CN113321230A - Method for preparing aluminum oxide and silicon fertilizer by using fly ash - Google Patents
Method for preparing aluminum oxide and silicon fertilizer by using fly ash Download PDFInfo
- Publication number
- CN113321230A CN113321230A CN202010130969.6A CN202010130969A CN113321230A CN 113321230 A CN113321230 A CN 113321230A CN 202010130969 A CN202010130969 A CN 202010130969A CN 113321230 A CN113321230 A CN 113321230A
- Authority
- CN
- China
- Prior art keywords
- ammonium
- ammonium bicarbonate
- ammonium sulfate
- fly ash
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
- C01F7/26—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with sulfuric acids or sulfates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention provides a method for preparing alumina and silicon fertilizer by using fly ash, which comprises the following steps: step S1: mixing the fly ash with a mixed solution of ammonium sulfate and ammonium bicarbonate, and reacting to obtain a reaction product; step S2: carrying out solid-liquid separation on the reaction product to obtain filtrate and filter residue; step S3: introducing NH3 into the filtrate, crystallizing, and carrying out solid-liquid separation to obtain basic ammonium aluminum carbonate solid; step S4: roasting the basic ammonium aluminum carbonate solid to obtain aluminum oxide; preferably, the CO generated by the calcination decomposition2And/or NH3Introducing gas into the ammonium bicarbonate solution after solid-liquid separation for recycling; step S5: and mixing the filter residue with calcium hydroxide, and activating by microwave treatment to obtain the mixed silicon fertilizer. The method of the invention can solve the problem of pulverized coalThe environmental pollution caused by the ash can also convert the ash into nutrient elements of plants, and can generate certain economic benefit.
Description
Technical Field
The invention relates to a method for preparing alumina and silicon fertilizer by using fly ash.
Background
Fly ash is fine ash collected from flue gas generated after coal combustion, and is main solid waste discharged from a coal-fired power plant. The main oxide composition of the fly ash of the thermal power plant in China is as follows: SiO 22、Al2O3、FeO、Fe2O3、CaO、TiO2And the like. Along with the development of the power industry, the emission amount of fly ash of a coal-fired power plant is increased year by year to become one of the current industrial waste residues with large discharge capacity in China, according to the '2016 Chinese fly ash industry development report', the 2016 year fly ash production amount is 5.65 hundred million t, the annual production amount of fly ash is increased, the main application of the fly ash is a building material, abundant aluminum-containing minerals exist in part of coal resources in the midwest part of inner Mongolia, the northern part of Shanxi and other areas, the content of aluminum oxide in the fly ash generated after power generation reaches 40-50%, and the fly ash is a precious aluminum-containing resource with high economic development value.
Silicon fertilizer is prepared from silicon oxide (SiO)2) And calcium oxide (CaO) is one of indispensable nutrient elements on crops such as rice, silicon is currently determined as the fourth major element fertilizer after nitrogen, phosphorus and potassium by the international soil academy, and the silicon can improve the oxidizing capability of plant roots, so that manganese and cadmium are oxidized and deposited on the plant roots in a plasma manner, and the absorption of the crops on the plant roots is reduced.
Nitrogen fertilizer is a unit fertilizer which takes nitrogen (N) as a main component, has the quantity indicated by N and can provide plant nitrogen nutrition when applied to soil. The nitrogen fertilizer is a fertilizer variety with the largest production and use amount of fertilizers in the world; the proper nitrogen fertilizer dosage plays an important role in improving the crop yield and the quality of agricultural products, and ammonium sulfate and ammonium carbonate are the most important nitrogen fertilizer varieties.
At present, the utilization of high-alumina fly ash mainly extracts metals such as aluminum, gallium and the like, the yield of the silicon slag left after aluminum extraction accounts for about 60% of the fly ash, the silicon slag obtained after the aluminum extraction by the fly ash has certain acidity or alkalinity, the existing disposal mode is stockpiling, and secondary pollution is caused to the environment if the high-alumina fly ash cannot be well utilized.
