WO2016134552A1 - Inorganic cement material and manufacturing method thereof - Google Patents
Inorganic cement material and manufacturing method thereof Download PDFInfo
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- WO2016134552A1 WO2016134552A1 PCT/CN2015/073569 CN2015073569W WO2016134552A1 WO 2016134552 A1 WO2016134552 A1 WO 2016134552A1 CN 2015073569 W CN2015073569 W CN 2015073569W WO 2016134552 A1 WO2016134552 A1 WO 2016134552A1
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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
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
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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
- 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
Definitions
- the invention relates to the technical field of building materials, in particular to an inorganic cementing material with fly ash and lime as main raw materials and a preparation method thereof.
- cement As the largest amount of cementing material for production and application, cement is not only a high-resource, high-energy-consumption product, but also a product with high greenhouse gas emissions and high pollution.
- the environmental pollution caused by the production process is not Problems such as excessive consumption of renewable resources have long attracted people's attention, and new raw material resources and alternative preparation methods that can be supplemented or supplemented are urgently needed.
- Thermal power generation enterprises have to discharge a large amount of fly ash every year. Although most of the fly ash discharged from power plants in recent years has been used by building materials, rubber, agricultural fertilizer industry and civil engineering, it was wet before the 1980s and 1990s. The large amount of fly ash discharged by the method has a relatively high grain size and high carbon content.
- the technical problem to be solved by the present invention is to provide a high-performance inorganic cementing material which can utilize a large amount of low-quality fly ash as a main raw material, in view of the problems existing in the prior art mentioned above.
- Another object of the present invention is to provide a process for the preparation of such an inorganic cementitious material.
- the present invention provides an inorganic cementitious material, characterized in that the cementitious material is composed of 65 to 80 parts by mass of fly ash, lime to 20 to 35 parts by effective CaO, and an activator. 0.5 to 2 parts and 30 to 50 parts of water are obtained by preparing a pellet or a pellet obtained by steaming and calcining 90 to 95 parts of clinker and 5 to 10 parts of gypsum.
- the fly ash is used in cement and concrete according to GBT 1596 Fly ash with technical indicators above grade III of fly ash;
- the lime is calcareous lime that meets the technical specifications of JC/T 479 building lime and calcium hydrated lime that meets the technical indicators of slaked lime of JC/T 481; a combination of one or more of dihydrate gypsum, hemihydrate gypsum, and anhydrite;
- the activator is one or more of an alkali metal hydroxide, an alkali metal carbonate, and an alkali metal sulfate combination.
- the present invention also provides a method for preparing an inorganic cementing material, the main steps of which are as follows:
- Step (1) mixing fly ash, lime and activator in proportion, and grinding together to a batch with a fineness of 45 ⁇ m and a sieve residue of less than 10%;
- Step (2) uniformly mixing the batch material with water, aging for 2 to 3 hours, forming a material block having a maximum size of 10 to 240 mm or a material ball having a diameter of 8 to 16 mm;
- Step (3) steaming the pellets at a temperature of 90 to 98 ° C for 8 to 16 hours to obtain a steaming nutrient
- Step (4) calcining the steaming material at 750-1000 ° C for 15 to 120 minutes, then air-cooling or cooling in air to obtain clinker;
- Step (5) 90 to 95 parts of the clinker and 5 to 10 parts of gypsum are ground together to a specific surface area of 350 to 500 m 2 /kg to prepare an inorganic cementitious material.
- the invention utilizes steam curing to react lime and activated silica in the fly ash to form hydrated calcium silicate and calcium hydrated calcium aluminate, and calcined at a lower temperature to form dicalcium silicate and heptaluminate.
- the activator in the invention can react with the aluminosilicate glass body in the fly ash, destroy the vitreous network structure, reduce the polymerization degree of the vitreous network structure, greatly improve the reaction rate of the silicon oxide and the alumina with the lime and the hydrated silicic acid.
- the formation rate of calcium and hydrated calcium aluminate further increases the content of dicalcium silicate and heptaluminate in the inorganic cementitious material, and improves the gelation of the inorganic cementitious material.
- Figure 1 is a flow chart of the production process of the present invention.
- the batch contains the following ingredients in parts by mass:
- the batch contains the following ingredients in parts by mass:
- the clinker was crushed into particles of less than 16 mm by a crusher, and 93 parts of clinker and 7 parts of hemihydrate gypsum were ground together to a specific surface area of 425 m 2 /kg to prepare an inorganic cementitious material.
