CN115259703B - Anti-erosion quick-setting marine cement based on solid waste materials and preparation method thereof - Google Patents
Anti-erosion quick-setting marine cement based on solid waste materials 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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- 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
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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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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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
- C04B7/44—Burning; Melting
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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
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
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Abstract
The invention discloses a solid waste material-based anti-erosion quick-setting marine cement and a preparation method thereof, belonging to the technical field of marine engineering construction. The marine cement provided by the invention 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 admixture. The marine cement has the advantages of excellent performance, controllable setting time, better strength development and strong corrosion resistance. The marine cement can meet the standard requirements of marine construction, and various solid waste materials used by the marine cement can improve the cement performance and simultaneously achieve 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 a solid waste material-based anti-erosion quick-setting ocean engineering cement and a preparation method thereof.
Background
At present, energy conservation, carbon reduction and synergy actions, circular economy, power assistance, carbon reduction actions and the like are emphasized, the utilization of large solid wastes is emphasized, smelting slag, industrial byproduct gypsum, mine dressing and smelting solid wastes are emphasized, on the premise of ensuring safety and environmental protection, the comprehensive treatment of solid waste materials is explored, and the comprehensive treatment is applied to soil improvement, underground filling, building materials and the like, and at present, the resource utilization of industrial solid wastes is urgent.
The 21 st century is a well-known "ocean century", and the world is very important for the development of ocean resources. In the ocean development process, cement is an indispensable raw material in the ocean engineering infrastructure. The traditional cement is affected by seawater corrosion and sea wave scouring due to long-term soaking in seawater, and has poor durability and corrosion resistance, so that the traditional cement cannot meet the requirements of ocean engineering.
Therefore, the research of comprehensively treating the solid wastes and being applied to the research, development and application of cement and concrete-based building materials has important significance. The existing researches show that the performances of cement and concrete prepared by adding special treated solid wastes are superior to those of ordinary silicate cement concrete in terms of certain performances such as durability, corrosion resistance and the like, and the problems of solid waste utilization can be solved while the production cost of marine cement is reduced.
Disclosure of Invention
Aiming at the problems of difficult utilization of solid waste, high cost and high price of marine concrete at present, the invention provides anti-erosion quick-setting marine cement mainly made of solid waste materials, and further discloses a specific preparation method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the solid waste material-based corrosion-resistant quick-setting 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 admixture.
Further, the preparation method of the cement admixture comprises the following steps: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and 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 tailings 2 +Al 2 O 3 ≥85%。
Further, the preparation method of the modified phosphogypsum comprises the following steps: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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, and obtaining the modified phosphogypsum.
Further, siO in the garnet 2 +Al 2 O 3 ≥40%、CaO＞32.34%、Fe 2 O 3 ＞16.12%。
The preparation method of the solid waste material-based corrosion-resistant quick-setting marine cement comprises the following steps:
(1) Preparing marine cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and mixing with gold tailings, garnet and phosphogypsum, and then calcining the mixture at high temperature and quenching to obtain the marine cement clinker;
(2) Preparation of modified phosphogypsum: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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 modified phosphogypsum;
(3) Preparing a cement admixture: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and 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 an additive, and grinding the mixture until the specific surface area is 360+/-10 m 2 And (3) kg to obtain the solid waste material-based corrosion-resistant quick setting marine cement.
Further, the high-temperature calcination temperature is 1225-1300 ℃, the calcination heat preservation time is 30-50min, and the quenching treatment mode adopts air cooling.
The invention is designed according to the following clinker composition design examples: the chemical composition of clinker is SiO 2 20-30%，Al 2 O 3 5-12%，CaO60-70%、Fe 2 O 3 16.12%，SO 3 4-8%；C3S45-60%，C2S20-35%，C3A8-15%，C4AF10-20%。
The main chemical component of the phosphogypsum is CaSO 4 ·2H 2 O is acidic, contains phosphorus, fluorine and other impurities, and 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 coco diethanolamide are industrial grade.
The calcium oxide, anhydrous sodium sulfate, aluminum oxide and sodium hydroxide are analytically pure.
The calcium formate, the monoethanol diisopropanolamine and the polyaluminium sulfate are industrial grade and are sold in the market.
