CN113769564B - Semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and recycling method thereof - Google Patents
Semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and recycling method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
Abstract
The invention discloses a semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and a recycling method thereof, wherein the method comprises the steps of grinding and size mixing the semi-dry desulfurization ash to obtain slurry; introducing industrial flue gas I into the slurry to carry out sulfur dioxide absorption reaction and oxidation reaction to obtain suspension slurry I and industrial flue gas II; adding ammonia water into the suspension slurry I, and introducing the industrial flue gas II to perform a solidification carbon dioxide reaction to obtain suspension slurry II; and filtering and washing the suspension slurry II by two stages to obtain an ammonium sulfate salt product from a washing liquid, wherein the solid residue is a calcium carbonate product. The method realizes purification of sulfur dioxide and solidification of carbon dioxide in industrial flue gas while realizing large, harmless and high-quality utilization of semi-dry desulfurized fly ash, and is beneficial to large-scale popularization, production and application.
Description
Technical Field
The invention relates to a method for treating semi-dry desulfurized fly ash, in particular to a method for solidifying carbon dioxide in industrial flue gas by using semi-dry desulfurized fly ash and realizing resource utilization of desulfurized fly ash to obtain high-value ammonium sulfate, belonging to the technical field of resource utilization of solid waste.
Background
At present, compared with the mainstream wet desulphurization technology and dry desulphurization technology in industry, the semi-dry desulphurization technology has the advantages of high desulphurization efficiency, no wastewater generation, simple and convenient treatment and transportation, less investment, small occupied area and the like, and is widely applied to the industries of ferrous metallurgy, thermal power generation and the like. The semi-dry desulfurized fly ash produced in the process produces about 1000 million tons every year, has large yield and large reserves, and belongs to solid waste. Most of the solid wastes are treated in a stacking and burying way, which not only damages the environment but also occupies land resources, and simultaneously causes the waste of resources. Therefore, the development of the resource utilization technology of the semi-dry desulfurization ash is significant.
The semidry desulfurization ash mainly contains substances such as calcium sulfite, calcium sulfate, calcium chloride, calcium hydroxide, free calcium oxide, a small amount of calcium carbonate and the like. Because the free calcium oxide is expanded in volume in the hydration process, and the calcium chloride is easy to get damp and turn yellow, and a large amount of chloride ions can corrode reinforcing steel bars, the safety of buildings is seriously threatened, and the utilization of the calcium chloride in the traditional fields of cement, building materials and the like is greatly limited. Meanwhile, calcium sulfite is easy to decompose under acidic or high-temperature conditions, and if the calcium sulfite is not properly treated, a large amount of SO is released by decomposition 2 Causing secondary pollution. Therefore, a clean, efficient, economical and feasible utilization technology of semi-dry desulfurization ash is urgently needed to be found.
As is well known, carbon dioxide is the major greenhouse gas and published data indicates that atmospheric carbon dioxide concentrations increase from less than 300ppm prior to the industrial revolution to around 410ppm today. The emission of carbon dioxide far exceeds the self-balancing capability of nature, the emission of carbon dioxide in the process of utilizing fossil fuel is reduced, and the reduction of the concentration of carbon dioxide in the atmosphere is a major problem facing the world. The industrial production is a main emission source of carbon dioxide, and the emitted flue gas has the characteristics of large quantity, high temperature and low carbon dioxide content, is difficult to capture, store and utilize, and the captured large quantity of carbon dioxide also lacks application examples. The invention aims to utilize semi-dry desulfurized fly ash to solidify carbon dioxide, solve the problem that low-concentration carbon dioxide industrial flue gas is difficult to absorb and fix, reduce the treatment cost of the industrial flue gas, prepare calcium carbonate and ammonium chemical products and increase the production benefit.
Disclosure of Invention
The invention aims to provide a method for simultaneously fixing low-concentration carbon dioxide and sulfur dioxide industrial flue gas by using semi-dry desulfurization ash as a main raw material, and the method uses the semi-dry desulfurization ash, industrial ammonia and industrial flue gas as main reaction materials, and purifies the industrial flue gas through two main stages of sulfur dioxide absorption and carbon dioxide curing reaction.
