CN112592126B - 一种水泥基热电材料 - Google Patents
一种水泥基热电材料 Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 35
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004576 sand Substances 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000011398 Portland cement Substances 0.000 claims abstract description 3
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 3
- 239000010959 steel Substances 0.000 claims abstract description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/142—Steelmaking slags, converter slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- 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
- C04B2111/90—Electrical properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种水泥基热电材料，属于冶金固废资源综合利用领域。该热电材料包括如下重量组分的混合料：水泥450份、碳化渣1080～1350份、标准砂0～270份、水325～345份。所述水泥为硅酸盐水泥，强度等级为42.5。所述碳化渣由攀钢含钛高炉渣经高温碳化后所得，且经破碎后过200目标准筛。该热电材料的热电动势率≥640μv/℃，抗压强度≥72.8MPa。本发明实现了高钛型高炉渣的碳化产物的全组分、高附加值利用，且不产生二次污染，因而在太阳能及工业余热等一些低品位热源领域具有广泛的应用前景。
Description
技术领域
本发明属于冶金固废资源综合利用领域，具体涉及一种利用高钛型高炉渣的碳化产物制备的水泥基热电材料。
背景技术
我国钒钛磁铁矿储量丰富，其中四川攀枝花-西昌地区已探明储量近100亿吨，约占全球储量的50％。目前，我国主要采用高炉-转炉冶炼工艺提取钒钛磁铁矿中的铁、钒资源，而对于其中的钛资源利用尚未有经济、成熟的处理工艺。钒钛磁铁矿经选矿和高炉冶炼工艺处理后，超过50％的钛元素进入高炉渣中，形成我国特有的高钛型高炉渣，其中TiO2含量可达20％～30％。含钛高炉渣作为固体废弃物，堆弃于渣场，给社会带来钛资源浪费和环境污染的双重压力。
从含钛高炉渣中提取钛资源最主要的方式是制备钛白粉TiO2，但由于含钛高炉渣中含钛量比钛精矿要低，以含钛高炉渣为原料生产钛白粉的成本高，且所生产的钛白粉质量相对较低。由攀钢集团公司开发的“高温碳化-低温氯化”工艺可有效提取含钛高炉渣中的钛，并建成了年产万吨的产业化示范线。该工艺先将液态含钛高炉渣经高温(1600～1800℃)碳化后生成含TiC的碳化渣；然后将碳化渣细颗粒在流化床上进行低温(400～550℃)氯化生成TiCl4气体，冷却后得到TiCl4颗粒；废渣可作为建筑材料。该法渣中TiO2的还原率可稳定控制在85％以上，但低温氯化率低，且在废渣中带入大量氯离子，对环境危害较大。
热电材料是一种能将热能和电能相互转换的功能材料。当材料的两端存在温度差异时，使用热电材料制备的温差发电器件可以直接将热能转换成电能，转换过程绿色环保。水泥基复合材料作为最主要的建筑材料，其内外两壁经常会出现较大的温度差异，因此，水泥基热电材料在太阳能及工业余热等一些低品位热源领域具有广泛的应用前景。
发明内容
为克服现有技术的不足，本发明要解决的技术问题是提供一种用高钛型高炉渣的碳化产物制备的水泥基热电材料，以期实现对高钛型高炉渣的全组分利用，且不产生二次污染。
本发明是通过以下技术方案予以实现的。
本发明提供了一种水泥基热电材料，它是由以下重量份数的组份制备而成：
进一步的，所述水泥为硅酸盐水泥，强度等级为42.5。
进一步的，所述碳化渣由攀钢含钛高炉渣经高温碳化后所得，且经破碎后过200目标准筛。
本发明同时提供了上述水泥基热电材料的制备方法，具体包括如下步骤：(1)将水泥、碳化渣、标准砂和水放入净浆搅拌机内先进行30s的慢拌再进行30s的高速搅拌；(2)将胶砂装入试模中并放到振实台上振平；(3)将装有胶砂的试模放入标准恒温恒湿养护箱养护24h，养护温度为20℃，湿度≥95％；(4)脱模，将试件水平置于水中并放入养护箱中养护28d，水温为20℃；(5)将试件置于90℃烘箱中，干燥24h。
