CN111422885B - Mixed salt based on coke oven flue gas desulfurization ash, preparation method and application - Google Patents
Mixed salt based on coke oven flue gas desulfurization ash, preparation method and application Download PDFInfo
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- CN111422885B CN111422885B CN202010317169.5A CN202010317169A CN111422885B CN 111422885 B CN111422885 B CN 111422885B CN 202010317169 A CN202010317169 A CN 202010317169A CN 111422885 B CN111422885 B CN 111422885B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/004—Preparation in the form of granules, pieces or other shaped products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/24—Crystallisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/38—Preparation in the form of granules, pieces or other shaped products
- C01D7/40—Influencing the crystallisation process
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The invention discloses a mixed salt based on coke oven flue gas desulfurization ash, a preparation method and application, belongs to the technical field of environmental protection, and relates to coke oven flue gas desulfurization ash. A mixed salt based on the desulfurized fly ash of coke oven flue gas is a mixed salt of sodium sulfate and sodium sulfate, which is obtained by dissolving the desulfurized fly ash after high-temperature calcination in water and evaporating and crystallizing at the temperature of less than 100 ℃. The invention solves a series of environmental protection problems generated after the flue gas of the coke oven is desulfurized, changes waste into valuable, is suitable for large-scale popularization in the coking industry, and realizes environment-friendly, resource recycling and sustainable development.
Description
Technical Field
The invention belongs to the technical field of environmental protection, relates to coke oven flue gas desulfurization ash, and particularly relates to a mixed salt based on coke oven flue gas desulfurization ash, a preparation method and application.
Background
With the increase of national environmental governance, the governance of waste gas is the top trend of national environmental governance, and the total 612 enterprises related to national coking (statistics bureau data, including machine coke, semi coke and heat recovery coke oven manufacturers) have more than two thousand coke ovens. The pollution of sulfide, nitride and dust in the coke oven flue gas to the atmosphere, and further the damage to all important environmental elements such as water, soil, organisms and the like are concerned more and more. At present, the state requires desulfurization and denitrification treatment on coke oven flue gas, and a medium-low temperature semi-dry desulfurization and denitrification technology is a main process route for the treatment of the coke oven flue gas, but the process can generate new first-grade dangerous solid waste desulfurization ash in the production process, so the treatment of the desulfurization ash can be scheduled.
The coke oven flue gas desulfurization and denitrification device takes sodium carbonate or sodium bicarbonate as a desulfurizing agent, the main components of the generated desulfurization ash are sodium carbonate, sodium chloride and sodium sulfate, the device belongs to dangerous and first-level solid waste, and the mixture is easy to dissolve in water. The desulfurization ash is piled up or the garbage is buried, and the desulfurization ash can infiltrate into soil after dripping rainwater, change soil texture and soil structure, influence the activity of microorganisms in the soil, hinder the root growth of surrounding plants, or accumulate in surrounding organisms, and damage food chains; or the water permeates into the underground water, so that the drinking water is polluted to cause poisoning accidents and even death accidents; and the water enters a water body, so that the water body is subjected to changes such as acidity, alkalinity, eutrophication, mineralization, increase of suspended matters, even poisoning and the like, and the biological and human health are harmed. Therefore, the development of the resource utilization technology of the coke oven flue gas desulfurization ash can separate the desulfurization ash, comprehensively utilize the product, reduce the discharge amount of solid waste and change waste into valuable, thereby becoming a necessary way for solving the problem of solid waste of the desulfurization ash.
Disclosure of Invention
The invention aims to provide a mixed salt based on coke oven flue gas desulfurization ash, a preparation method and application.
The invention is realized by the following technical scheme:
a mixed salt based on coke oven flue gas desulfurization ash is a mixed salt of sodium sulfate and glauber's salt, and is obtained by dissolving the desulfurization ash after high-temperature calcination in water and evaporating and crystallizing at the temperature of less than 100 ℃.
Furthermore, the invention also provides a preparation method of the mixed salt based on the coke oven flue gas desulfurization ash, which is to add the desulfurization ash to the mixed salt at a temperature of more than or equal to 600 DEG C o And C, calcining at high temperature for 2 hours, dissolving in deionized water, filtering, and then evaporating and crystallizing at the temperature of less than 100 ℃ to obtain the mixed salt of sodium sulfate and glauber salt.
The desulfurized fly ash is dissolved in deionized water to form Na 2 CO 3 -Na 2 SO 4 -NaCl- H 2 O quaternary water salt system.
The desulfurization ash is dissolved in deionized water, a solution with the mass percent of 26-28% is formed under the heating and stirring conditions, and then evaporation crystallization is carried out.
Furthermore, the invention also provides application of the mixed salt of the coke oven flue gas desulfurization ash in preparation of washing powder.
The invention develops a resource utilization technology of the coke oven flue gas desulfurization ash by analyzing and researching a phase diagram of an inorganic salt water salt system for forming the desulfurization ash on the basis of comprehensively analyzing the phase, the composition and relevant physicochemical properties of the coke oven flue gas desulfurization ash. By adopting a four-stage treatment process of high-temperature calcination, dissolution and filter pressing, filtrate evaporation and salt precipitation and mixed salt for washing powder ingredients, 90% of components of desulfurized ash are converted into ingredients for preparing washing powder, the prepared mixed salt is applied to the washing powder, and the detergency of the obtained washing powder is basically consistent with that of the washing powder normally added with sodium sulfate and sodium carbonate; and the technology ensures that cyanide, thiocyanide and heavy metal ions in the desulfurized fly ash do not enter the product mixed salt, thereby ensuring the use safety of the washing powder.
