CN113135704B - Activation utilization method for adverse factors of steel slag stability under autoclaved condition - Google Patents
Activation utilization method for adverse factors of steel slag stability under autoclaved condition Download PDFInfo
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
- B28B11/245—Curing concrete articles
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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
- 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
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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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
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
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Abstract
本发明提供了一种蒸压条件下钢渣安定性问题的活化利用方法：将钢渣粉、尾矿、水泥、垃圾焚烧飞灰、钡渣、磷酸二氢铵及硫酸镁混合，然后加水将物料混合均匀后制成砖坯；砖坯先在50℃～55℃湿热条件下预养护，然后于180℃～200℃条件下蒸压养护。本发明消除解决了钢渣中的f‑CaO的体积膨胀性，能够明显改善钢渣安定性差的问题，减少钢渣的活性损失，优化钢渣蒸压建材的生产工艺。本发明在改善钢渣安定性的同时，能够缩短蒸压砖的生产工艺流程，大幅度降低水泥用量，提高钢渣掺加量。The invention provides a method for activating and utilizing the stability of steel slag under autoclaved conditions: mixing steel slag powder, tailings, cement, waste incineration fly ash, barium slag, ammonium dihydrogen phosphate and magnesium sulfate, and then adding water to mix the materials After uniformity, the bricks are made; the bricks are pre-cured at 50°C to 55°C damp heat, and then autoclaved at 180°C to 200°C. The invention solves the volume expansion of f-CaO in the steel slag, can obviously improve the problem of poor stability of the steel slag, reduce the activity loss of the steel slag, and optimize the production process of the steel slag autoclaved building materials. While improving the stability of the steel slag, the invention can shorten the production process of the autoclaved brick, greatly reduce the amount of cement, and increase the amount of steel slag added.
Description
技术领域technical field
本发明涉及一种蒸压条件下钢渣安定性问题的活性化利用方法，通过对钢渣-尾矿-水泥体系在蒸压条件下进行预养护及改性改善试块安定性，提高体系强度，制备性能优良的蒸压建材。The invention relates to a method for activating and utilizing the stability problem of steel slag under autoclaved conditions. The steel slag-tailings-cement system is pre-cured and modified under autoclaved conditions to improve the stability of test blocks and improve the strength of the system. Autoclaved building materials with excellent performance.
背景技术Background technique
钢渣是钢铁制造过程中的副产品，我国每年钢渣产生量可达1亿吨，巨大的产生量却未有相匹配的高利用率，超过70%未能有效利用，这导致其堆存量持续增加。这不仅占用土地，对生态环境和安全造成严重威胁，也造成巨大的资源浪费。提高钢渣利用率，实现高质量安全利用，不但是产废企业的当务之急，也是国家的重大需求。Steel slag is a by-product of the steel manufacturing process. The annual production of steel slag in my country can reach 100 million tons. However, the huge amount of steel slag produced has not been matched with high utilization rate. This not only occupies land, but also poses a serious threat to the ecological environment and safety, and also causes huge waste of resources. Improving the utilization rate of steel slag and realizing high-quality and safe utilization is not only the top priority of waste-producing enterprises, but also a major demand of the country.
利用钢渣与水泥相似的C2S、C3S矿物成分，使其在道路工程领域有较大进展，在建筑墙材方面也有一定研究。但由于钢渣里含有f-CaO和f-MgO，遇水发生水化反应生成氢氧化物致使试块膨胀1.5～2倍，严重影响了钢渣的利用率。中国专利CN103524058A介绍了一种钢渣安定性处理办法，提供了一种常温或较低温度下的钢渣安定性处理办法，提高钢渣在建材制品中的掺量，为实现钢渣大规模利用提供了技术支持。中国专利CN104909634A介绍了一种大掺量钢渣粉制备的蒸压砖及其制备方法，提出在抑制剂的作用下对砖块预养护，消除了钢渣引起的安定性不良问题，有效提高钢渣蒸压试块的强度，但是钢渣胶凝活性损失较大。Utilizing the C 2 S and C 3 S mineral composition of steel slag and cement, it has made great progress in the field of road engineering, and there is also some research in building wall materials. However, due to the presence of f-CaO and f-MgO in the steel slag, the hydration reaction occurs when encountering water to form hydroxide, which causes the test block to expand by 1.5 to 2 times, which seriously affects the utilization rate of the steel slag. Chinese patent CN103524058A introduces a method for treating steel slag stability, provides a method for treating steel slag stability at room temperature or lower temperature, increases the content of steel slag in building materials, and provides technical support for realizing large-scale utilization of steel slag . Chinese patent CN104909634A introduces an autoclaved brick prepared with a large amount of steel slag powder and its preparation method, and proposes pre-curing the bricks under the action of inhibitors, which eliminates the problem of poor stability caused by steel slag and effectively improves the autoclaved steel slag. The strength of the test block, but the loss of the slag cementing activity is relatively large.
