CN112266188A - Method for preparing phosphorus modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash - Google Patents
Method for preparing phosphorus modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B7/24—Cements from oil shales, residues or waste other than slag
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Abstract
The invention discloses a method for preparing phosphorus modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash, which comprises the following steps: (1) mixing water and phosphoric acid, and stirring uniformly to prepare a phosphoric acid aqueous solution; (2) mixing phosphoric acid aqueous solution and municipal solid waste incineration fly ash, and stirring to obtain phosphorus-carrying fly ash; (3) introducing the phosphorus-loaded fly ash slurry into an electrolytic cell sample area, then switching on a power supply to remove the phosphorus-loaded fly ash electrically, pouring out the slurry from the electrolytic cell sample area to obtain dechlorinated fly ash, and discharging electrolyte from an electrolytic cell cathode chamber to obtain catholyte; (4) mixing the catholyte obtained in the step (3) with aluminum ash, and stirring to obtain aluminum alkali slurry; (5) and (4) mixing the aluminum alkali slurry with the dechlorinated fly ash obtained in the step (3), sequentially stirring, drying, firing, cooling to normal temperature, and grinding to obtain the phosphorus modified calcium aluminate cement. The invention has simple preparation process, and the required raw materials have few varieties and are easy to obtain, and comprise municipal solid waste incineration fly ash, phosphoric acid and aluminum ash.
Description
Technical Field
The invention belongs to the technical field of harmless disposal and resource utilization of municipal solid waste incineration fly ash, and particularly relates to a method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash.
Background
Cement is one of the main raw materials for engineering construction in various fields. The aluminate cement has the characteristics of high early strength and short setting time, and is widely applied to pouring construction. The calcium aluminate cement, also called alumina cement and aluminate cement, is fine powder with gelling activity obtained by mixing bauxite and calcareous materials according to a proper proportion, sintering and grinding. Calcium aluminate cement was used primarily as a refractory binder in the early days and started to be formally commercially produced in approximately 1916 years. The main minerals of calcium aluminate cement include monocalcium aluminate, calcium dialuminate, dodecacalcium heptaluminate, and the like. After the calcium aluminate cement is mixed with water, the contained monocalcium aluminate and calcium dialuminate can generate hydration reaction to generate a plurality of hydration products. The hydration products interact to form a crystal-gel network structure that bonds the aggregate and fines together, allowing the interface to gain strength. Nowadays, calcium aluminate cement is mainly applied to special projects such as sulfate corrosion resistance, rush repair and rush construction, winter construction and the like. Meanwhile, the material has better high temperature resistance, and can be used for preparing heat-resistant concrete and unshaped refractory materials. However, as mines are continuously mined, the amount of bauxite and calcareous minerals is reduced. The research and development of the aluminate cement prepared by using the industrial solid waste to replace the mineral material meet the concept of green development and sustainable development. The fly ash from burning urban domestic garbage belongs to CaO-SiO2-Al2O3-Fe2O3System mainly containing CaO and SiO2、Al2O3And the like, and has certain gelling activity. However, the fly ash from incineration of municipal solid waste contains a large amount of chloride, trace heavy metal pollutants and trace dioxin pollutantsHas teratogenic, carcinogenic, mutagenic properties, and can be harmful to human health and the surrounding ecological environment. Meanwhile, the calcium aluminate cement prepared by using the municipal solid waste incineration fly ash does not only need to fully utilize the self-gelling property of the fly ash, but also needs to effectively solve the pollution problem of high chlorine, heavy metals and dioxin contained in the fly ash.
