CN117486514A - High corrosion resistant belite sulphoaluminate cement clinker, and preparation method and application thereof - Google Patents
High corrosion resistant belite sulphoaluminate cement clinker, and preparation method and application thereof Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 142
- 235000012241 calcium silicate Nutrition 0.000 title claims abstract description 61
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 61
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000005260 corrosion Methods 0.000 title claims abstract description 49
- 230000007797 corrosion Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 9
- 239000011707 mineral Substances 0.000 claims abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 54
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 23
- 239000010440 gypsum Substances 0.000 claims description 23
- 229910052602 gypsum Inorganic materials 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000004683 dihydrates Chemical class 0.000 claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 19
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 19
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 9
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052742 iron Inorganic materials 0.000 abstract description 17
- 230000003628 erosive effect Effects 0.000 abstract description 16
- 239000013535 sea water Substances 0.000 abstract description 15
- 238000011161 development Methods 0.000 abstract description 7
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 21
- 238000006703 hydration reaction Methods 0.000 description 11
- 230000036571 hydration Effects 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 229910052925 anhydrite Inorganic materials 0.000 description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 238000009991 scouring Methods 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- -1 alcohol amine ester Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000003469 silicate cement Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 101150034433 terC gene Proteins 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
- C04B7/3453—Belite cements, e.g. self-disintegrating cements based on dicalciumsilicate
-
- 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
Landscapes
- 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 invention discloses a belite sulphoaluminate cement clinker with high corrosion resistance, a preparation method and application thereof, wherein the mineral composition of the cement clinker comprises the following components in percentage by mass: c (C) 3 S 6％～15％、C 2 S42％～54％、C 4 A 3 20 to 30 percent and C 4 AF 15-22%. The high corrosion resistant belite sulphoaluminate cement clinker of the invention introduces a proper amount of C in the phase composition 3 S, and improve C 4 AF content, which is a four-phase cement clinker complemented by belite, she Limi special dominant alite and iron phase, is used for the development coordination of the strength of each age in cement, has good 28d bonding strength and has good seawater erosion resistance.
Description
Technical Field
The invention relates to the technical field of cement, in particular to belite sulphoaluminate cement clinker with high corrosion resistance, and a preparation method and application thereof.
Background
Portland Cement (OPC) in Aliskit (C) 3 S) is the main mineral phase and is widely used throughout the world. However, the production of OPC releases a large amount of CO 2 At the same time, it also needs a firing temperature above 1450 deg.C, and needs to eliminateConsuming a great amount of fuel. Therefore, the total carbon dioxide emission produced in the cement industry is always high. And silicate cement contains a large amount of C 3 S。C 3 Hydration products of S, in particular Ca (OH) 2 Are more vulnerable to attack by sulfate ions when used in ocean engineering.
Compared with the traditional common silicate cement, the calcination temperature of the high belite sulphoaluminate cement is reduced by about 100-200 ℃, and the limestone consumption required by clinker calcination is reduced by 20-30%, so that the energy consumption and carbon emission in the cement production process can be obviously reduced, and the method has great advantages in the aspect of solving the energy conservation and emission reduction problems in the cement industry. Meanwhile, the high belite sulphoaluminate cement is prepared by the method of preparing belite (C 2 S) and calcium sulfoaluminate (She Limi terC) 4 A 3 Of the main minerals, C 4 A 3 The high belite sulphoaluminate cement has the excellent performances of quick setting and hardening, high early strength, micro expansion, low shrinkage, good freezing resistance, good impermeability, good corrosion resistance and the like, and has very good prospects in the projects of rush repair, rush construction, seepage prevention and leakage stoppage, maritime work construction, repair and reinforcement and the like.
