CN116161885A - Method for preparing silicate cement by using copper tailings - Google Patents

Method for preparing silicate cement by using copper tailings Download PDF

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CN116161885A
CN116161885A CN202310070540.6A CN202310070540A CN116161885A CN 116161885 A CN116161885 A CN 116161885A CN 202310070540 A CN202310070540 A CN 202310070540A CN 116161885 A CN116161885 A CN 116161885A
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copper tailings
cement
clinker
preparing
temperature
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郭其正
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Yichun Hongshi Cement Co ltd
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Yichun Hongshi Cement Co ltd
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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
    • 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
    • C04B7/02—Portland cement
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • 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
    • C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
    • 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
    • C04B7/42—Active ingredients added before, or during, the burning process
    • C04B7/428—Organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the field of building materials, in particular to a method for preparing silicate cement by using copper tailings; the method adopts copper tailings as siliceous raw materials to prepare cement raw material to prepare silicate cement clinker, and f-CaO content is equal at 1450℃ calcination temperatureLess than 1%; the clinker lime saturation coefficient is lower than 0.92, and the silicate cement clinker with f-CaO meeting the standard requirement can be prepared at the calcining temperature of 1400 ℃; the main mineral of clinker is C 3 S、C 2 S、C 3 A and C 4 AF; compared with sandstone ingredients, when the silicate cement clinker is burned by adopting copper tailings as siliceous raw material ingredients, the liquid phase has the temperature and C 3 The starting temperature of S is lower, and the raw material is easier to burn; preparation of silicate cement clinker by using copper tailings as siliceous raw material, C 3 The S size is about 20 mu m, and the clinker structure is more compact.

Description

Method for preparing silicate cement by using copper tailings
Technical Field
The invention relates to the field of building materials, in particular to a method for preparing silicate cement by using copper tailings.
Background
Copper tailings are industrial wastes which are discharged from copper ores after crushing, grinding, flotation and other processes and exist in the form of ore pulp. Copper tailings in China have huge yield, but the comprehensive utilization rate is only 8.2% at present, and copper tailings which cannot be utilized are treated by adopting a mode of a tailings pond; the economic cost of copper tailing stacking treatment is very high, the construction investment cost of a tailing pond is 1-3 yuan/ton, and the production operation management cost is up to 3-5 yuan/ton; the long-term stacking of copper tailings not only occupies a large amount of land resources and pollutes the environment, but also has potential safety hazards.
Cn2020101568946. X: belongs to the technical field of cement preparation, and in particular relates to a preparation method of composite silicate cement, which comprises the following steps: step one, preparing raw meal powder: uniformly mixing limestone and sandstone, then feeding into a raw material mill, and grinding into raw material powder; step two, preparing raw material balls: adding water into the raw meal powder to prepare raw meal balls with uniform volume; step three, sintering clinker: mixing raw material balls and gypsum powder, and adding the mixture into a rotary kiln to be fired into composite silicate cement clinker; step four, clinker cooling: taking out the silicate cement clinker, grinding, cooling, mixing with gypsum powder, and finally adding retarder and stirring uniformly to obtain composite silicate cement; wherein, the second step is completed by adopting a compound silicate cement preparation device. In the process of preparing raw material balls from silicate cement raw material powder, the invention ensures that the raw material balls have uniform volume and size and the raw material balls cannot collide with each other; the invention does not need to take out the raw material balls manually, is convenient to operate and avoids damaging the raw material balls.
CN202011108768.2: the silicate cement mixing equipment comprises a mixing cylinder, wherein the upper end of the mixing cylinder is provided with at least one group of feeding devices, and a primary mixing device and a secondary mixing device for mixing feeding materials are also arranged in the mixing cylinder; the invention has the effects of higher efficiency and more fully and uniformly mixing cement components in the stirring process of silicate cement preparation.
