WO2022057104A1 - Method for preparing mine filling material using heavy metal tailings cemented by solid wastes in steel industry - Google Patents

Method for preparing mine filling material using heavy metal tailings cemented by solid wastes in steel industry Download PDF

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Publication number
WO2022057104A1
WO2022057104A1 PCT/CN2020/134298 CN2020134298W WO2022057104A1 WO 2022057104 A1 WO2022057104 A1 WO 2022057104A1 CN 2020134298 W CN2020134298 W CN 2020134298W WO 2022057104 A1 WO2022057104 A1 WO 2022057104A1
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Prior art keywords
heavy metal
tailings
mine filling
cementing
metal tailings
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PCT/CN2020/134298
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French (fr)
Chinese (zh)
Inventor
熊敬超
姜明明
郭华军
宋自新
邵雁
刘子豪
刘颖
劳德平
胡国锋
向浩
陈堃
覃慧
史记熙
蒋庆肯
杨振
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中冶南方都市环保工程技术股份有限公司
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Publication of WO2022057104A1 publication Critical patent/WO2022057104A1/en

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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
    • C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
    • 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
    • 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 relates to the resource utilization of industrial solid waste in the iron and steel industry, in particular to a method for preparing mine filling by cementing the solid waste in the iron and steel industry with heavy metal tailings.
  • Steel slag is an industrial waste slag produced in the steelmaking process of the iron and steel industry.
  • the steel slag is limited in its resource utilization due to factors such as low gelling activity, poor grindability, and poor volume stability.
  • my country's steel slag output reached 120 million tons.
  • the stockpile is over 1 billion tons, and the comprehensive utilization rate of steel slag is about 25%.
  • Desulfurized ash is an industrial solid waste produced by the semi - dry flue gas desulfurization technology in the iron and steel industry . 2 O) and ammonium salts, etc., CaSO 3 is easily oxidized to calcium sulfate (CaSO 4 ) in the oxidant environment, and its comprehensive utilization rate is low due to the unstable properties of desulfurized ash. Ash, occupying valuable land resources, causing serious environmental pollution.
  • Tailings is the raw ore that enters the concentrator and undergoes a series of processes such as crushing, grinding, and sorting, and the remaining parts that cannot be used for production are discharged in the form of slurry. , stacking takes up valuable land resources, and the heavy metals in the tailings penetrate into the surrounding soil, causing serious ecological environment pollution.
  • cement is the first cementing agent for mine filling.
  • the high price of cement increases the cost of mine filling materials and limits the large-scale utilization of tailings in the field of mine filling.
  • cement has poor solidification/stabilization effect of heavy metal tailings when cementing heavy metal tailings, resulting in low utilization of heavy metal tailings in the field of mine filling. Therefore, low preparation cost, high strength and good heavy metal solidification effect. Resource utilization is of great significance.
  • the object of the present invention is to overcome the defects of the prior art, and provides a method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry, replacing cement for cementing tailings as mine filling materials, reducing mine filling costs, and improving steel slag. , Desulfurization ash, tailings comprehensive utilization of bulk solid waste.
  • the present invention is realized in this way:
  • the invention provides a method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry, comprising the following steps:
  • the hydration activity of steel slag powder in the cement is low, and the activity of steel slag is stimulated under the action of alkali activator.
  • Steel slag and slag are hydrated to produce hydrated products such as calcium silicate hydrate (CSH) and calcium aluminate hydrate (CAH).
  • Calcium sulfate in ash acts as a sulfate activator, which further stimulates the hydration activity of steel slag and slag on the basis of alkali excitation, and generates needle-shaped and thin rod-shaped ettringite (AFt), which can interact with steel slag, slag and slag under the action of the activator.
  • Potentially active minerals in the slag react to form ettringite-like calcium chloroaluminate, calcium aluminum ferrite, calcium ferrite and other hydraulic minerals.
  • CSH is a network structure gel with good adsorption and cementation. CSH is wrapped on the surface of tailings particles to increase the cohesion between tailings particles.
  • the surface of CSH plays the role of fixing heavy metals; the alkali activator and calcium sulfate in the desulfurization ash can chemically react with heavy metals to form precipitation, reduce the toxicity of heavy metals, reduce the leaching rate of heavy metal ions, and have the effect of solidifying/stabilizing heavy metals.
  • Calcium sulfite in desulfurization ash is a good reducing agent, and highly toxic hexavalent chromium (Cr 6+ ) in heavy metal tailings is oxidizing, and can be converted into low-toxicity trivalent chromium (Cr 3+ ) under the action of calcium sulfite reducing agent At the same time, calcium sulfite is converted into calcium sulfate, and calcium sulfate participates in the hydration reaction to form needle-like or thin rod-like AFt minerals.
  • the desulfurized ash particles are fine and uniform.
  • the calcium sulfate and calcium sulfate hemihydrate contained in desulfurization ash the crystal structure is formed by the loss of crystal water with a diameter of Pores have a strong adsorption effect.
  • Heavy metals are adsorbed in the pores of gypsum crystals and fixed into dihydrate gypsum crystals, which play the role of solidifying and stabilizing heavy metals. Therefore, desulfurization ash acts as sulfate activator and reducing agent in heavy metal tailings cement. and adsorption of heavy metals.
  • the ettringite (AFt) mineral has a needle-like or thin rod-like structure, and overlaps with each other in the solid tailings to form a stable skeleton structure.
  • the ion exchange rate of AFt crystals and the heavy metal ions are ion-exchanged, and the heavy metal ions are fixed into the stable AFt minerals, which further reduces the leaching toxicity of heavy metals. Therefore, the cementing agent of the present invention has the characteristics of good heavy metal solidification/stabilization effect, high mechanical strength of the filling body and good fluidity in cementing the heavy metal tailings.
  • the gel material, alkali activator and activator are stirred and mixed evenly into the cementing agent bin; the tailings in the tailings bin first enter the stirring bin for uniform stirring, and the corresponding dispersant, heavy metal curing agent and binder are added into the stirring bin. Mix evenly, increase the contact between heavy metal metal curing agent and heavy metal in tailings under the action of dispersing agent; add cementing agent to tailings mixing silo through a flow meter, and stir evenly; empty area.
  • the weight proportion of each component in the gel material is: 40-55% of slag, 25-40% of steel slag, and 5-35% of desulfurized ash.
  • the weight ratio of the cementing agent of S1 and the heavy metal tailings after stirring by S2 in the mine filling is 1:6 to 1:5.
  • the remaining steel slag in S1 is ball-milled to prepare steel slag powder, the slag powder is ground into slag powder, and the steel slag powder and slag powder are sieved and mixed with desulfurized ash to make a gel material. .
  • the alkali activator is composed of one or more of calcium oxide, calcium hydroxide, calcium carbide slag, and caustic soda, and the dosage accounts for 1-5% of the weight of the cementitious material.
