WO2016155343A1 - 一种利用冶金中间包覆渣生产陶瓷材料的方法 - Google Patents

一种利用冶金中间包覆渣生产陶瓷材料的方法 Download PDF

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WO2016155343A1
WO2016155343A1 PCT/CN2015/095729 CN2015095729W WO2016155343A1 WO 2016155343 A1 WO2016155343 A1 WO 2016155343A1 CN 2015095729 W CN2015095729 W CN 2015095729W WO 2016155343 A1 WO2016155343 A1 WO 2016155343A1
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ceramic
intermediate coating
coating slag
metallurgical
raw material
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PCT/CN2015/095729
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English (en)
French (fr)
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李宇
裴德健
赵立华
苍大强
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北京科技大学
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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
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
    • 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
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Definitions

  • the invention relates to a method for directly producing metal materials by using metallurgical intermediate coating slag, and belongs to the field of comprehensive utilization of solid waste resources.
  • the intermediate coating slag is a metallurgical continuous casting process, and the tundish covering agent is added to the tundish to carry out the solid waste discharged after the relevant tundish metallurgy.
  • China is a large steel producing country with an annual output of about 800 million tons of crude steel.
  • the proportion of high-quality steel in crude steel is gradually increasing. High-quality steel will pass through the continuous casting process, so the output of metallurgical intermediate coating slag will gradually increase.
  • the invention applies the metallurgical intermediate coating slag as a raw material to the ceramic material industry, and after a simple process, completes a large amount of metallurgical intermediate coating slag consumption, produces high-strength materials, and solid-dissolves heavy metal Mn, Cr ions in the material. In the crystal, the metallurgical intermediate coating slag is efficiently and greenly utilized.
  • China's urbanization construction requires a large amount of non-metallic mineral resources every year, making full use of industrial solid waste to replace natural mineral resources, can reduce the development of natural non-metallic mineral resources, and avoid the risk of ecosystem damage caused by over-exploitation.
  • the inventors have found in long-term experiments that it is possible to make a large amount of metallurgical intermediate coating slag and prepare a ceramic material product with good properties, and it is possible to simultaneously add a part of clay and feldspar material, so that the green body has good plasticity, and Further ceramic materials such as quartz may be further added to supplement the chemical components.
  • the purpose of the invention is to make up for the vacancy of the high value-added utilization of the intermediate coating slag, and to provide a method for effectively producing metal materials by using metallurgical intermediate coating slag, which makes the metallurgical tundish scum resource effective and high.
  • the use of value, while using low temperature firing, is simple and feasible, is conducive to industrial production, and has obvious environmental, social and economic benefits.
  • the invention relates to a method for producing ceramic materials by using metallurgical intermediate coating slag, which is characterized in that: metallurgical intermediate coating slag is crushed, and other ingredients are used to prepare ceramic materials, mainly including the following steps:
  • the formed ceramic material green body is sent to the kiln for firing.
  • the metallurgical intermediate coating slag is a solid waste formed by tundish transportation or metallurgical continuous casting process, and its chemical composition is characterized by 28% ⁇ SiO 2 ⁇ 50%, 12% ⁇ CaO ⁇ 26%, 10% ⁇ MnO ⁇ 25%, 1.5% ⁇ Fe 2 O 3 ⁇ 20%, 10% ⁇ (MgO + Al 2 O 3 ) ⁇ 35%.
  • the weight ratio of the components of the raw materials used in the step a is 25-100% of the metallurgical intermediate coating slag, 0-50% of the clay, 0-25% of the feldspar, and 0-15% of the quartz.
  • the raw material powder is directly mixed with the aggregate and processed, and the aggregate is one or several mixed materials of river sand, coarse sand, tailings sand and waste ceramic brick inert aggregate, ceramic raw material powder and The incorporation ratio of the aggregate is 50-95% of the raw material powder and 5-50% of the aggregate.
  • the maximum firing temperature of the green body is 1050-1150 °C.