In order to realize the technical purpose, the invention provides a semidry desulfurization ash solidified industrial flue gas carbon dioxide and a resource recycling method thereof, which comprises the following steps:
1) grinding and size mixing the semidry desulfurization ash to obtain slurry;
2) introducing industrial flue gas I into the slurry to carry out sulfur dioxide absorption reaction and oxidation reaction to obtain suspended slurry I and industrial flue gas II;
3) adding ammonia water into the suspension slurry I, and introducing the industrial flue gas II to carry out a solidification carbon dioxide reaction to obtain suspension slurry II;
4) and filtering and washing the suspension slurry II by two sections to obtain an ammonium sulfate salt product from a washing liquid, wherein solid residues are calcium carbonate products.
The invention takes the semidry desulfurization ash and the industrial flue gas as main raw materials, and realizes the resource utilization of the semidry desulfurization ash to obtain the ammonium sulfate product with high added value through two-stage absorption, and can convert the carbon dioxide in the flue gas into relatively stable calcium carbonate to be effectively fixed. According to the technical scheme of the invention, the semi-dry desulfurization ash is utilized to carry out two-stage absorption reaction on the industrial flue gas according to the characteristics that the semi-dry desulfurization ash contains calcium sulfite, calcium sulfate, calcium oxide, calcium chloride, a small amount of calcium hydroxide and calcium carbonate and the characteristics that the industrial flue gas has high temperature and contains sulfur dioxide, oxygen, carbon dioxide and the like. In the first-stage absorption process, calcium hydroxide in the semi-dry desulfurization ash and calcium hydroxide generated by calcium oxide are mainly used for absorbing sulfur dioxide in the industrial flue gas to convert the sulfur dioxide into calcium sulfite, and the high-temperature characteristics of oxygen in the industrial flue gas and the industrial flue gas are utilized to realize the efficient and rapid oxidation of the calcium sulfite to generate calcium sulfate. After the first-stage absorption, the sulfur dioxide in the industrial flue gas is basically removed to reach the emission standard, and the sulfur dioxide is converted into calcium sulfate. In the two-stage absorption process, ammonia water is introduced, so that the alkalinity of the slurry can be improved, the absorption efficiency of carbon dioxide can be enhanced, a nitrogen source is introduced, a sulfur source in calcium sulfate can be converted into ammonium sulfate with a higher added value, the ammonia water is added into the slurry, the carbon dioxide can be efficiently adsorbed to generate ammonium carbonate, the ammonium carbonate is subjected to double decomposition reaction with the calcium sulfate and calcium chloride to generate ammonium sulfate which is easily dissolved in water, a small amount of ammonium chloride components and calcium carbonate solid which is difficultly dissolved in water, and finally the carbon dioxide is absorbed and fixed by the calcium and is completely converted into the calcium carbonate. In conclusion, the method utilizes the calcium resource in the semidry desulfurization ash to realize the fixation of carbon dioxide and sulfur dioxide in the industrial flue gas, and the heat energy of the industrial flue gas can be recycled without external heating reaction.
As a preferred embodiment, the semi-dry desulfurized fly ash comprises calcium sulfite, calcium sulfate, calcium oxide, calcium chloride, a small amount of calcium hydroxide and calcium carbonate. The semi-dry desulfurized fly ash is a byproduct of semi-dry desulfurization of flue gas of a steel plant or a power plant, and is common solid waste in the industry.
Preferably, the semi-dry desulfurization ash is ground to a particle size of below 325 meshes and is subjected to size mixing according to a solid-liquid mass ratio of 1: 4-20.
As a preferable scheme, the temperature of the industrial flue gas I is 90-160 ℃, and the content of sulfur dioxide is not higher than 2000mg/m 3 The carbon dioxide content is 6-25 vol.%, and the oxygen content is not less than 2 vol.%. Under the preferable temperature and oxygen-containing conditions, the temperature and oxygen content in the slurry can be adjusted, the absorption and oxidation process of the sulfur dioxide can be improved, and the sulfur dioxide can be converted into sulfite and quickly oxidized into sulfate. The industrial flue gas I is mainly derived from high-temperature flue gas generated after dust removal in the industries of thermal power generation, steel and the like.