Cn201811476488.X: belongs to the technical field of cement production, in particular to a composite silicate cement preparation device, which comprises a supporting mechanism, a sorting mechanism, a friction charging mechanism, a spiral feeding mechanism and a feeding hopper; the supporting mechanism comprises a supporting plate and supporting legs, wherein the left part of the supporting plate is provided with mounting notches, and the supporting legs are provided with four supporting legs and are vertically and fixedly arranged at four corner positions of the lower surface of the supporting plate; the sorting mechanism include preceding curb plate, posterior lateral plate, right portion positive high-voltage electrode plate, left portion negative high-voltage electrode plate and bottom plate, preceding curb plate, posterior lateral plate, right portion positive high-voltage electrode plate, left portion negative high-voltage electrode plate enclose into a mouthful font frame form structure, mouthful font frame form structure card establish in the installation breach and fixed, right portion positive high-voltage electrode plate level seted up bar bin outlet, right portion positive high-voltage electrode plate and left portion negative high-voltage electrode plate between constitute high-voltage electrostatic sorting chamber. Also relates to a preparation method by adopting the composite silicate cement preparation device.
The prior art and the above patent mostly adopt the traditional raw materials such as limestone, sandstone, gypsum powder, retarder and the like to prepare silicate cement, the production cost is relatively high, copper tailings are adopted to replace sandstone, the combustibility of raw materials is better, and the structure of clinker is more compact.
Disclosure of Invention
The embodiment of the invention aims to provide a method for preparing Portland cement by using copper tailings, which aims to solve the technical problems that the prior art provided in the background art adopts limestone, sandstone, gypsum powder, retarder and other traditional raw materials to prepare the Portland cement, and the production cost is relatively high.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
s1: weighing 5-15 parts of copper tailings, 75-85 parts of limestone, 5-10 parts of sandstone, 2-10 parts of phyllite and 3-6 parts of nonferrous metal ash, and 0.02-0.4 part of cement auxiliary agent according to parts by weight, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
Further, the particle size of the crushed powder is 1-2mm.
Further, the fineness after grinding is controlled to be 0.06-0.08mm.
Further, the drying temperature is 95-105 ℃ and the time is 20-24 hours.
Further, the mixing time of the three-dimensional mixer is 10-15min.
Further, the preheating temperature is 850-1000 ℃ and the preheating time is 20-40min.
Further, the calcination temperature of the high-temperature furnace is 1350-1450 ℃ and the calcination time is 20-40min.
Another object of the embodiment of the invention is to provide a preparation method of the cement auxiliary agent, wherein the terpolymer is obtained by copolymerizing copper acrylate, allyl boric acid neopentyl glycol ester and maleic acid alcohol amine ester, and the terpolymer can be used as the cement auxiliary agent. Whereas conventional amine compounds, alcohols, fatty acids, etc. have excellent pulverizing efficiency, they are inferior in characteristic functions such as strength and functionality. Therefore, the cement auxiliary agent improves the dispersion and grinding efficiency and strength, the maleamine ester functional group of the terpolymer can prevent agglomeration, and the carboxyl copper can improve the compatibility of the auxiliary agent and copper tailings, thereby being more beneficial to the full dispersion of quartz and potassium feldspar.
Further, the preparation method of the cement auxiliary agent comprises the following steps:
step one: mixing maleic anhydride and diethanolamine, adding the mixture into a reactor, adding 0.3 to 2.0 mass percent of methyl benzene sulfonic acid of the maleic anhydride into the reactor, reacting for 2 to 4 hours at the temperature of between 90 and 102 ℃, and obtaining the alcohol amine maleate after the reaction is finished;
step two: the weight ratio of copper acrylate, allyl boric acid neopentyl glycol ester, maleic acid alcohol amine ester, potassium persulfate, gelatin and water is (1-5): 10-20): 40-50): 0.5-2: (0.5-2): (200-300), uniformly mixing, introducing nitrogen, reacting for 2-4h at 70-80 ℃, filtering and drying after the reaction is finished to obtain the cement auxiliary agent.
Further, in the first step, the mass ratio of maleic anhydride to diethanolamine is 100:10-18.
In the first step, the catalyst added in the amidation of the alcohol amine maleate is sodium methoxide or sodium ethoxide.