  • the ceramic material prepared by using the ceramic raw material powder in the step b has high flexural strength and low water absorption, the flexural strength value can exceed 60 MPa, and the water absorption value is less than 2%; in the ceramic raw material powder in the step b It is mixed into the aggregate and prepared as a ceramic sintered brick, and its compressive strength value can exceed 260 MPa.
  • the color of the above prepared ceramic material is naturally black or brown, and no coloring agent is added.
  • the intermediate coating slag can be used as a raw material for the production of architectural ceramics and high-strength industrial ceramics, as well as ceramic reinforcing agent addition and glass-ceramic frit.
  • the innovation of the invention lies in that according to its composition characteristics, a new utilization method for preparing ceramics by using the intermediate coating slag is proposed; and the harmful Mn and Fe ions are transformed into favorable ceramic components and mineral phases by composition design. Thereby, the strength of the ceramic can be increased, and the preparation of the high-strength ceramic can be realized; at the same time, the low-temperature energy-saving preparation can be realized by using the high-temperature melting and the uniform composition of the intermediate coating slag.
  • the experimental and application results show that the flexural strength of ceramics prepared by using the intermediate coating slag reaches or exceeds 2-4 times of the national standard of 35 MPa of ceramic tile, and the sintering temperature is about 100 ° C lower than that of traditional ceramic 1130-1230.
  • the invention utilizes metallurgical intermediate coating slag to manufacture a novel ceramic material, and the method fully utilizes the characteristics of rich SiO 2 and CaO, so that the metallurgical intermediate coating slag is obtained with high efficiency and high value, and the utilization thereof is utilized.
  • the rate reaches 25-100%.
  • the invention adopts metallurgical intermediate coating slag which has been melted at a high temperature and has uniform composition, and is suitable for low temperature firing, and the firing temperature is 1050-1150 ° C, which is lower than the traditional building ceramics preparation temperature of about 100 ° C, which significantly reduces energy consumption. Obvious environmental and economic benefits.
  • the invention is a novel high-strength silicon-calcium system ceramic material, and also utilizes the characteristics of manganese oxide, aluminum oxide and the like in the content of the intermediate coating slag.
  • ceramic materials with good mechanical properties can be prepared. All the ceramics obtained by the experiment have the superior performance of high strength and low water absorption.
  • the flexural strength is generally above 60Mpa, the highest is up to 155.94Mpa, the water absorption rate is generally 0.25%, and the lowest is 0.1%. Therefore, the intermediate coating slag can be used as a raw material for the production of architectural ceramics and high-strength industrial ceramics, and can also be used as a ceramic reinforcing agent and a glass-ceramic frit.
  • the present invention realizes the incorporation of a large amount of inexpensive inert aggregate on the basis of the above high-strength ceramic material as a ceramic sintering process.
  • the raw material of the brick reduces the cost of the sintered brick.
  • the prepared ceramic sintered brick has high compressive strength, the compressive strength value can exceed 260 MPa, and the prepared color is natural black or brown, without adding expensive coloring agent, greatly reducing The cost of sintered bricks.
  • the composition of the intermediate coating slag composition is as shown in Table 1 (tested by a fluorescence analyzer), wherein the intermediate coating slag 1 was used in Examples 1-4; and the intermediate coating slag 2 was used in Examples 5-7.
  • the weight distribution ratio of each component is: metallurgical intermediate coating slag 100%, clay 0%, feldspar 0%, quartz 0%, spray-dried after making mud, dry powder after spraying to suppress
  • the moisture content of the green body after drying is ⁇ 1%, and it is calcined in a roller kiln.
  • the optimum firing temperature is 1130 °C.
  • the product After firing, the product has a flexural strength of 155.94 MPa and a water absorption rate of 0.13%. It is an excellent ceramic. material.
