WO2020073427A1 - 一种制备合金铁和水泥材料的方法 - Google Patents

一种制备合金铁和水泥材料的方法 Download PDF

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WO2020073427A1
WO2020073427A1 PCT/CN2018/115888 CN2018115888W WO2020073427A1 WO 2020073427 A1 WO2020073427 A1 WO 2020073427A1 CN 2018115888 W CN2018115888 W CN 2018115888W WO 2020073427 A1 WO2020073427 A1 WO 2020073427A1
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Prior art keywords
fly ash
red mud
incineration fly
iron
preparation
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English (en)
French (fr)
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耿超
刘建国
吴世超
于书尧
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Tsinghua University
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Tsinghua University
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Priority to US16/492,586 priority Critical patent/US11459272B2/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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/35—Shredding, crushing or cutting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C2201/00—Details of magnetic or electrostatic separation
    • B03C2201/20—Magnetic separation of bulk or dry particles in mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/30—Incineration ashes
    • 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
    • C04B2290/00—Organisational aspects of production methods, equipment or plants
    • C04B2290/20—Integrated combined plants or devices, e.g. combined foundry and concrete plant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods

Definitions

  • the invention relates to the technical field of solid waste recycling, in particular to a method for preparing alloy iron and cement materials.
  • Red mud is the waste residue produced during the production of alumina. As the grade of bauxite has decreased in recent years, the amount of red mud produced has increased year by year. At present, the cumulative stock of red mud in China has reached over 300 million tons. Except for a small part used in cement production, brick making, etc., most of the wet open dam construction and storage. At present, people are paying more and more attention to the harm caused by red mud stacking. For example, the stacking of red mud not only occupies a lot of land, but also consumes a lot of yard construction and maintenance costs, and the harmful substances present in the red mud penetrate underground, causing Groundwater and soil pollution.
  • red mud treatment methods mainly use high-cost coke or pulverized coal to reduce roasting and recover iron, and the resulting tailings are still solid waste, which cannot achieve the utilization of red mud.
  • the object of the present invention is to provide a method for preparing alloy iron and cement materials.
  • the invention uses the waste incineration fly ash and red mud as raw materials to obtain alloy iron and cement materials, and realizes the resource utilization of the waste incineration fly ash and red mud.
  • the invention provides a method for preparing alloy iron and cement materials, which includes the following steps:
  • the mixture obtained by mixing waste incineration fly ash and red mud is subjected to reduction roasting to obtain a roasted product;
  • the roasted product is subjected to grinding-magnetic separation to obtain alloy iron and cement materials.
  • the mass percentage of waste incineration fly ash in the mixture is 30-70%, and the mass percentage of red mud is 30-70%.
  • the mixture further includes an aluminum-containing additive, and the mass percentage content of the aluminum-containing additive in the mixture is 0-30%.
  • the aluminum-containing additive includes one or more of alumina, aluminum powder, aluminum slag and aluminum ash.
  • the waste incineration fly ash includes the following components in mass percentage: CaO 10 to 70%, C 5 to 20%, SiO 2 0.1 to 10%, Al 2 O 3 0.1 to 10%, Cl 0.1 to 30 %, Na 2 O 0.1-10%, K 2 O 0.1-10%, MgO 0.1-10%, SO 3 0.1-10%, Fe 2 O 3 0.1-10%, TiO 2 0-10%, P 2 O 5 0 to 10%.
  • the waste incineration fly ash also includes the following components with a mass percentage: ZnO 0 to 1%, PbO 0 to 1%, Cr 2 O 3 0 to 1%, CuO 0 to 1%, MnO 0 to 1 %, NiO 0 to 1%, BaO 0 to 1%, SrO 0 to 1%, CdO 0 to 1%, Hg 0 to 1%.
  • the red mud includes the following components in mass percentage: Fe 2 O 3 30-50%, Al 2 O 3 10-30%, SiO 2 15-50%, CaO 0.1-10%, MgO 0.1 ⁇ 5%, Na 2 O 1 ⁇ 10%, K 2 O 0.1 ⁇ 0.5%, TiO 2 0.5 ⁇ 10%; the burning loss of the red mud is 1 ⁇ 15%.
  • the temperature of the reduction roasting is 1100-1350 ° C, and the time of the reduction roasting is 30-90 min.
  • the grinding-magnetic separation includes primary grinding, magnetic separation and secondary fine grinding in sequence;
  • the obtained primary grinding product has a mass fraction of -0.043mm of 50-80%, and the second fine grinding has a mass fraction of -0.043mm of 90-100% and a specific surface area of 350-600m 2 / kg.
  • the magnetic field strength of the magnetic separation is 1.8-2.0 kGs.
  • the invention provides a method for preparing alloy iron and cement materials, comprising the following steps: the mixture obtained by mixing waste incineration fly ash and red mud is subjected to reduction roasting to obtain a roasted product; the roasted product is subjected to grinding-magnetic separation, Get alloyed iron and cement materials.
  • the invention efficiently utilizes the synergistic effect of carbon, calcium, heavy metal components in waste incineration fly ash and iron, aluminum, silicon main components in red mud, and finally can obtain alloy iron and cement materials.
