WO2022160711A1 - 一种用于固化尾矿中重金属离子的胶凝剂及其使用方法 - Google Patents

一种用于固化尾矿中重金属离子的胶凝剂及其使用方法 Download PDF

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WO2022160711A1
WO2022160711A1 PCT/CN2021/115999 CN2021115999W WO2022160711A1 WO 2022160711 A1 WO2022160711 A1 WO 2022160711A1 CN 2021115999 W CN2021115999 W CN 2021115999W WO 2022160711 A1 WO2022160711 A1 WO 2022160711A1
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tailings
heavy metal
metal ions
chelating
gelling agent
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PCT/CN2021/115999
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English (en)
French (fr)
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杨晓军
徐修平
华绍广
刘龙
于先坤
Original Assignee
中钢集团马鞍山矿山研究总院股份有限公司
华唯金属矿产资源高效循环利用国家工程研究中心有限公司
中钢集团马鞍山矿院工程勘察设计有限公司
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Publication of WO2022160711A1 publication Critical patent/WO2022160711A1/zh

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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
    • C04B28/14—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 containing calcium sulfate cements
    • C04B28/141—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 containing calcium sulfate cements containing dihydrated gypsum before the final hardening step, e.g. forming a dihydrated gypsum product followed by a de- and rehydration step
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C04B18/142—Steelmaking slags, converter slags
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • 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
    • C04B28/14—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 containing calcium sulfate cements
    • C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
    • 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
    • C04B28/14—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 containing calcium sulfate cements
    • C04B28/16—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 containing calcium sulfate cements containing anhydrite, e.g. Keene's cement
    • 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
    • C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
    • 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
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention belongs to the technical field of solid waste cementitious material preparation, and in particular relates to a gelling agent for solidifying heavy metal ions in tailings, which can be used for solidifying and stabilizing heavy metal ions in tailings filling, and can also be used in tailings drying. It is widely used in the solidification and stabilization of heavy metal ions in heaps and metallurgical slag fields, especially for the solidification and stabilization of tailings containing harmful elements of Pb, Cd, Zn, Mn, and S.
  • the backfill mining method is to backfill the waste rock produced by mining and/or the tailings produced by beneficiation into the goaf for cementation and solidification.
  • my country's environmental protection requirements for mineral resources development are getting higher and higher and mineral resources are decreasing day by day, filling mining method has become the main method of underground mining.
  • the cementitious material which is an important raw material for filling, has been developed from cement used for graded filling to a special cementing material with water slag micropowder as the main component, which solves the problem that cement is difficult to cement full tailings or the strength is too low, and makes full tailing filling possible. Promote the application.
  • the Chinese authorized patent application 202010772265.9 discloses a tailings-based cementitious material and a preparation method thereof.
  • the tailings raw material is dried and then subjected to mechanical ball milling activation treatment, thermal activation treatment and chemical agent activation treatment in sequence to obtain tailings-based cementitious material.
  • the method activates the tailings through the combined excitation method of mechanical activation, thermal activation and chemical activation, and utilizes its potential pozzolanic activity to obtain a gelling material with good gelling performance.
  • the compressive strength of the gel material after consolidation is The highest can reach 10MPa.
  • the production process of the cementitious material is complicated, the production cost is high, and the market competitiveness is low.
  • FIG. 102924005A Another example is Chinese patent application CN102924005A, which discloses a method for using industrial waste slag such as steel slag and water-quenched blast furnace slag as main raw materials to produce a mine cemented filling material with a micro-expansion effect. 400-800m2/L, plus 0.5%-1% water reducing agent. Under the conditions of filling concentration of 75% and lime-sand ratio of 1:4, the strength is about 12MPa in 28 days, with high strength and good performance.
  • industrial waste slag such as steel slag and water-quenched blast furnace slag
  • 400-800m2/L plus 0.5%-1% water reducing agent.
  • the strength is about 12MPa in 28 days, with high strength and good performance.
  • the disadvantage is that the filling concentration is as high as 75%, and the concentration equipment of the existing mine filling station cannot reach such a high concentration in industrial large-scale production, and the lime-sand ratio is as high as 1:4, the amount of cementitious materials used is large, and the cost of use is high. .
  • the object of the present invention is to provide a method for solidifying heavy metal ions in tailings without considering the problems of high production cost, large amount of use, high use cost and solidification and stabilization of heavy metals in tailings in the prior art.
