CN114180863B - High-strength cement and production process thereof - Google Patents
High-strength cement and production process thereof Download PDFInfo
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- CN114180863B CN114180863B CN202111557116.1A CN202111557116A CN114180863B CN 114180863 B CN114180863 B CN 114180863B CN 202111557116 A CN202111557116 A CN 202111557116A CN 114180863 B CN114180863 B CN 114180863B
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- cement
- clinker
- slag
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- 239000004568 cement Substances 0.000 title claims abstract description 148
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- 239000002893 slag Substances 0.000 claims abstract description 103
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000227 grinding Methods 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- 238000001354 calcination Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 239000010440 gypsum Substances 0.000 claims abstract description 22
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 22
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 18
- 235000019738 Limestone Nutrition 0.000 claims abstract description 11
- 239000004927 clay Substances 0.000 claims abstract description 11
- 239000006028 limestone Substances 0.000 claims abstract description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 239000010881 fly ash Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 229910001294 Reinforcing steel Inorganic materials 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 31
- 230000000694 effects Effects 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 239000002440 industrial waste Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- -1 calcium carbonate aluminate Chemical class 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000003518 caustics Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 210000004127 vitreous body Anatomy 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001164 aluminium sulphate Substances 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000404 calcium aluminium silicate Substances 0.000 description 2
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 2
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 2
- 229940078583 calcium aluminosilicate Drugs 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B7/12—Natural pozzuolanas; Natural pozzuolana cements; Artificial pozzuolanas or artificial pozzuolana cements other than those obtained from waste or combustion residues, e.g. burned clay; Treating inorganic materials to improve their pozzuolanic characteristics
- C04B7/13—Mixtures thereof with inorganic cementitious materials, e.g. Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/47—Cooling ; Waste heat management
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The application relates to the technical field of cement, and particularly discloses high-strength cement and a production process thereof. The high-strength cement comprises cement clinker, a mixed material and gypsum, wherein the cement clinker comprises the following raw materials in parts by mass: 55-62 parts of limestone, 13-17 parts of clay, 3-8 parts of copper slag, 2-6 parts of alkaline slag and 1-3 parts of granulated blast furnace slag. The high-strength cement is made into raw materials after primary grinding, then the raw materials are homogenized, the homogenized raw materials are calcined, calcium salt suspension is sprayed to cool the calcined raw materials after the calcination, and the cooled clinker is ground for the second time to obtain a cement finished product. The operation of the process is simple, the cement prepared by matching the raw materials has the characteristic of high strength, and meanwhile, the corrosion of the reinforcing steel bars can be effectively slowed down in the application process of the cement.
Description
Technical Field
The application relates to the technical field of cement, in particular to high-strength cement and a production process thereof.
Background
With the development of urban construction, roads and buildings are increasing, and the demand of cement is increasing. The cement is a powdery hydraulic inorganic cementing material, is added with water and stirred to form slurry which can be hardened in the air or in the water, and the concrete prepared by mixing and stirring the cement, sand and stone is a base material for building and road construction.
Meanwhile, as a large industrial country, the copper slag accumulation is more serious, the recycling of copper slag resources is less, resources are wasted, and the influence on the environment is large. Researches verify that the copper slag has good application in the cement production process, but the untreated copper slag has low activity and poor effect when being directly applied to cement, and the strength of the prepared cement is easy to cause poor.
Disclosure of Invention
In order to enable the copper slag to have a good application effect in the cement and prepare the cement with high strength, the application provides the high-strength cement and the production process thereof.
In a first aspect, the present application provides a high strength cement, which adopts the following technical scheme:
the high-strength cement comprises cement clinker, a mixed material and gypsum, wherein the cement clinker comprises the following raw materials in parts by mass: 55-62 parts of limestone, 13-17 parts of clay, 3-8 parts of copper slag, 2-6 parts of alkaline slag and 1-3 parts of granulated blast furnace slag.
By adopting the technical scheme, the cement clinker, the mixed material and the gypsum are used as the base materials for cement production, and the cement clinker is added with the copper slag, the alkali slag and the granulated blast furnace slag, so that the waste utilization is realized, the sustainable development principle is conformed, the strength of the prepared cement is higher under the interaction of the copper slag, the alkali slag and the granulated blast furnace slag, and meanwhile, the corrosion of a steel bar structure can be effectively slowed down in the application process of the prepared cement.