- the batch contains the following ingredients in parts by mass:
- the batch contains the following ingredients in parts by mass:
- fly ash, quicklime and anhydrous sodium sulfate were weighed and ground to a batch with a fineness of 45 ⁇ m and a 8.1% residue; the batch was poured into a mixer, and 50 parts of water was added and stirred for 3 minutes. After 3 hours of aging, it is extruded into a 50 mm ⁇ 50 mm ⁇ 30 mm block; the block is steamed in a steaming box at 98 ° C for 12 h to obtain a steaming nutrient, and the steaming material is calcined in a small kiln at 800 ° C for 60 min and then naturally cooled in the air.
- Clinker is obtained; after the clinker is crushed into particles of less than 16 mm by a crusher, 95 parts of clinker and 5 parts of hemihydrate gypsum are co-milled to a specific surface area of 440 m 2 /kg to prepare an inorganic cementitious material.
- the batch contains the following ingredients in parts by mass:
- the batch contains the following ingredients in parts by mass:
- the clinker was naturally cooled in the air; an inorganic cementitious material was prepared by taking 92 parts of clinker together with 4 parts of anhydrite and 4 parts of hemihydrate gypsum to a specific surface area of 370 m 2 /kg.
- the batch contains the following ingredients in parts by mass:
- the batch contains the following ingredients in parts by mass:
- GBT 17671-1999 cement mortar strength test method the standard mortar strength of each inorganic cementitious material is measured according to GBT749-2008 cement sulfate attack test method, and the inorganic cementitious materials are resistant to sulfate.
- the erosion coefficient is shown in Table 1.
- the inorganic cementitious material of the invention can be made of low-quality fly ash with high carbon content as raw material, and the utilization rate of fly ash is large, and the utilization of the stored fly ash can be realized, the occupation of land is reduced, and natural resources are saved. ,Improve the environment;
- the invention uses an alkaline activator to accelerate the reaction between the components in the steaming process block or the ball, accelerates the acceleration and complete completion of the reaction, reduces the steaming heat consumption, shortens the steaming time, and improves the production efficiency and Equipment use efficiency;
- the preparation method of the inorganic cementing material of the invention is simple, no large equipment is needed, the calcination temperature is low, the greenhouse gas emission is small, the composition and performance are flexible and adjustable, easy to control, and the applicability is good;
- the inorganic cementitious material of the invention has the characteristics of fast setting and fast hardening, high long-term strength, good water resistance and sulfate attacking property, and is particularly suitable for tunnel, underwater, saline-alkali zone and coastal area engineering.
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Abstract
Provided are an inorganic cement material and a manufacturing method thereof, the cement material being manufactured from, in parts by mass, 90-95 parts clinker obtained from steam curing and calcining material blocks or material balls manufactured from 65-80 parts fly ash, 20-35 parts of lime measured in terms of active CaO, 0.5-2 parts stimulating agent, and 15-50 parts water; and 5-10 parts gypsum. The present inorganic cement material uses low-quality fly ash with high carbon content as the main raw material, with a low calcination temperature and low heat consumption.
Description
本发明涉及建筑材料技术领域，特别是一种以粉煤灰和石灰为主要原料的无机胶凝材料及其制备方法。The invention relates to the technical field of building materials, in particular to an inorganic cementing material with fly ash and lime as main raw materials and a preparation method thereof.
水泥作为生产和应用的最大量的胶凝材料，既是一种高资源、高能源消耗的产品，也是一种高温室气体排放和高污染的产品，其生产过程引起的对环境的污染和对不可再生资源的过度消耗等问题早已引起人们的关注，亟待寻求新的原材料资源和可替代的或者可作为补充的新的制备方法。火力发电企业每年要排出大量粉煤灰，尽管近年来电厂干法排出的粉煤灰一大部分已被建材、橡胶、农肥工业和土木交通工程所利用，但上世纪八、九十年代以前湿法排放的大量粉煤灰，由于其一般粒度较粗，含碳量较高，其物理性质和反应活性不能满足作为水泥混合材和混凝土掺合料的要求，不能直接大量地应用于水泥与混凝土中，因此尚未能有效利用而被长期堆存。长期堆存的粉煤灰不仅占有大量的土地，还严重污染周围环境，因此有效资源化利用是一亟待解决的问题。用堆存粉煤灰为主要原料制备无机胶凝材料，不仅可以节省不可再生资源，而且节能、环保，是节能、减排的环境友好新型胶凝材料。但现有用粉煤灰制备无机胶凝材料的技术存在粉煤灰用量少、对粉煤灰品质要求高和产品性能较差的问题。As the largest amount of cementing material for production and application, cement is not only a high-resource, high-energy-consumption product, but also a product with high greenhouse gas emissions and high pollution. The environmental pollution caused by the production process is not Problems such as excessive consumption of renewable resources have long attracted people's attention, and new raw material resources and alternative preparation methods that can be supplemented or supplemented are urgently needed. Thermal power generation enterprises have to discharge a large amount of fly ash every year. Although most of the fly ash discharged from power plants in recent years has been used by building materials, rubber, agricultural fertilizer industry and civil engineering, it was wet before the 1980s and 1990s. The large amount of fly ash discharged by the method has a relatively high grain size and high carbon content. Its physical properties and reactivity cannot meet the requirements of cement admixture and concrete admixture, and cannot be directly applied to cement and concrete. Medium, so it has not been effectively utilized and has been stored for a long time. The long-term accumulation of fly ash not only occupies a large amount of land, but also seriously pollutes the surrounding environment. Therefore, effective resource utilization is an urgent problem to be solved. The use of stored fly ash as the main raw material for the preparation of inorganic cementitious materials not only saves non-renewable resources, but also saves energy and protects the environment. It is an environmentally friendly new cementitious material that saves energy and reduces emissions. However, the existing technology for preparing inorganic cementitious materials from fly ash has the problems of less consumption of fly ash, high quality requirements for fly ash and poor product performance.
