CN101851072A - Alite-sulphoaluminate strontium calcium cement - Google Patents

Alite-sulphoaluminate strontium calcium cement Download PDF

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Publication number
CN101851072A
CN101851072A CN201010188057A CN201010188057A CN101851072A CN 101851072 A CN101851072 A CN 101851072A CN 201010188057 A CN201010188057 A CN 201010188057A CN 201010188057 A CN201010188057 A CN 201010188057A CN 101851072 A CN101851072 A CN 101851072A
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China
Prior art keywords
cement
strontium calcium
aluminium sulphate
strontium
calcium aluminium
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CN201010188057A
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Chinese (zh)
Inventor
芦令超
王守德
常钧
叶正茂
周宗辉
黄世峰
程新
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Jinan University
University of Jinan
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University of Jinan
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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
    • C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
    • C04B7/3453—Belite cements, e.g. self-disintegrating cements based on dicalciumsilicate
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0004—Compounds chosen for the nature of their cations
    • C04B2103/001—Alkaline earth metal or Mg-compounds
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses an alite-sulphoaluminate strontium calcium cement, clinker aggregates of the alite-sulphoaluminate strontium calcium cement comprises the following ore phase systems by weight percent: 2-15 percent of sulphoaluminate strontium calcium, 50-66 percent of tricalcium silicate, 10-20 percent of dicalcium silicate; 5-15 percent of tricalcium aluminate and 5-15 percent of tetracalcium aluminoferrite, wherein the chemical formula of the tetracalcium aluminoferrite is (3-x)CaO.xSrO.3Al2O3.CaSO4, and x =1-3. The invention has the advantages of improving the early performance of silicate cement, saving energy sources and resources, improving the volume stability of the cement, recycling wastes and improving the environment.