However, due to C in high belite cements 4 A 3 Hydration is fast only beneficial to improving early strength, C 2 The slow S hydration mainly contributes to the later strength, but the whole cement can lead to the phenomena of high early strength, insufficient medium strength increase and even inverted later strength of the high belite cement. At the same time due to C 4 A 3 Hydration does not produce OH - The pH value of the pore solution of the hydration product in early and middle stages is lower, which is unfavorable for resisting Cl in seawater - Erosion. The common high belite sulphoaluminate cement cannot cope with the problem of marine environment scouring due to the excessively low iron phasor, and the application range of the sulphoaluminate cement in marine engineering is limited.
At present, aiming at the problem that the strength of the high belite sulphoaluminate cement is slowly increased or even is inversely contracted, partial scholars propose a method for adding an active additive to improve the mechanical property of the high belite sulphoaluminate cement, and patent CN113880484A proposes an additive for improving the mechanical strength of the high belite sulphoaluminate cement, wherein the additive mainly comprises amino carboxylate, polyalcohol alcohol amine ester, dihydric alcohol, strong electrolyte and water. The strength of each period of age is improved along with the addition of 0.1 weight percent of the additive into the high belite sulphoaluminate cement, and the highest 28d mechanical strength can be improved by 14.1MPa. Meanwhile, aiming at the condition that the early pH value of the high belite sulphoaluminate cement is too low, partial scholars propose a method for adding alkali to improve the seawater erosion resistance, and patents
CN201910835165.3 invented an early strength sea water erosion resistant sulphoaluminate cement, through the synergistic hydration reaction of clinker, gypsum and calcium hydroxide, a large amount of ettringite and gel phase are formed, the structure is compact, and the pH of early pore solution is higher, so that the early sea water erosion resistance of cement is improved. Meanwhile, the addition of some mineral admixtures can also improve the seawater erosion resistance of the high belite sulphoaluminate cement. However, the addition of the additive is too much depending on the alkali excitation and the additive, and the effect is insufficient when the addition amount is small, and the cost is increased when the addition amount is large.
Disclosure of Invention
The invention aims to overcome the technical defects, provide a belite sulphoaluminate cement clinker with high corrosion resistance, and a preparation method and application thereof, and solve the technical problems of weak strength and weak corrosion resistance of the belite cement in the prior art.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:
in a first aspect, the present invention provides a belite sulphate aluminium cement clinker with high corrosion resistance, the mineral composition of the cement clinker comprising, in mass percent: c (C) 3 S 6％～15％、C 2 S 42％～54％、C 4 A 3 20 to 30 percent and C 4 AF 15～22％。
In a second aspect, the invention provides a preparation method of belite sulphoaluminate cement clinker with high corrosion resistance, which comprises the following steps: uniformly mixing raw materials of cement clinker in proportion, tabletting, heating, calcining, and quenching to obtain cement clinker; wherein the raw material comprises calcium carbonate, silicon oxide, aluminum oxide, ferric oxide, dihydrate gypsum, mineralizer and activator.
In a third aspect, the invention provides an application of the cement clinker in preparing belite sulphoaluminate cement with high corrosion resistance.
Compared with the prior art, the invention has the beneficial effects that:
the high corrosion resistant belite sulphoaluminate cement clinker of the invention introduces a proper amount of C in the phase composition 3 S, and improve C 4 AF content, a four-phase cement clinker complemented by belite, she Limi special dominant alite and iron phase. C (C) 3 S and C 4 Early hydration of AF solves the problem of no Ca (OH) in early hydration products 2 Resulting in a low pH and weak resistance to attack by chloride ions. At the same time due to C 3 The mechanical property of the cement in the early and middle stages can be improved, the adhesive property can be improved, and the problem of uncoordinated development of the mechanical property in the middle stage is solved. The excellent seawater erosion resistance and scouring ability of the iron phase are utilized to resist the severe environment in the seawater. Meanwhile, the iron phase is used as a liquid phase in cement, the content of the iron phase is controlled, and the problem of C is solved 3 S and C 4 A 3 And the coexistence of the two. The high corrosion resistant belite sulphoaluminate cement prepared by the cement clinker has coordinated strength development in each age, good 28d bonding strength, proper alkalinity (12.1-12.5) and good seawater erosion resistance. Compared with the traditional means of alkali excitation and additives to improve the performance of the high belite sulphoaluminate cement, the invention only adjusts the phase composition of clinker, adds a small amount of active agent and mineralizer for application, optimizes the mechanical properties from the viewpoint of cement and simultaneously obtains good seawater erosion and scouring resistance.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Aiming at the requirements of the ocean engineering on strength and seawater erosion resistance, the invention provides the belite sulphoaluminate cement with high corrosion resistance and the preparation method thereof, and the belite sulphoaluminate cement is a cement clinker with high strength, high adhesion and high erosion resistance, and can solve the problems of the high belite sulphoaluminate cement clinker in the ocean engineering in the prior art.