  • the dispersing agent is composed of one or more of sodium hexametaphosphate, sodium tripolyphosphate, trisodium phosphate, hydroxymethyl cellulose, wood calcium, sugar calcium, sodium lauryl sulfate, and the mixing amount accounts for the glue. 0.1 to 2% of the weight of the solidifying material.
  • the activator is made of one or more of calcium chloride, aluminum chloride, ferric chloride, aluminum sulfate, mirabilite, triethanolamine, sodium nitrite, water glass, calcium carbonate, calcium formate, calcium acetate and aluminum sulfate.
  • the dosage accounts for 0.5 to 5% of the weight of the cementitious material.
  • the binder is composed of one or more of polypropylene fibers and glass fibers, and the dosage accounts for 0.05-1% of the dry weight of the heavy metal tailings.
  • the heavy metal solidifying agent is composed of one or more of calcium phosphate slag, phosphogypsum, zeolite, silica fume, plant ash, modified bentonite and iron salt, and the dosage accounts for 0.2 to 3% of the dry weight of the heavy metal tailings. .
  • the cementitious materials in the heavy metal tailings cement are all derived from the waste slag of the iron and steel industry, which can improve the resource utilization of steel slag and desulfurized ash.
  • the raw materials of the cement are rich in source and low in price.
  • the steel slag and slag in the raw materials are simply ground, and the desulfurized ash is directly used without processing. Compared with cement, the production cost of cement can be significantly reduced.
  • the heavy metal curing agent and the cementing agent are fully in contact with the heavy metals in the tailings, and the binding agent and the heavy metal curing agent can improve the adsorption, precipitation and ion exchange of heavy metals.
  • the average value of the compressive strength of the three samples (the difference between the maximum and minimum values and the median value was less than 15%), and the central part of the broken sample was taken.
  • the toxic leaching solution of consolidated heavy metal tailings was prepared.
  • the concentration of heavy metals in the leachate was detected by coupled plasma mass spectrometry (ICP-MS).
  • the heavy metal tailings cement prepared by the present invention is used to consolidate the heavy metal tailings as a mine filling material.
  • the cement-sand ratio is 1:5
  • the cement consolidates the heavy metal tailings as a mine filling material.
  • the leaching concentration is lower than the index of underground class III water, and the leaching concentration of heavy metals gradually decreases with the increase of curing time, and the leaching concentration of heavy metals in the filling material at 28d is significantly lower than the limit of heavy metal in class III groundwater;
  • the 28d compressive strength distribution reaches 1.36MPa, 3.36MPa and 6.73MPa, and the 28d compressive strength of the backfill reaches 3MPa, which can meet the strength requirements of mine backfills in different parts. Therefore, the strength of the backfill body consolidated by the cement is much greater than that of mine backfill.
  • Body strength index the fluidity of the mine filling material is 276mm, and different filling methods have different indicators for the fluidity of the filling slurry.
  • the fluidity of the slurry is greater than or equal to 250mm, and the fluidity of the pumped filling slurry is greater than or equal to 180mm.
  • pumping filling will increase the filling cost, so the cementing agent prepared by the present invention consolidates the heavy metal tailings and is used for mine filling, which is conducive to realizing self-flow transportation and further reducing the filling cost.
  • the content of binder is 0.5% (accounting for the dry weight of heavy metal tailings), and the content of heavy metal curing agent is 0.9% (accounting for the dry weight of heavy metal tailings); , Stir the binder and heavy metal tailings evenly in the mixing bin, test the fluidity of the slurry with a fluidity test instrument, put the remaining slurry into a 70.7mm*70.7mm*70.7mm test mold, and put it into a cement standard curing box In order to ensure the accuracy of the data, the average compressive strength of the three samples (the difference between the maximum and minimum values and the median value) The difference is less than 15%), take the central part of the broken sample, prepare the toxic leaching solution of consolidated heavy metal tailings according to the requirements of "Solid Waste Leaching Toxicity Leaching Method - Sulfuric Acid and Nitric Acid Method" (HJT299-2007), adopt “Solid Waste Metal Element Determination Inductive Coupling”
  • the heavy metal tailings cement prepared by the present invention can consolidate the heavy metal tailings as a mine filling material when the cement-sand ratio is 1:6.
  • the heavy metal leaching concentration is lower than the underground Class III water index.
  • the leaching concentration of heavy metals in the consolidated heavy metal tailings filling gradually decreases, which meets the requirements for the leaching concentration of heavy metals in class III groundwater in the groundwater quality standard (GB/T14848-2017).
  • the 28d compressive strength distribution reaches 1.05MPa, 2.68MPa and 5.06MPa, and the 28d compressive strength of the filling body reaches 3MPa, which can meet the strength requirements of the mine filling body in different parts. Therefore, the cementing agent of the present invention is consolidated when the cement-sand ratio is 1:6.
  • the strength of the heavy metal tailings backfill is 1.68 times that of the mine backfill strength index; the fluidity of the mine backfill material is 267mm, and different backfilling methods have different indicators for the backfill fluidity. 250mm, the fluidity of the pumped filling slurry is ⁇ 180mm, but the pumped filling will increase the filling cost. Therefore, the cement prepared by the invention consolidates the heavy metal tailings and is used for mine filling, which is conducive to realizing self-flow transportation and further reducing the filling cost.
  • the content of binder is 1.0% (accounting for the dry weight of heavy metal tailings), and the content of heavy metal curing agent is 1.2% (accounting for the dry weight of heavy metal tailings); , Stir the binder and heavy metal tailings evenly in the mixing bin, test the fluidity of the slurry with a fluidity test instrument, put the remaining slurry into a 70.7mm*70.7mm*70.7mm test mold, and put it into a cement standard curing box In order to ensure the accuracy of the data, the average compressive strength of the three samples (the difference between the maximum and minimum values and the median value) The difference is less than 15%), take the central part of the broken sample, prepare the toxic leaching solution of consolidated heavy metal tailings according to the requirements of "Solid Waste Leaching Toxicity Leaching Method - Sulfuric Acid and Nitric Acid Method" (HJT299-2007), adopt “Solid Waste Metal Element Determination Inductive Coupling”
  • the heavy metal tailings cement prepared by the present invention consolidates the heavy metal tailings as a mine filling material when the ratio of cement to sand is 1:5, and the leaching concentration of heavy metals is lower than the underground class III water index when curing for 7d and 28d.
  • the leaching concentration of heavy metals shows a decreasing trend with the increase of curing age, which meets the requirements for leaching concentration of heavy metals in class III groundwater in the groundwater quality standard (GB/T14848-2017). It can reach 1.09MPa, 3.08MPa and 5.76MPa, and the 28d compressive strength of the backfill body reaches 3MPa, which can meet the strength requirements of mine backfill bodies in different parts.
  • the cementing agent of the present invention consolidates the heavy metal tailings backfill body when the cement-sand ratio is 1:5.