Disclosure of Invention
The invention provides a method for preparing alumina and silicon fertilizer by using fly ash, which is characterized in that the fly ash is solid waste of a coal-fired power plant, and the method comprises the following steps: ammonium sulfate, ammonium bicarbonate and alumina and ferric oxide in the fly ash are reacted to generate ammonium sulfate salts such as aluminum ammonium sulfate and ferric ammonium sulfate, and solid-liquid separation is carried out to obtain solution and silicon slag; introducing NH into the solution3The gas can obtain basic ammonium aluminum carbonate crystal and ammonium sulfate solution, and the basic ammonium aluminum carbonate is roasted and decomposed to obtain alumina and CO2And NH3Gas of CO2And NH3Introducing the ammonium bicarbonate solution to absorb to obtain a mixed solution of ammonium sulfate and ammonium bicarbonate for continuous recycling; because the silicon slag contains SiO2Activating, and forming the silicon fertilizer which can be absorbed by plants by a microwave heating method, wherein the obtained silicon fertilizer also comprises ammonium bicarbonate and ammonium sulfate.
In a first aspect, the present invention provides a method for preparing alumina and silicon fertilizer by using fly ash, which comprises:
step S1: mixing the fly ash with a mixed solution of ammonium sulfate and ammonium bicarbonate, and reacting to obtain a reaction product;
step S2: carrying out solid-liquid separation on the reaction product to obtain filtrate and filter residue;
step S3: introducing NH into the filtrate3Crystallizing, and carrying out solid-liquid separation to obtain basic ammonium aluminum carbonate solid;
step S4: roasting the basic ammonium aluminum carbonate solid to obtain aluminum oxide;
step S5: and mixing the filter residue with calcium hydroxide, and activating by microwave treatment to obtain the mixed silicon fertilizer.
According to some embodiments of the invention, in step S4, the roasting decomposes CO produced2And/or NH3And introducing the gas into the ammonium sulfate solution after solid-liquid separation for recycling.
According to some embodiments of the present invention, the mixed solution of ammonium sulfate and ammonium bicarbonate has a molar concentration of 0.5 to 5.0mol/l ammonium sulfate and a molar concentration of 0.1 to 1.5mol/l ammonium bicarbonate.
According to some embodiments of the invention, the mixed solution of ammonium sulfate and ammonium bicarbonate has a molar ratio of ammonium sulfate to ammonium bicarbonate of 10:1 to 1: 3.
According to a preferred embodiment of the present invention, in the mixed solution of ammonium sulfate and ammonium bicarbonate, the molar ratio of ammonium sulfate to ammonium bicarbonate is 5:1 to 1: 1.
According to some embodiments of the invention, a ratio of a mass of the fly ash to a volume of the mixed solution of ammonium sulfate and ammonium bicarbonate (hereinafter referred to as a solid-to-liquid ratio) is 1:1 to 1:10(g: ml).
According to some preferred embodiments of the present invention, the solid-to-liquid ratio of the fly ash to the mixed solution of ammonium sulfate and ammonium bicarbonate is 1:3 to 1:6(g: ml).
According to some embodiments of the present invention, the temperature of the reaction is 100-200 ℃, such as 100 ℃, 130 ℃, 150 ℃, 180 ℃, 200 ℃ in step S1.
According to some embodiments of the invention, in step S1, the reaction time is 0.5 to 2 hours, such as 0.5 hour, 1 hour, 1.5 hours, 2 hours.
According to some embodiments of the invention, in step S2, the filtrate includes ammonium aluminum sulfate and ammonium bicarbonate.
According to a preferred embodiment of the present invention, in step S2, the concentration of the aluminum ammonium sulfate in the filtrate is 0.2 to 2 mol/l.
According to some embodiments of the invention, the pH of the crystallization in step S3 is 8 to 11.
According to some embodiments of the present invention, in step S4, the baking temperature is 700-1000 ℃ and the baking time is 30-90 min.
According to some embodiments of the invention, in step S5, the filter residue is SiO2Meter, Ca (OH)2Calculated by CaO, the filter residue is mixed with Ca (OH)2In a molar ratio of (0.5-1.5): 1.
according to some embodiments of the invention, the mixing is performed at a temperature of 30 to 50 ℃ for 0.5 to 5 hours in step S5.
According to some embodiments of the invention, in step S5, the microwave treatment has a power of 10 to 30kW and a time of 0.5 to 5 hours.
