CN112408821A - Method for producing high-iron sulphoaluminate cement by utilizing red mud and aluminum ash - Google Patents
Method for producing high-iron sulphoaluminate cement by utilizing red mud and aluminum ash Download PDFInfo
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- CN112408821A CN112408821A CN202011351993.9A CN202011351993A CN112408821A CN 112408821 A CN112408821 A CN 112408821A CN 202011351993 A CN202011351993 A CN 202011351993A CN 112408821 A CN112408821 A CN 112408821A
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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
- C04B7/32—Aluminous cements
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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
Abstract
The invention relates to the technical field of special cement, in particular to a method for producing high-iron sulphoaluminate cement by using red mud and aluminum ash. The method for producing the high-iron sulphoaluminate cement by utilizing the red mud and the aluminum ash comprises the following steps: mixing and reacting carbide slag and waste sulfuric acid, and drying to obtain waste slag containing calcium sulfate; mixing red mud, secondary aluminum ash, waste cathode carbon blocks, calcium sulfate-containing waste residues and/or waste gypsum, grinding and drying limestone serving as a correction material to obtain cement raw materials, and calcining the cement raw materials to obtain cement clinker; mixing the modified red mud and the waste gypsum to obtain a mixture A; mixing the modified red mud, the waste gypsum and the limestone to obtain a mixture B; and mixing the cement clinker with the mixture A or the mixture B, and grinding to obtain the high-iron sulphoaluminate cement. The invention treats and utilizes the waste sulfuric acid while utilizing the industrial solid waste, and the produced high-iron sulphoaluminate cement has high strength, no heavy metal dissolution and low cost.
Description
Technical Field
The invention relates to the technical field of special cement, in particular to a method for producing high-iron sulphoaluminate cement by using red mud and aluminum ash.
Background
The red mud is the most main solid waste residue produced in the production of alumina, and is the solid waste left after alumina is extracted from bauxite through a series of physical and chemical reaction processes, and 0.8-1.6 tons of red mud are produced when 1 ton of alumina is produced. At present, the annual red mud production of domestic alumina factories is about more than 1 hundred million tons, and the stockpiling amount is about more than 5 hundred million tons. Due to the high alkali content of the red mud, the resource utilization difficulty is high, the stacking cost is high, and the environmental risk is high.
The aluminum ash is the most main solid waste residue in the process of processing and smelting electrolytic aluminum and aluminum, and is the scum of various additives and metal oxides and the furnace body deposition slag added in the process of smelting metal aluminum. At present, the production amount of the domestic aluminum ash is about more than 200 ten thousand tons per year. The aluminum ash is listed as a national list of dangerous solid wastes, and because no economic and effective treatment method exists, the stockpiling quantity of a slag producer is large, and the stockpiling cost is high.
In addition, sulfuric acid is widely applied to the industries of chemical industry, steel and the like, the utilization rate of the sulfuric acid is very low in a plurality of production processes, and a large amount of sulfuric acid is discharged along with acid-containing wastewater. The waste sulfuric acid contains heavy metals, and if the waste sulfuric acid is discharged into the environment without being treated, the waste sulfuric acid can acidify water bodies or soil, causes harm to the ecological environment and wastes a large amount of resources. The existing treatment methods of the waste sulfuric acid comprise a concentration method, an oxidation method, an extraction method, a crystallization method and the like, the treatment cost is higher, the price of the finished sulfuric acid is lower, and the overall economic benefit is low.
The economic treatment of industrial solid wastes such as red mud, aluminum ash and the like and waste sulfuric acid becomes a heart of industry and environmental protection, and the effective and economic realization of the resource utilization of industrial wastes in large quantity is particularly urgent.
The sulphoaluminate cement can well utilize the main components of industrial solid wastes such as aluminum ash, red mud and the like, such as: alumina, calcium oxide, silicon oxide and the like, therefore, the current research aims at how to prepare sulphoaluminate cement by using a large amount of red mud and aluminum ash.
