WO2023015619A1 - Ciment de sulfoaluminate blanc à base de déchets solides, le procédé de préparation à cet effet et son utilisation - Google Patents

Ciment de sulfoaluminate blanc à base de déchets solides, le procédé de préparation à cet effet et son utilisation Download PDF

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Publication number
WO2023015619A1
WO2023015619A1 PCT/CN2021/115074 CN2021115074W WO2023015619A1 WO 2023015619 A1 WO2023015619 A1 WO 2023015619A1 CN 2021115074 W CN2021115074 W CN 2021115074W WO 2023015619 A1 WO2023015619 A1 WO 2023015619A1
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Prior art keywords
solid waste
sulphoaluminate cement
parts
white
based white
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PCT/CN2021/115074
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English (en)
Chinese (zh)
Inventor
王文龙
姚永刚
吴长亮
姚星亮
武双
蒋稳
王旭江
李敬伟
毛岩鹏
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山东大学
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Publication of WO2023015619A1 publication Critical patent/WO2023015619A1/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
    • C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • 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 belongs to the field of building decoration materials, and relates to a solid waste-based white sulphoaluminate cement and a preparation method and application thereof.
  • white Portland cement accounts for a relatively high proportion in the white cement market, but white Portland cement clinker has high requirements on raw material quality and calcination temperature.
  • the limestone content in the raw meal accounts for more than 80%, and the calcination temperature is relatively ordinary.
  • Portland cement clinker is about 100 °C higher than sulphoaluminate cement clinker and more than 200 °C higher, and the carbon emission is higher; moreover, white Portland cement generally has the problem of low early strength, which not only makes it In engineering applications, it is easy to crack, easy to efflorescence and high damage rate, which also greatly affects the production and construction efficiency. Therefore, it is urgent to invent a kind of low-carbon environmental protection, early-strength, high-strength white cement to meet the urgent needs of the market.
  • White sulfoaluminate cement is a hydraulic cementitious material composed of anhydrous calcium sulfoaluminate, dicalcium silicate and calcium sulfate as main minerals. Because of its special mineral composition, the calcination temperature and The demand for calcium carbonate is much lower than that of white Portland cement. It is a low-carbon environmentally friendly cement; and because of its own characteristics such as rapid hardening, early strength, high strength and micro-expansion, it can not only meet the strength of construction It can also greatly improve the production and construction efficiency, so it is an ideal white cement. The inventor found that although white sulphoaluminate cement is an ideal white cement, it has taken up a relatively small proportion in the white cement market since its invention.
  • white sulphoaluminate cement is ripe
  • the production of raw materials relies heavily on high-quality raw materials such as bauxite, which leads to high costs; another reason is that the strength of ordinary white sulphoaluminate cement does not increase significantly in the later stage, and even shrinks.
  • the object of the present invention is to provide a solid waste-based white sulphoaluminate cement and its preparation method and application.
  • the solid waste-based white sulphoaluminate cement provided by the invention can not only effectively reduce
  • the production cost of white sulphoaluminate cement can also reduce the harm of industrial solid waste to the environment, realize the reduction, recycling and high-value utilization of industrial solid waste, and the prepared solid waste-based white sulphoaluminate
  • the strength of cement increases significantly in the later stage, which can effectively promote its large-scale application in decorative engineering.
  • a kind of solid waste-based white sulphoaluminate cement clinker the ingredients of the raw material are counted in parts by mass, including: 41-46 parts of aluminum profile electroplating residue, 10-17 parts of white desulfurized gypsum from steel mills, wollastonite 10-13 parts, limestone 29-34 parts.
  • White cement is a series of cement that requires high cement whiteness.
  • White cement can be used as building decoration materials.
  • the technology of using solid waste to prepare sulphoaluminate cement mainly focuses on the phase composition of sulphoaluminate cement, and selects different solid wastes for batching and calcining to make sulphoaluminate cement.
  • solid waste contains a variety of trace elements, such as chromium, manganese, iron, vanadium, nickel, titanium, etc. These trace elements not only affect the performance of sulphoaluminate cement, but also have a strong effect on cement clinker calcination.