  • Gelling agent used in tailings filling, tailings dry heaping or heavy metal pollution control in metallurgical dressing and smelting slag field, not only has excellent cementing performance, but also strengthens anti-carbonation and anti-acid hydrolysis through various functions such as chelation. It can maintain the stability of solidified heavy metal ions for a long time and avoid the migration of heavy metal ions.
  • Another object of the present invention is to provide a method of using a gelling agent for solidifying heavy metal ions in tailings.
  • a gelling agent for solidifying heavy metal ions in tailings of the present invention adopts the following technical solutions:
  • the present invention is a gelling agent for solidifying heavy metal ions in tailings.
  • the mass percentage of each component in the raw material is: 0.25-0.7% of a chelating scavenger, 0.15-0.3% of a chelating accelerator, and chelating early strength.
  • the amount of the three complexing early-strength agents accounts for 0.8-1.4% of the total mass of each component in the raw material; the preparation process is as follows;
  • the mass percentage content of each component in the raw material is preferably: 0.3-0.6% of chelating scavenger, 0.16-0.26% of chelating accelerator, 0.35-0.6% of complex early-strength agent, 2-6% of lime, 0-0.6% of cement 10%, 8-20% gypsum, 0-15% steel slag powder, 65-80% slag powder.
  • Described chelating scavenger is dithiocarbamate, can be sodium dimethyl dithiocarbamate, sodium diethyl dithiocarbamate (abbreviated as DDTC), sodium dibutyl dithiocarbamate (abbreviated as sodium dithiocarbamate). SDBC)), sodium diisobutyl dithiocarbamate, sodium dipentyl dithiocarbamate, any one or two or more compounds.
  • the chelating accelerator is a dithiocarbamate star-shaped hyperbranched polymer, preferably trimethylolpropane triacrylate core dithiocarboxylate star-shaped hyperbranched polymer (TMPTA/ADA-9CSSM), See patent CN201410520218.X for this substance.
  • TMPTA/ADA-9CSSM trimethylolpropane triacrylate core dithiocarboxylate star-shaped hyperbranched polymer
  • the chelating scavenger reacts with heavy metal ions to form water-insoluble heavy metal chelates with good acid and alkali resistance.
  • the polymer is slightly soluble in water, and is less involved in the formation of heavy metal chelates in the early stage, but is evenly distributed in the gel. Release, the released heavy metal ions react with the chelating scavenger to generate more stable heavy metal chelates to avoid the migration of heavy metal ions.
  • the complex early-strength agent is calcium acetate, the purity of calcium acetate is greater than or equal to 95%, and the particle size is less than or equal to 0.076mm.
  • Calcium acetate is calcium acetate monohydrate or calcium acetate anhydrous. Acetate is a good complex ion, and forms a water-soluble complex with various heavy metal ions, and the complex reacts with the boiled scavenger to form a stable , Water-insoluble heavy metal chelate; at the same time, calcium acetate promotes the hydration reaction of tricalcium silicate, which is conducive to the formation of ettringite and improves the early strength of the filling.
  • lime is used as the alkali activator, the mass content of effective calcium in the lime is ⁇ 90%, and the particle size is ⁇ 0.076mm.
  • the lime reacts with water first, which can change the water content between the particles, and the calcium hydroxide produced by the reaction has a strong Alkaline, can destroy the surface of SiO 2 and Al 2 O 3 particles, promote the hydration reaction and pozzolanic reaction of slag micropowder and steel slag micropowder, Ca 2+ can react with Al 3+ , SO 4 2- to form ettringite, which forms Early strength;
  • the cement is ordinary Portland cement, with a grade of ⁇ 425#, which has good self-hydration reaction performance, cementing and solidifying heavy metals, and heavy metal ions can enter the crystal grid through ion exchange, and the hydration reaction produces
  • the alkaline substance further activates the reactivity of the slag micro-powder and the steel slag micro-powder;
  • the cement is ordinary
  • the steel slag micropowder is the micropowder with a specific surface area ⁇ 420m 2 /L by grinding the steel slag. Longer strength growth period can inhibit the reaction of alkali aggregates, and has the characteristics of compactness and sulfate resistance; the slag micropowder is water-quenched slag powder ground into micropowder with a specific surface area ⁇ 390m 2 /L, which is the slag that has been subjected to slag processing.