  • the strength is 1.92 times of the strength index of the mine filling body; the fluidity of the mine filling material is 265mm, and different filling methods have different indicators for the fluidity of the filling slurry.
  • the fluidity of the slurry is ⁇ 180mm, but pumping filling will increase the filling cost. Therefore, the cementing agent prepared by the present invention consolidates the heavy metal tailings and is used for mine filling, which is conducive to realizing self-flow transportation and further reducing the filling cost.
  • the present invention uses industrial solid wastes such as steel slag, desulfurization ash, tailings, etc., as gel materials to make cementing agent cementing heavy metal tailings as mine fillings, and carries out the treatment of solid wastes in the iron and steel industry.
  • the cementing agent prepared by the invention has the characteristics of good heavy metal solidification effect, high filling body strength and good filling material fluidity in consolidating heavy metal tailings.

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  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A method for preparing a mine filling material using heavy metal tailings cemented by solid wastes in steel industry, comprising the following steps: S1, using steel slag, desulfurization ash, and slag as a gel material, adding an alkali activator and an activating agent to the gel material, and performing uniform stirring to prepare a cementing agent; S2, adding a dispersing agent, a binder, and a heavy metal curing agent to the heavy metal tailings, and performing uniform stirring; and S3, uniformly stirring and mixing the cementing agent of S1 and the heavy metal tailings of S2 in a certain ratio to prepare the mine filling material. The heavy metal tailings cemented by the solid wastes in the steel industry are used as the mine filling material instead of cement-consolidated tailings, thereby reducing mine filling costs, increasing the comprehensive utilization amount of the bulk solid wastes of the steel slag, the desulfurization ash, and the tailings, and improving the mechanical strength of a mine filling body.

Description

钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法Method for preparing mine filling by cementing heavy metal tailings with solid waste in iron and steel industry 技术领域technical field
本发明涉及钢铁行业工业固体废物资源化利用，尤其涉及钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法。The invention relates to the resource utilization of industrial solid waste in the iron and steel industry, in particular to a method for preparing mine filling by cementing the solid waste in the iron and steel industry with heavy metal tailings.
背景技术Background technique
钢渣是钢铁行业在炼钢过程中产生的工业废渣，钢渣因胶凝活性低，易磨性差、体积稳定性不良等因素限制钢渣的资源化利用量，2018年我国钢渣产量高达1.2亿吨，历史堆存量超过10亿吨，钢渣的综合利用率为25％左右。Steel slag is an industrial waste slag produced in the steelmaking process of the iron and steel industry. The steel slag is limited in its resource utilization due to factors such as low gelling activity, poor grindability, and poor volume stability. In 2018, my country's steel slag output reached 120 million tons. The stockpile is over 1 billion tons, and the comprehensive utilization rate of steel slag is about 25%.
脱硫灰是钢铁行业采用半干法烟气脱硫技术产生的一种工业固废，主要成分为有亚硫酸钙(CaSO 3)、硫酸钙(CaSO 4)、半水硫酸钙(CaSO 4·0.5H 2O)和铵盐等，CaSO 3在氧化剂环境中容易被氧化成硫酸钙(CaSO 4)，由于脱硫灰性质不稳定造成其综合利用率较低，目前钢铁企业多数采用集中堆积的方式处理脱硫灰，占用宝贵的土地资源，造成严重的环境污染。 Desulfurized ash is an industrial solid waste produced by the semi - dry flue gas desulfurization technology in the iron and steel industry . 2 O) and ammonium salts, etc., CaSO 3 is easily oxidized to calcium sulfate (CaSO 4 ) in the oxidant environment, and its comprehensive utilization rate is low due to the unstable properties of desulfurized ash. Ash, occupying valuable land resources, causing serious environmental pollution.
尾砂是原矿进入选矿厂经过破碎、磨矿、选别等一系列工艺后，剩余的无法用于生产的部分以浆液形式排出，大量的尾砂无法进行资源化利用，常年堆积在尾矿库，堆存占用宝贵的土地资源，尾砂中的重金属渗透到周围土壤中，造成严重的生态环境污染。Tailings is the raw ore that enters the concentrator and undergoes a series of processes such as crushing, grinding, and sorting, and the remaining parts that cannot be used for production are discharged in the form of slurry. , stacking takes up valuable land resources, and the heavy metals in the tailings penetrate into the surrounding soil, causing serious ecological environment pollution.
目前，固结尾砂作为矿山充填材料是快速大量消纳尾砂的首选方法，水泥是矿山充填首先的胶结剂，但是水泥价格昂贵增加矿山充填材料成本，限制了尾砂在矿山充填领域的大量利用，而水泥在胶结重金属尾砂时重金属固化/稳定化效果不良，导致重金属尾砂在矿山充填领域利用量较低，因此制备成本低、强度高和重金属固化效果好的胶结剂对提高重金属尾砂资源化利用量具有重要的意义。At present, the consolidation of tailings as a mine filling material is the preferred method to quickly and massively dissipate tailings. Cement is the first cementing agent for mine filling. However, the high price of cement increases the cost of mine filling materials and limits the large-scale utilization of tailings in the field of mine filling. , and cement has poor solidification/stabilization effect of heavy metal tailings when cementing heavy metal tailings, resulting in low utilization of heavy metal tailings in the field of mine filling. Therefore, low preparation cost, high strength and good heavy metal solidification effect. Resource utilization is of great significance.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术之缺陷，提供了一种钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，替代水泥用于固结尾砂作为矿山充填材料，降低矿山充填成本，提高钢渣、脱硫灰、尾砂大宗固体废物的综合利用量。The object of the present invention is to overcome the defects of the prior art, and provides a method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry, replacing cement for cementing tailings as mine filling materials, reducing mine filling costs, and improving steel slag. , Desulfurization ash, tailings comprehensive utilization of bulk solid waste.
本发明是这样实现的：The present invention is realized in this way:
本发明提供一种钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，包括以下步骤：The invention provides a method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry, comprising the following steps:
S1、利用钢渣、脱硫灰和矿渣作为凝胶材料，向凝胶材料中添加碱激发剂、活化剂并搅拌均匀制成胶结剂；S1. Using steel slag, desulfurized ash and slag as gel material, adding alkali activator and activator to the gel material and stirring evenly to make a cementing agent;
S2、重金属尾砂中添加分散剂、粘结剂和重金属固化剂并搅拌均匀；S2. Add dispersant, binder and heavy metal curing agent to heavy metal tailings and stir evenly;
S3、将S1的胶结剂和S2的重金属尾砂按一定比例搅拌混合均匀制成矿山充填物。S3. The cementing agent of S1 and the heavy metal tailings of S2 are stirred and mixed evenly in a certain proportion to make mine filling.