针对上述问题，本发明在蒸压砖生产过程中通过利用预养护和改性剂及助剂协同的方式实现对钢渣的安定性处理利用，使钢渣中的游离氧化物与飞灰、钡渣以及助剂发生水化反应生成难溶性复盐，使得对材料有害的游离氧化物转化为有益矿物，提高材料的力学性能，节省钢渣安定性单独预处理费用，缩短工艺流程，大幅度降低水泥和石灰用量，提高钢渣掺加量。In view of the above-mentioned problems, the present invention realizes the stable treatment and utilization of steel slag by using pre-curing, modifiers and auxiliary agents in the production process of autoclaved bricks, so that free oxides in steel slag and fly ash, barium slag and The hydration reaction of the additives generates insoluble double salts, which converts free oxides that are harmful to materials into beneficial minerals, improves the mechanical properties of materials, saves the cost of separate pretreatment for steel slag stability, shortens the process flow, and greatly reduces cement and lime. increase the amount of steel slag added.
发明内容SUMMARY OF THE INVENTION
本发明提供了一种在蒸压条件下进行钢渣安定性活化利用的办法，所采用的技术方案为：将钢渣粉、尾矿、水泥、垃圾焚烧飞灰、钡渣、磷酸二氢铵及硫酸镁混合，然后加水将物料混合均匀后制成砖坯；砖坯先在50℃～55℃湿热条件下预养护，然后于180℃～200℃条件下蒸压养护。The invention provides a method for activating and utilizing the stability of steel slag under autoclaved conditions. Magnesium is mixed, and then water is added to mix the materials evenly to make bricks; bricks are pre-cured at 50 ℃ ~ 55 ℃ moist heat conditions, and then autoclaved at 180 ℃ ~ 200 ℃ conditions.
在所述方法中，按重量计物料配比为：钢渣粉30%～40%、尾矿43%～52%、水泥4%～5%，垃圾焚烧飞灰3.5%～8.5%，钡渣1%～3%、磷酸二氢铵2.5%～3.5%、硫酸镁0.5%～1.5%。In the method, the proportion of materials by weight is: steel slag powder 30%-40%, tailings 43%-52%, cement 4%-5%, waste incineration fly ash 3.5%-8.5%, barium slag 1% %～3%, ammonium dihydrogen phosphate 2.5%～3.5%, magnesium sulfate 0.5%～1.5%.
所述钢渣粉为转炉钢渣经破碎、热焖、磁选除铁后干燥、粉磨得到，比表面积为400m2/kg～500m2/kg，其游离氧化钙含量2%～4%。The steel slag powder is obtained from converter steel slag by crushing, thermal stewing, magnetic separation, iron removal, drying and grinding, with a specific surface area of 400m 2 /kg to 500m 2 /kg, and a free calcium oxide content of 2% to 4%.
所述垃圾焚烧飞灰为垃圾焚烧过程中产生，其组成主要为CaO 16%～36%、SiO2 5%～20%、Al2O3 1%～13%、MgO 1%～4%、K2O 0.5%～8%、Na2O 1%～4%、Fe2O3 1%～4%、无机氯化物和硫酸盐等。The waste incineration fly ash is produced during the waste incineration process, and its composition is mainly CaO 16%-36%, SiO 2 5%-20%, Al 2 O 3 1%-13%, MgO 1%-4%, K 2 O 0.5% to 8%, Na 2 O 1% to 4%, Fe 2 O 3 1% to 4%, inorganic chlorides and sulfates, etc.
所述钡渣为制备硫酸钡过程产生的废渣，粉磨至比表面积为300m2/kg～450m2/kg，其二氧化硅含量20%～30%、氧化钡含量15%～20%。The barium slag is the waste slag produced in the process of preparing barium sulfate, and is ground to a specific surface area of 300m 2 /kg～450m 2 /kg, the content of silicon dioxide is 20% to 30%, and the content of barium oxide is 15% to 20%.