  • the weight distribution ratio of each component is: metallurgical intermediate coating slag 85%, clay 10%, feldspar 5%, quartz 0%, sprayed and dried after spraying, dry powder after spraying to suppress
  • the moisture content of the green body after drying is less than 1%, and it is calcined in a roller kiln.
  • the optimum firing temperature is 1110 °C.
  • the product After firing, the product has a flexural strength of 115.61 MPa and a water absorption rate of 0.12%. It is an excellent ceramic. material.
  • the weight distribution ratio of each component is: metallurgical intermediate coating slag 55%, clay 30%, feldspar 15%, quartz 0%, sprayed and dried after spraying, dry powder after spraying to suppress
  • the optimum firing temperature is 1080 °C.
  • the product After firing, the product has a flexural strength of 73.93 MPa and a water absorption of 0.35%. It is an excellent ceramic. material.
  • the weight distribution ratio of each component is: metallurgical intermediate coating slag 25%, clay 50%, 25% feldspar, 0% quartz, spray-dried after being made into a slurry, dry powder after spraying to form by pressing, after drying, the moisture content of the green body is ⁇ 1%, and calcined in a roller kiln, the optimum firing temperature is 1100 °C. After firing, the product has a flexural strength of 74.22 MPa and a water absorption of 0.20%, which is an excellent ceramic material.
  • the weight distribution ratio of each component is: metallurgical intermediate coating slag 25%, clay 45%, feldspar 25%, quartz 5%, sprayed and dried after spraying, dry powder after spraying to suppress
  • the moisture content of the green body after drying is ⁇ 1%, and it is calcined in a roller kiln.
  • the optimum firing temperature is 1110 °C.
  • the product After firing, the product has a flexural strength of 69.52 MPa and a water absorption rate of 0.19%. It is an excellent ceramic. material.
  • the weight distribution ratio of each component is: metallurgical intermediate coating slag 70%, clay 20%, feldspar 10%, as a ceramic raw material, and based on the 20% river sand
  • the aggregate is uniformly stirred with water, and the moisture content of the mixture is up to 10%. Then, it is dry-formed by a press and calcined in a roller kiln.
  • the optimum firing temperature is 1080 ° C, and the compressive strength of the product after firing is 320.20 MPa. It is an excellent ceramic sintered brick.
