WO2022142138A1 - Method for regulating and controlling mineral composition of high-iron sulphoaluminate clinker - Google Patents

Method for regulating and controlling mineral composition of high-iron sulphoaluminate clinker Download PDF

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WO2022142138A1
WO2022142138A1 PCT/CN2021/098462 CN2021098462W WO2022142138A1 WO 2022142138 A1 WO2022142138 A1 WO 2022142138A1 CN 2021098462 W CN2021098462 W CN 2021098462W WO 2022142138 A1 WO2022142138 A1 WO 2022142138A1
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ferric
cementitious material
cao
content
performance
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PCT/CN2021/098462
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French (fr)
Chinese (zh)
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王文龙
姚星亮
武双
姚永刚
杨世钊
王旭江
李敬伟
蒋稳
毛岩鹏
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山东大学
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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
    • C04B7/32—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
    • C04B7/36—Manufacture of hydraulic cements in general
    • 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
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • 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

Definitions

  • the invention relates to the technical field of cement production, in particular to a method for regulating and controlling the mineral composition of clinker of a high-performance high-iron sulfoaluminate cementitious material.
  • the cement industry is one of the largest energy-consuming and carbon-emitting industries in the world, producing 0.87 tons of CO 2 for every ton of cement produced. According to statistics, the world produces about 4 billion tons of ordinary Portland cement every year, and the CO2 emissions account for about 7% of the global emissions. Therefore, the development of a low-carbon cement is imminent. As a common low-carbon cement, sulfoaluminate cement is gradually attracting more and more attention due to its lower CaO content, lower calcination temperature, and ease of grinding.
  • the main active mineral of sulfoaluminate cement is calcium sulfoaluminate (Ca 4 Al 6 SO 16 , ), the content of Al 2 O 3 is relatively high, and a large amount of bauxite or other high-grade aluminum sources needs to be consumed in the production process.
  • solid waste as raw material to produce sulfoaluminate cementitious materials
  • solid waste with high aluminum content is also required as raw material. Therefore, sulfoaluminate cementing materials are expensive and have limited applications.
  • the prior art has mentioned the use of Fe 2 O 3 to replace Al 2 O 3 to reduce the amount of Al 2 O 3 used, but it cannot control the active minerals in high-iron sulfoaluminate cementitious materials
  • the composition instead, were treated with C 4 AF that had reacted too quickly. Therefore, the mineral hydration in the prepared high-iron sulfoaluminate cementitious material is too fast, which is not conducive to the sustainable development of the performance of the high-iron sulfoaluminate cementitious material.
  • the present invention aims to provide a high-performance ferric ferric aluminate cementitious material.
  • a method for regulating the mineral composition of material clinker adopts the method of regulating the total amount of CaO in the raw material and the content ratio of CaO/CaSO 4 to directionally regulate the composition of iron-bearing minerals in the clinker of the sulphur-iron-aluminate cementitious material.
  • the Fe 2 O 3 in clinker can be increased in the amount of incorporation in the The content of C 4 AF and C 2 F is reduced, and the effective utilization rate of Fe 2 O 3 and Al 2 O 3 is improved. Therefore, when the Fe 2 O 3 /Al 2 O 3 in the raw material is constant, the directional regulation of iron-bearing minerals can be achieved by adjusting the content of CaO/CaSO 4 , and a ferric-pyroaluminate cementitious material with better properties can be obtained.
  • the first aspect of the present invention provides a high-performance ferric sulphur aluminate cementitious material, in terms of mass percentage, the cementitious material is composed of the following components: 50%-70% 20%-40% C 2 S, 0%-10% CaSO 4 , 0%-10% C 4 AF, wherein the value range of x is 0-1.5.
  • the technical key of this patent lies in the directional regulation of the mineral composition of the high-iron sulphoaluminate cementitious material by regulating the CaO/CaSO 4 content ratio.
  • the prior art focuses on the preparation of high-speed iron Belite sulfoaluminate cement, in which the mineral composition is C 2 S and C 4 AF, without mentioning any Relevant technical guidance, not to mention about Techniques for the regulation of C 4 AF content.
  • a second aspect of the present invention provides a method for preparing a high-performance ferric sulphur aluminate cementitious material, comprising:
  • the calcium source, sulfur source, silicon source, aluminum source and iron source are used as raw materials, the raw materials are prepared according to the target product, and the mixture is obtained by grinding with a pulverizer;
  • the mixture is added to the homogenization tank, and the homogenized material is obtained after washing;
  • the homogenized material is filtered, dried and ground to obtain a powdery mixture
  • the powdery mixture is calcined and cooled to obtain a high active mineral content sulphur-ferric aluminate cementitious material.
  • the invention realizes the directional regulation of the mineral composition of the high-iron sulphoaluminate cementitious material by regulating the CaO/CaSO 4 content ratio. Increased high iron sulfoaluminate cementitious material in clinker
  • the content of Al 2 O 3 reduces the consumption of Al 2 O 3 , reduces the demand for raw materials of sulfoaluminate cementing materials, realizes the resource utilization of low-grade aluminum-containing solid waste, broadens the source of raw materials, and improves the mineral composition of high-iron sulfoaluminate cement.
  • the mechanical properties of solidified materials continue to develop.
  • the third aspect of the present invention provides the application of the above-mentioned high-performance ferric sulfoaluminate cementitious material in the manufacture of cement and the fields of construction engineering.
  • this method can prepare high content of sulfur aluminum ferrite cementitious material.
  • the activity is higher than that of C 4 AF. Therefore, the sulphoaluminoferrite cementitious material has better mechanical properties.
  • this method can realize the directional control of the composition of iron-bearing minerals in the clinker by regulating the content of CaO/CaSO 4 in the raw material, the calcination temperature of the clinker, the holding time, etc. content, and in the clinker
  • the substitution amount of Fe 2 O 3 to Al 2 O 3 can reach 40-50%, thereby reducing the content of Al 2 O 3 in the clinker of the sulphur ferric aluminate cementitious material.
  • the method not only reduces the content of Al 2 O 3 in the clinker of the sulphur-iron-aluminate cementitious material, but also increases the effective utilization rate of alumina by more than 50%, thereby reducing the sulphoaluminate glue
  • the demand for aluminum in the clinker of the cementitious material increases the selection of raw materials, so that the solid waste or low-grade aluminum-containing minerals with low aluminum content can be used as the calcining raw material of the ferric ferric aluminate cementitious material clinker.