Patent CN201410105340.0 discloses a process for producing sulphoaluminate cement by using aluminum ash, which comprises the steps of mixing aluminum ash, dealkalized red mud, desulfurized gypsum and carbide slag as raw materials, grinding by a wet method, continuously stirring to fully mix various components in a water phase, reacting and homogenizing, calcining the dried raw materials, and finally rapidly cooling by a cooling machine to obtain sulphoaluminate cement clinker. Although the technical scheme uses the industrial solid wastes such as the red mud, the aluminum ash and the like for producing the sulphoaluminate cement clinker, the red mud is only limited to the Bayer process red mud and needs dealkalization, the process adopts 'mixed wet grinding, filter pressing, drying and calcining', the energy consumption is high, the application of the red mud is limited, and the economical efficiency of the project is influenced to a certain extent.
Patent CN202010161255.1 discloses a method and system for preparing sulphoaluminate cement from aluminum ash pretreated whole solid waste, wherein the aluminum ash is heated to not less than 900 ℃ for heat treatment, the heat-treated aluminum ash is homogenized and mixed with red mud, desulfurized gypsum and carbide slag, the mixed material is dried by using hot gas generated by the heat treatment, the dried material is ground in a raw powder proportioning manner, and the ground material in the raw powder proportioning manner is calcined to obtain sulphoaluminate cement clinker. Although the invention realizes that the bauxite is completely replaced by the aluminum ash, the tail part of the rotary kiln is not easy to form a ring and the blockage of a condenser is avoided, the aluminum ash needs to be pretreated at high temperature, the treatment process has large energy consumption, and the waste gas is discharged and is harmful to the environment.
Patent CN201710159979.0 discloses a system and method for preparing sulphoaluminate cement by using organic wastewater in cooperation with industrial solid waste, in which dealkalized red mud, carbide slag, aluminum ash, desulfurized gypsum and a part of organic wastewater are mixed to obtain a mixed solution, the mixed solution is subjected to wet grinding, the wet ground material is homogenized to obtain slurry, the slurry is subjected to mechanical filter pressing and dehydration to obtain slurry, the other part of organic wastewater is concentrated and then enters a rotary kiln together with the slurry to be subjected to high-temperature calcination to obtain sulphoaluminate clinker, and coal powder is sprayed into the rotary kiln during the high-temperature calcination process to combust the coal powder, the organic waste in the slurry and the organic waste in the concentrated wastewater. According to the technical scheme, the red mud needs to be subjected to dealkalization pretreatment, and the organic wastewater concentrated solution and the raw meal are calcined together, so that part of toxic substances are remained in cement clinker, and harm is caused to human bodies and the environment in the use process of the cement.
In the prior art, in order to increase the doping amount of red mud and aluminum ash in sulphoaluminate cement, dealkalization pretreatment needs to be carried out on the red mud, or high-temperature pretreatment needs to be carried out on the aluminum ash, so that the utilization difficulty is increased; and the wet process for producing cement clinker can mix raw materials uniformly, and has little dust flying, but has high energy consumption and difficult equipment upsizing. Furthermore, the use of waste sulfuric acid for the production of sulphoaluminate cement has not been reported.
Disclosure of Invention
The invention aims to provide a method for producing high-iron sulphoaluminate cement by using red mud and aluminum ash, which does not need to pretreat the red mud and the aluminum ash, treats and utilizes waste sulfuric acid while utilizing industrial solid wastes, solves the problem that the industrial wastes such as the red mud, the aluminum ash and the waste sulfuric acid are difficult to be recycled in large quantities, and has the advantages of high strength, no heavy metal dissolution and low cost.
The method for producing the high-iron sulphoaluminate cement by utilizing the red mud and the aluminum ash comprises the following steps:
(1) pretreatment of waste sulfuric acid: mixing and reacting carbide slag and waste sulfuric acid, and drying to obtain waste slag containing calcium sulfate;
(2) preparing cement clinker: mixing red mud, secondary aluminum ash, waste cathode carbon blocks, calcium sulfate-containing waste residues and/or waste gypsum, grinding and drying limestone serving as a correction material to obtain cement raw materials, calcining the cement raw materials to obtain cement clinker, wherein the cement clinker meets the following requirements of oxides in percentage by weight: SiO 225-13% of Al2O320-30% of Fe2O34-10% of CaO, 40-50% of CaO, and SO35-12% of the total;
(3) preparing a mixture: mixing the modified red mud and the waste gypsum according to the mass ratio of 10: 1-4 to obtain a mixture A; mixing the modified red mud, the waste gypsum and the limestone according to a mass ratio of 10: 1-4 to obtain a mixture B;
(4) preparing cement: and mixing the cement clinker with the mixture A or the mixture B according to the mass ratio of 10: 1-4, and grinding to obtain the high-iron sulphoaluminate cement.
