherein the weight ratio of dimethylacetamide to p-aminobenzoic acid is 7-9: 4;
the settling step specifically comprises: adding a high molecular compound and a coagulant into arsenic-containing tailings according to a weight ratio, feeding the arsenic-containing tailings into a concentration tank, stirring the arsenic-containing tailings for 35 to 45 minutes under the condition that the stirring intensity is 165 to 175r/min, and then, working at a pressure of 5 to 9kg/cm2Performing filter pressing for 35-45 min under the condition of (1), and controlling the water content of a filter cake to be 16-20% to obtain concentrated ore pulp;
the repeated wheel milling step is as follows: adding 5-15 parts by weight of a consolidation agent, 0.03-0.3 part by weight of a water reducing agent and 0.04-0.2 part by weight of a cementing material into the digestion material, and then sending the digestion material into a wheel mill for repeated grinding and mixing for 5-15 min to obtain a filling material, wherein the water content of the mixture of the raw materials is controlled to be 10-17%;
the consolidating agent is a hydraulic cementing material;
the cementing material comprises resin, polyamide-imide and polyimide;
the arsenic leaching concentration of the filler obtained by comprehensively treating the arsenic-containing tailings is less than 2.5 mg/L.
2. The integrated treatment method for arsenic-containing tailings as claimed in claim 1, wherein the integrated treatment method comprises the following steps: the wheel milling step is as follows: and (3) feeding the concentrated ore pulp into a wheel mill, adding 10-18 parts by weight of industrial waste residues, 0.5-2.5 parts by weight of F14 exciting agent and 0.5-5 parts by weight of heavy metal stabilizer, and grinding and mixing for 5-15 min to obtain a mixture.
3. The integrated treatment method for arsenic-containing tailings as claimed in claim 1, wherein the integrated treatment method comprises the following steps: the digestion step is as follows: and (3) feeding the mixture into a continuous digestion bin for material digestion, wherein the digestion temperature is 40-70 ℃, and the digestion time is 2-4 hours, so as to obtain a digestion material.
4. The integrated treatment method for arsenic-containing tailings as claimed in claim 1, wherein the integrated treatment method comprises the following steps: the maintenance step is as follows: placing the filling material into a curing room, and naturally pre-curing for 36-60 h when the indoor temperature is higher than 10 ℃; introducing hot air at the temperature of less than 10 ℃, and precuring for 4-10 h at the temperature of 50-70 ℃; after precuring, hot air circulation is carried out, autoclaved curing is carried out, the temperature is increased to the working temperature within 2.5 hours, the autoclaved working temperature is controlled to be 174-194 ℃, and the pressure is controlled to be 0.8-1.3 MPa; and then keeping the temperature for 6-8 h, and cooling to 60-80 ℃.
5. The integrated treatment method for arsenic-containing tailings as claimed in claim 1, wherein the integrated treatment method comprises the following steps: the backfilling step is as follows: and (4) the filling materials are conveyed through a pipeline or are piled to a tailing pond in a dumping mode.
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| CA2378721A1 (en) * | 2002-03-22 | 2003-09-22 | Nichromet Extraction Inc. | Metals recovery from serpentine ores |
| CN1621159A (en) * | 2004-12-28 | 2005-06-01 | 中国铝业股份有限公司 | Flotation gangue subsidence method of alumyte |
| CN104071953A (en) * | 2014-07-16 | 2014-10-01 | 长春黄金研究院 | Cyanide-containing wastewater treating method for gold mine |
| CN107488019A (en) * | 2017-09-12 | 2017-12-19 | 宁波纯恒固废科技有限公司 | A kind of non-sintered gold tailings brick and its preparation technology |
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| CA2378721A1 (en) * | 2002-03-22 | 2003-09-22 | Nichromet Extraction Inc. | Metals recovery from serpentine ores |
| CN1621159A (en) * | 2004-12-28 | 2005-06-01 | 中国铝业股份有限公司 | Flotation gangue subsidence method of alumyte |
| CN104071953A (en) * | 2014-07-16 | 2014-10-01 | 长春黄金研究院 | Cyanide-containing wastewater treating method for gold mine |
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