According to some embodiments of the invention, in step S5, the mixed silicon fertilizer includes activated calcium silicate, ammonium bicarbonate and ammonium sulfate.
According to some embodiments of the invention, the method further comprises packaging the silicon fertilizer, the ammonium sulfate and ammonium bicarbonate mixed fertilizer obtained in the step S5 to obtain a silicon fertilizer mixed fertilizer product.
The invention has the beneficial effects that:
the invention adopts the mixing of ammonium sulfate, ammonium bicarbonate and fly ash, generates ammonium aluminum carbonate through a series of reactions, and obtains alumina after roasting decomposition, the cost of raw materials is low, and the mixed solution of ammonium sulfate and ammonium bicarbonate has low acidity, low corrosivity to reaction equipment, low repeated requirement to equipment, and can obviously reduce the equipment cost. Meanwhile, the silicon slag after solid-liquid separation is converted into a mixed fertilizer of silicon fertilizer and nitrogen fertilizer, so that the environmental pollution can be solved, the silicon slag can be converted into nutrient elements of plants, the problem of stacking is solved, and a certain economic benefit can be generated.
Drawings
FIG. 1 is a flow chart of the preparation of alumina and silicon fertilizer from fly ash according to one embodiment of the invention.
Fig. 2 is an XRD analysis pattern of basic ammonium aluminum carbonate according to example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The examples are intended to be illustrative of the invention and not limiting.
Example 1
The high-alumina fly ash for an internal combustion coal-fired power plant selected in the embodiment has the following chemical composition:
the specific process flow is as follows:
preparing a mixed solution of ammonium sulfate and ammonium bicarbonate, wherein the molar concentration of the ammonium sulfate is 3.0mol/L, the molar concentration of the ammonium bicarbonate is 1.0mol/L, and the molar ratio of the ammonium sulfate to the ammonium bicarbonate is 3: 1; the solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate (the mass ratio of the fly ash to the volume ratio of the mixed solution of the ammonium sulfate and the ammonium bicarbonate) is 1:3 (g: ml), reacting at 100 ℃ for 2 hours, and carrying out solid-liquid separation after the reaction is finished to obtain filtrate and filter residue.
Introducing NH into the filtrate3And (3) adjusting the pH value to 8, producing basic ammonium aluminum carbonate precipitate in the solution, and filtering to obtain basic ammonium aluminum carbonate crystals and an ammonium sulfate solution. XRD of basic ammonium aluminum carbonate is shown in figure 2.
And (3) roasting and decomposing the basic ammonium aluminum carbonate crystal at 900 ℃ for 30min to obtain an aluminum oxide product, wherein the recovery rate of the aluminum oxide is 85.41%, and the purity of the aluminum oxide product is 95.37%.
Decomposing the roasting to obtain CO2And NH3And introducing the gas into the ammonium bicarbonate solution after solid-liquid separation to generate a mixed solution of ammonium sulfate and ammonium bicarbonate, supplementing a small amount of ammonium sulfate and ammonium bicarbonate, and mixing the mixed solution with the fly ash for the next reaction.
Mixing the filter residue with Ca (OH)2Mixing, filtering with SiO2Meter, Ca (OH)2Calculated by CaO, the filter residue is mixed with Ca (OH)2In a molar ratio of 0.5: 1; the temperature of the mixing is 30 ℃ and the time is 0.5 hour, and the mixed material is obtained. And (3) treating the mixed material by using microwaves, wherein the microwave power is 10kW, and the microwave time is 0.5 hour. And packaging the obtained silicon fertilizer, ammonium sulfate and ammonium bicarbonate mixed fertilizer to obtain a silicon fertilizer mixed fertilizer product, wherein the effective silicon of the silicon fertilizer is 25.15%.
Example 2
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 0.5mol/L, the molar concentration of ammonium bicarbonate was 1.5mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 1: 3. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1:3 (g: ml) were mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 80.56%, and the purity of the alumina product is 93.83%. The effective silicon of the silicon fertilizer is 21.47 percent.
Example 3
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 1.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 1: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1:3 (g: ml) were mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 85.23%, and the purity of the alumina product is 94.06%. The effective silicon of the silicon fertilizer is 27.86 percent.
