CN108101399A - A kind of method that split-phase combination prepares calcium sulphoaluminate-alite-belite-iron phase system clinker - Google Patents
A kind of method that split-phase combination prepares calcium sulphoaluminate-alite-belite-iron phase system clinker Download PDFInfo
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- CN108101399A CN108101399A CN201711458388.XA CN201711458388A CN108101399A CN 108101399 A CN108101399 A CN 108101399A CN 201711458388 A CN201711458388 A CN 201711458388A CN 108101399 A CN108101399 A CN 108101399A
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
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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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
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Abstract
The invention discloses a kind of methods that split-phase combination prepares sulphoaluminate_alite belite iron phase system clinker, the identical mineral of temperature range are formed according to calcining to prepare together, calcine the principle that forms the different mineral of temperature range and be prepared separately, and the different tricalcium silicate dicalcium silicate iron phase system clinker of temperature range and calcium sulphoaluminate belite iron phase system clinker are formed by calcining（That is sulphoaluminate cement clinker）It is uniformly mixed and obtains at normal temperatures.Exist jointly the invention avoids tricalcium silicate and calcium sulphoaluminate and prepare the problem that sulfur trioxide in difficult and gypsum inhibits alite generation, reduce preparation difficulty, simplify technical operation flow, improve the performance of clinker.The early strength and later strength of gained clinker are very high and setting time is controllable, and early strength obtains matching development with later strength.In addition, the appearance for situations such as setting time is abnormal, additive adaptability is bad is avoided without aluminium mineral material in clinker.
Description
Technical field
The present invention relates to a kind of preparation methods of clinker, and in particular to a kind of to prepare high-performance using split-phase combined method
The method of calcium sulphoaluminate-alite-belite-iron phase system clinker, belongs to clinker technical field.
Background technology
Ante-sulphoaluminate cement, which is one, to be had development prospect, utilizes calcium sulphoaluminate modified portland cement
Kind.The cement introduces suitable calcium sulphoaluminate to substitute tricalcium aluminate in traditional portland clinker, while introduces few
The calcium sulfate of amount is burnt till at 1250 DEG C~1350 DEG C, then is filled suitable gypsum, mixing material etc. and be made.The clinker of the cement
The general range of mineral composition is（wt%）：Tricalcium silicate content is 30%~50%, the content of dicalcium silicate is 30%~40%, sulphur
The content of calcium aluminate is in 5%~20%, iron phase mineral<10% and a small amount of calcium sulfate.
The calcium sulphoaluminate temperature that it is largely formed in clinker system is at 1200 DEG C or so, when temperature is more than 1350 DEG C,
Calcium sulphoaluminate can decompose.Tricalcium silicate largely occurs in the presence of formation has liquid phase in clinker, optimal to form temperature
Degree is generally at 1450 DEG C.Under normal conditions, tricalcium silicate and calcium sulphoaluminate cannot coexist in clinker.Currently used method is
Adding in mineralizer reduces the firing temperature of tricalcium silicate, and then realizes coexisting for calcium sulphoaluminate and tricalcium silicate, but this method
Alite content is relatively low in the clinker of preparation, its hydrating capacity is made to be not achieved most preferably, causes strength development slow；Mineralizer simultaneously
Use certain corrosion can be brought to cement kiln system, pollute the environment.In addition, calcium sulphoaluminate is in calcination process
The raw materials such as substantial amounts of gypsum are needed, when calcining heat is excessively high, the sulfur trioxide in gypsum can inhibit the generation of alite, make A Li
The special content with calcium sulphoaluminate reduces, and free calcium oxide content increases, and the early strength for causing cement is relatively low, and the later stage stabilizes
Situations such as property is bad；The decomposition of calcium sulphoaluminate causes the appearance of aluminium mineral material, and aluminium mineral material hydration rate is fast, and intensity is absolute
It is worth low, and the setting time for being easy to cause cement is abnormal, additive applicability is bad, it is impossible to meet practical application.
To solve the above-mentioned problems, there are the linguistic term for this respect, such as a kind of patent " high strength silicate at present
Clinker and preparation method thereof "（CN 103232176B）With secondary firing in the case of one kind is proposed without using mineralizer
The method that the mode of synthesis introduces calcium sulphoaluminate in Portland clinker, but this method needs secondary firing, it is actual raw
Production operation relative difficulty.Patent 201410532393.0 discloses a kind of method of sulphoaluminate cement clinker, in order to solve silicon
Temperature is first risen to tricalcium silicate and forms temperature, so by the problem of sour tricalcium is difficult to coexist with calcium sulphoaluminate in preparation process
It is down to calcium sulphoaluminate again afterwards and forms temperature, obtained that free calcium levels are few, the clinker of later stage good security.Although the patent
Solve the problems, such as that tricalcium silicate is difficult to coexist with calcium sulphoaluminate in preparation process, but when calcining heat is more than 1350 DEG C
When, the gypsum decomposition in raw material can cause the generation temperature of tricalcium silicate to become higher, and consume more fuel；Secondly in temperature-fall period
In, the problems such as being easy to cause tricalcium silicate decomposition, equally exist actual production operating difficulties.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of split-phase combination prepare calcium sulphoaluminate-alite-
The method of belite-iron phase system clinker.This method will calcine that form the different mineral group system of temperature range standby, then
Obtained clinker is mixed, tricalcium silicate is avoided well and there is the problem of preparing hardly possible, and institute jointly with calcium sulphoaluminate
It obtains in clinker without aluminate, avoids the appearance for situations such as cement setting time is abnormal, additive adaptability is bad.