发明公开Invention disclosure
本发明所要解决的技术问题是针对上述现有技术存在的问题，提供一种用可以大量利用堆存低品质粉煤灰为主要原料的高性能无机胶凝材料。The technical problem to be solved by the present invention is to provide a high-performance inorganic cementing material which can utilize a large amount of low-quality fly ash as a main raw material, in view of the problems existing in the prior art mentioned above.
本发明的另一目的是提供这种无机胶凝材料的制备方法。Another object of the present invention is to provide a process for the preparation of such an inorganic cementitious material.
为了实现上述目的，本发明提供了一种无机胶凝材料，其特征在于该胶凝材料是由用按质量份计粉煤灰65～80份、石灰以有效CaO计20～35份、激发剂0.5～2份和水30～50份制得的料块或料球经蒸养和煅烧所得的熟料90～95份和石膏5～10份制得。所述粉煤灰为符合GBT 1596用于水泥和混凝土中
的粉煤灰III级以上技术指标的粉煤灰；所述石灰为满足JC/T 479建筑生石灰技术指标的钙质石灰和满足JC/T 481建筑消石灰技术指标的钙质消石灰；所述石膏为二水石膏、半水石膏和无水石膏中的一种或几种的组合；所由述激发剂为碱金属氢氧化物、碱金属碳酸盐和碱金属硫酸盐的一种或几种的组合。In order to achieve the above object, the present invention provides an inorganic cementitious material, characterized in that the cementitious material is composed of 65 to 80 parts by mass of fly ash, lime to 20 to 35 parts by effective CaO, and an activator. 0.5 to 2 parts and 30 to 50 parts of water are obtained by preparing a pellet or a pellet obtained by steaming and calcining 90 to 95 parts of clinker and 5 to 10 parts of gypsum. The fly ash is used in cement and concrete according to GBT 1596
Fly ash with technical indicators above grade III of fly ash; the lime is calcareous lime that meets the technical specifications of JC/T 479 building lime and calcium hydrated lime that meets the technical indicators of slaked lime of JC/T 481; a combination of one or more of dihydrate gypsum, hemihydrate gypsum, and anhydrite; the activator is one or more of an alkali metal hydroxide, an alkali metal carbonate, and an alkali metal sulfate combination.
为了更好地实现上述目的，本发明还提供了了一种无机胶凝材料的制备方法，其主要步骤如下：In order to better achieve the above object, the present invention also provides a method for preparing an inorganic cementing material, the main steps of which are as follows:
步骤(1)：将粉煤灰、石灰、激发剂按比例配合，共同粉磨至细度为45μm筛余小于10％的配合料；Step (1): mixing fly ash, lime and activator in proportion, and grinding together to a batch with a fineness of 45 μm and a sieve residue of less than 10%;
步骤(2)：将所述配合料与水后均匀混合，陈化2～3h，成型成最大尺寸为10～240mm的料块或直径为8～16mm的料球；Step (2): uniformly mixing the batch material with water, aging for 2 to 3 hours, forming a material block having a maximum size of 10 to 240 mm or a material ball having a diameter of 8 to 16 mm;
步骤(3)：将所述料块料球在90～98℃蒸汽养护8～16h得蒸养料；Step (3): steaming the pellets at a temperature of 90 to 98 ° C for 8 to 16 hours to obtain a steaming nutrient;
步骤(4)：将所述蒸养料在750～1000℃下煅烧15～120min后风冷或在空气中冷却得熟料；Step (4): calcining the steaming material at 750-1000 ° C for 15 to 120 minutes, then air-cooling or cooling in air to obtain clinker;
步骤(5)：将所述熟料90～95份与石膏5～10份共同粉磨至比表面积为350～500m2/kg制得一种无机胶凝材料。Step (5): 90 to 95 parts of the clinker and 5 to 10 parts of gypsum are ground together to a specific surface area of 350 to 500 m 2 /kg to prepare an inorganic cementitious material.
