WO2024066530A1 - 一种利用工业固废制备用于冬季施工的路面修补材料 - Google Patents

一种利用工业固废制备用于冬季施工的路面修补材料 Download PDF

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Publication number
WO2024066530A1
WO2024066530A1 PCT/CN2023/102582 CN2023102582W WO2024066530A1 WO 2024066530 A1 WO2024066530 A1 WO 2024066530A1 CN 2023102582 W CN2023102582 W CN 2023102582W WO 2024066530 A1 WO2024066530 A1 WO 2024066530A1
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parts
solid waste
aluminum
sulfur
based iron
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English (en)
French (fr)
Inventor
王旭江
王文龙
孙德强
李敬伟
毛岩鹏
王子良
宋占龙
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Shandong University
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Shandong University
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Priority to GB2407985.7A priority Critical patent/GB2628055A/en
Publication of WO2024066530A1 publication Critical patent/WO2024066530A1/zh
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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
    • 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
    • C04B28/06—Aluminous cements
    • C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • 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
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • 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
    • C04B28/06—Aluminous 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
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • 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
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • 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
    • 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
    • C04B7/32—Aluminous 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
    • C04B7/00—Hydraulic cements
    • C04B7/32—Aluminous cements
    • C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • 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
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C11/00—Details of pavings
    • E01C11/005—Methods or materials for repairing pavings
    • 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
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
    • 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
    • C04B2111/72—Repairing or restoring existing buildings or building materials
    • 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
    • C04B2111/76—Use at unusual temperatures, e.g. sub-zero
    • 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
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
    • E01C7/00—Coherent pavings made in situ
    • E01C7/08—Coherent pavings made in situ made of road-metal and binders
    • E01C7/18—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders
    • E01C7/187—Repairing bituminous covers, e.g. regeneration of the covering material in situ, application of a new bituminous topping
    • 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
    • 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

Definitions

  • the present invention belongs to the field of solid waste utilization and relates to cement concrete materials, and specifically relates to a solid waste-based cement concrete pavement rapid repair material suitable for winter construction, which can be mainly used for emergency repair operations in low temperature environments of cement pavements, airport runways, bridges, culverts, tunnels and other projects.
  • the present invention provides a method for preparing road repair materials for winter construction using industrial solid waste, which effectively overcomes the problem that road repair materials are difficult to harden during winter construction.
  • the repair material preparation cost is low, carbon emissions are low, and the process is simple, and the problem of solid waste resource utilization is also solved.
  • the present invention adopts the following technical solution:
  • the first aspect of the present invention provides a solid waste-based iron-rich, sulfur-aluminum-based cementitious material clinker, which is composed of the following raw materials in parts by weight: 35-43 parts of steel slag powder, 23-29 parts of desulfurized gypsum, 21-26 parts of aluminum ash powder, and 9-19 parts of limestone tailings powder; after the above raw materials are evenly mixed, they are calcined at 1150-1250°C for 15-45min to obtain the solid waste-based iron-rich, sulfur-aluminum-based cementitious material clinker.
  • the second aspect of the present invention provides a solid waste-based iron-sulfur-aluminum-rich cementitious material.
  • the obtained clinker is ground with 5%-15% desulfurized gypsum to a specific surface area greater than 300m2 /kg to obtain the solid waste-based iron-sulfur-aluminum-rich cementitious material.
  • the third aspect of the present invention provides a method for preparing a solid waste-based iron-sulfur-aluminum-rich negative temperature pavement repair material, comprising:
  • the solid waste-based iron-sulfur-aluminum-rich cementitious material is dry-mixed evenly with calcium chloride, lithium carbonate, polycarboxylic acid water reducer, redispersible latex powder and hydroxyethyl methyl cellulose ether, and then aggregate is added for secondary mixing to obtain the solid waste-based iron-sulfur-aluminum-rich negative temperature pavement repair material.