Specific technical solution of the present invention is as follows：
A kind of method that split-phase combination prepares calcium sulphoaluminate-alite-belite-iron phase system clinker, this method include：
Calcining is formed into the different tricalcium silicate-dicalcium silicate of temperature range-iron phase system clinker（It is abbreviated as：C3S -C2S- iron phase bodies
It is clinker, similarly hereinafter）With anhydrous calcium sulphoaluminate-dicalcium silicate-iron phase system clinker（That is C4A3$-C2S- iron phase system clinkers, write a Chinese character in simplified form
For：Sulphoaluminate cement clinker, similarly hereinafter）It is uniformly mixed at normal temperatures, obtains calcium sulphoaluminate-alite-belite-iron phase system
Clinker.
In the above method of the present invention, so-called split-phase combination refers to the meaning for being combined the mineral facies of identical temperature range
Think.Wherein, calcining formed temperature range it is identical refer to calcining formed mineral calcining heat it is same or similar, mix mineral
It is combined and is prepared.C3S -C2The calcining of S- iron phase system clinkers formed temperature range for 1380 DEG C and more than, such as
1380~1500 DEG C；The calcining of calcium sulphoaluminate-dicalcium silicate-iron phase system clinker forms temperature range as 1250~1300 DEG C.
The present invention forms the identical mineral of temperature range according to calcining and prepares together, calcines and form the different ore deposit of temperature range
The mineral composition of calcium sulphoaluminate-alite-belite-iron phase system clinker is grouped by the principle that object is prepared respectively,
Calcining is formed the identical mineral assemblage of temperature range to prepare together, different calcinings is first prepared respectively and forms the ripe of temperature range
Material, then each calcining is formed into the different clinker of temperature range and is mixed according to proportioning, obtain needed for mineral composition calcium sulphoaluminate-Ah
Li Te-belite-iron phase system clinker.I.e. the present invention according to calcining formed the identical mineral of temperature range prepare together,
Calcining forms the principle that the different mineral of temperature range are prepared respectively, first prepares tricalcium silicate-dicalcium silicate-iron phase system respectively
Clinker and calcium sulphoaluminate-dicalcium silicate-iron phase system clinker, then both clinkers are mixed in proportion.
In the above method, the mineral composition of the calcium sulphoaluminate-alite-belite-iron phase system clinker is：Ah
Li Te（That is tricalcium silicate, C3S）, belite（That is dicalcium silicate, C2S）, iron phase, anhydrous calcium sulphoaluminate（C4A3$）, free oxidation
Calcium, dead plaster；Wherein the chemical formula of iron phase is C4AxF2-x（C=Ca, A=Al, F=Fe, similarly hereinafter）, 0≤X ＜ 2.
Preferably, the mineral composition of calcium sulphoaluminate-alite-belite-iron phase system clinker and weight percent contain
It measures and is（wt%）：Alite, that is, tricalcium silicate 15~55%, belite, that is, dicalcium silicate 25~50%, iron phase 8~15%, anhydrous sulphur aluminium
Sour calcium 1~45%, free calcium oxide 0~1.5%, dead plaster 0~3%；It is furthermore preferred that calcium sulphoaluminate-alite-belite-
The mineral composition of iron phase system clinker and weight percentage are（wt%）：Alite, that is, tricalcium silicate 15~20%, Baily
Spy i.e. dicalcium silicate 25~40%, iron phase 8~15%, anhydrous calcium sulphoaluminate 30-45%, free calcium oxide 0~1%, dead plaster 0
~3%；Wherein the chemical formula of iron phase is C4AxF2-x, 0≤X ＜ 2.The clinker has calcium sulphoaluminate-alite-belite-iron
The characteristics of phase system clinker, calcium sulphoaluminate and alite hydration rate are fast, provide good early and middle portion performance, Baily
Special hydration rate is slow, can prevent the retraction of later strength, while alite and belite generate largely in hydration process
Calcium hydroxide to excite the aquation of mixing material, water mudrock structure is made to become finer and close, performance is more excellent.In addition, suitable sulphur
Calcium aluminate can control the setting time of cement.
Further, calcium sulphoaluminate-alite-belite-iron phase system clinker is divided into C by the present invention3S -C2S-
Iron phase system clinker and calcium sulphoaluminate-dicalcium silicate-two groups of iron phase system clinker.Calcium sulphoaluminate-dicalcium silicate-iron phase system is ripe
The mineral composition of material is：Calcium sulphoaluminate, belite, that is, dicalcium silicate, iron phase, dead plaster, wherein free calcium oxide, iron phase
Chemical formula be C4AxF2-x, 0≤X ＜ 2.C3S -C2The mineral composition of S- iron phase system clinkers is：Alite, belite, iron
The chemical formula of phase, free calcium oxide, wherein iron phase is C4AxF2-x, 0≤X ＜ 2.When preparing clinker, this is first prepared respectively
Then two groups of clinkers mix this two groups of clinkers according to the mineral composition of required clinker in proportion, you can obtain expected
Clinker.Wherein, because calcium sulphoaluminate-dicalcium silicate-iron phase system clinker is commercial product, can directly buy, therefore
C can only be prepared3S -C2S- iron phase system clinkers, simplify technique and operating process.But can also voluntarily prepare calcium sulphoaluminate-
Dicalcium silicate-iron phase system clinker.
Further, the mineral composition of the calcium sulphoaluminate-dicalcium silicate-iron phase system clinker and mass percentage can
To obtain from the prior art, it is preferred that the mineral composition of calcium sulphoaluminate-dicalcium silicate-iron phase system clinker is（wt%）：Sulphur
Calcium aluminate 50~70%, dicalcium silicate 15~30%, iron phase 2~10%, dead plaster 0~8%, free calcium oxide 0~0.5%.