As a preferable scheme, the temperature of the industrial flue gas II is 30-40 ℃ lower than that of the industrial flue gas I, and the content of sulfur dioxide is lower than 35mg/m 3 . After the industrial flue gas I is absorbed by a first stage, the sulfur dioxide content is rapidly reduced to 35mg/m 3 The interference to the absorption process of carbon dioxide can be avoided, ultralow emission standard can be reached simultaneously to flue gas temperature is too high to be unfavorable for the absorption of aqueous ammonia to carbon dioxide, and through one section absorption after the temperature reduce certain degree, is favorable to the absorption of two-stage absorption process to carbon dioxide.
Preferably, the concentration of the ammonia water is 20-28 wt.%, and the addition amount of the ammonia water relative to the semi-dry desulfurization ash is 1.6-2.2L/kg.
As a preferable scheme, a spraying absorption mode is adopted in the sulfur dioxide absorption reaction and oxidation reaction processes, the slurry is sprayed from top to bottom to be in countercurrent contact reaction with the industrial flue gas I, the temperature of the suspension slurry I is controlled to be 40-70 ℃, and the pH value of the suspension slurry I is controlled to be 5.5-6.5. Under the optimized reaction conditions, the absorption and oxidation efficiency of the slurry on the sulfur dioxide are improved, so that the sulfur dioxide is converted into sulfite and is quickly oxidized into sulfate. The process does not substantially absorb carbon dioxide.
In a preferable scheme, in the process of the solidified carbon dioxide reaction, industrial flue gas II is dispersed into suspension slurry I added with ammonia water through a bubbling reactor to carry out the solidified carbon dioxide reaction, the size of bubbles is controlled to be less than 100 micrometers, the reaction is assisted through a stirring mode, the reaction is stirred at the speed of 300-800 r/min for 30-120 min, and meanwhile, the temperature of the suspension slurry II is controlled to be 30-60 ℃ and the pH value is controlled to be 7.2-8.0. Because calcium carbonate solid is generated in the reaction process of curing carbon dioxide to reduce the absorption efficiency of the slurry on the carbon dioxide, the conversion of the carbon dioxide and the generation efficiency of the calcium carbonate can be ensured by controlling conditions such as proper bubble size, stirring speed, temperature and the like.
As a preferred scheme, the two-stage filtration washing process comprises the following steps: and carrying out first-stage filtration and washing on the suspension slurry II to obtain solid slag I and filtrate I, carrying out evaporative crystallization on the filtrate I to obtain an ammonium sulfate product, adding water into the solid slag I to carry out second-stage filtration and washing to obtain solid slag II and filtrate II, wherein the solid slag II is a calcium carbonate product, and returning the filtrate II to first-stage filtration and washing.
As a preferable scheme, the solid slag II is dried by hot air at the temperature of 100-110 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) in the technical scheme of the invention, the semi-dry desulfurized fly ash is dissolved in water, calcium hydroxide generated by calcium oxide in the solution and a small amount of calcium hydroxide in the original ash have the capacity of absorbing and fixing sulfur dioxide in the industrial flue gas I again, about 200 million tons of sulfur dioxide generated by industry can be theoretically fixed every year according to the annual output of 1000 million tons of desulfurized fly ash, and at least 1 multiplied by 10 of the sulfur dioxide is treated for treating the industrial flue gas 8 m 3 The usage amount of a desulfurizer in flue gas desulfurization can be reduced, and the flue gas treatment cost is reduced.
2) In the technical scheme of the invention, in the sulfur dioxide absorption stage, calcium sulfite can be efficiently oxidized to generate calcium sulfate with stable chemical properties under the high-temperature condition and the oxygen-containing condition of the flue gas to obtain suspended slurry, so that the problem that the semi-dry desulfurization ash is difficult to utilize due to unstable properties of the calcium sulfite is solved.