  • the fourth aspect of the present invention provides a solid waste-based iron-sulfur-aluminum-based negative temperature pavement repair material, which is composed of the following raw materials in parts by weight: 45-55 parts of the above-mentioned solid waste-based iron-sulfur-aluminum-based cementitious material, 45-55 parts of aggregate, 2-5 parts of calcium chloride, 0.2-0.8 parts of lithium carbonate, 0.1-0.3 parts of polycarboxylic acid water reducer, 1-3 parts of redispersible latex powder, and 0.1-0.3 parts of hydroxyethyl methyl cellulose ether.
  • the use temperature of the above road repair materials is ⁇ -20°C. When used at negative temperature, the raw materials do not need to be heated, and appropriate After adding the proportion of water, construction can begin.
  • the pavement repair material of the present invention has an operating temperature of ⁇ -20°C and can be used in negative temperature environments without any additional measures.
  • the main difference between the iron-rich sulfoaluminate cementitious material clinker of the present invention and the ordinary sulfoaluminate cement clinker is that the content of Fe2O3 in the iron-rich sulfoaluminate cementitious material clinker is 12-15wt %, while the content of Fe2O3 in the ordinary sulfoaluminate cement clinker is only 1-3wt%.
  • the increase of Fe2O3 content changes the mineral system of the material.
  • Fe2O3 As the content of Fe2O3 increases , a part of Fe2O3 promotes the main minerals of the cementitious material to The crystal transformation makes the orthorhombic Convert to cubic It has a higher hydration heat release and a faster hydration heat release rate, so it can better resist the frost damage caused by negative temperature environment; part of Fe 2 O 3 forms iron phase (C 2 F ⁇ C 4 AF), and the heat release rate of the iron phase is earlier, which further enhances the heat release advantage of the material.
  • the hydration products are mainly mineral phases such as calcium sulfonate, aluminum gel, and iron gel.
  • the hydration reaction is very rapid, and the calcium sulfonate crystals quickly overlap to provide early strength.
  • the aluminum gel and iron gel are filled between the calcium sulfonate crystals, which effectively reduces the porosity of the material, making the pore size in the system mostly distributed below 200nm.
  • the saturated vapor pressure theory the smaller the pore size, the higher the saturated vapor pressure in the pore, and the lower the freezing point of the solution in the pore, thereby ensuring that most of the water in the slurry is not frozen under negative temperature conditions. Therefore, cubic type Iron-rich sulfoaluminate cementitious materials with higher iron-phase mineral content are more suitable for negative temperature repair than ordinary sulfoaluminate cement.
  • the admixtures used in the present invention include antifreeze components, water-reducing components, early strength components, bonding components and water-retaining components.
  • the selected admixtures can be well adapted to the solid waste-based iron-sulfur-aluminum-rich cementitious materials without introducing other impurity ions.
  • the amount of admixture added is small, which can ensure the strength performance of the material while maintaining the workability of the material.
  • the present invention uses a large amount of solid waste, reduces the production cost of repair materials, and solves the problem of large-scale storage of solid waste.
  • the present invention can enable the repair material to obtain better performance at a lower production cost.
  • FIG1 is a flow chart of the preparation of the repair material of the present invention.
  • a solid waste-based iron-sulfur-aluminum-rich cementitious material clinker includes the following raw materials by weight: 35-43 parts of steel slag powder, 23-29 parts of desulfurized gypsum, 21-26 parts of aluminum ash powder, and 9-19 parts of limestone tailings powder.
  • the raw materials are calcined at a temperature of 1150-1250° C. for a calcination time of 15-45 minutes to obtain the solid waste-based iron-sulfur-aluminum-rich cementitious material clinker.
  • the present invention also provides a solid waste-based iron-sulfur-aluminum-rich cementitious material.
  • the solid waste-based iron-sulfur-aluminum-rich cementitious material is obtained by grinding the above-mentioned clinker and 5%-15% desulfurized gypsum to a specific surface area greater than 300m2 /kg.
