CN115259703A - Solid waste material based anti-erosion rapid-hardening marine cement and preparation method thereof - Google Patents
Solid waste material based anti-erosion rapid-hardening marine cement and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B7/36—Manufacture of hydraulic cements in general
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
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- C04B7/00—Hydraulic cements
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- C04B7/48—Clinker treatment
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Abstract
The invention discloses a solid waste material-based anti-erosion rapid-hardening marine cement and a preparation method thereof, belonging to the technical field of ocean engineering construction. The marine engineering cement comprises the following raw materials in parts by weight: 65-80 parts of marine cement clinker, 0-12 parts of slag, 0-12 parts of fly ash, 2-5 parts of modified phosphogypsum, 5-15 parts of garnet and 0.1-0.12 part of cement additive. The marine cement has the advantages of excellent performance, controllable setting time, better strength development and strong corrosion resistance. The marine engineering cement can meet the standard requirements of marine construction, and simultaneously, various solid waste materials used by the marine engineering cement improve the performance of the cement and have the effects of energy conservation, consumption reduction and environmental protection.
Description
Technical Field
The invention belongs to the technical field of ocean engineering construction, and particularly relates to solid waste material-based anti-erosion rapid-hardening marine engineering cement and a preparation method thereof.
Background
At the present stage, energy-saving carbon-reducing synergistic action, circular economy power-assisted carbon-reducing action and the like are mainly implemented, the utilization of a large amount of solid wastes is enhanced, the large amount of solid wastes such as smelting slag, industrial byproduct gypsum, mine selecting and smelting solid wastes are taken as key points, the comprehensive treatment of solid waste materials is explored on the premise of ensuring safety and environment protection, the solid waste materials are applied to soil improvement, underground filling, building materials and the like, and at present, the resource utilization of the industrial solid wastes is urgent.
The 21 st century is a well-known 'ocean century', and the development of ocean resources is very important for all countries in the world. In the ocean development process, cement is an indispensable raw material in ocean engineering infrastructure. The traditional cement is affected by seawater corrosion and sea wave scouring due to long-term soaking in seawater, so that the durability and corrosion resistance are poor, and the use requirement of ocean engineering cannot be met.
Therefore, the research and the application of comprehensively treating the solid wastes and researching and developing the cement and concrete-based building materials have important significance. The existing research shows that the performance of cement and concrete prepared by adding specially treated solid waste is superior to that of common Portland cement concrete in certain performances, such as durability, corrosion resistance and the like, and the difficult problem of solid waste utilization can be solved while the production cost of marine engineering cement is reduced.
Disclosure of Invention
The invention provides an anti-erosion rapid hardening marine cement taking solid waste materials as main materials, aiming at the problems of difficult solid waste utilization, high cost of marine concrete and high price at present, and further discloses a specific preparation method thereof.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the solid waste material-based anti-erosion rapid-hardening marine cement is prepared from the following raw materials in parts by weight: 65-80 parts of marine cement clinker, 0-12 parts of slag, 0-12 parts of fly ash, 2-5 parts of modified phosphogypsum, 5-15 parts of garnet and 0.1-0.12 part of cement additive.
Further, the preparation method of the cement admixture comprises the following steps: mixing alumina, sodium hydroxide and deionized water according to the mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminum sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5.
further, the marine cement clinker is prepared from the following raw materials in parts by weight: 65-80 parts of limestone, 8-15 parts of garnet, 10-20 parts of gold tailings and 3-5 parts of phosphogypsum.
Further, siO in the gold tailings2+Al2O3≥85%。
Further, the preparation method of the modified phosphogypsum comprises the following steps: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5: and 4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum.