  • the activator used in the present invention is gypsum, generally selected from natural dihydrate gypsum, hemihydrate gypsum or anhydrite, a mixture of any two or three, or desulfurized gypsum dried at 110°C to 120°C, Purity ⁇ 90%.
  • a method of using a gelling agent for solidifying heavy metal ions in tailings of the present invention is as follows: in the filling of underground mine tailings, adding a gelling agent C for solidifying heavy metal ions in tailings into tailings slurry, The mass concentration of the tailings slurry is controlled between 60-72%, and the ratio of lime to sand is controlled within the range of 1:7-1:10.
  • the optimized process parameters are as follows: the mass concentration of the tailings slurry is controlled between 62-68%, and the lime-sand ratio is controlled within the range of 1:8-1:9.
  • a gelling agent for solidifying heavy metal ions in tailings of the present invention Compared with the prior art, a gelling agent for solidifying heavy metal ions in tailings of the present invention and a method for using the same have the following beneficial effects:
  • the gelling agent of the heavy metal ions in the solidified tailings of the present invention can realize the combination of full tail cementation and filling with heavy metal solidification and stabilization, and the targeted chemical passivation technology is adopted to strengthen the effects of heavy metal solidification and stabilization, which can not only satisfy the The strength of the backfill is required, and it can solidify and stabilize the heavy metal ions in the tailings;
  • the present invention adopts a more stable chelating agent, and the generated heavy metal chelating compound has strong acid and alkali shock resistance, and PH ⁇ 2 can exist stably;
  • the slag micropowder and/or the slag micropowder form a more compact filling body, which has strong resistance to carbonization and sulfate corrosion;
  • the raw material of the gelling agent of the heavy metal ion in the solidified tailings of the present invention is basically industrial solid waste, the source of raw materials is wide, the preparation process is simple, the energy consumption is low, the carbon emission is low, and the demand for the product is large, which is especially suitable for metallurgical mines. It is an urgently needed cementitious material for tailings filling of non-ferrous metal mines, which can bring better economic, social and environmental benefits.
  • the gelling agent developed by the present invention for solidifying heavy metal ions in tailings is used in tailings filling engineering applications under the condition of 60-72% tailings concentration, which is the current underground mine filling It is widely used, does not require special concentration equipment, and is easy to use.
  • the gelling agent developed by the present invention for solidifying heavy metal ions in tailings is used in tailings filling engineering, and the ratio of lime to sand is in the range of 1:8 to 1:9, and the amount of gelling agent used is relatively low. , the use of low cost.
  • a gelling agent for solidifying heavy metal ions in tailings of the present invention is formed by mixing the raw materials of the following components in proportion, and the mass percentages of the components in the raw materials are:
  • the process is: measuring the chelating scavenger, chelating accelerator, and complex early-strength agent according to the mass ratio, stirring evenly to prepare mixture M, and then mixing mixture M with alkali activator, cement, activator, steel slag micropowder, slag
  • the micropowder is mixed and homogenized to prepare the gelling agent C of the present invention for solidifying heavy metal ions in tailings.
  • the chelating scavenger adopts sodium diethyldithiocarbamate (abbreviation: DDTC)
  • the chelating accelerator adopts trimethylolpropane triacrylate core dithiocarboxylate star hyperbranched polymerization (abbreviation: TMPTA /ADA-9CSSM)
  • calcium acetate is used as complex early strength agent
  • quicklime is used as alkali activator
  • dihydrate gypsum is used as activator.
  • the purity of calcium acetate is greater than or equal to 95%, and the particle size is less than or equal to 0.076mm; the mass content of effective calcium in the quicklime is greater than or equal to 90%, and the particle size is less than or equal to 0.076mm; the cement is ordinary Portland cement, with a grade of greater than or equal to 425#;
  • the micropowder with specific surface area ⁇ 420m 2 /L; the slag micropowder is water-quenched slag pulverized into micropowder with specific surface area ⁇ 390m 2 /L.
  • the chelating scavenger, chelating accelerator and early-strength complexing agent are statically weighed according to 0.25-0.7%, 0.15-0.3%, 0.2-0.6% of the total weight, and mixed to make Obtain mixture A, control the weight of mixture A to account for 0.8-1.5% of the total weight of the raw materials; then mix and homogenize mixture A with alkali activator, cement, activator, steel slag micropowder, and slag micropowder to prepare the present invention for use in A gelling agent that solidifies heavy metal ions in tailings.