胶结剂中钢渣粉水化活性低，在碱激发剂作用下激发钢渣活性，钢渣、矿渣水化生产水化硅酸钙 (C-S-H)、水化铝酸钙(C-A-H)等水化产物，利用脱硫灰中硫酸钙成分作为硫酸盐激发剂，在碱激发的基础上进一步激发钢渣、矿渣的水化活性，生成针状和细棒状的钙矾石(AFt)，在活化剂的作用下与钢渣、矿渣中的潜在活性矿物反应生成类钙矾石结构的氯铝酸钙、铝铁酸钙、碳铁酸钙等水硬性矿物。The hydration activity of steel slag powder in the cement is low, and the activity of steel slag is stimulated under the action of alkali activator. Steel slag and slag are hydrated to produce hydrated products such as calcium silicate hydrate (CSH) and calcium aluminate hydrate (CAH). Calcium sulfate in ash acts as a sulfate activator, which further stimulates the hydration activity of steel slag and slag on the basis of alkali excitation, and generates needle-shaped and thin rod-shaped ettringite (AFt), which can interact with steel slag, slag and slag under the action of the activator. Potentially active minerals in the slag react to form ettringite-like calcium chloroaluminate, calcium aluminum ferrite, calcium ferrite and other hydraulic minerals.
C-S-H是一种网状结构凝胶，具有良好的吸附和胶结作用，C-S-H包裹在尾砂颗粒表面，增加尾砂颗粒间粘结力，同时网状C-S-H具有强吸附作用，可将重金属离子吸附到C-S-H表面，起到固定重金属的作用；碱激发剂和脱硫灰中硫酸钙可与重金属发生化学反应形成沉淀，降低重金属毒性，减少重金属离子的浸出率，对重金属起到固化/稳定化的效果。CSH is a network structure gel with good adsorption and cementation. CSH is wrapped on the surface of tailings particles to increase the cohesion between tailings particles. The surface of CSH plays the role of fixing heavy metals; the alkali activator and calcium sulfate in the desulfurization ash can chemically react with heavy metals to form precipitation, reduce the toxicity of heavy metals, reduce the leaching rate of heavy metal ions, and have the effect of solidifying/stabilizing heavy metals.
脱硫灰中亚硫酸钙是一种良好的还原剂，重金属尾砂中高毒性六价铬(Cr 6+)具有氧化性，在亚硫酸钙还原剂作用下转化低毒性三价铬(Cr 3+)，同时亚硫酸钙转化为硫酸钙，硫酸钙再参与水化反应生成针状或细棒状AFt矿物，脱硫灰颗粒粒度细小均匀，亚硫酸钙是一种难溶性矿物，填充在尾砂颗粒间孔隙中，调节重金属尾砂颗粒级配，使固结重金属尾砂呈现出良好的流动性；脱硫灰含有的硫酸钙和半水硫酸钙，晶体结构因失去结晶水而形成直径为
Figure PCTCN2020134298-appb-000001
孔隙，具有强吸附作用，重金属被吸附石膏晶体孔隙中固定到二水石膏晶体中，起到固化稳定化重金属的作用，因此脱硫灰在重金属尾砂胶结剂中起到硫酸盐激发剂、还原剂和吸附重金属的多重作用。 Calcium sulfite in desulfurization ash is a good reducing agent, and highly toxic hexavalent chromium (Cr 6+ ) in heavy metal tailings is oxidizing, and can be converted into low-toxicity trivalent chromium (Cr 3+ ) under the action of calcium sulfite reducing agent At the same time, calcium sulfite is converted into calcium sulfate, and calcium sulfate participates in the hydration reaction to form needle-like or thin rod-like AFt minerals. The desulfurized ash particles are fine and uniform. medium, adjust the particle gradation of heavy metal tailings, so that the consolidated heavy metal tailings show good fluidity; the calcium sulfate and calcium sulfate hemihydrate contained in desulfurization ash, the crystal structure is formed by the loss of crystal water with a diameter of
Figure PCTCN2020134298-appb-000001
Pores have a strong adsorption effect. Heavy metals are adsorbed in the pores of gypsum crystals and fixed into dihydrate gypsum crystals, which play the role of solidifying and stabilizing heavy metals. Therefore, desulfurization ash acts as sulfate activator and reducing agent in heavy metal tailings cement. and adsorption of heavy metals.
钙矾石(AFt)矿物呈针状或细棒状结构，在固结尾砂充填体中相互搭接形成稳定的骨架结构，同时AFt可穿插到尾砂颗粒间的孔隙中起到填充作用，降低孔隙率，增加密实度，提高固结尾砂充填体力学强度，降低重金属浸出毒性；AFt晶体中的离子与重金属离子发生离子交换，将重金属离子固定到稳定的AFt矿物中，进一步减少重金属的浸出毒性。因此本发明的胶结剂在胶结重金属尾砂具有重金属固化/稳定化效果良好，充填体力学强度高和流动性好的特点。The ettringite (AFt) mineral has a needle-like or thin rod-like structure, and overlaps with each other in the solid tailings to form a stable skeleton structure. The ion exchange rate of AFt crystals and the heavy metal ions are ion-exchanged, and the heavy metal ions are fixed into the stable AFt minerals, which further reduces the leaching toxicity of heavy metals. Therefore, the cementing agent of the present invention has the characteristics of good heavy metal solidification/stabilization effect, high mechanical strength of the filling body and good fluidity in cementing the heavy metal tailings.
凝胶材料与碱激发剂、活化剂搅拌混合均匀进入胶结剂仓；尾砂仓中尾砂先进入搅拌仓进行均匀搅拌，向搅拌仓中投加相应的分散剂、重金属固化剂和粘结剂，混合均匀，在分散剂作用下增加重金属金属固化剂和尾砂中的重金属接触；胶结剂仓通过流量计向尾砂搅拌仓中投加胶结剂，搅拌均匀；然后通过输送管输送到地下矿山采空区。The gel material, alkali activator and activator are stirred and mixed evenly into the cementing agent bin; the tailings in the tailings bin first enter the stirring bin for uniform stirring, and the corresponding dispersant, heavy metal curing agent and binder are added into the stirring bin. Mix evenly, increase the contact between heavy metal metal curing agent and heavy metal in tailings under the action of dispersing agent; add cementing agent to tailings mixing silo through a flow meter, and stir evenly; empty area.
进一步地，凝胶材料中各组分的重量占比为：矿渣40～55％，钢渣25～40％，脱硫灰5～35％。Further, the weight proportion of each component in the gel material is: 40-55% of slag, 25-40% of steel slag, and 5-35% of desulfurized ash.
进一步地，矿山充填物中S1的胶结剂和S2搅拌后的重金属尾砂的重量比为1:6～1:5。Further, the weight ratio of the cementing agent of S1 and the heavy metal tailings after stirring by S2 in the mine filling is 1:6 to 1:5.
