CN116947346A - Preparation method of novel low-carbon clinker and high-activity SCM material - Google Patents
Preparation method of novel low-carbon clinker and high-activity SCM material Download PDFInfo
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- CN116947346A CN116947346A CN202310759936.1A CN202310759936A CN116947346A CN 116947346 A CN116947346 A CN 116947346A CN 202310759936 A CN202310759936 A CN 202310759936A CN 116947346 A CN116947346 A CN 116947346A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 142
- 230000000694 effects Effects 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 74
- 238000003763 carbonization Methods 0.000 claims abstract description 47
- 239000004568 cement Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003546 flue gas Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000002918 waste heat Substances 0.000 claims abstract description 21
- 239000004567 concrete Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010248 power generation Methods 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 14
- 239000011707 mineral Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 239000010440 gypsum Substances 0.000 claims description 12
- 229910052602 gypsum Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001732 Lignosulfonate Polymers 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000033558 biomineral tissue development Effects 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims description 2
- 239000010436 fluorite Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 208000031339 Split cord malformation Diseases 0.000 description 47
- 238000004645 scanning capacitance microscopy Methods 0.000 description 47
- 238000013068 supply chain management Methods 0.000 description 47
- 239000007789 gas Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 229910021532 Calcite Inorganic materials 0.000 description 11
- 238000006703 hydration reaction Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000011398 Portland cement Substances 0.000 description 6
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000001238 wet grinding Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- 239000003469 silicate cement Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
- F26B21/14—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects using gases or vapours other than air or steam, e.g. inert gases
-
- F27D17/004—
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a preparation method of a novel low-carbon clinker and high-activity SCM material, which comprises the following steps: s1, crushing novel low-carbon clinker, controlling the particle size to be less than or equal to 30mm, conveying qualified novel low-carbon clinker particles into a grinding system, and spraying carbonization auxiliary agent mixed liquor in the conveying process; the temperature after indirect heat exchange is less than or equal to 80 ℃ and CO 2 Introducing low-temperature flue gas with the concentration of more than or equal to 20% and the moisture content of 5-15% into a grinding system; s2, carbonizing for 10-20min, wherein the humidity in the grinding system is controlled to be more than 50% and the temperature is controlled to be less than or equal to 100 ℃; s3, after proper carbonization is completed, switching the flue gas, and introducing the hot flue gas at 280-320 ℃ before waste heat power generation into a grinding system for drying, grinding and cyclone collection to obtain the high-activity catalystSCM material. The invention can prepare the SCM material with higher activity by moderately carbonizing the novel low-carbon clinker, and can be applied to cement and concrete to produce carbon-bearing cement and carbon-bearing concrete.
Description
Technical Field
The invention relates to the technical field of carbon emission reduction, in particular to a preparation method of a novel low-carbon clinker and high-activity SCM material.
Background
Cement production consumes a lot of natural resources while discharging a lot of carbon dioxide. The cement industry is the third largest carbon dioxide emission source in China, and the carbon emission amount accounts for about 13% of the total carbon emission of the industry in China. In 2022, the cement yield in China is up to 21.18 hundred million tons, and the carbon dioxide emission is about 13 hundred million tons. Therefore, various strategies for energy conservation and emission reduction are proposed and adopted in academia and industry, such as reducing the cement dosage in concrete, reducing the clinker coefficient in cement, reducing carbon emission in the cement clinker production process, adopting novel biomass fuel, carbon capture, utilization and storage and the like. The use of ordinary Portland cement raw materials to fire carbonizable novel low-carbon cement at low temperatures to cope with dual-carbon emission reduction is recognized as a technically feasible path, but because carbonizable low-carbon cement is mainly applied to the concrete product industry, the popularization and application of the technology are severely restricted. Thus, if the carbonizable novel low-carbon clinker is prepared into a high-activity supplementary cementitious material, and is used in cement and concrete, so that the prepared cement and concrete become carbon-negative cement and concrete, the application range of the carbonizable novel low-carbon cement is solved, and the application range is one of effective paths for reducing carbon emission in the cement industry.