本发明通过蒸汽养护使得石灰与粉煤灰中活性氧化硅和活性氧化铝反应形成水化硅酸钙和水化铝酸钙，在较低温度下煅烧后形成硅酸二钙和七铝十二钙，其中七铝十二钙有很高的水化活性，硅酸二钙也由于在较低的温度下形成，存在大量结构缺陷，因此也具有很高的水化活性，容易与水反应形成具有高胶凝性的水化产物。The invention utilizes steam curing to react lime and activated silica in the fly ash to form hydrated calcium silicate and calcium hydrated calcium aluminate, and calcined at a lower temperature to form dicalcium silicate and heptaluminate. Calcium, in which hepta-dano-calcium has high hydration activity, and dicalcium silicate is also formed at a lower temperature, and has a large number of structural defects, so it also has high hydration activity and easily reacts with water. A hydration product with high gelation.
本发明中激发剂可以与粉煤灰中的铝硅酸盐玻璃体反应，破坏玻璃体网络结构，降低玻璃体网络结构的聚合程度，大大提高其中氧化硅和氧化铝与石灰的反应速率及水化硅酸钙和水化铝酸钙的形成率，进而提高无机胶凝材料中硅酸二钙和七铝十二钙的含量，提高无机胶凝材料的胶凝性。The activator in the invention can react with the aluminosilicate glass body in the fly ash, destroy the vitreous network structure, reduce the polymerization degree of the vitreous network structure, greatly improve the reaction rate of the silicon oxide and the alumina with the lime and the hydrated silicic acid. The formation rate of calcium and hydrated calcium aluminate further increases the content of dicalcium silicate and heptaluminate in the inorganic cementitious material, and improves the gelation of the inorganic cementitious material.
以下结合附图和具体实施例对本实用新型进行详细描述，但不作为对本实用新型的限定。The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but not to limit the invention.
附图简要说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明的生产工艺流程图。
Figure 1 is a flow chart of the production process of the present invention.
实现本发明的最佳方式The best way to implement the invention
下面通过实施例的方式对本发明技术方案进行详细说明，但是本发明的保护范围不局限于所述实施例。各实施例无机胶凝材料的凝结时间、净浆试体强度、标准胶砂强度和耐硫酸盐侵蚀性检测结果见表1。The technical solution of the present invention will be described in detail below by way of embodiments, but the scope of protection of the present invention is not limited to the embodiments. The test results of the setting time, the strength of the pure pulp sample, the strength of the standard mortar and the resistance to sulfate attack of the inorganic cementitious materials of each example are shown in Table 1.
实施例1Example 1
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
粉煤灰 80份Fly ash 80 parts
生石灰以CaO计 20份Quicklime in terms of CaO 20 parts
氢氧化钠 0.5份Sodium hydroxide 0.5 parts
按上述质量比称取粉煤灰、生石灰、氢氧化钠，共同粉磨至细度为45μm筛余为5.2％的配合料；将配合料倒入搅拌机中，加入45份水后搅拌3min，陈化2h后用成球盘成型成直径为8～16mm的料球；将料球在蒸养箱中90℃蒸养10h得蒸养料，将蒸养料用小型窑炉750℃煅烧120min后吹风冷却得熟料；取熟料90份与无水石膏10份共同粉磨至比表面积为350m2/kg制得一种无机胶凝材料。Weigh fly ash, quicklime, sodium hydroxide according to the above mass ratio, and grind together to 5.2% of the fineness of 45μm sieve; pour the batch into the mixer, add 45 parts of water and stir for 3min, Chen After 2 hours, the pellets were formed into pellets with a diameter of 8-16 mm. The pellets were steamed in a steaming tank at 90 °C for 10 h to obtain steamed nutrients. The steaming materials were calcined in a small furnace at 750 ° C for 120 min and then cooled by a blower. Clinker; 90 parts of clinker and 10 parts of anhydrite were ground together to a specific surface area of 350 m 2 /kg to prepare an inorganic cementitious material.
