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CN-121974585-A - Copper slag-based cementing material synergistically excited by calcium oxide and phosphate as well as preparation method and application thereof

CN121974585ACN 121974585 ACN121974585 ACN 121974585ACN-121974585-A

Abstract

The invention discloses a copper slag-based cementing material excited by calcium oxide-phosphate and a preparation method and application thereof, belonging to the technical field of industrial solid waste recycling, and comprising the following raw materials, by weight, 60-80 parts of copper slag, 15-30 parts of high-alumina admixture, 5-10 parts of phosphogypsum, 3-8 parts of calcium oxide, 4-12 parts of dipotassium hydrogen phosphate and 0.05-0.3 part of triisopropanolamine. The invention destroys the fayalite structure through the alkali excitation of calcium oxide, dipotassium hydrogen phosphate and dissolved Fe 2+ form phosphate gel, triisopropanolamine chelates to accelerate ion dissolution, and combines ettringite generated by high-alumina materials and phosphogypsum to construct a 'phosphate- & ettringite' composite gel system. The material mainly uses solid wastes such as copper slag and the like, and has the advantages of good heavy metal solidification effect, environmental protection and low carbon. When the filler is applied to filling of gold mine tailings, the prepared filler can still keep good working performance and mechanical strength under the working conditions of a sand ratio of 1:8 and a filling concentration of 64- & lt 66 & gt, and has excellent curing effect on characteristic pollutant arsenic (As) in the gold mine tailings, and the leaching concentration is obviously lower than the standard limit value.

Inventors

  • Dang Shuaike
  • ZHONG XIAORONG
  • Nong Bu
  • ZHAO FAXIANG
  • WANG HONGWU
  • JIANG DEFU
  • WU WEI
  • XIONG GUOTAO
  • ZHANG JIN
  • AI YINGYING
  • WANG LONG

Assignees

  • 中国十五冶金建设集团有限公司
  • 河北长安育才科技股份有限公司

Dates

Publication Date
20260505
Application Date
20260206

Claims (9)

  1. 1. The copper slag-based cementing material is characterized by comprising the following raw materials in parts by weight: 60-80 parts of copper slag, 15-30 parts of high-alumina admixture, 5-10 parts of phosphogypsum, 3-8 parts of calcium oxide, 4-12 parts of dipotassium hydrogen phosphate and 0.05-0.3 part of triisopropanolamine.
  2. 2. The copper slag-based cementing material synergistically excited by calcium oxide and phosphate according to claim 1, wherein the mass fraction of Al 2 O 3 in the high-alumina admixture is more than or equal to 30%.
  3. 3. The copper slag-based cementing material cooperatively excited by calcium oxide-phosphate according to claim 1, wherein the high-alumina admixture comprises one or more of fly ash, red mud and coal gangue.
  4. 4. A method for preparing the copper slag-based cementing material cooperatively excited by calcium oxide and phosphate as claimed in any one of claims 1 to 3, which comprises the following steps: spraying ethanol solution of triisopropanolamine into copper slag and calcium oxide, and grinding to obtain ground copper slag composite powder; And mixing the high-alumina admixture and phosphogypsum with the finely ground copper slag composite powder uniformly, adding dipotassium hydrogen phosphate, and stirring in a sealing way to obtain the copper slag-based cementing material.
  5. 5. The method for preparing a copper slag based cementing material synergistically excited by calcium oxide and phosphate according to claim 4, wherein the grinding is carried out until the specific surface area is more than or equal to 450m 2 /kg.
  6. 6. Use of a copper slag-based cement material synergistically stimulated from calcium oxide to phosphate according to any one of claims 1 to 3 in mine filling.
  7. 7. A mine filling slurry is characterized by comprising the following raw materials of the copper slag-based cementing material, gold mine tailings and water according to any one of claims 1& # x2011 and 3, wherein the mass ratio of the copper slag-based cementing material to the gold mine tailings is 1:8, and the mass concentration of the filling slurry is 64& # x2011 and 66%.
  8. 8. A mine filling slurry according to claim 7, wherein the slump of the mine filling slurry is 210-240mm.
  9. 9. A method for preparing the mine filling slurry according to any one of claims 7 to 8, wherein the copper slag-based cementing material, gold mine tailings and water are mixed according to a mass ratio, and stirred until a homogeneous slurry is obtained, so that the mine filling slurry is obtained.