Chinese patent publication No. CN113072311a discloses a steel slag auxiliary cementing material, a preparation method and application thereof, which refers to using industrial tail gas for carbonizing steel slag micropowder, and introducing industrial tail gas with carbon dioxide concentration of 20% in the grinding process, but does not refer to the temperature range of industrial tail gas and the utilization flow of tail gas. The grinding system in the cement industry generally needs that the industrial tail gas carries a certain amount of heat to dry the materials in the grinding process, and if the industrial tail gas does not carry heat and contains a certain amount of humidity, thenThe water accounting for 8% of the steel slag can bring technical problems to a grinding system, namely, the problems that a tube mill is burnt, a vertical mill cannot discharge materials, qualified powder materials are screened and the like. The invention does not mention drying, and water is not added in the second carbonization, and as the carbonization process needs to be carried out under the condition of certain moisture, the grinding system has no drying function, namely the used industrial tail gas does not basically carry heat, the grinding belongs to semi-wet grinding, continuous grinding operation can not be realized, and the efficiency is lower. It can be seen that C is contained in the powder grinding by the semi-wet method 3 A、C 3 S、C 4 A 3 $、C 5 S 2 When the cementing materials which can be quickly hydrated when meeting water are properly carbonized, the mineral hydration process is faster than the carbonization process, so that the proper carbonization process is difficult to realize in the technology.
Low-CO published by Solida technologies Inc. at International Cement Review, 2021, 9 2 As reported in synhetic SCMs, the use of low carbon clinker with a major component of carbonizable minerals in slurry or semi-wet state with carbon dioxide-containing industrial tail gas to produce SCM materials is reported, the low carbon clinker used being mainly CS and C 3 S 2 Mainly, these two minerals do not substantially hydrate with water, but can carbonize with carbon dioxide to form calcite and amorphous silica. The technology is mainly characterized in that carbonizable minerals with basically no hydration activity are fully carbonized in a slurry state, and after carbonized products are collected and dried, SCM materials with calcite and amorphous silicon dioxide as main products are obtained. When the mixing amount of the SCM material is 20%, the activity index of 28 days is smaller than 90%, and the domestic cement industry is required to judge the good and bad activity according to the activity index of 28 days when the mixing amount of the SCM material is 30%, which means that the activity deviation of the SCM material prepared after carbonization of the carbonizable clinker of Solidar company is indicated, so that the technology is not applicable to moderate carbonization of mineral containing rapid hydration.
Generally, a relatively sufficient carbonization reaction will form a relatively large amount of calcite product with a good degree of crystallization, and the literature of the Solidar company mentions that the SCM prepared by the method contains a relatively large amount of calcite product. However, the standard of general Portland cement GB175-2021 has clear requirements on the loss on ignition of cement, and if the mixing amount of SCM is 30%, about 15% calcite can be formed by fully carbonizing. Because the content of limestone required by the PII type Portland cement is less than or equal to 5%, the ignition loss required by the Portland cement (PII and PII) is less than 3.0% and 3.5%, respectively, and the ignition loss required by the ordinary Portland cement is less than or equal to 5.0%, the ignition loss required by the standard of the fly ash GB/T1596-2017 used in cement and concrete is also less than or equal to 8.0% as a mixed material, and the doping range of the SCM material prepared after full carbonization is severely limited. The steel slag must be completely carbonized to solve the problem of poor stability, and under the technology, even if proper carbonization can be realized, the obtained SCM material mainly containing calcite has much poorer activity than that of SCM material containing amorphous calcium carbonate or poorly crystallized striations, vaterite and the like.
In summary, the carbonization process performed in the slurry state or the semi-wet state in the above two documents is relatively sufficient, and carbonized products mainly comprising calcite and amorphous silica are easily formed, wherein calcite belongs to a calcium carbonate crystal form with relatively good crystallization degree, but the activity of calcite is far lower than that of amorphous calcium carbonate, aragonite and vaterite, which are main factors affecting the activity of the mixture in the above two documents.