  • the present invention also provides a method for preparing the above-mentioned solid waste-based iron-rich sulfur-aluminum-based negative temperature pavement repair material, which comprises dry-mixing the above-mentioned solid waste-based iron-rich sulfur-aluminum-based cementitious material with additives such as calcium chloride, lithium carbonate, polycarboxylic acid water reducer, redispersible latex powder, hydroxyethyl methyl cellulose ether, etc., and then adding aggregate for secondary mixing to obtain the solid waste-based iron-rich sulfur-aluminum-based negative temperature pavement repair material.
  • additives such as calcium chloride, lithium carbonate, polycarboxylic acid water reducer, redispersible latex powder, hydroxyethyl methyl cellulose ether, etc.
  • the aggregate used in the present invention is at least one of steel slag/coal gangue/stone powder.
  • the aggregate does not need to be ground, but is directly used as the aggregate of the repair material after the screening-crushing-screening process, and the screening intervals are 0-1.25mm, 1.25-2.5mm, and 2.5-5mm. Among them, the aggregate accounts for 2.5-5mm at 15-45%, 1.25-2.5mm at 35%-75%, and 0-1.25mm at 10%-25%.
  • the free CaO content shall not be higher than 7% to ensure the stability of the material, and no requirements are made for coal gangue or stone powder.
  • 45-55 parts by weight of solid waste-based iron-sulfur-aluminum-rich cementitious material 45-55 parts by weight of aggregates such as steel slag/coal gangue/stone powder, 2-5 parts by weight of calcium chloride, 0.2-0.8 parts by weight of lithium carbonate, 0.1-0.3 parts by weight of polycarboxylic acid water reducer, 1-3 parts by weight of redispersible latex powder, and 0.1-0.3 parts by weight of hydroxyethyl methyl cellulose ether.
  • the use temperature of the above road repair materials is ⁇ -20°C.
  • the raw materials When used at negative temperature, the raw materials do not need to be heated, and construction can be carried out after adding an appropriate proportion of water.
  • the material mixing water is required to have a water temperature above 5°C and a water-to-material ratio of 0.12-0.15 to ensure the hydration reaction.
  • the polycarboxylate water reducer was a chemically pure high-performance water reducer purchased from Shandong Huadi Building Technology Co., Ltd.
  • Redispersible latex powder was purchased from Shandong Yousuo Chemical Technology Co., Ltd.
  • Hydroxyethyl methyl cellulose ether was purchased from Shandong Yousuo Chemical Technology Co., Ltd.
  • the temperature of the mixing water was 5°C.
  • the preparation method of aggregate is as follows: crush and screen the steel slag, 2.5-5mm is 15%, 1.25-2.5mm is 75%, and 0-1.25mm is 10%.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a road repair material comprises the following components: 47.8 parts by weight of cementitious material, 47.8 parts by weight of aggregate, a water-to-material ratio of 0.12, 3 parts by weight of calcium chloride, 0.2 parts by weight of lithium carbonate, 0.1 parts by weight of polycarboxylic acid water reducer, 1 part by weight of redispersible latex powder, and 0.1 parts by weight of hydroxyethyl methyl cellulose ether.
  • the preparation method of the cementitious material is as follows: 37 parts of steel slag, 28 parts of desulfurized gypsum, 24 parts of aluminum ash, 11 parts of limestone tailings, calcined at 1250°C for 45 minutes, and ground evenly with 5% desulfurized gypsum powder to a specific surface area of 300m2 /kg.
  • the water-to-material ratio of the above concrete pavement repair materials when used is 0.12.
  • the curing temperature is -20°C, and the compressive strength and bonding strength of the materials are measured.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • a road repair material comprises the following ingredients: 45 parts by weight of cementitious material, 50 parts by weight of aggregate, a water-to-material ratio of 0.12, 1.9 parts by weight of calcium chloride, 0.8 parts by weight of lithium carbonate, 0.2 parts by weight of polycarboxylate water reducer, 2 parts by weight of redispersible latex powder, and 0.1 parts by weight of hydroxyethyl methyl cellulose ether.
