WO2022016924A1 - 一种γ型硅酸二钙的制备方法及以γ型硅酸二钙为主要物相组成的高强碳化材料 - Google Patents

一种γ型硅酸二钙的制备方法及以γ型硅酸二钙为主要物相组成的高强碳化材料 Download PDF

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WO2022016924A1
WO2022016924A1 PCT/CN2021/088207 CN2021088207W WO2022016924A1 WO 2022016924 A1 WO2022016924 A1 WO 2022016924A1 CN 2021088207 W CN2021088207 W CN 2021088207W WO 2022016924 A1 WO2022016924 A1 WO 2022016924A1
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temperature
dicalcium silicate
type dicalcium
raw material
type
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PCT/CN2021/088207
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English (en)
French (fr)
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罗树琼
赵明慧
刘松辉
江壮壮
杨雷
潘崇根
毛宇翔
张海波
王雨利
管学茂
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河南理工大学
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Priority to PCT/CN2021/088207 priority Critical patent/WO2022016924A1/zh
Priority to CN202180006710.3A priority patent/CN114829317A/zh
Publication of WO2022016924A1 publication Critical patent/WO2022016924A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/24—Alkaline-earth metal silicates
    • 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
    • C04B7/44—Burning; Melting

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  • the invention belongs to the field of building materials, and in particular relates to a preparation method for preparing ⁇ -type dicalcium silicate using a microwave sintering method with calcium carbonate and silicon dioxide as main materials, and a preparation method using ⁇ -type dicalcium silicate as the main phase composed of high-strength carbonized materials.
  • Gamma-dicalcium silicate ( ⁇ -C 2 S, ⁇ -type dicalcium silicate) is a crystal form of dicalcium silicate (C 2 S), the main phase of cement.
  • C 2 S dicalcium silicate
  • the cooling rate is too slow, C 2 S is converted into ⁇ -C 2 S and self-pulverization occurs, which can reduce the energy consumption required for cement clinker grinding.
  • the dominant phase in the cement is ⁇ -C 2 S can greatly reduce the CO 2 emissions of the cement industry.
  • ⁇ -C 2 S has good carbonization activity, can be used as a durability modifier for cement concrete, and can also develop fast-hardening and high-strength carbonized materials, which has a good application prospect.
  • the preparation of ⁇ -type dicalcium silicate adopts the method of sintering the raw materials at high temperature (generally about 1400 ° C) in a sintering furnace after ball milling. Moreover, the heat is transferred from the outside of the system to the inside of the system, which will produce a temperature gradient and uneven heating, and most of the energy will be absorbed by the wall of the system, resulting in large energy loss and slow heating rate, which makes the preparation efficiency of ⁇ -type dicalcium silicate low. It is not conducive to its large-scale industrial application.
  • the purpose of the present invention is to overcome the problems of high temperature, high energy consumption and uneven heating in the preparation of ⁇ -C 2 S by the traditional high-temperature sintering method, provide a preparation method of ⁇ -type dicalcium silicate, and reduce the sintering temperature and the energy consumption required for preparation .
  • the invention also provides a high-strength carbonized material composed of ⁇ -type dicalcium silicate as the main phase, wherein the mass proportion of ⁇ -type dicalcium silicate is more than 60%, the carbonization activity is very good, and it has important industrial application value. .
  • the present invention provides the following technical solutions:
  • a preparation method of ⁇ -type dicalcium silicate comprising the following steps:
  • the sample is placed in a microwave sintering furnace, heated to the first temperature, kept for 30min, then heated to the second temperature, kept warm, and cooled to obtain ⁇ -type dicalcium silicate;
  • the first temperature is 900°C
  • the second temperature is 1100-1350°C.
  • the calcium raw material is calcium carbonate, calcium hydroxide or waste containing calcium carbonate or calcium hydroxide.
  • the calcium raw material is calcium carbonate.
  • Calcium carbonate is of analytical grade.
  • the siliceous raw materials are amorphous silica and diatomite, bentonite or other wastes containing active silica.
  • the siliceous raw material is amorphous silica.
  • step (1) the fineness of the siliceous raw material is 500 mesh or more.
  • step (1) the drying temperature is 60-100°C.
  • step (2) the heating rate of heating to the first temperature is 10-15° C./min.