In the face of the problem of proper carbonization of novel low-carbon cement clinker having a faster hydration reaction property, the prior art has no moderate carbonization condition and drying function under the conditions of semi-wet grinding and slurry, so that the semi-wet grinding is difficult to realize under the condition that the existing grinding equipment in the cement industry does not have drying hot air. Therefore, with the gradual implementation of double carbon, a novel low-carbon cement clinker is sought, moderate carbon is changed into a high-activity SCM material, and the low-carbon cement clinker is finally used for forming the carbon-negative cement or the carbon-negative concrete in a silicate cement system, so that the problem to be solved is needed to be solved currently.
Disclosure of Invention
The invention provides a preparation method of a novel low-carbon clinker and high-activity SCM material for solving the problems in the prior art, wherein the novel low-carbon clinker adopts siliceous raw materials, calcareous raw materials, gypsum and mineralization additives as raw materials, the prepared novel low-carbon clinker has better carbonization capability and better hydration reaction capability, and the novel low-carbon clinker can be moderately carbonized to prepare the SCM material with higher activity and can be applied to cement and concrete to produce negative-carbon cement and negative-carbon concrete; the invention can directly utilize the carbon dioxide in the hot flue gas of the cement kiln tail generated by producing the novel low-carbon clinker without separation and purification, and can carbonize the low-carbon clinker in situ, so that the problem of poor stability can be solved without completely carbonizing like steel slag.
The invention is realized in such a way that the preparation method of the novel low-carbon clinker and high-activity SCM material comprises the following steps:
s1, conveying the novel low-carbon clinker to a crusher for crushing, controlling the particle size of the novel low-carbon clinker to be less than or equal to 30mm, conveying the crushed qualified novel low-carbon clinker particles to a grinding system through a belt, and spraying carbonization auxiliary agent mixed liquor accounting for 2-5% of the mass of the novel low-carbon clinker in the process of conveying the novel low-carbon clinker to the grinding system through the belt;
wherein, the mineral composition of the novel low-carbon clinker is as follows: comprising alpha' -C 2 S、C 4 A 3 $、C 5 S 2 $、CS、β-C 2 S, wherein alpha' -C 2 S and beta-C 2 The sum of the S content accounts for more than 40 percent of the total mass of the novel low-carbon clinker, C 4 A 3 And C 5 S 2 The sum of the contents of CS and CS accounts for more than 20% of the total mass of the novel low-carbon clinker, and the rest is a glass phase;
the temperature after indirect heat exchange is less than or equal to 80 ℃ and CO 2 Introducing low-temperature flue gas with the concentration of more than or equal to 20% and the moisture content of 5-15% into a grinding system;
s2, carbonizing the novel low-carbon clinker for 10-20min in a proper amount in the grinding process of the novel low-carbon clinker, and spraying proper amount of water to control the humidity in a grinding system to be more than 50% and the temperature to be less than or equal to 100 ℃;
s3, after the carbonization reaction of a proper amount is completed, switching the flue gas, introducing the hot flue gas at 280-320 ℃ before waste heat power generation into a grinding system for drying, grinding and cyclone collection, and collecting the dry fine powder by a powder selector to obtain the high-activity SCM material.
Preferably, in step S1, the novel low-carbon clinker is prepared by grinding siliceous raw materials, calcareous raw materials, gypsum and mineralized additives according to a certain proportion to obtain raw materials, preheating and decomposing the raw materials by a preheating and pre-decomposing system at the kiln tail, then sending the raw materials into a rotary kiln to be calcined at a calcining temperature of 1150-1250 ℃ and a rotating speed of 2-5r/min, and sending the calcined clinker into a grate cooler to be cooled to obtain the novel low-carbon clinker;
wherein, siO in the siliceous raw material 2 The content of CaO in the calcareous raw material is more than or equal to 50 percent, and the content of CaO in the calcareous raw material is more than or equal to 35 percent.
Further preferably, the mineralization additive is one or a combination of any two of fluorite, calcium fluoride, borax and boric acid; the gypsum is one of desulfurized gypsum, phosphogypsum and natural gypsum.
Preferably, in step S1, the carbonization aid mixed solution is a mixed solution composed of 99% of water, 0.5% of water reducing agent and 0.5% of grinding aid.