Disclosure of Invention
The invention aims to provide a method for preparing phosphorus modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash, so as to fully utilize the gelling property of the fly ash and solve the pollution problem of high chlorine, heavy metals and dioxin contained in the fly ash.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing phosphorus modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash comprises the following steps:
(1) mixing water and phosphoric acid, and stirring uniformly to prepare a phosphoric acid aqueous solution;
(2) mixing phosphoric acid aqueous solution and municipal solid waste incineration fly ash, and stirring to obtain phosphorus-carrying fly ash;
(3) introducing the phosphorus-loaded fly ash slurry into an electrolytic cell sample area, then switching on a power supply to remove the phosphorus-loaded fly ash electrically, pouring out the slurry from the electrolytic cell sample area to obtain dechlorinated fly ash, and discharging electrolyte from an electrolytic cell cathode chamber to obtain catholyte;
(4) mixing the catholyte obtained in the step (3) with aluminum ash, and stirring to obtain aluminum alkali slurry;
(5) and (4) mixing the aluminum alkali slurry with the dechlorinated fly ash obtained in the step (3), sequentially stirring, drying, firing, cooling to normal temperature, and grinding to obtain the phosphorus modified calcium aluminate cement.
Preferably, in the step (1), a phosphoric acid aqueous solution with a mass fraction of 2.5% -17.5% is prepared.
Preferably, in the step (2), the liquid-solid ratio of the phosphoric acid aqueous solution to the municipal solid waste incineration fly ash is 0.5-1.5: 1mL: mg, and the stirring time is 1-3 hours.
Preferably, in the step (3), the electric removal is performed for 3-9 hours, the initial voltage is set to be 50-250V in the electric removal process, and the initial current is set to be 100-500A.
Preferably, in the step (4), the liquid-solid ratio of the catholyte to the aluminum ash is 1-4: 1mL: mg, and the stirring time is 1-3 hours.
Preferably, in the step (5), the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash is 0.5-2.5: 1, and the stirring time is 1-3 hours.
Preferably, in the step (5), the drying temperature is 100-200 ℃.
Preferably, in the step (5), the firing temperature is 500 to 700 ℃, and the firing time is 0.5 to 1.5 hours.
Preferably, in the step (5), the mixture is ground and sieved by a 200-400-mesh sieve.
The principle of the invention is as follows: after the phosphoric acid aqueous solution and the municipal solid waste incineration fly ash are mixed, hydrogen ions released by hydrolysis of phosphoric acid in the stirring process can promote chloride ions and heavy metal ions in the fly ash to be dissolved into a liquid phase. Phosphate radical can be combined with heavy metal ions to generate phosphate precipitation. The phosphorus-loaded fly ash slurry is electrically removed, chloride ions in the slurry are transferred to an anode chamber under the action of electromigration to be converted into chlorine and hypochlorous acid, and free phosphate radicals in the slurry are transferred to an anode chamber under the action of electromigration so as to avoid the influence on the quality of the calcium aluminate cement caused by excessive residual free phosphate radicals in the slurry. The water is hydrolyzed on the surface of the cathode to generate hydroxide ions. The hydroxide ions in the cathode compartment combine with the sodium and potassium ions migrating from the sample area to produce sodium hydroxide and potassium hydroxide. Mixing the catholyte and the aluminum ash, and dissolving the aluminum ash in the stirring process to convert the aluminum ash into aluminate. After the aluminum alkali slurry and the dechlorinated fly ash are mixed, aluminate, calcium ions and phosphate radicals can be partially combined to generate the aluminum-calcium mineral, hydroxyl tuff and aluminum-calcium-phosphorus colloid. The aluminum-calcium mineral, the hydroxyl tuff and the aluminum-calcium-phosphorus colloid can increase the stability of chloride ions and heavy metal ions and reduce the leachable activity of the chloride ions and the heavy metal ions by chemical adsorption and physical coating. The fly ash is fired under the condition of proper firing temperature to prepare the calcium-aluminum mixture, so that the decomposition of calcium hydroxide can be realized, the activity of the prepared calcium aluminate cement is improved, and the sodium salt and the potassium salt are prevented from melting.