The marine cement clinker is prepared by mixing and calcining limestone, garnet, gold tailing and phosphogypsum, wherein the garnet and the gold tailing are mine dressing and smelting solid waste, the recycling difficulty is high, the storage quantity is large, the environmental pollution is easy to cause, and the mine accident risk is increased. Phosphogypsum is a solid waste generated in the wet-process phosphoric acid process, and the component of phosphogypsum is mainly calcium sulfate dihydrate. The phosphogypsum has complex composition, besides calcium sulfate, phosphorus ore which is not completely decomposed, residual phosphoric acid, fluoride, acid insoluble substances, organic matters and the like, and the random discharge and accumulation of the phosphogypsum seriously damages the ecological environment, so that not only the underground water resource is polluted, but also the land resource is 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 not only can the index requirements of the clinker firing material be met, but also the problems of environmental pollution and solid waste utilization can be solved, and part of common clinker raw materials are replaced, so that the resources are greatly saved, and the cost is saved.
The present invention uses garnet as a corrective material, which mainly contains lime garnet (Ca 3 Fe 2 （SiO 4 ） 3 ) Lime garnet (Ca) 3 Al 2 （SiO 4 ） 3 ) Spodumene (CaFe [ Si ] 2 O 6 ]) The content of effective substances is more than 87%, and the gold tailing sand (SiO 2 、Al 2 O 3 ) The content of the effective substances is more than 85%, the iron, aluminum, silicon and calcium elements with high content play an important role in the sintering process of the clinker, on one hand, iron cement formed by hydration of iron phases in the clinker can adsorb chloride ions and can also improve the structural compactness, and on the other hand, the hydration reaction of cement can be accelerated, and the early strength and erosion resistance of marine 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 in the clinker firing process, the limestone decomposition is promoted, the liquid phase property is changed, the cement sintering temperature is reduced, the raw material combustibility is improved, and the composition and quality of clinker minerals are improved.
Furthermore, phosphogypsum can replace gypsum commonly used for cement, such as desulfurized gypsum, dihydrate gypsum and the like, so that the production cost is reduced and the problem of environmental pollution is solved. However, the use of phosphogypsum can prolong the setting time of cement, so that the phosphogypsum is modified to meet the performance requirement of cement.
In order to improve the performances of quick hardening, early strength and strong cohesiveness of the marine cement, the invention also uses an additive with quick hardening early strength in the cement preparation process, and is further suitable for environmental applications such as marine rush repair and the like.
Advantageous effects
1. According to the invention, garnet, gold tailing and phosphogypsum are introduced to replace iron, aluminum and calcium correction materials of marine cement clinker, and common materials such as bauxite, red mud are replaced, so that the shortage problem of bauxite minerals is relieved, and various mineral elements contained in the bauxite minerals can play a considerable mineralization role while the quality of the clinker is met and ensured, on one hand, although the impurity elements are harmful in the common environment, the combustibility of raw materials can be improved in the clinker calcination process, the 'chemical doping' effect is utilized to generate optimized clinker mineral composition, the mineral crystal structure change (lattice distortion) is influenced, the liquid phase composition is changed and the like, and the mineralization effects can further influence factors such as process electricity consumption, kiln-entering decomposition rate, kiln table yield, decomposition furnace temperature, f-CaO and the like in the clinker production process, for example, the process electricity consumption, f-CaO content and the calcination temperature are reduced, and the clinker quality is improved; the cement can also be used as a cement mixture to solve the problems of environmental pollution and safety risk of bulk 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, can solve the problem of large solid waste utilization, can enhance the corrosion resistance of cement, prevent heavy metal from dissolving out, and improve the impermeability and durability of the cement.
3. As an exciting agent, the rapid hardening early-strength admixture can be used for preparing 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 at normal temperatureIn the environment of high temperature or slightly high temperature, the structure of the material is changed by the formation of depolymerization and polycondensation to form a material mainly comprising ionic bond and covalent bond, and the material is prepared from [ SiO 4 ]And [ AlO ] 4 ]The tetrahedral structural units are alternately bonded through shared oxygen to form the polyaluminosilicate cementing material with a three-dimensional space network structure. Because of the unique structure, the silicate cement-based material has a plurality of excellent properties which are difficult to achieve, and is particularly outstanding in the aspects of mechanical property, chemical erosion resistance, heat resistance, heavy metal fixation and the like.