  • the gelling agent C of the present invention for solidifying heavy metal ions in tailings is mixed uniformly with tailings slurry with a certain moisture content in a certain proportion to obtain a slurry used in experiments similar to filling slurry.
  • the mixed slurry was poured into a trial mold of 70.7 ⁇ 70.7 ⁇ 70.7. After demoulding, under the conditions of temperature 20 ⁇ 1°C, humidity 90% ⁇ 5%, carry out curing, The uniaxial compressive strength test and heavy metal leaching test were carried out in different curing periods of 3 days, 7 days and 28 days.
  • the gelling agent C used to solidify heavy metal ions in tailings is added to the tailings slurry, and the mass concentration of the tailings slurry is controlled at 60-72 %, the lime-sand ratio is controlled in the range of 1:7 to 1:10.
  • the mass concentration of tailings slurry is generally around 65%; the lime-sand ratio is determined by experiments according to tailings particle size and tailings slurry concentration.
  • the lime-sand ratio is generally in the range of 1:9 to 1:10; for high tailings slurry concentration and coarse tailings particle size, the lime-sand ratio is generally in the range of 1:7 to 1:8.
  • TMPTA/ADA-9CSSM is represented by TM.
  • the gelling agent developed by the invention for solidifying heavy metal ions in tailings has been industrially tested in a lead-zinc mine tailings mining and filling project.
  • the tailings are filled and solidified for 28 days and sampled.
  • the Pb, Cd, Zn, Cd, and As in the leaching solution were 0.012mg/L, 0.0042mg/L, 0.18mg/L, 0.005mg/L, 0.09mg/L, respectively. It is lower than the standard limit of hazardous waste leaching toxicity identification, and has achieved unexpected technical results.

Abstract