Description

A Lite-strontium calcium aluminium sulphate cement
Technical field
The invention belongs to the cement material technical field, particularly a kind of strontium slag that utilizes is taken ore deposit A Lite-strontium calcium aluminium sulphate cement mutually for feedstock production as the leading factor with Dicalcium Phosphate (Feed Grade) and tricalcium silicate.
Background technology
At present, the traditional portland of mass production and use still comes with some shortcomings, and mainly shows as: the cement clinker firing temperature is up to 1450 ℃, the energy consumption height; Cement early strength is low; Hydration and hardening process generation volumetric shrinkage, and produce the contraction tiny crack, influenced the weather resistance of cement concrete.Therefore, how further to reduce the firing temperature of silicate cement, improving its early strength, improving volume stability is the key issue that cement technology field emphasis solves.
The major technique measure that raising traditional portland performance is taked is to improve cement clinker mesosilicic acid DFP (C 3S) content, thereby raising strength of cement, but this can cause the cement clinker firing temperature further to improve, cement kiln output further reduces, and need to select fat lime stone resource to produce, will cause cement to make energy consumption increase, production efficiency reduction, high-quality resource consumption increase, and cement shrinkage cracking phenomenon can not get improving.
Calcium sulfoaluminate minerals 3CaO3Al 2O 3CaSO 4Be a kind of early-strength type mineral, if with strontium ion (Sr 2+) part replacement calcium ion (Ca wherein 2+), strontium calcium aluminium sulphate mineral (3-x) CaOxSrO3Al of formation 2O 3CaSO 4(x=1 ~ 3) are a kind of hydraulicity mineral with outstanding high-early-strength performance, and its firing temperature is low.To make the employed main raw material of these mineral be Wingdale, bauxitic clay, contain strontium industrial residue and gypsum etc., and calcining temperature is 1300-1350 ℃.The ultimate compression strength of the strontium calcium aluminium sulphate mineral of manufacturing was at 1 day, 3 days and reach 30.5MPa, 55.8MPa and 68.5MPa respectively the 7 day length of time, and high-early-strength is functional.
Summary of the invention
Problem for solution cement clinker firing temperature height, the increase of cement manufacturing energy consumption, production efficiency reduction, high-quality resource consumption increase, cement shrinkage cracking phenomenon can not get improving provides a kind of A Lite-strontium calcium aluminium sulphate cement.
The present invention realizes by following measure:
The invention discloses a kind of A Lite-strontium calcium aluminium sulphate cement, its cement clinker is made up of the ore deposit phase system of following weight proportion:
Strontium calcium aluminium sulphate: 2-15%
Tricalcium silicate: 30-55%
Dicalcium Phosphate (Feed Grade): 15-25%
Tricalcium aluminate: 5-15%
Tetracalcium aluminoferrite: 5-15%;
Described strontium calcium aluminium sulphate chemical formula is (3-x) CaOxSrO3Al 2O 3CaSO 4, x=1 in the formula ~ 3.
A Lite-the strontium calcium aluminium sulphate cement of the invention described above, the composition of its ore deposit phase system:
Strontium calcium aluminium sulphate: 5-12%
Tricalcium silicate: 55-62%
Dicalcium Phosphate (Feed Grade): 12-18%
Tricalcium aluminate: 7-12%
Tetracalcium aluminoferrite: 8-12%.
A Lite-the strontium calcium aluminium sulphate cement of the invention described above is to be made by following materials of weight proportions:
CaO：50-70％
SiO 2：5-25％
Al 2O 3：2-16％
Fe 2O 3：2-7％
SO 3：0.2-2％
SrO：0.7-6％。
A Lite-the strontium calcium aluminium sulphate cement of the invention described above, described SrO are the strontium slag.
The preparation method of above-mentioned A Lite-strontium calcium aluminium sulphate cement: with each reactant feed CaO, SiO 2, Al 2O 3, Fe 2O 3, SrO, SO 3Put into the calcining of Si-Mo rod High Temperature Furnaces Heating Apparatus, calcining temperature is controlled at 1320 ℃-1400 ℃, forms grog by low-temperature solid phase reaction.
The present invention is that because this mineral firing temperature is low, early strength is high, the hydration process microdilatancy, and these mineral contain SO by introducing early-strength type mineral strontium calcium aluminium sulphate mineral in the Portland clinker mineral system 3And SrO, can in the burning clinker of cement process, play the mineralizer effect.Thereby it is low, early stage and later strength is high, shrinkage cracking reduces, the hardened paste compact structure that the A Lite-strontium calcium aluminium sulphate cement of manufacturing has a firing temperature, and can improve the weather resistance of cement.Simultaneously, can utilize to contain the production of strontium industrial residue, and eliminate the strontium slag and pollute, turn waste into wealth.
Traditional portland adopts four components batching, mainly contains: CaO, SiO 2, Al 2O 3, Fe 2O 3, four kinds of essential mineral phases by high temperature solid state reaction formation cement clinker mainly contain: tricalcium silicate (C 3S), Dicalcium Phosphate (Feed Grade) (C 2S), tricalcium aluminate (C 3A), tetracalcium aluminoferrite (C 4AF).The grog firing temperature is 1450 ℃.
A Lite of the present invention--strontium calcium aluminium sulphate cement adopts six components batching, mainly contains: CaO, SiO 2, Al 2O 3, Fe 2O 3, SrO, SO 3, by five kinds of essential mineral phases of low-temperature solid phase reaction formation cement clinker, tricalcium silicate (C 3S), Dicalcium Phosphate (Feed Grade) (C 2S), tricalcium aluminate (C 3A), tetracalcium aluminoferrite (C 4AF), strontium calcium aluminium sulphate consists of (3-x) CaOxSrO3Al 2O 3CaSO 4(x=1 ~ 3), grog firing temperature are 1320-1400 ℃.
Main points of the present invention are that (it is a kind of industrial residue of chemical plant production strontium salt to a small amount of strontium slag of adding in the silicate cement raw material, and contaminate environment and land occupation are deposited.Its main component is SrO, SO 3, CaO, SiO 2Deng), component such as vitriol, burn till being lower than under 1400 ℃ the cold condition, and add a spot of fluorite mineralizer, in the clinker mineral system, form the strontium calcium aluminium sulphate mineral of some amount by solid state reaction, form new grog ore deposit phase system, reach the reduction firing temperature, improve the purpose of early strength.
The invention has the beneficial effects as follows: the early stage performance that 1, has improved silicate cement.The strontium calcium aluminium sulphate mineral be a kind of have good morning epistasis can hydraulicity mineral, with it and C 3The S ore deposit is mutually compound, and cement early strength is improved a lot, and accelerates the setting and harden speed of cement simultaneously, shortens cement setting time; 2, the energy and resource have been saved.This cement firing temperature is lower than 1400 ℃, has reduced by 50 ℃ at least than the firing temperature of silicate cement, has saved the energy; C in the grog 3The content of S reduces, and has saved Wingdale, has reduced the produced quantity to the mine, has saved resource; 3, improved the cement volume stability.Owing to have micro-expansibility in the strontium calcium aluminium sulphate mineral hydration process, partial offset the volumetric shrinkage that produced of silicate cement hydration process, reduced cement shrinkage crack or cracking, thereby made cement and concrete weather resistance better; 4, changing rejected material to useful resource.Can use to contain the strontium industrial residue strontium component is provided, make it be converted into nontoxic strontium calcium aluminium sulphate mineral, both realize waste utilization, eliminate the strontium slag again to the pollution of environment and to appropriation of land; 5, improve environment.C in this cement system 3The content of S reduces, and has reduced amount of lime, and then has reduced CO 2Quantity discharged has alleviated environmental pollution.
Description of drawings
The XRD analysis figure of Fig. 1 A Lite-strontium calcium aluminium sulphate cement grog.Among the figure: ■ C 3S, ▲ C 2S, ★
Figure BSA00000146838100031
◆ C 4AF.
C in Fig. 2 cement clinker 3S, C 2The petrographic map of S (with the same scale of Fig. 3).
In Fig. 3 cement clinker
Figure BSA00000146838100032
Petrographic map.
Embodiment
The specific embodiment of A Lite-strontium calcium aluminium sulphate cement of the present invention sees Table 1 and table 2
Table 1 cement slurry chemical component weight %
Numbering ??Loss ??CaO ??SiO 2 ??Al 2O 3 ??Fe 2O 3 ??SO 3 ??SrO
??1# ??34.23 ??43.56 ??14.31 ??4.25 ??2.29 ??0.32 ??1.04
??2# ??33.48 ??42.62 ??13.91 ??5.01 ??2.24 ??0.65 ??2.09
??3# ??32.71 ??41.73 ??13.53 ??5.72 ??2.17 ??0.98 ??3.16
??4# ??32.00 ??40.73 ??13.14 ??6.49 ??2.10 ??1.31 ??4.23
??5# ??31.13 ??39.63 ??13.05 ??7.23 ??2.03 ??1.64 ??5.29
Above grog is burnt till with silicon molybdenum rod furnace in the laboratory, the firing temperature of embodiment is 1320 ℃-1400 ℃.
Cement physical properties sees Table 2.
Table 2 cement physical properties
The ore deposit phase composite of cement clinker sees Table 3
The ore deposit phase composite (weight %) of table 3 cement clinker
Numbering Strontium calcium aluminium sulphate Tricalcium silicate Dicalcium Phosphate (Feed Grade) Tricalcium aluminate Tetracalcium aluminoferrite
??1# ??2 ??63.77 ??15.24 ??8.24 ??10.75
??2# ??5 ??62.01 ??14.8 ??7.72 ??10.47
??3# ??8 ??60.01 ??14.21 ??7.64 ??10.14
??4# ??12 ??57.85 ??13.34 ??7.16 ??9.65
??5# ??15 ??56.19 ??12.68 ??6.95 ??9.18