Has the advantages that: the invention has simple preparation process, and the required raw materials have few varieties and are easy to obtain, and comprise municipal solid waste incineration fly ash, phosphoric acid and aluminum ash. The invention realizes the conversion of the fly ash from the incineration of the household garbage into the phosphorus-modified calcium aluminate cement through the links of phosphoric acid regulation, electric operation, mixing of aluminum and alkali slurry and firing. The leaching concentrations of heavy metals of zinc, lead and cadmium in the phosphorus modified calcium aluminate cement prepared by the invention are 0.781mg/L, 0.312mg/L and 0.026mg/L, the lowest chlorine content is 0.019%, the lowest dioxin content is 9.23ng-TEQ/kg, and the highest uniaxial compressive strength is 34.71 MPa.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Detailed Description
The invention is further explained below with reference to the drawings.
As shown in figure 1, the method for preparing the phosphorus modified calcium aluminate cement by using the municipal solid waste incineration fly ash and the aluminum ash comprises the following steps:
(1) mixing water and phosphoric acid, and stirring uniformly to prepare a phosphoric acid water solution with the mass fraction of 2.5-17.5%;
(2) mixing phosphoric acid aqueous solution and municipal solid waste incineration fly ash according to a liquid-solid ratio of 0.5-1.5: 1mL: mg, and stirring for 1-3 hours to obtain phosphorus-carrying fly ash;
(3) introducing the phosphorus-loaded fly ash slurry into an electrolytic cell sample area, then switching on a power supply to electrically remove the phosphorus-loaded fly ash slurry for 3-9 hours, pouring out the slurry from the electrolytic cell sample area to obtain dechlorinated fly ash, and discharging electrolyte from an electrolytic cell cathode chamber to obtain catholyte; wherein the initial voltage is set to be 50-250V and the initial current is set to be 100-500A in the electric removal process;
(4) mixing the catholyte obtained in the step (3) with aluminum ash according to a liquid-solid ratio of 1-4: 1mL: mg, and stirring for 1-3 hours to obtain aluminum alkaline slurry;
(5) and (3) mixing the aluminum alkali slurry with the dechlorinated fly ash obtained in the step (3) according to the mass ratio of 0.5-2.5: 1, stirring for 1-3 hours, drying at the temperature of 100-200 ℃, firing at the temperature of 500-700 ℃ for 0.5-1.5 hours, cooling to normal temperature, grinding and sieving with a 200-400-mesh sieve to obtain the phosphorus modified calcium aluminate cement.
The present invention will be further described with reference to the following examples. The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
In the following examples, some of the raw materials were derived from:
incineration fly ash of municipal solid waste: the fly ash from burning municipal solid waste is collected by a bag-type dust collector from a certain waste burning power plant which is normally cooked. The waste incineration fly ash sample contains 61.37 percent of CaO and 3.62 percent of SO3、4.68％SiO2、1.64％Al2O3、6.32％Na2O、3.46％K2O、15.37％Cl、1.12％MgO、1.17％ZnO、0.76％PbO、0.49％CdO。
The aluminum ash is from Guangzhou Jinghong renewable resources Co., Ltd, and contains 39.27% Al and 54.92% Al2O3、3.46％SiO2、1.08％MgO、0.82％CaO、0.45％FeO。
EXAMPLE 1 Effect of phosphoric acid Mass fraction on the Properties of phosphorus-modified calcium aluminate cements produced
Mixing water and phosphoric acid, and stirring uniformly to prepare a phosphoric acid aqueous solution with the mass fractions of 1%, 1.5%, 2%, 2.5%, 10%, 17.5%, 18%, 19% and 20%. And (3) weighing the phosphoric acid aqueous solution and the municipal solid waste incineration fly ash respectively according to the ratio of the phosphoric acid aqueous solution to the municipal solid waste incineration fly ash liquid to be solid of 0.5:1mL, mixing, and stirring for 1 hour to obtain the phosphorus-carrying fly ash. Introducing the phosphorus-loaded fly ash slurry into an electrolytic cell sample area, then switching on a power supply to perform electric removal for 3 hours, pouring out the slurry from the electrolytic cell sample area to obtain dechlorinated fly ash, discharging electrolyte from an electrolytic cell cathode chamber to obtain catholyte, and setting the initial voltage to be 50V and the initial current to be 100A in the electric removal process. Weighing the catholyte and the aluminum ash according to the solid-to-liquid ratio of the catholyte to the aluminum ash of 1:1mL: mg, mixing, and stirring for 1 hour to obtain the aluminum alkali slurry. Respectively weighing the aluminum alkali slurry and the dechlorinated fly ash according to the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash of 0.5:1, mixing, stirring for 1 hour, drying at the temperature of 100 ℃, firing for 0.5 hour at the temperature of 500 ℃, cooling to normal temperature, grinding and sieving with a 200-mesh sieve to obtain the phosphorus modified calcium aluminate cement.