First, the copper slag contains a large amount of components such as alumina and iron, and can be used as a mineralizer instead of iron powder, thereby contributing to increase the amount of the raw material forming a liquid phase, and thus promoting the reaction rate, and a large amount of metal oxide contributes to increase the strength of cement. The caustic sludge contains more calcium components which mainly exist in the forms of calcium carbonate, calcium hydroxide and calcium oxide, the caustic sludge can be used as a supplementary cementing material in a system, hydration products mainly comprise hydrated calcium silicate, hydrated calcium aluminosilicate and hydrated calcium carbonate aluminate, and the hydration products are mutually overlapped to form a three-dimensional network structure, so that the cost is saved, and the strength of the cement is improved. Meanwhile, the percentage content of calcium oxide in the copper slag is low, so that the polymerization degree of tetrahedron in the vitreous body structure in the copper slag is easily high, and the activity of the copper slag is influenced. The pH range of the alkaline residue is 10-12, and calcium hydroxide in the alkaline residue can effectively destroy the vitreous body structure in the copper residue in the alkaline environment to promote the hydrolysis of the vitreous body, so that the crystalline phase in the copper residue is effectively reduced, the activity of the copper residue is excited, and the copper residue can better participate in the system reaction. Meanwhile, under the synergistic action of the granulated blast furnace slag, the damaged crystalline phase is combined with calcium ions and aluminum ions in an alkali environment to generate C (Al) -S-H gel, so that the strength of the cement is better.
In addition, because the chloride ion content in the alkaline residue is higher, the corrosion of the steel bar structure is easily accelerated. The cement system contains more calcium oxide, the pH value of the system is alkaline, the content of aluminum oxide in copper slag and granulated blast furnace slag is higher, and more meta-aluminate exists in the system under the chemical action. The calcium oxide and the metaaluminate can generate Ca with free chloride ions in the system 2 AlCl(OH) 6 And precipitating, thereby effectively reducing the content of free chloride ions in the system and further slowing down the corrosion of the reinforcing steel bar in the cement application process.
To sum up, copper sediment, alkaline residue and the mutual effect of granulation blast furnace slay three in this application promote the intensity that makes cement in coordination to the three is industrial waste residue, and green just is favorable to practicing thrift the cost. The alkaline slag and the granulated blast furnace slag are beneficial to exciting the activity of the copper slag, and the copper slag and the granulated blast furnace slag have a good binding effect on chloride ions in the alkaline slag, so that the content of free chloride ions in a system can be effectively reduced, and the corrosion of reinforcing steel bars is slowed down. Therefore, the synergistic effect of the copper slag, the alkaline slag and the granulated blast furnace slag forms a closed loop, and the performance of the prepared cement is comprehensively improved.
Preferably, the mass ratio of the cement clinker to the mixed material to the gypsum is (12-15): (3-5): 1.
by adopting the technical scheme, the mass ratio of the cement clinker to the mixed material to the gypsum is controlled to be (12-15): (3-5): 1, the cement is beneficial to cement production, and the prepared cement has good performances in all aspects.
Preferably, Al in the granulated blast furnace slag is one hundred percent by mass 2 O 3 The content of (A) is 13.6-18.2%.
By adopting the technical scheme, Al is selected 2 O 3 The granulated blast furnace slag with the content of 13.6-18.2% so as to ensure that Al in the system 2 O 3 The content is proper, thereby being beneficial to preparing cement and being beneficial to optimizing the cement performance. Simultaneously, the copper slag is matched for chlorine ion combined extractionThe supply of an aluminum source with a proper content is helpful for reducing free chloride ions in the system, thereby slowing down the corrosion of the reinforcing steel bar in the cement application process.
Preferably, the mixed material comprises the following raw materials in percentage by mass: 50-60% of fly ash, 1-3% of grinding aid and the balance of pozzolanic matter.
By adopting the technical scheme, the fly ash and the pozzolanic are used as the active mixed materials, so that the content of the cementing material in the system can be effectively increased, and the strength of the prepared cement is better. And grinding aid is added to improve the grinding effect of the raw materials and reduce the phenomenon of being far away from agglomeration, thereby being beneficial to the production effect of cement.