3) According to the technical scheme, ammonia water is introduced into the slurry and is used as a nitrogen source of ammonium sulfate, and the absorption efficiency of carbon dioxide in industrial flue gas is improved, so that the carbon dioxide is firstly converted into ammonium carbonate salt which is easily dissolved in water, and the ammonium carbonate and calcium sulfate undergo a double decomposition reaction to transfer carbon in gaseous carbon dioxide into calcium carbonate, so that the fixation of the carbon dioxide is realized; according to the annual output of the desulfurized ash of 1000 ten thousand tons, the carbon dioxide generated by the industry can be theoretically fixed by more than 370 ten thousand tons every year, and the emission of greenhouse gases is reduced.
4) According to the technical scheme, the reaction temperature of the suspended slurry can be controlled through the industrial flue gas, the waste heat of the hot flue gas is fully and effectively recycled, the efficiency of absorbing sulfur dioxide and fixing carbon dioxide is further improved, and the problems of low content of carbon dioxide and sulfur dioxide in the industrial flue gas, difficulty in capturing and the like are solved.
5) According to the technical scheme, double decomposition reaction is carried out on calcium chloride and ammonium carbonate in the carbon dioxide solidification stage to finally generate the ammonium chloride and calcium carbonate, so that the problem that the calcium chloride is easy to mildew and deliquesce and the like due to high chlorine content of semidry desulfurization ash is solved.
6) The technical scheme of the invention has the advantages of simple process flow, easy operation, high resource utilization rate, no generation of three wastes, high added-value product generation, high economic benefit and easy realization of industrial application.
7) The technical scheme of the invention has high efficiency, the whole process is green and environment-friendly, no pollutant is discharged, the treatment capacity is strong, and the method is easy to popularize in industrial application.
In conclusion, the method can realize full component utilization of calcium and sulfur in the semidry desulfurization ash and bulk and harmless treatment of the semidry desulfurization ash; the method can realize that the desulfurized fly ash has reabsorption capability, and reduce the use amount of the desulfurizer; the method can realize the solidification of carbon dioxide, reduce the emission of carbon dioxide, is beneficial to the realization of the global carbon neutralization target, and has good environmental protection benefit, economic benefit and social benefit.
Drawings
FIG. 1 is a process flow diagram of a semi-dry desulfurized fly ash solidified industrial flue gas carbon dioxide and a resource utilization method thereof.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments, and based on the embodiments of the present invention, all other embodiments obtained by a person skilled in the art without making creative efforts belong to the protection scope of the present invention.
Example 1
Taking 1kg of semi-dry desulfurized ash from a certain steel plant, grinding the desulfurized ash into fine particles with the particle size of less than 325 meshes, and mixing the fine particles according to the solid-liquid mass ratio of 1:4 a suspension slurry was made with a chemical composition of 39.2 wt.% calcium sulfite, 16.6 wt.% calcium sulfate, 28.8 wt.% calcium oxide, 3.8 wt.% calcium chloride, 6.4 wt.% calcium hydroxide and 5.2 wt.% calcium carbonate. Then, the industrial flue gas I with the temperature of 90 ℃ is reversely fed into the suspension slurry to react to generate suspension slurry I and industrial flue gas II, and the sulfur dioxide content in the industrial flue gas I is 2000mg/m 3 6.0 vol.% carbon dioxide and 2.0 vol.% oxygen; the temperature of the suspension slurry I is 40 ℃, and the pH value is 5.5; the carbon dioxide content of the industrial flue gas II is 5.9 vol%, and the sulfur dioxide content is 34mg/m 3 The temperature was 60 ℃. And then adding 2.2L of industrial ammonia water with the concentration of 20 wt.% into the suspension slurry I, adjusting the pH of the slurry to 7.2, dispersing the industrial flue gas II by adopting a bubbling reactor, controlling the size of bubbles of the industrial flue gas II to be less than 100 mu m, introducing the industrial flue gas II at the stirring speed of 300r/min, maintaining the temperature of the solution to be 30 ℃, carrying out carbon dioxide solidification reaction, carrying out stirring reaction for 30min, and obtaining the suspension slurry II after the reaction is finished, wherein no new solid is generated in the suspension slurry. Finally, filtering the suspension slurry II, adding the filtrate II, washing to obtain a filtrate I and solid residue I, and evaporating and crystallizing the filtrate I to obtain an ammonium sulfate product; and adding water into the solid slag I for washing to obtain a solid slag II and a filtrate II, drying the solid slag II in hot air at 100 ℃ to obtain a high-purity calcium carbonate product, and recycling the filtrate II for the first-stage washing. Of the final product ammonium sulfateThe conversion was 95.8% and the conversion of calcium carbonate was 97.1%.