Further, in a preferred embodiment of this invention, the C3S -C2The mineral composition of S- iron phase system clinkers and
Weight percentage is：Alite 40~60%, belite 30~50%, iron phase 8~20%, free calcium oxide 0.1~1.5%；Its
The chemical formula of middle iron phase is C4AxF2-x, 0≤X ＜ 2.
Further, C3S -C2S- iron phase systems three rate values of clinker are respectively：KH=0.80~0.87, SM=2.5~
3.66, IM=0~0.64.
Further, C of the present invention3S -C2The preparation method of S- iron phase system clinkers comprises the following steps:
（1）Raw material amount is calculated in mineral composition according to tricalcium silicate-dicalcium silicate-iron phase system clinker, by raw material amount into
Row dispensing obtains uniformly mixed raw material.
（2）Raw material are calcined at 1380~1500 DEG C, then chilling, obtains C3S -C2S- iron phase system clinkers.
The present invention also provides a kind of preparation method of calcium sulphoaluminate-alite-belite-iron phase system cement, the party
Method includes:The method that calcium sulphoaluminate-alite-belite-iron phase system clinker is prepared according to above-mentioned split-phase combination is made
Calcium sulphoaluminate-alite-belite-iron phase system clinker, then mixes the clinker with gypsum, mixing material, powder
Mill, obtains calcium sulphoaluminate-alite-belite-iron phase system cement.
Further, calcium sulphoaluminate-alite-belite-iron phase system cement clinker mineral composition is same as above, mixing used
The species of material, clinker, gypsum, the dosage of mixing material can be adjusted according to the performance of the prior art and cement.
Further, when prepared by cement, grinding to specific surface area is 330~400 m2/kg。
The present invention proposes a kind of split-phase combination and prepares calcium sulphoaluminate-alite-belite-iron phase system clinker
Method improves the preparation process of existing alite-sulphoaluminate cement clinker, and calcining is formed temperature by this method
The identical mineral in section are combined, and then form temperature range according to different calcinings prepares respectively, finally forges gained difference
Burn common mixing in proportion under the clinker progress room temperature for forming temperature range.Split-phase combination of the present invention avoids silicon well
Sour tricalcium exists jointly with calcium sulphoaluminate prepares the problem that sulfur trioxide in difficult and gypsum inhibits alite generation, reduces preparation
Difficulty simplifies technical operation flow, improves the performance of clinker.The cement prepared by split-phase combined method of the present invention is ripe
Material has the characteristics that calcium sulphoaluminate-alite-belite-iron phase system clinker, and tricalcium silicate and calcium sulphoaluminate content are equal
Can be higher, make clinker that there is good early strength and later strength simultaneously, and setting time is controllable, early strength and later stage
Intensity obtains matching development.In addition, cement setting time exception is avoided without aluminium mineral material, additive is fitted in clinker
The appearance for situations such as answering property is bad.The present invention prepares thinking and is not limited solely to this calcium sulphoaluminate-alite-belite-iron phase
The preparation of system clinker can be also used for preparing aluminophosphates-silicate systems/aluminates system/aluminium sulfate system
Etc. various special cement systems.
Description of the drawings
Fig. 1 is the XRD spectrum of industrial sulphoaluminate cement clinker；
Fig. 2 is C prepared by embodiment 13S -C2The XRD spectrum of S- iron phase system clinkers；
Fig. 3 is C prepared by embodiment 22S -C2The XRD spectrum of S- iron phase system clinkers；
Fig. 4 is C prepared by embodiment 33S -C2The XRD spectrum of S- iron phase system clinkers.
Fig. 5 is C prepared by comparative example 13The XRD spectrum of S-iron phase clinker.
Specific embodiment
In order to be better understood from the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
The preparation method of calcium sulphoaluminate-alite-belite-iron phase system clinker of the present invention, clinker burn till with
Exemplified by electric furnace process, it is as follows：
1st, the principle of the identical mineral assemblage preparation of temperature range is formed according to calcining, the present invention divides clinker by screening
Into C3S -C2S- iron phase system clinkers and sulphoaluminate cement clinker（That is calcium sulphoaluminate-dicalcium silicate-iron phase system clinker）Two
Group, wherein sulphoaluminate cement clinker use commercial product.In the preparation, first according to calcium sulphoaluminate-alite-shellfish of setting
The mineral composition of Li Te-iron phase system clinker and the mineral composition of existing sulphoaluminate cement clinker calculate C3S -
C2The percentage composition of each mineral of S- iron phase system clinkers.
2. prepare C3S -C2S- iron phase system clinkers：
（1）Raw material mix：According to C3S -C2The mineral composition of S- iron phase system clinkers, obtains three ratio（KH、SM、IM）, calculate
Raw material amount.
（2）Raw material are calcined：Raw material are calcined, are warming up to 800-1000 DEG C with 5~10 DEG C/min of heating rate, heat preservation
30~50 min（Ensure CaCO3It decomposes）, 1380~1500 DEG C then are warming up to the rate of 3~5 DEG C/min, heat preservation 1~2
H, the clinker burnt till chilling in air, obtains C3S -C2S- iron phase system clinkers.
3. common mixing：According to the mineral composition of required clinker, by C3S -C2S- iron phase system clinkers and sulphur aluminic acid
Salt cement clinker mixes in proportion, and obtains calcium sulphoaluminate-alite-belite-iron phase system clinker.