Example 4
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 0.5mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 6: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1:3 (g: ml) were mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 83.52%, and the purity of the alumina product is 95.88%. The effective silicon of the silicon fertilizer is 25.45 percent.
Example 5
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 1.0mol/L, the molar concentration of ammonium bicarbonate was 0.1mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 10: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1:3 (g: ml) were mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 78.68%, and the purity of the alumina product is 92.25%. The effective silicon of the silicon fertilizer is 20.16 percent.
Example 6
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1:1 (g: ml) was mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 75.12%, and the purity of the alumina product is 90.97%. The effective silicon of the silicon fertilizer is 19.23 percent.
Example 7
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 5 (g: ml) were mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 85.84%, and the purity of the alumina product is 95.07%. The effective silicon of the silicon fertilizer is 23.76 percent.
Example 8
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 1.5mol/L, the molar concentration of ammonium bicarbonate was 0.5mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 8 (g: ml) were mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 76.37%, and the purity of the alumina product is 91.82%. The effective silicon of the silicon fertilizer is 20.37 percent.
Example 9
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 0.75mol/L, the molar concentration of ammonium bicarbonate was 0.25mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1:10(g: ml) were mixed and reacted at 100 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 78.72%, and the purity of the alumina product is 90.89%. The effective silicon of the silicon fertilizer is 20.70 percent.
Example 10
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 4 (g: ml) were mixed and reacted at 150 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 87.65%, and the purity of the alumina product is 95.91%. The effective silicon of the silicon fertilizer is 26.23 percent.
Example 11
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 4 (g: ml) were mixed and reacted at 180 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 88.26%, and the purity of the alumina product is 95.53%. The effective silicon of the silicon fertilizer is 26.78 percent.
Example 12
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 4 (g: ml) were mixed and reacted at 200 ℃ for 1 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 89.02%, and the purity of the alumina product is 95.17%. The effective silicon of the silicon fertilizer is 27.16 percent.
Example 13
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 4 (g: ml) were mixed and reacted at 150 ℃ for 0.5 hour.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 85.34%, and the purity of the alumina product is 94.29%. The effective silicon of the silicon fertilizer is 26.60 percent.
Example 14
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 4 (g: ml) were mixed and reacted at 150 ℃ for 1.5 hours.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 87.99%, and the purity of the alumina product is 94.55%. The effective silicon of the silicon fertilizer is 26.26 percent.
Example 15
The only difference from example 1 is that a mixed solution of ammonium sulfate and ammonium bicarbonate was prepared, wherein the molar concentration of ammonium sulfate was 3.0mol/L, the molar concentration of ammonium bicarbonate was 1.0mol/L, and the molar ratio of ammonium sulfate and ammonium bicarbonate was 3: 1. The solid-liquid ratio of the mixed solution of the fly ash and the ammonium sulfate and ammonium bicarbonate is 1: 4 (g: ml) were mixed and reacted at 150 ℃ for 2.0 hours.
The other procedures were the same as in example 1.
In the obtained product, the recovery rate of alumina is 88.30%, and the purity of the alumina product is 95.12%. The effective silicon of the silicon fertilizer is 26.89 percent.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for preparing alumina and silicon fertilizer by using fly ash comprises the following steps:
step S1: mixing the fly ash with a mixed solution of ammonium sulfate and ammonium bicarbonate, and reacting to obtain a reaction product;
step S2: carrying out solid-liquid separation on the reaction product to obtain filtrate and filter residue;
step S3: introducing NH into the filtrate3Crystallizing, and carrying out solid-liquid separation to obtain basic ammonium aluminum carbonate solid;
step S4: roasting the basic ammonium aluminum carbonate solid to obtain aluminum oxide; preferably, the CO generated by the calcination decomposition2And/or NH3Introducing gas into the ammonium bicarbonate solution after solid-liquid separation for recycling;
step S5: and mixing the filter residue with calcium hydroxide, and activating by microwave treatment to obtain the mixed silicon fertilizer.
2. The method according to claim 1, wherein the mixed solution of ammonium sulfate and ammonium bicarbonate has a molar concentration of 0.5 to 5.0mol/l ammonium sulfate and a molar concentration of 0.1 to 1.5mol/l ammonium bicarbonate; and/or the mixed solution of ammonium sulfate and ammonium bicarbonate has a molar ratio of 10:1-1:3, preferably 5:1-1: 1.