Further, siO in the garnet2+Al2O3≥40%、CaO＞32.34%、Fe2O3＞16.12%。
A preparation method of solid waste material-based anti-erosion rapid-hardening marine cement comprises the following steps:
(1) Preparing marine engineering cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% by weight and controlling the screen residue to be 80 mu m, mixing the limestone with gold tailings, garnet and phosphogypsum, and then carrying out high-temperature calcination and quenching treatment on the mixed material to obtain marine cement clinker;
(2) Preparing modified phosphogypsum: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5:4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum;
(3) Preparing a cement additive: mixing aluminum oxide, sodium hydroxide and deionized water according to a mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5;
(4) Mixing the marine cement clinker, the modified phosphogypsum, the slag, the fly ash and the garnet according to a proportion, placing the mixture into a standard small mill testing machine, adding the additive, and grinding the mixture until the specific surface area is 360 +/-10 m2And/kg, namely obtaining the solid waste material-based anti-erosion rapid-hardening marine engineering cement.
Furthermore, the temperature of the high-temperature calcination is 1225-1300 ℃, the calcination heat preservation time is 30-50min, and the quenching treatment mode adopts air cooling.
The embodiment of the invention is designed according to the following clinker composition: clinker formationChemical composition is SiO220-30%，Al2O35-12%，CaO60-70%、Fe2O316.12%，SO34-8%；C3S45-60%，C2S20-35%，C3A8-15%，C4AF10-20%。
The main chemical component of the phosphogypsum is CaSO4·2H2O, is acidic, has impurities such as phosphorus, fluorine and the like, and the phosphogypsum crystal is long plate-shaped, has the size of about 10-55 mu m and contains 15-20% of crystal water.
The slag is blast furnace slag, and the fly ash is secondary fly ash.
The octyl phenol polyoxyethylene ether and the coconut diethanolamide are of industrial grade.
The calcium oxide, the anhydrous sodium sulfate, the aluminum oxide and the sodium hydroxide are analytically pure.
The calcium formate, the monoethanol diisopropanolamine and the polyaluminium sulfate are industrial grade and are commercially available.
The marine engineering cement clinker is prepared by mixing and calcining limestone, garnet, gold tailings and phosphogypsum, wherein the garnet and the gold tailings are solid wastes for mine selection and metallurgy, the recycling difficulty is high, the stockpiling amount is large, the environmental pollution is easily caused, and the risk of mine accidents is increased. Phosphogypsum is a solid waste produced in a wet-process phosphoric acid process, and the components of the phosphogypsum are mainly calcium sulfate dihydrate. The composition of the phosphogypsum is complex, besides calcium sulfate, incompletely decomposed phosphorite, residual phosphoric acid, fluoride, acid insoluble substances, organic matters and the like exist, the ecological environment is seriously damaged by random discharge and accumulation of the phosphogypsum, not only is underground water resources polluted, but also land resources are wasted. Garnet is used as an iron-aluminum correction material of the marine cement clinker, and gold tailings are used as a siliceous correction material, so that the index requirements of clinker firing materials can be met, the problems of environmental pollution and solid waste utilization can be solved, part of common clinker raw materials can be replaced, resources are greatly saved, and the cost is saved.
The present invention uses garnets as corrective material, which mainly comprises calcium iron garnet (Ca)3Fe2（SiO4）3) Calcium aluminum garnet (Ca)3 Al 2（SiO4）3) Perovskite (CaFe [ Si ]) or a mixture thereof2O6]) The content of effective substances is more than 87 percent, and the gold tailing Sand (SiO)2、Al2O3) The content of effective substances is more than 85%, and high-content iron, aluminum, silicon and calcium elements play an important role in the clinker sintering process, on one hand, the iron glue formed by hydration of iron phases in the clinker can adsorb chloride ions and improve structural compactness, on the other hand, the hydration reaction of cement can be accelerated, and the early strength and the erosion resistance of marine engineering cement are improved.
Meanwhile, the added phosphogypsum can be used as a mineralizer of clinker, so that the content of free calcium oxide in cement clinker can be reduced, the decomposition of limestone is promoted, the liquid phase property is changed, the cement sintering temperature is reduced, the raw material easy combustibility is improved, and the composition and quality of clinker minerals are improved in the clinker sintering process.
Furthermore, the phosphogypsum can replace common gypsum of cement, such as desulfurized gypsum, dihydrate gypsum and the like, and the problem of environmental pollution is solved while the production cost is reduced. However, the use of phosphogypsum prolongs the setting time of cement, so the phosphogypsum is modified to meet the performance requirement of the cement.