Further, by above-mentioned calcium sulphoaluminate-alite-belite-iron phase system clinker and gypsum, mixing material etc.
Mixing, grinding can obtain calcium sulphoaluminate-alite-belite-iron phase system cement of different performance.
Further, the mineral composition of the calcium sulphoaluminate-alite-belite-iron phase system clinker and weight
Percentage composition is：Tricalcium silicate 15~55%, dicalcium silicate 25~50%, iron phase 8~15%, anhydrous calcium sulphoaluminate 1~45% dissociate
Calcium oxide 0~1.5%, dead plaster 0~3%, preferred mineral composition content are（wt%）：Tricalcium silicate 15~20%, silicic acid
Dicalcium 25~40%, iron phase 8~15%, anhydrous calcium sulphoaluminate 30-45%, free calcium oxide 0~1%, dead plaster 0~3%；More
Preferably, mineral composition content is（wt%）：Tricalcium silicate 17~20%, dicalcium silicate 26~32%, iron phase 11~14%, anhydrous sulphur
Calcium aluminate 32-44%, free calcium oxide 0.3~0.35%, dead plaster 0~3%；Wherein the chemical formula of iron phase is C4AxF2-x, 0
≤ X ＜ 2.
Further, the mineral composition of sulphoaluminate cement clinker of the present invention is：Calcium sulphoaluminate, belite, that is, silicic acid two
Calcium, iron phase, dead plaster；C3S -C2The mineral composition of S- iron phase system clinkers is：Alite, belite, iron phase, free oxygen
Change calcium.The mineral composition content of sulphoaluminate cement clinker is（wt%）：Calcium sulphoaluminate 50~70%, dicalcium silicate 15~30%, iron
Phase 2~10%, dead plaster 0~8%, free calcium oxide 0~0.5%.Under the preferred embodiment for the present invention, sulphur aluminic acid used
The mineral composition content of salt cement clinker is（wt%）：Calcium sulphoaluminate 65%, belite, that is, dicalcium silicate 23.1%, iron phase 6.1%, nothing
H 2 O calcium sulphate 5.51%, free calcium oxide 0.29%；Wherein the chemical formula of iron phase is C4AxF2-x, 0≤X ＜ 2.
In the case where sulphoaluminate cement clinker is above-mentioned mineral composition content, C3S -C2The ore deposit of S- iron phase system clinkers
Object forms content（wt%）：Alite 40~60%, belite 30~50%, iron phase 8~20%, free calcium oxide 0.1~1.5%,
Preferably mineral composition content is：Alite 40~47.5%, belite 41~43.5%, iron phase 9~18.5%, free calcium oxide
0.2~0.45%.Wherein the chemical formula of iron phase is C4AxF2-x, 0≤X ＜ 2.
Further, three ratio is：KH=0.80~0.87, such as 0.80,0.82,0.84,0.86,0.87.SM=2.5~
3.66, such as 2.5,2.7,2.9,3.1,3.3,3.5,3.66.IM=0~0.64, such as 0.1,0.3,0.5,0.6.
Under the preferred embodiment for the present invention, C3S -C2Content of the S- iron phase system clinkers in clinker for 33~
95wt%, content of the sulphoaluminate cement clinker in clinker are 5~67wt%.
Under the preferred embodiment for the present invention, by calcium sulphoaluminate-alite-belite-iron phase system clinker and stone
Cream mix, through ball mill grinding into powder to specific surface area be 330~400 m2/ kg, obtain calcium sulphoaluminate-alite-belite-
Iron phase system cement.In the cement, the content of calcium sulphoaluminate-alite-belite-iron phase system clinker for 80~
95wt%, the content of gypsum is 5~20wt%.
In the following, specifically enumerate several the embodiment of the present invention.Unless otherwise instructed, following percentage compositions are quality percentage
Content.
Embodiment 1
The mineral composition of sulphoaluminate cement clinker is calculated by Rietveld Full _ pattern fittings, the results are shown in Table 1.Fig. 1 is sulphur aluminic acid
The XRD spectrum of salt cement clinker.According to the mineral group of calcium sulphoaluminate-alite-belite-iron phase system clinker of setting
Into and sulphoaluminate cement clinker mineral composition, C is calculated3S -C2The rate value of S- iron phase system clinkers is KH=0.86,
SM=3.09, IM=0.64.
Dispensing：Raw material amount is calculated according to three ratio, specific oxide ratios are shown in Table 2.Using material by wet type mixing, by life
Material：Ball：Water=1：1：1 carries out.Load weighted sample is packed into the mixing tank of sealing, is taken out after 1~2 h of ball milling mixing, drying.
Uniformly mixed raw material add the water of about 7~10wt%, with 40 mm*40 mm molds of φ, 15~20 MPa of load, and it is pressed into 10~
The raw material piece of 15 g.
Calcining system：Raw material piece is calcined, is raised to 800~1000 DEG C with the heating rate of 5 DEG C/min, heat preservation 40
Then min is warming up to firing temperature as 1400~1500 DEG C using the speed of 3 DEG C/min, 60 min are kept the temperature, then by clinker in sky
Chilling in gas, obtains C3S -C2S- iron phase system clinkers.Gained C3S -C2The XRD spectrum of S- iron phase system clinkers such as 2 institute of attached drawing
Show, C is calculated by Rietveld Full _ pattern fittings3S -C2The mineral composition of S- iron phase system clinkers is：Alite 54.75%, Baily
Spy 31.25%, iron phase 13.75%, free calcium oxide 0.25%.
