WO2022142138A1 - Procédé de régulation et de réglage d'une composition minérale de clinker de sulphoaluminate à haute teneur en fer - Google Patents

Procédé de régulation et de réglage d'une composition minérale de clinker de sulphoaluminate à haute teneur en fer Download PDF

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Publication number
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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Prior art keywords
ferric
cementitious material
cao
content
performance
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PCT/CN2021/098462
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English (en)
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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Publication of WO2022142138A1 publication Critical patent/WO2022142138A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne le domaine de la production de ciment, et concerne un procédé de régulation et de réglage de la composition minérale d'un clinker de matériau cimentaire de sulpho-ferro-aluminate de haute performance. Selon la présente invention, un procédé de régulation et de réglage de la quantité totale de CaO dans les matières premières et du rapport des teneurs de CaO/CaSO4 est utilisé, et la composition de minéraux contenant du fer dans le clinker de matériau cimentaire de sulpho-ferro-aluminate est régulée et réglée de manière directionnelle. Par la régulation et le réglage de la teneur de CaO/CaSO4, la quantité de dopage de Fe2O3 dans C4A(3-x)FxS dans le clinker est accrue, de sorte que la teneur de C4A(3-x)FxS est accrue, la teneur de C4AF et de C2F est réduite, et les taux d'utilisation effectifs de Fe2O3 et Al2O3 sont accrus. Par conséquent, lorsque le Fe2O3/Al2O3 dans les matières premières est certain, la régulation et le réglage directionnels des minéraux contenant du fer sont atteintes par la régulation et le réglage de la teneur de CaO/CaSO44, et un matériau cimentaire de sulpho-ferro-aluminate ayant une meilleure performance est obtenu.
PCT/CN2021/098462 2020-12-31 2021-06-04 Procédé de régulation et de réglage d'une composition minérale de clinker de sulphoaluminate à haute teneur en fer WO2022142138A1 (fr)

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CN202011638958.5 2020-12-31

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CN112645616A (zh) * 2020-12-31 2021-04-13 山东大学 一种高铁硫铝酸盐熟料矿物组成的调控方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837121A (zh) * 2006-04-20 2006-09-27 中国地质大学（北京） 一种赤泥制备硫铝酸盐水泥的方法
CN102482148A (zh) * 2009-08-17 2012-05-30 拉法基公司 用于以贝利特-钙-硫铝酸盐-铁酸盐熟料为基础的水硬粘合剂的添加剂
US20130118384A1 (en) * 2010-07-21 2013-05-16 Vicat Iron-doped sulfo-belitic clinker
CN105658598A (zh) * 2013-09-03 2016-06-08 海德堡水泥公司 硫铝酸钙复合粘结剂
CN105683121A (zh) * 2013-09-03 2016-06-15 海德堡水泥公司 用于硫铝酸钙水泥的熔剂/矿化剂
CN112645616A (zh) * 2020-12-31 2021-04-13 山东大学 一种高铁硫铝酸盐熟料矿物组成的调控方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1219719C (zh) * 2003-12-01 2005-09-21 济南大学 含钡硫铁铝酸盐水泥
CN109369043A (zh) * 2018-11-02 2019-02-22 济南大学 一种白色硫铝酸盐水泥熟料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837121A (zh) * 2006-04-20 2006-09-27 中国地质大学（北京） 一种赤泥制备硫铝酸盐水泥的方法
CN102482148A (zh) * 2009-08-17 2012-05-30 拉法基公司 用于以贝利特-钙-硫铝酸盐-铁酸盐熟料为基础的水硬粘合剂的添加剂
US20130118384A1 (en) * 2010-07-21 2013-05-16 Vicat Iron-doped sulfo-belitic clinker
CN105658598A (zh) * 2013-09-03 2016-06-08 海德堡水泥公司 硫铝酸钙复合粘结剂
CN105683121A (zh) * 2013-09-03 2016-06-15 海德堡水泥公司 用于硫铝酸钙水泥的熔剂/矿化剂
CN112645616A (zh) * 2020-12-31 2021-04-13 山东大学 一种高铁硫铝酸盐熟料矿物组成的调控方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Master Thesis", 1 June 2017, JIANGSU UNIVERSITY, CN, article WANG CHUN: "Research on Low Temperature Synthesis of Calcium Sulphoaluminate Cement from Industrial Waste", pages: 1 - 72, XP055948256 *
"Master Thesis", 1 May 2018, CHONGQING UNIVERSITY, CN, article LIANG JIAO: "Synthesis of Iron-Rich Calcium Sulfoaluminate-belite Cement with Steel Slag", pages: 1 - 67, XP055948252 *

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