Determination of chlorine content: the content of chlorine in the phosphorus modified calcium aluminate cement is measured according to chemical analysis method of chloride ions in cement raw materials (JC/T420-2006).
And (3) performance testing: the phosphorus modified calcium aluminate cement material is prepared into the tested mortar, wherein the doped sand is ISO standard sand specified in the Cement mortar Strength test method (ISO method) GB/T17671-1999, and the water is tap water. The preparation of the mortar, the preparation of the test piece, the maintenance of the test piece and the measurement of the compression strength of the 28d test piece are all carried out according to the standard GB/T17671-1999 in the Cement mortar Strength test method (ISO method).
Leaching test of heavy metals in phosphorus modified calcium aluminate cement: the phosphorus-modified calcium aluminate cement is prepared into leachate according to the method of the horizontal oscillation method of the leaching method of the solid waste leaching toxicity (HJ 557), and the concentration of heavy metal in the leachate is measured by an inductively coupled plasma mass spectrometer (Thermo Scientific)TMELEMENTTM) And (6) detecting.
A detection test of the content of dioxin in phosphorus modified calcium aluminate cement comprises the following steps: the detection of the content of dioxin in the phosphorus-modified calcium aluminate cement is carried out according to research on the law of hydrothermal degradation of dioxin in municipal refuse incineration fly ash.
The test results of this example are shown in Table 1.
TABLE 1 influence of phosphoric acid mass fraction on the Properties of the prepared phosphorus-modified calcium aluminate Cement
As can be seen from Table 1, the total amount of the phosphorus-modified calcium aluminate cement dioxin residues is reduced along with the increase of the mass fraction of phosphoric acid, but the total amount of the phosphorus-modified calcium aluminate cement dioxin residues does not exceed 50ng-TEQ/kg, and both the phosphorus-modified calcium aluminate cement dioxin residues and the phosphorus-modified calcium aluminate cement dioxin residues meet the technical Specification for controlling pollution of municipal solid waste incineration fly ash (HJ 1134-2020). With the increase of the phosphoric acid mass fraction, the amorphous formThe formation of aluminum calcium phosphate hydrate increases, and 3 CaO. Al having a crystal form is formed due to the formation of a large amount of calcium phosphate2O3·6H2CaO & Al with O in amorphous form2O3·10H2O conversion, resulting in a gradual decrease in uniaxial compressive strength with increasing acid mass fraction. Meanwhile, as can be seen from table 1, when the phosphoric acid mass fraction is less than 2% (as in table 1, when the phosphoric acid mass fraction is 2%, 1.5%, 1% and lower values not listed in table 1), the amount of phosphoric acid added is small, so that the amounts of phosphate precipitation and hydroxyapatite production are reduced, resulting in a significant decrease in the zinc, lead, cadmium leaching concentration values and the measured value of the residual chlorine content in the fly ash as the phosphoric acid mass fraction decreases. When the phosphoric acid mass fraction is equal to 2.5% -17.5% (as in table 1, when the phosphoric acid mass fraction is 2.5%, 10%, 17.5%), the amount of phosphoric acid added is small, so that the amounts of phosphate precipitation and hydroxyapatite production are reduced, resulting in that the leaching concentration values of zinc, lead and cadmium and the measured value of the residual chlorine content in the fly ash are all significantly reduced as the phosphoric acid mass fraction is