  • the carbon in the waste incineration fly ash can provide a reducing agent for reducing roasting, thereby promoting the reduction of iron minerals in red mud to metallic iron; the formation of metallic iron, It also promotes the entry of ferrophilic heavy metal elements in the waste incineration fly ash into the iron phase, so that the waste incineration fly ash and red mud, two important hazardous wastes and bulk industrial solid wastes in China that need to be treated urgently, can be comprehensively utilized.
  • the cement material formed by A1 2 O 3 in red mud and CaO and SiO 2 in waste incineration fly ash has realized the recycling of solid waste, improved the comprehensive utilization rate of resources, and is conducive to the construction of a resource-saving society.
  • High economic value, and alloy iron products obtained through reduction roasting are more expensive than iron concentrates, and because they contain trace elements of Ni, Cu, Cr and other elements, they are more valuable than direct reduced iron products.
  • Cement material can be used for cement production, its production cost is lower, and a lot of natural stone is saved.
  • the present invention can not only realize the reduction and harmlessness of fly ash, but also realize the resourceization of fly ash; compared with the existing waste incineration fly ash fusion process, The temperature is lower, the melting temperature of the waste incineration fly ash is above 1400 °C, the reduction roasting reaction temperature of the invention is below 1350 °C, saving energy consumption; compared with the existing red mud-direct reduction process, the solid waste incineration fly ash Efficient use, on the one hand, turn harmful waste into valuable products, at the same time avoid the relatively high cost of coke and coal powder, reduce production costs and environmental pollution in the coking process; compared with the existing red mud-direct reduction process In contrast, the present invention not only realizes the recovery of iron in red mud, but also utilizes other components in red mud to avoid secondary pollution of the environment by other components.
  • the data of the examples show that the iron grade of the alloy iron prepared by the present invention is 91.96 ⁇ 93.73%, the iron recovery rate is 83.22 ⁇ 85.94%, the specific surface area of the cement material is 480 ⁇ 550m 2 / kg, and the main phase of the cement material is The vitreous body and tricalcium silicate, using sodium silicate and sodium hydroxide as the alkali activator, the 28-day compressive strength is 78-86Mpa.
  • FIG. 1 is a flow chart of the method for preparing alloy iron and cement material of the present invention.
  • the invention provides a method for preparing alloy iron and cement materials, which includes the following steps:
  • the mixture obtained by mixing waste incineration fly ash and red mud is subjected to reduction roasting to obtain a roasted product;
  • the roasted product is subjected to grinding-magnetic separation to obtain alloy iron and cement materials.
  • the mixture obtained by mixing waste incineration fly ash and red mud is subjected to reduction roasting to obtain a roasted product.
  • the mass percentage of waste incineration fly ash in the mixture is preferably 30-70%, more preferably 34-38%, most preferably 35%, and the mass percentage of red mud is preferably 30- 70%, more preferably 48-50%.
  • the mixture preferably further includes an aluminum-containing additive, and the mass percentage content of the aluminum-containing additive in the mixture is preferably 0 to 30%, more preferably 14 to 16%, and most preferably 15%.
  • the aluminum-containing additive preferably includes one or more of alumina, aluminum powder, aluminum slag, and aluminum ash.
  • the aluminum-containing additive is preferably a mixture
  • the present invention has no particular limitation on the amount of each component in the mixture, and a mixture in any ratio may be used.
  • the invention determines whether to add an aluminum-containing additive according to the aluminum content in the red mud. If the aluminum content in the red mud is 25% -30%, the aluminum-containing additive is added to induce the generation of more calcium aluminate to obtain calcium aluminate cement Material; when the aluminum content in the red mud is 10-25%, no aluminum-containing additives are added, and a cement material whose main phase is vitreous and tricalcium silicate is generated.
  • the waste incineration fly ash preferably includes the following mass percent components: CaO 10 to 70%, C 5 to 20%, SiO 2 0.1 to 10%, Al 2 O 3 0.1 to 10%, Cl 0.1-30%, Na 2 O 0.1-10%, K 2 O 0.1-10%, MgO 0.1-10%, SO 3 0.1-10%, Fe 2 O 3 0.1-10%, TiO 2 0-10% , P 2 O 5 0 to 10%, more preferably CaO 40.11 to 43.76%, C11.2 to 15.87%, SiO 2 4.53 to 6.60%, Al 2 O 3 1.21 to 1.68%, Cl 15.87 to 19.61%, Na 2 O 2.12 ⁇ 3.18%, K 2 O 4.32 ⁇ 5.17%, MgO 1.68 ⁇ 2.87%, SO 3 2.86 ⁇ 4.79%, Fe 2 O 3 2.08 ⁇ 4.08%, TiO 2 0.38 ⁇ 0.43%, P 2 O 5 0.35 ⁇ 0.39 %, Most preferably CaO42.26%, C 14.13%
  • the waste incineration fly ash preferably further includes the following components in mass percentage: ZnO 0 to 1%, PbO 0 to 1%, Cr 2 O 3 0 to 1%, CuO 0 to 1%, MnO 0 to 1%, NiO 0 to 1%, BaO 0 to 1%, SrO 0 to 1%, CdO 0 to 1%, Hg 0 to 1%, more preferably ZnO 0.52 to 0.85%, PbO 0.16 to 0.17% , Cr 2 O 3 0.04 to 0.12%, CuO 0.05 to 0.08%, MnO 0.07 to 0.11%, NiO 0.02 to 0.07%, SrO 0.02 to 0.03%, Hg 0.001%, most preferably ZnO 0.58%, MnO 0.08%, NiO 0.06%.