In the step (1), the molar ratio of calcium ions in the carbide slag to sulfate ions in the waste sulfuric acid is 1.1-1.3: 1. The water content in the waste residue containing calcium sulfate is less than 5 wt%. The carbide slag is kept in excess to fully react the waste sulfuric acid.
The main component of the waste sulfuric acid is H2SO4And salts thereof, which contain heavy metals.
The main component of the carbide slag is Ca (OH)2。
In the step (2), the red mud is one or two of Bayer process red mud and sintering process red mud. The red mud is separately dried and loosened before mixing, and the aged red mud is selected. The mixing amount of the red mud is 25-40%.
The Bayer process red mud comprises the following components in percentage by mass: al (Al)2O3 18～22％，SiO2 20～30％，CaO 1～5％，Fe2O3 20～30％，Na2O 4～8％。
The sintering red mud comprises the following components in percentage by mass: al (Al)2O3 5～7％，SiO2 20～30％，CaO 38～45％，Fe2O3 5～8％，Na2O 1～3％。
The secondary aluminum ash is the aluminum ash after the metal aluminum is extracted. The doping amount of the secondary aluminum ash is 10-30%.
The secondary aluminum ash comprises the following components in percentage by mass: al (Al)2O360～70％，SiO2 1～10％，CaO 1～5％，Fe2O31-3%, 1-10% of MgO, 0.5-8% of fluoride and 0-1% of chloride.
The waste cathode carbon blocks are ground to 80-100 meshes before mixing, and the mixing amount of the waste cathode carbon blocks is 0-5%, preferably 1-5%.
The waste cathode carbon block comprises the following components in percentage by mass: al (Al)2O350～70％，C20～30％，NaF-N3AlF65～10％。
The waste gypsum is one or more of fluorgypsum, phosphogypsum and desulfurized gypsum, the water content of the waste gypsum is less than 5 wt%, and the main component is CaSO4。
The mixing amount of the waste residue and/or waste gypsum containing calcium sulfate is 10-20%.
After the raw materials are mixed, the mixture is ground until the 80 mu m sieve residue is less than 10 percent.
The calcination temperature is 1200-1280 ℃, and the calcination time is 30-50 min.
The mineral composition of the cement clinker comprises (by mass percent):
C2S14～37％，C6AF215-35%. Wherein C is CaO and A is Al2O3，
Is SO3S is SiO2F is Fe2O3。
When cement clinker is produced, the aluminum ash mainly provides an alumina component, fluoride contained in the alumina component is converted into calcium fluoride and low-melting-point salt carried in the calcium fluoride plays a role of a mineralizer, the sintering of materials is promoted, and the roasting temperature is reduced; the red mud can provide iron oxide and silicon oxide, and also provide partial aluminum oxide and calcium oxide; the waste sulfuric acid, the carbide slag and the waste gypsum are mainly used for providing calcium sulfate; f element contained in the waste cathode carbon block plays a role in mineralization in the sintering process, the material sintering is promoted, the roasting temperature is reduced, and the contained carbon is fully combusted during high-temperature calcination to provide heat energy for the calcination.
In the step (3), the preparation method of the modified red mud comprises the following steps: calcining the sintering-process red mud at the temperature of 700-800 ℃ for 30-50min, and then rapidly cooling to obtain the modified red mud.
Modifying red mudThe function is to remove C in the red mud2Conversion of the S-form to the beta-C required for cement performance2And S, the hydration activity of the red mud in concrete is improved, so that the mixing amount of the red mud is improved, and the strength of cement is improved.
In the step (4), grinding is carried out until the 80 mu m sieve residue is less than 10%.