  • this method reduces the content of Al 2 O 3 in the clinker, which not only saves the consumption of Al 2 O 3 of the reserve material, but also reduces the price of the ferric sulphur aluminate cementitious material and increases the ferric sulphur The scope of use of aluminate cementitious materials.
  • the preparation method of the present invention is simple, convenient to operate, strong practicability, and easy to popularize.
  • Fig. 1 is the XRD pattern of different Cm ferric sulphur aluminate cementitious materials in the present invention.
  • One of the objects of the present invention is to provide a high-performance ferric sulphur aluminate cementitious material.
  • the second purpose of the present invention is to provide a preparation method of a high-active mineral content sulphur-ferric aluminate cementitious material.
  • the third object of the present invention is to provide a method for regulating the mineral composition of a high-performance ferric pyrite aluminate cementitious material clinker.
  • the present invention discloses a high-performance ferric ferric aluminate cementitious material.
  • the cementitious material is composed of the following components: 50%-70% 20%-40% C2S , 0 %-10% CaSO4, 0%-10% C4AF .
  • the present invention separates a method for preparing a high active mineral content sulphur ferric aluminate cementitious material. It includes the following steps:
  • step (2) drying and pulverizing the homogenized material in step (2) to obtain powdery mixture;
  • step (3) calcining the powdery mixture in step (3), and placing it in the air to rapidly cool after the calcination to obtain a high-active mineral content sulphur-ferric aluminate cementitious material.
  • step 1) when preparing raw materials for the clinker, the chemical composition ratio of SiO 2 , Fe 2 O 3 and Al 2 O 3 in the target clinker is constant, about 8%-14%: 18%-26%: 6%-16%; the total amount of CaO is defined by the alkalinity coefficient C m , which is about 0.80-1.10; the total amount of CaSO 4 is 0%-20%.
  • the total amount of CaO is controlled between C m of 0.85-1.00 , the theoretical residual amount of CaSO 4 is kept in the range of 5%-15% ; The amount is kept at 15 %-30% to ensure that CaSO4 is left in the clinker, thus promoting the target product Formation.
  • the content of CaO/CaSO 4 in the raw material the calcined high content of ferric pyrite aluminate cementitious material clinker raw material.
  • step 2) the mass ratio of mixture and water during the washing is 1:3-4.
  • soluble ions such as sodium and chlorine in aluminum ash and carbide slag can be removed, and the influence of soluble ions on the performance of the cementitious material can be reduced.
  • step 2) the time of the water washing is 2-4h.
  • the drying after filtration refers to: pressure filtration of the homogenized material to a moisture content of less than 25% (mass), and drying at 600° C. for 2 hours.
  • step 3 the fineness of the homogenized mixture after grinding is 30% of the sieve residue of 45 ⁇ m.
  • step 4 the calcination temperature is 1150-1250°C, and the calcination time is 0.5-1.5h. After cooling, a high active mineral content pyrite ferric aluminate cementitious material is obtained.
  • the calcination temperature of the traditional sulfoaluminate cement clinker is 1250-1300°C. Compared with this, the present invention not only has a lower calcination temperature, but also has more significant energy-saving effect; The content of high-performance ferric sulphur aluminate cementitious materials can be obtained.
  • the present invention discloses a method for regulating the mineral composition of high-performance ferric sulphur aluminate cementitious material clinker.
  • the raw materials are prepared according to a certain target product, and pulverized by a pulverizer to obtain Raw material mixture composed of target minerals;
  • step 1) the chemical composition ratio of SiO 2 , Fe 2 O 3 and Al 2 O 3 in the target clinker is constant, and the ratio is about 8%-14%: 18%-26%: 6%-16%.
  • step 1) the mineral composition of clinker is regulated by changing the content of CaO and CaSO 4 .
  • the total amount of CaO is controlled between C m of 0.85-1.00 , the theoretical residual amount of CaSO 4 is kept in the range of 5%-15% ; The amount is kept at 15 %-30% to ensure that CaSO4 is left in the clinker, thus promoting the target product Formation.
  • the ratio of raw materials realizes the directional regulation of the mineral composition of clinker.
  • the appropriate calcination temperature can be reduced to 1150-1200°C or the holding time can be shortened to 10-20min; From the production point of view, when the temperature or calcination time is reduced, and the CaO content C m is greater than 1.00, the theoretical residual amount of CaSO 4 is kept at 10%-20%, and Fe 2 O 3 and Al 2 O 3 are realized.
  • the improvement of the effective utilization rate increases the dosage of Fe 2 O 3 , thereby reducing the use of aluminum raw materials.
  • the method for regulating and controlling the mineral composition of clinker of high-iron sulphur ferric aluminate cementitious materials utilizes the CaO and CaSO 4 contents in the raw materials to control the C 4 AF and C 4 AF and the The effect of the formation reaction kinetics to realize the formation of Fe 2 O 3 to C 4 AF and directional regulation. Not only enhance the active minerals in clinker The content of aluminum oxide is increased, and the effective utilization rate of alumina is improved. At the same time, the amount of iron oxide is increased in the raw materials, thereby reducing the use of aluminum raw materials and broadening the source of raw materials.
  • a method for regulating and controlling the mineral composition of clinker of a high-performance ferric pyrite aluminate cementitious material comprising the following steps:
  • the raw materials of pyrite ferric aluminate cementitious material clinker are composed of electroplating sludge, red mud, carbide slag, phosphogypsum and fly ash, and their chemical compositions are shown in Table 1.
  • the mineral composition C 2 S:CaSO 4 :C 4 AF was 40%:30%:10%:20%.
  • Table 2 according to the requirements of SiO 2 , Fe 2 O 3 and Al 2 O 3 in the target product, a certain proportion of electroplating sludge, red mud, phosphogypsum and fly ash were first prepared. Subsequently, the alkalinity coefficient C m of the batch is adjusted by adding different amounts of carbide slag to obtain raw materials with different C m .
  • step (2) Throwing the pulverized raw material in step (1) into a homogenization tank, adding water at a mass ratio of 1:4 (raw material and water) to obtain a slurry, washing and stirring for 3h, so that aluminum ash and calcium carbide slag are mixed with The soluble substances are dissolved into the homogenization tank;
  • phase composition of the gelling material prepared in this example was mainly: and C 2 S, indicating that the mineral is well formed and similar to the expected mineral.