Further preferably, the water reducing agent is one or a combination of any two of lignosulfonate, polycyclic aromatic salt and water-soluble resin sulfonate;
the grinding aid is one or the combination of any two of triethanolamine, polyalcohol amine, polyalcohol, triisopropanolamine, ethylene glycol, propylene glycol and diethylene glycol.
Preferably, in step S1, the low-temperature flue gas is obtained by introducing 150-200 ℃ waste heat flue gas discharged from an outlet of a C1 preheater at the top of a preheating and pre-decomposition system for preparing the novel low-carbon clinker into a heat exchanger for indirect heat exchange after passing through a waste heat power generation system, and a cooling medium for indirect heat exchange of the heat exchanger is air or water.
Preferably, in step S1, the grinding system is a vertical mill system or a raymond mill system.
Preferably, in the step S2, the novel low-carbon clinker is carbonized in an appropriate amount in the grinding process to account for 5-15% of the total mass of the novel low-carbon clinker.
Preferably, in step S3, the hot flue gas is hot flue gas discharged from an outlet of a C1 preheater at the top of the preheating and pre-decomposition system for preparing the novel low-carbon clinker.
Preferably, in step S3, the sum of the contents of micro-nano amorphous calcium carbonate, aragonite and vaterite in the high-activity SCM material is 3-12%, the content of amorphous silica is 2-9%, and the 28-day activity index of the high-activity SCM material is 90-110%.
The invention also provides a high-activity SCM material, which is prepared by adopting the preparation method.
The invention also provides application of the high-activity SCM material in producing carbon-bearing cement and carbon-bearing concrete in cement and concrete.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention prepares a novel low-carbon clinker by using the existing cement process and raw materials, prepares a high-activity SCM material by carbonizing the novel low-carbon clinker and cement kiln tail flue gas, can be used as a mixed material to be mixed into ordinary Portland cement to obtain a carbon-bearing cement product, and realizes the whole-process carbon reduction, carbon capture and sealing utilization from the processes of raw materials, sintering, grinding and the like. The method comprises the steps of forming low-carbon clinker, firing at low temperature, carbonizing a novel low-carbon clinker by a grinding system to prepare a high-activity mixed material, and particularly utilizing 20-30% concentration CO in flue gas after waste heat power generation 2 And the waste heat enters a grinding system to carbonize a proper amount of the novel low-carbon clinker, the carbonized SCM material is dried by utilizing the waste heat before the waste heat power generation, and finally the high-activity SCM material is obtained by cyclone collection.
2. The invention utilizes the novel low-carbon clinker and the proper amount of the cement kiln tail flue gas to carbonize in situ to form the high-activity carbonized products of micro-nano amorphous calcium carbonate, striation stone, vaterite and the like, and the carbonized products have higher hydration reaction activity than calcite crystals formed after full carbonization in a silicate cement systemSex. In addition, the calcium-containing mineral phase in the novel low-carbon clinker is CO-treated during carbonization 2 Takes away CaO and forms amorphous SiO with surface defects at the same time of carbonate formation 2 The high-activity silica fume has higher reactivity than silica fume, so that the high-activity silica fume has high chemical reactivity in a common silicate cement composite system, and the early strength performance of the low-carbon gel material can be improved.
3. The invention overcomes the difficulty that proper carbonization can not be realized in semi-wet grinding or slurry by utilizing industrial tail gas in the prior art, and proper carbonization and waste heat drying are realized by utilizing a grinding system, so that the high-activity SCM material containing micro-nano amorphous calcium carbonate, aragonite and vaterite is prepared, excessive calcite with activity deviation is avoided being generated under full carbonization, and the doping amount of the high-activity SCM material can be increased under the condition of meeting cement standards after proper carbonization.
4. The invention uses C in novel low-carbon cement 4 A 3 And C 5 S 2 The micro-nano amorphous calcium carbonate, the striation stone, the vaterite and the amorphous silicon dioxide with hydration reaction activity can be obtained after carbonization, the early strength is improved, and the later strength is not reduced, in particular to alpha' -C in novel low-carbon cement clinker 2 S can improve the later strength, so that the SCM material prepared by carbonization has higher activity.