3. The method according to claim 1 or 2, wherein the volume ratio of the mass of the fly ash to the mixed solution of ammonium sulfate and ammonium bicarbonate is 1:1 to 1:10(g: ml), preferably 1:3 to 1:6(g: ml).
4. The method as claimed in any one of claims 1 to 3, wherein the temperature of the reaction is 100 ℃ to 200 ℃ and/or the time of the reaction is 0.5 to 2 hours in step S1.
5. The method according to any one of claims 1 to 4, wherein in step S2, the filtrate comprises ammonium aluminum sulfate and ammonium bicarbonate, preferably the concentration of the ammonium aluminum sulfate is 0.2mol/l to 2 mol/l.
6. The method according to any one of claims 1 to 5, wherein the crystallization is performed at a pH of 8 to 11 in step S3.
7. The method as claimed in any one of claims 1 to 6, wherein in step S4, the roasting temperature is 700-1000 ℃ and the roasting time is 30-90 min.
8. The method according to any one of claims 1 to 7, wherein in step S5, the filter residue is SiO2Meter, Ca (OH)2Calculated by CaO, the filter residue is mixed with Ca (OH)2In a molar ratio of (0.5-1.5): 1; and/or the mixing temperature is 30-50 ℃ and the mixing time is 0.5-5 hours.
9. The method according to any of claims 1-8, wherein in step S5, the microwave treatment has a power of 10-30kW and a time of 0.5-5 hours.
10. The method of any one of claims 1-9, wherein in step S5, the mixed silicon fertilizer comprises activated calcium silicate, ammonium bicarbonate, and ammonium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010130969.6A CN113321230B (en) | 2020-02-28 | 2020-02-28 | Method for preparing aluminum oxide and silicon fertilizer by using fly ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010130969.6A CN113321230B (en) | 2020-02-28 | 2020-02-28 | Method for preparing aluminum oxide and silicon fertilizer by using fly ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113321230A true CN113321230A (en) | 2021-08-31 |
| CN113321230B CN113321230B (en) | 2022-06-14 |
Family
ID=77412899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010130969.6A Active CN113321230B (en) | 2020-02-28 | 2020-02-28 | Method for preparing aluminum oxide and silicon fertilizer by using fly ash |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321230B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053579A (en) * | 1975-05-29 | 1977-10-11 | Agency Of Industrial Science & Technology | Method for manufacture of sintered alumina from ammonium aluminum carbonate hydroxide |
| CN1696060A (en) * | 2005-03-24 | 2005-11-16 | 上海大学 | Method for preparing Nano powder of alumina from industrial waste |
| CN1775687A (en) * | 2005-12-09 | 2006-05-24 | 上海大学 | Method for preparing nano alumina powder jointed with synthetic ammonic plant production |
| CN101591197A (en) * | 2008-05-26 | 2009-12-02 | 同方环境股份有限公司 | A kind of method of utilizing pre-desiliconizing with high alumina fly ash to prepare calcium silicate fertilizer |
| US20130343971A1 (en) * | 2011-05-11 | 2013-12-26 | Inner Mongolia Datang International Recycling Resource Development Co., Ltd. | Method for co-producing alumina and activated calcium silicate from high-alumina fly ash |
| CN108424206A (en) * | 2018-06-04 | 2018-08-21 | 国家能源投资集团有限责任公司 | Flyash acid system residue of aluminum-extracted prepares the method containing silicon composite fertilizer and the utilization method containing silicon composite fertilizer and flyash |
| CN110272299A (en) * | 2018-03-15 | 2019-09-24 | 国家能源投资集团有限责任公司 | Coal ash for manufacturing for siliceous fertilizer method |
-
2020
- 2020-02-28 CN CN202010130969.6A patent/CN113321230B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053579A (en) * | 1975-05-29 | 1977-10-11 | Agency Of Industrial Science & Technology | Method for manufacture of sintered alumina from ammonium aluminum carbonate hydroxide |
| CN1696060A (en) * | 2005-03-24 | 2005-11-16 | 上海大学 | Method for preparing Nano powder of alumina from industrial waste |
| CN1775687A (en) * | 2005-12-09 | 2006-05-24 | 上海大学 | Method for preparing nano alumina powder jointed with synthetic ammonic plant production |