The method for preparing the silicate cement by using the copper tailings has the following beneficial effects:
1. the copper tailings are used as siliceous raw materials to prepare cement raw materials, and the silicate cement clinker is burned, and the f-CaO content is lower than 1% at the calcination temperature of 1450 ℃. The clinker lime saturation coefficient is lower than 0.92, and the silicate cement clinker with f-CaO meeting the standard requirement can be prepared at the calcining temperature of 1400 ℃; the main mineral of clinker is C 3 S、C 2 S、C 3 A and C 4 AF；
2. Compared with sandstone ingredients, when the silicate cement clinker is burned by adopting copper tailings as siliceous raw material ingredients, the liquid phase has the temperature and C 3 The starting temperature of S is lower, and the raw material is easier to burn;
3. preparation of silicate cement clinker by using copper tailings as siliceous raw material, C 3 The S size is about 20 mu m, and the clinker structure is more compact.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The content of free calcium oxide (f-CaO) in the sample was determined by the glycol method with reference to GB/T176-2017 method for Cement chemistry analysis. Under the condition of heating and stirring, free calcium oxide in the sample and ethylene glycol react chemically to generate alkalescent ethylene glycol calcium. And taking phenolphthalein as an indicator, and titrating with a benzoic acid-absolute ethyl alcohol solution to calculate the content of free calcium oxide in the sample.
The cement production device is the experimental device of Zhejiang red lion cement Co., ltd.
The components of the raw copper tailings are shown in the following table
Component (A) LOI CaO SiO 2 Al 2 O 3 Fe 2 O 3 MgO SO 3 Na 2 O K 2 O
Content of 2.39％ 1.13％ 69.18％ 12.84 1.55％ 0.73％ 1.69％ 0.23％ 6.94％
Example 1
The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: weighing 5kg of copper tailings, 75kg of limestone, 5kg of sandstone, 2kg of phyllite, 3kg of nonferrous metal ash and 0.02kg of cement auxiliary agent, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
The grain diameter after crushing is 1mm.
The fineness after grinding is controlled to be 0.06mm.
The drying temperature is 95 ℃ and the time is 20 hours.
The mixing time of the three-dimensional mixer is 10min.
The preheating temperature is 850 ℃ and the preheating time is 20min.
The calcination temperature of the high-temperature furnace is 1350 ℃ and the calcination time is 20min.
The preparation method of the cement auxiliary agent comprises the following steps:
s1: 1000g of maleic anhydride and diethanolamine are mixed and then added into a reactor, and 0.3 percent of methyl benzene sulfonic acid with the mass of maleic anhydride is added into the reactor to react for 2 hours at 90 ℃, and after the reaction is finished, the alcohol amine maleate is obtained;
s2: copper acrylate, allyl boric acid neopentyl glycol ester, maleic acid alcohol amine ester, potassium persulfate, gelatin and water, wherein the mass ratio of the copper acrylate to the allyl boric acid neopentyl glycol ester to the maleic acid alcohol amine ester is 1:10:40:0.5:0.5:200, uniformly mixing, introducing nitrogen, reacting for 2 hours at 70 ℃, filtering and drying after the reaction is finished, thus obtaining the cement auxiliary agent.
In the step S1, the mass ratio of maleic anhydride to diethanolamine is 100:10.
In the step S1, the catalyst added in amidation of the alcohol amine maleate is sodium methoxide.
Example 2
The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: weighing 8kg of copper tailings, 78kg of limestone, 6kg of sandstone, 4kg of phyllite and 4kg of nonferrous metal ash, and 0.1kg of cement auxiliary agent, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
The grain diameter after crushing is 1mm.
The fineness after grinding is controlled to be 0.07mm.
The drying temperature is 100 ℃ and the time is 21h.
The mixing time of the three-dimensional mixer is 12min.
The preheating temperature is 900 ℃ and the preheating time is 25min.
The calcination temperature of the high-temperature furnace is 1380 ℃ and the time is 25min.
The preparation method of the cement auxiliary agent comprises the following steps:
s1: 1000g of maleic anhydride and diethanolamine are mixed and then added into a reactor, 1% by mass of methyl benzene sulfonic acid of the maleic anhydride is added into the reactor, and the mixture is reacted for 3 hours at 95 ℃ to obtain alcohol amine maleate after the reaction is finished;
s2: copper acrylate, allyl boric acid neopentyl glycol ester, maleic acid alcohol amine ester, potassium persulfate, gelatin and water, wherein the mass ratio of the copper acrylate to the allyl boric acid neopentyl glycol ester to the maleic acid alcohol amine ester is 2:14:44:1:1:240, uniformly mixing, introducing nitrogen, reacting for 3 hours at 75 ℃, filtering and drying after the reaction is finished, thus obtaining the cement auxiliary agent.