According to C3S -C2S- iron phase system clinkers：Sulphoaluminate cement clinker=9.5：0.5 mass ratio is mixed, and is obtained
Calcium sulphoaluminate-alite-belite-iron phase system clinker.Gained clinker is calculated with Rietveld Full _ pattern fittings
Mineral composition, result are：Alite 52.01%, belite 30.84%, iron phase 13.36%, anhydrous calcium sulphoaluminate 3.25%, free oxygen
Change calcium 0.3%, dead plaster 0.24%, each mineral content is consistent with setting.
Intergrinding prepares cement：By above-mentioned clinker and gypsum according to 95:5 mass ratio mixing, grinding is to than table
Area is 330~400 m2/ kg obtains calcium sulphoaluminate-alite-belite-iron phase system cement.With Rietveld Full _ pattern fittings
The mineral composition of gained cement is calculated, result is：Alite 49.53%, belite 29.37%, iron phase 12.61%, anhydrous sulphur aluminic acid
Calcium 3.1%, free calcium oxide 0.28%, dead plaster 5.11%.
With the automatic control program of SJ-160 type twin shaft rotating speed agitator for cement mortar, first mix slowly 120 seconds, then adjust
To quick rotation gear stirring 120 seconds, cement slurry, w/c=0.45 is made.It is tested under the conditions of 20 DEG C of environment temperature with Vicat apparatus
The setting time of slurry, slurry is in addition packed into mold（20×20×20 mm）, measure the strong of net slurry test block in 3,7 and 28 days
Degree, wherein forcing press loading velocity are 2 mm/min, and intensity and setting time the results are shown in Table 3.Meanwhile it sees during the experiment
Net slurry test block surface is examined, without cracking phenomena in 3 months.
Embodiment 2
The mineral composition of sulphoaluminate cement clinker used is the same as embodiment 1.According to calcium sulphoaluminate-alite-belite of setting-
The mineral composition of iron phase system clinker and the mineral composition of sulphoaluminate cement clinker, are calculated C3S -C2S- iron phases
The rate value of system clinker be KH=0.82, SM=3.44, IM=0.
Dispensing：Raw material amount is calculated according to three ratio, specific oxide ratios are shown in Table 4.Using material by wet type mixing, by life
Material：Ball：Water=1：1：1 carries out.Load weighted sample is packed into the mixing tank of sealing, is taken out after 1~2 h of ball milling mixing, drying.
Uniformly mixed raw material add the water of about 7~10wt%, with 40 mm*40 mm molds of φ, 15~20 MPa of load, and it is pressed into 10~
The raw material piece of 15 g.
Calcining system：The raw material piece of compression moulding is calcined, 800~1000 are raised to the heating rate of 5 DEG C/min
DEG C, 50 min are kept the temperature, firing temperature is then warming up to as 1400~1500 DEG C using the speed of 3 DEG C/min, keep the temperature 60 min, then
Clinker chilling in air, obtains C3S -C2S- iron phase system clinkers.Gained C3S-C2The XRD spectrum of S- iron phase system clinkers is for example attached
Shown in Fig. 3, C is calculated by Rietveld Full _ pattern fittings3S-C2The mineral composition of S- iron phase system clinkers is：Alite 47.15%,
Belite 43.25%, iron phase 9.15%, free calcium oxide 0.45%.
According to C3S-C2S- iron phase system clinkers：Sulphoaluminate cement clinker=33：67 mass ratio is mixed, and obtains sulphur aluminium
Sour calcium-alite-belite-iron phase system clinker.The mineral of gained clinker are calculated with Rietveld Full _ pattern fittings
Composition, result are：Alite 17.55%, belite 26.5%, iron phase 11.8%, anhydrous calcium sulphoaluminate 43.5%, free calcium oxide
0.35%, dead plaster 0.3%, each mineral content is consistent with setting.
Intergrinding prepares cement：By above-mentioned clinker and gypsum according to 9：1 mass ratio mixing, grinding to specific surface
Product is 330~400 m2/ kg obtains calcium sulphoaluminate-alite-belite-iron phase system cement.With Rietveld Full _ pattern fitting meters
The mineral composition of gained cement is calculated, result is：Alite 15.80%, belite 24.8%, iron phase 9.45%, anhydrous calcium sulphoaluminate
39.15%, free calcium oxide 0.3%, dead plaster 10.5%.
Method according to embodiment 1 carries out setting time and intensity test, and test block is starched only for 20 × 20 × 20 mm
Test block, w/c=0.45 the results are shown in Table 5.Meanwhile test block surface is starched in observation only during the experiment, without cracking phenomena in 3 months.
Embodiment 3
The mineral composition of sulphoaluminate cement clinker used is the same as embodiment 1.According to calcium sulphoaluminate-alite-belite of setting-
The mineral composition of iron phase system clinker and the mineral composition of sulphoaluminate cement clinker, are calculated C3S-C2S- iron phases
The rate value of system clinker be KH=0.80, SM=2.54, IM=0.42.
Dispensing：Raw material amount is calculated according to three ratio, specific oxide ratios are shown in Table 6.Using material by wet type mixing, by life
Material：Ball：Water=1：1：1 carries out.Load weighted sample is packed into the mixing tank of sealing, is taken out after 1~2 h of ball milling mixing, drying.
Uniformly mixed raw material add the water of about 7~10wt%, with 40 mm*40 mm molds of φ, 15~20 MPa of load, and it is pressed into 10~
The raw material piece of 15 g.