本发明的有益效果：本发明通过在蒸压砖生产过程中利用预养护和改性剂、助剂协同的方式实现对钢渣安定性问题的活性化利用，采取“疏”和“用”的思想，与传统的消除钢渣中的f-CaO的体积膨胀性（即体积安定性不良问题）思路（“堵”和“消”）完全相反。本发明旨在减少钢渣的活性损失，实现物尽其用。本发明在改善钢渣安定性的同时，能够缩短蒸压砖的生产工艺流程，大幅度降低水泥用量，提高钢渣掺加量。Beneficial effects of the present invention: The present invention realizes the activated utilization of the stability of steel slag by utilizing pre-curing, modifiers and auxiliary agents in the production process of autoclaved bricks, and adopts the ideas of "sparse" and "use". , which is completely opposite to the traditional idea ("blocking" and "elimination") of eliminating the volume expansion of f-CaO in steel slag (that is, the problem of poor volume stability). The invention aims to reduce the activity loss of the steel slag and realize the best use of the material. While improving the stability of the steel slag, the invention can shorten the production process of the autoclaved brick, greatly reduce the amount of cement, and increase the amount of steel slag added.
具体实施方式Detailed ways
下面结合实施例对本发明做详细说明，蒸压砖的测试参照《砌墙砖试验方法》GB/T2542-2012。实施方式所用钡渣比表面积为365m2/kg，钢渣比表面积为443m2/kg。The present invention is described in detail below with reference to the examples, and the test of autoclaved bricks refers to "Test Method for Wall Bricks" GB/T2542-2012. The specific surface area of the barium slag used in the embodiment is 365 m 2 /kg, and the specific surface area of the steel slag is 443 m 2 /kg.
实施例一Example 1
将40%的钢渣、43.5%的尾矿、4%的水泥、7.5%的垃圾焚烧飞灰、1%的钡渣、2.5%的磷酸二氢铵、1.5%的硫酸镁计量后加入到搅拌机中，加适量水搅拌均匀后压制成砖坯；水料比为0.09，成型压力为30MPa。Add 40% steel slag, 43.5% tailings, 4% cement, 7.5% waste incineration fly ash, 1% barium slag, 2.5% ammonium dihydrogen phosphate and 1.5% magnesium sulfate into the mixer , add an appropriate amount of water and stir evenly and press into bricks; the water-material ratio is 0.09, and the molding pressure is 30MPa.
将上述砖坯在50℃～55℃湿热养护8h，然后以3.5h升温—180℃恒温4h—自然降温的蒸压制度进行养护。The above bricks were cured at 50°C to 55°C for 8h in damp heat, and then cured in an autoclave system of 3.5h heating-180°C constant temperature 4h-natural cooling.
实施例二Embodiment 2
将35%的钢渣、45%的尾矿、4.5%的水泥、3.5%的垃圾焚烧飞灰、3%的钡渣、3.5%的磷酸二氢铵、1.5%的硫酸镁计量后加入到搅拌机中，加适量水搅拌均匀后压制成砖坯；水料比为0.09，成型压力为30MPa。Add 35% steel slag, 45% tailings, 4.5% cement, 3.5% waste incineration fly ash, 3% barium slag, 3.5% ammonium dihydrogen phosphate and 1.5% magnesium sulfate into the mixer , add an appropriate amount of water and stir evenly and press into bricks; the water-material ratio is 0.09, and the molding pressure is 30MPa.
将上述砖坯在50℃～55℃湿热养护8h，然后以3.5h升温—190℃恒温4h—自然降温的蒸压制度进行养护。The above bricks were cured at 50℃～55℃ for 8h in damp heat, and then cured in the autoclave system of 3.5h temperature rise-190℃ constant temperature for 4h-natural cooling.
实施例三Embodiment 3
将40%的钢渣、41.5%的尾矿、4%的水泥、5%的垃圾焚烧飞灰、3%的钡渣、2.5%的磷酸二氢铵、1%的硫酸镁计量后加入到搅拌机中，加适量水搅拌均匀后压制成砖坯；水料比为0.09，成型压力为30MPa。Add 40% steel slag, 41.5% tailings, 4% cement, 5% waste incineration fly ash, 3% barium slag, 2.5% ammonium dihydrogen phosphate and 1% magnesium sulfate into the mixer , add an appropriate amount of water and stir evenly and press into bricks; the water-material ratio is 0.09, and the molding pressure is 30MPa.
将上述砖坯在50℃～55℃湿热养护8h，然后以3.5h升温—100℃恒温4h—自然降温的蒸压制度进行养护。The above bricks were cured at 50℃～55℃ for 8h, and then cured in the autoclave system of 3.5h heating-100℃ constant temperature 4h-natural cooling.
实施例四Embodiment 4
将30%的钢渣、51.5%的尾矿、4.5%的水泥、8%的垃圾焚烧飞灰、2%的钡渣、3.5%的磷酸二氢铵、0.5%的硫酸镁计量后加入到搅拌机中，加适量水搅拌均匀后压制成砖坯；水料比为0.09，成型压力为30MPa。Add 30% steel slag, 51.5% tailings, 4.5% cement, 8% waste incineration fly ash, 2% barium slag, 3.5% ammonium dihydrogen phosphate and 0.5% magnesium sulfate into the mixer , add an appropriate amount of water and stir evenly and press into bricks; the water-material ratio is 0.09, and the molding pressure is 30MPa.
