CN107117838A - A kind of sulphoaluminate cement clinker containing tricalcium silicate and preparation method thereof - Google Patents

A kind of sulphoaluminate cement clinker containing tricalcium silicate and preparation method thereof Download PDF

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CN107117838A
CN107117838A CN201710390145.0A CN201710390145A CN107117838A CN 107117838 A CN107117838 A CN 107117838A CN 201710390145 A CN201710390145 A CN 201710390145A CN 107117838 A CN107117838 A CN 107117838A
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cement clinker
sulphoaluminate cement
parts
mineral
sulphoaluminate
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CN107117838B (en
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程新
叶正茂
卢晓磊
李传海
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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
    • C04B7/32—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
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • C04B7/42—Active ingredients added before, or during, the burning process
    • C04B7/421—Inorganic materials
    • C04B7/424—Oxides, Hydroxides
    • 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
    • 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
    • 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
    • Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods

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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)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention relates to a kind of sulphoaluminate cement clinker containing tricalcium silicate and preparation method thereof, in mineral composition, iron phase is 2CaOFe2O3(C2F)；Sulphoaluminate phase is 3CaO3Al2O3·BaSO4(C3BA3$)；Its mineral percentage composition is constituted：C3S 5~30%, C3BA3$ 20~65%, C2S 30~60%, C2F 3~25%；Wherein, oxide is abbreviated as C=CaO, S=SiO2、A=Al2O3、F=Fe2O3、$=SO3、B=BaO.Constituted by adjusting iron phase, while using ion doping technique, successfully realizing and C being introduced in sulphoaluminate cement clinker3S mineral, have been prepared containing C3S sulphoaluminate cement clinker.The present invention is low to consumption of limestone amount and low to lime stone grade requirement；Avoid traditional mineralizer CaF2Environment is polluted and cement kiln system corrosion；Simultaneously because introducing C3S improves the basicity of system, adds the volume of mixing material, has great importance in the green manufacturing application field of cement.

Description

A kind of sulphoaluminate cement clinker containing tricalcium silicate and preparation method thereof
Technical field
The present invention relates to cement material preparing technical field, more particularly to containing C3S sulphoaluminate cement clinker and its Preparation method.
Background technology
Sulphate aluminium cement is a kind of with performance binder materials, its main mine such as early strong, high-strength, high impervious and microdilatancies Thing calcium sulphoaluminate（C4A3$）The temperature that it is largely formed in clinker system is in 1200 DEG C or so, at a higher temperature, C4A3$ It can decompose, it is considered that its ceiling temperature being stabilized is 1350 DEG C.The main ore deposit phase tricalcium silicate of Portland clinker（C3S） Formed in the presence of having liquid phase, and liquid phase forming temperature at least will be at 1250 DEG C, C3S a large amount of formation temperature one As more than 1350 DEG C.And there is high SO in clinker system3Under content, C can be suppressed3S mineral formations, therefore, generally, C3S can not exist in sulphoaluminate cement clinker.Oxide is abbreviated as：C=CaO、S=SiO2、A=Al2O3、F=Fe2O3、$= SO3、B=BaO。
Prior art introduces C in sulphoaluminate cement clinker3S mineral, substantially by adding ore deposit in clinker system Agent CaF2, reduce C3S firing temperatures, and then realize C3S is incorporated into sulphoaluminate cement clinker system.Patent calcium sulphoaluminate-Ah Sharp spy's grandidierite phase cement clinker and preparation method thereof（Publication number CN 1951853A）With a kind of C of patent3S type aluminium sulfate water Mud clinker and preparation method thereof（CN 104326687 A）It is to have used mineralizer CaF2Realize C3S and C4A3$ coexists.But Mineralizer CaF2Use environment can be polluted, and there is corrosivity to cement kiln system, while with CaF2Volume increases Plus cement performance can be adversely affected, limit its application in clinker preparation.
Therefore, develop and a kind of new contain C3The research of S sulphoaluminate cement clinker and preparation method thereof is to clinker industry Development is significant.