4. The invention takes solid waste materials as main raw materials and prepares the cement clinker by preparing a proper amount of garnet, the prepared marine concrete has high strength and good chloride ion and sulfate erosion resistance, can be applied to various marine engineering, realizes the efficient recycling of solid waste, and has potential application value and obvious economic and social benefits.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The solid waste material-based corrosion-resistant quick-setting 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: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and the polyaluminium sulfate is 0.24:3:2.5.
the marine 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 tailings 2 +Al 2 O 3 ≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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, and obtaining the modified phosphogypsum.
SiO in the garnet 2 +Al 2 O 3 ≥40%、CaO＞32.34%、Fe 2 O 3 ＞16.12%。
The preparation method of the solid waste material-based corrosion-resistant quick-setting marine cement comprises the following steps:
(1) Preparing marine cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and mixing with gold tailings, garnet and phosphogypsum, and then calcining the mixture at high temperature and quenching to obtain the marine cement clinker;
(2) Preparing modified phosphogypsum;
(3) Preparing a cement admixture;
(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 an additive, and grinding the mixture until the specific surface area is 360+/-10 m 2 And (3) kg to obtain the solid waste material-based corrosion-resistant quick setting marine cement.
The high-temperature calcination temperature is 1225 ℃, the calcination heat preservation time is 35min, and the quenching treatment mode adopts air cooling.
Example 2
The solid waste material-based corrosion-resistant quick-setting 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: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and the polyaluminium sulfate is 0.24:3:2.5.
the marine 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 tailings 2 +Al 2 O 3 ≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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, and obtaining the modified phosphogypsum.
SiO in the garnet 2 +Al 2 O 3 ≥40%、CaO＞32.34%、Fe 2 O 3 ＞16.12%。
The preparation method of the solid waste material-based corrosion-resistant quick-setting marine cement comprises the following steps:
(1) Preparing marine cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and mixing with gold tailings, garnet and phosphogypsum, and then calcining the mixture at high temperature and quenching to obtain the marine cement clinker;
(2) Preparing modified phosphogypsum;
(3) Preparing a cement admixture;
(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 an additive, and grinding the mixture until the specific surface area is 360+/-10 m 2 And (3) kg to obtain the solid waste material-based corrosion-resistant quick setting marine cement.
Further, the high-temperature calcination temperature is 1250 ℃, the calcination heat preservation time is 40min, and the quenching treatment mode adopts air cooling.
Example 3
The solid waste material-based corrosion-resistant quick-setting 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 additive.
The preparation method of the cement admixture comprises the following steps: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and the polyaluminium sulfate is 0.24:3:2.5.
the marine 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 tailings 2 +Al 2 O 3 ≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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, and obtaining the modified phosphogypsum.
SiO in the garnet 2 +Al 2 O 3 ≥40%、CaO＞32.34%、Fe 2 O 3 ＞16.12%。
The preparation method of the solid waste material-based corrosion-resistant quick-setting marine cement comprises the following steps:
(1) Preparing marine cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and mixing with gold tailings, garnet and phosphogypsum, and then calcining the mixture at high temperature and quenching to obtain the marine cement clinker;
(2) Preparation of modified phosphogypsum: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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 modified phosphogypsum;
(3) Preparing a cement admixture: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and 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 an additive, and grinding the mixture until the specific surface area is 360+/-10 m 2 And (3) kg to obtain the solid waste material-based corrosion-resistant quick setting marine cement.
The high-temperature calcination temperature is 1250 ℃, the calcination heat preservation time is 35min, and the quenching treatment mode adopts air cooling.
Example 4
The solid waste material-based corrosion-resistant quick-setting 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 additive.
The preparation method of the cement admixture comprises the following steps: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and the polyaluminium sulfate is 0.24:3:2.5.
the marine 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 tailings 2 +Al 2 O 3 ≥85%。
The preparation method of the modified phosphogypsum comprises the following steps: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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, and obtaining the modified phosphogypsum.
SiO in the garnet 2 +Al 2 O 3 ≥40%、CaO＞32.34%、Fe 2 O 3 ＞16.12%。
The preparation method of the solid waste material-based corrosion-resistant quick-setting marine cement comprises the following steps:
(1) Preparing marine cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and mixing with gold tailings, garnet and phosphogypsum, and then calcining the mixture at high temperature and quenching to obtain the marine cement clinker;
(2) Preparation of modified phosphogypsum: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to 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 modified phosphogypsum;
(3) Preparing a cement admixture: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and 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 an additive, and grinding the mixture until the specific surface area is 360+/-10 m 2 And (3) kg to obtain the solid waste material-based corrosion-resistant quick setting marine cement.