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Abstract

The present invention belongs to the field of cement production, and relates to a method for regulating and controlling the mineral composition of a high-performance sulpho-ferro-aluminate cementing material clinker. According to the present invention, a method for regulating and controlling the total amount of CaO in raw materials and the content ratio of CaO/CaSO4 is used, and the composition of iron-containing minerals in the sulpho-ferro-aluminate cementing material clinker is directionally regulated and controlled. By regulating and controlling the content of CaO/CaSO4, the doping amount of Fe2O3 in C4A(3-x)FxS in the clinker is increased, so that the content of C4A(3-x)FxS is increased, the content of C4AF and C2F is reduced, and the effective utilization rates of Fe2O3 and Al2O3 are increased. Therefore, when Fe2O3/Al2O3 in the raw materials is certain, directional regulation and control of the iron-containing minerals are achieved by regulating and controlling the content of CaO/CaSO44, and a sulpho-ferro-aluminate cementing material having a better performance is obtained.

Description

一种高铁硫铝酸盐熟料矿物组成的调控方法A kind of regulation method of high iron sulfoaluminate clinker mineral composition 技术领域technical field
本发明涉及水泥生产技术领域，具体涉及一种高性能高铁硫铝酸盐胶凝材料熟料矿物组成的调控方法。The invention relates to the technical field of cement production, in particular to a method for regulating and controlling the mineral composition of clinker of a high-performance high-iron sulfoaluminate cementitious material.
背景技术Background technique
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。The disclosure of information in this Background section is only for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
水泥行业是全球最大的能源消耗和碳排放行业之一，每生产1吨水泥将产生0.87吨的CO 2。据统计，全世界每年约生产40亿吨普通硅酸盐水泥，排放的CO 2约占全球排放量的7％。因此，发展一种低碳水泥迫在眉睫。硫铝酸盐水泥作为一种常见的低碳水泥，由于其较低的CaO含量、较低的煅烧温度以及易磨性，正逐渐引起越来越多的关注。但是，硫铝酸盐水泥的主要活性矿物是硫铝酸钙(Ca 4Al 6SO 16，
Figure PCTCN2021098462-appb-000001
)，Al 2O 3的含量较高，其生产过程中需要消耗大量的铝矾土或其他高品位铝源。尽管已经有很多利用固废为原料生产硫铝酸盐胶凝材料的研究，但是同样需要含铝量高的固废作为原料。因此，硫铝酸盐胶凝材料的价格昂贵，应用有限。 The cement industry is one of the largest energy-consuming and carbon-emitting industries in the world, producing 0.87 tons of CO 2 for every ton of cement produced. According to statistics, the world produces about 4 billion tons of ordinary Portland cement every year, and the CO2 emissions account for about 7% of the global emissions. Therefore, the development of a low-carbon cement is imminent. As a common low-carbon cement, sulfoaluminate cement is gradually attracting more and more attention due to its lower CaO content, lower calcination temperature, and ease of grinding. However, the main active mineral of sulfoaluminate cement is calcium sulfoaluminate (Ca 4 Al 6 SO 16 ,
Figure PCTCN2021098462-appb-000001
), the content of Al 2 O 3 is relatively high, and a large amount of bauxite or other high-grade aluminum sources needs to be consumed in the production process. Although there have been many researches on using solid waste as raw material to produce sulfoaluminate cementitious materials, solid waste with high aluminum content is also required as raw material. Therefore, sulfoaluminate cementing materials are expensive and have limited applications.
当制备高铁硫铝酸盐胶凝材料时，Fe 2O 3能够取代
Figure PCTCN2021098462-appb-000002
矿物中Al 2O 3形成
Figure PCTCN2021098462-appb-000003
该矿物具有与
Figure PCTCN2021098462-appb-000004
相似的水化活性。因此，掺加一部分Fe 2O 3作为煅烧熟料原料取代Al 2O 3可降低Al 2O 3的使用量，从而降低原料中Al 2O 3的含量 要求。然而，除生成
Figure PCTCN2021098462-appb-000005
一部分Fe 2O 3将会生成Ca 4Al 2Fe 2O 10(C 4AF)或Ca 2Fe 2O 5(C 2F)。其中，C 4AF水化速率过快，C 2F没有水化活性，均不利于水泥强度的长期稳定增长。 When preparing high iron sulfoaluminate cementitious materials, Fe2O3 can replace
Figure PCTCN2021098462-appb-000002
Al 2 O 3 formation in minerals
Figure PCTCN2021098462-appb-000003
This mineral has
Figure PCTCN2021098462-appb-000004
Similar hydration activity. Therefore, adding a part of Fe 2 O 3 as the raw material of calcined clinker to replace Al 2 O 3 can reduce the amount of Al 2 O 3 used, thereby reducing the content requirement of Al 2 O 3 in the raw material. However, in addition to generating
Figure PCTCN2021098462-appb-000005
A portion of Fe 2 O 3 will form Ca 4 Al 2 Fe 2 O 10 (C 4 AF) or Ca 2 Fe 2 O 5 (C 2 F). Among them, the hydration rate of C 4 AF is too fast, and C 2 F has no hydration activity, which is not conducive to the long-term stable growth of cement strength.
现有技术已经提到了使用Fe 2O 3取代Al 2O 3降低Al 2O 3的使用量，但是不能够控制高铁硫铝酸盐胶凝材料中活性矿物
Figure PCTCN2021098462-appb-000006
的组成，而是均已反应过快的C 4AF对待。因此，所制得的高铁硫铝酸盐胶凝材料中矿物水化过快，不利于高铁硫铝酸盐胶凝材料性能的持续发展。 The prior art has mentioned the use of Fe 2 O 3 to replace Al 2 O 3 to reduce the amount of Al 2 O 3 used, but it cannot control the active minerals in high-iron sulfoaluminate cementitious materials
Figure PCTCN2021098462-appb-000006
The composition, instead, were treated with C 4 AF that had reacted too quickly. Therefore, the mineral hydration in the prepared high-iron sulfoaluminate cementitious material is too fast, which is not conducive to the sustainable development of the performance of the high-iron sulfoaluminate cementitious material.
因此，行业内主要面临一些问题：Therefore, the industry is mainly faced with some problems:
(1)如何提升硫铁铝酸盐胶凝材料中活性矿物
Figure PCTCN2021098462-appb-000007
的含量。 (1) How to improve the active minerals in ferric ferric aluminate cementitious materials
Figure PCTCN2021098462-appb-000007
content.
(2)如何提高硫铁铝酸盐胶凝材料熟料中Fe 2O 3的掺入量。 (2) How to increase the content of Fe 2 O 3 in the clinker of ferric ferric aluminate cementitious materials.