5. The invention fully utilizes the heat and CO contained in the flue gas generated by the waste heat 2 The method is used for carbonization and grinding processes, and utilizes hot flue gas which is discharged from the top outlet of the preheating pre-decomposition system and enters before waste heat power generation to carry out drying, grinding and powder selection collection, so that energy conservation and consumption reduction are fully realized, meanwhile, the problem that heat generated by carbonization reaction in the grinding process is insufficient to have a drying function is solved, moderate carbonization is effectively realized to obtain a high-activity SCM material, and the method accords with domestic double carbon development trend.
Drawings
FIG. 1 is a process flow diagram of the preparation of the novel low carbon clinker, high activity SCM material provided in example 1 of the present invention.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1, the preparation method of the novel low-carbon clinker and high-activity SCM material comprises the following steps:
s1, grinding siliceous raw materials, calcareous raw materials, gypsum and mineralized additives into raw materials according to a certain proportion, preheating and decomposing the raw materials by a preheating and pre-decomposing system at the kiln tail, then sending the raw materials into a rotary kiln to be calcined at the calcining temperature of 1150 ℃ and the rotating speed of 2r/min, and sending the calcined clinker into a grate cooler to be cooled to obtain the alpha' -C with the mineral composition of 40 percent 2 S and beta-C 2 S,20% C 4 A 3 And C 5 S 2 New low carbon clinker of 20% CS and 20% glass phase.
S2, conveying the novel low-carbon clinker to a crusher from a clinker warehouse for crushing, controlling the particle size of the novel low-carbon clinker to be less than or equal to 30mm, conveying the crushed qualified novel low-carbon clinker particles to a grinding system through a belt, and spraying carbonization auxiliary agent mixed liquor accounting for 2% of the mass of the novel low-carbon clinker in the process of conveying the novel low-carbon clinker to the grinding system through the belt; the carbonization auxiliary agent mixed solution is a mixed solution composed of 99% of water, 0.5% of lignosulfonate and 0.5% of triethanolamine.
S3, discharging low-temperature flue gas (the temperature is less than or equal to 80 ℃ and CO) after waste heat power generation and indirect heat exchange from an outlet of a C1 preheater at the top of a preheating and pre-decomposition system for preparing novel low-carbon clinker 2 Introducing the mixture with the concentration of more than or equal to 20 percent and the moisture content of 5-15 percent into a vertical mill system for carbonization and grinding; carbonizing a proper amount of low-carbon clinker for 10min in the grinding process of the novel low-carbon clinker, spraying a proper amount of water to control the humidity in a grinding system to be more than 50%, controlling the temperature to be less than or equal to 100 ℃, and discharging the tail gas discharged from the grinding system after dust removal to reach the standard;
s4, after 5% carbonization degree is finished, switching flue gas, introducing 280-320 ℃ hot flue gas before waste heat power generation into a grinding system for drying, grinding and cyclone collection, introducing the dried tail gas into a tail gas treatment system for treatment, discharging after reaching standards, and collecting the dry fine powder to obtain the high-activity SCM material, wherein the sum of the contents of micro-nano amorphous calcium carbonate, the texite and the vaterite in the high-activity SCM material is 3%, the content of amorphous silicon dioxide is 2%, and the 28-day activity index of the high-activity SCM material is 90%.
Example 2
A preparation method of a novel low-carbon clinker and high-activity SCM material comprises the following steps:
s1, grinding siliceous raw materials, calcareous raw materials, gypsum and mineralized additives into raw materials according to a certain proportion, preheating and decomposing the raw materials by a preheating and pre-decomposing system at the kiln tail, then delivering the raw materials into a rotary kiln to be calcined at a calcining temperature of 1250 ℃ and a rotating speed of 5r/min, delivering the calcined clinker into a grate cooler to be cooled, and obtaining the alpha' -C with a mineral composition of 40% 2 S and beta-C 2 S,20% C 4 A 3 And C 5 S 2 New low carbon clinker of 20% CS and 20% glass phase.