According to the invention, the specific conditions of the components and properties of the waste materials such as aluminum ash, red mud and the like are combined with the production process and the technical index requirements of the sulphoaluminate cement or clinker thereof, and through the synergistic effect of the raw materials, the doping amount of the red mud is increased, the resource treatment is carried out on the refractory industrial hazardous waste such as the waste cathode carbon blocks, the waste sulfuric acid and the like, and the prepared high-iron sulphoaluminate cement has high strength and meets the industrial application standard.
The red mud contains a large amount of alkali, in portland cement concrete, the presence of the alkali aggravates the erosion of hydration products to concrete aggregate, the later performance of the concrete is affected, and when the red mud is used for producing portland cement, the red mud needs to be subjected to dealkalization treatment, so that the alkali content of the cement is reduced to below 0.6 percent, and therefore, the red mud cannot be used for producing ordinary portland cement in a large amount. By researching the characteristics of high-iron sulphoaluminate cement, the sulphoaluminate cement is discovered to belong to low-alkalinity cement, hydration products are different, the compactness and the erosion resistance of the hydration products are strong, the alkali-aggregate reaction is weak, and the existence of alkali can accelerate the hydration products, namely ettringite (3 CaO. Al)2O3·3CaSO4·32H2O), which is favorable for the strength stability of the concrete, and the mineral phase of the high-iron sulphoaluminate cement clinker, especially the iron phase mineral, continues to play a solid solution role for sodium oxide and potassium oxide after hydration, part of the iron phase mineral is converted into colloidal ferric hydroxide, the ferric hydroxide colloid plays a strong accommodation role for sodium oxide and potassium oxide, and plays a great role in the aspects of permeability resistance, salt erosion resistance and freeze-thaw resistance, so that the red mud does not need to be dealkalized. However, the cement clinker has too much red mud doping amount, and the flue is easy to scab during calcination, so the invention adds the red mud into the cement clinker in two parts according to the specific production condition, and dopes one part of the red mud into the cement clinker, and adds the red mud into waterA part of the modified red mud is mixed into the mud mixture, so that flue scabbing is avoided, the red mud mixing amount is increased, and the modified red mud contains beta-C required by cement performance2And S, the hydration activity of the cement in concrete is improved, so that the strength of the cement is further improved.
The chloride ions contained in the aluminum ash form calcium chloroaluminate silicate with other components under high-temperature calcination, and are dissolved in the cement minerals in a solid mode, so that the stability of the chloride ions is improved, and the corrosion resistance of the cement to chlorine-containing solutions is improved.
The waste cathode carbon block is generally used as fuel for combustion treatment, but carbon in the waste cathode carbon block is graphitized and is not easy to combust, and the waste cathode carbon block is easy to combust insufficiently when used as fuel and cannot be completely treated. The method grinds the waste cathode carbon blocks into powder, mixes the powder in a raw material mode, and carries out high-temperature calcination, so that the contact area of the waste cathode carbon blocks and air is increased, the high-temperature sintering time is prolonged, the carbon contained in the waste cathode carbon blocks is ensured to be fully combusted, and the heat energy of the waste cathode carbon blocks is fully utilized; in addition, the waste cathode carbon blocks contain a large amount of F elements, and play a role in mineralization in the sintering process, and in a main mineral multi-phase diagram sintered by sulphoaluminate cement clinker, the participation of calcium fluoride can shift down the liquidus line and reduce the generation temperature of required minerals, thereby reducing the sintering temperature and controlling the content of free calcium oxide.