  • the preparation method of cementitious material is as follows: 37 parts of steel slag, 28 parts of desulfurized gypsum, 24 parts of aluminum ash, and limestone. 11 parts of tailings were calcined at 1250°C for 45 minutes and ground evenly with 5% desulfurized gypsum powder to a specific surface area of 300m2 /kg.
  • the preparation method of aggregate is as follows: crush and screen the steel slag, 2.5-5mm is 15%, 1.25-2.5mm is 75%, and 0-1.25mm is 10%.
  • the water-to-material ratio of the above concrete pavement repair materials when used is 0.12.
  • the curing temperature is -20°C, and the compressive strength of the materials is measured.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the cementitious material preparation method is 37 parts of steel slag, 28 parts of desulfurized gypsum, 24 parts of aluminum ash, 11 parts of limestone tailings, calcined at 1180°C for 15 minutes, and ground evenly with 15% desulfurized gypsum to a specific surface area of 300m2 /kg.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the aggregate preparation method is: crushing and screening the coal gangue, 2.5-5 mm for 15%, 1.25-2.5 mm for 75%, 0-1.25 mm for 10%.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • Example 1 The difference from Example 1 is that the curing temperature is 20°C.
  • the compressive performance of the pavement repair material prepared by the present invention obviously meets the requirements for repair materials in JT/T1211.1-2018 "Rapid Repair Materials for Cement Concrete in Highway Engineering".
  • the present invention effectively overcomes the many defects of similar products in the prior art, and has the advantages of rapid hardening at negative temperatures, low cost, low carbon emissions, and large solid waste utilization. It can meet the requirements for rapid and high-strength repair of pavements in negative temperature environments and has extremely high industrial utilization value.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Architecture (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Road Paving Structures (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