  • the red mud preferably includes the following components in mass percentage: Fe 2 O 3 30-50%, Al 2 O 3 10-30%, SiO 2 15-50%, CaO 0.1-10% , MgO 0.1 to 5%, Na 2 O 1 to 10%, K 2 O 0.1 to 0.5%, TiO 2 0.5 to 10%, more preferably Fe 2 O 3 36.86 to 42.31%, Al 2 O 3 20.33 to 26.43% , SiO 2 18.50 to 19.21%, CaO 1.79 to 2.92%, MgO 0.24 to 0.44%, Na 2 O 7.69 to 9.33%, K 2 O 0.10 to 0.37%, TiO 2 2.01 to 4.51%, most preferably Fe 2 O 3 42.31%, Al 2 O 3 20.33%, SiO 2 19.21%, CaO 2.41%, MgO 0.23%, Na 2 O 8.87%, K 2 O 0.19%, TiO 2 2.01%.
  • the burning loss of the red mud is preferably 1 to 15%, more preferably 3.14 to 6.18%, and most preferably 4.11%.
  • the source of the waste incineration fly ash and red mud is not particularly limited, and a product well known to those skilled in the art may be used.
  • the invention efficiently utilizes the synergistic effect of carbon, calcium, heavy metal components in the waste incineration fly ash and the main components of iron, aluminum and silicon in the red mud, and finally can obtain alloy iron and cement materials to treat waste, Using the complementarity of the two waste components, the carbon in the waste incineration fly ash can provide a reducing agent for the reduction, thereby promoting the reduction of the iron minerals in the red mud to metallic iron.
  • the formation of metallic iron also promotes the waste incineration fly.
  • the iron-heavy heavy metal elements in the ash enter the iron phase, so that waste incineration fly ash and red mud, two important hazardous wastes and bulk industrial solid wastes in China that are urgently needed to be treated, can be comprehensively utilized.
  • the cement materials formed by A1 2 O 3 and SiO 2 in red mud and CaO in waste incineration fly ash have realized the recycling of solid waste, improved the comprehensive utilization rate of resources, which is conducive to the construction of a resource-saving society and can achieve more High economic value, while alloy iron products obtained through reduction are more expensive than iron concentrates, and because they contain trace elements of Ni, Cu, Cr and other elements, they are more valuable than direct reduced iron products.
  • the material can be used for the production of cement, the production cost is lower, and a lot of natural stone is saved.
  • the temperature of the reduction calcination is preferably 1100 ° C to 1350 ° C, more preferably 1250 ° C, and the time of the reduction reaction is preferably 30 to 90 min, more preferably 60 min.
  • the reduction reaction is preferably carried out in a muffle furnace.
  • the present invention preferably cools the calcined product.
  • the specific cooling method such as natural cooling or water quenching.
  • the present invention subject the roasted product to grinding-magnetic separation to obtain alloy iron and cement materials.
  • the grinding-magnetic separation preferably includes primary grinding, magnetic separation and secondary fine grinding performed in sequence;
  • the mass fraction of -0.043mm is preferably 50-80%.
  • the mass fraction of -0.043mm is 90-100%, and the specific surface area is 350-600m 2 / kg.
  • the mass fraction of the primary grinding product is -0.043mm, more preferably 69.32-73.48%, and most preferably 71.32%; the secondary fine grinding product is -0.043mm
  • the mass fraction is more preferably 92.14-97.36%, the specific surface area of the secondary finely ground mineral product is preferably 480-571 m 2 / kg, most preferably 94.58%, and the specific surface area is 550 m 2 / kg.
  • the magnetic field strength of the magnetic separation is preferably 1.8 to 2.0 kGs.
  • the magnetic separation is preferably performed in a magnetic separator.
  • FIG. 1 is a flow chart for preparing alloy iron and cement materials according to an embodiment of the present invention: the mixture obtained by mixing waste incineration fly ash and red mud is subjected to reduction roasting, in which it is determined whether to add an aluminum-containing additive according to the raw materials; Ore, magnetic separation and secondary fine grinding to obtain alloy iron and cement materials.
  • the amount of waste incineration fly ash is 35wt%, and the amount of red mud is 65wt%; the waste incineration fly ash and red mud are mixed according to the proportion and then put into the crucible.
  • the crucible is placed in a muffle furnace at 1200 °C for reduction and roasting for 90min; cooling, grinding once
  • the product fineness -0.043mm is 71.32%, and the resulting product is magnetically separated under the condition of magnetic field strength of 1.8kGs, which can obtain alloy iron containing trace amounts of Ni, Cu, Cr and other ferrophilic metals with an iron grade of 92.56% and an iron recovery rate of 83.22%.