Calcining system：The raw material piece of compression moulding is calcined, 800~1000 are raised to the heating rate of 5 DEG C/min
DEG C, 60 min are kept the temperature, firing temperature is then warming up to as 1380~1500 DEG C using the speed of 3 DEG C/min, keep the temperature 60 min, then
Clinker chilling in air, obtains C3S-C2S- iron phase system clinkers.Gained C3S-C2The XRD spectrum of S- iron phase system clinkers is for example attached
Shown in Fig. 4, C is calculated by Rietveld Full _ pattern fittings3S-C2The mineral composition of S- iron phase system clinkers is：Alite 40.3%,
Belite 41.26%, iron phase 18.24%, free calcium oxide 0.2%.
According to C3S-C2S- iron phase system clinkers：Sulphoaluminate cement clinker=48:52 mass ratio is mixed, and obtains sulphur aluminium
Sour calcium-alite-belite-iron phase system clinker.The mineral of gained clinker are calculated with Rietveld Full _ pattern fittings
Composition, result are：Alite 19.01%, belite 31.82%, iron phase 13.47%, anhydrous calcium sulphoaluminate 32.8%, free calcium oxide
0.3%, dead plaster 2.6%, each mineral content is consistent with setting.
Intergrinding prepares cement：By above-mentioned clinker and gypsum 8.5:1.5 mass ratio mixing, grinding to specific surface
Product is 330~400 m2/ kg obtains calcium sulphoaluminate-alite-belite-iron phase system cement.With Rietveld Full _ pattern fitting meters
The mineral composition of gained cement is calculated, result is：Alite 16.16%, belite 27.04%, iron phase 11.45%, anhydrous calcium sulphoaluminate
27.9%, free calcium oxide 0.3%, dead plaster 17.15%.
Method according to embodiment 1 carries out setting time and intensity test, and test block is starched only for 20 × 20 × 20 mm
Test block, w/c=0.45 the results are shown in Table 7.Meanwhile test block surface is starched in observation only during the experiment, without cracking phenomena in 3 months.
Embodiment 4
The mineral composition of sulphoaluminate cement clinker used is the same as embodiment 1.According to calcium sulphoaluminate-alite-belite of setting-
The mineral composition of iron phase system clinker and the mineral composition of sulphoaluminate cement clinker, are calculated C3S-C2S- iron phases
The rate value of system clinker is KH=0.80, SM=3. 2, IM=0.42.
Dispensing：Raw material amount is calculated according to three ratio, specific oxide ratios are shown in Table 8.Using material by wet type mixing, by life
Material：Ball：Water=1：1：1 carries out.Load weighted sample is packed into the mixing tank of sealing, is taken out after 1~2 h of ball milling mixing, drying.
Uniformly mixed raw material add the water of about 7~10wt%, with 40 mm*40 mm molds of φ, 15~20 MPa of load, and it is pressed into 10~
The raw material piece of 15 g.
Calcining system：The raw material piece of compression moulding is calcined, 800~1000 are raised to the heating rate of 5 DEG C/min
DEG C, 60 min are kept the temperature, firing temperature is then warming up to as 1380~1500 DEG C using the speed of 3 DEG C/min, keep the temperature 60 min, then
Clinker chilling in air, obtains C3S-C2S- iron phase system clinkers.C is calculated by Rietveld Full _ pattern fittings3S-C2S- iron phase bodies
The mineral composition for being clinker is：Alite 37.3%, belite 48.26%, iron phase 14.24%, free calcium oxide 0.2%.
According to C3S-C2S- iron phase system clinkers：Sulphoaluminate cement clinker=90:10 mass ratio is mixed, and obtains sulphur aluminium
Sour calcium-alite-belite-iron phase system clinker.The mineral of gained clinker are calculated with Rietveld Full _ pattern fittings
Composition, result are：Alite 33.57%, belite 45.75%, iron phase 13.43%, anhydrous calcium sulphoaluminate 6.5%, free calcium oxide
0.3%, dead plaster 0.45%, each mineral content is consistent with setting.
Intergrinding prepares cement：By above-mentioned clinker and gypsum 9:1 mass ratio mixing, grinding to specific surface area are
330~400 m2/ kg obtains calcium sulphoaluminate-alite-belite-iron phase system cement.Institute is calculated with Rietveld Full _ pattern fittings
The mineral composition of cement is obtained, result is：Alite 30.12%, belite 42.18%, iron phase 11.5%, anhydrous calcium sulphoaluminate
5.85%, free calcium oxide 0.2%, dead plaster 10.15%.
Method according to embodiment 1 carries out setting time and intensity test, and test block is starched only for 20 × 20 × 20 mm
Test block, w/c=0.45 the results are shown in Table 9.Meanwhile test block surface is starched in observation only during the experiment, without cracking phenomena in 3 months.
Comparative example 1
According to the mineral composition of calcium sulphoaluminate-alite-belite-iron phase system clinker, tricalcium silicate-iron is classified as
Two groups of clinkers of phase system clinker and sulphoaluminate cement clinker.The raw material chemical composition of tricalcium silicate-iron phase system clinker is designed,
It is shown in Table 10.
Dispensing：Using material by wet type mixing, by raw material：Ball：Water=1：1：1 carries out.Load weighted sample is packed into the batch mixing of sealing
Tank is taken out after 1~2 h of ball milling mixing, drying.Uniformly mixed raw material add the water of about 7~10wt%, with 40 mm*40 mm of φ
Mold, 15~20 MPa of load are pressed into the raw material piece of 10~15 g.
Calcining system：The raw material piece of compression moulding is calcined, 800~1000 are raised to the heating rate of 5 DEG C/min
DEG C, 40 min are kept the temperature, firing temperature is then warming up to as 1400~1450 DEG C using the speed of 3 DEG C/min, keep the temperature 60 min, then
Clinker chilling in air, obtains tricalcium silicate-iron phase clinker.