本发明属于固废利用领域，提供了一种利用工业固废制备用于冬季施工的路面修补材料，由如下重量份的原料组成：固废基富铁硫铝系胶凝材料45-55份，骨料45-55份，氯化钙2-5份，碳酸锂0.2-0.8份，聚羧酸减水剂0.1-0.3份，可再分散性乳胶粉1-3份，羟乙基甲基纤维素醚0.1-0.3份。上述修补材料具有负温迅速硬化、成本低、碳排放少、固废利用量大等优点，可满足路面在负温环境下快速高强修补的要求，具极高的产业利用价值。

Description

一种利用工业固废制备用于冬季施工的路面修补材料
本发明要求于2022年09月29日提交中国专利局、申请号为202211199528.7、发明名称为“一种利用工业固废制备用于冬季施工的路面修补材料”的中国专利申请的优先权，其全部内容通过引用结合在本发明中。
技术领域
本发明属于固废利用领域，涉及水泥混凝土材料，具体涉及一种适用于冬季施工的固废基水泥混凝土路面快速修补材料，可主要应用于水泥路面、机场跑道及桥梁、涵洞、隧道等工程的低温环境下抢修作业。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
目前，当温度处于负温或者处于正负温交替的环境中，大多数现有的混凝土路面修补材料无法满足快速硬化、性能高强等要求。根据《混凝土结构工程施工及验收规范》、《混凝土质量控制标准》中的要求，冬季施工时需要采取额外措施以保证施工进行。主要包括：拌合水应加热至60～70℃、混凝土浇筑的温度不低于15℃。但此类方法成本高昂、耗能巨大、操作繁琐，难以保证施工质量。同时，目前普遍的修补材料多采用硅酸盐水泥、高铝水泥、磷酸镁水泥等作为胶凝材料，石英砂、河砂等作为骨料，这些胶凝材料和骨料面临着生产成本高、碳排放量大等缺点，限制了修补材料的实际应用。
发明内容
为了解决上述问题，本发明提供一种利用工业固废制备应用于冬季施工的路面修补材料的制备方法，有效地克服了路面修补材料在冬季施工过程中难以硬化的问题，修补材料制备成本低、碳排放低、工艺简单，还解决了固废资源化利用的问题。
为了实现上述目的，本发明采用如下技术方案：
本发明的第一个方面，提供了一种固废基富铁硫铝系胶凝材料熟料，由如下重量份的原料组成：钢渣粉35-43份，脱硫石膏23-29份，铝灰粉21-26份，石灰石尾矿粉9-19份；将以上原料混合均匀后在1150-1250℃煅烧15-45min，可得固废基富铁硫铝系胶凝材料熟料。
本发明的第二个方面，提供了一种固废基富铁硫铝系胶凝材料，将所得熟料与5％-15％脱硫石膏粉磨至比表面积大于300m2/kg，即得固废基富铁硫铝系胶凝材料。
本发明的第三个方面，提供了一种固废基富铁硫铝系负温路面修补材料的制备方法，包括：
将固废基富铁硫铝系胶凝材料与氯化钙、碳酸锂、聚羧酸减水剂、可再分散性乳胶粉、羟乙基甲基纤维素醚一次干混均匀，后加入骨料进行二次混合，从而得到固废基富铁硫铝系负温路面修补材料。
本发明的第四个方面，提供了一种固废基富铁硫铝系负温路面修补材料，由如下重量份的原料组成：将上述的固废基富铁硫铝系胶凝材料45-55份，骨料45-55份，氯化钙2-5份，碳酸锂0.2-0.8份，聚羧酸减水剂0.1-0.3份，可再分散性乳胶粉1-3份，羟乙基甲基纤维素醚0.1-0.3份。
以上路面修补材料使用温度≥-20℃。负温使用时，原料无需加热，加入适当 比例的水后，即可施工。
本发明的有益效果
(1)本发明的路面修补材料使用温度≥-20℃，无需额外措施，即可以实现负温环境应用。