  • step (2) the heating rate of heating to the second temperature is 10-15° C./min.
  • the holding time after heating to the second temperature is 1 to 3 hours.
  • the second temperature was 1250°C.
  • the present invention also provides a high-strength carbonized material with ⁇ -type dicalcium silicate as the main phase composition prepared by the above method.
  • the mass percentage of ⁇ -type dicalcium silicate in the high-strength carbonized material is more than 60%, and the preparation of the high-strength carbonized material includes the following steps:
  • the sample is placed in a microwave sintering furnace, heated to the first temperature, kept for 30min, then heated to the second temperature, kept warm, and cooled, and all the products obtained are high-strength carbonized materials;
  • the first temperature is 900°C
  • the second temperature is 1100-1350°C.
  • the second temperature is 1250-1350°C.
  • the present invention adopts microwave sintering method to prepare ⁇ -C 2 S (that is, ⁇ -type dicalcium silicate).
  • Microwave heating is the bulk heating of the material caused by the dielectric loss of the dielectric material in the electromagnetic field. The inside and outside of the material are heated at the same time. Compared with traditional heating, it has significant advantages such as strong penetrating power, fast heating speed, timely control, and sensitive response.
  • the preparation of ⁇ -C 2 S by microwave sintering can increase the molecular motion speed of the material, reduce the activation energy of the reaction, thereby increasing the reaction rate, and the reaction can be carried out at a lower temperature than the traditional sintering method to obtain high-quality product ⁇ -C 2 S, reduce production energy consumption and meet the development requirements of energy saving and emission reduction.
  • Fig. 1 is the product XRD test result figure of the embodiment of the present invention 1;
  • Fig. 2 is the product XRD test result figure of the embodiment of the present invention 2;
  • Fig. 3 is the product XRD test result diagram of the embodiment of the present invention 3.
  • Fig. 4 is the product XRD test result diagram of the embodiment of the present invention 4.
  • Fig. 5 is the product XRD test result graph of the embodiment of the present invention 5;
  • Fig. 6 is the product XRD test result graph of the embodiment of the present invention 6;
  • Fig. 7 is the product XRD test result graph of the embodiment of the present invention 7;
  • Fig. 8 is the product XRD test result figure of the comparative example 1 of the present invention.
  • Fig. 9 is the product XRD test result figure of comparative example 2 of the present invention.
  • Fig. 10 is the product XRD test result figure of comparative example 3 of the present invention.
  • FIG. 11 is a graph of the XRD test results of the product of Comparative Example 4 of the present invention.
  • the preparation method of ⁇ -type dicalcium silicate of the present invention comprises the following steps:
  • the calcareous raw materials are calcium carbonate, calcium hydroxide or wastes containing calcium carbonate or calcium hydroxide
  • the siliceous raw materials are amorphous silica and diatomite, bentonite and other wastes containing active silica.
  • the quality of the corresponding raw materials required shall be calculated based on the calcium content of the calcareous raw materials and the silicon content of the siliceous raw materials.
  • the use of solid wastes for calcareous raw materials and siliceous raw materials can comprehensively utilize solid wastes in the environment and reduce solid waste pollution in the environment.
  • the fineness of the siliceous raw material is 500 mesh or more.
  • calcareous feedstocks For calcareous feedstocks, analytically pure calcium carbonate is preferably used to minimize the influence of impurities on the reaction results.
  • siliceous raw material amorphous silica of 500 mesh or more is preferably used.
  • the drying temperature is preferably 60°C. If the temperature is high, black spots appear on the dried sample.
  • the above-mentioned microwave sintering furnace is preferably a high-temperature microwave muffle furnace, which has the characteristics of fast heating rate, high heating efficiency, safety, hygiene and pollution-free, and can improve the uniformity and yield of products, and improve the microstructure and performance of the sintered material.
  • the high-temperature microwave muffle furnace of the present invention has a total microwave power of 8kW, a temperature range of 50-1600°C, an accuracy of ⁇ 0.1°C, and a microwave frequency of 2450MHz.