Example 2
Taking 1kg of semi-dry process desulfurized ash of a certain power plant, grinding the semi-dry process desulfurized ash into fine particles with the particle size of less than 350 meshes, and mixing the fine particles according to the solid-liquid mass ratio of 1: 10 a suspension slurry is made having a chemical composition of 42.0 wt.% calcium sulfite, 17.6 wt.% calcium sulfate, 29.3 wt.% calcium oxide, 4.6 wt.% calcium chloride, 3.6 wt.% calcium hydroxide, and 2.9 wt.% calcium carbonate. Then, the industrial flue gas I with the temperature of 120 ℃ is reversely fed into the suspension slurry to react to generate suspension slurry I and industrial flue gas II, wherein the sulfur dioxide content in the industrial flue gas I is 1900mg/m 3 15 vol.% carbon dioxide and 2.4 vol.% oxygen; the temperature of the suspension slurry I is 60 ℃, and the pH value is 6; the carbon dioxide content of the industrial flue gas II is 14.8 vol%, and the sulfur dioxide content is 28mg/m 3 The temperature was 80 ℃. And then adding 2.0L of industrial ammonia water with the concentration of 24 wt.% into the suspension slurry I, adjusting the pH of the slurry to 7.6, dispersing the industrial flue gas II by adopting a bubbling reactor, controlling the size of bubbles of the industrial flue gas II to be less than 100 mu m, introducing the industrial flue gas II at the stirring speed of 500r/min, maintaining the temperature of the solution to be 45 ℃, and carrying out carbon dioxide solidification reaction for 60min, wherein no new solid is generated in the suspension slurry, and the suspension slurry II is prepared after the reaction is finished. Finally, filtering the suspension slurry II, adding the filtrate II, washing to obtain a filtrate I and solid residue I, and evaporating and crystallizing the filtrate I to obtain an ammonium sulfate product; and adding water into the solid slag I for washing to obtain a solid slag II and a filtrate II, drying the solid slag II in hot air at 105 ℃ to obtain a high-purity calcium carbonate product, and recycling the filtrate II for the first-stage washing. The conversion rate of the final product ammonium sulfate is 96.4%, and the conversion rate of the calcium carbonate is 98.1%.
Example 3
Taking 1kg of semi-dry desulfurized ash of a power plant, grinding the semi-dry desulfurized ash into fine particles with the particle size of less than 400 meshes, and mixing the fine particles according to the solid-liquid mass ratio of 1: 20A suspension slurry was made having a chemical composition of 43.2 wt.% calcium sulfite, 21.3 wt.% calcium sulfate, 28.1 wt.% calcium oxide, 3.5 wt.% calcium chloride, 2.7 wt.% calcium hydroxide, and 1.2 wt.% calcium carbonate. Then, industrial flue gas I with the temperature of 160 ℃ is reversely fed into the suspension slurry to react to generate suspension slurry I and industrial flue gas IThe sulfur dioxide content in the flue gas II and the industrial flue gas I is 1800mg/m 3 25 vol.% carbon dioxide and 2.6 vol.% oxygen; the temperature of the suspension slurry I is 70 ℃, and the pH value is 6.5; the carbon dioxide content of the industrial flue gas II is 24.9 vol%, and the sulfur dioxide content is 26mg/m 3 The temperature was 120 ℃. Adding 1.6L of industrial ammonia water with the concentration of 28 wt.% into the suspension slurry I, adjusting the pH of the slurry to 8.0, dispersing industrial flue gas II by adopting a bubbling reactor, controlling the size of bubbles of the industrial flue gas II to be less than 100 mu m, introducing the industrial flue gas II at the stirring speed of 800r/min, maintaining the temperature of the solution to be 60 ℃, carrying out carbon dioxide solidification reaction, carrying out stirring reaction for 120min, and obtaining the suspension slurry II after the reaction is finished, wherein no new solid is generated in the suspension slurry. Finally, filtering the suspension slurry II, adding the filtrate II, washing to obtain a filtrate I and solid residue I, and evaporating and crystallizing the filtrate I to obtain an ammonium sulfate product; and adding water into the solid slag I for washing to obtain a solid slag II and a filtrate II, drying the solid slag II in hot air at 110 ℃ to obtain a high-purity calcium carbonate product, and recycling the filtrate II for the first-stage washing. The conversion rate of the final product ammonium sulfate is 98.7%, and the conversion rate of the calcium carbonate is 99.5%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (6)