进一步地，S1中钢渣经过破碎、磁选后，对剩余的钢渣进行球磨制备钢渣粉，将矿渣粉磨制成矿渣粉，将钢渣粉、矿渣粉过筛后与脱硫灰混合制成凝胶材料。Further, after the steel slag in S1 is crushed and magnetically separated, the remaining steel slag is ball-milled to prepare steel slag powder, the slag powder is ground into slag powder, and the steel slag powder and slag powder are sieved and mixed with desulfurized ash to make a gel material. .
进一步地，所述碱激发剂由氧化钙、氢氧化钙、电石渣、烧碱的一种或多种组成，掺量占胶凝材料重量的1～5％。Further, the alkali activator is composed of one or more of calcium oxide, calcium hydroxide, calcium carbide slag, and caustic soda, and the dosage accounts for 1-5% of the weight of the cementitious material.
进一步地，所述分散剂由六偏磷酸钠、三聚磷酸钠、磷酸三钠、羟甲基纤维素、木钙、糖钙、月桂醇硫酸钠的一种或多种组成，掺量占胶凝材料重量的0.1～2％。Further, the dispersing agent is composed of one or more of sodium hexametaphosphate, sodium tripolyphosphate, trisodium phosphate, hydroxymethyl cellulose, wood calcium, sugar calcium, sodium lauryl sulfate, and the mixing amount accounts for the glue. 0.1 to 2% of the weight of the solidifying material.
进一步地，所述活化剂由氯化钙、氯化铝、氯化铁、硫酸铝、芒硝、三乙醇胺、亚硝酸钠、水玻璃、碳酸钙、甲酸钙、醋酸钙和硫酸铝的一种或多种组成，掺量占胶凝材料重量的0.5～5％。Further, the activator is made of one or more of calcium chloride, aluminum chloride, ferric chloride, aluminum sulfate, mirabilite, triethanolamine, sodium nitrite, water glass, calcium carbonate, calcium formate, calcium acetate and aluminum sulfate. A variety of compositions, the dosage accounts for 0.5 to 5% of the weight of the cementitious material.
进一步地，所述粘结剂由聚丙烯纤维、玻璃纤维的一种或多种组成，掺量占重金属尾砂干重量的0.05～1％。Further, the binder is composed of one or more of polypropylene fibers and glass fibers, and the dosage accounts for 0.05-1% of the dry weight of the heavy metal tailings.
进一步地，所述重金属固化剂由磷酸钙渣、磷石膏、沸石、硅灰、草木灰、改性膨润土和铁盐的一种或多种组成，掺量占重金属尾砂干重量的0.2～3％。Further, the heavy metal solidifying agent is composed of one or more of calcium phosphate slag, phosphogypsum, zeolite, silica fume, plant ash, modified bentonite and iron salt, and the dosage accounts for 0.2 to 3% of the dry weight of the heavy metal tailings. .
本发明具有以下有益效果：The present invention has the following beneficial effects:
1、重金属尾砂胶结剂中胶凝材料全部来源钢铁行业废渣，可提高钢渣、脱硫灰资源化利用量。1. The cementitious materials in the heavy metal tailings cement are all derived from the waste slag of the iron and steel industry, which can improve the resource utilization of steel slag and desulfurized ash.
2、胶结剂原料来源丰富，价格低廉，原料中钢渣、矿渣简单粉磨，脱硫灰不加工处理直接利用，对比水泥可显著降低胶结剂生产成本。2. The raw materials of the cement are rich in source and low in price. The steel slag and slag in the raw materials are simply ground, and the desulfurized ash is directly used without processing. Compared with cement, the production cost of cement can be significantly reduced.
3、在分散剂作用下重金属固化剂和胶结剂与尾砂中重金属接触充分，提高胶结剂和重金属固化剂对重金属吸附、沉淀、离子交换作用。3. Under the action of the dispersant, the heavy metal curing agent and the cementing agent are fully in contact with the heavy metals in the tailings, and the binding agent and the heavy metal curing agent can improve the adsorption, precipitation and ion exchange of heavy metals.
4、胶结剂固结尾砂强度满足可不同条件下矿山充填强度要求。4. The strength of the cemented final sand meets the mine filling strength requirements under different conditions.
具体实施方式detailed description
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
利用钢铁行业工业固废胶结重金属尾砂进行矿山充填制备工艺方法：按照重量配比计算重金属尾砂胶结剂配方由矿渣粉50％、钢渣粉35％、脱硫灰15％，外掺碱激发剂4％、活化剂3％，机械搅拌混合均匀。重金属尾砂先在搅拌仓中与分散剂、粘结剂和重金属固化剂搅拌混合均匀，其中分散剂掺量占胶凝材料重量的0.6，粘结剂掺量0.25％(占重金属尾砂干重量)，重金属固化剂掺量0.5％(占重金属尾砂干重量)；胶结剂在矿山充填材料的计量是胶结剂：重金属尾砂＝1:5，将胶结剂和重金属尾砂在搅拌仓中搅拌均匀，通过流动度测试仪器测试浆体流动度，将剩余浆体装入70.7mm*70.7mm*70.7mm试模中，放入水泥标准养护箱中养护相应的龄期测试试验抗压强度，每组试样抗压强度取三个平行样，为保证数据准确性，三个试样抗压强度平均值(最大值和最小值与中间值的差小于15％)，取破碎试样中心部位，根据《固体废物浸出毒性浸出方法-硫酸硝酸法》(HJT299-2007)要求制备固结重金属尾砂毒性浸出液，采用《固体废物金属元素测定电感耦合等离子体质谱法》(HJ766-2015)中的电感耦合等离子体质谱仪(ICP-MS)检测浸出液中重金属浓度。Using industrial solid waste cementing heavy metal tailings in the iron and steel industry to carry out mine filling preparation process: Calculate the heavy metal tailings cementing agent formula according to the weight ratio: 50% of slag powder, 35% of steel slag powder, 15% of desulfurized ash, mixed with alkali activator 4% %, activator 3%, mechanically stir and mix evenly. The heavy metal tailings are firstly stirred and mixed with dispersant, binder and heavy metal curing agent in the stirring bin, wherein the content of dispersant accounts for 0.6 of the weight of the cementitious material, and the content of the binder is 0.25% (account for the dry weight of the heavy metal tailings). ), the content of heavy metal curing agent is 0.5% (accounting for the dry weight of heavy metal tailings); the measurement of cementing agent in mine filling materials is cementing agent: heavy metal tailings = 1:5, and the cementing agent and heavy metal tailings are stirred in the mixing bin Evenly, test the fluidity of the slurry by a fluidity test instrument, put the remaining slurry into a 70.7mm*70.7mm*70.7mm test mold, and put it into a standard cement curing box to test the compressive strength of the corresponding age test. Three parallel samples were taken for the compressive strength of the group of samples. In order to ensure the accuracy of the data, the average value of the compressive strength of the three samples (the difference between the maximum and minimum values and the median value was less than 15%), and the central part of the broken sample was taken. According to the requirements of "Solid Waste Leaching Toxicity Leaching Method-Sulfuric and Nitric Acid Method" (HJT299-2007), the toxic leaching solution of consolidated heavy metal tailings was prepared. The concentration of heavy metals in the leachate was detected by coupled plasma mass spectrometry (ICP-MS).