S2, conveying the novel low-carbon clinker to a crusher from a clinker warehouse for crushing, controlling the particle size of the novel low-carbon clinker to be less than or equal to 30mm, conveying the crushed qualified novel low-carbon clinker particles to a grinding system through a belt, and spraying carbonization auxiliary agent mixed liquor accounting for 5% of the mass of the novel low-carbon clinker in the process of conveying the novel low-carbon clinker to the grinding system through the belt; the carbonization auxiliary agent mixed solution is a mixed solution composed of 99% of water, 0.5% of lignosulfonate and 0.5% of triethanolamine.
S3, discharging low-temperature flue gas (the temperature is less than or equal to 80 ℃ and CO) after waste heat power generation and indirect heat exchange from an outlet of a C1 preheater at the top of a preheating and pre-decomposition system for preparing novel low-carbon clinker 2 Introducing the mixture with the concentration of more than or equal to 20 percent and the moisture content of 5-15 percent into a vertical mill system for carbonization and grinding; carbonizing the low-carbon clinker for 20min in the grinding process of the novel low-carbon clinker, and spraying water to control the humidity in the grinding system to be more than 50% and the temperature to be less than or equal to 100 ℃ and discharging the tail from the grinding systemThe gas is discharged after dust removal after reaching the standard;
s4, after 5-15% carbonization degree is finished, switching flue gas, introducing 280-320 ℃ hot flue gas before waste heat power generation into a grinding system for drying, grinding and cyclone collection, introducing the tail gas after drying into a tail gas treatment system for treatment, discharging after reaching standards, and collecting the dry fine powder to obtain the high-activity SCM material, wherein the sum of the contents of micro-nano amorphous calcium carbonate, the texite and the vaterite in the high-activity SCM material is 12%, the content of amorphous silicon dioxide is 9%, and the 28-day activity index of the high-activity SCM material is 110%.
Example 3
A preparation method of a novel low-carbon clinker and high-activity SCM material comprises the following steps:
s1, grinding siliceous raw materials, calcareous raw materials, gypsum and mineralized additives into raw materials according to a certain proportion, preheating and decomposing the raw materials by a preheating and pre-decomposing system at the kiln tail, then sending the raw materials into a rotary kiln to be calcined at a calcining temperature of 1205 ℃ and a rotating speed of 3r/min, and sending the calcined clinker into a grate cooler to be cooled to obtain the alpha' -C with a mineral composition of 40% 2 S and beta-C 2 S,20% C 4 A 3 And C 5 S 2 New low carbon clinker of 20% CS and 20% glass phase.
S2, conveying the novel low-carbon clinker to a crusher from a clinker warehouse for crushing, controlling the particle size of the novel low-carbon clinker to be less than or equal to 30mm, conveying the crushed qualified novel low-carbon clinker particles to a grinding system through a belt, and spraying carbonization auxiliary agent mixed liquor accounting for 3.5% of the mass of the novel low-carbon clinker in the process of conveying the novel low-carbon clinker to the grinding system through the belt; the carbonization auxiliary agent mixed solution is a mixed solution composed of 99% of water, 0.5% of lignosulfonate and 0.5% of triethanolamine.
S3, discharging low-temperature flue gas (the temperature is less than or equal to 80 ℃ and CO) after waste heat power generation and indirect heat exchange from an outlet of a C1 preheater at the top of a preheating and pre-decomposition system for preparing novel low-carbon clinker 2 Introducing the mixture with the concentration of more than or equal to 20 percent and the moisture content of 5-15 percent into a vertical mill system for carbonization and grinding; carbonizing the low-carbon clinker for 15min while sprayingA proper amount of water is added to control the humidity in the grinding system to be more than 50 percent and the temperature to be less than or equal to 100 ℃, and the tail gas from the grinding system is discharged after dust removal to reach the standard;
s4, after 5-15% carbonization degree is finished, flue gas is switched, hot flue gas at 280-320 ℃ before waste heat power generation is introduced into a grinding system for drying, grinding and cyclone collection, the tail gas after drying enters a tail gas treatment system for treatment and then is discharged after reaching standards, and the collected dry fine powder is obtained to obtain the high-activity SCM material, wherein the sum of the contents of micro-nano amorphous calcium carbonate, the texite and the vaterite in the high-activity SCM material is 8%, the content of amorphous silicon dioxide is 6.5%, and the 28-day activity index of the high-activity SCM material is 98%.