The content of the invention
It is an object of the invention to for the above-mentioned problems in the prior art, there is provided a kind of sulphur aluminium containing tricalcium silicate Acid salt cement clinker, using CaCO3、BaCO3、SiO2、Al(OH)3、Fe2O3And CaSO4·2H2O is raw material, is solved to sulphur aluminic acid C is introduced in salt cement clinker3S mineral problems.
The present invention also provides the preparation method of the above-mentioned sulphoaluminate cement clinker containing tricalcium silicate, by adjusting clinker body It is iron phase composition and content, using ion doping technique, prepares and contain tricalcium silicate（C3S）Sulphoaluminate cement clinker.
To achieve the above object, technical solution of the present invention is as follows：
A kind of sulphoaluminate cement clinker containing tricalcium silicate, in mineral composition, in mineral composition, iron phase is C2F；Aluminium sulfate Mineral are C3BA3$；
The C2F, i.e. dicalcium ferrite, stoichiometric equation are 2CaOFe2O3；The C3BA3$, i.e. barium-bearing calcium sulfo-aluminate, chemistry meter Measure as 3CaO3Al2O3·BaSO4。
The sulphoaluminate cement clinker containing tricalcium silicate, its mineral percentage composition, which is constituted, is：
C3S 5~30%,
C3BA3$ 20~65%,
C2S 30~60%,
C2F 3~25%；
Wherein, oxide is abbreviated as C=CaO, S=SiO2、A=Al2O3、F=Fe2O3、$=SO3、B=BaO。
The sulphoaluminate cement clinker containing tricalcium silicate, chemical composition and percentage composition are：
CaO 47~60%,
SiO211~29%,
Al2O38~28%,
Fe2O31~15%,
BaO 5~17%,
SO32~8%.
The preparation method of the above-mentioned sulphoaluminate cement clinker containing tricalcium silicate, step includes：
1）Dispensing：Raw materials of Ca CO is weighed by following weight parts3 83~107 parts, BaCO36.4~21.8 parts, SiO211~29 Part, Al (OH)3 12.2~43.8 parts, Fe2O31~15 part and CaSO4·2H24.3~17.2 parts of O, then by the raw material prepared After wet-mixing, drying, tabletting is standby；
2）Calcining：By step 1）Raw materials treated, 900 DEG C are risen to 5 DEG C/min from room temperature, then insulation calcining 1h, then with 3 DEG C/min rises to 1300~1410 DEG C, and is incubated 0.5~1.5h of calcining；
3）Cooling：After calcining terminates, air quenching obtains the sulphoaluminate cement clinker containing tricalcium silicate.
Preferably, step 1）In, raw material granularity is below 80 μm.
Preferably, step 1）In, drying temperature is 105 DEG C.
Preferably, step 1）In, tabletting method is：The water that mass fraction is 7% is added after drying in raw material, is well mixed Afterwards, the mm of mm of φ 35 × 5 raw material piece is pressed under 16 MPa in punching block, then 4h are dried in 105 DEG C.
Preferably, step 2）In, 1320 DEG C are risen to 3 DEG C/min, and be incubated calcining 1h.
Liquid phase is mainly by CaO, Al in sulphoaluminate cement clinker of the invention containing tricalcium silicate, calcination process2O3With Fe2O3Deng composition, clinkersintering formation C3S process, with liquid phase forming temperature, amount of liquid phase, property of liquid phase and CaO, C2S is molten Solution is relevant in each factors such as dissolution velocity, the ion diffusion velocities of liquid phase.Therefore by adjusting iron phase composition and content, adopt simultaneously With ion doping technique, solution generates a certain amount of C in sulphoaluminate cement clinker3S mineral.So as to avoid introducing CaF2 Influence to cement performance and equipment.By regulating and controlling clinker system property of liquid phase, prepare that middle and later periods intensity continuous is increased to be contained C3S sulphoaluminate cement clinker, while overcoming sulphate aluminium cement because basicity is low and limits the use of mixing material.