(3)如何利用低品位含铝矿或固废作为烧制硫铁铝酸盐胶凝材料的原料。(3) How to use low-grade bauxite or solid waste as a raw material for firing pyrite ferric aluminate cementitious materials.
发明内容SUMMARY OF THE INVENTION
针对上述现有技术中存在的硫铁铝酸盐胶凝材料熟料原料含铝量要求高，含铁矿物活性低等缺点，本发明旨在提供一种高性能硫铁铝酸盐胶凝材料熟料矿物组成的调控方法。本发明采用调控原料中的CaO的总量及CaO/CaSO 4含量比的方法，定向调控硫铁铝酸盐胶凝材料熟料含铁矿物的组成。通过调控CaO/CaSO 4的含量，提高熟料中Fe 2O 3在
Figure PCTCN2021098462-appb-000008
中的掺入量，从而提高
Figure PCTCN2021098462-appb-000009
的含量，降低C 4AF和C 2F的含量，提高Fe 2O 3和Al 2O 3的有效利用率。因此，原料中Fe 2O 3/Al 2O 3一定时，通过调控CaO/CaSO 4的含量实现含铁矿物的定向调控，得到具备更优性能的硫铁铝酸盐胶凝材料。 Aiming at the shortcomings of the above-mentioned prior art such as the high requirement of aluminum content in the clinker raw material of the ferric ferric aluminate cementitious material and the low activity of iron-containing minerals, the present invention aims to provide a high-performance ferric ferric aluminate cementitious material. A method for regulating the mineral composition of material clinker. The invention adopts the method of regulating the total amount of CaO in the raw material and the content ratio of CaO/CaSO 4 to directionally regulate the composition of iron-bearing minerals in the clinker of the sulphur-iron-aluminate cementitious material. By regulating the content of CaO/CaSO 4 , the Fe 2 O 3 in clinker can be increased in
Figure PCTCN2021098462-appb-000008
the amount of incorporation in the
Figure PCTCN2021098462-appb-000009
The content of C 4 AF and C 2 F is reduced, and the effective utilization rate of Fe 2 O 3 and Al 2 O 3 is improved. Therefore, when the Fe 2 O 3 /Al 2 O 3 in the raw material is constant, the directional regulation of iron-bearing minerals can be achieved by adjusting the content of CaO/CaSO 4 , and a ferric-pyroaluminate cementitious material with better properties can be obtained.
为实现上述技术目的，本发明采用如下技术方案：For realizing the above-mentioned technical purpose, the present invention adopts following technical scheme:
本发明的第一个方面，提供了一种高性能硫铁铝酸盐胶凝材料，按质量百分数计，所述胶凝材料由以下组分组成：50％-70％
Figure PCTCN2021098462-appb-000010
20％-40％C 2S、0％-10％CaSO 4、0％-10％C 4AF，其中，x的取值范围是0-1.5.。 The first aspect of the present invention provides a high-performance ferric sulphur aluminate cementitious material, in terms of mass percentage, the cementitious material is composed of the following components: 50%-70%
Figure PCTCN2021098462-appb-000010
20%-40% C 2 S, 0%-10% CaSO 4 , 0%-10% C 4 AF, wherein the value range of x is 0-1.5.
目前，本专利的技术关键在于通过调控CaO/CaSO 4含量比实现高铁硫铝酸盐胶凝材料矿物组成的定向调控。现有技术均聚焦于高铁贝利特硫铝酸盐水泥的制备工作，其中矿物组成均为
Figure PCTCN2021098462-appb-000011
C 2S和C 4AF，而没有提到任何与
Figure PCTCN2021098462-appb-000012
Figure PCTCN2021098462-appb-000013
相关的技术指导，更没有关于
Figure PCTCN2021098462-appb-000014
与C 4AF含量的调控技术。 At present, the technical key of this patent lies in the directional regulation of the mineral composition of the high-iron sulphoaluminate cementitious material by regulating the CaO/CaSO 4 content ratio. The prior art focuses on the preparation of high-speed iron Belite sulfoaluminate cement, in which the mineral composition is
Figure PCTCN2021098462-appb-000011
C 2 S and C 4 AF, without mentioning any
Figure PCTCN2021098462-appb-000012
Figure PCTCN2021098462-appb-000013
Relevant technical guidance, not to mention about
Figure PCTCN2021098462-appb-000014
Techniques for the regulation of C 4 AF content.
本发明的第二个方面，提供了一种高性能硫铁铝酸盐胶凝材料的制备方法，包括：A second aspect of the present invention provides a method for preparing a high-performance ferric sulphur aluminate cementitious material, comprising:
将钙源、硫源、硅源、铝源和铁源作为原料，按照目标产物配置原料，经粉碎机粉磨，得到混合料；The calcium source, sulfur source, silicon source, aluminum source and iron source are used as raw materials, the raw materials are prepared according to the target product, and the mixture is obtained by grinding with a pulverizer;
将所述混合料加入均化池，水洗后得到均化物料；The mixture is added to the homogenization tank, and the homogenized material is obtained after washing;
将均化物料滤干后干燥、粉磨，得到粉末状混合料；The homogenized material is filtered, dried and ground to obtain a powdery mixture;
将粉末状混合料进行锻烧，冷却，即得到高活性矿物含量硫铁铝酸盐胶凝材料。The powdery mixture is calcined and cooled to obtain a high active mineral content sulphur-ferric aluminate cementitious material.
本发明通过调控CaO/CaSO 4含量比实现高铁硫铝酸盐胶凝材料矿物组成的定向调控。提高了高铁硫铝酸盐胶凝材料熟料中
Figure PCTCN2021098462-appb-000015
的含量，降低了Al 2O 3消耗，降低硫铝酸盐胶凝材料原料需求，实现低品位含铝固废的资源化利用，拓宽原料来源，并且从矿物组成上提升高铁硫铝酸盐胶凝材料的机械性能持续发展。 The invention realizes the directional regulation of the mineral composition of the high-iron sulphoaluminate cementitious material by regulating the CaO/CaSO 4 content ratio. Increased high iron sulfoaluminate cementitious material in clinker
Figure PCTCN2021098462-appb-000015
The content of Al 2 O 3 reduces the consumption of Al 2 O 3 , reduces the demand for raw materials of sulfoaluminate cementing materials, realizes the resource utilization of low-grade aluminum-containing solid waste, broadens the source of raw materials, and improves the mineral composition of high-iron sulfoaluminate cement. The mechanical properties of solidified materials continue to develop.