In the step S1, the mass ratio of maleic anhydride to diethanolamine is 100:12.
In the step S1, the catalyst added in amidation of the alcohol amine maleate is sodium methoxide.
Example 3
The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: weighing 12kg of copper tailings, 82kg of limestone, 8kg of sandstone, 8kg of phyllite, 5kg of nonferrous metal ash and 0.3kg of cement auxiliary agent, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
The grain diameter after crushing is 2mm.
The fineness after grinding is controlled to be 0.07mm.
The drying temperature is 100 ℃ and the time is 23 hours.
The mixing time of the three-dimensional mixer is 14min.
The preheating temperature is 950 ℃ and the preheating time is 35min.
The calcination temperature of the high-temperature furnace is 1420 ℃, and the time is 35min.
The preparation method of the cement auxiliary agent comprises the following steps:
s1: 1000g of maleic anhydride and diethanolamine are mixed and then added into a reactor, and toluene sulfonic acid with the mass of 1.5% of the maleic anhydride is added into the reactor to react for 3 hours at 100 ℃, and after the reaction is finished, the alcohol amine maleate is obtained;
s2: copper acrylate, allyl boric acid neopentyl glycol ester, maleic acid alcohol amine ester, potassium persulfate, gelatin and water, wherein the mass ratio of the copper acrylate to the allyl boric acid neopentyl glycol ester to the maleic acid alcohol amine ester is 4:18:48:1.5:1.5:280, uniformly mixing, introducing nitrogen, reacting for 3 hours at 75 ℃, filtering and drying after the reaction is finished, thus obtaining the cement auxiliary agent.
In the step S1, the mass ratio of maleic anhydride to diethanolamine is 100:16.
In the step S1, the catalyst added in amidation of the alcohol amine maleate is sodium ethoxide.
Example 4
The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: 15kg of copper tailings, 85kg of limestone, 10kg of sandstone, 10kg of phyllite, 6kg of nonferrous metal ash and 0.4kg of cement auxiliary agent are weighed, sent into a jaw crusher to be crushed, and then ground by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
The grain diameter after crushing is 2mm.
The fineness after grinding is controlled to be 0.08mm.
The drying temperature is 105 ℃ and the time is 24 hours.
The mixing time of the three-dimensional mixer is 15min.
The preheating temperature is 1000 ℃ and the preheating time is 40min.
The calcination temperature of the high-temperature furnace is 1450 ℃ and the calcination time is 40min.
The preparation method of the cement auxiliary agent comprises the following steps:
s1: 1000g of maleic anhydride and diethanolamine are mixed and then added into a reactor, and methylbenzenesulfonic acid with the mass of 2.0% of that of the maleic anhydride is added into the reactor to react for 4 hours at 102 ℃, and after the reaction is finished, the alcohol amine maleate is obtained;
s2: copper acrylate, allyl boric acid neopentyl glycol ester, maleic acid alcohol amine ester, potassium persulfate, gelatin and water, wherein the mass ratio of the copper acrylate to the allyl boric acid neopentyl glycol ester to the maleic acid alcohol amine ester is 5:20:50:2:2:200, uniformly mixing, introducing nitrogen, reacting for 4 hours at 80 ℃, filtering and drying after the reaction is finished, thus obtaining the cement auxiliary agent.
In the step S1, the mass ratio of maleic anhydride to diethanolamine is 100:18.
In the step S1, the catalyst added in amidation of the alcohol amine maleate is sodium ethoxide.
Comparative example 1
The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: weighing 5kg of copper tailings, 75kg of limestone, 5kg of sandstone, 2kg of phyllite, 3kg of nonferrous metal ash and 0.02kg of cement auxiliary agent, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
The grain diameter after crushing is 1mm.
The fineness after grinding is controlled to be 0.06mm.
The drying temperature is 95 ℃ and the time is 20 hours.
The mixing time of the three-dimensional mixer is 10min.
The preheating temperature is 850 ℃ and the preheating time is 20min.
The calcination temperature of the high-temperature furnace is 1350 ℃ and the calcination time is 20min.