(2)本发明的富铁硫铝系胶凝材料熟料与普通硫铝酸盐水泥熟料的主要区别在于：富铁硫铝系胶凝材料熟料中Fe2O3的含量为12～15wt％，而普通硫铝酸盐水泥熟料中Fe2O3的含量仅为1～3wt％，Fe2O3含量的提升使材料矿物体系改变，随着Fe2O3含量增加，一部分Fe2O3促进了胶凝材料主要矿物的晶型转变，使得正交型转为立方型具有更高的水化放热量和更快的水化放热速率，从而更加能够抵御负温环境所带来的冻害；一部分Fe2O3形成了铁相(C2F～C4AF)，铁相的放热速率更加提前，进一步提升了材料的放热优势。另一方面，富铁硫铝系胶凝材料水化后，水化产物主要为钙矾石、铝胶、铁胶等矿相，水化反应进行十分迅速，钙矾石晶体快速搭接，提供早期强度，铝胶、铁胶填充于钙矾石晶体之间，有效降低了材料的孔隙率，使得体系中孔径大多分布于200nm以下，根据饱和蒸汽压理论，孔径越小，孔内的饱和蒸汽压越高，孔内溶液冰点越低，从而保证负温条件下浆体内大部分水不被冻结。因此，立方型与铁相矿物含量更高的富铁硫铝系胶凝材料要比普通硫铝酸盐水泥更适宜于负温修补。
(3)本发明使用的外加剂包括防冻组分、减水组分、早强组分、粘结组分和保水组分，所选用的外加剂能够与固废基富铁硫铝系胶凝材料很好地适配，未引入其他杂质离子，同时，外加剂添加量较少，能够在维持材料的可施工性的同时保证材料的强度性能。
(4)本发明大量使用固废，降低修补材料生产成本。同时，解决了固废大量堆存问题。
(5)本发明可以让修补材料在生产成本更低的情况下获得更好的性能。
(6)本发明制备方法简单、实用性强，易于推广。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示例性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为本发明的修补材料制备流程图。
具体实施方式
应该指出，以下详细说明都是示例性的，旨在对本发明提供进一步的说明。除非另有指明，本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
一方面，一种固废基富铁硫铝系胶凝材料熟料，按照质量份数计，包括以下原料：其中钢渣粉35-43份，脱硫石膏23-29份，铝灰粉21-26份，石灰石尾矿粉9-19份。原料煅烧温度为1150-1250℃，煅烧时间为15-45min，可得固废基富铁硫铝系胶凝材料熟料。
本发明还提供了一种固废基富铁硫铝系胶凝材料，将上述熟料与5％-15％脱硫石膏粉磨至比表面积大于300m2/kg，即得固废基富铁硫铝系胶凝材料。
本发明还提供了一种上述固废基富铁硫铝系负温路面修补材料的制备方法，将上述固废基富铁硫铝系胶凝材料与氯化钙、碳酸锂、聚羧酸减水剂、可再分散性乳胶粉、羟乙基甲基纤维素醚等添加剂一次干混均匀，后加入骨料进行二次混合，从而得到固废基富铁硫铝系负温路面修补材料。
本发明所采用的骨料为钢渣/煤矸石/石粉中的至少一种。
在一些实施例中，所述骨料不需粉磨，经筛分-破碎-筛分工艺后直接作为修补材料骨料使用，其筛分区间为0-1.25mm、1.25-2.5mm、2.5-5mm。其中，骨料占比2.5-5mm为15-45％，1.25-2.5mm为35％-75％，0-1.25mm为10％～25％。
在一些实施例中，钢渣作为骨料时游离CaO含量不得高于7％，以保证材料安定性，煤矸石、石粉不作要求。
在一些实施例中，固废基富铁硫铝系胶凝材料45-55重量份，钢渣/煤矸石/石粉等骨料45-55重量份，氯化钙2-5重量份，碳酸锂0.2-0.8重量份，聚羧酸减水剂0.1-0.3重量份，可再分散性乳胶粉1-3重量份，羟乙基甲基纤维素醚0.1-0.3重量份。
以上路面修补材料使用温度≥-20℃。负温使用时，原料无需加热，加入适当比例的水后，即可施工。
在一些实施例中，材料拌合水要求水温在5℃以上，水料比0.12-0.15，从而保证水化反应的进行。
下面结合具体的实施例，对本发明做进一步的详细说明，应该指出，所述具体实施例是对本发明的解释而不是限定。
以下实施例中，
氯化钙、碳酸锂为购自国药集团的分析纯试剂。
聚羧酸减水剂为购自山东华迪建筑科技有限公司的化学纯高性能减水剂。
可再分散性乳胶粉购自山东优索化工科技有限公司。
羟乙基甲基纤维素醚购自山东优索化工科技有限公司。
拌合水的温度为5℃。
胶凝材料中各原料成分如表1所示。
表1原材料的化学成分(wt.％)
骨料的制备方法为：将钢渣破碎筛分，2.5-5mm为15％，1.25-2.5mm为75％，0-1.25mm为10％。
实施例1：
一种路面修补材料，包括以下成分：胶凝材料47.8重量份，骨料47.8重量份，水料比0.12，氯化钙3重量份，碳酸锂0.2重量份，聚羧酸减水剂0.1重量份，可再分散性乳胶粉1重量份，羟乙基甲基纤维素醚0.1重量份。