Claims (4)

1. Yi Zhong A Lite-strontium calcium aluminium sulphate cement, it is characterized in that: its cement clinker is made up of the ore deposit phase system of following weight proportion:
Strontium calcium aluminium sulphate: 2-15%
Tricalcium silicate: 50-66%
Dicalcium Phosphate (Feed Grade): 10-20%
Tricalcium aluminate: 5-15%
Tetracalcium aluminoferrite: 5-15%;
Described strontium calcium aluminium sulphate chemical formula is (3-x) CaOxSrO3Al 2O 3Ca8O 4, x=1 in the formula ~ 3.
2. A Lite-strontium calcium aluminium sulphate cement according to claim 1 is characterized in that: the composition of described ore deposit phase system:
Strontium calcium aluminium sulphate: 5-12%
Tricalcium silicate: 55-62%
Dicalcium Phosphate (Feed Grade): 12-18%
Tricalcium aluminate: 7-12%
Tetracalcium aluminoferrite: 8-12%.
3. A Lite-strontium calcium aluminium sulphate cement according to claim 1 and 2 is characterized in that: be to be made by following materials of weight proportions:
CaO：50-70％
SiO 2：5-25％
Al 2O 3：2-16％
Fe 2O 3：2-7％
SO 3：0.2-2％
SrO：0.7-6％。
4. A Lite-strontium calcium aluminium sulphate cement according to claim 3 is characterized in that: described SrO is the strontium slag.
CN201010188057A 2010-06-01 2010-06-01 Alite-sulphoaluminate strontium calcium cement Pending CN101851072A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ304997B6 (en) * 2013-06-28 2015-03-18 Vysoké Učení Technické V Brně Shaped material based on strontium-aluminate cement and use thereof
CN106673476A (en) * 2017-01-08 2017-05-17 北京工业大学 Regulation and control method suitable for volume stability of aluminum-containing mineral composite cement system
CN107540251A (en) * 2017-09-19 2018-01-05 嘉华特种水泥股份有限公司 A kind of commerical ready-mixed concrete clinker and preparation method thereof
CN109592918A (en) * 2019-01-11 2019-04-09 济南大学 A kind of resistance to subzero temperature Anti-radiation type Quinary system sulphoaluminate cement clinker

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1513786A (en) * 2003-08-14 2004-07-21 济南大学 Alite-barium calcium sulfur aluminate cement
CN101343152A (en) * 2008-08-29 2009-01-14 济南大学 Strontium calcium aluminium sulphate cement

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1513786A (en) * 2003-08-14 2004-07-21 济南大学 Alite-barium calcium sulfur aluminate cement
CN101343152A (en) * 2008-08-29 2009-01-14 济南大学 Strontium calcium aluminium sulphate cement

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ304997B6 (en) * 2013-06-28 2015-03-18 Vysoké Učení Technické V Brně Shaped material based on strontium-aluminate cement and use thereof
CN106673476A (en) * 2017-01-08 2017-05-17 北京工业大学 Regulation and control method suitable for volume stability of aluminum-containing mineral composite cement system
CN107540251A (en) * 2017-09-19 2018-01-05 嘉华特种水泥股份有限公司 A kind of commerical ready-mixed concrete clinker and preparation method thereof
CN109592918A (en) * 2019-01-11 2019-04-09 济南大学 A kind of resistance to subzero temperature Anti-radiation type Quinary system sulphoaluminate cement clinker
CN109592918B (en) * 2019-01-11 2021-07-23 济南大学 Negative temperature resistant anti-radiation five-element system sulphoaluminate cement clinker

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Application publication date: 20101006