The first aspect of the invention provides a belite sulphoaluminate cement clinker with high corrosion resistance, which comprises the following mineral compositions in percentage by mass: c (C) 3 6 to 15 percent of S (alite, tricalcium silicate) and C 2 S (belite, dicalcium silicate) 42-54%, C 4 A 3 20 to 30 percent of (She Limi T, calcium sulfoaluminate) and C 4 AF (tetracalcium iron aluminate, iron phase) 15-22%.
Preferably, the raw material of the cement clinker comprises, by mass, 64-68 parts of calcium carbonate, 12-14.5 parts of silicon oxide, 9.5-13 parts of aluminum oxide, 3-13 parts of ferric oxide, 4-6 parts of dihydrate gypsum, 0-0.9 part of mineralizer and 0-0.5 part of activator.
Still more preferably, the raw material of the cement clinker comprises, by mass, 64 to 68 parts of calcium carbonate, 12 to 14.5 parts of silicon oxide, 9.5 to 13 parts of aluminum oxide, 4 to 13 parts of ferric oxide, 4 to 6 parts of dihydrate gypsum, 0.1 to 0.9 part of mineralizer and 0.1 to 0.5 part of activating agent.
Preferably, the activator is copper oxide.
Preferably, the mineralizer is CaF 2 。
The second aspect of the invention provides a preparation method of belite sulphoaluminate cement clinker with high corrosion resistance, which comprises the following steps:
mixing calcium carbonate, aluminum oxide, ferric oxide, silicon oxide, dihydrate gypsum, mineralizer and activator in a polyurethane mixing pipe according to a proportion, tabletting, heating in an electric furnace, calcining, rapidly taking out, and quenching by a fan to obtain cement clinker.
Preferably, the calcination temperature is 1300-1380 ℃, and the calcination time is 30-45 min.
Preferably, in the heating process, the heating rate is 5-15 ℃/min; and (5) heat preservation is carried out for 1h when the temperature is increased to 900 ℃, and then heating and calcination are continued.
A third aspect of the present invention provides the use of the above cement clinker in the preparation of a highly corrosion resistant belite-sulphate aluminium cement made from a mixture of cement clinker and gypsum.
Preferably, the mass ratio of the cement clinker to the gypsum is (80-95): (20-5).
The main mechanisms and advantages of the invention include:
(1) Compared with the common high belite sulphoaluminate cement, the high corrosion-resistant belite sulphoaluminate cement introduces a proper amount of C in the phase composition 3 S, and improve C 4 The AF content constitutes a four-phase cement complemented by belite, she Limi T dominant alite and iron phases. C (C) 3 S and C 4 Early hydration of AF solves the problem of no Ca (OH) in early hydration products 2 Resulting in a low pH and weak resistance to attack by chloride ions. At the same time due to C 3 The mechanical properties of cement in early and middle stages are improved by adding S, and the adhesive property is improved, so that the problem of uncoordinated development of the mechanical properties in middle stages is solved. The excellent seawater erosion resistance and scouring ability of the iron phase are utilized to resist the severe environment in the seawater.