  • the weight distribution ratio of each component is: metallurgical intermediate coating slag 55%, clay 45%, as a ceramic raw material, and based on the 30% waste ceramic tile aggregate, add water Stirring evenly, the moisture content of the mixture reaches 35%, and then extruded into a tunnel kiln for calcination.
  • the optimum firing temperature is 1090 ° C, and the compressive strength of the product after calcination is 287.50 MPa, which is an excellent ceramic.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Structural Engineering (AREA)
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Abstract

一种利用冶金中间包覆渣生产陶瓷材料的方法。其中，中间包覆渣组成为28%<SiO ２<50%，12%<CaO<26%，10%<MnO<25%，1.5%<Fe 2O 3<20%，10%<(MgO+Al 2O 3) <35%；陶瓷原料中，中间包覆渣占25-100%，粘土0-50%、长石0-25%和石英0-15%。原料经传统陶瓷工艺加工烧制获得陶瓷产品，其最高烧结温度为1050-1150℃。

Description

一种利用冶金中间包覆渣生产陶瓷材料的方法 技术领域：
本发明涉及直接利用冶金中间包覆渣生产陶瓷材料的方法，属于固体废弃物资源综合利用领域。
背景技术：
中间包覆渣是冶金连铸过程，在中间包加入中间包覆盖剂进行相关的中间包冶金后排出的固体废弃物。我国是钢铁生产大国，年产粗钢约8亿吨，而随着国家建设步伐加快，对高品质钢材的需求量也越来越大，高品质钢材在粗钢中比例也逐步提高，在冶炼高品质钢材，都会经过连续铸造过程，故此冶金中间包覆渣产出量也会逐步提高。
现在关于冶金中间包覆渣的综合利用的研究尚未提出，现用的处理方式仅为先磁选出铁后再堆积或填埋的简单方式，而这样的处理方式，势必占用大面积的土地，同时长期的堆积和填埋，使得中间包覆渣里面的重金属Mn、Cr等离子浸出，污染土地。
本发明将冶金中间包覆渣作为原料应用于陶瓷材料行业，经过简单的工艺过程，完成冶金中间包覆渣大量的消耗，生产高强度的材料，并且将重金属Mn、Cr等离子固溶于材料的晶体中，实现冶金中间包覆渣的高效、绿色利用。
同时，我国城镇化建设每年需要大量的非金属矿物资源，充分利用工业固体废渣代替天然矿物资源，可以减少天然非金属矿物资源的开发，也避免过度开采带来的生态系统破坏的风险。
发明内容：
本发明人在长期的实验中发现，要能够大量利用冶金中间包覆渣并制备出具有良好性能的陶瓷材料产品，可以同时加入部分粘土和长石的物料，使得生坯有良好的塑性，并且可以进一步加入石英等其他陶瓷原料补充化学组分。
本发明的目的是为了弥补对中间包覆渣高附加值利用的空缺，提供的一种有效利用冶金中间包覆渣生产陶瓷材料的方法，该方法使冶金中间包浮渣资源得到了有效且高值的利用，同时采用低温烧成，简单可行，有利于工业化生产，具有明显的环境、社会和经济效益。
一种利用冶金中间包覆渣生产陶瓷材料的方法，其特征在于：采用冶金中间包覆渣经破碎，并配以其它配料，制备陶瓷材料，主要包括如下步骤，
a、取经过破碎处理的中间包覆渣，或者中间包覆渣与粘土、长石和石英的一种或几种混料后作为陶瓷原料进行研磨，采用干法研磨制粉或者湿法研磨制粉工艺；
b、对所得原料粉末进行加湿或干燥，并进一步造粒、成型或直接与骨料混合后加工成型；
c、将成型后的陶瓷材料生坯送进窑炉烧成。
所述冶金中间包覆渣是中间包运输或冶金连铸过程形成的固体废弃物，其化学组成的特征为28％<SiO2<50％，12％<CaO<26％，10％<MnO<25％，1.5％<Fe2O3<20％，10％<(MgO+Al2O3)<35％。
在步骤a中采用的原料各组分的重量百分配比为：冶金中间包覆渣25-100％，粘土0-50％、长石0-25％，石英0-15％。
在步骤b将原料粉末直接与骨料混合后加工成型中，骨料为加入的河砂、粗砂、尾矿砂、废弃陶瓷砖惰性骨料中的一种或几种混料，陶瓷原料粉末与骨料的掺入比例为原料粉末50-95％，骨料5-50％。
在步骤c过程中，坯体最高烧成温度为1050-1150℃。
在步骤b中使用陶瓷原料粉末制备的陶瓷材料具有较高的抗折强度和较低的吸水率，抗折强度值能够超过60MPa，吸水率值小于2％；在步骤b中将陶瓷原料粉末中混入骨料并制备为陶瓷烧结砖，其抗压强度值可超过260MPa。以上制备陶瓷材料颜色呈自然黑色或褐色，无需添加着色剂。中间包覆渣可用于生产建筑陶瓷和高强工业用陶瓷的原料，也可以作为陶瓷增强剂添加和微晶玻璃熔块使用。
本发明的创新之处在于，根据其组成特点，提出利用中间包覆渣制备陶瓷的新利用方法；并通过组成设计，巧妙将有害的Mn、Fe离子转变成有利的陶瓷组分和矿相，从而能够增加陶瓷的强度，实现高强陶瓷制备；同时利用中间包覆渣经过高温熔化和成分较均一的特点，实现其低温节能制备。实验及应用结果证明，利用中间包覆渣制备的陶瓷抗折强度达到甚至超过陶瓷砖国家标准35MPa的2-4倍，同时烧结温度比传统陶瓷1130-1230低约100℃.