本发明的第三个方面，提供了上述的高性能硫铁铝酸盐胶凝材料在制造水泥，及建筑工程领域中的应用。The third aspect of the present invention provides the application of the above-mentioned high-performance ferric sulfoaluminate cementitious material in the manufacture of cement and the fields of construction engineering.
本发明的有益效果在于：The beneficial effects of the present invention are:
(1)相比于传统方法，本方法可制备得到高
Figure PCTCN2021098462-appb-000016
含量的硫铝铁酸盐胶凝材料。其中，
Figure PCTCN2021098462-appb-000017
的活性高于C 4AF。因此，硫铝铁酸盐胶凝材料具有更优的机械性能。 (1) Compared with the traditional method, this method can prepare high
Figure PCTCN2021098462-appb-000016
content of sulfur aluminum ferrite cementitious material. in,
Figure PCTCN2021098462-appb-000017
The activity is higher than that of C 4 AF. Therefore, the sulphoaluminoferrite cementitious material has better mechanical properties.
(2)相比于传统方法，本方法通过调控原料中CaO/CaSO 4的含量，熟料的煅烧温度、保温时间等可实现熟料中含铁矿物组成的定向调控，不仅能够提高
Figure PCTCN2021098462-appb-000018
的含量，而且熟料中
Figure PCTCN2021098462-appb-000019
中Fe 2O 3对Al 2O 3的取代量可达到40-50％，从而降低硫铁铝酸盐胶凝材料熟料中Al 2O 3的含量。 (2) Compared with the traditional method, this method can realize the directional control of the composition of iron-bearing minerals in the clinker by regulating the content of CaO/CaSO 4 in the raw material, the calcination temperature of the clinker, the holding time, etc.
Figure PCTCN2021098462-appb-000018
content, and in the clinker
Figure PCTCN2021098462-appb-000019
The substitution amount of Fe 2 O 3 to Al 2 O 3 can reach 40-50%, thereby reducing the content of Al 2 O 3 in the clinker of the sulphur ferric aluminate cementitious material.
(3)相比于传统方法，本方法不仅降低硫铁铝酸盐胶凝材料熟料中Al 2O 3的含量，而且氧化铝的有效利用率提高50％以上，从而降低硫铝酸盐胶凝材料熟料中对铝元素的需求，增加原料的选择种类，使得含铝较低的固废或者低品位含铝矿物可以作为硫铁铝酸盐胶凝材料熟料的煅烧原料。 (3) Compared with the traditional method, the method not only reduces the content of Al 2 O 3 in the clinker of the sulphur-iron-aluminate cementitious material, but also increases the effective utilization rate of alumina by more than 50%, thereby reducing the sulphoaluminate glue The demand for aluminum in the clinker of the cementitious material increases the selection of raw materials, so that the solid waste or low-grade aluminum-containing minerals with low aluminum content can be used as the calcining raw material of the ferric ferric aluminate cementitious material clinker.
(4)相比于传统方法，本方法降低熟料中Al 2O 3的含量，既节省储备材料Al 2O 3的消耗，又可降低硫铁铝酸盐胶凝材料的价格，增加硫铁铝酸盐胶凝材料的使用范围。 (4) Compared with the traditional method, this method reduces the content of Al 2 O 3 in the clinker, which not only saves the consumption of Al 2 O 3 of the reserve material, but also reduces the price of the ferric sulphur aluminate cementitious material and increases the ferric sulphur The scope of use of aluminate cementitious materials.
(5)本发明的制备方法简单、操作方便、实用性强，易于推广。(5) The preparation method of the present invention is simple, convenient to operate, strong practicability, and easy to popularize.
附图说明Description of drawings
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，本发明的示意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。The accompanying drawings forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1为本发明中不同Cm硫铁铝酸盐胶凝材料的XRD图。Fig. 1 is the XRD pattern of different Cm ferric sulphur aluminate cementitious materials in the present invention.
具体实施方式Detailed ways
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。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components, and/or combinations thereof.
本发明的目的之一是提供一种高性能硫铁铝酸盐胶凝材料。One of the objects of the present invention is to provide a high-performance ferric sulphur aluminate cementitious material.
本发明的目的之二是提供一种高活性矿物含量硫铁铝酸盐胶凝材料的制备方法。The second purpose of the present invention is to provide a preparation method of a high-active mineral content sulphur-ferric aluminate cementitious material.
本发明的目的之三是提供一种高性能硫铁铝酸盐胶凝材料熟料的矿物组成调控方法。The third object of the present invention is to provide a method for regulating the mineral composition of a high-performance ferric pyrite aluminate cementitious material clinker.
为实现上述发明目的，具体的，本发明公开了下述技术方案：In order to achieve the above-mentioned purpose of the invention, specifically, the present invention discloses the following technical solutions:
首先，本发明公开了一种高性能硫铁铝酸盐胶凝材料，按质量百分数计，所述胶凝材料由以下组分组成：50％-70％
Figure PCTCN2021098462-appb-000020
20％-40％C 2S、0％-10％CaSO 4、0％-10％C 4AF。 First of all, the present invention discloses a high-performance ferric ferric aluminate cementitious material. In terms of mass percentage, the cementitious material is composed of the following components: 50%-70%
Figure PCTCN2021098462-appb-000020
20%-40% C2S , 0 %-10% CaSO4, 0%-10% C4AF .
其次，本发明分开了一种高活性矿物含量硫铁铝酸盐胶凝材料的制备方法。包括如下步骤：Secondly, the present invention separates a method for preparing a high active mineral content sulphur ferric aluminate cementitious material. It includes the following steps:
1)将电石渣等钙源、脱硫石膏等硫源、粉煤灰等硅源和铝源、赤泥、钢渣等铁源作为原料，按照一定的目标产物配置原料，经粉碎机粉磨，得到混合料；1) Use calcium sources such as calcium carbide slag, sulfur sources such as desulfurized gypsum, silicon sources such as fly ash, and iron sources such as aluminum sources, red mud, and steel slag as raw materials, prepare raw materials according to certain target products, and grind them through a pulverizer to obtain Mixture;
2)将步骤(1)中的混合料加入均化池，水洗后得到均化物料；2) adding the mixture in the step (1) into a homogenizing tank, and washing with water to obtain a homogenized material;
3)对步骤(2)中的均化物料滤干后干燥、粉磨，得到粉末状混合料；3) drying and pulverizing the homogenized material in step (2) to obtain powdery mixture;
4)对步骤(3)中的粉末状混合料进行锻烧，煅烧结束置于空气中快速冷却， 即得到高活性矿物含量硫铁铝酸盐胶凝材料。4) calcining the powdery mixture in step (3), and placing it in the air to rapidly cool after the calcination to obtain a high-active mineral content sulphur-ferric aluminate cementitious material.