重金属尾砂充填材料重金属浸出毒性表1Heavy metal tailings filling material heavy metal leaching toxicity table 1
Figure PCTCN2020134298-appb-000002
Figure PCTCN2020134298-appb-000002
矿山充填材料性能指标表1Mine filling material performance index table 1
Figure PCTCN2020134298-appb-000003
Figure PCTCN2020134298-appb-000003
通过上述表格可知，本发明制备的重金属尾砂胶结剂用于固结重金属尾砂作为矿山充填料，在胶砂比1:5，胶结剂固结重金属尾砂作为矿山充填材料在养护7d时重金属浸出浓度低于地下III类水指标，同时养护时间增加重金属浸出浓度逐渐减小，在28d充填材料重金属浸出浓度明显低于III类地下水重金属限值；固结重金属尾砂矿山充填材料7d、14d和28d抗压强度分布达到1.36MPa、3.36MPa和6.73MPa，而充填体28d抗压强度达到3MPa可满足不同部位矿山充填体强度要求，因此该胶结剂固结重金属尾砂充填体强度远大于矿山充填体强度指标；矿山充填材料流动度为276mm，不同的充填方式对充填浆体流动度具有不同的指标，矿山充填采用自流输送时浆体流动度≥250mm，泵送充填浆体流动度≥180mm，但泵送充填会增加充填成本，因此本发明制备的胶结剂固结重金属尾砂，用于矿山充填有利于实现自流输送，进一步降低充填成本。It can be seen from the above table that the heavy metal tailings cement prepared by the present invention is used to consolidate the heavy metal tailings as a mine filling material. When the cement-sand ratio is 1:5, the cement consolidates the heavy metal tailings as a mine filling material. When curing heavy metals for 7 days The leaching concentration is lower than the index of underground class III water, and the leaching concentration of heavy metals gradually decreases with the increase of curing time, and the leaching concentration of heavy metals in the filling material at 28d is significantly lower than the limit of heavy metal in class III groundwater; The 28d compressive strength distribution reaches 1.36MPa, 3.36MPa and 6.73MPa, and the 28d compressive strength of the backfill reaches 3MPa, which can meet the strength requirements of mine backfills in different parts. Therefore, the strength of the backfill body consolidated by the cement is much greater than that of mine backfill. Body strength index; the fluidity of the mine filling material is 276mm, and different filling methods have different indicators for the fluidity of the filling slurry. When the mine is filled with self-flow conveying, the fluidity of the slurry is greater than or equal to 250mm, and the fluidity of the pumped filling slurry is greater than or equal to 180mm. But pumping filling will increase the filling cost, so the cementing agent prepared by the present invention consolidates the heavy metal tailings and is used for mine filling, which is conducive to realizing self-flow transportation and further reducing the filling cost.
实施例2Example 2
利用钢铁行业工业固废胶结重金属尾砂进行矿山充填制备工艺方法：按照重量配比计算重金属尾砂胶结剂配方由矿渣粉43％、钢渣粉40％、脱硫灰17％，外掺碱激发剂3％、活化剂5％，机械搅拌混合均匀。重金属尾砂先在搅拌仓中与分散剂、粘结剂和重金属固化剂搅拌混合均匀，然后再相尾砂搅拌仓中添加胶结剂，其中分散剂掺量占胶凝材料重量的1.0％，粘结剂掺量0.5％(占重金属尾砂干重量)，重金属固化剂掺量0.9％(占重金属尾砂干重量)；胶结剂在矿山充填材料的重量是胶结剂：重金属尾砂＝1:6，将胶结剂和重金属尾砂在搅拌仓中搅拌均匀，通过流动度测试仪器测试浆体流动度，将剩余浆体装入70.7mm*70.7mm*70.7mm试模中，放入水泥标准养护箱中养护相应的龄期测试试验抗压强度，每组试样抗压强度取三个平行样，为保证数据准确性，三个试样抗压强度平均值(最大值和最小值与中间值的差小于15％)，取破碎试样中心部位，根据《固体废物浸出毒性浸出方法-硫酸硝酸法》(HJT299-2007)要求制备固结重金属尾砂毒性浸出液，采用《固体废物金属元素测定电感耦合等离子体质谱法》(HJ766-2015)中的电 感耦合等离子体质谱仪(ICP-MS)检测浸出液中重金属浓度。Using industrial solid waste cementing heavy metal tailings in the iron and steel industry to carry out mine filling preparation process: Calculate the heavy metal tailings cementing agent formula according to the weight ratio: 43% of slag powder, 40% of steel slag powder, 17% of desulfurized ash, mixed with alkali activator 3% %, activator 5%, mechanically stir and mix evenly. The heavy metal tailings are first stirred and mixed with dispersant, binder and heavy metal curing agent in the mixing tank, and then cementing agent is added to the tailings mixing tank. The content of binder is 0.5% (accounting for the dry weight of heavy metal tailings), and the content of heavy metal curing agent is 0.9% (accounting for the dry weight of heavy metal tailings); , Stir the binder and heavy metal tailings evenly in the mixing bin, test the fluidity of the slurry with a fluidity test instrument, put the remaining slurry into a 70.7mm*70.7mm*70.7mm test mold, and put it into a cement standard curing box In order to ensure the accuracy of the data, the average compressive strength of the three samples (the difference between the maximum and minimum values and the median value) The difference is less than 15%), take the central part of the broken sample, prepare the toxic leaching solution of consolidated heavy metal tailings according to the requirements of "Solid Waste Leaching Toxicity Leaching Method - Sulfuric Acid and Nitric Acid Method" (HJT299-2007), adopt "Solid Waste Metal Element Determination Inductive Coupling" The inductively coupled plasma mass spectrometer (ICP-MS) in "Plasma Mass Spectrometry" (HJ766-2015) detects the concentration of heavy metals in the leachate.