  • the dyeing ability can greatly reduce the whiteness of sulphoaluminate cement, so it is difficult to prepare white sulphoaluminate cement from solid waste.
  • the preparation of ordinary sulphoaluminate cement needs to use bauxite, while the preparation of white sulphoaluminate cement requires higher purity of bauxite, so the cost is significantly increased.
  • the present invention selects aluminum profile electroplating residues, white desulfurized gypsum from steel mills, wollastonite, and limestone for batching.
  • a method for preparing the above-mentioned solid waste-based white sulphoaluminate cement clinker comprises uniformly mixing aluminum profile electroplating residue, white desulfurized gypsum from steel mills, wollastonite and limestone according to the ratio of raw materials, and then calcining, Cool to obtain solid waste-based white sulphoaluminate cement clinker.
  • a solid waste-based white sulphoaluminate cement in parts by mass, comprising: 50-80 parts of the above-mentioned solid waste-based white sulphoaluminate cement clinker, 5-20 parts of white desulfurized gypsum from steel mills , 10-30 parts of limestone.
  • a method for preparing the above-mentioned solid waste-based white sulphoaluminate cement, the solid waste-based white sulphoaluminate cement clinker, white desulfurized gypsum from steel mills, and limestone are mixed uniformly according to the proportion, and then ground and sieved Obtain solid waste-based white sulphoaluminate cement.
  • the solid waste-based white sulphoaluminate cement prepared by the present invention uses industrial solid waste as the main raw material, which not only effectively reduces the production cost of white sulphoaluminate cement, but also reduces the environmental pollution caused by industrial solid waste.
  • the reduction, recycling and high-value utilization of industrial solid waste are realized; the strength of the solid waste-based white sulphoaluminate cement prepared by the invention is significantly improved in the later stage, which can effectively promote the decorative performance of the white sulphoaluminate cement. large-scale applications in engineering.
  • the present invention proposes a solid waste-based white sulphoaluminate cement and its preparation method and application.
  • a typical implementation of the present invention provides a solid waste-based white sulphoaluminate cement clinker.
  • the raw material ingredients are calculated in parts by mass, including: 41-46 parts of aluminum profile electroplating residue, white desulfurized gypsum from steel mills 10-17 parts, wollastonite 10-13 parts, limestone 29-34 parts.
  • the present invention selects aluminum profile electroplating residue, white desulfurized gypsum from steel mills, wollastonite and limestone for raw material batching.
  • solid waste-based white sulphoaluminate cement clinker is prepared by using the combination of raw materials, and then by further compounding steel
  • the solid waste-based white sulphoaluminate cement prepared from factory white desulfurized gypsum and limestone not only has a higher whiteness than ordinary white sulphoaluminate cement, but also has a continuous increase in strength in the later stage, and its mechanical properties are significantly better than ordinary white sulphoaluminate cement.
  • Sulphoaluminate cement is clinker.
  • the solid waste-based white sulphoaluminate cement clinker prepared under this ratio is more conducive to improving the whiteness and mechanical properties of solid waste-based white sulphoaluminate cement.
  • the sum of the parts by mass of aluminum profile electroplating residue, white desulfurized gypsum from steel mills, wollastonite and limestone is 100 parts.
  • Another embodiment of the present invention provides a method for preparing the above-mentioned solid waste-based white sulphoaluminate cement clinker.
  • the electroplating residue of aluminum profiles, white desulfurized gypsum from steel mills, wollastonite and limestone are mixed according to the ratio of raw materials Mix evenly, then calcinate, and cool to obtain solid waste-based white sulphoaluminate cement clinker.
  • the homogeneously mixed material is pressed into shape by adding water, and then calcined, and the calcined and cooled clinker block is broken and ground.
  • the calcination temperature is 1220-1250°C.
  • the third embodiment of the present invention provides a solid waste-based white sulphoaluminate cement, which comprises: 50-80 parts of the above-mentioned solid waste-based white sulphoaluminate cement clinker in parts by mass. 5-20 parts of white desulfurized gypsum, 10-30 parts of limestone.