胶凝材料的制备方法为：钢渣37份、脱硫石膏28份、铝灰24份、石灰石尾矿11份，煅烧温度为1250℃，煅烧时间为45min，与5％脱硫石膏粉磨均匀至比表面积为300m2/kg。
以上混凝土路面修补材料在使用时的水料比为0.12。养护温度为-20℃，测量材料抗压强度及粘结强度。
实施例2：
一种路面修补材料，包括以下成分：胶凝材料45重量份，骨料50重量份，水料比0.12，氯化钙1.9重量份，碳酸锂0.8重量份，聚羧酸减水剂0.2重量份，可再分散性乳胶粉2重量份，羟乙基甲基纤维素醚0.1重量份，
胶凝材料的制备方法为：钢渣37份、脱硫石膏28份、铝灰24份、石灰石 尾矿11份，煅烧温度为1250℃，煅烧时间为45min，与5％脱硫石膏粉磨均匀至比表面积为300m2/kg。
骨料的制备方法为：将钢渣破碎筛分，2.5-5mm为15％，1.25-2.5mm为75％，0-1.25mm为10％。
以上混凝土路面修补材料在使用时的水料比为0.12。养护温度为-20℃，测量材料抗压强度。
实施例3：
与实施例1不同的是，胶凝材料制备方法为钢渣37份、脱硫石膏28份、铝灰24份、石灰石尾矿11份，煅烧温度为1180℃，煅烧时间为15min，与15％脱硫石膏粉磨均匀至比表面积为300m2/kg。
实施例4：
与实施例1不同的是，骨料制备方法为：将煤矸石破碎筛分，2.5-5mm为15％，1.25-2.5mm为75％，0-1.25mm为10％。
实施例5：
与实施例1不同的是，养护温度为20℃。
配制的快速修补材料成型后,参照《水泥胶砂强度检验方法》进行力学性能测试，参照《建筑砂浆基本性能试验方法标准》进行拉伸粘结强度测试。

从抗压强度可以看出，本发明所制备的路面修补材料抗压性能明显满足JT/T1211.1-2018《公路工程水泥混凝土用快速修补材料》中对修补材料的要求，综上所述，本发明有效地克服了现有技术中同类产品的诸多缺陷，具有负温迅速硬化、成本低、碳排放少、固废利用量大等优点,可满足路面在负温环境下快速高强修补的要求，具极高的产业利用价值。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

  1. 一种固废基富铁硫铝系负温路面修补材料的制备方法，其特征在于：固废基富铁硫铝系负温路面修补材料由如下重量份的原料组成：固废基富铁硫铝系胶凝材料45-55份，骨料45-55份，氯化钙2-5份，碳酸锂0.2-0.8份，聚羧酸减水剂0.1-0.3份，可再分散性乳胶粉1-3份，羟乙基甲基纤维素醚0.1-0.3份；固废基富铁硫铝系胶凝材料熟料由如下重量份的原料组成：钢渣粉35-43份，脱硫石膏23-29份，铝灰粉21-26份，石灰石尾矿粉9-19份；原料煅烧温度为1150-1250℃，煅烧时间为15-45min；所述固废基富铁硫铝系胶凝材料熟料中Fe2O3的含量为12-15wt％；将固废基富铁硫铝系胶凝材料熟料与5％-15％脱硫石膏均化粉磨至比表面积大于300m2/kg，制成固废基富铁硫铝系胶凝材料；将所述固废基富铁硫铝系胶凝材料与氯化钙、碳酸锂、聚羧酸减水剂、可再分散性乳胶粉、羟乙基甲基纤维素醚一次干混均匀，后加入骨料进行二次混合，从而得到固废基富铁硫铝系负温路面修补材料；固废基富铁硫铝系负温路面修补材料的使用温度≥-20℃。
  2. 如权利要求1所述固废基富铁硫铝系负温路面修补材料的制备方法，其特征在于，加水拌合即可使用，拌合水的水温在5℃以上，水料比0.12-0.15。
  3. 一种固废基富铁硫铝系负温路面修补材料，其特征在于，是由权利要求1所述的制备方法制得的固废基富铁硫铝系负温路面修补材料。
  4. 如权利要求3所述固废基富铁硫铝系负温路面修补材料，其特征在于，所述骨料为钢渣、煤矸石、石粉中的至少一种。
  5. 如权利要求3所述固废基富铁硫铝系负温路面修补材料，其特征在于，所述骨料不需粉磨，经筛分、破碎、筛分工艺后直接作为修补材料骨料使用，其筛分区间为0-1.25mm、1.25-2.5mm、2.5-5mm。
  6. 如权利要求3所述固废基富铁硫铝系负温路面修补材料，其特征在于，骨料占比：2.5-5mm为15-45％，1.25-2.5mm为35％-75％，0-1.25mm为10％-25％。
  7. 如权利要求3所述固废基富铁硫铝系负温路面修补材料，其特征在于，钢渣作为骨料时，游离CaO含量不得高于7％。
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