  • the preparation method of the ⁇ -type dicalcium silicate of the present embodiment comprises the following steps:
  • the preparation method of the ⁇ -type dicalcium silicate of the present embodiment comprises the following steps:
  • the preparation method of the ⁇ -type dicalcium silicate of the present embodiment comprises the following steps:
  • the preparation method of the ⁇ -type dicalcium silicate of the present embodiment comprises the following steps:
  • the preparation method of the ⁇ -type dicalcium silicate of the present embodiment comprises the following steps:
  • the preparation method of the ⁇ -type dicalcium silicate of the present embodiment comprises the following steps:
  • the preparation method of the ⁇ -type dicalcium silicate of the present embodiment comprises the following steps:
  • Example 1 In the preparation method of ⁇ -type dicalcium silicate of this comparative example, the high-temperature microwave muffle furnace in Example 1 was replaced with a traditional muffle furnace, and other parameters were the same as those in Example 1. After natural cooling, the samples were self-powdered. Quantitative analysis results of XRD show that ⁇ -type dicalcium silicate accounts for 79.4% and ⁇ -type dicalcium silicate accounts for 20.6% in the product. The XRD pattern is shown in FIG. 8 .
  • Example 1 Compared with the XRD test results of Example 1, at the same temperature, although the proportion of ⁇ -type dicalcium silicate in the product of Example 1 is relatively low, dicalcium silicate with lower calcium content is generated in Example 1. Tricalcium silicate C 3 S 2 , and the proportion is as high as 23.2%. That is to say, at a sintering temperature of 1350° C., the content of low calcium components in the product obtained by microwave sintering is 84.7%, which is higher than that of Comparative Example 1.
  • Example 2 In the preparation method of ⁇ -type dicalcium silicate of this comparative example, the high-temperature microwave muffle furnace in Example 2 was replaced with a traditional muffle furnace, and other parameters were the same as those in Example 2. After natural cooling, the samples were self-powdered. Quantitative analysis results of XRD show that ⁇ -type dicalcium silicate accounts for 68.1% and ⁇ -type dicalcium silicate accounts for 31.9% in the product. The XRD pattern is shown in Figure 9.
  • Example 3 In the preparation method of ⁇ -type dicalcium silicate of this comparative example, the high-temperature microwave muffle furnace in Example 3 was replaced with a traditional muffle furnace, and other parameters were the same as those in Example 3. After natural cooling, the samples were self-powdered. Quantitative analysis results of XRD show that ⁇ -type dicalcium silicate accounts for 36.0% and ⁇ -type dicalcium silicate accounts for 64.0% in the product. The XRD pattern is shown in Figure 10.
  • Example 4 In the preparation method of ⁇ -type dicalcium silicate of this comparative example, the high-temperature microwave muffle furnace in Example 4 was replaced with a traditional muffle furnace, and other parameters were the same as those in Example 4. After natural cooling, the samples were self-powdered. Quantitative analysis results of XRD show that ⁇ -type dicalcium silicate accounts for 15.4% and ⁇ -type dicalcium silicate accounts for 84.6% in the product. The XRD pattern is shown in Figure 11.
  • Table 1 shows the experimental conditions and product composition comparisons of the above Examples 1 to 7 and Comparative Examples 1 to 4.
  • Example 2 Comparing the results of Example 2, Example 3 and Comparative Example 1, Comparative Example 2, and Comparative Example 3, it can be seen that by using high-temperature microwave sintering, a relatively high sintering temperature (1250 ° C) can be obtained.
  • ⁇ -type dicalcium silicate the proportion of ⁇ -type dicalcium silicate in the product is as high as 96.4%.
  • the reason may be that under the condition of microwave heating, there are athermal effects other than thermal effects, which reduce the activation energy of the reaction, so that the sintering temperature is lower than that under the traditional heating method.