实施例2Example 2
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
粉煤灰 75份Fly ash 75 parts
生石灰以CaO计 25份Quicklime in terms of CaO 25 parts
碳酸钠 1.4份Sodium carbonate 1.4 parts
按上述质量比称取粉煤灰、生石灰、碳酸钠，共同粉磨至细度为45μm筛余为9.8％的配合料；将配合料倒入搅拌机中，加入48份水后搅拌3min，陈化3h后挤压成240mm×115mm×53mm的料块，将料块在蒸养箱中90℃蒸养16h得蒸养料，将蒸养料用小型窑炉750℃煅烧90min后在空气中自然冷却得熟料；将熟料用破碎机破碎成小于16mm的颗粒，取熟料93份与半水石膏7份共同粉磨至比表面积为425m2/kg制得一种无机胶凝材料。Weigh fly ash, quicklime, sodium carbonate according to the above mass ratio, and grind together to a batch with a fineness of 45μm and a 9.8% mixture; pour the batch into the mixer, add 48 parts of water, stir for 3min, and age. After 3h, it was extruded into a block of 240mm×115mm×53mm. The block was steamed in a steaming box at 90°C for 16h to obtain steaming nutrients. The steaming material was calcined in a small furnace at 750°C for 90 minutes and then naturally cooled in the air. The clinker was crushed into particles of less than 16 mm by a crusher, and 93 parts of clinker and 7 parts of hemihydrate gypsum were ground together to a specific surface area of 425 m 2 /kg to prepare an inorganic cementitious material.
实施例3Example 3
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
粉煤灰 70份Fly ash 70 parts
生石灰以CaO计 30份Quicklime in terms of CaO 30 parts
氢氧化钠 1.0份
Sodium hydroxide 1.0 part
按上述质量比称取粉煤灰、生石灰、氢氧化钠，共同粉磨至细度为45μm筛余为5.8％的配合料；将配合料倒入搅拌机中，加入50份水后搅拌2min，陈化2.5h后用成球盘成型成直径为8～16mm的料球；将料球在蒸养箱中95℃蒸养8h得蒸养料，将蒸养料用小型窑炉800℃煅烧60min后吹风冷却得熟料；取熟料93份与二水石膏7份共同粉磨至比表面积为495m2/kg制得一种无机胶凝材料。Weigh fly ash, quicklime, sodium hydroxide according to the above mass ratio, and grind together to 5.7% of the fineness of 45μm sieve; pour the batch into the mixer, add 50 parts of water and stir for 2min, Chen After 2.5 hours, the ball was formed into a ball with a diameter of 8 to 16 mm. The ball was steamed in a steaming box at 95 ° C for 8 hours to obtain a steaming nutrient. The steaming material was calcined at 800 ° C for 60 minutes in a small kiln and then cooled by air. Clinker was obtained; 93 parts of clinker and 7 parts of dihydrate gypsum were ground together to a specific surface area of 495 m 2 /kg to prepare an inorganic cementitious material.
实施例4Example 4
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
粉煤灰 65份Fly ash 65 parts
生石灰以CaO计 35份Quicklime in terms of CaO 35 parts
无水硫酸钠 2.0份Anhydrous sodium sulfate 2.0 parts
按上述质量比称取粉煤灰、生石灰、无水硫酸钠，共同粉磨至细度为45μm筛余为8.1％的配合料；将配合料倒入搅拌机中，加入50份水后搅拌3min，陈化3h后挤压成50mm×50mm×30mm的料块；将料块在蒸养箱中98℃蒸养12h得蒸养料，将蒸养料用小型窑炉800℃煅烧60min后在空气中自然冷却得熟料；将熟料用破碎机破碎成小于16mm的颗粒后，取熟料95份与半水石膏5份共同粉磨至比表面积为440m2/kg制得一种无机胶凝材料。According to the above mass ratio, fly ash, quicklime and anhydrous sodium sulfate were weighed and ground to a batch with a fineness of 45 μm and a 8.1% residue; the batch was poured into a mixer, and 50 parts of water was added and stirred for 3 minutes. After 3 hours of aging, it is extruded into a 50 mm × 50 mm × 30 mm block; the block is steamed in a steaming box at 98 ° C for 12 h to obtain a steaming nutrient, and the steaming material is calcined in a small kiln at 800 ° C for 60 min and then naturally cooled in the air. Clinker is obtained; after the clinker is crushed into particles of less than 16 mm by a crusher, 95 parts of clinker and 5 parts of hemihydrate gypsum are co-milled to a specific surface area of 440 m 2 /kg to prepare an inorganic cementitious material.