Sulphoaluminate cement clinker of the invention containing tricalcium silicate, raw material mineral use CaCO3、BaCO3、SiO2、Al (OH)3、Fe2O3And CaSO4·2H2O dispensings, clinkersintering formation C3S process needs liquid phase environment, and the present invention is by designing iron Phase composition is C2F, iron phase amount can effectively facilitate C between 3~25%2S is more to be dissolved in liquid phase and absorbs CaO and be converted into C3S, Designing introducing BaO simultaneously makes sulphoaluminate phase decomposition temperature improve 30 DEG C, expands C3S and sulphoaluminate phase temperature coexist It is interval.
The beneficial effect and feature of technical solution of the present invention：
1）Constituted by adjusting iron phase, can substantially reduce C3S mineral formation temperature, is conducive to energy-saving.
2）Sulphoaluminate phase is containing barium-bearing calcium sulfo-aluminate in sulphoaluminate cement clinker of the invention containing tricalcium silicate （3CaO·3Al2O3·BaSO4）, its decomposition temperature is compared with C4A3$ is high 30 DEG C, expands C3Interval coexists in S and sulphoaluminate phase.
3）Sulphoaluminate cement clinker of the invention containing tricalcium silicate can increase blending amount of mixture material in sulphate aluminium cement.
Brief description of the drawings
Fig. 1 is the sulphoaluminate cement clinker mineral composition XRD spectrum containing tricalcium silicate prepared by embodiment 1；
Fig. 2 is the sulphoaluminate cement clinker mineral composition XRD spectrum containing tricalcium silicate prepared by embodiment 2；
Fig. 3 is the sulphoaluminate cement clinker mineral composition XRD spectrum containing tricalcium silicate prepared by embodiment 3；
Fig. 4 is cement clinker mineral composition XRD spectrum prepared by comparative example 1；
Fig. 5 is cement clinker mineral composition XRD spectrum prepared by comparative example 2；
Fig. 6 is cement clinker mineral composition XRD spectrum prepared by comparative example 3.
Embodiment
For a better understanding of the present invention, following with embodiment, the present invention is furture elucidated, but present invention can not Think the scope of limitation invention.
Embodiment 1
A kind of preparation method of the sulphoaluminate cement clinker containing tricalcium silicate, step includes：
1）Dispensing：Raw materials of Ca CO is weighed by following weight parts3 89.8 parts, BaCO36.4 parts, SiO218.6 parts, Al (OH)315.2 parts, Fe2O311.7 parts and CaSO4·2H25.6 parts of O, each raw material granularity is below 80 μm, then by the raw material prepared After wet-mixing, 105 DEG C of drying add the water that mass fraction is 7%, after being well mixed, are pressed into punching block under 16 MPa The mm of mm of φ 35 × 5 raw material piece, then dries 4h in 105 DEG C, standby；
2）Calcining：By step 1）Raw materials treated, 900 DEG C are risen to 5 DEG C/min from room temperature, then insulation calcining 1h, then with 3 DEG C/min rises to 1320 DEG C, and is incubated calcining 1h；
3）Cooling：After calcining terminates, air quenching obtains the sulphoaluminate cement clinker containing tricalcium silicate.
Sulphoaluminate cement clinker of the embodiment 1 containing tricalcium silicate, its mineral percentage composition, which is constituted, is：C3S 15%, C2S 42%, C2F 20%, C3BA3$ 23%.Wherein, oxide is abbreviated as C=CaO, S=SiO2、A=Al2O3、F=Fe2O3、$=SO3、B= BaO.Gained clinker sample mineral composition refers to the XRD spectrum of accompanying drawing 1, it is seen then that in mineral composition, iron phase is C2F；Aluminium sulfate Mineral are C3BA3$；
Its chemical composition and percentage composition are：CaO 52.1%, SiO218.6%, Al2O39.9%, Fe2O311.8%, BaO 5.0%, SO3 2.6%。
Embodiment 2
A kind of preparation method of the sulphoaluminate cement clinker containing tricalcium silicate, step includes：
1）Dispensing：Raw materials of Ca CO is weighed by following weight parts3 91.9 parts, BaCO36.4 parts, SiO220.4 parts, Al (OH)315.2 parts, Fe2O38.8 parts and CaSO4·2H25.6 parts of O, each raw material granularity is below 80 μm, then by the raw material prepared After wet-mixing, 105 DEG C of drying add the water that mass fraction is 7%, after being well mixed, are pressed into punching block under 16 MPa The mm of mm of φ 35 × 5 raw material piece, then dries 4h in 105 DEG C, standby；
2）Calcining：By step 1）Raw materials treated, 900 DEG C are risen to 5 DEG C/min from room temperature, then insulation calcining 1h, then with 3 DEG C/min rises to 1350 DEG C, and is incubated calcining 1h；
3）Cooling：After calcining terminates, air quenching obtains the sulphoaluminate cement clinker containing tricalcium silicate.