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Abstract

本发明属于建筑材料领域，特别涉及一种γ型硅酸二钙的制备方法及一种以γ型硅酸二钙为主要物相组成的高强碳化材料。本发明的γ型硅酸二钙的制备方法，包括以下步骤：（1）将钙质原料与硅质原料按钙与硅的摩尔比为2：1混合均匀，然后加去离子水充分混合均匀，得混合料，使用压片机将混合料压制成片，于真空干燥箱中干燥，得到样片；（2）将样片置于微波烧结炉中，加热至第一温度，保温30min，然后再加热至第二温度，保温，冷却，即得γ型硅酸二钙。本发明的方法实现反应在较传统烧结法低的温度下进行，获得高质量的产物γ-C 2S，降低生产能耗，具有重要的工业应用价值。

Description

一种γ型硅酸二钙的制备方法及以γ型硅酸二钙为主要物相组成的高强碳化材料 技术领域
本发明属于建筑材料领域，具体涉及一种以碳酸钙与二氧化硅为主料，利用微波烧结法制备γ型硅酸二钙的制备方法以及一种以γ型硅酸二钙为主要物相组成的高强碳化材料。
背景技术
γ-硅酸二钙(γ-C 2S，γ型硅酸二钙)是水泥主要物相硅酸二钙(C 2S)的一种晶型。在生产水泥熟料时，如果冷却速度过慢，C 2S转变成γ-C 2S发生自粉化现象，可以减少水泥熟料粉磨所需的能耗，如果水泥中的主导物相为γ-C 2S，则可以大大降低水泥工业的CO 2排放量。γ-C 2S的碳化活性很好，可以作为水泥混凝土的耐久性改性剂，也可以发展快硬高强碳化材料，具有良好的应用前景。
目前，γ型硅酸二钙的制备采用将原料经过球磨后在烧结炉中高温(温度一般为1400℃左右)烧结的方法，不仅烧结温度高，烧结的时间相对也较长，能耗大，而且热量从体系外部传至体系内部，会产生温度梯度，加热不均匀，而且大部分能量会被器壁吸收，能量损耗大，加热速率慢，使得γ型硅酸二钙的制备效率较低，不利于其大规模的工业化应用。
因此，需要提供一种针对上述现有技术不足的改进技术方案。
发明内容
本发明的目的在于克服传统高温烧结法制备γ-C 2S的温度高、能耗大、加热不均匀的问题，提供γ型硅酸二钙的制备方法，降低烧结温度和制备所需能耗。
本发明还提供一种以γ型硅酸二钙为主要物相组成的高强碳化材料，其中γ型硅酸二钙的质量占比在60％以上，碳化活性很好，具有重要的工业应 用价值。
为实现上述目的，本发明提供如下技术方案：
一种γ型硅酸二钙的制备方法，包括以下步骤：
(1)将钙质原料与硅质原料按钙与硅的摩尔比为2：1混合均匀，然后加入原料总质量8～12％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6～10MPa的压力下压制成片，于真空干燥箱中干燥，得到样片；
(2)将样片置于微波烧结炉中，加热至第一温度，保温30min，然后再加热至第二温度，保温，冷却，即得γ型硅酸二钙；
第一温度为900℃，第二温度为1100～1350℃。
优选，步骤(1)中，钙质原料为碳酸钙、氢氧化钙或者含有碳酸钙或氢氧化钙的废弃物。
钙质原料为碳酸钙。
碳酸钙为分析纯。
步骤(1)中，硅质原料为无定形的二氧化硅以及硅藻土、膨润土或其他含有活性二氧化硅的废弃物。
硅质原料为无定形的二氧化硅。
步骤(1)中，硅质原料的细度为500目或500目以上。
步骤(1)中，干燥的温度为60～100℃。
步骤(2)中，加热至第一温度的升温速率为10～15℃/min。
步骤(2)中，加热至第二温度的升温速率为10～15℃/min。
加热至第二温度后的保温时间为1～3h。
第二温度为1250℃。
本发明还提供采用以上方法制备的以γ型硅酸二钙为主要物相组成的高强碳化材料。高强碳化材料中γ型硅酸二钙的质量百分数为60％以上，高强碳化材料的制备包括以下步骤：
(1)将钙质原料与硅质原料按钙与硅的摩尔比为2：1混合均匀，然后加入原料总质量8～12％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6～10MPa的压力下压制成片，于真空干燥箱中干燥，得到样片；
(2)将样片置于微波烧结炉中，加热至第一温度，保温30min，然后再加热至第二温度，保温，冷却，所得全部产物即为高强碳化材料；
第一温度为900℃，第二温度为1100～1350℃。
优选，第二温度为1250～1350℃。
有益效果：
本发明采用微波烧结法制备γ-C 2S(即γ型硅酸二钙)。微波加热是材料在电磁场中由电介质材料的介质损耗引起的体加热，物料的内外部同时加热，与传统加热相比，具有穿透力强、加热速度快、控制及时、反应灵敏等显著优点。因此，用微波烧结法制备γ-C 2S，可以提高物料分子运动速度，降低反应活化能，从而提高反应速率，可以实现反应在较传统烧结法低的温度下进行，获得高质量的产物γ-C 2S，降低生产能耗，符合节能减排的发展要求。
附图说明