The XRD spectrum of gained tricalcium silicate-iron phase system clinker as shown in Figure 5, passes through Rietveld Full _ pattern fitting meters
Calculate tricalcium silicate-iron phase system clinker mineral composition be：Alite 65.75%, belite 11.21%, iron phase 13.24% are dissociated
Calcium oxide 9.8%.Free calcium oxide content is excessive, and the stability that can cause later stage Behavior of Hardened Cement Paste is bad, phenomena such as cracking.
Comparative example 2
The mineral composition of sulphoaluminate cement clinker used and C3S -C2The mineral composition of S- iron phase system clinkers is the same as embodiment 3.
According to C3S -C2S- iron phase system clinkers：Sulphoaluminate cement clinker=15：85 mass ratio is mixed, and obtains sulphur
Calcium aluminate-alite-belite-iron phase system clinker.The ore deposit of gained clinker is calculated with Rietveld Full _ pattern fittings
Object forms, and result is：Alite 6.78%, belite 24.75%, iron phase 7.91%, anhydrous calcium sulphoaluminate 55.25%, dissociate oxidation
Calcium 0.41%, dead plaster 4.9%.
Intergrinding prepares cement：By above-mentioned clinker and gypsum according to 9:1 mass ratio mixing, grinding to specific surface
Product is 330~400 m2/ kg obtains calcium sulphoaluminate-alite-belite-iron phase system cement, with Rietveld Full _ pattern fitting meters
The mineral composition of gained cement is calculated, result is：Alite 4.8%, belite 22.4%, iron phase 6.7%, anhydrous calcium sulphoaluminate
51.2%, free calcium oxide 0.4%, dead plaster 14.5%.
Method according to embodiment 1 carries out setting time and intensity test, and test block is starched only for 20 × 20 × 20 mm
Test block, w/c=0.45 the results are shown in Table 11.
By the number of upper table it has been found that the cement setting time under the match ratio is rapid, early anti pressured intension is high, but 28
Its intensity is not greatly improved, and strength retraction phenomenon occurs, fails the standard for reaching design.
Claims (10)
1. a kind of method that split-phase combination prepares calcium sulphoaluminate-alite-belite-iron phase system clinker, it is characterized in that：
Calcining is formed into the different tricalcium silicate-dicalcium silicate-iron phase system clinker of temperature range and calcium sulphoaluminate-dicalcium silicate-iron
Phase system clinker is uniformly mixed at normal temperatures, obtains calcium sulphoaluminate-alite-belite-iron phase system clinker.
2. according to the method described in claim 1, it is characterized in that：The identical mineral of temperature range are formed according to calcining to make together
Standby, calcining forms the principle that the different mineral of temperature range are prepared separately, and first prepares tricalcium silicate-dicalcium silicate-iron phase respectively
System clinker and calcium sulphoaluminate-dicalcium silicate-iron phase system clinker, then both clinkers are mixed in proportion.
3. method according to claim 1 or 2, it is characterized in that：Calcium sulphoaluminate-alite-belite-iron phase system cement
The mineral composition of clinker is：Tricalcium silicate, dicalcium silicate, iron phase, anhydrous calcium sulphoaluminate, free calcium oxide, dead plaster；Sulphur
The mineral composition of calcium aluminate-dicalcium silicate-iron phase system clinker is：Calcium sulphoaluminate, dicalcium silicate, iron phase, dead plaster, trip
From calcium oxide；The mineral composition of tricalcium silicate-dicalcium silicate-iron phase system clinker is：Tricalcium silicate, dicalcium silicate, iron phase, trip
From calcium oxide.
4. according to the method described in claim 1,2 or 3, it is characterized in that：Calcium sulphoaluminate-alite-belite-iron phase the body
The mineral composition of series cement clinker and content are（wt%）：Tricalcium silicate 15~55%, dicalcium silicate 25~50%, iron phase 8~15%,
Anhydrous calcium sulphoaluminate 1~45%, free calcium oxide 0~1.5%, dead plaster 0~3%；Preferably, tricalcium silicate 15~20%,
Dicalcium silicate 25~40%, iron phase 8~15%, anhydrous calcium sulphoaluminate 30-45%, free calcium oxide 0~1%, dead plaster 0~
3%。
5. according to the method described in claim 1,3 or 4, it is characterized in that：Calcium sulphoaluminate-dicalcium silicate-iron phase system clinker
Mineral composition and weight percentage are：Calcium sulphoaluminate 50~70%, dicalcium silicate 15~30%, iron phase 2~10%, anhydrous slufuric acid
Calcium 0~8%, free calcium oxide 0~0.5%；The mineral composition of tricalcium silicate-dicalcium silicate-iron phase system clinker and weight percent
Content is：Tricalcium silicate 40~60%, dicalcium silicate 30~50%, iron phase 8~20%, free calcium oxide 0.1~1.5%.
6. according to the method any one of claim 1-5, it is characterized in that：The iron phase chemical formula is C4AxF2-x, wherein 0
≤ X ＜ 2, wherein, C=Ca, A=Al, F=Fe.
7. according to the method any one of claim 1-5, it is characterized in that：Calcining forms that temperature range is identical to be referred to calcine
The calcining heat of formation mineral is same or similar, and the calcining of tricalcium silicate-dicalcium silicate-iron phase system clinker forms temperature range
To be more than or equal to 1380 DEG C, the calcining of calcium sulphoaluminate-dicalcium silicate-iron phase system clinker forms temperature range as 1250~1300
℃。
8. according to the method any one of claim 1-5, it is characterized in that：Tricalcium silicate-dicalcium silicate-iron phase system is ripe
Expect that three rate values are respectively：KH=0.80~0.87, SM=2.5~3.66, IM=0~0.64.
