CN1047372C - Process for producing ultra-quick cement from calcium-aluminium sulfate - Google Patents

Process for producing ultra-quick cement from calcium-aluminium sulfate Download PDF

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CN1047372C
CN1047372C CN95104019A CN95104019A CN1047372C CN 1047372 C CN1047372 C CN 1047372C CN 95104019 A CN95104019 A CN 95104019A CN 95104019 A CN95104019 A CN 95104019A CN 1047372 C CN1047372 C CN 1047372C
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calcium
cement
aluminium sulfate
ultra
quick
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CN1124723A (en
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具龙善
全宗协
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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

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

Abstract

The present invention relates to a method for making overspeed hardening cement by utilizing calcium-aluminium sulfate, which is basically composed of ordinary cement clinker or ordinary cement, anhydrous gypsum and calcium-aluminium sulfate. The method for making overspeed hardening cement by utilizing calcium-aluminium sulfate is characterized in that the method for making overspeed hardening cement is that pulverized anhydrous gypsum and calcium-aluminium sulfate clinker which is burnt by a high temperature are mixed in the ordinary cement clinker or the ordinary cement, and overspeed hardening cement is made by adding a proper amount of high fluidizing agent by pulverizing and mixing, wherein the ordinary cement clinker or the ordinary cement is from 30 percent to 70 percent, the calcium-aluminium sulfate clinker is form 25 percent to 45 percent, the anhydrous gypsum is from 5 percent to 25 percent and the high fluidizing agent has a proper amount. Thus, overspeed hardening, high-intensity performing and unexpanded cement can be made.

Description

A kind of preparation method of ultra-quick cement
The present invention relates to the manufacture method of cement, refer to a kind of preparation method who utilizes calcium-aluminium sulfate to make ultra-quick cement especially.
Ultra-quick cement goods in the past mainly contain (the 11CaO.7AL of calcium fluorine aluminium salt system 2O 3.CaF 2), its preparation method is: the dihydrate gypsum that adds 10-20% in calcium fluorine aluminium salt grog is made, do not use portland cement clinker, be to be main raw material such as: the hard calcium fluorine aluminium salt cement that exceeds the speed limit, and do not use cheap portland cement clinker with calcium fluorine aluminium sulfate.And for example: quick hardening sulphoaluminate cement, adopt 90% C 4A 3S adds 10% dihydrate gypsum composition.Do not use cheap portland cement clinker yet.
The objective of the invention is to: providing a kind of is main raw material with portland cement clinker or Portland cement, utilizes calcium-aluminium sulfate to make the preparation method of ultra-quick cement, provides a kind of cheap, the product of remarkable in economical benefits.
The object of the present invention is achieved like this: a kind of preparation method of ultra-quick cement is the calcium-aluminium sulfate grog that burns till under dehydrated gyp-and the 1250-1400 ℃ of high temperature mixing in the portland cement clinker, the high flowing agent of three's added weight 1% after pulverizing mixing is made, wherein, proportion of raw materials (weight %) is: portland cement clinker 30%-70%, dehydrated gyp-5%-25%, calcium-aluminium sulfate grog 25%-45% get final product.Above-mentioned preparation method also can carry out in Portland cement, and its method is identical with effect.
The present invention further specifies by following examples and accompanying drawing thereof:
Fig. 1 is process flow sheet of the present invention
Fig. 2 is the XRD (inflection of X line resembles figure) of the cement slurry of the present invention after three days
Fig. 3 is water of the present invention and heat and water and time relation figure
The present invention: a kind of preparation method of ultra-quick cement is the calcium-aluminium sulfate grog that burns till under dehydrated gyp-and the 1250-1400 ℃ of high temperature mixing in the portland cement clinker, the high flowing agent of three's added weight 1% after pulverizing mixing is made, wherein, proportion of raw materials (weight %) is: portland cement clinker 30%-70%, dehydrated gyp-5%-25%, calcium-aluminium sulfate grog 25%-45% get final product.Also can carry out in Portland cement, its method is identical with effect.
Principle of work of the present invention is as follows: calcium-aluminium sulfate has following feature: calcium-aluminium sulfate 4Ca.3AL 2O 3.SO 3(be called for short C 4A 3S) be CaO-AL 2O 3System, along with the variation of chemical constitution composition, performance also and then changes, and promptly the CaO composition is many more, and swelling property is big more, AL 2O 3Composition is many more, and is just fast more hard, SO 3Composition is many more, and intensity increases more, referring to CaO-AL 2O 3-SO 3The chemical constitution and the properties relation variation diagram of system:
Figure C9510401900041
The three becomes the relation of equilateral triangle, and big triangle representative amount is big among the figure, and little triangle representative amount is little, and arrow is represented the trend of performance variation.
The water of calcium-aluminium sulfate and structure were ettringite (3CaO.AL in the past 2O 3.3CaSO 4.32H 2O) generation, its generative process is sclerosis-high strength discovery-expansion rapidly-expansion damage process, so be out of use mineral composition always.But in order to make ultra-quick cement, be necessary strength of cement found to induce from (A) to be (B), see Table solid line in the lattice (A) and the variation of dotted line (B) and the forming process and the performance thereof of ettringite.
Figure C9510401900042
Among the present invention, pure 4CaO.3AL in the calcium-aluminium sulfate grog 2O 3.SO =3Content be more than 55%, all the other are more than the lime saturation ratio CM=0.8, anhydrous slufuric acid and aluminum oxide are than A/ S=2.5-5.0, free lime is below 4.0%.High flowing agent is naphthalene vitriol system, melamine vitriol system, Sulfite lignin system.
The concrete practice is: 1, pure in the calcium-aluminium sulfate grog that uses in the ultra-quick cement manufacturing:
4CaO.3AL 2O 3.SO 3Content be more than 55%, this is to be drawn by following formula:
C 4A 3S(％)=1.995AL 2O 3+1.63Fe 2O 3。
Pure 4CaO.3AL in the cement that ultra-quick cement of the present invention is made 2O 3.SO 3The content that requires be: 10%-30%.
2, use raw material and proportioning
Use raw material The quality specification of raw material Proportioning
Portland cement clinker Generally cement clinker is a kind of 30-70％
The calcium-aluminium sulfate grog More than the full composition and division in a proportion CM=0.8 of 1 lime 25-45％
2 anhydrous slufuric acids and aluminum oxide are than (A/S)=2.5-5.0
3 free limes (%): below 4.0%
4C 4A 3S (%): more than 55%
Dehydrated gyp- CaSO 4More than the %:70% 5-25％
High flowing agent Cement is with high flowing agent (naphthalene vitriol system, melamine vitriol system, Sulfite lignin system) 1％
Annotate: Cm=CaO-0.7 (Fe 2O 3+ TiO 2+ SO 3)/1.87SiO 2+ 0.55AL 2O 3
A/S=AL 2O 3.SO 3
C 4A 3S=1.995AL 2O 3+1.63Fe 2O 3
4, producing apparatus and manufacturing process: see that Fig. 1 is a process flow sheet of the present invention.
The correct proportioning of adjusting raw material is pulverized afterwards earlier and is mixed in manufacturing processed, also can mix afterwards earlier and pulverize, and increases flowing agent at last and gets final product.Embodiments of the invention:
The raw material that the present invention uses is portland cement clinker, calcium-aluminium sulfate grog and dehydrated gyp-, and its Chemical Composition is as follows:
Table 1, the Chemical Composition of use raw material
Just use material SIo 2 AL 2O 3 Fe 2O 3 TiO 2 CaO HgO SO 3 Ig- Loss Free CaO Add up to
Portland cement clinker 22.18 5.46 3.50 64.89 2.72 0.28 0.67 0.70 99.75
The calcium-aluminium sulfate grog 11.18 30.76 2.38 1.8 43.21 2.00 8.31 tr 0.65 99.64
Dehydrated gyp- 0.68 0.10 0.08 40.62 tr 0.56 2.85 98.89
Annotate: the loss amount of LgLoss-Chemical Composition
The Free----free calcium oxide, tr----refers generally to below 0.01
Raw material is ground into specific surface area in ball mill pulverizer be 4,800+50cmz/g, and by cooperating as ultra-quick cement test portion of the present invention as following table 2, proportioning is pressed C in the ultra-quick cement 4A 3S content respectively accounts for 22% (test portion 1): 21% (test portion 2): 20% (test portion 3), adding high flowing agent 1% is in order to improve the flowability of cement, use the good high flowing agent of diminishing and dispersion effect to be Sulfite lignin systems (Lignin Sulphonate) in this regard, naphthalene vitriol system (Naphthalein Sulphonate) and melamine sulfonates system (Melamine Sulphonate) etc., what use in the present invention is naphthalene vitriol system.
Table 2, the cooperation of ultra-quick cement
Test portion NO Proportioning (increment %)
Portland cement clinker The calcium-aluminium sulfate grog Dehydrated gyp- High flowing agent
1 50 34 16 1 (additionally)
2 50 32 18 1 (additionally)
3 50 30 20 1 (additionally)
Ultra-quick cement physicals according to table 2 proportioning---see Table 3:
Test portion NO Specific surface area CM/q Time of coagulation Ultimate compression strength (Kq/cm)
Just tie Termination 3 hours 6 hours One day Three days
1 4,830 0:25 0:35 125 152 189 203
2 4,830 0:35 0:50 220 258 297 305
3 4,830 0:40 0:55 218 254 300 308
Calcium-aluminate, the water and the structure of the ultra-quick cement of the present invention that portland cement clinker and dehydrated gyp-are formed are ettringite (3CaO.Al 2O 3.3CaSO 4.32H 2O) generation, with the formation speed connection pass of ettringite (ettringite), the rigid intensity that exceeds the speed limit finds that it rises because CaO-Al 2O 3-SO 3Its water of content and the reaction formula of three compositions of system are as follows: --① --②--①+②
Referring to the XRD (X line inflection resemble figure) of Fig. 2 for the cement slurry of ultra-quick cement after three days
Shown in the figure: H representative: C 4AH 13, O representative--C 4A 3S, △ representative: SaSO 4.
Water of this ultra-quick cement and ratio of specific heat Portland cement are quite high, and the water of ultra-quick cement and heat are the good raw materials of winter construction.
Fig. 3 be the water of ultra-quick cement and Portland cement (general cement a kind of) and ratio of specific heat.
Shown in the figure: X-axis is water and time (branch), and Y-axis is water and heat.
Solid line is represented ultra-quick cement, and dotted line is represented Portland cement.
Illustrate by above test: ultra-quick cement (4Ca.3Al of the present invention 2O 3.SO 3) advantage be: have the intensity height, winter construction is effective, anti-sulfuric acid (extra large sand, seawater can use), high workability, characteristics such as corrosion-resistant.
So practicality, economy is better, is that a kind of price is low, quality, purposes, easy construction, the product of performance utmost point Cui.To have developed hypervelocity rigid--high strength performance--unexpanded from frontier such as trying hard to keep often for the ultra-quick cement manufacture method simultaneously.