(2) Due to C 3 S has a bulk formation temperature of 1400 ℃ or higher, and C 4 A 3 At this temperature, a large amount of decomposition occurs, so that C needs to be solved 3 S and C 4 A 3 And the coexistence of the two. The iron phase of the invention is used as the liquid phase in cement, silicate minerals and aluminate minerals grow in the liquid phase, and the content of the iron phase can be reduced by properly increasing the content of the iron phase 3 S and C 4 The formation temperature of A3$ increases the coexistence of both. However, the high iron phase content can cause sintering agglomeration, the cement is not easy to grind and simultaneously can cause C 4 A 3 Decomposing at a lower temperature. Therefore, the invention adds proper amount of iron phase to lead C 3 S and C 4 A 3 The coexisting temperature range is improved, and simultaneously, the seawater erosion resistance of the cement is improved, and the mechanical properties in the middle and later stages are also improved.
(3) Mineralizer CaF 2 The introduction of (C) can promote C 3 S is formed at a lower temperature. The CuO as an activator is mainly promoted in the process of promoting the formation of an iron phaseC at low temperature 3 S、C 4 A 3 Growth of the crystals. The solid solution of the copper oxide improves the hydration activity of the iron phase while reducing the firing temperature, and plays a role of the iron phase in ocean engineering greatly.
(4) The process mode of firstly preserving heat and then calcining is adopted, so that the full decomposition of calcium carbonate is ensured; quenching after calcining is completed, so that the strength of the obtained clinker is ensured to be high.
(5) The cement has coordinated strength development at each age, good 28d bonding strength and good seawater erosion resistance.
The invention is further illustrated by the following specific examples.
Example 1
The raw material for preparing the cement clinker comprises the following components in parts by weight: 66.3 parts of calcium carbonate, 13.3 parts of silicon oxide, 11.4 parts of aluminum oxide, 4.1 parts of ferric oxide and 4.9 parts of dihydrate gypsum.
The concrete preparation process of the high corrosion resistance belite sulphoaluminate cement comprises the following steps:
(1) Mixing calcium carbonate, aluminum oxide, ferric oxide, silicon dioxide and dihydrate gypsum in a polyurethane mixing pipe according to a proportion, tabletting, heating in an electric furnace, and calcining to obtain cement clinker. The temperature rising rate is 10 ℃/min, the temperature is kept at 900 ℃ for 1h to ensure the full decomposition of calcium carbonate, and then the calcination is carried out at 1380 ℃ for 30min.
(2) After quenching the cement clinker and anhydrite according to 90:10 to obtain the belite sulphoaluminate cement with high corrosion resistance, wherein the mass ratio is that the particles are ground together to be 0.75 mu m.
The cement clinker obtained in this example has the following composition measured by the Rietveld non-calibration method: c (C) 3 S：9.63％、C 2 S：47.12％、C 4 A 3 $：25.01％、C 4 AF：18.24％。
Example 2
The raw material for preparing the cement clinker comprises the following components in parts by weight: 66.7 parts of calcium carbonate, 12.9 parts of silicon oxide, 11.3 parts of aluminum oxide, 4.1 parts of ferric oxide and 5 parts of dihydrate gypsum.
The specific preparation process of the high corrosion resistance high belite sulphoaluminate cement comprises the following steps:
(1) Mixing calcium carbonate, aluminum oxide, ferric oxide, silicon oxide and dihydrate gypsum in a polyurethane mixing pipe according to a proportion, tabletting, heating in an electric furnace, and calcining to obtain cement clinker. The temperature rising rate is 10 ℃/min, the temperature is kept at 900 ℃ for 1h to ensure the full decomposition of calcium carbonate, and then the calcination is carried out at 1380 ℃ for 30min.
(2) After quenching the cement clinker and anhydrite according to 90:10 to obtain the high corrosion resistance belite sulphoaluminate cement, wherein the mass ratio of the high corrosion resistance belite sulphoaluminate cement is commonly ground to the grain diameter of 0.75 mu m.