重金属尾砂充填材料重金属浸出毒性表2Heavy metal tailings filling material heavy metal leaching toxicity table 2
Figure PCTCN2020134298-appb-000004
Figure PCTCN2020134298-appb-000004
矿山充填材料性能指标表2Mine filling material performance index table 2
Figure PCTCN2020134298-appb-000005
Figure PCTCN2020134298-appb-000005
通过上述表格可知，本发明制备的重金属尾砂胶结剂，在胶砂比＝1:6时固结重金属尾砂作为矿山充填材料在养护7d时重金属浸出浓度低于地下III类水指标，随着养护时间增加固结重金属尾砂充填体重金属浸出浓度逐渐减小，满足地下水质量标准(GB/T14848-2017)中III类地下水对重金属浸出浓度要求；固结重金属尾砂矿山充填材料7d、14d和28d抗压强度分布达到1.05MPa、2.68MPa和5.06MPa，而充填体28d抗压强度达到3MPa可满足不同部位矿山充填体强度要求，因此本发明胶结剂在胶砂比为1:6时固结重金属尾砂充填体强度是矿山充填体强度指标的1.68倍；矿山充填材料流动度为267mm，不同的充填方式对充填浆体流动度具有不同的指标，矿山充填采用自流输送时浆体流动度≥250mm，泵送充填浆体流动度≥180mm，但泵送充填会增加充填成本，因此本发明制备的胶结剂固结重金属尾砂，用于矿山充填有利于实现自流输送，进一步降低充填成本。It can be seen from the above table that the heavy metal tailings cement prepared by the present invention can consolidate the heavy metal tailings as a mine filling material when the cement-sand ratio is 1:6. When curing for 7d, the heavy metal leaching concentration is lower than the underground Class III water index. With the increase of curing time, the leaching concentration of heavy metals in the consolidated heavy metal tailings filling gradually decreases, which meets the requirements for the leaching concentration of heavy metals in class III groundwater in the groundwater quality standard (GB/T14848-2017). The 28d compressive strength distribution reaches 1.05MPa, 2.68MPa and 5.06MPa, and the 28d compressive strength of the filling body reaches 3MPa, which can meet the strength requirements of the mine filling body in different parts. Therefore, the cementing agent of the present invention is consolidated when the cement-sand ratio is 1:6. The strength of the heavy metal tailings backfill is 1.68 times that of the mine backfill strength index; the fluidity of the mine backfill material is 267mm, and different backfilling methods have different indicators for the backfill fluidity. 250mm, the fluidity of the pumped filling slurry is ≥180mm, but the pumped filling will increase the filling cost. Therefore, the cement prepared by the invention consolidates the heavy metal tailings and is used for mine filling, which is conducive to realizing self-flow transportation and further reducing the filling cost.
实施例3Example 3
利用钢铁行业工业固废胶结重金属尾砂进行矿山充填制备工艺方法：按照重量配比计算重金属尾砂胶结剂配方由矿渣粉40％、钢渣粉25％、脱硫灰35％，外掺碱激发剂5％、活化剂2％，机械搅拌混合均匀。重金属尾砂先在搅拌仓中与分散剂、粘结剂和重金属固化剂搅拌混合均匀，然后再相尾砂搅拌仓中添加胶结剂，其中分散剂掺量占胶凝材料重量的0.3％，粘结剂掺量1.0％(占重金属尾砂干重量)，重金属固化剂掺量1.2％(占重金属尾砂干重量)；胶结剂在矿山充填材料的重量是胶结剂：重金属尾砂＝1:5，将胶结剂和重金属尾砂在搅拌仓中搅拌均匀，通过流动度测试仪器测试浆体流动度，将剩余浆体装入70.7mm*70.7mm*70.7mm试模中，放入水泥标准养护箱中养护相应的龄期测试试验抗压强度，每组试样抗压强度取三个平行样，为保证数据准确性，三个试样抗压强度平均值(最大值和最小值与中间值的差小于 15％)，取破碎试样中心部位，根据《固体废物浸出毒性浸出方法-硫酸硝酸法》(HJT299-2007)要求制备固结重金属尾砂毒性浸出液，采用《固体废物金属元素测定电感耦合等离子体质谱法》(HJ766-2015)中的电感耦合等离子体质谱仪(ICP-MS)检测浸出液中重金属浓度。Using industrial solid waste cementing heavy metal tailings in the iron and steel industry to carry out mine filling preparation process: Calculate the heavy metal tailings cementing agent formula according to the weight ratio: 40% of slag powder, 25% of steel slag powder, 35% of desulfurized ash, and 5% of alkali activator. %, activator 2%, mechanically stir and mix evenly. The heavy metal tailings are first stirred and mixed with dispersant, binder and heavy metal solidifying agent in the mixing tank, and then the cementing agent is added to the tailings mixing tank. The content of binder is 1.0% (accounting for the dry weight of heavy metal tailings), and the content of heavy metal curing agent is 1.2% (accounting for the dry weight of heavy metal tailings); , Stir the binder and heavy metal tailings evenly in the mixing bin, test the fluidity of the slurry with a fluidity test instrument, put the remaining slurry into a 70.7mm*70.7mm*70.7mm test mold, and put it into a cement standard curing box In order to ensure the accuracy of the data, the average compressive strength of the three samples (the difference between the maximum and minimum values and the median value) The difference is less than 15%), take the central part of the broken sample, prepare the toxic leaching solution of consolidated heavy metal tailings according to the requirements of "Solid Waste Leaching Toxicity Leaching Method - Sulfuric Acid and Nitric Acid Method" (HJT299-2007), adopt "Solid Waste Metal Element Determination Inductive Coupling" The inductively coupled plasma mass spectrometer (ICP-MS) in "Plasma Mass Spectrometry" (HJ766-2015) detects the concentration of heavy metals in the leachate.
重金属尾砂充填材料重金属浸出毒性表3Heavy metal tailings filling material heavy metal leaching toxicity table 3
Figure PCTCN2020134298-appb-000006
Figure PCTCN2020134298-appb-000006
矿山充填材料性能指标表3Mine filling material performance index table 3
Figure PCTCN2020134298-appb-000007
Figure PCTCN2020134298-appb-000007
通过上述表格可知，本发明制备的重金属尾砂胶结剂，在胶砂比＝1:5时固结重金属尾砂作为矿山充填材料在养护7d和28d时重金属浸出浓度均低于地下III类水指标，养护龄期增加重金属浸出浓度呈降低趋势，满足地下水质量标准(GB/T14848-2017)中III类地下水对重金属浸出浓度要求；固结重金属尾砂矿山充填材料7d、14d和28d抗压强度分布达到1.09MPa、3.08MPa和5.76MPa，而充填体28d抗压强度达到3MPa可满足不同部位矿山充填体强度要求，因此本发明胶结剂在胶砂比为1:5时固结重金属尾砂充填体强度是矿山充填体强度指标的1.92倍；矿山充填材料流动度为265mm，不同的充填方式对充填浆体流动度具有不同的指标，矿山充填采用自流输送时浆体流动度≥250mm，泵送充填浆体流动度≥180mm，但泵送充填会增加充填成本，因此本发明制备的胶结剂固结重金属尾砂，用于矿山充填有利于实现自流输送，进一步降低充填成本。It can be seen from the above table that the heavy metal tailings cement prepared by the present invention consolidates the heavy metal tailings as a mine filling material when the ratio of cement to sand is 1:5, and the leaching concentration of heavy metals is lower than the underground class III water index when curing for 7d and 28d. , the leaching concentration of heavy metals shows a decreasing trend with the increase of curing age, which meets the requirements for leaching concentration of heavy metals in class III groundwater in the groundwater quality standard (GB/T14848-2017). It can reach 1.09MPa, 3.08MPa and 5.76MPa, and the 28d compressive strength of the backfill body reaches 3MPa, which can meet the strength requirements of mine backfill bodies in different parts. Therefore, the cementing agent of the present invention consolidates the heavy metal tailings backfill body when the cement-sand ratio is 1:5. The strength is 1.92 times of the strength index of the mine filling body; the fluidity of the mine filling material is 265mm, and different filling methods have different indicators for the fluidity of the filling slurry. The fluidity of the slurry is ≥180mm, but pumping filling will increase the filling cost. Therefore, the cementing agent prepared by the present invention consolidates the heavy metal tailings and is used for mine filling, which is conducive to realizing self-flow transportation and further reducing the filling cost.