The waste sulfuric acid contains heavy metals which can cause harm to the environment and human bodies, so the heavy metals are required to be removed when the waste sulfuric acid is recycled. In the research of the invention, the solidification rate of heavy metal elements in the high-iron sulphoaluminate cement clinker is very high, because each molecular unit cell of the mineral C3A of the high-iron sulphoaluminate cement clinker has 8 holes with the radius of 1.47nm, and the electronegativity of Zn, As, Co, Cu and Ni is close to that of Fe and Al, thereby providing conditions for the solid solution of Zn, As, Co, Cu and Ni. The clinker minerals are selective to the solidification of heavy metal elements, Zn is concentrated in the intermediate minerals of the clinker, As, Co, Cu and Ni are mostly present in the intermediate mineral phase of the clinker, but are also present in C3S and C2In S, Cd and Pb are distributed in main minerals of clinker more uniformly. Heavy metals being either encapsulated in the cement hydration phase or by waterThe compound is adsorbed, and the leaching of heavy metals after cement curing is very low. The invention uses the waste sulfuric acid to produce the high-iron sulphoaluminate cement, not only solidifies the heavy metal contained in the waste sulfuric acid to avoid the harm of the heavy metal dissolving out to the environment and human body, but also solidifies the heavy metal in the cement clinker to the beta-C required by the cement performance2S also has a stabilizing effect, e.g. CuO accelerates beta-C2S formation, silver and vanadium oxides both prevent beta-C2S direction gamma-C2S conversion, MnO2The beta form can be stabilized to further improve the strength of the cement.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention improves the resource utilization limit of the industrial hazardous solid waste and the waste sulfuric acid to the maximum extent, the doping amount of the red mud can reach 30-50%, and the doping of the aluminum ash also replaces the precious bauxite resource, so that the product cost is greatly reduced;
(2) the invention adds the red mud into two parts, mixes a part of red mud into the cement clinker, mixes a part of modified red mud into the cement mixture, not only avoids flue scabbing and increases the mixing amount of the red mud, but also contains beta-C required by the cement performance in the modified red mud2S, the hydration activity of the cement in concrete is improved, so that the strength of the cement is further improved;
(3) according to the invention, the aluminum ash is not required to be pretreated, and chloride ions contained in the aluminum ash and other components form calcium chloroaluminate silicate under high-temperature calcination, and the calcium chloroaluminate silicate is dissolved in cement minerals, so that the stability of the chloride ions is improved, and the corrosion resistance of the cement to chlorine-containing solution is improved;
(4) the waste cathode carbon blocks are doped as raw materials, so that the combustion heat energy of the waste cathode carbon blocks is fully utilized, the mineralization of F elements contained in the waste cathode carbon blocks is utilized, the sintering temperature is reduced, the low-temperature sintering is favorable for crystallization of liquid-phase materials during cooling, the formation of glass bodies is reduced in the clinker sintering process, the cement hydration reaction is favorable, and the cement strength is improved;
(5) the invention uses the waste sulfuric acid to produce the high-iron sulphoaluminate cement, and the waste sulfuric acid contains heavy mattersThe metal is solidified, thereby avoiding the heavy metal from dissolving out to cause harm to the environment and human body, and the heavy metal is solidified in the cement clinker and has beta-C required by the cement performance2S also has a stabilizing effect, so that the strength of the cement is further improved;
(6) the high-iron sulphoaluminate cement prepared by the invention belongs to low-alkalinity cement, has good compactness and strong corrosion resistance, has strong solid solubility on metal sodium, potassium, magnesium and titanium, avoids the adverse effect of alkali on the cement, and meets the standard requirement of sulphoaluminate cement;
(7) the invention adopts the dry process to prepare the high-iron sulphoaluminate cement, and compared with the conventional wet process, the energy consumption is low and the production cost is low.
Detailed Description
Example 1
(1) Pretreatment of waste sulfuric acid: mixing 5.91kg of carbide slag containing 10% of water and 20kg of waste sulfuric acid containing 68% of water for reaction, and drying until the water content is 3 wt% to obtain 14.6kg of waste slag containing calcium sulfate for later use;
(2) preparing cement clinker: mixing 5.5kg of sintering red mud, 3.5kg of secondary aluminum ash, 0.5kg of waste cathode carbon block, 2.5kg of waste slag containing calcium sulfate and 4.5kg of limestone, drying until the moisture content is lower than 5 wt%, grinding until the 80 mu m screen residue is less than 10% to obtain cement raw material, calcining the cement raw material at 1250 ℃ for 45min, cooling to 300 ℃ by air, and naturally cooling to room temperature to obtain cement clinker;
(3) preparing a mixture: calcining the sintering-process red mud at the temperature of 750 ℃ for 40min, and then rapidly cooling to obtain modified red mud; mixing the modified red mud and the fluorgypsum according to the mass ratio of 10:2 to obtain a mixture A;
(4) preparing cement: and mixing the cement clinker with the mixture A according to the mass ratio of 10:2, and grinding until the 80 mu m sieve residue is less than 10 percent to obtain the high-iron sulphoaluminate cement.