图1为本发明实施例1的产物XRD测试结果图；
图2为本发明实施例2的产物XRD测试结果图；
图3为本发明实施例3的产物XRD测试结果图；
图4为本发明实施例4的产物XRD测试结果图；
图5为本发明实施例5的产物XRD测试结果图；
图6为本发明实施例6的产物XRD测试结果图；
图7为本发明实施例7的产物XRD测试结果图；
图8为本发明对比例1的产物XRD测试结果图；
图9为本发明对比例2的产物XRD测试结果图；
图10为本发明对比例3的产物XRD测试结果图；
图11为本发明对比例4的产物XRD测试结果图。
具体实施方式
本发明的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将钙质原料与硅质原料按钙与硅的摩尔比为2：1混合均匀，然后加入原料总质量8～12％(例如8％、9％、10％、11％、12％)的去离子水充分混合均匀以便于后续压制样片时的定型，得混合料，使用压片机将混合料在6～10MPa(例如6MPa、7MPa、8MPa、9MPa、10MPa)的压力下压制成片，于真空干燥箱中以60～100℃(例如60℃、70℃、80℃、90℃、100℃)下干燥14～18h(例如14h、15h、16h、17h、18h)，得到样片。
钙质原料为碳酸钙、氢氧化钙或者含有碳酸钙或氢氧化钙的废弃物，硅 质原料为无定形的二氧化硅以及硅藻土、膨润土和其他含有活性二氧化硅的废弃物。在计量时，以钙质原料中的含钙量、硅质原料的含硅量为准计算所需对应原料的质量。钙质原料和硅质原料采用固体废弃物能够对环境中的固体废弃物综合利用，减少环境中的固废污染。硅质原料的细度为500目或500目以上。
对于钙质原料，优选使用分析纯的碳酸钙，以尽可能降低杂质对反应结果的影响。对于硅质原料，优选使用500目或500目以上的无定形二氧化硅。
干燥温度优选为60℃，若温度高，干燥的样片出现黑点。
(2)将样片置于坩埚内放入微波烧结炉中，以10～15℃/min(例如10℃/min、11℃/min、12℃/min、13℃/min、14℃/min、15℃/min)的升温速率加热至900℃，保温25～35min(例如25min、26min、27min、28min、29min、30min、31min、32min、33min、34min、35min)，然后以10～15℃/min(例如10℃/min、11℃/min、12℃/min、13℃/min、14℃/min、15℃/min)的升温速率加热至1100～1350℃(例如1100℃、1150℃、1200℃、1350℃)下保温1～3h(例如1、1.5h、2h、2.5h、3h)，自然冷却，得γ型硅酸二钙。
上述微波烧结炉优选为高温微波马弗炉，其具有升温速度快、加热效率高和安全卫生无污染等特点，并能提高产品的均匀性和成品率，改善被烧结材料的微观结构和性能。
本发明的高温微波马弗炉，其微波总功率为8kW，温度范围为50～1600℃，精度为±0.1℃；微波频率是：2450MHz。
以下结合具体的实施例对本发明进行进一步的说明。
实施例1
本实施例的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将摩尔比为2：1的碳酸钙与二氧化硅混合均匀，然后加入原料总质量的10％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6MPa的压力下压制成片，于真空干燥箱中以60℃下干燥16h，得样片。
(2)将样片置于坩埚内放入高温微波马弗炉中，以10℃/min的升温速率加热至900℃，在900℃下保温30min，然后以10℃/min的升温速率加热至1350℃下保温2h，自然冷却，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙(即γ-C 2S)占61.5％(为质量百分含量，下同，不再赘述)， β型硅酸二钙(即β-C 2S)占15.3％，二硅酸三钙(即Ca 3Si 2O 7或C 3S 2)占23.2％，XRD图谱如图1所示。
实施例2
本实施例的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将摩尔比为2：1的碳酸钙与二氧化硅混合均匀，然后加入原料总质量10％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6MPa的压力下压制成片，于真空干燥箱中以60℃下干燥16h，得样片。
(2)将样片置于坩埚内放入高温微波马弗炉中，以10℃/min的升温速率加热至900℃，在900℃下保温30min，然后以10℃/min的升温速率加热至1300℃下保温2h，自然冷却，样片自粉化，XRD测试定量分析表明产物中γ型硅酸二钙占93.5％，β型硅酸二钙占6.5％，XRD图谱如图2所示。