9. according to the method any one of claim 1-5, it is characterized in that：Tricalcium silicate-dicalcium silicate-iron phase system is ripe
The preparation method of material comprises the following steps:
（1）Raw material amount is calculated in mineral composition according to tricalcium silicate-dicalcium silicate-iron phase system clinker, by raw material amount into
Row dispensing obtains uniformly mixed raw material；
（2）Raw material at 1380~1500 DEG C are calcined, then chilling, obtain tricalcium silicate-dicalcium silicate-iron phase system
Clinker.
10. a kind of preparation method of calcium sulphoaluminate-alite-belite-iron phase system cement, it is characterized in that：It will according to right
The method that the split-phase combination any one of 1-9 is asked to prepare calcium sulphoaluminate-alite-belite-iron phase system clinker
Calcium sulphoaluminate-alite-belite-iron phase system clinker is made, then mixes the clinker and gypsum, mixing material
It closes, grinding, obtains calcium sulphoaluminate-alite-belite-iron phase system cement.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128038A (en) * | 2019-05-15 | 2019-08-16 | 盐城工学院 | Tricalcium silicate-dicalcium silicate-calcium sulphoaluminate cement and its low temperature preparation method |
| CN115286267A (en) * | 2022-08-18 | 2022-11-04 | 河北鼎星水泥有限公司 | Low-alkali high-strength cement clinker and processing technology thereof |
| CN116161883A (en) * | 2023-03-07 | 2023-05-26 | 南京工业大学 | High-alite-belite-calcium sulfoaluminate gelled material synthesized at low temperature by utilizing industrial solid waste and method |
| CN116768505A (en) * | 2023-06-19 | 2023-09-19 | 南京工业大学 | Ion doping prepared alite-belite-calcium sulfoaluminate cement clinker and method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103649A (en) * | 1986-05-28 | 1987-12-09 | 国家建筑材料工业局建筑材料科学研究院 | The composition and the manufacture method of A Lite calcium sulphoaluminate cement |
| EP0476941A1 (en) * | 1990-09-14 | 1992-03-25 | Capitol Aggregates, Inc. | Cementitious compositions and method |
| CN1165118A (en) * | 1996-05-14 | 1997-11-19 | 范宗锡 | Separately fired combination series cement and its production method |
| CN1785876A (en) * | 2005-10-24 | 2006-06-14 | 南京工业大学 | High alite silicate cement clinker and its preparation method |
| CN101560066A (en) * | 2008-04-16 | 2009-10-21 | 朱成林 | Low-clinker cement |
| CN104326687A (en) * | 2014-10-16 | 2015-02-04 | 中国建筑材料科学研究总院 | C3S (3CaO.SiO2) type sulfoaluminate cement clinker and preparation method |
| CN104761165A (en) * | 2015-03-23 | 2015-07-08 | 苏州市德莱尔建材科技有限公司 | Composite portland cement and preparation method thereof |
-
2017
- 2017-12-28 CN CN201711458388.XA patent/CN108101399B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86103649A (en) * | 1986-05-28 | 1987-12-09 | 国家建筑材料工业局建筑材料科学研究院 | The composition and the manufacture method of A Lite calcium sulphoaluminate cement |
| EP0476941A1 (en) * | 1990-09-14 | 1992-03-25 | Capitol Aggregates, Inc. | Cementitious compositions and method |
| CN1165118A (en) * | 1996-05-14 | 1997-11-19 | 范宗锡 | Separately fired combination series cement and its production method |
| CN1785876A (en) * | 2005-10-24 | 2006-06-14 | 南京工业大学 | High alite silicate cement clinker and its preparation method |
| CN101560066A (en) * | 2008-04-16 | 2009-10-21 | 朱成林 | Low-clinker cement |
| CN104326687A (en) * | 2014-10-16 | 2015-02-04 | 中国建筑材料科学研究总院 | C3S (3CaO.SiO2) type sulfoaluminate cement clinker and preparation method |
| CN104761165A (en) * | 2015-03-23 | 2015-07-08 | 苏州市德莱尔建材科技有限公司 | Composite portland cement and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴红: "硅酸盐水泥和硫铝酸盐水泥复合的生态设计", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 曹文聪等: "《普通硅酸盐工艺学》", 31 August 1996, 武汉工业大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128038A (en) * | 2019-05-15 | 2019-08-16 | 盐城工学院 | Tricalcium silicate-dicalcium silicate-calcium sulphoaluminate cement and its low temperature preparation method |
| CN115286267A (en) * | 2022-08-18 | 2022-11-04 | 河北鼎星水泥有限公司 | Low-alkali high-strength cement clinker and processing technology thereof |
| CN116161883A (en) * | 2023-03-07 | 2023-05-26 | 南京工业大学 | High-alite-belite-calcium sulfoaluminate gelled material synthesized at low temperature by utilizing industrial solid waste and method |
| CN116161883B (en) * | 2023-03-07 | 2023-11-24 | 南京工业大学 | High-alite-belite-calcium sulfoaluminate gelled material synthesized at low temperature by utilizing industrial solid waste and method |
| CN116768505A (en) * | 2023-06-19 | 2023-09-19 | 南京工业大学 | Ion doping prepared alite-belite-calcium sulfoaluminate cement clinker and method |
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