reduced. Phosphate radical can be combined with heavy metal ions to generate phosphate precipitation. After the aluminum alkali slurry and the dechlorinated fly ash are mixed, aluminate, calcium ions and phosphate radicals can be partially combined to generate the aluminum-calcium mineral, hydroxyl tuff and aluminum-calcium-phosphorus colloid. The aluminum-calcium mineral, the hydroxyl tuff and the aluminum-calcium-phosphorus colloid can increase the stability of chloride ions and heavy metal ions and reduce the leachable activity of the chloride ions and the heavy metal ions by chemical adsorption and physical coating. Finally, the leaching values of zinc are all lower than 1.563mg/L, lead is all lower than 0.874mg/L, cadmium is all lower than 0.096mg/L, and the chlorine content is all lower than 0.053%. When the phosphoric acid mass fraction is more than 17.5% (as in table 1, when the phosphoric acid mass fraction is 18%, 19%, 20%, and higher values not listed in table 1), the amount of phosphoric acid added is too large so that 3CaO · Al having a crystal form is present2O3·6H2CaO & Al with O in amorphous form2O3·10H2And O conversion and physical encapsulation of heavy metals and chlorine by the aluminum-calcium series minerals are deteriorated, so that leaching concentration values of zinc, lead and cadmium and measurement values of residual chlorine content in fly ash are obviously reduced along with further increase of the mass fraction of phosphoric acid. Thus, taken together, the knotThe composite benefit and the cost are favorable for the performance of the prepared phosphorus modified calcium aluminate cement when the mass fraction of the phosphoric acid is equal to 2.5 to 17.5 percent.
Example 2 quality ratio of Alkali pulp to dechlorinated fly ash Effect on the Properties of the prepared phosphorus-modified calcium aluminate Cement
Mixing water and phosphoric acid, stirring uniformly, and preparing a phosphoric acid aqueous solution with the mass fraction of 17.5%. And (3) weighing the phosphoric acid aqueous solution and the municipal solid waste incineration fly ash respectively according to the liquid-solid ratio of 1:1mL: mg of the phosphoric acid aqueous solution to the municipal solid waste incineration fly ash, mixing, and stirring for 2 hours to obtain the phosphorus-carrying fly ash. Introducing the phosphorus-loaded fly ash slurry into an electrolytic cell sample area, then switching on a power supply to perform electric removal for 6 hours, pouring the slurry out of the electrolytic cell sample area to obtain dechlorinated fly ash, discharging electrolyte from an electrolytic cell cathode chamber to obtain catholyte, and setting the initial voltage to be 150V and the initial current to be 300A in the electric removal process. And weighing the catholyte and the aluminum ash according to the liquid-solid ratio of the catholyte to the aluminum ash of 2.5:1mL: mg, mixing, and stirring for 2 hours to obtain the aluminum alkali slurry. Respectively weighing the aluminum alkali slurry and the dechlorinated fly ash according to the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash of 0.25:1, 0.35:1, 0.45:1, 0.5:1, 1.5:1, 2.5:1, 2.6:1, 2.8:1 and 3.0:1, mixing, stirring for 2 hours, drying at the temperature of 150 ℃, firing for 1 hour at the temperature of 600 ℃, cooling to normal temperature, grinding and sieving with a 300-mesh sieve to obtain the phosphorus modified calcium aluminate cement.
The determination of chlorine content, performance test, leaching test of heavy metals in the phosphorus-modified calcium aluminate cement, and detection test of dioxin content in the phosphorus-modified calcium aluminate cement are the same as those in example 1.
The test results of this example are shown in Table 2.
