CN104058617B - A kind of Portland clinker and preparation method thereof - Google Patents
A kind of Portland clinker and preparation method thereof Download PDFInfo
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- CN104058617B CN104058617B CN201410265848.7A CN201410265848A CN104058617B CN 104058617 B CN104058617 B CN 104058617B CN 201410265848 A CN201410265848 A CN 201410265848A CN 104058617 B CN104058617 B CN 104058617B
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Abstract
The invention discloses a kind of Portland clinker, wherein the R type alites containing trace magnesium and trace amounts of phosphorus, and percentage by weight 52%~64%.A kind of preparation method of Portland clinker is also disclosed, is comprised the following steps：Step 1, raw material component is selected according to the composition of required clinker and determines the weight proportion of each raw material component, raw material component includes at least one containing magnesium raw material, including at least one phosphorous raw material；Step 2, above-mentioned raw material component is sufficiently mixed, then through high-temperature calcination, quickly cooling to room temperature is prepared into clinker；In the clinker, phosphorus content presses oxide P2O5Meter, weight/mass percentage composition is 0.5%~1.2%；Content of magnesium is based on oxide M gO, and weight/mass percentage composition is 1%~5%.It is R types that the inventive method, which prepares tricalcium silicate in gained clinker, and clinker compression strength can be greatly improved compared with the clinker that this technology is not carried out.
Description
Technical field
The present invention relates to building material technical field, more particularly to a kind of Portland clinker, and the silicate
The preparation method of clinker.
Background technology
Portland cement has been used till today, has been most widely used inorganic coagulation material since the invention always.China's cement
Yield occupies the first in the world for continuous more than 20 years, accounts for the 60% of world's cement total output up to 24.1 hundred million tons within 2013, its
In, portland cement accounts for more than 98%.Huge quantity meets national construction demand, but oeverall quality is advanced apart from the world
Level still has gap：Intensity is relatively low, energy consumption is larger, restricts industry value chain.
Portland cement is, by Portland clinker, to be mixed into a small amount of gypsum and mixing material is prepared from.The water of high-quality
Mud depends primarily on clinker.The Mineral Composition Features of Portland clinker are all with alite mineral (tricalcium silicate 3CaO
SiO2=C3S solid solution) based on, it is other to also have belite mineral (dicalcium silicate 2CaOSiO2=C2S solid solution), aluminium
Sour DFP (3CaOAl2O3=C3A), tetra calcium aluminoferrite (4CaOAl2O3·Fe2O3=C4The mineral such as AF).Alite is several
Preferably, content highest determines a series of basic performances such as condensation and the intensity of cement to comprehensive physical and chemical performance in mineral.Therefore carry
The key of high portland cement quality is to improve alite content or improves alite activity.But improving alite content can not
Cause the problems such as sinter leaching is difficult with avoiding.Alite there are 7 kinds of crystal formations of 3 crystallographic systems, i.e., three tiltedly (T comprising T1,
T2, T3), monocline (M include M1, M2, M3), tripartite (R), they can mutually be converted in different temperatures scope.This 7 kinds of crystalline structures
Symmetry is gradually raised by T1 to R, and activity also increases successively.Therefore, the stable R types C for obtaining high activity Gao Jiewen3S is to improve
Clinker quality it is most basic the problem of.C can also be adjusted by heat treatment etc. by changing sinter leaching technique3S crystal formations, but its preparation
Cross in range request natural cooling or cooling procedure and be incubated, this not only conforms to existing clinker production technology, and can produce greatly
Energy waste.It can be seen that, do not changing existing firing process, do not increasing under sinter leaching energy consumption, it is steady by Doped ions
Determine high activity Alite crystal, play the effect that Doped ions optimization improves alite intensity, be the basic of raising clinker strength
Approach.Different crystal forms C can be prepared by ion doping3S, the pure C of existing document report3Introducing high additive Zn, Cu or Ti in S can
Stablize R types, but these technical schemes are not only limited by raw material sources, and the heavy metal Zn and Cu of introducing can also prepared or applied
The certain destruction of Cheng Zhonghui generations or potential safety hazard.Especially clinker is that a baroque Ca-Si-Al-Fe of composition is more
First system, causes the Modulatory character for being difficult to break through crystal formation, not yet obtains the stable R types C of high efficient and reliable suitable for clinker3S is carried
The method of high clinker strength.