步骤1)中，所述熟料在配制原料时，目标熟料中SiO 2、Fe 2O 3和Al 2O 3的化学组成比例一定，约为8％-14％：18％-26％：6％-16％；CaO总量由碱度系数C m定义，约为0.80-1.10；CaSO 4的总量为0％-20％。当CaO总量控制在C m为0.85-1.00之间，将CaSO 4的理论剩余量保持在5％-15％的范围内；当CaO含量配量C m大于1.00时，将CaSO 4的理论剩余量保持在15％-30％以确保CaSO 4在熟料中有剩余，从而促进目标产物中
Figure PCTCN2021098462-appb-000021
的形成。通过调控原料中CaO/CaSO 4的含量，即可得到煅烧高
Figure PCTCN2021098462-appb-000022
含量的硫铁铝酸盐胶凝材料熟料原料。 In step 1), when preparing raw materials for the clinker, the chemical composition ratio of SiO 2 , Fe 2 O 3 and Al 2 O 3 in the target clinker is constant, about 8%-14%: 18%-26%: 6%-16%; the total amount of CaO is defined by the alkalinity coefficient C m , which is about 0.80-1.10; the total amount of CaSO 4 is 0%-20%. When the total amount of CaO is controlled between C m of 0.85-1.00 , the theoretical residual amount of CaSO 4 is kept in the range of 5%-15% ; The amount is kept at 15 %-30% to ensure that CaSO4 is left in the clinker, thus promoting the target product
Figure PCTCN2021098462-appb-000021
Formation. By adjusting the content of CaO/CaSO 4 in the raw material, the calcined high
Figure PCTCN2021098462-appb-000022
content of ferric pyrite aluminate cementitious material clinker raw material.
步骤2)中，所述水洗时混合料和水的质量比为1：3-4。经过均化池水洗，可以除去铝灰、电石渣中的纳、氯等可溶性离子，降低可溶性离子对胶凝材料性能的影响。In step 2), the mass ratio of mixture and water during the washing is 1:3-4. After washing in the homogenization tank, soluble ions such as sodium and chlorine in aluminum ash and carbide slag can be removed, and the influence of soluble ions on the performance of the cementitious material can be reduced.
步骤2)中，所述水洗的时间为2-4h。In step 2), the time of the water washing is 2-4h.
步骤3)中，所述滤干后干燥指：将均化物料压滤至含水率25％(质量)以下，在600℃下烘干2h。In step 3), the drying after filtration refers to: pressure filtration of the homogenized material to a moisture content of less than 25% (mass), and drying at 600° C. for 2 hours.
步骤3)中，所述均化混料粉磨后的细度为45μm筛余30％。In step 3), the fineness of the homogenized mixture after grinding is 30% of the sieve residue of 45 μm.
步骤4)中，所述煅烧温度为1150-1250℃，煅烧时间为0.5-1.5h。冷却后即得到了高活性矿物含量硫铁铝酸盐胶凝材料。In step 4), the calcination temperature is 1150-1250°C, and the calcination time is 0.5-1.5h. After cooling, a high active mineral content pyrite ferric aluminate cementitious material is obtained.
传统硫铝酸盐水泥熟料制备时的煅烧温度为1250-1300℃，与其相对比，本发明不仅煅烧温度更低，节能效果更加显著；而且通过原料调配，增加熟料中活性矿物
Figure PCTCN2021098462-appb-000023
的含量，可得到高性能硫铁铝酸盐胶凝材料。 The calcination temperature of the traditional sulfoaluminate cement clinker is 1250-1300°C. Compared with this, the present invention not only has a lower calcination temperature, but also has more significant energy-saving effect;
Figure PCTCN2021098462-appb-000023
The content of high-performance ferric sulphur aluminate cementitious materials can be obtained.
最后，本发明公开了一种高性能硫铁铝酸盐胶凝材料熟料的矿物组成调控方 法。Finally, the present invention discloses a method for regulating the mineral composition of high-performance ferric sulphur aluminate cementitious material clinker.
1)将电石渣等钙源、脱硫石膏等硫源、粉煤灰等硅源和铝源、赤泥、钢渣等铁源作为原料，按照一定的目标产物配制原料，经粉碎机粉磨，得到目标矿物组成的原料混合料；1) Using calcium sources such as calcium carbide slag, sulfur sources such as desulfurized gypsum, silicon sources such as fly ash, and iron sources such as aluminum sources, red mud, and steel slag as raw materials, the raw materials are prepared according to a certain target product, and pulverized by a pulverizer to obtain Raw material mixture composed of target minerals;
步骤1)中，目标熟料中SiO 2、Fe 2O 3和Al 2O 3的化学组成比例一定，其比例约为8％-14％：18％-26％：6％-16％。 In step 1), the chemical composition ratio of SiO 2 , Fe 2 O 3 and Al 2 O 3 in the target clinker is constant, and the ratio is about 8%-14%: 18%-26%: 6%-16%.
步骤1)中，通过改变CaO和CaSO 4的含量调控熟料的矿物组成。当CaO总量控制在C m为0.85-1.00之间，将CaSO 4的理论剩余量保持在5％-15％的范围内；当CaO含量配量C m大于1.00时，将CaSO 4的理论剩余量保持在15％-30％以确保CaSO 4在熟料中有剩余，从而促进目标产物中
Figure PCTCN2021098462-appb-000024
的形成。原料配比实现对熟料矿物组成的定向调控。同理，当CaO总量控制在C m为0.85-1.00之间，CaSO 4的理论剩余量不足时，可将适当煅烧温度降低至1150-1200℃或者保温时间缩短至10-20min；反之，从生产角度来讲，将温度降低或者煅烧时间减少，而将CaO含量配量C m大于1.00时，将CaSO 4的理论剩余量保持在10％-20％，实现Fe 2O 3和Al 2O 3有效利用率的提高，增加Fe 2O 3的配入量，从而减少铝质原料的使用。 In step 1), the mineral composition of clinker is regulated by changing the content of CaO and CaSO 4 . When the total amount of CaO is controlled between C m of 0.85-1.00 , the theoretical residual amount of CaSO 4 is kept in the range of 5%-15% ; The amount is kept at 15 %-30% to ensure that CaSO4 is left in the clinker, thus promoting the target product
Figure PCTCN2021098462-appb-000024
Formation. The ratio of raw materials realizes the directional regulation of the mineral composition of clinker. Similarly, when the total amount of CaO is controlled between 0.85-1.00 C m and the theoretical residual amount of CaSO 4 is insufficient, the appropriate calcination temperature can be reduced to 1150-1200°C or the holding time can be shortened to 10-20min; From the production point of view, when the temperature or calcination time is reduced, and the CaO content C m is greater than 1.00, the theoretical residual amount of CaSO 4 is kept at 10%-20%, and Fe 2 O 3 and Al 2 O 3 are realized. The improvement of the effective utilization rate increases the dosage of Fe 2 O 3 , thereby reducing the use of aluminum raw materials.