Sulphoaluminate cement clinker of the embodiment 2 containing tricalcium silicate, its mineral percentage composition, which is constituted, is：C3S 15%, C2S 47%, C2F 15%, C3BA3$ 23%.Wherein, oxide is abbreviated as C=CaO, S=SiO2、A=Al2O3、F=Fe2O3、$=SO3、B= BaO.Gained clinker sample mineral composition refers to the XRD spectrum of accompanying drawing 2, it is seen then that in mineral composition, iron phase is C2F；Aluminium sulfate Mineral are C3BA3$；
Its chemical composition and percentage composition are：CaO 53.3%, SiO220.4%, Al2O39.9%, Fe2O38.8%, BaO 5.0%, SO3 2.6%。
Embodiment 3
A kind of preparation method of the sulphoaluminate cement clinker containing tricalcium silicate, step includes：
1）Dispensing：Raw materials of Ca CO is weighed by following weight parts3 86.3 parts, BaCO37.5 parts, SiO217.2 parts, Al (OH)317.9 parts, Fe2O311.7 parts and CaSO4·2H26.6 parts of O, each raw material granularity is below 80 μm, then by the raw material prepared After wet-mixing, 105 DEG C of drying add the water that mass fraction is 7%, after being well mixed, are pressed into punching block under 16 MPa The mm of mm of φ 35 × 5 raw material piece, then dries 4h in 105 DEG C, standby；
2）Calcining：By step 1）Raw materials treated, 900 DEG C are risen to 5 DEG C/min from room temperature, then insulation calcining 1h, then with 3 DEG C/min rises to 1380 DEG C, and is incubated calcining 1h；
3）Cooling：After calcining terminates, air quenching obtains the sulphoaluminate cement clinker containing tricalcium silicate.
Sulphoaluminate cement clinker of the embodiment 3 containing tricalcium silicate, its mineral percentage composition, which is constituted, is：C3S 15%, C2S 38%, C2F 20%, C3BA3$ 27%.Wherein, oxide is abbreviated as C=CaO, S=SiO2、A=Al2O3、F=Fe2O3、$=SO3、B= BaO.Gained clinker sample mineral composition refers to clearly visible C in the XRD spectrum of accompanying drawing 3, figure3S diffraction maximum (d=1.76) And C3BA3$ (d=3.77).
Its chemical composition and percentage composition are：CaO 50.5%, SiO217.2%, Al2O311.7%, Fe2O311.7%, BaO 5.8%, SO3 3.1%。
Comparative example 1
Preparation method be the same as Example 1, difference is step 1）Composition：Raw materials of Ca CO is weighed by following weight parts3 94.6 parts, SiO218.6 parts, Al (OH)3 17.6 parts, Fe2O311.7 parts and CaSO4·2H26.5 parts of O.
The gained clinker of comparative example 1, its mineral percentage composition, which is constituted, is：Mainly C2S, C2F, C4A3$ (d=3.75) And free calcium, do not find C3S characteristic diffraction peaks（D=1.76）；Gained clinker sample mineral composition refers to the XRD of accompanying drawing 4 Spectrum, it is seen then that in mineral composition, iron phase is C2F；Sulphoaluminate phase is C4A3$。
Comparative example 2
Preparation method be the same as Example 2, difference is step 1 composition：CaCO3 98.0 parts, SiO220.3 parts, Al (OH)322.5 parts, Fe2O34.9 parts and CaSO4·2H26.5 parts of O.