  • the non-magnetic cement material is subjected to secondary fine grinding to obtain a cement material with a fineness of -0.043mm of 97.36% specific surface area of 480m 2 / kg.
  • the main phases of the cement material are vitreous and tricalcium silicate, with water Glass and sodium hydroxide are used as alkali activators, and the compressive strength of 28 days is 78Mpa.
  • fly ash contains trace impurities, the sum of the following chemical components in fly ash is less than 100%:
  • the red mud is Bayer red mud.
  • the main chemical components of the red mud are Fe 2 O 3 39.15%, Al 2 O 3 20.81%, SiO 2 18.91%; CaO 2.41%, MgO 0.24%, Na 2 O 7.69%, K 2 O 0.10%, TiO 2 4.51%, loss on ignition 6.18%.
  • the amount of waste incineration fly ash is 40wt%, and the amount of red mud is 60wt%.
  • the fineness of the grinding product is -0.043mm is 73.48%, and the resulting product is magnetically separated under the condition of magnetic field strength of 1.8kGs, which can obtain iron grade 91.96% and iron recovery rate 84.13% containing traces of Ni, Cu, Cr and other ferrophilic metals Alloy iron;
  • the non-magnetic cement material is finely ground twice to obtain a cement material with a fineness of -0.043mm and a specific surface area of 550m 2 / kg of 94.58%.
  • the main phases of the cement material are vitreous and tricalcium silicate. Sodium hydroxide and sodium hydroxide are used as alkali activ
  • the red mud component is Bayer red mud, and its main chemical components are:
  • the amount of waste incineration fly ash is 34% by weight, the amount of red mud is 50% by weight, and the alumina reagent is 16% by weight. Mix the waste incineration fly ash with red mud and alumina reagent according to the ratio and put it into the crucible.
  • the primary grinding product fineness -0.043mm is 69.32%
  • the resulting product is magnetically separated under the condition of magnetic field strength of 1.8kGs, and can obtain iron grade 93.73% and iron recovery rate of 85.94% containing trace Ni, Alloy iron of ferrophilic metals such as Cu and Cr;
  • the non-magnetic cement material is subjected to secondary fine grinding to obtain a fineness of -0.043mm of 92.14%, a specific surface area of 571m 2 / kg, and CaO 29.34%, Al 2 O 3 51.14%, calcium aluminate material product whose main phase is calcium aluminate, which can be used as calcium aluminate cement material.