The content of the invention
The purpose of the present invention is to propose to a kind of preparation method of Portland clinker, make the Portland clinker of preparation
Middle alite is the R types of high activity, improves clinker strength, to solve to need in the prior art to change sinter leaching technique or need
Mix the problem of heavy metal Zn, Cu or F etc. cause environmental pollution.
In order to solve the above-mentioned technical problem, present invention employs following technical scheme：
A kind of preparation method of Portland clinker, comprises the following steps：
Step 1, raw material component is selected according to the composition of required clinker and determines the weight proportion of each raw material component, it is raw
Expect that component includes at least one containing magnesium raw material, and including at least one phosphorous raw material；
Step 2, above-mentioned raw material component is sufficiently mixed, then through high-temperature calcination, quickly cooling to room temperature is prepared into cement
Clinker；
In the clinker, phosphorus content presses oxide P2O5Meter, weight/mass percentage composition is 0.5%~1.2%；Magnesium contains
Amount is based on oxide M gO, and weight/mass percentage composition is 1%~5%.
The preparation method of Portland clinker as described above, further, the temperature range of high-temperature calcination is at 1400 DEG C
~1500 DEG C.
The preparation method of Portland clinker as described above, further, grinding, control is carried out by gained clinker
Sample fineness grinding is to 320~360m of specific surface area2/kg。
There is Portland clinker prepared by the above method, wherein containing trace magnesium and trace amounts of phosphorus, and percentage by weight
52%~64% R type alites.
Portland clinker as described above, comprising following components, percentage,
R type alites C3S：52%~64%；
Belite C2S：14%~26%；
Tricalcium aluminate C3A：6%~11%；
Tetra calcium aluminoferrite C4AF：9~15%；
Free calcium oxide f-CaO：0~1.5%；
Surplus is other phases, wherein the trace magnesium is calculated as 1%~5% with MgO；The trace amounts of phosphorus is with P2O5It is calculated as 0.5%
~1.2%.
Portland clinker as described above, further, the percentage by weight of R type alites is 54%~60%.
Compared with prior art, the beneficial effects of the present invention are：
1st, preparation method of the invention realizes stable R types C by ensureing the content of magnesium and phosphorus in clinker3It is strong that S improves clinker
The purpose of degree, additionally addition fluorine, sulphur etc. do not pollute the component of environment, and Environmental Safety is reliable, and raw materials used wide material sources, application
Property is strong.
2nd, preparation method of the invention does not change existing production technology, does not increase sinter leaching energy consumption, greatly improved ripe
Expect intensity.
3rd, clinker strength prepared by the present invention is high, when preparing the cement of equality strength grade, can reduce clinker dosage, plus
Big mixing material consumption, improves the effectiveness of clinker, energy-conserving profit waste emission reduction.
4th, it is R types that the inventive method, which prepares tricalcium silicate in gained clinker, and this skill is relatively not carried out in clinker compression strength
The clinker of art can be greatly improved.
Brief description of the drawings
The alite local feature fingerprint region schematic diagram that Fig. 1 a are sample A in the embodiment of the present invention 1；
The alite local feature fingerprint region schematic diagram that Fig. 1 b are sample B in the embodiment of the present invention 1；
The alite local feature fingerprint region schematic diagram that Fig. 1 c are sample C in the embodiment of the present invention 1；
The alite local feature fingerprint region schematic diagram that Fig. 1 d are sample D in the embodiment of the present invention 1；
Fig. 2 is the alite local feature fingerprint region schematic diagram of sample C0 and C1 in the embodiment of the present invention 2；
The alite local feature fingerprint region schematic diagram that Fig. 3 is sample E in the embodiment of the present invention 4；
Fig. 4 is the alite local feature fingerprint region schematic diagram of sample F in the embodiment of the present invention 4；
The alite local feature fingerprint region schematic diagram that Fig. 5 is sample G in the embodiment of the present invention 4；
The alite local feature fingerprint region schematic diagram that Fig. 6 is sample H in the embodiment of the present invention 4.