In order to improve the properties of rapid hardening, early strength and strong cohesiveness of the marine engineering cement, the invention also uses the admixture with rapid hardening and early strength in the cement preparation process, and is further suitable for environmental applications such as marine engineering rush repair and the like.
Advantageous effects
1. The invention introduces garnet, gold tailings and phosphogypsum to replace iron, aluminum and calcium correcting materials of marine cement clinker, replaces common materials such as bauxite and red mud, relieves the shortage problem of bauxite minerals, meets and ensures the quality of the clinker, and simultaneously contains a plurality of mineral elements which can play a considerable mineralization effect; can also be used as a cement admixture, and solves the problems of environmental pollution and safety risk of a large amount of solid wastes.
2. The modified phosphogypsum is introduced as an auxiliary material, can replace common dihydrate gypsum and desulfurized gypsum, can save resources, reduce production cost, solve the problem of large solid waste utilization, and can enhance the corrosion resistance of cement, prevent heavy metals from dissolving out and improve the impermeability and durability of the cement.
3. The quick-setting early-strength additive is used as an exciting agent, and materials such as natural minerals (such as metakaolin) containing aluminosilicate substances, industrial solid wastes (such as fly ash, slag, steel slag, red mud, various tailings and the like) and the like can be subjected to depolymerization at first and then polycondensation to change the structure of the materials under the normal temperature or slightly high temperature environment to form a material which mainly takes ionic bonds and covalent bonds and is prepared from [ SiO ]4]And [ AlO ]4]The tetrahedral structure unit is formed by sharing oxygen to bond alternately, and the polysilicate aluminate gelled material with a three-dimensional space network structure is formed. Due to the unique structure, the material has excellent performances which are difficult to achieve by a plurality of Portland cement-based materials, and is particularly outstanding in the aspects of mechanical property, chemical erosion resistance, heat resistance, heavy metal fixation and the like.
4. The invention uses solid waste materials as main raw materials, and prepares cement clinker by preparing a proper amount of garnet, the obtained marine concrete has high strength and good resistance to chloride ion and sulfate erosion, can be applied to various ocean engineering, realizes the high-efficiency cyclic utilization of solid waste, and has potential application value and obvious economic and social benefits.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
The solid waste material-based anti-erosion rapid-hardening marine cement is prepared from the following raw materials in parts by weight: 73 parts of marine cement clinker, 9 parts of slag, 0 part of fly ash, 4 parts of modified phosphogypsum, 14 parts of garnet and 0.1 part of cement additive.
The preparation method of the cement admixture comprises the following steps: mixing aluminum oxide, sodium hydroxide and deionized water according to a mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminum sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5.
the marine engineering cement clinker is prepared from the following raw materials in parts by weight: 68.9 parts of limestone, 11.36 parts of garnet, 14.94 parts of gold tailings and 4.8 parts of phosphogypsum.
SiO in the gold tailings2+Al2O3≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5: and 4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum.
SiO in the garnet2+Al2O3≥40%、CaO＞32.34%、Fe2O3＞16.12%。
A preparation method of solid waste material-based anti-erosion rapid-hardening marine cement comprises the following steps:
(1) Preparing marine engineering cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and controlling the screen residue to be less than or equal to 80 mu m, mixing the limestone with the gold tailings, garnet and phosphogypsum, and then carrying out high-temperature calcination and quenching treatment on the mixed material to obtain the marine cement clinker;
(2) Preparing modified phosphogypsum;
(3) Preparing a cement additive;
(4) Mixing the marine cement clinker, the modified phosphogypsum, the slag, the fly ash and the garnet according to a proportion, placing the mixture into a standard small mill testing machine, adding the additive, and grinding the mixture until the specific surface area is 360 +/-10 m2And/kg, namely obtaining the solid waste material-based anti-erosion rapid-hardening marine engineering cement.
The temperature of the high-temperature calcination is 1225 ℃, the calcination heat preservation time is 35min, and the quenching treatment mode adopts air cooling.