Comparative example 1
Calcining the novel low-carbon clinker obtained in the example 1 in a rotary kiln at the calcining temperature of 1150 ℃ and the rotating speed of 2r/min, and cooling the calcined low-carbon clinker in a grate cooler to obtain the alpha' -C with the mineral composition of 40 percent 2 S and beta-C 2 S,20% C 4 A 3 And C 5 S 2 Novel low-carbon clinker with CS of 20% and glass phase of 20%, and grinding the clinker into powder with specific surface area of 350m 2 According to the activity detection standard of GB/T1596-2005 'fly ash used in cement and concrete', the activity detection is carried out by replacing the high-activity SCM material in equal proportion, and the activity index is 72% after 28 days.
Comparative example 2
Calcining the novel low-carbon clinker obtained in the example 2 in a rotary kiln at a calcining temperature of 1250 ℃ and a rotating speed of 5r/min, and cooling the calcined low-carbon clinker in a grate cooler to obtain a mineral composition comprising 40 percent of alpha' -C 2 S and beta-C 2 S,20% C 4 A 3 And C 5 S 2 Novel low-carbon clinker with CS of 20% and glass phase of 20%, and grinding the clinker into powder with specific surface area of 350m 2 According to the activity detection standard of GB/T1596-2005 'fly ash used in cement and concrete', the activity detection is carried out by replacing the high-activity SCM material in equal proportion, and the activity index is 85% after 28 days.
Comparative example 3
In example 3Calcining in rotary kiln at 1205 deg.C and 3r/min, cooling the calcined low-carbon clinker in grate cooler to obtain alpha' -C with mineral composition of 40% 2 S and beta-C 2 S,20% C 4 A 3 And C 5 S 2 Novel low-carbon clinker with CS of 20% and glass phase of 20%, and grinding the clinker into powder with specific surface area of 350m 2 According to the activity detection standard of GB/T1596-2005 'fly ash used in cement and concrete', the activity detection is carried out by replacing high-activity SCM material in equal proportion, and the activity index is 80% after 28 days.
As can be seen from examples 1-3, the novel low carbon cement contains C 4 A 3 And C 5 S 2 The micro-nano amorphous calcium carbonate, the striation stone, the vaterite and the amorphous silicon dioxide with hydration reaction activity can be obtained after carbonization, the early strength is improved, and the later strength is not reduced, in particular to alpha' -C in novel low-carbon cement clinker 2 S can improve the later strength, so that the SCM material prepared by carbonization has higher activity. As is clear from comparative examples 1 to 3, the activity measured by grinding the novel low-carbon cement clinker directly into cement is far lower than that of the high-activity SCM material prepared by carbonization according to the activity detection standard, because the novel low-carbon cement clinker contains more than 40% of low-activity C 2 S and 20% or more of CS having substantially no hydration activity, and C having a part capable of promoting early strength but causing a strong collapse in the latter stage 4 A 3 $。
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the novel low-carbon clinker and high-activity SCM material is characterized by comprising the following steps of:
s1, conveying the novel low-carbon clinker to a crusher for crushing, controlling the particle size of the novel low-carbon clinker to be less than or equal to 30mm, conveying the crushed qualified novel low-carbon clinker particles to a grinding system through a belt, and spraying carbonization auxiliary agent mixed liquor accounting for 2-5% of the mass of the novel low-carbon clinker in the process of conveying the novel low-carbon clinker to the grinding system through the belt;
wherein, the mineral composition of the novel low-carbon clinker is as follows: comprising alpha' -C 2 S、C 4 A 3 $、C 5 S 2 $、CS、β-C 2 S, wherein alpha' -C 2 S and beta-C 2 The sum of the S content accounts for more than 40 percent of the total mass of the novel low-carbon clinker, C 4 A 3 And C 5 S 2 The sum of the contents of CS and CS accounts for more than 20% of the total mass of the novel low-carbon clinker, and the rest is a glass phase;
the temperature after indirect heat exchange is less than or equal to 80 ℃ and CO 2 Introducing low-temperature flue gas with the concentration of more than or equal to 20% and the moisture content of 5-15% into a grinding system;
s2, carbonizing the novel low-carbon clinker for 10-20min in a proper amount in the grinding process of the novel low-carbon clinker, and spraying proper amount of water to control the humidity in a grinding system to be more than 50% and the temperature to be less than or equal to 100 ℃;
s3, after the carbonization reaction of a proper amount is completed, switching the flue gas, introducing the hot flue gas at 280-320 ℃ before waste heat power generation into a grinding system for drying, grinding and cyclone collection, and collecting the dry fine powder by a powder selector to obtain the high-activity SCM material.