本发明公开了一种用于固化尾矿中重金属离子的胶凝剂及其使用方法，原料中各组份的质量百分含量为：螯合捕捉剂0.25～0.7％，螯合促进剂0.15～0.3％，络合早强剂0.2～0.6％，石灰1～7％，水泥0～10％，石膏8～20％，钢渣微粉0～20％，矿渣微粉50～82％。先将螯合捕捉剂螯合促进剂络合早强剂混合均匀，再与其它组份混合均匀。本发明制备的胶凝剂不仅通过水化反应胶结全尾矿，实现充填开采，还通过浸出、螯合、包裹、化学吸附、化学钝化和离子替代等多种作用协同固化尾矿中重金属离子，长期保持固化的稳定性，特别适用于重金属离子含量高的全尾矿胶结充填，显著降低尾矿充填后充填体重金属离子含量高的环境风险。

Description

一种用于固化尾矿中重金属离子的胶凝剂及其使用方法 技术领域
本发明属于固废胶凝材料制备技术流域，具体涉及一种用于固化尾矿中重金属离子的胶凝剂，可在尾矿充填中用于固化、稳定化重金属离子，也可以在尾矿干堆及冶金选冶渣场重金属离子固化、稳定化中广泛应用，对固化、稳定化含Pb、Cd、Zn、Mn、S有害元素的尾矿尤为适用。
背景技术
矿产资源的开发是人类和社会不断发展的重要途径之一，随着矿产资源的不断开采，金属尾矿对生态环境造成的污染和破坏已经成为一个全球关注的重要问题，特别是尾矿中的重金属污染一直是个亟待解决的严峻问题，尾矿中的重金属在自然环境件下被不断的溶出进入地表水、地下水以及土壤中，对生态环境造成不可逆转的污染破坏，同时对人类健康造成巨大的威胁。由于重金属污染具有潜伏性、不可逆性和长期性以及影响后果严重等特点，因而尾矿重金属污染的研究与治理受到了国内外生态、环境科学领域的高度重视。
充填采矿法是将采矿产生的废石和/或选矿产生的尾矿回填到采空区胶结固化，具有损失率小、贫化率低、控制地压、保护地表、消除尾矿库等优点,在我国对矿产资源开发环保要求越来越高和矿产资源日趋减少的情况，充填采矿法已经成为地下矿山开采的主要方法。作为充填重要原料的胶凝材料已经从分级充填使用的水泥发展成以水渣微粉为主要成分的专用胶凝材料，解决了水泥难以胶结全尾矿或强度太低的问题，使得全尾充填得以推广应用。
如中国授权专利申请202010772265.9公开了一种尾矿基胶凝材料及其制备方法。该方法是将尾矿原料经过干燥后，依次进行机械 球磨活化处理、热活化处理以及化学药剂活化处理，即得尾矿基胶凝材料。该方法通过机械活化、热活化以及化学活化联合激发方法对尾矿进行活化，利用其潜在火山灰活性，获得一种胶凝性能较好的胶凝材料，该凝胶材料固结后的抗压强度最高可以达到10MPa。但该胶凝材料生产工艺复杂，生产成本高，市场竞争力低。
又如中国专利申请CN102924005A公开了一种利用钢渣、水淬高炉矿渣等工业废渣为主要原料生产具有微膨胀效应的矿山胶结充填材料的方法，其将钢渣、矿渣、石膏等原材料粉磨到比表面积400-800㎡/L，外加0.5％-1％减水剂。在充填浓度75％，灰砂比1:4条件下，达到28天强度12MPa左右，强度高，性能好。其不足之处在于充填浓度高达75％，现有矿山充填站浓缩设备在工业大规模生产中无法达到这么高的浓度，且灰砂比高达1:4，胶凝材料使用量大，使用成本高。
这些专利的应用都很好的解决了充填强度、固废利用等问题，但对尾矿中重金属离子的固化未有说明。充填胶凝材料一般在碱性条件下进行水化反应、胶结固化尾矿，通过反应会产生水化硅酸钙、钙矾石和熟石灰等物质，水化硅酸钙成网状或蜂巢状结构，具有很大的比表面积，可吸附溶解态的重金属离子；钙矾石呈针状或柱状结构，当以离子交换的形式使其组分发生变化时，钙矾石的结构不发生变化，其离子交换可发生在Ca 2+和Al 3+的位置上，Ca 2+可以被许多二价阳离子如：Pb 2+、Zn 2+、Cr 3+和Cd 2+等取代；碱性条件下重金属离子易产生难溶于水的氢氧化物和硫化物沉淀，从而很好的固化了尾矿中的重金属。
但当充填体受硫酸盐侵蚀、碳化和硫杆菌氧化等作用会破坏C-S-H和钙矾石结构，会导致重金属离子重新释放出来。随着国家环保要求的进一步提高，充填体中重金属离子重新释放可能会导致超 出相关标准、法规的问题，影响企业的生存和发展；此外，充填体中重金属离子迁移可能还会带来潜在的环境问题。
发明内容