The gained clinker of comparative example 2, its mineral percentage composition, which is constituted, is：Mainly C2S, C4AF, C4A3$ (d= 3.75) and free calcium, C is not found3S characteristic diffraction peaks（D=1.76）；
Mineral composition refers to the XRD spectrum of accompanying drawing 5, it is seen then that in mineral composition, and iron phase is C4AF；Sulphoaluminate phase is C4A3$。
Comparative example 3
Preparation method be the same as Example 1, difference is step 1）：Raw materials of Ca CO is weighed by following weight parts3 94.6 parts, SiO2 18.6 parts, Al (OH)3 17.6 parts, Fe2O311.7 parts and CaSO4·2H26.5 parts of O, then mixes the raw material prepared through wet method After conjunction, tabletting is dried, it is standby；
By step 1）Raw materials treated, 900 DEG C are risen to 5 DEG C/min from room temperature, then insulation calcining 1h, then with 3 DEG C/min liters To 1380 DEG C, and it is incubated calcining 1h.
The gained clinker of comparative example 3, its mineral percentage composition, which is constituted, is：Mainly C2S, C2F, C4A3$ and free calcium, Do not find C3S characteristic diffraction peaks；Gained clinker sample mineral composition refers to the XRD spectrum of accompanying drawing 6, it is seen then that in mineral composition, Iron phase is C2F；Sulphoaluminate phase is C4A3$。

Claims (6)

1. a kind of sulphoaluminate cement clinker containing tricalcium silicate, it is characterised in that：In mineral composition, iron phase is C2F；Sulphur aluminic acid Salt mineral are C3BA3$；The C2F, i.e. dicalcium ferrite, stoichiometric equation are 2CaOFe2O3；The C3BA3$, i.e. sulphur barium aluminate Calcium, stoichiometric equation is 3CaO3Al2O3·BaSO4。
2. sulphoaluminate cement clinker according to claim 1, it is characterised in that：Its mineral percentage composition is constituted：
C3S 5~30%,
C3BA3$ 20~65%,
C2S 30~60%,
C2F 3~25%；
Wherein, oxide is abbreviated as C=CaO, S=SiO2、A=Al2O3、F=Fe2O3、$=SO3、B=BaO。
3. sulphoaluminate cement clinker according to claim 1, it is characterised in that：Chemical composition and percentage composition are：
CaO 47~60%,
SiO211~29%,
Al2O38~28%,
Fe2O31~15%,
BaO 5~17%,
SO32~8%.
4. a kind of preparation method of the sulphoaluminate cement clinker described in any one of claims 1 to 3, it is characterised in that step Including：
1）Dispensing：Raw materials of Ca CO is weighed by following weight parts3 83~107 parts, BaCO36.4~21.8 parts, SiO211~29 Part, Al (OH)3 12.2~43.8 parts, Fe2O31~15 part and CaSO4·2H24.3~17.2 parts of O, then by the raw material prepared After wet-mixing, drying, tabletting is standby；
2）Calcining：By step 1）Raw materials treated, 900 DEG C are risen to 5 DEG C/min from room temperature, then insulation calcining 1h, then with 3 DEG C/min rises to 1300~1410 DEG C, and is incubated 0.5~1.5h of calcining；
3）Cooling：After calcining terminates, air quenching obtains the sulphoaluminate cement clinker containing tricalcium silicate.
5. preparation method according to claim 4, it is characterised in that：Step 1）In, starting material particle size is below 80 μm.
6. preparation method according to claim 4, it is characterised in that：Step 2）In, rise to 1320 DEG C with 3 DEG C/min, and Insulation calcining 1h.
CN201710390145.0A 2017-05-27 2017-05-27 Sulphate aluminium cement clinker containing tricalcium silicate and preparation method thereof Active CN107117838B (en)

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