The preparation method of the cement auxiliary agent comprises the following steps:
s1: 1000g of maleic anhydride and triethanolamine are mixed and then added into a reactor, and 0.3 percent of methyl benzene sulfonic acid with the mass of maleic anhydride is added into the reactor to react for 2 hours at 90 ℃, and after the reaction is finished, the maleic acid alcohol amine ester is obtained;
s2: neopentyl glycol allylborate, alcohol maleate, potassium persulfate, gelatin and water in a mass ratio of 10:40:0.5:0.5:200, uniformly mixing, introducing nitrogen, reacting for 2 hours at 70 ℃, filtering and drying after the reaction is finished, thus obtaining the cement auxiliary agent.
In the step S1, the mass ratio of maleic anhydride to triethanolamine is 100:10.
In the step S1, the catalyst added in amidation of the alcohol amine maleate is sodium methoxide.
Comparative example 2
The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: weighing 5kg of copper tailings, 75kg of limestone, 5kg of sandstone, 2kg of phyllite, 3kg of nonferrous metal ash and 0.02kg of cement auxiliary agent, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
The grain diameter after crushing is 1mm.
The fineness after grinding is controlled to be 0.06mm.
The drying temperature is 95 ℃ and the time is 20 hours.
The mixing time of the three-dimensional mixer is 10min.
The preheating temperature is 850 ℃ and the preheating time is 20min.
The calcination temperature of the high-temperature furnace is 1350 ℃ and the calcination time is 20min.
The preparation method of the cement auxiliary agent comprises the following steps:
s1: 1000g of maleic anhydride and triethanolamine are mixed and then added into a reactor, and 0.3 percent of methyl benzene sulfonic acid with the mass of maleic anhydride is added into the reactor to react for 2 hours at 90 ℃, and after the reaction is finished, the maleic acid alcohol amine ester is obtained;
s2: copper acrylate, alcohol amine maleate, potassium persulfate, gelatin and water are mixed according to the mass ratio of 1:40:0.5:0.5:200, uniformly mixing, introducing nitrogen, reacting for 2 hours at 70 ℃, filtering and drying after the reaction is finished, thus obtaining the cement auxiliary agent.
In the step S1, the mass ratio of maleic anhydride to triethanolamine is 100:10.
In the step S1, the catalyst added in amidation of the alcohol amine maleate is sodium methoxide.
Comparative example 3
The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: weighing 5kg of copper tailings, 75kg of limestone, 5kg of sandstone, 2kg of phyllite, 3kg of nonferrous metal ash and 0.02kg of cement auxiliary agent, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
The grain diameter after crushing is 1mm.
The fineness after grinding is controlled to be 0.06mm.
The drying temperature is 95 ℃ and the time is 20 hours.
The mixing time of the three-dimensional mixer is 10min.
The preheating temperature is 850 ℃ and the preheating time is 20min.
The calcination temperature of the high-temperature furnace is 1350 ℃ and the calcination time is 20min.
The preparation method of the cement auxiliary agent comprises the following steps:
s1: 1000g of maleic anhydride and triethanolamine are mixed and then added into a reactor, and 0.3 percent of methyl benzene sulfonic acid with the mass of maleic anhydride is added into the reactor to react for 2 hours at 90 ℃, and after the reaction is finished, the maleic acid alcohol amine ester is obtained;
s2: copper acrylate, allyl boric acid neopentyl glycol ester, potassium persulfate, gelatin and water in the mass ratio of 1:10:0.5:0.5:200, uniformly mixing, introducing nitrogen, reacting for 2 hours at 70 ℃, filtering and drying after the reaction is finished, thus obtaining the cement auxiliary agent.
In the step S1, the mass ratio of maleic anhydride to triethanolamine is 100:10.
In the step S1, the catalyst added in amidation of the alcohol amine maleate is sodium methoxide.
f-CaO content/% Lime saturation coefficient of clinker
Example 1 0.5 0.90
Example 2 0.4 0.87
Example 3 0.3 0.79
Example 4 0.3 0.81
Comparative example 1 1.5 1.13
Comparative example 2 1.2 1.05
Comparative example 3 0.9 0.97
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (10)

1. The method for preparing the Portland cement by using the copper tailings comprises the following operation steps:
s1: weighing 5-15 parts of copper tailings, 75-85 parts of limestone, 5-10 parts of sandstone, 2-10 parts of phyllite and 3-6 parts of nonferrous metal ash, and 0.02-0.4 part of cement auxiliary agent according to parts by weight, feeding into a jaw crusher for crushing, and then grinding by a ball mill;
s2: and (3) drying the ground raw materials, uniformly mixing the raw materials by using a three-dimensional mixer, preheating the mixture in a high-temperature furnace, calcining the mixture in the high-temperature furnace, taking out clinker, placing the clinker in air, and quenching the clinker by using a fan to obtain the Portland cement prepared by using copper tailings.