本发明的目的就是针对现有技术存在的生产成本高、使用量大、使用成本高且未考虑对尾矿中重金属固化、稳定化的问题，而提供一种用于固化尾矿中重金属离子的胶凝剂，用于尾矿充填、尾矿干堆或冶金选冶渣场重金属污染治理中，不仅具有优良的胶结性能，还针对性地通过螯合等多种作用强化抗碳化、抗酸解能力，长久保持固化重金属离子的稳定性，避免重金属离子迁移。
本发明的另一个目的是提供一种用于固化尾矿中重金属离子的胶凝剂的使用方法。
为实现本发明的上述目的，本发明一种用于固化尾矿中重金属离子的胶凝剂采用以下技术方案：
本发明一种用于固化尾矿中重金属离子的胶凝剂，原料中各组份质量百分含量为：螯合捕捉剂0.25～0.7％，螯合促进剂0.15～0.3％，络合早强剂0.2～0.6％，石灰1～7％，水泥0～10％，石膏8～20％，钢渣微粉0～20％，矿渣微粉50～82％；所述螯合捕捉剂、螯合促进剂、络合早强剂三者的量占原料中各组份总质量的0.8～1.4％；其制备工艺为；
将螯合捕捉剂、螯合促进剂、络合早强剂按质量配比进行计量、搅拌均匀制备混合物M，再将混合物M与碱激活剂、水泥、激活剂、钢渣微粉、矿渣微粉进行混合、均化，制备出用于固化尾矿中重金属离子的胶凝剂C。
原料中各组份的质量百分含量优选为：螯合捕捉剂0.3～0.6％，螯合促进剂0.16～0.26％，络合早强剂0.35～0.6％，石灰2～6％，水泥0～10％，石膏8～20％，钢渣微粉0～15％，矿渣微粉65～80％。
所述的螯合捕捉剂为二硫代氨基甲酸盐，可以为二甲基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸钠(简称DDTC)、二丁基二硫代氨基甲酸钠(简称SDBC))、二异丁基二硫代氨基甲酸钠、二戊烷基二硫代氨基甲酸钠中的任意一种或两种及以上的化合物。
螯合促进剂为二硫代氨基甲酸盐星形超支化聚合物，以三羟甲基丙烷三丙烯酸酯芯二硫代羧酸盐星形超支化聚合(TMPTA/ADA-9CSSM)为优，该物质见专利CN201410520218.X。螯合捕捉剂与重金属离子反应，形成不溶于水的具备良好抗酸碱能力重金属螯合物。该聚合物微溶于水，早期较少参与重金属螯合物的形成，而均匀分布在胶凝体中，当胶凝体发生碳化或S氧化酸化后，胶凝体结构发生破坏，重金属离子重新释放，释放的重金属离子与螯合捕捉剂反应，生成更稳定的重金属螯合物，避免重金属离子的迁移。
所述的络合早强剂为醋酸钙，醋酸钙的纯度≥95％，粒度≤0.076mm。醋酸钙为一水醋酸钙或无水醋酸钙，醋酸根是良好的络合离子，与多种重金属离子形成溶于水的络合物，该络合物又与熬合捕捉剂反应，形成稳定、不溶于水的重金属螯合物；同时醋酸钙促进硅酸三钙水化反应，利于钙矾石形成，提高充填体的早期强度。
本发明选用石灰为碱激活剂，石灰中有效钙质量含量≥90％，粒度≤0.076mm，石灰首先与水反应，可改变颗粒之间含水量，反应产生的氢氧氢氧化钙具有较强的碱性，可破坏SiO 2和Al 2O 3颗粒表面，促进矿渣微粉和钢渣微粉发生水化反应和火山灰反应，Ca 2+可与AL 3+、SO 4 2-反应，生成钙矾石，形成早期强度；所述的水泥为普通硅酸盐水泥，标号≥425#，其具有良好的自水化反应性能，对重金属进行胶结固化，重金属离子可通过离子交换进入晶体网格，水化反应产生的碱性物质进一步激活矿渣微粉和钢渣微粉的反应活性；所述的水泥为普通硅酸盐水泥，标号≥425#。
所述的钢渣微粉为钢渣粉磨成比表面积≥420m 2/L的微粉，为钢渣经管磨粉磨生产的粉状物，是钢渣水泥的主要辅料，可以通过碱激活或硫酸盐激活，可提供更长的强度增长期，能抑制碱骨料反应，具有密实和抗硫酸盐侵蚀的特点；所述的矿渣微粉为水淬渣粉磨成比表面积≥390m 2/L的微粉，为矿渣经立磨或管磨粉磨生产的粉状物，其等级为S95或S105，是矿渣水泥的主要辅料，可碱激活或硫酸盐激活，具有较强活性，可提供适宜的早强和后期强度。
本发明采用的激活剂为石膏，一般选用天然二水石膏、半水石膏或无水石膏中的一种、任意两种或三种的混合物，或在110℃～120℃烘干的脱硫石膏，纯度≥90％。
本发明一种用于固化尾矿中重金属离子的胶凝剂的使用方法为：在地下矿山尾矿充填中，将用于固化尾矿中重金属离子的胶凝剂C加入到尾矿矿浆中，所述尾矿矿浆的质量浓度控制在60～72％之间，灰砂比控制在1:7～1：10范围。