The cement clinker obtained in this example has the following composition measured by the Rietveld non-calibration method: c (C) 3 S：13.57％、C 2 S：42.11％、C 4 A 3 $：25.79％、C 4 AF：18.53％。
Example 3
The raw material for preparing the cement clinker comprises the following components in parts by weight: 66.3 parts of calcium carbonate, 13.3 parts of silicon oxide, 11.4 parts of aluminum oxide, 4.1 parts of ferric oxide, 4.9 parts of dihydrate gypsum and 0.5 part of copper oxide.
The specific preparation process of the high corrosion resistance high belite sulphoaluminate cement comprises the following steps:
(1) The calcium carbonate, the aluminum oxide, the ferric oxide, the silicon oxide, the dihydrate gypsum and the copper oxide are uniformly mixed in a polyurethane mixing pipe according to the proportion, pressed into tablets, heated in an electric furnace and calcined to obtain the cement clinker. The temperature rising rate is 10 ℃/min, the temperature is kept at 900 ℃ for 1h to ensure the full decomposition of the calcium carbonate, and then the calcium carbonate is calcined at 1350 ℃ for 30min.
(2) After quenching the cement clinker and anhydrite according to 90:10 to obtain the high corrosion resistance belite sulphoaluminate cement, wherein the mass ratio of the high corrosion resistance belite sulphoaluminate cement is commonly ground to the grain diameter of 0.75 mu m.
The cement clinker obtained in this example has the following composition measured by the Rietveld non-calibration method: c (C) 3 S：8.57％、C 2 S：46.33％、C 4 A 3 $：23.76％、C 4 AF：21.34％。
Example 4
The raw material for preparing the cement clinker comprises the following components in parts by weight: calcium carbonate 66.3 parts of silicon oxide 13.3 parts, aluminum oxide 11.4 parts, ferric oxide 4.1 parts, dihydrate gypsum 4.9 parts, copper oxide 0.5 part and CaF 2 0.9 part.
The specific preparation process of the high corrosion resistance high belite sulphoaluminate cement comprises the following steps:
(1) Calcium carbonate, aluminum oxide, ferric oxide, silicon oxide, dihydrate gypsum, copper oxide and CaF 2 Mixing uniformly in polyurethane mixing pipe according to proportion, tabletting, heating in electric furnace, and calcining to obtain cement clinker. The temperature rising rate is 10 ℃/min, the temperature is kept at 900 ℃ for 1h to ensure the full decomposition of the calcium carbonate, and then the calcination is carried out at 1300 ℃ for 30min.
(2) After quenching the cement clinker and anhydrite according to 90:10 to obtain the high corrosion resistance belite sulphoaluminate cement, wherein the mass ratio of the high corrosion resistance belite sulphoaluminate cement is commonly ground to the grain diameter of 0.75 mu m.
The cement clinker obtained in this example has the following composition measured by the Rietveld non-calibration method: c (C) 3 S：9.85％、C 2 S：45.22％、C 4 A 3 $：24.69％、C 4 AF：20.24％。
Example 5
The raw material for preparing the cement clinker comprises the following components in parts by weight: 66.3 parts of calcium carbonate, 13.3 parts of silicon oxide, 11.4 parts of aluminum oxide, 4.1 parts of ferric oxide, 4.9 parts of dihydrate gypsum and CaF 2 0.9 part.
The concrete preparation process of the high corrosion resistance belite sulphoaluminate cement comprises the following steps:
(1) Calcium carbonate, aluminum oxide, ferric oxide, silicon oxide, dihydrate gypsum and CaF 2 Mixing uniformly in polyurethane mixing pipe according to proportion, tabletting, heating in electric furnace, and calcining to obtain cement clinker. The temperature rising rate is 10 ℃/min, the temperature is kept at 900 ℃ for 1h to ensure the full decomposition of the calcium carbonate, and then the calcination is carried out at 1300 ℃ for 30min.