  • the red mud component is Bayer red mud, and its main chemical components are:

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Abstract

本发明提供一种制备合金铁和水泥材料的方法，属于固体废物资源化领域。本发明高效利用垃圾焚烧飞灰中的碳、钙、重金属组分和赤泥中的铁、铝、硅组分的协同增效效应，最终可得到合金铁和水泥材料，以废治废，利用两种废弃物成分上的互补性，垃圾焚烧飞灰中的碳可以为还原提供还原剂，从而促进赤泥中的铁矿物还原成金属铁，金属铁的形成，又促进了垃圾焚烧飞灰中的亲铁重金属元素进入铁相中。同时，赤泥中的A1 2O 3、SiO 2和垃圾焚烧飞灰中的CaO形成的水泥材料实现了固体废物资源化，使垃圾焚烧飞灰和赤泥这两种我国亟待处理的重要危险废物和大宗工业固废得到资源化综合利用，提高了资源综合利用率。

Description

一种制备合金铁和水泥材料的方法
本申请要求于2018年10月11日提交中国专利局、申请号为CN201811183954.5、发明名称为“一种制备合金铁和水泥材料的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及固体废物资源化技术领域，特别涉及一种制备合金铁和水泥材料的方法。
背景技术
近年来，我国生活垃圾焚烧技术得到快速发展。截止2016年底，全国已建成生活垃圾焚烧厂近300座，日处理能力近30万吨，占我国城市生活垃圾无害化处理总量的比例已经超过32％。垃圾焚烧烟气净化过程产生大量的飞灰，按照垃圾焚烧量估算，2020年飞灰产生量将达到约1000万吨。垃圾焚烧飞灰由于富集重金属和二噁英类物质，且特性复杂，是列入《国家危险废物名录》的危险废物，需要进行特殊管理。但是目前我国飞灰无害化处置率较低，是我国垃圾焚烧污染控制及危险废物环境管理的薄弱环节。基于飞灰的基本性质，高温熔融被认为是一种减容效果显著、无害化彻底的较为理想的工艺。但是，高温熔融处置仅实现飞灰的减量化和无害化，而对于资源化还在研究中。
赤泥是氧化铝在生产过程中产生的废渣。由于近年来铝土矿的品位降低，导致赤泥的产生量逐年增加，目前我国赤泥的累计堆存量已达3亿多吨。除少部分应用于水泥生产、制砖等外，大多湿法露天筑坝堆存。目前，人们日益关注赤泥堆放给环境带来的危害，例如赤泥的堆放不仅占用大量土地，耗费较多的堆场建设和维护费用，而且存在于赤泥中的有害物质向地下渗透，造成地下水体和土壤污染。裸露赤泥形成的粉尘随风飞扬，污染大气，对人类和动植物的生存造成负面影响，恶化生态环境。随着赤泥产出量的日益增加和人们对环境保护意识的不断提高，最大限度地限制赤泥的危害，多渠道地利用和改善赤泥，已迫在眉睫。现有的赤泥处理方法 中，主要采用成本较高的焦炭或者煤粉还原焙烧回收其中的铁，得到的尾渣仍然为固体废弃物，不能实现赤泥的资源化利用。
发明内容
本发明的目的在于提供一种制备合金铁和水泥材料的方法。本发明以垃圾焚烧飞灰和赤泥为原料制得合金铁和水泥材料，实现了垃圾焚烧飞灰和赤泥的资源化利用。
本发明提供了一种制备合金铁和水泥材料的方法，包括以下步骤：
将垃圾焚烧飞灰和赤泥混合所得混合物进行还原焙烧，得到焙烧产物；
将所述焙烧产物经磨矿-磁选，得到合金铁和水泥材料。
优选地，所述混合物中垃圾焚烧飞灰的质量百分含量为30～70％，赤泥的质量百分含量为30～70％。
优选地，所述混合物中还包括含铝添加剂，所述混合物中含铝添加剂的质量百分含量为0～30％。
优选地，所述含铝添加剂包括氧化铝、铝粉、铝渣和铝灰中的一种或多种。
优选地，所述垃圾焚烧飞灰包括以下质量百分含量的组分：CaO10～70％、C 5～20％、SiO 2 0.1～10％、Al 2O 3 0.1～10％、Cl 0.1～30％、Na 2O0.1～10％、K 2O 0.1～10％、MgO 0.1～10％、SO 3 0.1～10％、Fe 2O 3 0.1～10％、TiO 2 0～10％、P 2O 5 0～10％。
优选地，所述垃圾焚烧飞灰还包括以下质量百分含量的组分：ZnO0～1％、PbO 0～1％、Cr 2O 3 0～1％、CuO 0～1％、MnO 0～1％、NiO 0～1％、BaO 0～1％、SrO 0～1％、CdO 0～1％、Hg 0～1％。
优选地，所述赤泥包括以下质量百分含量的组分：Fe 2O 3 30～50％、Al 2O 3 10～30％、SiO 2 15～50％、CaO 0.1～10％、MgO 0.1～5％、Na 2O 1～10％、K 2O 0.1～0.5％、TiO 2 0.5～10％；所述赤泥的烧失为1～15％。
优选地，所述还原焙烧的温度为1100～1350℃，还原焙烧的时间为30～90min。
优选地，所述磨矿-磁选包括依次进行的一次磨矿、磁选和二次细磨；
所得一次磨矿产品中细度是-0.043mm的质量分数为50～80％，所述 第二次细磨，细度是-0.043mm的质量分数为90～100％，比表面积350～600m 2/kg。
优选地，所述磁选的磁场强度为1.8～2.0kGs。