实施例3
本实施例的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将摩尔比为2：1的碳酸钙与二氧化硅混合均匀，然后加入原料总质量10％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6MPa的压力下压制成片，于真空干燥箱中以60℃下干燥16h，得样片。
(2)将样片置于坩埚内放入高温微波马弗炉中，以10℃/min的升温速率加热至900℃，在900℃下保温30min，然后以10℃/min的升温速率加热至1250℃下保温2h，自然冷却，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占96.4％，β型硅酸二钙占3.6％，XRD图谱如图3所示。
实施例4
本实施例的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将摩尔比为2：1的碳酸钙与二氧化硅混合均匀，然后加入原料总质量10％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6MPa的压力下压制成片，于真空干燥箱中以60℃下干燥16h，得样片。
(2)将样片置于坩埚内放入高温微波马弗炉中，以10℃/min的升温速率加热至900℃，在900℃下保温30min，然后以10℃/min的升温速率加热至1200℃下保温2h，自然冷却，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占21.8％，β型硅酸二钙占78.2％，XRD图谱如图4所示。
实施例5
本实施例的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将摩尔比为2：1的碳酸钙与二氧化硅混合均匀，然后加入原料总质量10％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6MPa的压力下压制成片，于真空干燥箱中以60℃下干燥16h，得样片。
(2)将样片置于坩埚内放入高温微波马弗炉中，以10℃/min的升温速率加热至900℃，在900℃下保温30min，然后以10℃/min的升温速率加热至1150℃下保温2h，自然冷却，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占6.4％，β型硅酸二钙占93.6％，XRD图谱如图5所示。
实施例6
本实施例的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将摩尔比为2：1的碳酸钙与二氧化硅混合均匀，然后加入原料总质量10％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6MPa的压力下压制成片，于真空干燥箱中以60℃下干燥16h，得样片。
(2)将样片置于坩埚内放入高温微波马弗炉中，以10℃/min的升温速率加热至900℃，在900℃下保温30min，然后以10℃/min的升温速率加热至1250℃下保温1h，自然冷却，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占48.1％，β型硅酸二钙占51.9％，XRD图谱如图6所示。
实施例7
本实施例的γ型硅酸二钙的制备方法，包括以下步骤：
(1)将摩尔比为2：1的碳酸钙与二氧化硅混合均匀，然后加入原料总质量10％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6MPa的压力下压制成片，于真空干燥箱中以60℃下干燥16h，得样片。
(2)将样片置于坩埚内放入高温微波马弗炉中，以10℃/min的升温速率加热至900℃，在900℃下保温30min，然后以10℃/min的升温速率加热至1250℃下保温3h，自然冷却，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占75.6％，β型硅酸二钙占24.4％，XRD图谱如图7所示。
对比例1
本对比例的γ型硅酸二钙的制备方法，将实施例1中的高温微波马弗炉替换为传统马弗炉，其他参数均与实施例1中的相同，自然冷却后，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占79.4％，β型硅酸二钙 占20.6％，XRD图谱如图8所示。
与实施例1的XRD测试结果相比，在相同的温度下，虽然实施例1的产物中γ型硅酸二钙的占比相对较低，但实施例1中生成了钙含量更低的二硅酸三钙C 3S 2，并且占比高达23.2％。也就是说，在1350℃的烧结温度下，采用微波烧结得到的产物中，低钙组分的含量占比为84.7％，高于对比例1。