(2) After quenching the cement clinker and anhydrite according to 90:10 to obtain the high corrosion resistance belite sulphoaluminate cement, wherein the mass ratio of the high corrosion resistance belite sulphoaluminate cement is commonly ground to the grain diameter of 0.75 mu m.
The cement clinker obtained in this example has the following composition measured by the Rietveld non-calibration method: c (C) 3 S：9.41％、C 2 S：48.12％、C 4 A 3 $：24.81％、C 4 AF：17.66％。
Example 6
The raw material for preparing the cement clinker comprises the following components in parts by weight: 67.2 parts of calcium carbonate, 13.6 parts of silicon oxide, 10.8 parts of aluminum oxide, 3.4 parts of ferric oxide and 4.8 parts of dihydrate gypsum.
The concrete preparation process of the high corrosion resistance belite sulphoaluminate cement comprises the following steps:
(1) Mixing calcium carbonate, aluminum oxide, ferric oxide, silicon oxide and dihydrate gypsum in a polyurethane mixing pipe according to a proportion, tabletting, heating in an electric furnace, and calcining to obtain cement clinker. The temperature rising rate is 10 ℃/min, the temperature is kept at 900 ℃ for 1h to ensure the full decomposition of calcium carbonate, and then the calcination is carried out at 1380 ℃ for 30min.
(2) After quenching the cement clinker and anhydrite according to 90:10 to obtain the high corrosion resistance belithioaluminate cement, wherein the mass ratio of the belioaluminate cement and the belioaluminate cement are jointly ground to the particle size of 0.75 mu m.
The cement clinker obtained in this example has the following composition measured by the Rietveld non-calibration method: c (C) 3 S：6.34％、C 2 S：53.43％、C 4 A 3 $：24.51％、C 4 AF：15.72％。
The cements obtained in examples 1 to 6 were subjected to performance tests, and the results are shown in Table 1. Wherein, the content of free calcium oxide (f-CaO) is measured: according to the analysis standard of GB/T176-2017 'cement chemistry analysis method', the content of f-CaO in cement clinker is measured by adopting a glycol method; the compressive strength of the cement was tested according to GB/T17671-1999 standard; the early pH of the cement was measured according to GB/T176-2017. The bond strength was measured according to JC/T2381-2016 using the mortar repair-immersion method. Testing the corrosion resistance coefficient of cement according to GB/T749-2008; the cement abrasion resistance was tested by the underwater steel ball method according to the DL/T5150-2001 test procedure.
TABLE 1 results of Cement Performance test obtained in examples 1 to 6
As can be seen from Table 1, the cements obtained in the examples of the present invention all have good compressive strength at each age, the compressive strength for 1 day is 25.1 to 31.7MPa, the compressive strength for 3 days is 32.8 to 40.9MPa, the compressive strength for 7 days is 45.8 to 53.4MPa, and the compressive strength for 28 days is 57.8 to 75.4MPa; excellent abrasion resistance (0.62-0.67 x 10) 3 h·cm 2 g -1 ) And suitable basicity (12.1 to 12.5) and corrosion resistance (corrosion resistance coefficient between 0.90 and 1.09). The method is suitable for concrete engineering projects in marine environments.
As is evident from comparison of examples 2 and 6 with example 1, the C content of cement is increased 3 The S ratio can improve the compressive strength, the bonding strength and the pH value of the cement. But increase C 3 The S content requires more liquid phase, equivalent to C 4 When AF content is low, liquid phase quantity is small, and C cannot be pushed 3 S is completely burned at 1380 ℃ to increase the f-CaO content. At the same time C 4 A low AF content also reduces the ability of the cement slurry to resist erosion and washout.