Preferably, the grinding aid is prepared from diethanol monoisopropanolamine, aluminum sulfate and propylene glycol according to a mass ratio of (2.5-3.2): (1-1.4): 1, in a mixture of the components.
In a second aspect, the present application provides a production process of high strength cement, which adopts the following technical scheme:
a production process of high-strength cement comprises the following steps:
primary grinding: mixing and grinding limestone, clay, copper slag, alkaline slag and granulated blast furnace slag to obtain a rough raw material;
raw material homogenization: homogenizing the rough raw material to obtain cement raw material;
calcining to prepare clinker: calcining the cement raw material, spraying calcium salt suspension on the surface of the calcined clinker, and cooling to obtain cement clinker;
secondary grinding: and mixing and grinding the cement clinker, the mixed material and the gypsum to obtain the cement.
By adopting the technical scheme, the rough raw material after primary grinding is homogenized, so that the properties of the cement raw material such as particle size and the like are relatively close, and the reaction effect of each raw material in the subsequent calcining process is favorably improved. Meanwhile, calcium salt suspension is sprayed on the surface of the calcined clinker, so that the effect of rapid cooling can be realized, and the quality and the grindability of the clinker are improved; and the cement strength of the clinker sprayed with the calcium salt suspension is better.
Preferably, in the primary grinding step, the grinding time is 1.5-3 h.
By adopting the technical scheme, the grinding time is controlled to be 1.5-3 h, active ingredients in the copper slag, the alkaline slag and the granulated blast furnace slag are fully exposed, and the specific surface area is increased, so that the reaction degree and the reaction rate of a system are facilitated.
Preferably, in the step of calcining to prepare the clinker, the calcining temperature is 1280-1350 ℃.
By adopting the technical scheme, the calcination temperature is controlled to be 1280-1350 ℃, the activity of each raw material is fully excited, the strength of the prepared cement is better, and the reaction rate is improved.
Preferably, in the step of calcining to prepare the clinker, the mass fraction of the calcium salt in the calcium salt suspension is 17-23%, and the mass ratio of the cement clinker before calcining to the sprayed calcium salt suspension is (12-15): 1.
by adopting the technical scheme, the mass fraction of the calcium salt in the calcium salt suspension is controlled to be 17-23%, and the mass ratio of the cement clinker before calcination to the sprayed calcium salt suspension is controlled to be (12-15): 1, the rapid cooling is realized, and simultaneously, the strength of the prepared cement is further improved.
Preferably, in the step of calcining to prepare the clinker, the prepared cement clinker has a lime saturation coefficient KH of 0.916 to 0.932 and a silicic acid ratio SM of 2.05 to 2.13.
By adopting the technical scheme, the content of magnesium oxide in the raw materials is high, so that C in the cement clinker is easy to cause 3 The content of S is reduced, so that the secondary grinding effect is influenced, and the performance of the prepared cement is poor. Therefore, the lime saturation coefficient KH of the cement clinker is controlled to be 0.916-0.932, the silicic acid rate SM is controlled to be 2.05-2.13, and the negative influence of magnesium oxide on cement production can be effectively improved.
In summary, the present application has the following beneficial effects:
1. according to the method, the copper slag, the alkaline slag and the granulated blast furnace slag are used as cement production auxiliary materials, waste resources are digested, and the method is green and environment-friendly and is beneficial to saving the cost; at the same time, the copper slag,The alkali slag and the granulated blast furnace slag are mutually cooperated to excite the activity and improve the self defect, so that the prepared cement has better performance in all aspects; the method specifically comprises the steps of giving a proper alkaline environment to copper slag through alkaline slag, giving a proper content of calcium compounds to a system, destroying a vitreous body structure in the copper slag, reducing a crystalline phase in the copper slag, exciting the activity of the copper slag, promoting the generation of a gel material through the cooperation of more aluminum elements in granulated blast furnace slag and calcium elements in the alkaline environment, and further enabling the strength of the prepared cement to be high. Aiming at the condition of high system chloride ion content caused by adding alkaline residue, calcium oxide in a high-alumina coordination system in the copper slag and the granulated blast furnace slag can combine free chloride ions in the system and generate Ca 2 AlCl(OH) 6 And precipitating, thereby effectively reducing the content of free chloride ions and achieving the effect of slowing down the corrosion of the steel bars in the application process of the cement.