| CN101591197A (en) * | 2008-05-26 | 2009-12-02 | 同方环境股份有限公司 | A kind of method of utilizing pre-desiliconizing with high alumina fly ash to prepare calcium silicate fertilizer |
| US20130343971A1 (en) * | 2011-05-11 | 2013-12-26 | Inner Mongolia Datang International Recycling Resource Development Co., Ltd. | Method for co-producing alumina and activated calcium silicate from high-alumina fly ash |
| CN110272299A (en) * | 2018-03-15 | 2019-09-24 | 国家能源投资集团有限责任公司 | Coal ash for manufacturing for siliceous fertilizer method |
| CN108424206A (en) * | 2018-06-04 | 2018-08-21 | 国家能源投资集团有限责任公司 | Flyash acid system residue of aluminum-extracted prepares the method containing silicon composite fertilizer and the utilization method containing silicon composite fertilizer and flyash |
Non-Patent Citations (1)
| Title |
|---|
| 肖永丰 等: "煤灰提取氧化铝及中间产物的利用和产品开发", 《中国环境科学学会学术年会论文集（2016）》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113321230B (en) | 2022-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108611494B (en) | Method for recycling arsenic alkali residue efficiently and comprehensively | |
| CN104495899B (en) | A kind of carbide slag and flyash work in coordination with the method for recycling | |
| CN106517621B (en) | Recycling process of ammonium chloride-containing wastewater | |
| CN102534187B (en) | Method for treating pyrite cinder by combining acidic leaching with alkaline dissolving | |
| CN101607834B (en) | Preparation method for preparing potash fertilizer and producing sulfuric acid simultaneously employing mineral with potassium, ardealite and high-sulphur coal | |
| CN108424207B (en) | Method for preparing silicon-potassium-containing compound fertilizer by using fly ash acid method aluminum extraction residues, silicon-potassium-containing compound fertilizer and fly ash utilization method | |
| CN102811977A (en) | Agricultural blend containing sulfate source and calcium silicate and method of forming the same | |
| CN107814370B (en) | Circulating environment-friendly process method for preparing phosphate concentrate, product and application thereof | |
| CN113337295B (en) | Method for producing soil conditioner by utilizing bulk industrial solid wastes and product | |
| CN104876253A (en) | Method for treating calcium in high-calcium fly ash | |
| CN101585522B (en) | Method for recovering phosphorus from urban mud anaerobic digestion solution | |
| CN108424206B (en) | Method for preparing silicon-containing compound fertilizer by using fly ash acid method aluminum extraction residues, silicon-containing compound fertilizer and fly ash utilization method | |
| CN101792154A (en) | Method for producing ammonium sulfur and potassium-calcium-silicon fertilizer by using phosphogypsum | |
| CN111592014A (en) | Method and system device for preparing potassium sulfate, calcium carbonate and ammonium chloride from phosphogypsum | |
| CN108101077A (en) | Integrated process for extracting lithium by utilizing spodumene and synthesizing mineral fertilizer | |
| CN1283552C (en) | Method of preparing election class potassium carbonate using potassium rich rock | |
| CN103641344A (en) | Production technology of 'zero-carbon emission' cement combined with industrial gypsum waste treatment | |
| CN111333050A (en) | Combined production of magnesium ammonium phosphate and MgCO from phosphorus tailings and phosphogypsum3And by-product NH4Cl process | |
| CN113321230B (en) | Method for preparing aluminum oxide and silicon fertilizer by using fly ash | |
| CN110217769B (en) | Method for producing calcium ammonium nitrate byproduct feed-grade DCP | |
| EP3495323B1 (en) | A process for obtaining a soluble phosphate fraction from phosphate containing ash | |
| CN104909396B (en) | A kind of method of alum deep decomposition | |
| CN102126735B (en) | Method for extracting tschermigite from coal gangue or stone coal | |
| CN113213444A (en) | Production method for decomposing phosphorite by using unconventional nitric acid and application thereof | |
| CN109825699A (en) | It is a kind of to contain SO using calcining molybdenum ore concentrate2The method of tail gas leaching nickel cobalt raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |