CN100357209C - Belite-calcium barium sulphoaluminate cement - Google Patents
Belite-calcium barium sulphoaluminate cement Download PDFInfo
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- CN100357209C CN100357209C CNB2006100455036A CN200610045503A CN100357209C CN 100357209 C CN100357209 C CN 100357209C CN B2006100455036 A CNB2006100455036 A CN B2006100455036A CN 200610045503 A CN200610045503 A CN 200610045503A CN 100357209 C CN100357209 C CN 100357209C
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- cement
- barium
- aluminate
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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
-
- 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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明属于水泥材料技术领域，特别涉及一种由硫铝酸钡钙矿物与贝利特矿物复合的贝利特-硫铝酸钡钙水泥。其水泥熟料主要是由C2S-CBAS-C3S-C3A-C4AF组成的矿相体系，各矿物的重量百分比为：硫铝酸钡钙：5-45%，硅酸二钙：30-70%，硅酸三钙：10-45%，铝酸三钙：2-20%，铁铝酸钙：2-20%，其中硫铝酸钡钙的分子式为：(3-X)CaO·XBaO·3Al2O3·CaSO4，X＝0.25～3。具有烧成温度低，可利用低品质石灰石资源，降低了高品质石灰石的用量，水泥早期强度提高，硬化水泥浆体具有微膨胀、密实度高、微裂纹减少，抗腐蚀和耐久性好和成本低的优点。
The invention belongs to the technical field of cement materials, in particular to a belite-barium calcium sulphoaluminate cement compounded with barium calcium sulphoaluminate minerals and belite minerals. Its cement clinker is mainly a mineral phase system composed of C 2 S-CBA S -C 3 SC 3 AC 4 AF. The weight percentage of each mineral is: barium calcium sulfoaluminate: 5-45%, dicalcium silicate: 30-70%, tricalcium silicate: 10-45%, tricalcium aluminate: 2-20%, calcium aluminoferrite: 2-20%, and the molecular formula of barium calcium sulfoaluminate is: (3-X) CaO·XBaO·3Al 2 O 3 ·CaSO 4 , X=0.25-3. With low firing temperature, low-quality limestone resources can be used, the amount of high-quality limestone is reduced, the early strength of cement is improved, and the hardened cement paste has micro-expansion, high compactness, reduced micro-cracks, good corrosion resistance and durability and low cost low pros.
Description
(1) technical field under
The invention belongs to the cement material technical field, particularly a kind of by barium-bearing calcium sulfo-aluminate
Mineral and Baily spy (C
2S) mineral compound Belite-calcium barium sulphoaluminate cement.
(2) background technology
At present, there is some shortcoming and defect in a large amount of silicate cements that use, mainly show as firing temperature height (being 1450 ℃), and production energy consumption is big; CaO content height in the grog consumes a large amount of fat lime stone resources; Cement hydration process produces volumetric shrinkage, causes shrinking tiny crack, influences mechanical properties of concrete; Form a large amount of Ca (OH) behind the hydrated cementitious
2, and be present in the hardened cement paste, influence cement and concrete corrosion stability and weather resistance.Therefore, how further reducing the firing temperature of silicate cement, save the high-quality Mineral resources, and improve the performance of cement and concrete works, is the key issue that cement technology field emphasis solves.
As the Chinese patent " titanate-containing sulpho-aluminate cement " that on September 13rd, 1989, disclosed publication number was CN1035486A, be to be the high-early-strength type cement that the essential mineral composition is made with the baric calcium sulphoaluminate, its firing temperature is low, is 1250-1350 ℃.The essential mineral of this cement is based on titanate-containing sulpho-aluminate, and ratio is 40-80%, and main raw material is a barite etc., and cost is higher, is applicable to special construction project, belongs to special engineered material, is not suitable for producing in enormous quantities.
As the Chinese patent " A Lite-barium-bearing calcium sulfo-aluminate cement " that on July 21st, 2003, disclosed publication number was CN1513786, the main ore deposit phase system of forming by A Lite (tricalcium silicate) and barium-bearing calcium sulfo-aluminate.Because tricalcium silicate need expend more high-quality limestone mineral resource, and C
3S need could form under 1450 ℃ of hot conditionss in a large number, causes energy consumption higher.In addition, C
3S content height will make the Ca (OH) in the hydrated product
2Amount increases, and reduces the erosion resistance and the weather resistance of cement.
(3) summary of the invention
The present invention is in order to overcome above deficiency, provides a kind of and taken the novel concrete of ore deposit phase system as the leading factor with Belite-calcium barium sulphoaluminate, and it is low to have a firing temperature, can use low-quality calcium carbonate resource, volumetric shrinkage is little, later strength enhancement rate height, with low cost, advantages such as good endurance.
The present invention is achieved through the following technical solutions:
Belite-calcium barium sulphoaluminate cement of the present invention, its cement clinker mainly are by C
2S-
-C
3S-C
3A-C
4The ore deposit phase system that AF forms, the weight percent of each mineral is:
Barium-bearing calcium sulfo-aluminate: 5-45%
Dicalcium Phosphate (Feed Grade): 30-70%
Tricalcium silicate: 10-45%
Tricalcium aluminate: 2-20%
Iron calcium aluminate: 2-20%
Wherein the molecular formula of barium-bearing calcium sulfo-aluminate is:
(3-X)CaO·XBaO·3Al
2O
3·CaSO
4，X＝0.25～3。Preferably, the weight percent of each mineral is in its cement clinker:
Barium-bearing calcium sulfo-aluminate: 10-37%
Dicalcium Phosphate (Feed Grade): 41-60%
Tricalcium silicate: 10-29%
Tricalcium aluminate: 6-15%
Iron calcium aluminate: 6-15%
The Belite-calcium barium sulphoaluminate cement of stating of the present invention, described barium-bearing calcium sulfo-aluminate
Molecular formula be preferably: 2.75CaO1.25BaO3Al
2O
3CaSO
4
The Belite-calcium barium sulphoaluminate cement of stating of the present invention, the raw material of its cement are formed:
CaO： 30-50％
SiO
2： 7-20％
Al
2O
3： 2-20％
Fe
2O
3： 1-4％
SO
3： 0.5-4％
BaO： 1-8％
CaF
2： 0.3-1.5％。
The barium-bearing calcium sulfo-aluminate mineral are a kind of hydraulicity mineral with outstanding high-early-strength performance, and its firing temperature is low, and can utilize industrial residue production.Making the employed main raw material of these mineral is Wingdale, low-grade bauxite and baric mine tailing or waste residue, just can easy fired below 1400 ℃.The ultimate compression strength of the barium-bearing calcium sulfo-aluminate mineral of manufacturing was at 1 day, 3 days and reach 35.5MPa, 59.3MPa and 72.1MPa the 7 day length of time respectively, and its hydration and hardening speed is very fast, was a kind of high gelling mineral with outstanding high-early-strength performance.
Present technique is that the guide mineral Baily spy of high-early-strength type barium-bearing calcium sulfo-aluminate mineral and belite cement grog is compound under cold condition, forms the novel concrete clinker mineral system of taking mineral with Baily spy-barium-bearing calcium sulfo-aluminate as the leading factor.This cement had both had the characteristic of belite cement intensity stabilization development, and the high advantage of early strength enhancement rate that again rapid hardening cement is arranged and had can be widely used in having the high quality requirement, the construction project of anticorrosive and good durability.Silicate cement is with tricalcium silicate (C
3S claims A Lite again), Dicalcium Phosphate (Feed Grade) (C
2S claims the Baily spy again), tricalcium aluminate (C
3A) and ferro-aluminate (C
4AF) be essential mineral, C
3The content of S can reach more than 60% sometimes generally more than 50%, need expend a large amount of high-quality limestone mineral resources, and C
3S need could form under 1450 ℃ of hot conditionss in a large number, causes energy consumption higher, and is seriously polluted.Belite cement has advantage above aspect several than silicate cement, and calcining temperature is lower about 100 ℃ than silicate cement, has reduced production energy consumption: its guide mineral C
2The CaO that S contains is low, can utilize low-quality limestone resource; The sustainable growth of the special mineral later strength of Baily, enhancement rate height: belite cement and concrete corrosion stability thereof and weather resistance are good.But the main drawback of belite cement is that early strength is lower, this be since in the grog minimizing of A Lite mineral quantity cause.And the barium-bearing calcium sulfo-aluminate mineral have outstanding high-early-strength performance, and have the microdilatancy characteristic, and firing temperature is low, and about about 1350 ℃ is a kind of low temp and early strength mineral of excellent property.