TABLE 2 quality ratio of the aluminum soda slurry to the dechlorinated fly ash for the impact of the properties of the prepared phosphorus modified calcium aluminate cement
As can be seen from table 2, when the mass ratio of the aluminum soda slurry to the dechlorinated fly ash is less than 0.5:1 (as shown in table 2, the mass ratio of the aluminum soda slurry to the dechlorinated fly ash is 0.45:1, 0.35:1, 0.25:1, and is not listed in table 1Lower value of the aluminum alkaline slurry), the aluminum alkaline slurry is less, the generation amount of aluminum calcium series minerals, hydroxyl tuff and aluminum calcium phosphorus series colloids is reduced, and the leaching values of zinc, lead and cadmium, the chlorine content, the dioxin content and the uniaxial compressive strength of the phosphorus modified calcium aluminate cement are obviously reduced along with the reduction of the mass ratio of the aluminum alkaline slurry to the dechlorinated fly ash. When the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash is 0.5-2.5: 1 (as shown in table 2, when the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash is 0.5:1, 1.5:1, or 2.5: 1), mixing the aluminum alkali slurry and the dechlorinated fly ash, and then partially combining aluminate, calcium ions, and phosphate radicals to generate the aluminum-calcium mineral, the hydroxyl tuff, and the aluminum-calcium-phosphorus colloid. The aluminum-calcium mineral, the hydroxyl tuff and the aluminum-calcium-phosphorus colloid can increase the stability of chloride ions and heavy metal ions and reduce the leachable activity of the chloride ions and the heavy metal ions by chemical adsorption and physical coating. Finally, the zinc leaching values are all lower than 1.505mg/L, the lead content is all lower than 0.711mg/L, the cadmium content is all lower than 0.076mg/L, the chlorine content is all lower than 0.045%, the dioxin content is all lower than 22ng-TEQ/kg, and the uniaxial compressive strength is all lower than 27 MPa. When the mass ratio of the aluminum soda slurry to the dechlorinated fly ash is more than 2.5:1 (as shown in Table 2, when the mass ratio of the aluminum soda slurry to the dechlorinated fly ash is 2.6:1, 2.8:1, 3.0:1 and higher values not listed in Table 2), the amount of the aluminum soda slurry is too large, and 3 CaO. Al is excessive2O3·6H2CaO & Al with O in amorphous form2O3·10H2And O conversion, which causes that the leaching values of zinc, lead and cadmium, the chlorine content, the dioxin content and the uniaxial compressive strength of the phosphorus modified calcium aluminate cement are obviously reduced along with the further increase of the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash. Therefore, in summary, the benefit and the cost are combined, and when the mass ratio of the aluminum alkaline slurry to the dechlorinated fly ash is equal to 0.5-2.5: 1, the performance of the prepared phosphorus modified calcium aluminate cement is most beneficial.
EXAMPLE 3 Effect of firing temperature on the Properties of the phosphorus-modified calcium aluminate cements produced
Mixing water and phosphoric acid, stirring uniformly, and preparing a phosphoric acid aqueous solution with the mass fraction of 17.5%. And weighing the phosphoric acid aqueous solution and the municipal solid waste incineration fly ash respectively according to the ratio of the phosphoric acid aqueous solution to the municipal solid waste incineration fly ash liquid to solid of 1.5:1mL, mixing, and stirring for 3 hours to obtain the phosphorus-carrying fly ash. Introducing the phosphorus-loaded fly ash slurry into an electrolytic cell sample area, then switching on a power supply to perform electric removal for 9 hours, pouring the slurry out of the electrolytic cell sample area to obtain dechlorinated fly ash, discharging electrolyte from an electrolytic cell cathode chamber to obtain catholyte, setting the initial voltage to be 250V and the initial current to be 500A in the electric removal process. And weighing the catholyte and the aluminum ash according to the solid-to-liquid ratio of 4:1mL: mg of the catholyte to the aluminum ash, mixing, and stirring for 3 hours to obtain the aluminum alkali slurry. Respectively weighing the aluminum alkali slurry and the dechlorinated fly ash according to the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash of 2.5:1, mixing, stirring for 3 hours, drying at the temperature of 200 ℃, firing at the temperature of 350 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ and 1000 ℃ for 1.5 hours, cooling to normal temperature, grinding and sieving with a 400-mesh sieve to obtain the phosphorus modified calcium aluminate cement.