本发明提供了一种制备合金铁和水泥材料的方法，包括以下步骤：将垃圾焚烧飞灰和赤泥混合所得混合物进行还原焙烧，得到焙烧产物；将所述焙烧产物经磨矿-磁选，得到合金铁和水泥材料。本发明高效利用垃圾焚烧飞灰中的碳、钙、重金属组分和赤泥中的铁、铝、硅主要组分的协同增效效应，最终可得到合金铁和水泥材料。以废治废，利用两种废弃物成分上的互补性，垃圾焚烧飞灰中的碳可以为还原焙烧提供还原剂，从而促进赤泥中的铁矿物还原成金属铁；金属铁的形成，又促进了垃圾焚烧飞灰中的亲铁重金属元素进入铁相中，使垃圾焚烧飞灰和赤泥这两种我国亟待处理的重要危险废物和大宗工业固废得到资源化综合利用。同时，赤泥中的A1 2O 3和垃圾焚烧飞灰中的CaO、SiO 2形成的水泥材料实现了固体废物资源化，提高了资源综合利用率，有利于建设资源节约型社会，能够实现更高的经济价值，同时经过还原焙烧获得的合金铁产品，比铁精矿价格更高，并且由于其中含有微量的Ni，Cu，Cr等元素，其比直接还原铁产品的价值更高，得到的水泥材料可以用做水泥的生产，其生产成本更低，节约了大量的天然石材。
并且，本发明与现有垃圾焚烧飞灰熔融相比，不仅能够实现飞灰的减量化和无害化，还实现了飞灰的资源化；与现有垃圾焚烧飞灰熔融工艺相比，温度更低，垃圾焚烧飞灰熔融温度1400℃以上，本发明还原焙烧反应温度在1350℃以下，节约能耗；与现有赤泥-直接还原工艺相比，对固体废弃物垃圾焚烧飞灰的有效利用，一方面变有害废料为有价产品，同时避免了使用成本相对较高的焦炭和煤粉，降低了生产成本以及炼焦过程中对环境的污染；与现有赤泥-直接还原工艺相比，本发明不仅实现了对赤泥中铁的回收，同时也利用了赤泥中的其他成分，避免了其他成分对环境的二次污染。实施例的数据表明，本发明制得的合金铁的铁品位为91.96～93.73％，铁回收率为83.22～85.94％，水泥材料的比表面积为480～550m 2/kg，水泥材料主要物相为玻璃体和硅酸三钙，以水玻璃和氢氧化钠做碱激发剂，28天的抗压强度为78～86Mpa。
说明书附图
图1为本发明制备合金铁和水泥材料的方法的流程图。
具体实施方式
本发明提供了一种制备合金铁和水泥材料的方法，包括以下步骤：
将垃圾焚烧飞灰和赤泥混合所得混合物进行还原焙烧，得到焙烧产物；
将所述焙烧产物经磨矿-磁选，得到合金铁和水泥材料。
本发明将垃圾焚烧飞灰和赤泥混合所得混合物进行还原焙烧，得到焙烧产物。在本发明中，所述混合物中垃圾焚烧飞灰的质量百分含量优选为30～70％，更优选为34～38％，最优选为35％，赤泥的质量百分含量优选为30～70％，更优选为48～50％。
在本发明中，所述混合物中优选还包括含铝添加剂，所述混合物中含铝添加剂的质量百分含量优选为0～30％，更优选为14～16％，最优选为15％。
在本发明中，所述含铝添加剂优选包括氧化铝、铝粉、铝渣和铝灰中的一种或多种。当所述含铝添加剂优选为混合物时，本发明对所述混合物中各组分的用量没有特殊的限定，采用任意比例的混合物均可。本发明根据赤泥中的铝含量确定是否添加含铝添加剂，若赤泥中的铝含量为25％～30％时，加入含铝添加剂，诱导生成更多的铝酸钙，得到铝酸钙水泥材料；当赤泥中的铝含量为10～25％时，不添加含铝添加剂，生成主要物相为玻璃体和硅酸三钙的水泥材料。
在本发明中，所述垃圾焚烧飞灰优选包括以下质量百分含量的组分：CaO 10～70％、C 5～20％、SiO 2 0.1～10％、Al 2O 3 0.1～10％、Cl 0.1～30％、Na 2O 0.1～10％、K 2O 0.1～10％、MgO 0.1～10％、SO 3 0.1～10％、Fe 2O 30.1～10％、TiO 2 0～10％、P 2O 5 0～10％，更优选为CaO 40.11～43.76％、C11.2～15.87％、SiO 2 4.53～6.60％、Al 2O 3 1.21～1.68％、Cl 15.87～19.61％、Na 2O 2.12～3.18％、K 2O 4.32～5.17％、MgO 1.68～2.87％、SO 3 2.86～4.79％、Fe 2O 3 2.08～4.08％、TiO 2 0.38～0.43％、P 2O 5 0.35～0.39％，最优选为CaO42.26％、C 14.13％、SiO 2 5.31％、Al 2O 3 1.43％、Cl 18.91％、Na 2O 2.90％、K 2O 4.34％、MgO 2.37％、SO 3 3.78％、Fe 2O 3 2.89％、TiO 2 0.40％、P 2O 5 0.36％。
在本发明中，所述垃圾焚烧飞灰优选还包括以下质量百分含量的组分：ZnO 0～1％、PbO 0～1％、Cr 2O 3 0～1％、CuO 0～1％、MnO 0～1％、NiO0～1％、BaO 0～1％、SrO 0～1％、CdO 0～1％、Hg 0～1％，更优选为ZnO0.52～0.85％、PbO 0.16～0.17％、Cr 2O 3 0.04～0.12％、CuO 0.05～0.08％、MnO0.07～0.11％、NiO 0.02～0.07％、SrO 0.02～0.03％、Hg 0.001％，最优选为ZnO 0.58％、MnO 0.08％、NiO 0.06％。