Example 2
The solid waste material-based anti-erosion rapid-hardening marine cement is prepared from the following raw materials in parts by weight: 71 parts of marine cement clinker, 8 parts of slag, 9 parts of fly ash, 3.5 parts of modified phosphogypsum, 8.5 parts of garnet and 0.1 part of cement additive.
The preparation method of the cement admixture comprises the following steps: mixing aluminum oxide, sodium hydroxide and deionized water according to a mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5.
the marine engineering cement clinker is prepared from the following raw materials in parts by weight: 75.01 parts of limestone, 9.89 parts of garnet, 10.6 parts of gold tailings and 4.5 parts of phosphogypsum.
SiO in the gold tailings2+Al2O3≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5: and 4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum.
SiO in the garnet2+Al2O3≥40%、CaO＞32.34%、Fe2O3＞16.12%。
A preparation method of solid waste material-based anti-erosion rapid-hardening marine cement comprises the following steps:
(1) Preparing marine engineering cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% by weight and controlling the screen residue to be 80 mu m, mixing the limestone with gold tailings, garnet and phosphogypsum, and then carrying out high-temperature calcination and quenching treatment on the mixed material to obtain marine cement clinker;
(2) Preparing modified phosphogypsum;
(3) Preparing a cement additive;
(4) Mixing the marine cement clinker, the modified phosphogypsum, the slag, the fly ash and the garnet according to a proportion, placing the mixture into a standard small mill testing machine, adding the additive, and grinding the mixture until the specific surface area is 360 +/-10 m2And/kg, namely obtaining the solid waste material-based anti-erosion rapid-hardening marine engineering cement.
Furthermore, the temperature of the high-temperature calcination is 1250 ℃, the calcination heat preservation time is 40min, and the quenching treatment mode adopts air cooling.
Example 3
The solid waste material-based anti-erosion rapid-hardening marine cement is prepared from the following raw materials in parts by weight: 77 parts of marine cement clinker, 0 part of slag, 8.5 parts of fly ash, 4.5 parts of modified phosphogypsum, 10 parts of garnet and 0.12 part of cement admixture.
The preparation method of the cement admixture comprises the following steps: mixing aluminum oxide, sodium hydroxide and deionized water according to a mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5.
the marine engineering cement clinker is prepared from the following raw materials in parts by weight: 73.43 parts of limestone, 12.67 parts of garnet, 10.55 parts of gold tailings and 3.35 parts of phosphogypsum.
SiO in the gold tailings2+Al2O3≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5: and 4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum.
SiO in the garnet2+Al2O3≥40%、CaO＞32.34%、Fe2O3＞16.12%。
A preparation method of solid waste material-based anti-erosion rapid-hardening marine cement comprises the following steps:
(1) Preparing marine engineering cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% by weight and controlling the screen residue to be 80 mu m, mixing the limestone with gold tailings, garnet and phosphogypsum, and then carrying out high-temperature calcination and quenching treatment on the mixed material to obtain marine cement clinker;
(2) Preparing modified phosphogypsum: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer in a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5:4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum;
(3) Preparing a cement additive: mixing aluminum oxide, sodium hydroxide and deionized water according to a mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5;
(4) Mixing the marine cement clinker, the modified phosphogypsum, the slag, the fly ash and the garnet according to a proportion, placing the mixture into a standard small mill testing machine, adding the additive and the powderGrinding to a specific surface area of 360 +/-10 m2And/kg, namely obtaining the erosion-resistant rapid-hardening marine engineering cement based on the solid waste material.
The temperature of the high-temperature calcination is 1250 ℃, the calcination heat preservation time is 35min, and the quenching treatment mode adopts air cooling.
Example 4
The solid waste material-based anti-erosion rapid-hardening marine cement is prepared from the following raw materials in parts by weight: 67 parts of marine cement clinker, 6.5 parts of slag, 11 parts of fly ash, 3.5 parts of modified phosphogypsum, 12 parts of garnet and 0.12 part of cement admixture.