Claims (3)

1, a kind of preparation method of ultra-quick cement, it is characterized in that: at the calcium-aluminium sulfate grog that mixes in the portland cement clinker under dehydrated gyp-and the 1250-1400 ℃ of high temperature, the high flowing agent of three's added weight 1% after pulverizing mixing is made, wherein, proportion of raw materials (weight %) is: portland cement clinker 30%-70%, dehydrated gyp-5%-25%, calcium-aluminium sulfate grog 25%-45%.
2, the preparation method of ultra-quick cement according to claim 1 is characterized in that: pure 4CaO.3AL in the above-mentioned calcium-aluminium sulfate grog 2O 3.SO 3Content be more than 55%, all the other are more than the lime saturation ratio CM=0.8, anhydrous slufuric acid and aluminum oxide are than A/ S=2.5-5.0, free lime is below 4.0%.
3, the preparation method of ultra-quick cement according to claim 1 is characterized in that: above-mentioned high flowing agent is naphthalene vitriol system, melamine vitriol system, Sulfite lignin system.
CN95104019A 1995-04-19 1995-04-19 Process for producing ultra-quick cement from calcium-aluminium sulfate Expired - Fee Related CN1047372C (en)

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FR2832402B1 (en) * 2001-11-19 2004-12-10 Carrieres Du Boulonnais CEMENTITIOUS COMPOSITION, PROCESS FOR PRODUCING WITHDRAWAL CAPS AND LIFTING OF REDUCED EDGES AND OBTAINED CAPS

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86104322A (en) * 1986-06-14 1987-12-23 四川建筑材料工业学院 Aluminate cement with high iron and surfur content
CN87106767A (en) * 1987-10-05 1988-10-26 武汉工业大学 The production method of aluminosulfate colour cement
CN1094383A (en) * 1994-03-29 1994-11-02 李乃珍 The vertical kiln producing method of aluminosulfate cement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86104322A (en) * 1986-06-14 1987-12-23 四川建筑材料工业学院 Aluminate cement with high iron and surfur content
CN87106767A (en) * 1987-10-05 1988-10-26 武汉工业大学 The production method of aluminosulfate colour cement
CN1094383A (en) * 1994-03-29 1994-11-02 李乃珍 The vertical kiln producing method of aluminosulfate cement

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