Description

Copper slag-based cementing material synergistically excited by calcium oxide and phosphate as well as preparation method and application thereof Technical Field The invention belongs to the technical field of industrial solid waste recycling, in particular to a cementing material taking copper slag as a main raw material and a preparation method thereof, and particularly relates to a copper slag-based cementing material excited by calcium oxide-phosphate in a synergic manner and application of the cementing material in mine filling, in particular gold mine tailing filling. Background The copper slag is waste slag generated during the pyrometallurgy of copper, and the discharge amount of the copper slag is about 2-3 times of the output of metallic copper. The copper slag has the characteristics of fine granularity, multiple types, complex components and the like, has low recycling utilization rate, is basically stored in a stacking mode, and is accumulated to hundreds of tons so far. The long-term disposal of copper slag occupies land, and has serious influence on water quality and environment, and the development of efficient resource utilization of copper slag is imperative. In order to solve the problem of stockpiling of copper slag, many students prepare novel cementing materials by using metallurgical slag, and the novel cementing materials are applied to cementing filling of mines. However, in the current copper smelting process by adopting a double flash furnace method, copper slag is tailings after slow cooling and flotation of smelting slag, the amorphous phase content of the copper slag is extremely low (usually < 5%), the main crystalline phases are inert fayalite (Fe 2SiO4) and magnetite (Fe 3O4), most of SiO 2 exists in the form of fayalite crystals (namely ferric silicate) and almost does not participate in hydration, so that the volcanic ash reactivity of the copper slag is poor, and the traditional alkali excitation efficiency is low. In addition, the copper slag has low content of aluminum oxide and calcium oxide, and C- (A) -S-H gel or ettringite is difficult to generate. In the existing solution, the traditional alkali-exciting agent such as sodium hydroxide, water glass and the like cannot dissociate the fayalite stable structure, and the high-aluminum admixture needs to rely on an external calcium source to generate ettringite, so that the compatibility with a copper slag system is poor. Meanwhile, a large amount of tailings generated by gold mining also needs to be safely disposed of. The cementing material prepared from the solid wastes such as copper slag and the like is used for filling gold mine tailings, so that the effect of treating wastes with the wastes can be realized, and the environment and economic benefits are achieved. Gold mine tailings are filled to control cost and meet pipeline conveying characteristics, and lower cementing material mixing amount (high gray sand ratio, such as 1:8) and specific slurry concentration (such as 64& # x2011; 66%) are usually adopted, so that higher requirements are placed on the excitation efficiency and early strength of the cementing material. A more serious challenge is that gold tailings may contain characteristic contaminants such As arsenic (As), which pose a threat to the long-term environmental safety of the pack. Therefore, the development of a novel cementing material which can dissociate fayalite stable structure, has good compatibility with a copper slag system and can effectively solidify harmful substances such as arsenic and the like is a key for pushing solid waste to cooperatively use for filling gold mine tailings. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides a copper slag-based cementing material which is cooperatively excited by calcium oxide & # x2011 and phosphate, and a preparation method and application thereof. The material can efficiently activate copper slag under the specific working conditions that the gray sand ratio is 1:8 and the filling concentration is 64 # x2011 and 66%, and can efficiently stabilize pollutants such as arsenic in gold mine tailings. In order to achieve the above purpose, the present invention provides the following technical solutions: In a first aspect, the invention provides a copper slag-based cementing material synergistically excited by calcium oxide and phosphate, which comprises the following raw materials in parts by weight: 60-80 parts of copper slag, 15-30 parts of high-alumina admixture, 5-10 parts of phosphogypsum, 3-8 parts of calcium oxide, 4-12 parts of dipotassium hydrogen phosphate and 0.05-0.3 part of triisopropanolamine. The calcium oxide (CaO) -dipotassium hydrogen phosphate (K 2HPO4) -Triisopropanolamine (TIPA) has triple-component synergistic effect, wherein the calcium oxide is dissolved in water to provide an alkaline environment (pH > 12), fe-O-Si bonds in Fe 2SiO4 are broken, fe 2+ is promoted to dissolve out,