Example 2
(1) Pretreatment of waste sulfuric acid: mixing 5.91kg of carbide slag containing 10% of water and 20kg of waste sulfuric acid containing 68% of water for reaction, and drying until the water content is 3 wt% to obtain 14.6kg of waste slag containing calcium sulfate for later use;
(2) preparing cement clinker: mixing 6.0kg of Bayer process red mud, 2.5kg of secondary aluminum ash, 0.6kg of waste cathode carbon block, 2.3kg of waste slag containing calcium sulfate and 6.5kg of limestone, drying until the moisture content is lower than 5 wt%, grinding until the 80 mu m of screen residue is less than 10% to obtain cement raw material, calcining the cement raw material at 1280 ℃ for 1h, cooling to 300 ℃ by air, and naturally cooling to room temperature to obtain cement clinker;
(3) preparing a mixture: calcining the sintering-process red mud at the temperature of 750 ℃ for 40min, and then rapidly cooling to obtain modified red mud; mixing the modified red mud and the phosphogypsum according to the mass ratio of 10:4 to obtain a mixture A;
(4) preparing cement: and mixing the cement clinker with the mixture A according to the mass ratio of 10:1, and grinding to obtain the high-iron sulphoaluminate cement.
Example 3
(1) Preparing cement clinker: mixing 5kg of sintering red mud, 3kg of secondary aluminum ash, 0.5kg of waste cathode carbon block, 2kg of fluorgypsum and 3kg of limestone, drying until the moisture content is lower than 5 wt%, grinding until the 80 mu m of the residue on a sieve is less than 10% to obtain cement raw material, calcining the cement raw material at 1250 ℃ for 50min, cooling to 300 ℃ by air, and naturally cooling to room temperature to obtain cement clinker;
(2) preparing a mixture: calcining the sintering-process red mud at the temperature of 750 ℃ for 40min, and then rapidly cooling to obtain modified red mud; mixing the modified red mud, the fluorgypsum and the limestone according to a mass ratio of 10:3:2 to obtain a mixture B;
(3) preparing cement: and mixing the cement clinker and the mixture B according to the mass ratio of 10:4, and grinding until the 80 mu m sieve residue is less than 10 percent to obtain the high-iron sulphoaluminate cement.
Example 4
(1) Preparing cement clinker: mixing 5kg of Bayer process red mud, 2.5kg of secondary aluminum ash, 0.7kg of waste cathode carbon block, 2.5kg of desulfurized gypsum and 6kg of limestone, drying until the moisture content is lower than 5 wt%, grinding until the sieve residue with the particle size of 80 mu m is less than 10% to obtain cement raw material, calcining the cement raw material at 1250 ℃ for 50min, cooling to 300 ℃ by air, and naturally cooling to room temperature to obtain cement clinker;
(2) preparing a mixture: calcining the sintering-process red mud at the temperature of 750 ℃ for 40min, and then rapidly cooling to obtain modified red mud; mixing the modified red mud, the desulfurized gypsum and the limestone according to a mass ratio of 10:2:4 to obtain a mixture B;
(3) preparing cement: and mixing the cement clinker with the mixture B according to the mass ratio of 10:3, and grinding to obtain the high-iron sulphoaluminate cement.
Example 5
(1) Pretreatment of waste sulfuric acid: mixing 6kg of carbide slag containing 12% of water and 18kg of waste sulfuric acid containing 60% of water for reaction, and drying until the water content is 4 wt% to obtain 15.6kg of waste slag containing calcium sulfate;
(2) preparing cement clinker: mixing 2.5kg of Bayer process red mud, 4kg of sintering process red mud, 3.5kg of secondary aluminum ash, 0.6kg of waste cathode carbon block, 3kg of waste slag containing calcium sulfate and 3kg of limestone, drying until the water content is lower than 5 wt%, grinding until the 80 mu m screen residue is less than 10% to obtain cement raw material, calcining the cement raw material at 1250 ℃ for 50min, cooling to 300 ℃ by air, and naturally cooling to room temperature to obtain cement clinker;
(3) preparing a mixture: calcining the sintering-process red mud at the temperature of 750 ℃ for 40min, and then rapidly cooling to obtain modified red mud; mixing the modified red mud, the fluorgypsum and the limestone according to a mass ratio of 10:4:1 to obtain a mixture B;
(4) preparing cement: and mixing the cement clinker with the mixture B according to the mass ratio of 10:1, and grinding to obtain the high-iron sulphoaluminate cement.