2. According to the method, the clinker is rapidly cooled by spraying the calcium salt suspension in the process of cooling the cement clinker, so that the secondary grinding effect of the cement clinker is better, and the strength of the prepared cement is improved.
3. According to the method, the lime saturation coefficient KH of the prepared cement clinker is controlled to be 0.916-0.932, the silicic acid rate SM is controlled to be 2.05-2.13, and the situation that secondary grinding effect of the clinker is poor due to the fact that the content of magnesium oxide is high in the process of being far away is reduced.
Detailed Description
The embodiment provides high-strength cement and a production process thereof.
The high-strength cement comprises cement clinker, a mixed material and gypsum, wherein the cement clinker comprises the following raw materials in parts by mass: 55-62 parts of limestone, 13-17 parts of clay, 3-8 parts of copper slag, 2-6 parts of alkaline slag and 1-3 parts of granulated blast furnace slag.
Wherein the mass ratio of the cement clinker to the mixed material to the gypsum is (12-15): (3-5): 1, the mixed material comprises the following raw materials in percentage by mass: 50-60% of fly ash, 1-3% of grinding aid and the balance of pozzolanic matter.
The production process of the high-strength cement comprises the following steps:
primary grinding: mixing and grinding limestone, clay, copper slag, alkaline slag and granulated blast furnace slag to obtain a rough raw material;
raw material homogenization: homogenizing the crude raw material to obtain cement raw material;
calcining to prepare clinker: calcining the cement raw material, spraying calcium salt suspension on the surface of the calcined clinker, and cooling to obtain cement clinker;
secondary grinding: and mixing and grinding the cement clinker, the mixed material and the gypsum to obtain the cement.
The clay in the cement clinker in this embodiment may be at least one of shale, kaolin, and sandstone.
In the embodiment, the copper slag in the cement clinker is waste slag generated in the copper smelting process, and the main component of the copper slag comprises 31-42% of SiO 2 、7～11％CaO，1～4％MgO、2～5％Al 2 O 3 23-35% of Fe and 2-3% of zinc.
The alkaline residue in the cement clinker in the embodiment refers to alkaline residue discharged in the alkali making and alkali treatment processes in industrial production, and the main component of the alkaline residue comprises 40-62% of CaCO 3 、4～15％CaCl 2 、4～11％NaCl、4～12％Ca(OH) 2 、2～13％CaSO 4 、3～11％MgO、1～3％Al 2 O 3 、1～10％SiO 2 、0.8～1.6％Fe 2 O 3 The pH value is 10-12.
The granulated blast furnace slag in the cement clinker in the embodiment is a glassy substance formed mostly without crystallization in the process of condensing the molten slag in the blast furnace iron making process, and the alumina content of the glassy substance is 13.6-18.2%.
The mass ratio of the cement clinker, the admixture, and the gypsum in the present embodiment is more preferably 14: 4: 1.
in the embodiment, the grinding aid in the mixed material is prepared from diethanol monoisopropanolamine, aluminum sulfate and propylene glycol according to the mass ratio of (2.5-3.2): (1-1.4): 1, and further preferably the mass ratio of the three components is 3:1.2: 1.
In the present embodiment, the fly ash in the admixture is the second-grade fly ash.
In the primary grinding step in the embodiment, the grinding time is 1.5 to 3 hours, and further preferably 2 to 3 hours.
In the step of calcining to prepare clinker in the embodiment, the calcining temperature is 1280 ℃ to 1350 ℃, and the calcining temperature is preferably 1300 ℃ to 1350 ℃.
In the step of calcining to prepare clinker, the mass fraction of calcium salt in the sprayed calcium salt suspension is 17-23%, more preferably 20-22%, and the mass ratio of the cement clinker before calcination to the sprayed calcium salt suspension is (12-15): 1, and the more preferable mass ratio is (13-14): 1.
in the step of calcining to produce clinker, the calcium salt in the calcium salt suspension includes at least one of calcium carbonate, calcium aluminosilicate and calcium carboaluminate.
In the step of calcining to prepare clinker, the lime saturation coefficient KH of the prepared cement clinker is 0.916 to 0.932, the silicic acid rate SM is 2.05 to 2.13, and further preferably the lime saturation coefficient KH of the cement clinker is 0.920 to 0.926, and the silicic acid rate SM is 2.08 to 2.10.