本发明采用上述技术解决方案所能达到的有益效果是：
1、本发明利用冶金中间包覆渣制造一种新型的陶瓷材料，该方法充分发挥了其富含SiO2和CaO的特点，使冶金中间包覆渣得到了高效且高值的利用，其利用率达到25-100％。
2、本发明采用冶金中间包覆渣已经过高温熔化，成分均匀，适合低温烧成，烧成温度为1050-1150℃，低于传统建筑陶瓷制备温度约100℃，显著减少能源消耗，有较为明显的环境和经济效益。
3、本发明是一种新型的高强硅钙体系陶瓷材料，同时还利用了中间包覆渣含量中氧化锰、氧化铝、等组成特点，经过原料匹配，可制备出具有力学性能好等陶瓷材料，所有实验得出的陶瓷具有高强度、低吸水率的优越性能，抗折强度普遍在60Mpa以上，最高可达155.94Mpa，吸水率普遍在0.25％水平，最低可达0.1％。故此中间包覆渣可用于生产建筑陶瓷和高强工业用陶瓷的原料，也可以作为陶瓷增强剂添加和微晶玻璃熔块使用。
4、本发明实现在上述高强度陶瓷材料基础上掺入大量廉价惰性骨料，作为制备陶瓷烧结 砖的原料，降低烧结砖成本，同时制备出的陶瓷烧结砖具有较高的抗压强度，抗压强度值能够超过260MPa，所制备颜色呈自然黑色或褐色，无需添加昂贵的着色剂，大大降低了烧结砖的成本。
具体实施方式：
中间包覆渣成分组成如表1(采用荧光分析仪测试获得)，其中实施例1-4采用中间包覆渣1；实施例5-7采用中间包覆渣2。
表1中间包覆渣成分组成
Figure PCTCN2015095729-appb-000001
实施例1
根据配方性能要求配料，各组分的重量百分配比为：冶金中间包覆渣100％，粘土0％，长石0％，石英0％，制成泥浆后喷雾干燥，将喷雾后干粉以压制成型，经干燥后坯体含水率<1％，入辊道窑煅烧，最佳烧成温度为1130℃，烧成后制品抗折强度为155.94MPa，吸水率0.13％，是一种优良的陶瓷材料。
实施例2
根据配方性能要求配料，各组分的重量百分配比为：冶金中间包覆渣85％，粘土10％，长石5％，石英0％，制成泥浆后喷雾干燥，将喷雾后干粉以压制成型，经干燥后坯体含水率<1％，入辊道窑煅烧，最佳烧成温度为1110℃，烧成后制品抗折强度为115.61MPa，吸水率0.12％，是一种优良的陶瓷材料。
实施例3
根据配方性能要求配料，各组分的重量百分配比为：冶金中间包覆渣55％，粘土30％，长石15％，石英0％，制成泥浆后喷雾干燥，将喷雾后干粉以压制成型，经干燥后坯体含水率<1％，入辊道窑煅烧，最佳烧成温度为1080℃，烧成后制品抗折强度为73.93MPa，吸水率0.35％，是一种优良的陶瓷材料。
实施例4
根据配方性能要求配料，各组分的重量百分配比为：冶金中间包覆渣25％，粘土50％， 长石25％，石英0％，制成泥浆后喷雾干燥，将喷雾后干粉以压制成型，经干燥后坯体含水率<1％，入辊道窑煅烧，最佳烧成温度为1100℃，烧成后制品抗折强度为74.22MPa，吸水率0.20％，是一种优良的陶瓷材料。
实施例5
根据配方性能要求配料，各组分的重量百分配比为：冶金中间包覆渣25％，粘土45％，长石25％，石英5％，制成泥浆后喷雾干燥，将喷雾后干粉以压制成型，经干燥后坯体含水率<1％，入辊道窑煅烧，最佳烧成温度为1110℃，烧成后制品抗折强度为69.52MPa，吸水率0.19％，是一种优良的陶瓷材料。
实施例6