By comparing examples 3, 4 and 5 with example 1, it is known that the mineralizer calcium fluoride and the activator copper oxide have important influence on the performance of cement, and the sintering temperature can be reduced; however, the performance of example 5 (calcium fluoride addition) is even lower than that of example 1 (calcium fluoride and copper oxide are not added), which shows that the calcium fluoride can reduce various performances and inhibit the calcium fluoride when singly doped; the performance of the embodiment 4 is superior to that of the embodiment 1 and the embodiment 3 (only copper oxide is doped), so that the calcium fluoride and a proper amount of copper oxide are doped in the invention, the sintering temperature can be reduced, the comprehensive performance is effectively improved, and the synergistic effect is generated.
Compared with the prior art, the invention provides the belite sulphoaluminate cement clinker with high corrosion resistance, and the preparation method and the application thereof, wherein the clinker mineral comprises the following components in percentage by mass: c (C) 3 S 6％～15％、C 2 S 42％～54％、C 4 A 3 $20％～30％、C 4 AF 15-22%, is made of high corrosion-resistant shellfishThe Litt sulphoaluminate cement clinker and gypsum are mixed to prepare the high corrosion resistant belite sulphoaluminate cement. The alite modified high belite sulphoaluminate cement has the advantages of high strength, stable development, excellent adhesive property, good erosion resistance, good anti-abrasion performance and the like, and is suitable for repairing engineering projects in marine environments; besides high strength and abrasion resistance, the sulphoaluminate cement has low firing temperature and low carbon emission, and accords with the green development concept of the cement industry.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (9)
1. A belite-sulphate aluminium cement clinker with high corrosion resistance, characterized in that the mineral composition of the cement clinker comprises, in mass percent: c (C) 3 S 6％～15％、C 2 S 42％～54％、C 4 A 3 20 to 30 percent and C 4 AF 15～22％。
2. The high corrosion resistant belite sulphoaluminate cement clinker according to claim 1, wherein the raw materials of the cement clinker comprise, by mass, 64-68 parts of calcium carbonate, 12-14.5 parts of silicon oxide, 9.5-13 parts of aluminum oxide, 3-13 parts of ferric oxide, 4-6 parts of dihydrate gypsum, 0-0.9 part of mineralizer and 0-0.5 part of activator.
3. The high corrosion resistant belite sulphoaluminate cement clinker according to claim 2, wherein the raw materials of the cement clinker comprise, by mass, 64-68 parts of calcium carbonate, 12-14.5 parts of silicon oxide, 9.5-13 parts of aluminum oxide, 4-13 parts of ferric oxide, 4-6 parts of dihydrate gypsum, 0.1-0.9 part of mineralizer and 0.1-0.5 part of activating agent.
4. The highly corrosion resistant belite sulphoaluminate cement clinker of claim 2, wherein the activator is copper oxide.
5. The highly corrosion resistant belite sulphoaluminate cement clinker of claim 2, wherein the mineralizer is CaF 2 。
6. A method for preparing a highly corrosion resistant belite sulphate aluminium cement clinker according to any one of claims 1 to 5, comprising the steps of: uniformly mixing raw materials of cement clinker in proportion, tabletting, heating, calcining, and quenching to obtain cement clinker;
wherein the raw material comprises calcium carbonate, silicon oxide, aluminum oxide, ferric oxide, dihydrate gypsum, mineralizer and activator.
7. The method for preparing belite-sulphate aluminum cement clinker with high corrosion resistance according to claim 6, wherein the calcination temperature is 1300-1380 ℃, and the calcination time is 30-45 min.
8. The method for preparing belite-sulphate aluminum cement clinker with high corrosion resistance according to claim 6, wherein the heating rate is 5-15 ℃/min during heating; and (5) heat preservation is carried out for 1h when the temperature is increased to 900 ℃, and then heating and calcination are continued.
9. Use of a cement clinker according to any of claims 1-5 for the preparation of a highly corrosion resistant belite-sulphate aluminium cement.
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