1. A semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and a resource method thereof are characterized in that: the method comprises the following steps:
1) grinding and mixing the semidry desulfurized fly ash to obtain slurry;
2) introducing industrial flue gas I into the slurry to carry out sulfur dioxide absorption reaction and oxidation reaction to obtain suspended slurry I and industrial flue gas II; the temperature of the industrial flue gas I is 90-160 ℃, and the content of sulfur dioxide is not higher than 2000mg/m 3 The carbon dioxide content is 6-25 vol.%, and the oxygen content is not less than 2 vol.%; the industrial flue gasThe temperature of II is 30-40 ℃ lower than that of the industrial flue gas I, and the content of sulfur dioxide is lower than 35mg/m 3 ；
3) Adding ammonia water into the suspension slurry I, and introducing the industrial flue gas II to perform a solidification carbon dioxide reaction to obtain suspension slurry II; the sulfur dioxide absorption reaction and the oxidation reaction process adopt a spraying absorption mode, the slurry is sprayed from top to bottom to be in countercurrent contact reaction with the industrial flue gas I, the temperature of the suspension slurry I is controlled to be 40-70 ℃, and the pH of the suspension slurry I is 5.5-6.5;
4) filtering and washing the suspension slurry II by two stages to obtain an ammonium sulfate salt product from a washing liquid, wherein solid residues are calcium carbonate products; in the process of the reaction of curing carbon dioxide, industrial flue gas II is dispersed into the suspension slurry I added with ammonia water through a bubbling reactor to perform the reaction of curing carbon dioxide, the size of bubbles is controlled to be less than 100 microns, the reaction is assisted through a stirring mode, the reaction is stirred at the speed of 300-800 r/min for 30-120 min, and meanwhile, the temperature of the suspension slurry II is controlled to be 30-60 ℃ and the pH value is controlled to be 7.2-8.0.
2. The semi-dry desulfurized ash solidified industrial flue gas carbon dioxide and the resource utilization method thereof according to claim 1, characterized in that: the semi-dry desulfurization ash contains calcium sulfite, calcium sulfate, calcium oxide, calcium chloride, a small amount of calcium hydroxide and calcium carbonate.
3. The semi-dry desulfurized ash solidified industrial flue gas carbon dioxide and the resource utilization method thereof according to claim 1, characterized in that: and grinding the semi-dry desulfurized fly ash until the granularity is below 325 meshes, and carrying out size mixing according to the solid-liquid mass ratio of 1: 4-20.
4. The semi-dry desulfurized ash solidified industrial flue gas carbon dioxide and the resource utilization method thereof according to claim 1, characterized in that: the concentration of the ammonia water is 20-28 wt.%, and the addition amount of the ammonia water relative to the semi-dry desulfurization ash is 1.6-2.2L/kg.
5. The method for recycling industrial flue gas carbon dioxide solidified by semidry desulfurization ash according to claim 1, which is characterized in that: the two-stage filtration washing process comprises the following steps: and carrying out first-stage filtration and washing on the suspension slurry II to obtain solid slag I and filtrate I, carrying out evaporative crystallization on the filtrate I to obtain an ammonium sulfate product, adding water into the solid slag I to carry out second-stage filtration and washing to obtain solid slag II and filtrate II, wherein the solid slag II is a calcium carbonate product, and returning the filtrate II to first-stage filtration and washing.
6. The semi-dry desulfurization ash solidification industrial flue gas carbon dioxide and the resource utilization method thereof according to claim 5 are characterized in that: and drying the solid slag II by adopting hot air at the temperature of 100-110 ℃.
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