综上所述，本发明为了降低矿山充填的成本，将钢渣、脱硫灰、尾砂等工业固体废物作为凝胶材料制成胶结剂胶结重金属尾砂作为矿山充填物，对钢铁行业固体废物进行了资源化利用，本发明制备的胶结剂在固结重金属尾砂方面具有重金属固化效果好，充填体强度高、充填材料流动度好的特点。To sum up, in order to reduce the cost of mine filling, the present invention uses industrial solid wastes such as steel slag, desulfurization ash, tailings, etc., as gel materials to make cementing agent cementing heavy metal tailings as mine fillings, and carries out the treatment of solid wastes in the iron and steel industry. Resource utilization, the cementing agent prepared by the invention has the characteristics of good heavy metal solidification effect, high filling body strength and good filling material fluidity in consolidating heavy metal tailings.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the scope of the present invention. within the scope of protection.

Claims (9)

  1. 钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于，包括以下步骤：The method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry is characterized by comprising the following steps:
    S1、利用钢渣、脱硫灰和矿渣作为凝胶材料，向凝胶材料中添加碱激发剂、活化剂并搅拌均匀制成胶结剂；S1. Using steel slag, desulfurized ash and slag as gel material, adding alkali activator and activator to the gel material and stirring evenly to make a cementing agent;
    S2、重金属尾砂中添加分散剂、粘结剂和重金属固化剂并搅拌均匀；S2. Add dispersant, binder and heavy metal curing agent to heavy metal tailings and stir evenly;
    S3、将S1的胶结剂和S2搅拌后的重金属尾砂按一定比例搅拌混合均匀制成矿山充填物。S3. The cementing agent of S1 and the heavy metal tailings stirred by S2 are stirred and mixed uniformly in a certain proportion to make mine filling.
  2. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：凝胶材料中各组分的重量占比为：矿渣40～55％，钢渣25～40％，脱硫灰5～35％。The method for preparing mine filling by cementing heavy metal tailings with solid waste in the iron and steel industry as claimed in claim 1, wherein the weight ratio of each component in the gel material is: 40-55% of slag, 25-40% of steel slag , 5 to 35% of desulfurized ash.
  3. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：矿山充填物中S1的胶结剂和S2搅拌后的重金属尾砂的重量比为1:6～1:5。The method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry as claimed in claim 1, wherein the weight ratio of the cementing agent of S1 and the heavy metal tailings after stirring S2 in the mine filling is 1:6～ 1:5.
  4. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：S1中钢渣经过破碎、磁选后，对剩余的钢渣进行球磨制备钢渣粉，将矿渣粉磨制成矿渣粉，将钢渣粉、矿渣粉过筛后与脱硫灰混合制成凝胶材料。The method for preparing mine filling by cementing heavy metal tailings with solid waste in the iron and steel industry as claimed in claim 1, wherein: after the steel slag in S1 is crushed and magnetically separated, the remaining steel slag is ball-milled to prepare steel slag powder, and the slag is ground. Slag powder is made, and the steel slag powder and slag powder are sieved and mixed with desulfurization ash to make gel material.
  5. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：所述碱激发剂由氧化钙、氢氧化钙、电石渣、烧碱的一种或多种组成，掺量占胶凝材料重量的1～5％。The method for preparing mine filling by cementing heavy metal tailings with solid waste in the iron and steel industry as claimed in claim 1, wherein the alkali activator is composed of one or more of calcium oxide, calcium hydroxide, calcium carbide slag and caustic soda , the dosage accounts for 1 to 5% of the weight of the cementitious material.
  6. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：所述分散剂由六偏磷酸钠、三聚磷酸钠、磷酸三钠、羟甲基纤维素、木钙、糖钙、月桂醇硫酸钠的一种或多种组成，掺量占胶凝材料重量的0.1～2％。The method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry as claimed in claim 1, wherein the dispersant is composed of sodium hexametaphosphate, sodium tripolyphosphate, trisodium phosphate, hydroxymethyl cellulose , one or more compositions of wood calcium, sugar calcium and sodium lauryl sulfate, and the mixing amount accounts for 0.1-2% of the weight of the cementitious material.
  7. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：所述活化剂由氯化钙、氯化铝、氯化铁、硫酸铝、芒硝、三乙醇胺、亚硝酸钠、水玻璃、碳酸钙、甲酸钙、醋酸钙和硫酸铝的一种或多种组成，掺量占胶凝材料重量的0.5～5％。The method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry as claimed in claim 1, wherein the activator is composed of calcium chloride, aluminum chloride, ferric chloride, aluminum sulfate, mirabilite, triethanolamine , sodium nitrite, water glass, calcium carbonate, calcium formate, calcium acetate and aluminum sulfate one or more components, the amount of which accounts for 0.5 to 5% of the weight of the cementitious material.
  8. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：所述粘结剂由聚丙烯纤维、玻璃纤维的一种或多种组成，掺量占重金属尾砂干重量的0.05～1％。The method for preparing mine filling by cementing heavy metal tailings with solid wastes in the iron and steel industry as claimed in claim 1, wherein the binder is composed of one or more of polypropylene fibers and glass fibers, and the amount of the binding agent accounts for 30% of the heavy metal. 0.05 to 1% of the dry weight of tailings.
  9. 如权利要求1所述的钢铁行业固体废物胶结重金属尾砂制备矿山充填物的方法，其特征在于：所述重金属固化剂由磷酸钙渣、磷石膏、草木灰、沸石、硅灰、改性膨润土和铁盐的一种或多种组成，掺量占重金属尾砂干重量的0.2～3％。The method for preparing mine filling by cementing heavy metal tailings with solid waste in the iron and steel industry as claimed in claim 1, wherein the heavy metal solidifying agent is composed of calcium phosphate slag, phosphogypsum, plant ash, zeolite, silica fume, modified bentonite and One or more compositions of iron salts, the content of which accounts for 0.2-3% of the dry weight of the heavy metal tailings.
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