The present invention is with C
2S with
Carry out compoundly, form with C by high temperature solid state reaction
2S-
Take the new cement clinker ore deposit phase system of mineral as the leading factor.Different with silicate cement, Portland clinker is by C
3S-C
2S-C
3A-C
4Four kinds of essential minerals of AF are formed, and the Belite-calcium barium sulphoaluminate cement grog is by C
2S-
-C
3S-C
3A-C
4The new system of five kinds of mineral compositions of AF, C in the system
2The content of S mineral is greater than C
3S.Simultaneously, the barium-bearing calcium sulfo-aluminate mineral just can form below 1400 ℃ in a large number, and C in the grog
3The reduction of S content makes the Belite-calcium barium sulphoaluminate cement grog just can burn till about 1320-1360 ℃, reduces 50-100 ℃ than the firing temperature of silicate cement.Compare with A Lite-barium-bearing calcium sulfo-aluminate cement, its firing temperature has reduced 20-40 ℃, has reduced the consumption of high-quality Wingdale, has saved the energy, has reduced cost.Because the barium-bearing calcium sulfo-aluminate mineral have outstanding high-early-strength performance, and, Ba
2+, SO
3Introducing, can effectively improve β-C
2The hydration activity of S is so Belite-calcium barium sulphoaluminate cement has overcome the shortcoming of the early stage poor performance of belite cement.This cement early strength reaches more than 40% than general belite cement raising approximately, and later strength also has increase to a certain degree, and the cement setting setting rate is obviously accelerated.The use of Belite-calcium barium sulphoaluminate cement has unusual effect to comprehensive raising construction quality, is particularly suitable for the large-scale construction project of Highrise buildings, high-grade highway, airport, the contour specification of quality of bridge and tunnel.In addition, because the effect that also has compensate for shrinkage of barium-bearing calcium sulfo-aluminate mineral, thereby can reduce the shrinking percentage of cement, reduce shrinkage crack, improve the weather resistance of concrete works.Present technique technology is simple, adopts the producing apparatus of existing silicate cement fully, and the barium salt component that needs can be provided by the natural barite mine tailing, also can utilize the baric industrial residue, and raw materials cost reduces.
Main points of the present invention are to utilize the raw material of silicate cement, allocate into simultaneously to contain barium ore (barite mine tailing etc.) or components such as baric industrial residue and fluorite, burn till under 1400 ℃ of conditions being lower than, and form with C by solid state reaction
2S-
Take the new cement clinker ore deposit phase system of mineral as the leading factor, reach the reduction firing temperature, improve the purpose of cement early strength.
The invention has the beneficial effects as follows that it is low to have a firing temperature, can utilize low-quality limestone resource, reduced the consumption of high-quality Wingdale, cement early strength improves, and hardened cement paste has microdilatancy, degree of compactness height, tiny crack minimizing, anticorrosive and good endurance and the low advantage of cost.
(4) description of drawings
Fig. 1 is the XRD analysis figure of cement clinker of the present invention: among the figure, ■ represents C
3S; ▲ represent C
2S; ◆ represent C
4AF; The ★ representative
Fig. 2 is the sem analysis of Belite-calcium barium sulphoaluminate cement grog: among the figure, and 1 point: barium-bearing calcium sulfo-aluminate mineral; 2 points: the special mineral of Baily; 3 points: A Lite mineral.
(5) embodiment
Embodiment:
The specific embodiment of Belite-calcium barium sulphoaluminate cement of the present invention sees Table 1, table 2 and table 3.
Table 1 proportioning raw materials (being chemical reagent) %
| Numbering | CaCO 3 | SiO 2 | Al 2O 3 | Fe 2O 3 | BaSO 4 | BaCO 3 |
| 1# | 75.31 | 15.50 | 4.81 | 2.85 | 1.28 | 0.28 |
| 2# | 73.44 | 15.09 | 6.38 | 2.75 | 1.94 | 0.42 |
| 3# | 72.11 | 14.85 | 6.79 | 2.84 | 2.61 | 0.57 |
| 4# | 71.83 | 15.59 | 6.92 | 2.51 | 2.61 | 0.56 |
| 5# | 68.52 | 11.10 | 9.63 | 2.03 | 3.72 | 0.91 |
| 6# | 67.21 | 13.78 | 12.03 | 1.89 | 4.86 | 1.19 |
By above six kinds of proportion schemes preparation raw material, allocate a small amount of fluorite simultaneously into, press CaF
2Count 0.5～1.2%.The raw material chemical ingredients sees Table 2
Table 2 cement slurry chemical ingredients %
| Numbering | Loss | CaO | SiO 2 | Al 2O 3 | Fe 2O 3 | BaO | |
| 1# | 32.93 | 42.17 | 15.50 | 4.81 | 2.85 | 1.30 | 0.44 |
| 2# | 32.38 | 41.13 | 15.09 | 6.38 | 2.75 | 1.60 | 0.67 |
| 3# | 32.09 | 40.38 | 14.85 | 6.79 | 2.84 | 2.15 | 0.90 |
| 4# | 31.72 | 40.22 | 15.59 | 6.92 | 2.51 | 2.14 | 0.90 |
| 5# | 34.44 | 38.37 | 11.10 | 9.63 | 2.03 | 3.15 | 1.28 |
| 6# | 28.88 | 37.64 | 13.78 | 12.03 | 1.89 | 4.11 | 1.67 |
Above grog is burnt till with silicon molybdenum rod furnace in the laboratory, firing temperature is 1320 ℃-1360 ℃.The physicals of cement sees Table 3.