The determination of chlorine content, performance test, leaching test of heavy metals in the phosphorus-modified calcium aluminate cement, and detection test of dioxin content in the phosphorus-modified calcium aluminate cement are the same as those in example 1.
The test results of this example are shown in Table 3.
TABLE 3 Effect of firing temperature on the Properties of the phosphorus-modified calcium aluminate cements produced
As can be seen from table 3, as the firing temperature increases, the leaching values of zinc, lead and cadmium, the chlorine content of the phosphorus-modified calcium aluminate cement and the dioxin content all decrease gradually. When the firing temperature is less than 500 ℃ (as in table 3, when the firing temperature is 450 ℃, 400 ℃, 350 ℃ and lower values not listed in table 3), the decomposition of calcium hydroxide is insufficient, the activity of the calcium aluminate cement is not significantly increased, resulting in a significant decrease in uniaxial compressive strength as the firing temperature is decreased. When the firing temperature is 500-700 ℃ (500 ℃, 600 ℃, 700 ℃) as shown in table 3), the fly ash prepared aluminum calcium mixture can realize calcium hydroxide decomposition to improve the activity of the prepared calcium aluminate cement and avoid the melting of sodium salt and potassium salt, and the final uniaxial compressive strength is more than 29 MPa. When the firing temperature is greater than 700 ℃ (as in table 3, when the firing temperature is 800 ℃, 900 ℃, 1000 ℃ and higher values not listed in table 3), the sodium salt and the potassium salt melt, so that the activity of the calcium aluminate cement decreases, resulting in a significant decrease in uniaxial compressive strength with further increase in firing temperature. Therefore, in summary, the benefit and the cost are combined, and when the firing temperature is equal to 500-700 ℃, the performance of the phosphorus modified calcium aluminate cement is most beneficial to preparation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for preparing phosphorus modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash is characterized in that: the method comprises the following steps:
(1) mixing water and phosphoric acid, and stirring uniformly to prepare a phosphoric acid aqueous solution;
(2) mixing phosphoric acid aqueous solution and municipal solid waste incineration fly ash, and stirring to obtain phosphorus-carrying fly ash;
(3) introducing the phosphorus-loaded fly ash slurry into an electrolytic cell sample area, then switching on a power supply to remove the phosphorus-loaded fly ash electrically, pouring out the slurry from the electrolytic cell sample area to obtain dechlorinated fly ash, and discharging electrolyte from an electrolytic cell cathode chamber to obtain catholyte;
(4) mixing the catholyte obtained in the step (3) with aluminum ash, and stirring to obtain aluminum alkali slurry;
(5) and (4) mixing the aluminum alkali slurry with the dechlorinated fly ash obtained in the step (3), sequentially stirring, drying, firing, cooling to normal temperature, and grinding to obtain the phosphorus modified calcium aluminate cement.
2. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (1), a phosphoric acid aqueous solution with the mass fraction of 2.5-17.5% is prepared.
3. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (2), the liquid-solid ratio of the phosphoric acid aqueous solution to the municipal solid waste incineration fly ash is 0.5-1.5: 1mL: mg, and the stirring time is 1-3 hours.
4. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (3), the electric removal is carried out for 3-9 hours, the initial voltage is set to be 50-250V in the electric removal process, and the initial current is set to be 100-500A.
5. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (4), the liquid-solid ratio of the catholyte to the aluminum ash is 1-4: 1mL: mg, and the stirring time is 1-3 hours.
6. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (5), the mass ratio of the aluminum alkali slurry to the dechlorinated fly ash is 0.5-2.5: 1, and the stirring time is 1-3 hours.
7. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (5), the drying temperature is 100-200 ℃.
8. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (5), the firing temperature is 500-700 ℃, and the firing time is 0.5-1.5 hours.
9. The method for preparing phosphorus-modified calcium aluminate cement by using municipal solid waste incineration fly ash and aluminum ash according to claim 1, wherein: in the step (5), the mixture is ground and sieved by a 200-400-mesh sieve.
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