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, according to the clinker chemical composition SiO 2 20-30%，Al 2 O 3 5-12%，CaO60-70%、Fe 2 O 3 16.12%，SO 3 4-8%; 45-60% of C3S, 20-35% of C2S, 8-15% of C3A and 10-20% of C4AF, and the garnet in the cement clinker raw material is replaced by the traditional raw materials of high-alumina clay and iron tailings. The other raw materials and preparation methods were the same as in example 4.
The specific raw material composition is shown in tables 1-3:
table 1 example sea work Cement clinker raw material composition (Unit: parts)
Table 2 comparative examples sea work cement clinker raw material composition (unit: parts)
TABLE 3 Marine Cement raw materials composition (Unit: parts)
Performance testing
The marine cements of examples 1 to 4 were subjected to performance tests, respectively, and experiments were required to be carried out with reference to the national standards GB/T20100972-T-609 and GB/T31289-2014, and compared with comparative example 1, commercially available ordinary 42.5 marine Portland cement (comparative example 2) as a comparative example. The test results are shown in table 4 below:
TABLE 4 Performance test results
The test results show 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 cement can meet the standard requirements of marine construction, and various solid waste materials used by the marine cement can improve the cement performance and simultaneously achieve the effects of energy conservation, consumption reduction and environmental protection.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
Claims (6)
1. The solid waste material-based corrosion-resistant quick-setting marine cement is characterized by comprising 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 admixture;
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;
SiO in the garnet 2 +Al 2 O 3 ≥40％、CaO＞32.34％、Fe 2 O 3 ＞16.12％。
2. The solid waste material-based corrosion-resistant rapid hardening marine cement according to claim 1, wherein the cement admixture is prepared by the following steps: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1;
the mass ratio of the calcium formate, the monoethanol diisopropanolamine and the polyaluminium sulfate is 0.24:3:2.5.
3. the solid waste material-based corrosion-resistant rapid hardening marine cement according to claim 1, wherein the gold tailings are
SiO 2 +Al 2 O 3 ≥85％。
4. The solid waste material-based corrosion-resistant quick setting marine cement according to claim 1, wherein the preparation method of the modified phosphogypsum is as follows: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to phosphogypsum is 5.5:4.5:400, continuously stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting, and obtaining the modified phosphogypsum.
5. A method for preparing the solid waste material-based corrosion-resistant quick setting marine cement according to any one of claims 1 to 4, comprising the steps of:
(1) Preparing marine cement clinker: crushing and grinding limestone, controlling the screen residue to be less than or equal to 16-20% and mixing with gold tailings, garnet and phosphogypsum, and then calcining the mixture at high temperature and quenching to obtain the marine cement clinker;
(2) Preparation of modified phosphogypsum: in a planetary mixer, phosphogypsum, calcium oxide and anhydrous sodium sulfate are sequentially added, wherein the weight ratio is 400:16:12, stirring and mixing uniformly for 20min, and then adding octyl phenol polyoxyethylene ether and coco diethanolamide, wherein the weight ratio of the octyl phenol polyoxyethylene ether to the coco diethanolamide to phosphogypsum is 5.5:4.5:400, continuing stirring and mixing for 45min, putting the mixture into a sample sealing belt for aging for 12h after mixing and contacting to obtain modified phosphogypsum;
(3) Preparing a cement admixture: alumina, sodium hydroxide and deionized water are mixed 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 a pre-reaction solution, adding a solid mixture of calcium formate, monoethanol diisopropanolamine and polyaluminium sulfate, and stirring and dissolving for 35min to obtain a cement additive; the mass ratio of the pre-reaction liquid to the solid mixture is 1:1; the mass ratio of the calcium formate, the monoethanol diisopropanolamine and 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 an additive, and grinding the mixture until the specific surface area is 360+/-10 m 2 And (3) kg to obtain the solid waste material-based corrosion-resistant quick setting marine cement.
6. The method for preparing the anti-erosion quick-setting marine cement based on the solid waste materials, which is characterized in that the high-temperature calcination temperature is 1225-1300 ℃, the calcination heat preservation time is 30-50min, and the quenching treatment mode adopts air cooling.
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