Embodiment
The present invention is described in further detail with reference to specific embodiment, but it is not as a limitation of the invention.
The present invention is directed to the main provider of this cement clinker strength of alite, by complicated multicomponent system clinker
It is middle to introduce regulation and control component, alite is retained the R crystal formations of high activity, prepare R type alite silicate cement clinkers, realize and improve
The purpose of cement clinker strength.In the clinker system of general typical case's composition, inevitably solid solution simultaneously has Na to alite+、K+、Mg2+、Al3+、Fe3+Phosphorus is not often contained etc. different kinds of ions, in clinker or containing very micro phosphorus (usual 0~0.3wt%
In terms of the oxide of phosphorus), alite is mainly monocline M3 crystal formations.The present invention is by adjusting Mg contents in clinker, separately in clinker
The phosphorus of certain content is introduced, the clinker of the type alites of R containing high activity can be prepared.
Embodiment 1：
Design clinker mineral composition is followed successively by C3S：61%, C2S：20%, C3A：7% and C4AF：12%, raw material rate value point
Wei not KH=0.898, n=2.5, p=1.31, content of MgO 2% in clinker, with containing CaHPO4·2H2Containing based on O mineral forms
Phosphorus raw material is phosphorus source (following examples are same), and phosphorus introduction volume is 1%P in clinker2O5.A as a comparison is free of magnesium in clinker
With phosphorus；B as a comparison contains magnesium but not phosphorous in clinker；C as a comparison is free of magnesium but phosphorous in clinker.Gained cement
Clinker chemical composition is shown in Table 1.Coordinate each raw material by the raw-meal ingredient of calculating and be mixed evenly, the raw material mixed are through high temperature furnace
Chilling after 1450 DEG C of calcinings.By the chamotte crushing grinding after cooling, clinker fineness ratio is controlled using Blain specific surface analyzer
Surface area is (340 ± 20) m2/kg。
The chemical composition of the clinker of table 1
Fig. 1 gives 32 °~33 ° of the local feature fingerprint region of alite in prepared clinker sample, 51 °~52 ° scopes
Diffraction peak figure (deducted Cu Kα2Diffraction).Mg and P is free of in sample A, because the solid solution of other impurity causesWith(224)
Interplanar distance approach, cause two crystallographic plane diffraction peaks to merge, between 51 °~52 °(620)Two acromions that diffraction maximum or so is present,
Monocline M1 crystal formations and monocline M3 crystal formations are corresponded to respectively(040)Diffraction maximum, shows the mix-crystal that alite is M1 and M3 in A samples
Type.P is free of containing 2%MgO in sample B, has the small peak of 3 bifurcateds between 32 °~33 °, is 2 points at 51 °~52 °
Small peak is pitched, typical M3 crystal formations are shown as.MgO presence can promote to burn till and influence solid solution reaction, contain 1% in sample C
P2O5But without Mg, cause the presence of larger amount of C in clinker2S, aliteWith(224)Crystal face diffraction despite the presence of conjunction
And still suffered between phenomenon, but 51-52 °(620)With(040)Two crystallographic plane diffraction peaks, it is M3 crystal formations to show it.(the sample of embodiment 1
D 2%MgO and 1%P is contained in) simultaneously2O5, 32 °~33 ° only two diffraction maximums, and an also only R between 51-52 °
Type(220)Crystallographic plane diffraction peak, shows that alite is R types in D clinkers.
Clinker obtained by above-mentioned preparation is mixed into 5% gypsum, resistance to compression has been carried out to clinker sample according to GB/T17671-1999
Intensity experiment.40mm × 40mm × 40mm glue sand test blocks are made in the ratio of mud 0.5, the mix that adds water, and by standard curing, determine respectively
Its 3 days, 7 days, 28 days and 90 days compression strength, are shown in Table 2.