  • the present invention adopts the white desulfurized gypsum of steel mills, which not only can further reduce the cost, but also has better effect of adjusting coagulation and promoting strength.
  • solid waste-based white sulphoaluminate cement clinker is 64.0-76.5 parts
  • steel plant white desulfurized gypsum is 8.0-13.5 parts
  • limestone is 10.0-20.0 parts.
  • the mechanical properties of solid waste-based white sulphoaluminate cement under this ratio are better.
  • the specific surface area is not less than 400 m 2 /kg.
  • the fourth embodiment of the present invention provides a method for preparing the above-mentioned solid waste-based white sulphoaluminate cement.
  • the solid waste-based white sulphoaluminate cement clinker, steel mill white desulfurized gypsum, and limestone are mixed according to the proportion Mix evenly, grind and sieve to obtain solid waste-based white sulphoaluminate cement.
  • the fifth embodiment of the present invention provides an application of the above-mentioned solid waste-based white sulphoaluminate cement in architectural decoration projects or sculpture products.
  • the used aluminum profile electroplating residue, white desulfurized gypsum from steel mills, wollastonite and limestone all need to be pretreated before use, and the pretreatment steps are crushing, drying and grinding.
  • the drying temperature is 105°C, and the raw materials need to be dried to constant weight; during grinding, the raw materials need to be ground until all of them pass through a 200-mesh sieve.
  • the aluminum profile electroplating residue used is a kind of white residue, which is obtained from the acidic electroplating solution that has treated the surface of the aluminum profile, after condensing adjustment, pressure filtration, and drying, and its Al 2 O 3 content is between 45 % ⁇ 55wt%, Fe 2 O 3 content is less than 0.8wt%.
  • the white desulfurized gypsum from steel mills used has a SO 3 content of 45-50 wt % and a Fe 2 O 3 content of less than 0.3 wt %.
  • the limestone used has a CaO content greater than 55% and a Fe 2 O 3 content less than 0.1 wt%.
  • the wollastonite used has a SiO 2 content of 45-50 wt % and a Fe 2 O 3 content of less than 0.1 wt %.
  • Aluminum profile electroplating residue, white desulfurized gypsum from steel mills, wollastonite and limestone are selected as raw materials, and the proportions are calculated as follows: 44.5wt% aluminum profile electroplating residue, 10.9wt% white desulfurized gypsum from steel mills, and 12.1wt% wollastonite wt%, limestone 32.5wt%.
  • Solid waste-based white sulphoaluminate cement is mainly prepared from cement clinker, setting and strengthening components, and filler components.
  • the cement clinker is solid waste-based white sulphoaluminate cement clinker produced in Part A
  • the coagulation-adjusting and strengthening-promoting component is steel mill white desulfurized gypsum
  • the filling auxiliary material is limestone.
  • Example 1 The raw materials for preparing solid waste-based white sulphoaluminate cement are exactly the same as in Example 1, which are respectively the solid waste-based white sulphoaluminate cement clinker and the steel mill white sulphoaluminate cement clinker prepared in Part A of Example 1. Desulfurization gypsum and limestone.
  • Example 1 The raw materials for preparing solid waste-based white sulphoaluminate cement are exactly the same as in Example 1, which are respectively the solid waste-based white sulphoaluminate cement clinker and the steel mill white sulphoaluminate cement clinker prepared in Part A of Example 1. Desulfurization gypsum and limestone.
  • Example 1 The raw materials for preparing solid waste-based white sulphoaluminate cement are exactly the same as in Example 1, which are respectively the solid waste-based white sulphoaluminate cement clinker and the steel mill white sulphoaluminate cement clinker prepared in Part A of Example 1. Desulfurization gypsum and limestone.
  • Example 1 The raw materials for preparing solid waste-based white sulphoaluminate cement are exactly the same as in Example 1, which are respectively the solid waste-based white sulphoaluminate cement clinker and the steel mill white sulphoaluminate cement clinker prepared in Part A of Example 1. Desulfurization gypsum and limestone.