Example 6
(1) Preparing cement clinker: mixing 5.5kg of sintering red mud, 3.5kg of secondary aluminum ash, 3.5kg of limestone, 0.7kg of waste cathode carbon block and 2.5kg of phosphogypsum, drying until the moisture content is lower than 3 wt%, grinding until the sieve residue with the particle size of 80 mu m is less than 10% to obtain cement raw material, calcining the cement raw material at 1260 ℃ for 55min, cooling to 300 ℃ by air, and naturally cooling to room temperature to obtain cement clinker;
(2) preparing a mixture: calcining the sintering-process red mud at the temperature of 750 ℃ for 40min, and then rapidly cooling to obtain modified red mud; mixing the modified red mud, the fluorgypsum and the limestone according to a mass ratio of 10:2:1 to obtain a mixture B;
(3) preparing cement: and mixing the cement clinker and the mixture B according to the mass ratio of 10:2, and grinding until the 80 mu m sieve residue is less than 10 percent to obtain the high-iron sulphoaluminate cement.
Example 7
(1) Preparing cement clinker: mixing 5kg of Bayer process red mud, 2.5kg of secondary aluminum ash, 2.5kg of fluorgypsum and 6kg of limestone, drying until the moisture content is lower than 4 wt%, grinding until the 80 mu m sieve residue is less than 10% to obtain cement raw materials, calcining the cement raw materials at 1270 ℃ for 50min, cooling to 300 ℃ by air, and naturally cooling to room temperature to obtain cement clinker;
(2) preparing a mixture: calcining the sintering-process red mud at the temperature of 720 ℃ for 50min, and then quickly cooling to obtain modified red mud; mixing the modified red mud, the fluorgypsum and the limestone according to a mass ratio of 10:2:3 to obtain a mixture B;
(3) preparing cement: and mixing the cement clinker with the mixture B according to the mass ratio of 10:4, and grinding to obtain the high-iron sulphoaluminate cement.
The high-iron sulphoaluminate cement prepared in the examples 1 to 7 is subjected to a performance test with the test standard of GB/T37125-2018.
The test results are shown in table 1.
TABLE 1 Performance test results for high iron sulphoaluminate cements prepared in examples 1-7
Claims (10)
1. A method for producing high-iron sulphoaluminate cement by using red mud and aluminum ash is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment of waste sulfuric acid: mixing and reacting carbide slag and waste sulfuric acid, and drying to obtain waste slag containing calcium sulfate;
(2) preparing cement clinker: mixing red mud, secondary aluminum ash, waste cathode carbon blocks, calcium sulfate-containing waste residues and/or waste gypsum, grinding and drying limestone serving as a correction material to obtain cement raw materials, calcining the cement raw materials to obtain cement clinker, wherein the cement clinker meets the following requirements of oxides in percentage by weight: SiO 225-13% of Al2O320-30% of Fe2O34-10% of CaO, 40-50% of CaO, and SO35-12% of the total;
(3) preparing a mixture: mixing the modified red mud and the waste gypsum according to the mass ratio of 10: 1-4 to obtain a mixture A; mixing the modified red mud, the waste gypsum and the limestone according to a mass ratio of 10: 1-4 to obtain a mixture B;
(4) preparing cement: and mixing the cement clinker with the mixture A or the mixture B according to the mass ratio of 10: 1-4, and grinding to obtain the high-iron sulphoaluminate cement.
2. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (1), the molar ratio of calcium ions in the carbide slag to sulfate ions in the waste sulfuric acid is 1.1-1.3: 1.
3. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (2), the red mud is one or two of Bayer process red mud and sintering process red mud, and the mixing amount of the red mud is 25-40%.
4. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (2), the doping amount of the secondary aluminum ash is 10-30%.
5. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (2), the mixing amount of the waste residue and/or waste gypsum containing calcium sulfate is 10-20%.
6. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (2), the waste cathode carbon blocks are ground to 80-100 meshes before mixing, and the mixing amount of the waste cathode carbon blocks is 0-5%.
7. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (2), the calcination temperature is 1200-1280 ℃, and the calcination time is 30-60 min.
8. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (2), the mineral composition of the cement clinker is as follows by mass percent:
C2S 14～37％，C6AF215-35%; wherein C is CaO and A is Al2O3，
Is SO3S is SiO2F is Fe2O3。
9. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (3), the preparation method of the modified red mud comprises the following steps: calcining the sintering-process red mud at the temperature of 700-800 ℃ for 30-50min, and then rapidly cooling to obtain the modified red mud.
10. The method for producing the high-iron sulphoaluminate cement by using the red mud and the aluminum ash according to claim 1, which is characterized in that: in the step (2) and the step (3), the waste gypsum is one or more of fluorgypsum, phosphogypsum and desulfurized gypsum.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113443643A (en) * | 2021-05-25 | 2021-09-28 | 昆明理工大学 | Method for cooperatively treating aluminum ash, carbon slag and desulfurized gypsum slag |
| CN113603375A (en) * | 2021-08-27 | 2021-11-05 | 中铝郑州有色金属研究院有限公司 | Alumina, mixed clinker for producing alumina and preparation method of mixed clinker |
| CN114133196A (en) * | 2021-11-22 | 2022-03-04 | 云南森博混凝土外加剂有限公司 | Cement grouting material and preparation method thereof |
| CN114315190A (en) * | 2022-01-20 | 2022-04-12 | 砼牛（上海）智能科技有限公司 | Production method of sulphoaluminate cement |
| CN114455617A (en) * | 2022-02-24 | 2022-05-10 | 肇庆南都再生铝业有限公司 | Method for producing calcium aluminate by using aluminum ash |
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| CN116730638A (en) * | 2023-06-15 | 2023-09-12 | 济南大学 | Alkali-resistant iron-rich sulphoaluminate cement composite cementing material and preparation process thereof |
| CN116969703A (en) * | 2023-09-18 | 2023-10-31 | 常熟理工学院 | Method for preparing geopolymerized sulphoaluminate cement by using lithium slag and secondary aluminum ash |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645453A (en) * | 2015-12-14 | 2016-06-08 | 河南开祥精细化工有限公司 | Method for disposing industrial waste sulfuric acid by utilizing carbide slag |
| WO2018166221A1 (en) * | 2017-03-17 | 2018-09-20 | 山东大学 | System and method for co-treating organic wastewater and industrial solid waste |
| CN109020274A (en) * | 2018-09-10 | 2018-12-18 | 嘉华特种水泥股份有限公司 | A kind of aluminate cement with high iron and surfur content clinker and preparation method thereof |
-
2020
- 2020-11-26 CN CN202011351993.9A patent/CN112408821A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645453A (en) * | 2015-12-14 | 2016-06-08 | 河南开祥精细化工有限公司 | Method for disposing industrial waste sulfuric acid by utilizing carbide slag |
| WO2018166221A1 (en) * | 2017-03-17 | 2018-09-20 | 山东大学 | System and method for co-treating organic wastewater and industrial solid waste |
| CN109020274A (en) * | 2018-09-10 | 2018-12-18 | 嘉华特种水泥股份有限公司 | A kind of aluminate cement with high iron and surfur content clinker and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 于兴敏: "《新型干法水泥使用技术全书 上册》", 31 August 2006, 中国建材工业出版社 * |
| 历衡隆: "《铝冶炼生产技术手册》", 31 July 2011, 北京冶金工业出版社 * |
| 房永广: "《赤泥资源化利用理论及技术》", 31 July 2020, 中国建材工业出版社 * |
| 程钰: "《赤泥资源化公路工程应用》", 31 December 2018, 山东大学出版社 * |
| 陈益民: "《高性能水泥基础研究——973项目研究进展》", 30 November 2004, 中国纺织出版社 * |
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| CN113443643B (en) * | 2021-05-25 | 2022-04-01 | 昆明理工大学 | Method for cooperatively treating aluminum ash, carbon slag and desulfurized gypsum slag |
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