将上述砖坯在50℃～55℃湿热养护8h，然后以3.5h升温—180℃恒温4h—自然降温的蒸压制度进行养护。The above bricks were cured at 50°C to 55°C for 8h in damp heat, and then cured in an autoclave system of 3.5h heating-180°C constant temperature 4h-natural cooling.
实施例五Embodiment 5
将35%的钢渣、46%的尾矿、4.5%的水泥、6%的垃圾焚烧飞灰、2%的钡渣、2.5%的磷酸二氢铵、1.5%的硫酸镁计量后加入到搅拌机中，加适量水搅拌均匀后压制成砖坯；水料比为0.09，成型压力为30MPa。Add 35% steel slag, 46% tailings, 4.5% cement, 6% waste incineration fly ash, 2% barium slag, 2.5% ammonium dihydrogen phosphate and 1.5% magnesium sulfate into the mixer , add an appropriate amount of water and stir evenly and press into bricks; the water-material ratio is 0.09, and the molding pressure is 30MPa.
将上述砖坯在50℃～55℃湿热养护8h，然后以3.5h升温—200℃恒温4h—自然降温的蒸压制度进行养护。The above bricks were cured at 50℃～55℃ for 8h, and then cured in the autoclave system of 3.5h heating-200℃ constant temperature 4h-natural cooling.
实施例六Embodiment 6
将30%的钢渣、50%的尾矿、5%的水泥、8.5%的垃圾焚烧飞灰、3%的钡渣、3%的磷酸二氢铵、0.5%的硫酸镁计量后加入到搅拌机中，加适量水搅拌均匀后压制成砖坯；水料比为0.09，成型压力为30MPa。Add 30% steel slag, 50% tailings, 5% cement, 8.5% waste incineration fly ash, 3% barium slag, 3% ammonium dihydrogen phosphate and 0.5% magnesium sulfate into the mixer , add an appropriate amount of water and stir evenly and press into bricks; the water-material ratio is 0.09, and the molding pressure is 30MPa.
将上述砖坯在50℃～55℃湿热养护8h，然后以3.5h升温—200℃恒温4h—自然降温的蒸压制度进行养护。The above bricks were cured at 50℃～55℃ for 8h, and then cured in the autoclave system of 3.5h heating-200℃ constant temperature 4h-natural cooling.
对比例Comparative ratio
将30%的钢渣、65%的尾矿、5%的水泥计量后加入到搅拌机中，加适量水搅拌均匀后压制成砖坯；水料比为0.09，成型压力为30MPa。30% steel slag, 65% tailings, and 5% cement are added to the mixer after metering, and an appropriate amount of water is added to mix evenly and pressed into bricks; the water-material ratio is 0.09, and the molding pressure is 30MPa.
将上述砖坯在50℃～55℃湿热养护8h，然后以3.5h升温—200℃恒温4h—自然降温的蒸压制度进行养护。The above bricks were cured at 50℃～55℃ for 8h, and then cured in the autoclave system of 3.5h heating-200℃ constant temperature 4h-natural cooling.
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| CN115677246B (en) * | 2021-07-23 | 2024-03-01 | 中国科学院过程工程研究所 | Method for preparing cement admixture by utilizing steel slag |
| CN114349413B (en) * | 2022-03-18 | 2022-05-27 | 中国科学院生态环境研究中心 | Barium slag harmless recycling treatment method and prepared building material |
| CN115259826B (en) * | 2022-09-29 | 2022-12-27 | 河北化工医药职业技术学院 | Solid waste base 3D printing material |
| CN116408330B (en) * | 2023-06-01 | 2023-08-04 | 北京建工环境修复股份有限公司 | Co-processing method of barium slag, fly ash and dangerous waste incinerator slag |
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| DE1104419B (en) * | 1957-02-14 | 1961-04-06 | Nikolaus Wilhelm Knauf | Method and device for the production of building structures |
| CN100455533C (en) * | 2006-04-21 | 2009-01-28 | 华南理工大学 | A new type of masonry cement |
| CN103524058B (en) * | 2013-10-10 | 2015-09-02 | 河北科技大学 | A kind of steel slag stability treatment process |
| CN104909634A (en) * | 2015-06-04 | 2015-09-16 | 河北科技大学 | Autoclaved brick prepared from large-mixing-amount steel slag powder and preparation method of autoclaved brick |
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