  • Aluminum profile electroplating residue, white desulfurized gypsum from steel mills, wollastonite and limestone are selected as raw materials, and the proportions are calculated as follows: 45.8wt% aluminum profile electroplating residue, 10.4wt% white desulfurized gypsum from steel mills, and 12.5% wollastonite wt%, limestone 31.3wt%.
  • Solid waste-based white sulphoaluminate cement is mainly prepared from cement clinker, setting and strengthening components, and filler components.
  • the cement clinker is solid waste-based white sulphoaluminate cement clinker produced in Part A
  • the coagulation-adjusting and strengthening-promoting component is steel mill white desulfurized gypsum
  • the filling auxiliary material is limestone.
  • Aluminum profile electroplating residue, steel mill white desulfurized gypsum, wollastonite and limestone are selected as raw materials, and the proportions are calculated as follows: aluminum profile electroplating residue 43.6wt%, steel mill white desulfurized gypsum 16.6wt%, wollastonite 10.4 wt%, limestone 29.4wt%.
  • Solid waste-based white sulphoaluminate cement is mainly prepared from cement clinker, setting and strengthening components, and filler components.
  • the cement clinker is solid waste-based white sulphoaluminate cement clinker produced in Part A
  • the coagulation-adjusting and strengthening-promoting component is steel mill white desulfurized gypsum
  • the filling auxiliary material is limestone.
  • Ordinary white Portland cement is mainly prepared from cement clinker, setting and strengthening components, and filling auxiliary components.
  • the cement clinker is commercially available ordinary white Portland cement clinker
  • the coagulation-adjusting and strengthening-promoting component is white desulfurized gypsum from steel mills
  • the filling auxiliary material is limestone.
  • Ordinary sulphoaluminate cement is mainly prepared from cement clinker, setting and strengthening components, and filler components.
  • the cement clinker is commercially available common sulphoaluminate cement clinker
  • the coagulation-adjusting and strengthening-promoting components are steel factory white desulfurized gypsum
  • the filling auxiliary material is limestone.
  • Ordinary white sulphoaluminate cement is mainly prepared from cement clinker, setting and strengthening components, and filling auxiliary components.
  • the cement clinker is commercially available ordinary white sulphoaluminate cement clinker
  • the coagulation-adjusting and strengthening-promoting component is steel factory white desulfurized gypsum
  • the filling auxiliary material is limestone.
  • Ordinary white sulphoaluminate cement is mainly composed of cement clinker and gypsum.
  • cement clinker is commercially available common white sulphoaluminate cement clinker
  • gypsum is commercially available anhydrite.
  • the solid waste-based white sulphoaluminate cement prepared in the above examples was sealed and dried.
  • commercially available ordinary sulphoaluminate cement clinker, commercially available white sulphoaluminate cement clinker, and commercially available ordinary white Portland cement clinker were used as the main raw materials for comparison.
  • the mechanical performance test of the cement of each embodiment and comparative example is carried out as follows: the water and the cement are mixed evenly in the slurry mixer with a water-to-binder ratio of 0.33, and then poured into a six-unit mold of 20mm ⁇ 20mm ⁇ 20mm Medium molding. After molding, put the test mold into a standard curing box (temperature 20 ⁇ 1°C, humidity 95 ⁇ 1%) for curing, and demould after 6 hours. After demoulding, put the test block in water for curing until the test age, and then use the pressure testing machine to test the compressive strength.