实施例5Example 5
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
粉煤灰 80份Fly ash 80 parts
消石灰以CaO计 20份Slaked lime in terms of CaO 20 parts
氢氧化钾 1.3份Potassium hydroxide 1.3 parts
按上述质量比称取粉煤灰、消石灰、氢氧化钾，共同粉磨至细度为45μm筛余为3.5％的配合料；将配合料倒入搅拌机中，加入15份水后搅拌3min，陈化3h后挤压成直径10mm、厚6mm的料块；将料块在蒸养箱中98℃蒸养12h得蒸养料，将蒸养料，用小型窑炉800℃煅烧60min后在空气中自然冷却得熟料；取熟料93份与二水石膏7份共同粉磨至比表面积为385m2/kg制得一种无机胶凝材料。Weigh fly ash, slaked lime and potassium hydroxide according to the above mass ratio, and grind together to a batch with a fineness of 45 μm and a 3.5% residue; pour the batch into a blender, add 15 parts of water and stir for 3 min, Chen After 3h, it is extruded into a block with a diameter of 10mm and a thickness of 6mm. The block is steamed in a steaming box at 98 °C for 12 hours to obtain steamed nutrients. The steamed nutrient is calcined in a small kiln at 800 ° C for 60 min and then naturally cooled in the air. Clinker was obtained; 93 parts of clinker and 7 parts of dihydrate gypsum were ground together to a specific surface area of 385 m 2 /kg to prepare an inorganic cementitious material.
实施例6Example 6
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
粉煤灰 75份
Fly ash 75 parts
消石灰以CaO计 25份Slaked lime in 25 parts by CaO
碳酸钾 1.5份Potassium carbonate 1.5 parts
按上述质量比称取粉煤灰、消石灰、碳酸钾，共同粉磨至细度为45μm方孔筛筛余为4.3％的配合料；将配合料倒入搅拌机中，加入20份水后搅拌3min，陈化2h后用成球盘成型成直径为8～16mm的料球；将料球在蒸养箱中90℃蒸养8h得蒸养料，将蒸养料用小型窑炉800℃煅烧60min在后空气中自然冷却得熟料；取熟料92份与无水石膏4份和半水石膏4份共同粉磨至比表面积为370m2/kg制得一种无机胶凝材料。Weigh fly ash, slaked lime and potassium carbonate according to the above mass ratio, and grind together to 4.3% of the mixture with a fineness of 45μm square hole sieve; pour the batch into the mixer, add 20 parts of water and stir for 3min After 2 hours of aging, the pellets were formed into pellets with a diameter of 8 to 16 mm; the pellets were steamed in a steaming tank at 90 ° C for 8 h to obtain steamed nutrients, and the steaming materials were calcined at 800 ° C for 60 min in a small kiln. The clinker was naturally cooled in the air; an inorganic cementitious material was prepared by taking 92 parts of clinker together with 4 parts of anhydrite and 4 parts of hemihydrate gypsum to a specific surface area of 370 m 2 /kg.
实施例7Example 7
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
粉煤灰 70份Fly ash 70 parts
消石灰以CaO计 30份Slaked lime in terms of CaO 30 parts
氢氧化钠 1.2份Sodium hydroxide 1.2 parts
按上述质量比称取粉煤灰、消石灰、氢氧化钠，共同粉磨至细度为45μm方孔筛筛余为7.6％的配合料；将配合料倒入搅拌机中，加入25份水后搅拌3min，陈化3h后用成球盘成型成直径为8～16mm的料球；将料球在蒸养箱中90℃蒸养10h得蒸养料，将蒸养料用小型窑炉1000℃煅烧15min后吹风冷却得熟料；取熟料94份与二水石膏6份共同粉磨至比表面积为445m2/kg制得一种无机胶凝材料。Weigh fly ash, slaked lime, sodium hydroxide according to the above mass ratio, and grind together to 7.6% of the mixture with a fineness of 45μm square hole sieve; pour the batch into the mixer, add 25 parts of water and stir After 3 hours, after 3 hours of aging, the ball was formed into a ball with a diameter of 8 to 16 mm. The ball was steamed in a steaming box at 90 ° C for 10 hours to obtain a steaming nutrient. The steaming material was calcined at 1000 ° C for 15 minutes in a small kiln. The clinker was cooled by blowing air; an inorganic cementitious material was prepared by taking 94 parts of clinker and 6 parts of dihydrate gypsum together to a specific surface area of 445 m 2 /kg.