2. The method for preparing the novel low-carbon clinker and high-activity SCM material according to claim 1, wherein in the step S1, the novel low-carbon clinker is ground into raw materials according to a certain proportion by siliceous raw materials, calcareous raw materials, gypsum and mineralization additives, the raw materials are preheated and decomposed by a preheating and pre-decomposition system at the kiln tail and then are sent into a rotary kiln to be calcined at a calcining temperature of 1150-1250 ℃ and a rotating speed of 2-5r/min, and the calcined clinker is sent into a grate cooler to be cooled to obtain the novel low-carbon clinker;
wherein, siO in the siliceous raw material 2 The content of CaO in the calcareous raw material is more than or equal to 50 percent, and the content of CaO in the calcareous raw material is more than or equal to 35 percent;
the mineralization additive is one or the combination of any two of fluorite, calcium fluoride, borax and boric acid; the gypsum is one of desulfurized gypsum, phosphogypsum and natural gypsum.
3. The preparation method of the novel low-carbon clinker and high-activity SCM material according to claim 1, wherein in the step S1, the carbonization auxiliary agent mixed solution is mixed solution composed of 99% of water, 0.5% of water reducer and 0.5% of grinding aid;
the water reducer is one or the combination of any two of lignosulfonate, polycyclic aromatic salt and water-soluble resin sulfonate;
the grinding aid is one or the combination of any two of triethanolamine, polyalcohol amine, polyalcohol, triisopropanolamine, ethylene glycol, propylene glycol and diethylene glycol.
4. The method for preparing the novel low-carbon clinker and high-activity SCM material according to claim 1, wherein in the step S1, the low-temperature flue gas is obtained by introducing 150-200 ℃ waste heat flue gas discharged from a C1 preheater outlet at the top of a preheating pre-decomposition system for preparing the novel low-carbon clinker into a heat exchanger for indirect heat exchange after the waste heat flue gas passes through a waste heat power generation system, and a cooling medium for indirect heat exchange of the heat exchanger is air or water.
5. The method for preparing a novel low-carbon clinker and high-activity SCM material according to claim 1, wherein in the step S1, the grinding system is a vertical mill system or a Raymond mill system.
6. The method for preparing a novel low-carbon clinker and high-activity SCM material according to claim 1, wherein in the step S2, the novel low-carbon clinker is carbonized in an amount of 5-15% of the total mass of the novel low-carbon clinker in the grinding process.
7. The method for preparing the novel low-carbon clinker and high-activity SCM material according to claim 1, wherein in the step S3, the hot flue gas is the hot flue gas discharged from the outlet of the C1 preheater at the top of the preheating and pre-decomposition system for preparing the novel low-carbon clinker.
8. The method for preparing the novel low-carbon clinker and high-activity SCM material according to claim 1, wherein in the step S3, the sum of the contents of micro-nano amorphous calcium carbonate, aragonite and vaterite in the high-activity SCM material is 3-12%, the content of amorphous silica is 2-9%, and the 28-day activity index of the high-activity SCM material is 90-110%.
9. A high activity SCM material, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. The application of the high-activity SCM material is characterized in that the high-activity SCM material is applied to cement and concrete to produce carbon-bearing cement and carbon-bearing concrete.
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