  • a standard curing box temperature 20 ⁇ 1°C, humidity 95 ⁇ 1%
  • Adopt the method described in the present invention take aluminum profile electroplating residue, white desulfurization gypsum of steel factory, wollastonite, limestone as raw material, make solid waste base white sulphoaluminate cement clinker, by further compounding 10- 20wt% steel mill white desulfurized gypsum and 10-30wt% limestone make solid waste-based white sulphoaluminate cement (Example 1-Example 7), and find that by testing and analyzing its whiteness and compressive strength respectively : one, the whiteness of the prepared solid waste base white sulphoaluminate cement has all reached more than 83%, which is higher than ordinary white portland cement (comparative example 1) and ordinary white sulphoaluminate cement (to Ratio 3) whiteness; Second, the prepared solid waste-based white sulphoaluminate cement not only has rapid early strength growth, but also has a 3D compressive strength exceeding 60MPa, which has the characteristics of early strength and rapid hardening, and
  • the solid waste-based white sulphoaluminate cement prepared by the method of the present invention has more than 70% of its raw materials as industrial solid waste, which illustrates that the solid waste-based white sulphoaluminate cement is prepared by the method of the present invention It can not only effectively reduce the production cost of white sulphoaluminate cement, but also reduce the environmental pollution caused by industrial solid waste, and realize the high-value utilization of industrial solid waste.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne un ciment de sulfoaluminate blanc à base de déchets solides, le procédé de préparation à cet effet et son utilisation. Le ciment de sulfoaluminate blanc à base de déchets solides comprend, en parties en masse, de 50 à 80 parties d'un clinker de ciment de sulfoaluminate blanc à base de déchets solides, de 5 à 20 parties d'un gypse de désulfuration blanche provenant d'une aciérie, et de 10 à 30 parties de calcaire. Le clinker de ciment de sulfoaluminate blanc à base de déchets solides comprend, en parties en masse, de 41 à 46 parties de résidus d'électrodéposition de profils d'aluminium, de 10 à 17 parties d'un gypse de désulfuration blanc provenant d'une aciérie, de 10 à 13 parties de wollastonite et de 29 à 34 parties de calcaire. Le ciment de sulfoaluminate blanc à base de déchets solides réduit non seulement efficacement le coût de production d'un ciment de sulfoaluminate blanc, mais peut également réduire les risques environnementaux provoqués par des déchets solides industriels et réaliser la réduction, la récupération des ressources et l'utilisation à grande valeur de déchets solides industriels. De plus, la résistance ultérieure du ciment de sulfoaluminate blanc à base de déchets solides préparés est augmentée de manière significative, de sorte que son application à grande échelle dans l'ingénierie décorative peut être efficacement favorisée.
PCT/CN2021/115074 2021-08-10 2021-08-27 Ciment de sulfoaluminate blanc à base de déchets solides, le procédé de préparation à cet effet et son utilisation WO2023015619A1 (fr)

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CN202110913089.0A CN113511826B (zh) 2021-08-10 2021-08-10 一种固废基白色硫铝酸盐水泥及其制备方法与应用

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CN115849851A (zh) * 2022-11-25 2023-03-28 山东大学 固废基硫铝酸盐水泥改性建筑石膏基自流平砂浆

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CN103979810A (zh) * 2014-05-22 2014-08-13 同济大学 一种综合利用造纸白泥、铝矾土和脱硫石膏制备硫铝酸盐水泥熟料的方法
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CN112456830A (zh) * 2020-12-09 2021-03-09 郑州市建文特材科技有限公司 一种微膨胀高贝利特硫铝酸盐水泥及其生产方法

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CN110078394A (zh) * 2019-05-15 2019-08-02 盐城工学院 低温制备硫硅酸钙-贝利特-硫铝酸盐水泥熟料的方法

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GB2055786A (en) * 1979-08-01 1981-03-11 Blue Circle Ind Ltd Portland cement clinker
EP2636654A1 (fr) * 2012-03-05 2013-09-11 HeidelbergCement AG Ternesite en tant qu'additif au ciment de sulfoaluminate de calcium
CN103979810A (zh) * 2014-05-22 2014-08-13 同济大学 一种综合利用造纸白泥、铝矾土和脱硫石膏制备硫铝酸盐水泥熟料的方法
CN105314902A (zh) * 2015-11-25 2016-02-10 天津水泥工业设计研究院有限公司 全部利用工业废渣煅烧贝利特硫铝酸盐水泥熟料的方法
CN110078393A (zh) * 2019-05-15 2019-08-02 盐城工学院 一种低温制备硫硅酸钙-硫铝酸盐水泥的方法
CN112456830A (zh) * 2020-12-09 2021-03-09 郑州市建文特材科技有限公司 一种微膨胀高贝利特硫铝酸盐水泥及其生产方法

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