实施例8Example 8
配合料按质量份计含有以下成分：The batch contains the following ingredients in parts by mass:
按上述质量比称取粉煤灰、消石灰、氢氧化钠和无水硫酸钠，共同粉磨至细度为45μm方孔筛筛余为6.2％的配合料；将配合料倒入搅拌机中，加入25份水后搅拌3min，陈化3h后用成球盘成型成直径为8～16mm的料球；将料球在蒸养箱中95℃蒸养14h得蒸养料，将蒸养料用小型窑炉900℃煅烧30min吹风冷却得熟料；取熟料94份与半水石膏6份共同粉磨至比表面积为440m2/kg制得一
种无机胶凝材料。Weigh fly ash, slaked lime, sodium hydroxide and anhydrous sodium sulfate according to the above mass ratio, and grind together to 6.2% of the batch material with a fineness of 45μm square hole sieve; pour the batch into the mixer and add After stirring for 25 minutes, the mixture was stirred for 3 minutes, and then formed into a ball with a diameter of 8 to 16 mm after being aged for 3 hours. The ball was steamed in a steaming box at 95 ° C for 14 hours to obtain a steaming material, and the steaming material was used in a small furnace. After calcination at 900 ° C for 30 min, the clinker was cooled by blowing air; 94 parts of clinker and 6 parts of hemihydrate gypsum were co-milled to a specific surface area of 440 m 2 /kg to prepare an inorganic cementitious material.
参照GBT 1346-2011水泥标准稠度用水量、凝结时间、安定性检验方法，测得实施例1～8无机胶凝材料的标准稠度需水量、凝结时间，及标准稠度水泥净浆试体各龄期的抗压强度，按GBT 17671-1999水泥胶砂强度试验方法测得各无机胶凝材料标准胶砂强度，按GBT749-2008水泥抗硫酸盐侵蚀试验方法，测得各无机胶凝材料耐硫酸盐侵蚀系数，结果见表1。Refer to GBT 1346-2011 cement standard consistency water consumption, setting time, stability test method, the standard consistency water requirement, setting time of the inorganic cement materials of Examples 1-8, and the standard consistency cement paste test body age According to GBT 17671-1999 cement mortar strength test method, the standard mortar strength of each inorganic cementitious material is measured according to GBT749-2008 cement sulfate attack test method, and the inorganic cementitious materials are resistant to sulfate. The erosion coefficient is shown in Table 1.
表1无机胶凝材料性能测定结果Table 1 Determination results of inorganic cementitious materials
虽然本发明已以实施例揭露如上，然其并非用以限定本发明，任何熟悉本领域的相关技术人员，在不脱离本发明的精神和范围内，当可作些许的更动与润饰，但这些相应的更动与润饰都应属于本发明所附的权利要求的保护范围。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. These corresponding modifications and refinements are intended to fall within the scope of the appended claims.
工业应用性Industrial applicability
本发明的有益效果为：The beneficial effects of the invention are:
(1)本发明无机胶凝材料可以用含碳量高的低品质粉煤灰为原料，粉煤灰利用率大，可以实现堆存粉煤灰资源化利用，减少土地的占用，节约自然资源，改善环境；(1) The inorganic cementitious material of the invention can be made of low-quality fly ash with high carbon content as raw material, and the utilization rate of fly ash is large, and the utilization of the stored fly ash can be realized, the occupation of land is reduced, and natural resources are saved. ,Improve the environment;
(2)本发明采用碱性激发剂加速蒸养过程料块或料球中各组分间的反应，促进反应的加速和彻底完成，降低蒸养热耗，缩短蒸养时间，提高生产效益和设备使用效率；(2) The invention uses an alkaline activator to accelerate the reaction between the components in the steaming process block or the ball, accelerates the acceleration and complete completion of the reaction, reduces the steaming heat consumption, shortens the steaming time, and improves the production efficiency and Equipment use efficiency;
(3)本发明无机胶凝材料的制备方法简单，无需大型的设备、煅烧温度低，温室气体排放量少，其组成和性能灵活可调，易于控制，适用性好；(3) The preparation method of the inorganic cementing material of the invention is simple, no large equipment is needed, the calcination temperature is low, the greenhouse gas emission is small, the composition and performance are flexible and adjustable, easy to control, and the applicability is good;
(4)本发明无机胶凝材料具有快凝快硬、长期强度高、耐水和硫酸盐侵蚀性好的特性，特别适用于坑道、水下、盐碱地带和沿海地区工程。
(4) The inorganic cementitious material of the invention has the characteristics of fast setting and fast hardening, high long-term strength, good water resistance and sulfate attacking property, and is particularly suitable for tunnel, underwater, saline-alkali zone and coastal area engineering.
Claims (6)
- 一种无机胶凝材料，其特征在于，所述胶凝材料是由用按质量份计粉煤灰65～80份、石灰以有效CaO计20～35份、激发剂0.5～2份和水15～50份制得的料块或料球经蒸养和煅烧所得的熟料90～95份和石膏5～10份制得。An inorganic cementitious material, characterized in that the cementitious material is used in an amount of 65 to 80 parts by mass of fly ash, lime is 20 to 35 parts by effective CaO, 0.5 to 2 parts of an activator, and water 15 ～50 parts of the obtained material or pellets are obtained by steaming and calcining the clinker obtained by 90 to 95 parts and gypsum 5 to 10 parts.