The clinker sample free calcium levels of table 2, specific surface area and strength character
Embodiment 2：
According to the chemical composition of the current special clinker of China's reference cement (hereinafter referred to as benchmark clinker) and mineral composition, design
Clinker mineral composition is followed successively by C3S：60%, C2S：23%, C3A：7% and C4AF：10%, raw material rate value is respectively KH=
Phosphorus introduction volume is 0.6%P in content of MgO 2.57%, clinker in 0.887, n=2.95, p=1.44, clinker2O5, clinker chemical group
Into being shown in Table 3.Coordinate each raw material by the raw-meal ingredient of calculating and be mixed evenly, the raw material mixed are after 1450 DEG C of calcinings of high temperature furnace
Chilling.By the chamotte crushing grinding after cooling, Blain specific surface analyzer is used to control clinker fineness specific surface area for (340
±20)m2/kg。
The chemical composition of the clinker of table 3
Fig. 2 gives 32 °~33 ° of the local feature fingerprint region of prepared clinker sample alite, 51 °~52 ° scopes
Diffraction peak figure (has deducted Cu Kα2Diffraction).Alite has the small of 3 bifurcateds between 32 °~33 ° in benchmark clinker sample C0
Peak, is 2 bifurcated small peaks at 51 °~52 °, is M3 crystal formations.Work as 0.6%P2O5After being incorporated into clinker, M3 crystal formations position pair
AnswerWith(224)Crystallographic plane diffraction peak disappears, and R crystal formations only occursCrystal face diffraction, M3 crystal formations are originally between 51-52 °
Exist(620)With(040)Two crystallographic plane diffraction peaks also disappear, and R types only occur(220)Crystal face diffraction, shows the C1 clinkers of embodiment 2
Middle alite is high activity R types.
Compression strength experiment has been carried out to clinker sample according to GB/T17671-1999.The ratio of mud 0.5, the mix that adds water is made
40mm × 40mm × 40mm glue sand test blocks, by standard curing, determines it 3 days respectively, and 7 days, 28 days and 90 days compression strength is shown in
Table 4.
The clinker sample free calcium levels of table 4, specific surface area and strength character
Embodiment 3：
According to the chemical composition of the current special clinker of China's reference cement and mineral composition, design clinker mineral composition is successively
For C3S：60%, C2S：23%, C3A：7% and C4AF：10%, raw material rate value is respectively KH=0.887, n=2.95, p=
1.44, content of MgO 2.56% in clinker, phosphorus introduction volume is 1%P in clinker2O5Dispensing, clinker chemical composition is shown in Table 5.By calculating
Raw-meal ingredient coordinate each raw material and be mixed evenly, raw material chilling after 1450 DEG C of calcinings of high temperature furnace.Clinker after cooling is broken
Flour is ground, and uses Blain specific surface analyzer to control clinker fineness specific surface area for (340 ± 20) m2/kg。
The chemical composition of the clinker of table 5
Compression strength experiment has been carried out to clinker sample according to GB/T17671-1999.The ratio of mud 0.5, the mix that adds water is made
40mm × 40mm × 40mm glue sand test blocks, by standard curing, determines it 3 days respectively, and 7 days, 28 days and 90 days compression strength is shown in
Table 6.