在本发明中，所述赤泥优选包括以下质量百分含量的组分：Fe 2O 330～50％、Al 2O 3 10～30％、SiO 2 15～50％、CaO 0.1～10％、MgO 0.1～5％、Na 2O 1～10％、K 2O 0.1～0.5％、TiO 2 0.5～10％，更优选为Fe 2O 336.86～42.31％、Al 2O 3 20.33～26.43％、SiO 2 18.50～19.21％、CaO 1.79～2.92％、MgO 0.24～0.44％、Na 2O 7.69～9.33％、K 2O 0.10～0.37％、TiO 2 2.01～4.51％，最优选为Fe 2O 3 42.31％、Al 2O 3 20.33％、SiO 2 19.21％、CaO 2.41％、MgO0.23％、Na 2O 8.87％、K 2O 0.19％、TiO 2 2.01％。
在本发明中，所述赤泥的烧失优选为1～15％，更优选为3.14～6.18％，最优选为4.11％。
本发明对所述垃圾焚烧飞灰和赤泥的来源没有特殊的限定，采用本领域技术人员熟知的产品即可。
本发明高效利用垃圾焚烧飞灰中的碳、钙、重金属组分和赤泥中的铁、铝、硅主要组分的协同增效效应，最终可得到合金铁和水泥材料，以废治废，利用两种废弃物成分上的互补性，垃圾焚烧飞灰中的碳可以为还原提供还原剂，从而促进赤泥中的铁矿物还原成金属铁，金属铁的形成，又促进了垃圾焚烧飞灰中的亲铁重金属元素进入铁相中，使垃圾焚烧飞灰和赤泥这两种我国亟待处理的重要危险废物和大宗工业固废得到资源化综合利用。同时，赤泥中的A1 2O 3、SiO 2和垃圾焚烧飞灰中的CaO形成的水泥材料实现了固体废物资源化，提高了资源综合利用率，有利于建设资源节约型社会，能够实现更高的经济价值，同时经过还原获得的合金铁产品，比铁精矿价格更高，并且由于其中含有微量的Ni，Cu，Cr等元素，其比直接还原铁产品的价值更高，得到的水泥材料可以用做水泥的生产，其生产成本更低，节约了大量的天然石材。
在本发明中，所述还原焙烧的温度优选为1100℃～1350℃，更优选为1250℃，还原反应的时间优选为30～90min，更优选为60min。
在本发明中，所述还原反应优选在马弗炉中进行。
得到焙烧产物后，本发明优选将所述焙烧产物冷却。本发明对所述冷却的具体方式没有特殊的限定，具体的，如自然冷却或者水淬。
得到焙烧产物后，本发明将所述焙烧产物经磨矿-磁选，得到合金铁和水泥材料。在本发明中，所述磨矿-磁选优选包括依次进行的一次磨矿、磁选和二次细磨；
所得一次磨矿产品中细度是-0.043mm的质量分数优选为50～80％，所述二次细磨，细度是-0.043mm的质量分数为90～100％，比表面积350～600m 2/kg。在本发明中，所述一次磨矿产品中细度是-0.043mm的质量分数更优选为69.32～73.48％，最优选为71.32％；所述二次细磨矿产品中细度是-0.043mm的质量分数为更优选92.14～97.36％，所述二次细磨矿产品的比表面积优选为480～571m 2/kg，最优选为94.58％，比表面积550m 2/kg。
在本发明中，所述磁选的磁场强度优选为1.8～2.0kGs。
在本发明中，所述磁选优选在磁选机中进行。
为了进一步说明本发明，下面结合实施例对本发明提供的制备合金铁和水泥材料的方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
图1为本发明实施例制备合金铁和水泥材料的流程图：将垃圾焚烧飞灰和赤泥混合所得混合物进行还原焙烧，其中根据原料确定是否添加含铝添加剂；将焙烧产物冷却后进行一次磨矿、磁选和二次细磨，得到合金铁和水泥材料。
实施例1
垃圾焚烧飞灰用量35wt％，赤泥用量65wt％；将垃圾焚烧飞灰与赤泥按照比例混合均匀后放入坩埚，将坩埚放置于马弗炉1200℃下还原焙烧90min；冷却，一次磨矿产品细度-0.043mm为71.32％，所得产品在磁场强度为1.8kGs条件下磁选，可以得到铁品位92.56％，铁回收率83.22％的含微量Ni，Cu，Cr等亲铁金属的合金铁；将无磁性的水泥材料进行二 次细磨，得到，细度是-0.043mm为97.36％比表面积480m 2/kg的水泥材料，该水泥材料主要物相为玻璃体和硅酸三钙，以水玻璃和氢氧化钠做碱激发剂，28天的抗压强度78Mpa。
本实施例中，垃圾焚烧飞灰的主要化学成分如下，因飞灰中含有微量杂质，故飞灰中下述化学成分之和低于100％：
CaO 42.26％、C 11.2％、Cl 19.61％、SiO 2 4.53％、SO 3 3.78％、MgO2.87％、Al 2O 3 1.68％、Fe 2O 3 2.89％、K 2O 5.17％、Na 2O 3.18％、ZnO 0.85、TiO 2 0.43％、P 2O 5 0.39％、PbO 0.17％、CuO 0.05％、NiO 0.07％、Cr 2O 30.04％、SrO 0.03％、MnO 0.11％、Hg 0.001％。
赤泥成分为拜耳法赤泥，其主要化学成分赤泥中Fe 2O 3 39.15％，Al 2O 320.81％，SiO 2 18.91％；CaO 2.41％，MgO 0.24％，Na 2O 7.69％，K 2O 0.10％，TiO 2 4.51％，烧失量6.18％。
实施例2
垃圾焚烧飞灰用量40wt％，赤泥用量60wt％；将垃圾焚烧飞灰与赤泥按照比例混合均匀后放入坩埚，将坩埚放置于马弗炉1250℃下还原焙烧60min；冷却，第一段磨矿产品细度-0.043mm为73.48％，所得产品在磁场强度为1.8kGs条件下磁选，可以得到铁品位91.96％，铁回收率84.13％的含微量Ni，Cu，Cr等亲铁金属的合金铁；将无磁性的水泥材料进行二次细磨，得到细度是-0.043mm为94.58％比表面积550m 2/kg的水泥材料，该水泥材料主要物相为玻璃体和硅酸三钙，以水玻璃和氢氧化钠做碱激发剂，28天的抗压强度86Mpa。