- 如权利要求1所述的一种无机胶凝材料，其特征在于，所述粉煤灰为符合GBT 1596用于水泥和混凝土中的粉煤灰III级以上技术指标的粉煤灰；所述石灰为满足JC/T 479建筑生石灰技术指标的钙质石灰和满足JC/T 481建筑消石灰技术指标的钙质消石灰；所述石膏为二水石膏、半水石膏和无水石膏中的一种或几种的组合。The inorganic cementitious material according to claim 1, wherein the fly ash is fly ash which meets the technical index of grade III or higher of fly ash in cement and concrete according to GBT 1596; Calcium lime to meet the JC/T 479 building quicklime technical index and calcium slaked lime satisfying the JC/T 481 building slaked lime technical specification; the gypsum is one or more of dihydrate gypsum, hemihydrate gypsum and anhydrite gypsum Combination of species.
- 如权利要求1所述的一种无机胶凝材料，其特征在于，所述激发剂为碱金属氢氧化物、碱金属碳酸盐和碱金属硫酸盐的一种或几种的组合。The inorganic cementitious material according to claim 1, wherein the activator is a combination of one or more of an alkali metal hydroxide, an alkali metal carbonate, and an alkali metal sulfate.
- 一种根据权利要求1所述的一种无机胶凝材料的制备方法，其特征在于，该方法的步骤如下：A method for preparing an inorganic cementitious material according to claim 1, wherein the steps of the method are as follows:第一步：将粉煤灰、石灰、激发剂按比例配合，共同粉磨至细度为45μm方孔筛筛余小于10％的配合料；The first step: mixing fly ash, lime and activator in proportion, and grinding together to a batch with a fineness of 45 μm square sieve and less than 10% of the sieve;第二步：将所述配合料与水搅拌混合，陈化2～3h后成型得料块或料球；The second step: mixing the batch material with water, and aging for 2 to 3 hours to form a material block or a material ball;第三步：将所述料块或料球蒸汽养护8～16h得蒸养料；The third step: steaming the material block or the ball for 8 to 16 hours to obtain a steaming nutrient;第四步：将所述蒸养料在设定煅烧温度下煅烧15～120min后风冷或在空气中冷却得熟料；The fourth step: calcining the steaming material at a set calcination temperature for 15 to 120 minutes, then air cooling or cooling in air to obtain clinker;第五步：将所述熟料90～95份与石膏5～10份共同粉磨至比表面积为350～500m2/kg制得一种无机胶凝材料。The fifth step: 90 to 95 parts of the clinker and 5 to 10 parts of gypsum are ground together to a specific surface area of 350 to 500 m 2 /kg to prepare an inorganic cementitious material.
- 如权利要求4所述的一种无机胶凝材料的制备方法，其特征在于，所述蒸养料的蒸汽养护温度为90～98℃。The method for preparing an inorganic cementitious material according to claim 4, wherein the steam curing material has a steam curing temperature of 90 to 98 °C.
- 如权利要求4所述的一种无机胶凝材料的制备方法，其特征在于，所述蒸养料的煅烧温度为750～1000℃。 The method for preparing an inorganic cementitious material according to claim 4, wherein the steaming material has a calcination temperature of 750 to 1000 °C.
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| CN110668720A (en) * | 2019-11-18 | 2020-01-10 | 北京化工大学 | Hydraulic cementing material and preparation device and method thereof |
| CN115321855A (en) * | 2022-07-29 | 2022-11-11 | 华润水泥技术研发有限公司 | Bi-component prepared cement and preparation method thereof |
| CN117447108A (en) * | 2023-10-25 | 2024-01-26 | 大连理工大学 | Composite cementing material and preparation method thereof |
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| WO2019232687A1 (en) * | 2018-06-05 | 2019-12-12 | 华智节能(香港)有限公司 | Ultra-rapid-hardening special inorganic cement material and preparation method therefor |
| CN109485278B (en) * | 2018-12-13 | 2021-05-04 | 扬州大学 | Cementing material using coal gangue as raw material and preparation method thereof |
| CN112456829A (en) * | 2021-01-05 | 2021-03-09 | 辽宁银盛水泥集团有限公司 | Process for producing cement by using solid waste |
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| CN115321855A (en) * | 2022-07-29 | 2022-11-11 | 华润水泥技术研发有限公司 | Bi-component prepared cement and preparation method thereof |
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