其优化的工艺参数为：所述尾矿矿浆的质量浓度控制在62～68％之间，灰砂比控制在1:8～1：9范围。
与现有技术相比，本发明一种用于固化尾矿中重金属离子的胶凝剂及其使用方法具有如下有益效果：
(1)本发明固化尾矿中重金属离子的胶凝剂可以实现全尾胶结充填与重金属固化、稳定化相结合，针对性采用化学钝化技术，强化重金属固化、稳定化的效果，不仅可以满足充填体强度的要求，而且可以固化、稳定化尾矿中的重金属离子；
(2)本发明采用更加稳定的螯合剂，生成的重金属螯合物具有很强的耐酸碱冲击性能，PH≥2都可以稳定存在；
(3)矿渣微粉和/或矿渣微粉形成更加密实的充填体，具有较强抗碳化和抗硫酸盐侵蚀的能力；
(4)本发明固化尾矿中重金属离子的胶凝剂的原料基本上为工业固体废物，原料来源广，制备工艺简单，能耗低，无碳排放，产品的需求量大，是冶金矿山特别是有色金属矿山尾矿充填急需的胶凝材料，可以带来较好的经济效益、社会效益和环境效益。
(5)本发明研制出的一种用于固化尾矿中重金属离子的胶凝剂在尾矿充填工程应用中，在60～72％的尾矿浓度条件下使用，该浓度为目前地下矿山充填普遍采用，不需要特殊的浓缩设备，使用方便。
(6)本发明研制出的一种用于固化尾矿中重金属离子的胶凝剂在尾矿充填工程应用中，灰砂比在1:8～1：9范围，胶凝剂使用量较低，使用成本低。
具体实施方式
为描述本发明，下面结合实施例对本发明一种用于固化尾矿中重金属离子的胶凝剂及其使用方法做进一步详细说明。但本发明并不局限于实施例。
本发明一种用于固化尾矿中重金属离子的胶凝剂是由以下组份的原料按比例混合而成，原料中各组份的质量百分含量为：
螯合捕捉剂0.25～0.7％，螯合促进剂0.15～0.3％，络合早强剂0.2～0.6％，碱激活剂1～7％，水泥0～10％，激活剂8～20％，钢渣微粉0～20％，矿渣微粉50～82％；所述螯合捕捉剂、螯合促进剂、络合早强剂三者的量占原料中各组份总质量的0.8～1.4％；其制备工艺为；将螯合捕捉剂、螯合促进剂、络合早强剂按质量配比进行计量、搅拌均匀制备混合物M，再将混合物M与碱激活剂、水泥、激活剂、钢渣微粉、矿渣微粉进行混合、均化，制备出本发明用于固化尾矿中重金属离子的胶凝剂C。
其中：螯合捕捉剂采用二乙基二硫代氨基甲酸钠(简称：DDTC)，螯合促进剂采用三羟甲基丙烷三丙烯酸酯芯二硫代羧酸盐星形超支 化聚合(简称：TMPTA/ADA-9CSSM)，络合早强剂采用醋酸钙，碱激活剂采用生石灰，激活剂采用二水石膏。醋酸钙的纯度≥95％，粒度≤0.076mm；生石灰中有效钙质量含量≥90％，粒度≤0.076mm；所述的水泥为普通硅酸盐水泥，标号≥425#；钢渣微粉为钢渣粉磨成比表面积≥420m 2/L的微粉；矿渣微粉为水淬渣粉磨成比表面积≥390m 2/L的微粉。
在实际应用中，先将螯合捕捉剂、螯合促进剂和早强络合剂按总重量的0.25～0.7％、0.15～0.3％、0.2～0.6％进行静态称取，并进行混匀制得混合物A，控制混合物A重量占原料总重量的0.8～1.5％；再将混合物A与碱激活剂、水泥、激活剂、钢渣微粉、矿渣微粉进行混合、均化，即制备出本发明用于固化尾矿中重金属离子的胶凝剂。
在实验室研究中，将本发明用于固化尾矿中重金属离子的胶凝剂C按一定比例与一定含水率的尾矿浆混合均匀，制得类似充填料浆的实验所用料浆。按照国标GB/T17671-1999，将混匀后的料浆浇筑成70.7×70.7×70.7的试模，脱模后，在温度20±1℃、湿度90％±5％的条件下，进行养护，并在3天、7天和28天不同养护期进行单轴抗压强度检测和重金属浸出检测。
在地下矿山尾矿充填中，在地下矿山尾矿充填中，将用于固化尾矿中重金属离子的胶凝剂C加入到尾矿矿浆中，所述尾矿矿浆的质量浓度控制在60～72％之间，灰砂比控制在1:7～1：10范围。尾矿矿浆的质量浓度一般在65％左右；灰砂比根据尾矿粒度、尾矿矿浆浓度，通过试验确定。尾矿浆浓度低、尾矿粒度细的，灰砂比一般在1:9～1：10范围；尾矿浆浓度高、尾矿粒度粗的，灰砂比一般在1:7～1：8范围。
将进行过单轴抗压强度检测的试块粉碎，以硫酸溶液为浸提剂，将放入浸提试样的去离子水PH值调到2±0.05，按照《固体废物浸 出毒性浸出方法硫酸硝酸法(HJT299-2007)》的浸出程序对充填体进行重金属浸出检测。试验结果如实施例1～实施例6。