2. A method for preparing portland cement using copper tailings according to claim 1, wherein: the grain diameter after crushing is 1-2mm.
3. A method for preparing portland cement using copper tailings according to claim 1, wherein: the fineness after grinding is controlled to be 0.06-0.08mm.
4. A method for preparing portland cement using copper tailings according to claim 1, wherein: the drying temperature is 95-105 ℃ and the time is 20-24 hours.
5. A method for preparing portland cement using copper tailings according to claim 1, wherein: the mixing time of the three-dimensional mixer is 10-15min.
6. A method for preparing portland cement using copper tailings according to claim 1, wherein: the preheating temperature is 850-1000 ℃ and the preheating time is 20-40min.
7. A method for preparing portland cement using copper tailings according to claim 1, wherein: the calcination temperature of the high-temperature furnace is 1350-1450 ℃ and the calcination time is 20-40min.
8. A method for preparing portland cement using copper tailings according to claim 1, wherein: the preparation method of the cement auxiliary agent comprises the following steps:
step one: mixing maleic anhydride and diethanolamine, adding the mixture into a reactor, adding 0.3 to 2.0 mass percent of methyl benzene sulfonic acid of the maleic anhydride into the reactor, reacting for 2 to 4 hours at the temperature of between 90 and 102 ℃, and obtaining the alcohol amine maleate after the reaction is finished;
step two: the weight ratio of copper acrylate, allyl boric acid neopentyl glycol ester, maleic acid alcohol amine ester, potassium persulfate, gelatin and water is (1-5): 10-20): 40-50): 0.5-2: (0.5-2): (200-300), uniformly mixing, introducing nitrogen, reacting for 2-4h at 70-80 ℃, filtering and drying after the reaction is finished to obtain the cement auxiliary agent.
9. The method for preparing silicate cement by using copper tailings according to claim 8, wherein: in the first step, the mass ratio of maleic anhydride to diethanolamine is 100:10-18.
10. The method for preparing silicate cement by using copper tailings according to claim 8, wherein: in the first step, the catalyst added in amidation of the alcohol amine maleate is sodium methoxide or sodium ethoxide.
CN202310070540.6A 2023-02-07 2023-02-07 Method for preparing silicate cement by using copper tailings Pending CN116161885A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62241855A (en) * 1986-04-11 1987-10-22 花王株式会社 Manufacture of finely grained cement admixer
JP2004210587A (en) * 2002-12-27 2004-07-29 Nippon Shiika Kk Cement dispersing agent and concrete composition containing the same
CN103601380A (en) * 2013-11-04 2014-02-26 葛洲坝当阳水泥有限公司 Cement clinker produced by use of copper-lead tailings and sulfuric acid residues and production method thereof
CN108117282A (en) * 2017-12-25 2018-06-05 葛洲坝宜城水泥有限公司 A kind of Portland clinker and preparation method thereof
CN109437618A (en) * 2019-01-11 2019-03-08 湖北三鑫金铜股份有限公司 A kind of clinker and preparation method thereof using the production of high calcium copper tailing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62241855A (en) * 1986-04-11 1987-10-22 花王株式会社 Manufacture of finely grained cement admixer
JP2004210587A (en) * 2002-12-27 2004-07-29 Nippon Shiika Kk Cement dispersing agent and concrete composition containing the same
CN103601380A (en) * 2013-11-04 2014-02-26 葛洲坝当阳水泥有限公司 Cement clinker produced by use of copper-lead tailings and sulfuric acid residues and production method thereof
CN108117282A (en) * 2017-12-25 2018-06-05 葛洲坝宜城水泥有限公司 A kind of Portland clinker and preparation method thereof
CN109437618A (en) * 2019-01-11 2019-03-08 湖北三鑫金铜股份有限公司 A kind of clinker and preparation method thereof using the production of high calcium copper tailing

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