本实施例中，垃圾焚烧飞灰的主要化学成分：
CaO 40.11％、C 15.87％、Cl 18.91％、SiO 2 5.31％、SO 32.86％、MgO2.37％、Al 2O 3 1.43％、Fe 2O 3 4.08％、K 2O 4.32％、Na 2O 2.12％、ZnO 0.58％、TiO 2 0.40％、P 2O 5 0.36％、PbO 0.17％、CuO 0.05％、NiO 0.06％、Cr 2O 30.04％、SrO 0.02％、MnO 0.08％、Hg 0.001％。
赤泥成分为拜耳法赤泥，其主要化学成分：
Fe 2O 3 42.31％、Al 2O 3 20.33％、SiO 2 19.21％、CaO 1.79％、MgO0.23％、Na 2O 8.87％、K 2O 0.19％、TiO 2 2.96％、烧失为4.11％。
实施例3
垃圾焚烧飞灰用量34wt％，赤泥用量50wt％，氧化铝试剂16wt％；将垃圾焚烧飞灰与赤泥、氧化铝试剂按照比例混合均匀后放入坩埚，将坩埚放置于马弗炉1350℃下还原焙烧90min；冷却，一次磨矿产品细度-0.043mm为69.32％，所得产品在磁场强度为1.8kGs条件下磁选，可以得到铁品位93.73％，铁回收率85.94％的含微量Ni，Cu，Cr等亲铁金属的合金铁；将无磁性的水泥材料进行二次细磨，得到细度是-0.043mm为92.14％，比表面积571m 2/kg，以及CaO 29.34％，Al 2O 3 51.14％，主要物相为铝酸钙的铝酸钙材料产品，该铝酸钙产品可用作铝酸钙水泥材料。
本实施例中，垃圾焚烧飞灰的主要化学成分：
CaO 43.76％、C 14.13％、Cl 15.87％、SiO 2 6.60％、SO 3 4.79％、MgO1.68％、Al 2O 3 1.21％、Fe 2O 3 2.08％、K 2O4.34％、Na 2O 2.90％、ZnO 0.52％、TiO 2 0.38％、P 2O 5 0.35％、PbO 0.16％、CuO 0.08％、NiO 0.02％、Cr 2O 30.12％、CdO 0.01％、Sb 2O 3 0.01％、MnO 0.07％、Hg 0.001％。
赤泥成分为拜耳法赤泥，其主要化学成分：
Fe 2O 3 36.86％、Al 2O 3 26.43％、SiO 2 18.50％、CaO 2.92％、MgO 0.44％、Na 2O 9.33％、K 2O 0.37％、TiO 2 2.01％、烧失为3.14％。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种制备合金铁和水泥材料的方法，包括以下步骤：
    将垃圾焚烧飞灰和赤泥混合所得混合物进行还原焙烧，得到焙烧产物；
    将所述焙烧产物经磨矿-磁选，得到合金铁和水泥材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述混合物中垃圾焚烧飞灰的质量百分含量为30～70％，赤泥的质量百分含量为30～70％。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述混合物中还包括含铝添加剂，所述混合物中含铝添加剂的质量百分含量为0～30％。
  4. 根据权利要求3所述的制备方法，其特征在于，所述含铝添加剂包括氧化铝、铝粉、铝渣和铝灰中的一种或多种。
  5. 根据权利要求1或2所述的制备方法，其特征在于，所述垃圾焚烧飞灰包括以下质量百分含量的组分：CaO 10～70％、C 5～20％、SiO 20.1～10％、Al 2O 30.1～10％、Cl 0.1～30％、Na 2O 0.1～10％、K 2O 0.1～10％、MgO 0.1～10％、SO 30.1～10％、Fe 2O 30.1～10％、TiO 20～10％、P 2O 50～10％。
  6. 根据权利要求5所述的制备方法，其特征在于，所述垃圾焚烧飞灰还包括以下质量百分含量的组分：ZnO 0～1％、PbO 0～1％、Cr 2O 30～1％、CuO 0～1％、MnO 0～1％、NiO 0～1％、BaO 0～1％、SrO 0～1％、CdO 0～1％、Hg 0～1％。
  7. 根据权利要求1或2所述的制备方法，其特征在于，所述赤泥包括以下质量百分含量的组分：Fe 2O 330～50％、Al 2O 310～30％、SiO 215～50％、CaO 0.1～10％、MgO 0.1～5％、Na 2O 1～10％、K 2O 0.1～0.5％、TiO 20.5～10％；所述赤泥的烧失为1～15％。
  8. 根据权利要求1所述的制备方法，其特征在于，所述还原焙烧的温度为1100～1350℃，还原焙烧的时间为30～90min。
  9. 根据权利要求1所述的制备方法，其特征在于，所述磨矿-磁选包括依次进行的一次磨矿、磁选和二次细磨；
    所得一次磨矿产品中细度是-0.043mm的质量分数为50～80％，所述 第二次细磨产品中细度是-0.043mm的质量分数为90～100％，比表面积350～600m 2/kg。
  10. 根据权利要求9所述的制备方法，其特征在于，所述磁选的磁场强度为1.8～2.0kGs。
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