根据配方性能要求配料，各组分的重量百分配比为：冶金中间包覆渣70％，粘土20％，长石10％，以此作为陶瓷原料，并在基础上掺入20％的河砂骨料，加水搅拌均匀，混合料的含水率达10％，然后经压机干压成型，入辊道窑煅烧，最佳烧成温度为1080℃，烧成后制品抗压强度为320.20MPa，是一种优良的陶瓷烧结砖。
实施例7
根据配方性能要求配料，各组分的重量百分配比为：冶金中间包覆渣55％，粘土45％，以此作为陶瓷原料，并在基础上掺入30％的废弃陶瓷砖骨料，加水搅拌均匀，混合料的含水率达35％，然后经挤压成型，入隧道窑煅烧，最佳烧成温度为1090℃，烧成后制品抗压强度为287.50MPa，，是一种优良的陶瓷烧结砖。
如上所述，仅为本发明的较佳实施例而已，不能以此来限定本发明的权利范围，因此依本发明申请专利范围所作的等同变化，仍属于本发明所涵盖的范围。

Claims (6)

  1. 一种利用冶金中间包覆渣生产陶瓷材料的方法，其特征在于：采用冶金中间包覆渣经破碎，并配以其它配料，制备陶瓷材料，主要包括如下步骤，
    a、取经过破碎处理的中间包覆渣，或者中间包覆渣与粘土、长石和石英的一种或几种混料后作为陶瓷原料进行研磨，采用干法研磨制粉或者湿法研磨制粉工艺；
    b、对所得原料粉末进行加湿或干燥，并进一步造粒、成型或直接与骨料混合后加工成型；
    c、将成型后的陶瓷材料生坯送进窑炉烧成。
  2. 根据权利要求1所述的一种利用冶金中间包覆渣生产陶瓷材料的方法，其特征在于：所述冶金中间包覆渣是中间包运输或冶金连铸过程形成的固体废弃物，其化学组成的特征为28％<SiO2<50％，12％<CaO<26％，10％<MnO<25％，1.5％<Fe2O3<20％，10％<(MgO+Al2O3)<35％。
  3. 根据权利要求1所述的一种利用冶金中间包覆渣生产陶瓷材料的方法，其特征在于：在步骤a中采用的原料各组分的重量百分配比为：冶金中间包覆渣25-100％，粘土0-50％、长石0-25％，石英0-15％。
  4. 根据权利要求1或3所述的一种利用冶金中间包覆渣生产陶瓷材料的方法，其特征在于：在步骤b将原料粉末直接与骨料混合后加工成型中，骨料为加入的河砂、粗砂、尾矿砂、废弃陶瓷砖惰性骨料中的一种或几种混料，陶瓷原料粉末与骨料的掺入比例为陶瓷原料粉末50-95％，骨料5-50％。
  5. 根据权利要求1所述的一种利用冶金中间包覆渣生产陶瓷材料的方法，其特征在于：在步骤c过程中，坯体最高烧成温度为1050-1150℃。
  6. 根据权利要求1所述的一种利用冶金中间包覆渣生产陶瓷材料的方法，其特征在于：在步骤b中使用陶瓷原料粉末制备的陶瓷材料具有较高的抗折强度和较低的吸水率，抗折强度值能够超过60MPa，吸水率值小于2％；在步骤b中将陶瓷原料粉末中混入骨料并制备为陶瓷烧结砖，抗压强度值可超过260MPa；以上制备陶瓷材料颜色呈自然黑色或褐色，无需添加着色剂；中间包覆渣可用于生产建筑陶瓷和高强工业用陶瓷的原料，也可以作为陶瓷增强剂添加和微晶玻璃熔块使用。
PCT/CN2015/095729 2015-04-03 2015-11-27 一种利用冶金中间包覆渣生产陶瓷材料的方法 WO2016155343A1 (zh)

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