本发明所述的高铁硫铁铝酸盐胶凝材料熟料矿物组成的调控方法，利用原料中CaO和CaSO 4含量对C 4AF和
Figure PCTCN2021098462-appb-000025
的生成反应动力学的影响，实现Fe 2O 3生成C 4AF和
Figure PCTCN2021098462-appb-000026
的定向调控。不仅提升熟料中活性矿物
Figure PCTCN2021098462-appb-000027
的含量，而且实现氧化铝有效利用率的提高，同时原料中增加氧化铁的配入量，从而减少铝质原料的使用，拓宽原料来源。 The method for regulating and controlling the mineral composition of clinker of high-iron sulphur ferric aluminate cementitious materials according to the present invention utilizes the CaO and CaSO 4 contents in the raw materials to control the C 4 AF and C 4 AF and the
Figure PCTCN2021098462-appb-000025
The effect of the formation reaction kinetics to realize the formation of Fe 2 O 3 to C 4 AF and
Figure PCTCN2021098462-appb-000026
directional regulation. Not only enhance the active minerals in clinker
Figure PCTCN2021098462-appb-000027
The content of aluminum oxide is increased, and the effective utilization rate of alumina is improved. At the same time, the amount of iron oxide is increased in the raw materials, thereby reducing the use of aluminum raw materials and broadening the source of raw materials.
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。The present invention will be described in further detail below in conjunction with specific embodiments. It should be pointed out that the specific embodiments are intended to illustrate rather than limit the present invention.
实施例1：Example 1:
一种高性能硫铁铝酸盐胶凝材料熟料矿物组成的调控方法，包括如下步骤：A method for regulating and controlling the mineral composition of clinker of a high-performance ferric pyrite aluminate cementitious material, comprising the following steps:
(1)硫铁铝酸盐胶凝材料熟料的原料由电镀污泥、赤泥、电石渣、磷石膏和粉煤灰组成，他们的化学组成如表1所示。目标熟料产物中，矿物组成
Figure PCTCN2021098462-appb-000028
C 2S：CaSO 4：C 4AF为40％：30％：10％：20％。如表2所示，根据目标产物中SiO 2、Fe 2O 3和Al 2O 3的需求，首先配制一定比例的电镀污泥、赤泥、磷石膏和粉煤灰。随后使用添加不同量的电石渣调节配料的碱度系数C m，得到不同C m的原料。 (1) The raw materials of pyrite ferric aluminate cementitious material clinker are composed of electroplating sludge, red mud, carbide slag, phosphogypsum and fly ash, and their chemical compositions are shown in Table 1. In the target clinker product, the mineral composition
Figure PCTCN2021098462-appb-000028
C 2 S:CaSO 4 :C 4 AF was 40%:30%:10%:20%. As shown in Table 2, according to the requirements of SiO 2 , Fe 2 O 3 and Al 2 O 3 in the target product, a certain proportion of electroplating sludge, red mud, phosphogypsum and fly ash were first prepared. Subsequently, the alkalinity coefficient C m of the batch is adjusted by adding different amounts of carbide slag to obtain raw materials with different C m .
(2)将步骤(1)中粉磨后的原料投到均化池中进行，按1:4的质量比(原料和水)加水，得浆液，水洗搅拌3h，使铝灰和电石渣中的可溶性物质溶出至均化池中；(2) Throwing the pulverized raw material in step (1) into a homogenization tank, adding water at a mass ratio of 1:4 (raw material and water) to obtain a slurry, washing and stirring for 3h, so that aluminum ash and calcium carbide slag are mixed with The soluble substances are dissolved into the homogenization tank;
(3)将浆液压滤至含水量18％(wt.％)，将其送到600℃烘干器中烘干2h，得混合料，用粉磨机将烘干的混合料粉磨；将粉磨后的混合料加入回转窑中在1200℃保温30min，煅烧完成后急速冷却，即可得到硫铁铝酸盐胶凝材料。(3) hydraulically filter the slurry to a water content of 18% (wt.%), send it to a 600°C dryer for drying for 2 hours to obtain a mixture, and grind the dried mixture with a pulverizer; The pulverized mixture is added to a rotary kiln and kept at 1200°C for 30 minutes, and after calcination is completed, it is rapidly cooled to obtain a sulphur-ferric aluminate cementitious material.
用XRD检测本实施例制备的胶凝材料的物相组成，结果如表3和图1所示，从图1中可以看出本实施例制备的胶凝材料物相主要为
Figure PCTCN2021098462-appb-000029
和C 2S，这说明矿物形成良好，与预期矿物相近。 XRD was used to detect the phase composition of the gelling material prepared in this example. The results are shown in Table 3 and Figure 1. It can be seen from Figure 1 that the phase of the gelling material prepared in this example is mainly:
Figure PCTCN2021098462-appb-000029
and C 2 S, indicating that the mineral is well formed and similar to the expected mineral.
表1 实施例1中不同工业固废的化学组成(wt.％)Table 1 Chemical composition (wt.%) of different industrial solid wastes in Example 1
Figure PCTCN2021098462-appb-000030
Figure PCTCN2021098462-appb-000030
Figure PCTCN2021098462-appb-000031
Figure PCTCN2021098462-appb-000031
表2 实施例1中制备的胶凝材料原料配比Table 2 The ratio of raw materials of cementitious materials prepared in Example 1
Figure PCTCN2021098462-appb-000032
Figure PCTCN2021098462-appb-000032
表3 不同硫铁铝酸盐胶凝材料的矿物组成Table 3 Mineral composition of different ferric ferric aluminate cementitious materials
Figure PCTCN2021098462-appb-000033
Figure PCTCN2021098462-appb-000033
最后应该说明的是，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，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分进行等同替换。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。上述虽然对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。Finally, it should be noted that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, the Modifications may be made to the technical solutions described in the foregoing embodiments, or equivalent replacements may be made to some of them. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention. Although the specific embodiments of the present invention are described above, they are not intended to limit the scope of protection of the present invention. Those skilled in the art should understand that on the basis of the technical solutions of the present invention, those skilled in the art do not need to pay creative work. Various modifications or deformations made are still within the protection scope of the present invention.