与现有技术相比，本发明具有以下技术效果：
1、本发明使用的高钛型高炉渣经高温碳化还原后产生的碳化渣中含有的大量的TiC和未反应完的焦炭等物质，而这些物质均具有一定的导电性能，使用碳化渣代替标准砂，既可降低复合材料的电阻率，又可使其具有热电效应。
2、本发明使用的碳化渣经高温处理，具有比标准砂更高的强度，可有效提升复合材料的强度。
3、本发明制备的复合材料热电动势率≥640μv/℃，抗压强度≥72.8MPa。与传统水泥砂浆相比，本发明所制备的水泥基复合材料既有热电性能，又具有更高的抗压强度。
4、本发明实现了碳化渣的全组分、高附加值利用，且不产生二次污染，因而在太阳能及工业余热等一些低品位热源领域具有广泛的应用前景。
具体实施方式
为了进一步了解本发明的技术内容，以下将结合具体实施例进行说明，但本发明不局限于下述实施例。
实施例1
原料重量份数如下：水泥450份，碳化渣1080份，标准砂270份，水325份。制备过程如下：(1)将水泥、碳化渣、标准砂和水放入净浆搅拌机内先进行30s的慢拌再进行30s的高速搅拌；(2)将胶砂装入试模中并放到振实台上振平；(3)将装有胶砂的试模放入标准恒温恒湿养护箱养护24h，养护温度为20℃，湿度95％；(4)脱模，将试件水平置于水中并放入养护箱中养护28d，水温为20℃；(5)将试件置于90℃烘箱中，干燥24h。
所得水泥基热电材料的热电动势率为640μv/℃，电阻率为2.0×104Ω·m，抗压强度为74.7MPa。作为对比，相同方法所制备的水泥砂浆(全部以标准砂为集料)不具有热电性能，电阻率为1.4×105Ω·m，抗压强度为59.4MPa。
实施例2
原料重量份数如下：水泥450份，碳化渣1215份，标准砂135份，水335份。制备过程与实施例1相同，在此不再赘述。
所得水泥基热电材料的热电动势率为648μv/℃，电阻率为1.9×104Ω·m，抗压强度为73.2MPa。
实施例3
原料重量份数如下：水泥450份，碳化渣1350份，水345份。制备过程与实施例1相同，在此不再赘述。
所得水泥基热电材料的热电动势率为660μv/℃，电阻率为1.7×104Ω·m，抗压强度为72.8MPa。
Claims (3)
1.一种水泥基热电材料，其特征在于，它是由以下重量份数的组份制备而成：
水泥 450份；
碳化渣 1080~1350份；
标准砂 0~270份；
水 325~345份；
所述碳化渣由攀钢含钛高炉渣经高温碳化后所得，且经破碎后过200目标准筛。
2.如权利要求1所述的水泥基热电材料，其特征在于，所述水泥为硅酸盐水泥，强度等级为42.5。
3.如权利要求1所述的水泥基热电材料的制备方法，其特征在于包括如下步骤：
（1）将水泥、碳化渣、标准砂和水放入净浆搅拌机内先进行30 s的慢拌再进行30 s的高速搅拌；
（2）将胶砂装入试模中并放到振实台上振平；
（3）将装有胶砂的试模放入标准恒温恒湿养护箱养护24 h，养护温度为20oC，湿度≥95%；
（4）脱模，将试件水平置于水中并放入养护箱中养护28 d，水温为20℃；（5）将试件置于90℃烘箱中，干燥24 h。
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| CN107555435A (zh) * | 2017-08-31 | 2018-01-09 | 攀枝花学院 | 一种碳热还原含钛高炉渣制备碳化钛的方法 |
| CN107827375A (zh) * | 2017-12-18 | 2018-03-23 | 攀枝花环业冶金渣开发有限责任公司 | 一种混凝土用高钛型高炉矿渣微粉及混凝土 |
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| CN107954615A (zh) * | 2017-12-18 | 2018-04-24 | 攀枝花环业冶金渣开发有限责任公司 | 一种含有高钛型高炉渣膨珠的水泥 |
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| CN107555435A (zh) * | 2017-08-31 | 2018-01-09 | 攀枝花学院 | 一种碳热还原含钛高炉渣制备碳化钛的方法 |
| CN107827375A (zh) * | 2017-12-18 | 2018-03-23 | 攀枝花环业冶金渣开发有限责任公司 | 一种混凝土用高钛型高炉矿渣微粉及混凝土 |
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