The preparation method of the cement admixture comprises the following steps: mixing alumina, sodium hydroxide and deionized water according to the mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5.
the marine engineering cement clinker is prepared from the following raw materials in parts by weight: 71.66 parts of limestone, 10.69 parts of garnet, 12.75 parts of gold tailings and 4.9 parts of phosphogypsum.
SiO in the gold tailings2+Al2O3≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5: and 4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum.
SiO in the garnet2+Al2O3≥40%、CaO＞32.34%、Fe2O3＞16.12%。
A preparation method of solid waste material-based anti-erosion rapid-hardening marine cement comprises the following steps:
(1) Preparing marine engineering cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% by weight and controlling the screen residue to be 80 mu m, mixing the limestone with gold tailings, garnet and phosphogypsum, and then carrying out high-temperature calcination and quenching treatment on the mixed material to obtain marine cement clinker;
(2) Preparing modified phosphogypsum: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5:4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum;
(3) Preparing a cement additive: mixing aluminum oxide, sodium hydroxide and deionized water according to a mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5;
(4) Mixing the marine cement clinker, the modified phosphogypsum, the slag, the fly ash and the garnet according to a proportion, placing the mixture into a standard small mill testing machine, adding the additive, and grinding the mixture until the specific surface area is 360 +/-10 m2And/kg, namely obtaining the erosion-resistant rapid-hardening marine engineering cement based on the solid waste material.
The high-temperature calcination temperature is 1300 ℃, the calcination heat preservation time is 38min, and the quenching treatment mode adopts air cooling.
Comparative example 1
In this comparative example, the clinker composition was fixed and SiO was used as the clinker chemical composition220-30%，Al2O35-12%，CaO60-70%、Fe2O316.12%，SO34 to 8 percent; 45-60% of C3S, 20-35% of C2S, 8-15% of C3A and 10-20% of C4AF, and garnet in the cement clinker raw material is replaced by high-aluminum clay and iron tailings which are traditional raw materials. The rest of the raw materials and the preparation method are the same as in example 4.
The specific raw material composition is shown in tables 1-3:
TABLE 1 example maritime work cement clinker raw material composition (unit: part)
TABLE 2 comparative example marine cement clinker raw material composition (unit: parts)
TABLE 3 Marine Cement Components (Unit: part)
Performance test
The marine engineering cements of examples 1 to 4 were subjected to performance tests, and tests were carried out according to the requirements of national standards GB/T20100972-T-609 and GB/T31289-2014, and compared with comparative example 1, which is commercially available ordinary 42.5 marine engineering portland cement (comparative example 2). The test results are shown in table 4 below:
table 4 results of performance testing
The test result shows that the marine cement provided by the embodiment of the invention has the advantages of excellent performance, controllable setting time, better strength development and strong corrosion resistance. The marine engineering cement can meet the standard requirements of marine construction, and simultaneously, various solid waste materials used by the marine engineering cement improve the performance of the cement and have the effects of energy conservation, consumption reduction and environmental protection.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons skilled in the art based on the above embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.
Claims (8)
1. The solid waste material-based anti-erosion rapid-hardening marine cement is characterized by being prepared from the following raw materials in parts by weight: 65-80 parts of marine cement clinker, 0-12 parts of slag, 0-12 parts of fly ash, 2-5 parts of modified phosphogypsum, 5-15 parts of garnet and 0.1-0.12 part of cement additive.
2. The solid waste material-based erosion-resistant rapid-hardening marine cement according to claim 1, wherein the preparation method of the cement admixture is: mixing aluminum oxide, sodium hydroxide and deionized water according to a mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5.
3. the solid waste material-based erosion-resistant rapid-hardening marine cement as claimed in claim 1, wherein the marine cement clinker is prepared from the following raw materials in parts by weight: 65-80 parts of limestone, 8-15 parts of garnet, 10-20 parts of gold tailings and 3-5 parts of phosphogypsum.