The present application will be described in further detail with reference to examples.
The raw materials in the examples and comparative examples of the present application are commercially available.
Examples
Examples 1 to 5 are different in the amount of each raw material.
The following description will be given by taking example 1 as an example.
Example 1
The high-strength cement comprises the following raw materials in mass: 85kg of cement clinker, 24.29kg of mixed materials and 6.07kg of gypsum, wherein the cement clinker comprises the following raw materials in parts by mass: 58kg of limestone, 15kg of clay, 6kg of copper slag, 4kg of alkaline slag and 2kg of granulated blast furnace slag.
The prepared cement is 42.5 in label;
the mass ratio of the cement clinker to the mixed material to the gypsum is 14: 4: 1;
the clay is shale;
the mass percent of the alumina in the granulated blast furnace slag is 15.3-16.8%;
the mass fraction of the fly ash in the mixed material is 55%, the mass fraction of the grinding aid is 2%, and the balance is pozzolanic; the concrete raw materials comprise 13.36kg of fly ash, 0.49kg of grinding aid and 10.44kg of volcanic ash, wherein the grinding aid is a mixture of diethanol monoisopropanolamine, aluminum sulfate and propylene glycol according to the mass ratio of 3:1.2: 1.
The production process of the high-strength cement comprises the following steps:
s1, primary grinding: mixing and grinding limestone, clay, copper slag, alkaline slag and granulated blast furnace slag for 2 hours to obtain crude raw materials;
s2 homogenization of raw material: homogenizing the rough raw material to obtain cement raw material;
s3 calcining to prepare clinker: calcining the cement raw material in a rotary kiln at 1300 ℃ for 25min, controlling the lime saturation coefficient KH of the cement clinker to be 0.924 and the silicic acid rate SM to be 2.10, spraying 6.07kg of calcium carbonate aluminate suspension with the mass fraction of 21% on the surface of the calcined clinker, and cooling to obtain the cement clinker;
s4 secondary grinding: and mixing and grinding the cement clinker, the mixed material and the gypsum for 1.5 hours to obtain the cement.
TABLE 1 Cement raw materials Components Table
Example 6
The difference between this example and example 1 is that the mass ratio of cement clinker, admixture and gypsum was 12:5:1, where the mass of cement clinker was 85 kg.
Example 7
The difference between this example and example 1 is that the mass ratio of cement clinker, admixture and gypsum was 12:3:1, where the mass of cement clinker was 85 kg.
Example 8
The difference between the embodiment and the embodiment 1 is that the mass ratio of the cement clinker to the admixture to the gypsum is 15: 3:1, wherein the mass of the cement clinker is 85 kg.
Example 9
The difference between this example and example 1 is that the mass ratio of cement clinker, admixture and gypsum was 15:5:1, where the mass of cement clinker was 85 kg.
Example 10
The present example is different from example 1 in that the mass fraction of alumina in granulated blast furnace slag is 13.6 to 15.3%.
Example 11
The present example is different from example 1 in that the mass fraction of alumina in the granulated blast furnace slag is 16.8 to 18.2%.
Example 12
The difference between the embodiment and the embodiment 1 is that the mass of the mixed material is 24.29kg, the mass fraction of the fly ash in the mixed material is 50%, the mass fraction of the grinding aid is 1%, and the balance is volcanic ash.
Example 13
The difference between the embodiment and the embodiment 1 is that the mass of the mixed material is 24.29kg, the mass fraction of the fly ash in the mixed material is 60%, the mass fraction of the grinding aid is 3%, and the balance is volcanic ash.
Example 14
This example differs from example 1 in that the grinding aid mass is 0.49kg and is a mixture of diethanol monoisopropanolamine, aluminium sulphate and propylene glycol in a mass ratio of 2.5:1.4: 1.
Example 15
This example differs from example 1 in that the grinding aid mass is 0.49kg and is a mixture of diethanol monoisopropanolamine, aluminium sulphate and propylene glycol in a mass ratio of 3.2:1: 1.
Example 16
The present embodiment is different from embodiment 1 in that in the one-time grinding step of S1, the grinding time is 1.5 h.