Table 3 cement physical properties
| Numbering | Fineness/% | f-CaO /％ | Ultimate compression strength/ | |
| 3d | 28d | |||
| 1# 2# 3# 4# 5# 6# | 3-3.5 3-3.5 3-3.5 3-3.5 3-3.5 3-3.5 | 1.1 1.3 1.3 1.1 0.8 1.0 | 16.4 17.3 16.5 21.8 23.2 24.9 | 49.2 45.8 43.9 53.0 56.9 54.1 |
Wherein 4# grog is carried out XRD analysis and sem analysis, seen Fig. 1 and Fig. 2 respectively.Can see in Belite-calcium barium sulphoaluminate cement clinker mineral system, formed the novel concrete of taking the ore deposit phase system with Belite-calcium barium sulphoaluminate as the leading factor, further specify the compound of these two kinds of mineral and coexistence, can reach the purpose that improves cement early strength.
Claims (3)
1. the special barium-bearing calcium sulfo-aluminate cement of a Baily is characterized in that: its cement clinker mainly be by
C
2S-
-C
3S-C
3A-C
4The ore deposit phase system that AF forms, the weight percent of each mineral is:
Barium-bearing calcium sulfo-aluminate: 10-37%
Dicalcium Phosphate (Feed Grade): 41-60%
Tricalcium silicate: 10-29%
Tricalcium aluminate: 6-15%
Iron calcium aluminate: 6-15%
Wherein the molecular formula of barium-bearing calcium sulfo-aluminate is:
(3-X)CaO·XBaO·3Al
2O
3·CaSO
4，X＝0.25～3。
2. cement according to claim 1 is characterized in that: the molecular formula of described barium-bearing calcium sulfo-aluminate is 2.75CaO1.25BaO3Al
2O
3CaSO
4
3. cement according to claim 1 and 2 is characterized in that: the raw material composition of its cement is by weight percentage:
CaO： 30-50％
SiO
2： 7-20％
Al
2O
3： 2-20％
Fe
2O
3： 1-4％
SO
3： 0.5-4％
BaO： 1-8％
CaF
2： 0.3-1.5％。
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|---|---|---|---|
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|---|---|---|---|
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|---|---|
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| CN100357209C true CN100357209C (en) | 2007-12-26 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425566C (en) * | 2007-05-24 | 2008-10-15 | 济南大学 | Cement-base concrete interface agent |
| CN101857388A (en) * | 2010-06-01 | 2010-10-13 | 济南大学 | Belite-calcium strontium sulfoaluminate cement |
| CN102701613B (en) * | 2012-06-18 | 2013-06-19 | 湖北大学 | Preparation method of radiation-proof cement clinker mineral phase system |
| EP2676943B2 (en) | 2012-06-20 | 2021-01-20 | HeidelbergCement AG | Method for producing a Belite cement with high reactivity and low calcium/silicate ratio |
| CN102910934A (en) * | 2012-10-19 | 2013-02-06 | 济南大学 | Light and flexible foaming cement insulation board and preparation method thereof |
| EP2801557B9 (en) * | 2013-05-11 | 2016-01-20 | HeidelbergCement AG | Method for producing a magnesium silicate belite calcium aluminate cement |
| CN104478247A (en) * | 2014-11-17 | 2015-04-01 | 济南大学 | Cooling way for belite-barium calcium sulfoaluminate cement clinker |
| CN105502978B (en) * | 2015-12-22 | 2017-12-26 | 济南大学 | A kind of composite mineralizer suitable for belite barium-bearing calcium sulfo-aluminate cement burning |
| CN107117838B (en) * | 2017-05-27 | 2020-04-03 | 济南大学 | A kind of sulfoaluminate cement clinker containing tricalcium silicate and preparation method thereof |
| CN109265031A (en) * | 2018-11-02 | 2019-01-25 | 济南大学 | A kind of baric white sulphoaluminate cement clinker and preparation method thereof |
| CN114213043B (en) * | 2022-01-06 | 2022-09-06 | 南京工业大学 | High belite-calcium sulfoaluminate-calcium sulfosilicate cement clinker and preparation method thereof |
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| RU2180325C1 (en) * | 2001-03-01 | 2002-03-10 | Усачев Алексей Николаевич | Sulfate-stable barium-containing portland cement |
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