4. The solid waste material-based erosion-resistant rapid-hardening marine cement as claimed in claim 3, wherein SiO in the gold tailings2+Al2O3≥85%。
5. The solid waste material-based erosion-resistant rapid hardening marine cement according to claim 1, wherein the preparation method of the modified phosphogypsum is as follows: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5: and 4.5, continuously stirring and mixing for 45min, placing the mixture into a sample sealing belt for aging for 12h after the mixture is contacted, and obtaining the modified phosphogypsum.
6. The solid waste material-based erosion-resistant rapid-setting marine cement as claimed in claim 1 or 3, wherein SiO in said garnet2+Al2O3≥40%、CaO ＞32.34%、Fe2O3＞16.12%。
7. A method for preparing the solid waste material-based erosion-resistant rapid-hardening marine cement as claimed in any one of claims 1 to 5, which comprises the following steps:
(1) Preparing marine engineering cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and controlling the screen residue to be less than or equal to 80 mu m, mixing the limestone with the gold tailings, garnet and phosphogypsum, and then carrying out high-temperature calcination and quenching treatment on the mixed material to obtain the marine cement clinker;
(2) Preparing modified phosphogypsum: sequentially adding phosphogypsum, calcium oxide and anhydrous sodium sulfate into a planetary mixer according to a weight ratio of 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coconut diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coconut diethanolamide to the phosphogypsum is 400:5.5:4.5, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain the modified phosphogypsum;
(3) Preparing a cement additive: mixing alumina, sodium hydroxide and deionized water according to the mass ratio of 5:1:40, mixing and adding the mixture into a reaction vessel, carrying out heat preservation reaction for 20min at the temperature of 55 ℃ to obtain pre-reaction liquid, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement admixture; the mass ratio of the pre-reaction liquid to the solid mixture is 1; the mass ratio of the calcium formate to the monoethanol diisopropanolamine to the polyaluminium sulfate is 0.24:3:2.5;
(4) Mixing the marine cement clinker, the modified phosphogypsum, the slag, the fly ash and the garnet according to a proportion, placing the mixture into a standard small mill testing machine, adding the additive, and grinding the mixture to a specific surfaceProduct of 360 +/-10 m2And/kg, namely obtaining the erosion-resistant rapid-hardening marine engineering cement based on the solid waste material.
8. The method for preparing the solid waste material-based anti-erosion rapid-hardening marine cement according to claim 7, wherein the high-temperature calcination is carried out at 1225-1300 ℃, the calcination heat-preservation time is 30-50min, and the quenching treatment mode adopts air cooling.
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| CN111138100A (en) * | 2020-01-13 | 2020-05-12 | 桂林理工大学 | Marine engineering cement and preparation method and application thereof |
| CN112125616A (en) * | 2019-06-24 | 2020-12-25 | 常州市建筑科学研究院集团股份有限公司 | Ultra-high performance concrete limited slip ramp |
| AU2020104285A4 (en) * | 2020-12-23 | 2021-03-11 | Guilin University Of Technology | Marine cement and preparation method and application thereof |
| CN112745054A (en) * | 2020-12-31 | 2021-05-04 | 临沂宏艺科技发展有限公司 | Salt erosion resistant marine concrete admixture and preparation method thereof |
| CN113698117A (en) * | 2021-09-17 | 2021-11-26 | 山东大学 | Solid waste based high-iron sulphoaluminate marine gelled material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112125616A (en) * | 2019-06-24 | 2020-12-25 | 常州市建筑科学研究院集团股份有限公司 | Ultra-high performance concrete limited slip ramp |
| CN111138100A (en) * | 2020-01-13 | 2020-05-12 | 桂林理工大学 | Marine engineering cement and preparation method and application thereof |
| AU2020104285A4 (en) * | 2020-12-23 | 2021-03-11 | Guilin University Of Technology | Marine cement and preparation method and application thereof |
| CN112745054A (en) * | 2020-12-31 | 2021-05-04 | 临沂宏艺科技发展有限公司 | Salt erosion resistant marine concrete admixture and preparation method thereof |
| CN113698117A (en) * | 2021-09-17 | 2021-11-26 | 山东大学 | Solid waste based high-iron sulphoaluminate marine gelled material and preparation method and application thereof |
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