Example 17
The present embodiment is different from embodiment 1 in that in the one-time grinding step of S1, the grinding time is 3 hours.
Example 18
The difference between this example and example 1 is that in the step of calcining clinker in S3, the calcining temperature is 1280 ℃.
Example 19
This example is different from example 1 in that in the step of calcining S3 to prepare clinker, the calcining temperature is 1350 ℃.
Example 20
This example differs from example 1 in that in the step of calcining at S3 to produce clinker, the sprayed calcium carbonate-aluminate suspension had a mass fraction of calcium carbonate-aluminate of 17%.
Example 21
This example differs from example 1 in that in the step of calcining at S3 to produce clinker, the sprayed calcium carbonate-aluminate suspension has a calcium carbonate-aluminate mass fraction of 23%.
Example 22
The difference between this example and example 1 is that in the step of calcining clinker at S3, the mass ratio of cement clinker to sprayed calcium carbonate aluminate suspension before calcination is 12: 1.
Example 23
The present example differs from example 1 in that in the step of calcining clinker at S3, the mass ratio of cement clinker to sprayed calcium carbonate aluminate suspension before calcination is 15: 1.
Example 24
The difference between this example and example 1 is that in the step of calcining clinker at S3, the lime saturation coefficient KH of cement clinker is controlled to be 0.916 and the silicic acid ratio SM is controlled to be 2.05.
Example 25
The difference between this example and example 1 is that in the step of calcining clinker at S3, the lime saturation coefficient KH of cement clinker is controlled to be 0.932, and the silicic acid ratio SM is controlled to be 2.13.
Comparative example
Comparative example 1
The comparative example differs from example 1 in that no copper dross is added.
Comparative example 2
The comparative example differs from example 1 in that no caustic sludge was added.
Comparative example 3
This comparative example differs from example 1 in that no granulated blast furnace slag was added.
Comparative example 4
The comparative example is different from example 1 in that copper slag and alkaline residue were not added.
Comparative example 5
This comparative example differs from example 1 in that no alkaline slag and granulated blast furnace slag were added.
Comparative example 6
This comparative example differs from example 1 in that no copper slag and no granulated blast furnace slag were added.
Comparative example 7
This comparative example differs from example 1 in that the copper slag was replaced by an equal amount of phosphorous slag.
Comparative example 8
This comparative example differs from example 1 in that the caustic sludge was replaced with an equal amount of calcium hydroxide.
Comparative example 9
This comparative example differs from example 1 in that the granulated blast furnace slag was replaced with an equal amount of fly ash.
Comparative example 10
This comparative example differs from example 1 in that no grinding aid was added to the mix.
Comparative example 11
The comparative example differs from example 1 in that no spraying of the calcareous suspension is carried out during the clinker preparation step by calcination at S3.
Comparative example 12
The comparative example differs from example 1 in that, in the step of calcining at S3 to produce clinker, the spraying is carried out with an equal amount of water instead of the calcareous suspension.
Comparative example 13
The high-strength cement in the related art comprises the following raw materials in mass: 80kg of limestone, 5kg of pyrite cinder, 16kg of sandstone, 6kg of fly ash, 2kg of copper slag and 1kg of gypsum.
The cement is designated 42.5.
The preparation method of the cement comprises the following steps:
preparation of raw material A1: homogenizing limestone, mixing with pyrite cinder, sandstone, fly ash and copper slag, and grinding for 1h to obtain a raw material; preparation of clinker A2: calcining the raw material in a rotary kiln at 1250 ℃, and cooling to obtain cement clinker;
preparation of A3 finished product: and mixing and grinding the cement clinker and the gypsum for 1.5 hours to obtain a finished cement product.
Performance test
Detection method/test method strength test: the compressive strength of the cement samples prepared in examples 1 to 25 and comparative examples 1 to 13 was tested according to the method of GB/T17671-1999 "Cement mortar Strength test".
Initial and final setting time test: the initial setting time and final setting time of the cement samples prepared in examples 1 to 25 and comparative examples 1 to 13 were measured according to the test method in JC/T453-2004 "physical inspection method for self-stressed cement".