对比例2
本对比例的γ型硅酸二钙的制备方法，将实施例2中的高温微波马弗炉替换为传统马弗炉，其他参数均与实施例2中的相同，自然冷却后，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占68.1％，β型硅酸二钙占31.9％，XRD图谱如图9所示。
对比例3
本对比例的γ型硅酸二钙的制备方法，将实施例3中的高温微波马弗炉替换为传统马弗炉，其他参数均与实施例3中的相同，自然冷却后，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占36.0％，β型硅酸二钙占64.0％，XRD图谱如图10所示。
对比例4
本对比例的γ型硅酸二钙的制备方法，将实施例4中的高温微波马弗炉替换为传统马弗炉，其他参数均与实施例4中的相同，自然冷却后，样片自粉化，XRD定量分析结果表明产物中γ型硅酸二钙占15.4％，β型硅酸二钙占84.6％，XRD图谱如图11所示。
以上实施例1～7、对比例1～4的实验条件和产物成分对比如表1所示。
表1 实施例1～7、对比例1～4的实验条件和产物成分对比
Figure PCTCN2021088207-appb-000001
将实施例2、实施例3与对比例1、对比例2、对比例3的结果对比可知，采用高温微波烧结的方式，在较低的烧结温度下(1250℃)即可获得较高产率的γ型硅酸二钙，产物中γ型硅酸二钙的占比高达高达96.4％。原因可能是在微波加热条件下，存在除热效应之外的非热效应，降低了反应的活化能，从而使得其烧成温度低于传统加热方式下的烧成温度。
将实施例1与实施例3、对比例1、对比例3对比可知，采用高温微波烧结的方式，在1350℃烧结，虽然所得产品中γ型硅酸二钙的占比有所降低，但是产物出现了另一种低钙组分，即二硅酸三钙C 3S 2。相较γ-C 2S，C 3S 2的钙含量更低，将其作为低钙胶凝材料可以进一步减少CO 2的排放量。

Claims (10)

  1. 一种γ型硅酸二钙的制备方法，其特征在于，包括以下步骤：
    (1)将钙质原料与硅质原料按钙与硅的摩尔比为2：1混合均匀，然后加入原料总质量8～12％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6～10MPa的压力下压制成片，于真空干燥箱中干燥，得到样片；
    (2)将样片置于微波烧结炉中，加热至第一温度，保温30min，然后再加热至第二温度，保温，冷却，即得γ型硅酸二钙；
    所述第一温度为900℃，所述第二温度为1100～1350℃。
  2. 根据权利要求1所述的γ型硅酸二钙的制备方法，其特征在于，步骤(1)中，所述钙质原料为碳酸钙、氢氧化钙或者含有碳酸钙或氢氧化钙的废弃物；
    所述钙质原料为碳酸钙；
    所述碳酸钙为分析纯。
  3. 根据权利要求1所述的γ型硅酸二钙的制备方法，其特征在于，步骤(1)中，所述硅质原料为无定形的二氧化硅以及硅藻土、膨润土或其他含有活性二氧化硅的废弃物；
    所述硅质原料为无定形的二氧化硅。
  4. 根据权利要求1所述的γ型硅酸二钙的制备方法，其特征在于，步骤(1)中，所述硅质原料的细度为500目或500目以上。
  5. 根据权利要求1所述的γ型硅酸二钙的制备方法，其特征在于，步骤(1)中，所述干燥的温度为60～100℃。
  6. 根据权利要求1所述的γ型硅酸二钙的制备方法，其特征在于，步骤(2)中，所述加热至第一温度的升温速率为10～15℃/min。
  7. 根据权利要求1所述的γ型硅酸二钙的制备方法，其特征在于，步骤(2)中，所述加热至第二温度的升温速率为10～15℃/min；
    加热至第二温度后的保温时间为1～3h。
  8. 根据权利要求1所述的γ型硅酸二钙的制备方法，其特征在于，步骤(2)中，所述第二温度为1250℃。
  9. 一种以γ型硅酸二钙为主要物相组成的高强碳化材料，其特征在于，所述高强碳化材料中γ型硅酸二钙的质量百分数为60％以上，所述高强碳化材料的制备包括以下步骤：
    (1)将钙质原料与硅质原料按钙与硅的摩尔比为2：1混合均匀，然后加入原料总质量8～12％的去离子水充分混合均匀，得混合料，使用压片机将混合料在6～10MPa的压力下压制成片，于真空干燥箱中干燥，得到样片；
    (2)将样片置于微波烧结炉中，加热至第一温度，保温30min，然后再加热至第二温度，保温，冷却，所得全部产物即为所述高强碳化材料；
    所述第一温度为900℃，所述第二温度为1100～1350℃。
  10. 根据权利要求9所述的以γ型硅酸二钙为主要物相组成的高强碳化材料，其特征在于，所述第二温度为1250～1350℃。
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