The clinker sample free calcium levels of table 6, specific surface area and strength character
Embodiment 4：
According to the chemical composition of the current special clinker of China's reference cement and mineral composition, design clinker mineral composition is successively
For C3S：60%, C2S：23%, C3A：7% and C4AF：10%, raw material rate value is respectively KH=0.887, n=2.95, p=
1.44, content of MgO is set to phosphorus introduction volume in 2.59%, 2.58%, 2.55%, 0.50% and 1%, clinker and distinguished in clinker
For 0%P2O5, 0.3%P2O5, 1.5%P2O5, 1.0%P2O5And 0.6%P2O5, clinker chemical composition is shown in Table 7.By the life of calculating
Material proportioning coordinates each raw material and is mixed evenly, the raw material mixed chilling after 1450 DEG C of calcinings of high temperature furnace.Will be ripe after cooling
Expect crushing and grinding, use Blain specific surface analyzer to control clinker fineness specific surface area for (340 ± 20) m2/kg。
The chemical composition of the clinker sample of table 7
Fig. 3, Fig. 4, Fig. 5 and Fig. 6 sets forth 32 ° of the local feature fingerprint region of alite in prepared clinker sample~
33 °, the diffraction peak figure of 51 °~52 ° scopes (has deducted Cu Kα2Diffraction).Contain 2.58%MgO and a small amount of 0.3% in sample E
P2O5Although,With(224)Two crystallographic plane diffraction peaks merge, but between 51 °~52 °(620)The short and small shoulder existed on the right side of diffraction maximum
Peak, correspondence monoclinic form(040)Diffraction maximum, shows that alite is monocline and the mixing crystal formation of R crystal formations in E samples.Contain in sample F
There are 2.55%MgO and high additive P2O5(1.5%), 32 °~33 ° only two diffraction maximums, and also only one between 51-52 °
R types(220)Crystallographic plane diffraction peak, shows that alite is R types in the clinker, but because P volumes are too high so that sinter leaching is difficult, ripe
There is a certain amount of C in material2S, and cause phosphate that non-solid solution is there are in clinker so that clinker Early-age behavior decline (see
Table 8).Contain a small amount of MgO (0.5%) and 1%P in sample G2O5, because the solid solution of the impurity such as Mg, P causesWith(224)Crystalline substance
Interplanar distance is approached, and causes two crystallographic plane diffraction peaks to merge, but between 51 °~52 °(620)The short and small acromion existed on the right side of diffraction maximum, it is right
Answer monoclinic form(040)Diffraction maximum, shows that alite is monocline and the mixing crystal formation of R crystal formations in G samples.Embodiment 4 (sample H)
In contain 1%MgO and 0.6%P2O5, 32 °~33 ° only two diffraction maximums, and an also only R type between 51-52 °(220)It is brilliant
Face diffraction maximum, shows that alite is R types in the clinker.
Compression strength experiment has been carried out to clinker sample according to GB/T17671-1999.The ratio of mud 0.5, the mix that adds water is made
40mm × 40mm × 40mm glue sand test blocks, by standard curing, determines it 3 days respectively, and 7 days, 28 days and 90 days compression strength is shown in
Table 8.
The clinker sample free calcium levels of table 8, specific surface area and strength character
Above example is only the exemplary embodiment of the present invention, is not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art can make respectively in the essence and protection domain of the present invention to the present invention
Modification or equivalent substitution are planted, this modification or equivalent substitution also should be regarded as being within the scope of the present invention.
Claims (6)
1. a kind of Portland clinker, it is characterised in that wherein containing trace magnesium and trace amounts of phosphorus, and percentage by weight 52%
~64% R type alites, magnesium is calculated as 2.01%~5% with MgO, and phosphorus is with P2O5It is calculated as 0.5%~1.2%.
2. Portland clinker according to claim 1, it is characterised in that include following components, weight percent
Meter,
R type alites：52%~64%；
Belite：14%~26%；
Tricalcium aluminate：6%~11%；
Tetra calcium aluminoferrite：9~15%；
Free calcium oxide：0~1.5%；
Surplus is other phases.
3. Portland clinker according to claim 1, it is characterised in that the percentage by weight of R type alites is
54%~60%.
4. the preparation method of Portland clinker according to claim 1, it is characterised in that methods described includes following
Step：
Step 1, raw material component is selected according to the composition of required clinker and determines the weight proportion of each raw material component, raw material group
Dividing includes at least one containing magnesium raw material, including at least one phosphorous raw material；
Step 2, above-mentioned raw material component is sufficiently mixed, then through high-temperature calcination, quickly cooling to room temperature is prepared into clinker；
In the clinker, phosphorus content presses oxide P2O5Meter, weight/mass percentage composition is 0.5%~1.2%.
5. the preparation method of Portland clinker according to claim 4, it is characterised in that the temperature model of high-temperature calcination
It is trapped among 1400 DEG C~1500 DEG C.
6. the preparation method of Portland clinker according to claim 4, it is characterised in that enter gained clinker
Row grinding, control sample fineness grinding to 320~360m of specific surface area2/kg。
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| CN1315749C (en) * | 2004-09-14 | 2007-05-16 | 中国建筑材料科学研究院 | High strength silicate clinker and its preparing method |
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