TABLE 2 test data sheet
The data detection results in table 2 show that, in combination with the detection results of examples 1 to 5 and comparative example 13, the cement prepared in the present application has good compressive strength under the premise of adding industrial waste residues, and the initial setting time and the final setting time are excellent, wherein the cement prepared in example 1 has the best performance, and thus the ratio of each raw material in example 1 is the best.
According to the detection results of the embodiment 1 and the comparative examples 1 to 6, the three industrial waste residues of the copper slag, the alkaline slag and the granulated blast furnace slag are used as auxiliary materials of the cement clinker, the three industrial waste residues have synergistic effects so that the advantages of the three industrial waste residues are superposed, the disadvantages of the three industrial waste residues are complemented and improved, the alkaline slag and the granulated blast furnace slag have better excitation effect on the activity of the copper slag, the copper slag and the granulated blast furnace slag can be effectively combined with free chloride ions in the alkaline slag, and the three industrial waste residues are synergistic, so that the prepared cement has better comprehensive performance.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (6)
1. A high-strength cement is characterized in that: the cement clinker aggregate comprises cement clinker, mixed materials and gypsum, wherein the cement clinker comprises the following raw materials in parts by mass: 55-62 parts of limestone, 13-17 parts of clay, 3-8 parts of copper slag, 2-6 parts of alkaline slag and 1-3 parts of granulated blast furnace slag; al in the granulated blast furnace slag in percentage by mass 2 O 3 The mass fraction of (A) is 13.6-18.2%; the mass ratio of the cement clinker to the mixed material to the gypsum is (12-15): (3-5): 1; the mixed material comprises the following raw materials in percentage by mass: 50-60% of fly ash, 1-3% of grinding aid and the balance of pozzolanic matter; the grinding aid is prepared from diethanol monoisopropanolamine, aluminum sulfate and propylene glycol according to a mass ratio of (2.5-3.2): (1-1.4): 1, in a mixture of the components.
2. A process for producing a high strength cement according to claim 1, wherein: the method comprises the following steps:
primary grinding: mixing and grinding limestone, clay, copper slag, alkaline slag and granulated blast furnace slag to obtain a rough raw material;
raw material homogenization: homogenizing the rough raw material to obtain cement raw material;
calcining to prepare clinker: calcining the cement raw material, spraying calcium salt suspension on the surface of the calcined clinker, and cooling to obtain cement clinker;
secondary grinding: and mixing and grinding the cement clinker, the mixed material and the gypsum to obtain the cement.
3. The process for producing high strength cement according to claim 2, wherein: in the primary grinding step, the grinding time is 1.5-3 h.
4. The process for producing high strength cement according to claim 2, wherein: in the step of calcining and firing the clinker, the calcining temperature is 1280-1350 ℃.
5. The process for producing high strength cement according to claim 2, wherein: in the step of calcining the clinker, the mass fraction of calcium salt in the calcium salt suspension is 17-23%, and the mass ratio of the cement clinker before calcining to the sprayed calcium salt suspension is (12-15): 1.
6. the process for producing high strength cement according to claim 2, wherein: in the step of calcining and firing the clinker, the prepared cement clinker has a lime saturation coefficient KH of 0.916-0.932 and a silicic acid ratio SM of 2.05-2.13.
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| US4179302A (en) * | 1976-08-20 | 1979-12-18 | Tashkentsky Nauchno-Issledovatelsky I Proektny Institut Stroitelnykh Materialov "Niistromproekt" | Raw mixture for the production of cement clinker |
| CN1718555A (en) * | 2004-07-11 | 2006-01-11 | 乔希海 | Method of manufacturing cement |
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| US4179302A (en) * | 1976-08-20 | 1979-12-18 | Tashkentsky Nauchno-Issledovatelsky I Proektny Institut Stroitelnykh Materialov "Niistromproekt" | Raw mixture for the production of cement clinker |
| CN1718555A (en) * | 2004-07-11 | 2006-01-11 | 乔希海 | Method of manufacturing cement |
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| 冷却水泥熟料的方法;苏联专利1521723;《砖瓦世界》;19911231(第11期);20 * |
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Denomination of invention: A high-strength cement and its production process Granted publication date: 20220906 Pledgee: Shandong Shanghe Rural Commercial Bank Co.,Ltd. Urban Branch Pledgor: Jinan Shanshui Cement Co.,Ltd. Registration number: Y2024980010356 |