Claims (10)

  1. 一种高性能硫铁铝酸盐胶凝材料，其特征在于，按质量百分数计，所述胶凝材料由以下组分组成：50％-70％
    Figure PCTCN2021098462-appb-100001
    20％-40％C 2S、0％-10％CaSO 4、0％-10％C 4AF，其中，x取值范围为0-1.5。     A high-performance ferric ferric aluminate cementitious material, characterized in that, in terms of mass percentage, the cementitious material consists of the following components: 50%-70%
    Figure PCTCN2021098462-appb-100001
    20%-40% C 2 S, 0%-10% CaSO 4 , 0%-10% C 4 AF, wherein the value of x ranges from 0-1.5.
  2. 一种高性能硫铁铝酸盐胶凝材料的制备方法，其特征在于，包括：A method for preparing a high-performance ferric sulphur aluminate cementitious material, comprising:
    将钙源、硫源、硅源、铝源和铁源作为原料，按照目标产物配置原料，经粉碎机粉磨，得到混合料；The calcium source, sulfur source, silicon source, aluminum source and iron source are used as raw materials, the raw materials are prepared according to the target product, and the mixture is obtained by grinding with a pulverizer;
    将所述混合料加入均化池，水洗后得到均化物料；The mixture is added to the homogenization tank, and the homogenized material is obtained after washing;
    将均化物料滤干后干燥、粉磨，得到粉末状混合料；The homogenized material is filtered, dried and ground to obtain a powdery mixture;
    将粉末状混合料进行锻烧，冷却，即得到高活性矿物含量硫铁铝酸盐胶凝材料。The powdery mixture is calcined and cooled to obtain a high active mineral content sulphur-ferric aluminate cementitious material.
  3. 如权利要求2所述的高性能硫铁铝酸盐胶凝材料的制备方法，其特征在于，目标熟料中，SiO 2、Fe 2O 3和Al 2O 3的化学组成比例一定，为8％-14％：18％-26％：6％-16％。 The method for preparing a high-performance ferric sulphur aluminate cementitious material according to claim 2, wherein in the target clinker, the chemical composition ratio of SiO 2 , Fe 2 O 3 and Al 2 O 3 is constant, which is 8 %-14%: 18%-26%: 6%-16%.
  4. 如权利要求2所述的高性能硫铁铝酸盐胶凝材料的制备方法，其特征在于，目标熟料中，CaO总量由碱度系数C m定义，为0.80-1.10；CaSO 4的总量为0％-20％。 The method for preparing high-performance ferric sulphur aluminate cementitious material according to claim 2, wherein, in the target clinker, the total amount of CaO is defined by the alkalinity coefficient Cm , and is 0.80-1.10; the total amount of CaSO4 is 0.80-1.10 ; The amount is 0%-20%.
  5. 如权利要求4所述的高性能硫铁铝酸盐胶凝材料的制备方法，其特征在于，目标熟料中，当CaO总量控制在C m为0.85-1.00之间，将CaSO 4的理论剩余量保持在5％-15％的范围内。 The method for preparing high-performance ferric sulfide aluminate cementitious material according to claim 4, characterized in that, in the target clinker, when the total amount of CaO is controlled between C m 0.85-1.00, the theoretical CaSO 4 The remaining amount remains in the range of 5%-15%.
  6. 如权利要求4所述的高性能硫铁铝酸盐胶凝材料的制备方法，其特征在于，当CaO含量配量C m大于1.00时，将CaSO 4的理论剩余量保持在15％-30％。 The preparation method of high-performance ferric sulphur aluminate cementitious material according to claim 4, wherein when the CaO content ratio C m is greater than 1.00, the theoretical residual amount of CaSO 4 is kept at 15%-30% .
  7. 如权利要求2所述的高性能硫铁铝酸盐胶凝材料的制备方法，其特征在于，当CaO总量控制在C m为0.85-1.00之间，CaSO 4的理论剩余量不足时，将煅烧 温度降低至1150-1200℃或者保温时间缩短至10-20min；反之，将温度降低或者煅烧时间减少，而将CaO含量配量C m大于1.00时，将CaSO 4的理论剩余量保持在10％-20％。 The method for preparing a high-performance ferric ferric aluminate cementitious material according to claim 2, wherein when the total amount of CaO is controlled to be between 0.85 and 1.00 C m , and the theoretical residual amount of CaSO 4 is insufficient, the The calcination temperature is reduced to 1150-1200 ℃ or the holding time is shortened to 10-20min; on the contrary, the temperature is reduced or the calcination time is reduced, and when the CaO content C m is greater than 1.00, the theoretical residual amount of CaSO 4 is kept at 10% -20%.
  8. 如权利要求2所述的高性能硫铁铝酸盐胶凝材料的制备方法，其特征在于，所述水洗时混合料和水的质量比为1：3-4，优选的，所述水洗的时间为2-4h；The method for preparing a high-performance ferric sulphur aluminate cementitious material according to claim 2, wherein the mass ratio of the mixture to water during the washing is 1:3-4, preferably, the washing The time is 2-4h;
    或，所述滤干后干燥指：将均化物料压滤至含水率25wt％以下，在600℃下烘干2h；Or, the drying after filtration refers to: pressure filtration of the homogenized material to a moisture content of less than 25 wt%, and drying at 600° C. for 2 hours;
    或，所述均化混料粉磨后的细度为45μm筛余30％；Or, the fineness of the homogenized mixture after grinding is 45 μm sieve residue 30%;
    或，所述煅烧温度为1150-1250℃，煅烧时间为0.5-1.5h。Or, the calcination temperature is 1150-1250°C, and the calcination time is 0.5-1.5h.
  9. 权利要求1-8任一项所述的方法制备的高性能硫铁铝酸盐胶凝材料。The high-performance ferric ferric aluminate cementitious material prepared by the method of any one of claims 1-8.
  10. 权利要求9所述的高性能硫铁铝酸盐胶凝材料在制造水泥，及建筑工程领域中的应用。Application of the high-performance ferric sulphur aluminate cementitious material according to claim 9 in the manufacture of cement and the fields of construction engineering.
PCT/CN2021/098462 2020-12-31 2021-06-04 Method for regulating and controlling mineral composition of high-iron sulphoaluminate clinker WO2022142138A1 (en)

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