从实施例1～实施例6可以看出，试验样品按照按照《固体废物浸出毒性浸出方法硫酸硝酸法(HJT299-2007)》进行浸出后，浸出液中Pb、Cu、Zn、Cd、As等远低于排放标准限值要求。实施例3～实施例6的中，TMPTA/ADA-9CSSM用TM表示。
实施例1
Figure PCTCN2021115999-appb-000001
实施例2
Figure PCTCN2021115999-appb-000002
实施例3
Figure PCTCN2021115999-appb-000003
Figure PCTCN2021115999-appb-000004
实施例4
Figure PCTCN2021115999-appb-000005
实施例5
Figure PCTCN2021115999-appb-000006
Figure PCTCN2021115999-appb-000007
实施例6
Figure PCTCN2021115999-appb-000008
本发明研制的用于固化尾矿中重金属离子的胶凝剂已经在某铅锌矿尾矿采矿充填工程中进行工业试验，尾矿充填固化28天取样，采用《固体废物浸出毒性浸出方法硫酸硝酸法(HJT299-2007)》进行浸出后，浸出液中Pb、Cd、Zn、Cd、As分别为0.012mg/L、0.0042mg/L、0.18mg/L、0.005mg/L、0.09mg/L，远低于危险废物浸出毒性鉴别标准限值，取得了意想不到的技术效果。

Claims (9)

  1. 一种用于固化尾矿中重金属离子的胶凝剂，其特征在于原料中各组份质量百分含量为：螯合捕捉剂0.25～0.7％，螯合促进剂0.15～0.3％，络合早强剂0.2～0.6％，石灰1～7％，水泥0～10％，石膏8～20％，钢渣微粉0～20％，矿渣微粉50～82％；所述螯合捕捉剂、螯合促进剂、络合早强剂三者的量占原料中各组份总质量的0.8～1.4％；其制备工艺为；
    将螯合捕捉剂、螯合促进剂、络合早强剂按质量配比进行计量、搅拌均匀制备混合物M，再将混合物M与碱激活剂、水泥、激活剂、钢渣微粉、矿渣微粉进行混合、均化，制备出用于固化尾矿中重金属离子的胶凝剂C。
  2. 如权利要求1所述的一种用于固化尾矿中重金属离子的胶凝剂，其特征在于原料中各组份质量百分含量为：螯合捕捉剂0.3～0.6％，螯合促进剂0.16～0.26％，络合早强剂0.35～0.6％，石灰2～6％，水泥0～10％，石膏8～20％，钢渣微粉0～15％，矿渣微粉65～80％。
  3. 如权利要求1或2所述的一种用于固化尾矿中重金属离子的胶凝剂，其特征在于：所述的螯合捕捉剂为二硫代氨基甲酸盐，所述的螯合促进剂为二硫代氨基甲酸盐星形超支化聚合物。
  4. 如权利要求3所述的一种用于固化尾矿中重金属离子的胶凝剂，其特征在于：所述的络合早强剂为醋酸钙，醋酸钙的纯度≥95％，粒度≤0.076mm。
  5. 如权利要求4所述的一种用于固化尾矿中重金属离子的胶凝剂，其特征在于：石灰中有效钙质量含量≥90％，粒度≤0.076mm；所述的水泥为普通硅酸盐水泥，标号≥425#。
  6. 如权利要求5所述的一种用于固化尾矿中重金属离子的胶凝剂，其特征在于：所述的钢渣微粉为钢渣粉磨成比表面积≥420m 2/L的微粉；所述的矿渣微粉为水淬渣粉磨成比表面积≥390m 2/L的微粉。
  7. 如权利要求6所述的一种用于固化尾矿中重金属离子的胶凝剂，其特征在于：所述的石膏为天然二水石膏、半水石膏或无水石膏中的一种、任意两种或三种的混合物，或在110℃～120℃烘干的脱硫石膏，纯度≥90％。
  8. 如权利要求7所述的一种用于固化尾矿中重金属离子的胶凝剂的使用方法，其特征在于：在地下矿山尾矿充填中，将含重金属尾矿充填用胶凝剂C加入到尾矿矿浆中，所述尾矿矿浆的质量浓度控制在60～72％之间，灰砂比控制在1:7～1：10范围。
  9. 如权利要求8所述的一种用于固化尾矿中重金属离子的胶凝剂的使用方法，其特征在于：所述尾矿矿浆的质量浓度控制在62～68％之间，灰砂比控制在1:8～1：9范围。
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