The component of the waste desulfurized fly ash of the invention is mainly inorganic salt Na 2 SO 4 、Na 2 CO 3 And NaCl, dissolved in water, to obtain Na as shown in FIG. 2 2 CO 3 -Na 2 SO 4 -NaCl- H 2 The phase diagram of O quaternary water salt system, in the diagram, point a is system point, it is located in the mirabilite (2 Na) 2 SO 4 •Na 2 CO 3 ) The crystallization line of the salt is a-b-E5, and the sections a-b areThe b-E5 section is an alkali mirabilite and sodium sulfate co-precipitation section, and the system is analyzed to obtain that pure single salt cannot be obtained in the system through evaporation crystallization and exists in the forms of double salt and mixed salt, and two products, namely sodium sulfate and sodium carbonate, need to be added in the formula of washing powder of daily chemical enterprises at the same time, so the technology dissolves and evaporates inorganic salt in the desulfurization ash to produce mixed salt of sodium sulfate and sodium sulfate, and the mixed salt replaces sodium sulfate and sodium carbonate in the ingredients of the washing powder.
In the specific preparation, the high-temperature calcination temperature of the desulfurized fly ash is 600 DEG C o C and 600 o The method comprises the following steps of C, calcining for 2 hours and 2 hours, wherein gas generated by calcining desulfurized ash is carbon dioxide and water, and is waste gas, the main component is carbon dioxide, the generated amount is small, the desulfurized ash is collected and is mechanically stirred and heated by deionized water to be dissolved, the optimal concentration of a prepared solution is 26-28%, a filtrate and a small amount of insoluble substances are obtained after filter pressing, the insoluble substances consist of metal oxides, water, ash, volatile matters, fixed carbon and coal slag through analysis, and can be used for doping and blending coal coking, the filtrate is taken as a raw material solution after filter pressing, 2000 ml of the raw material solution is evaporated to 1250 ml for filter pressing, a solid sample and a mother solution are obtained, about 1000 ml of the mother solution is added to 2000 ml for evaporation, the raw material solution is evaporated to 1250 ml, the solid sample and the mother solution are obtained again, and the solid sample and the mother solution are sequentially circulated for multiple times, so that a plurality of solid samples and corresponding mother solutions are obtained; drying the solid sample at 105 ℃ for 4 hours, and finally, leaving 1000 ml of final mother liquor; the circulating feeding times and the tail liquid discharge are determined by two indexes of whether the content of chloride ions in the mixed salt exceeds 2% and the whiteness of the mixed salt is more than 86%, and the experimental results show that: (1) Controlling the sodium chloride in the mixed salt of the product to be less than or equal to 2 percent, and controlling the extraction rate of the mixed salt in the desulfurized fly ash to be more than or equal to 89.3 percent, wherein the content of the sodium chloride in the mixed salt is close but still meets the standard requirement of the washing powder (the sodium chloride is less than or equal to 1 percent); (2) The whiteness of the product is not influenced by the cycle number at all, and meets 86% of the standard requirement of the washing powder; (3) The discharged tail liquid contains sodium chloride as main component, and can be used for evaporating and salting out when the tail liquid is accumulated to a certain amountTo prepare industrial salt; the heat of the waste gas generated by high-temperature calcination, and the steam and heat generated during evaporation and salt precipitation ensure the cyclic utilization of water and energy in the system through the heat exchange equipment.
The mixed salt is applied to the preparation of the washing powder instead of sodium sulfate and sodium carbonate, two aspects of free alkali and slurry viscosity are mainly considered, wherein the mixed salt is applied to the washing powder, the influence of the factors of the free alkali is small, and the influence on the alkalinity of a product system can not be considered and generated; when the mixed salt is applied to washing powder, if the total solid content is controlled to be more than 68%, the viscosity of slurry is high, the appearance of the slurry is rough, and powder spraying cannot be carried out; adding a certain amount of water to reduce the viscosity of the slurry, so that powder spraying can be realized; the mixed salt is applied to washing powder, and the detergency of the obtained washing powder is determined and is basically consistent with that of the washing powder added with sodium sulfate and sodium carbonate in comparison with that of the traditional washing powder.
The invention solves a series of environmental protection problems generated after the flue gas of the coke oven is desulfurized, changes waste into valuable, is suitable for large-scale popularization in the coking industry, and realizes environment-friendly, resource recycling and sustainable development.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a phase diagram of an inorganic salt brine system of desulfurized fly ash of this invention;
FIG. 3 is a compositional analysis report I of a desulfurized ash from example 1;
FIG. 4 is a compositional analysis report II of the desulfurized ash from example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The preparation method of the mixed salt based on the coke oven flue gas desulfurization ash comprises the following steps:
(1) The desulfurized ash of the coke oven flue gas is put in a rotary high-temperature calcining furnace at 600 DEG o C and 600 o The carbon C is calcined for 2 hours or more than 2 hours, the calcined gas is carbon dioxide and water vapor, and the carbon dioxide and the water vapor are merged into a coke oven smoke emission system for emission after heat is recovered;
(2) The compositional analysis report of the desulfurized fly ash calcined in the step (1) is shown in fig. 3 and 4, the desulfurized fly ash is heated and stirred by using a certain amount of deionized water to prepare a solution, the concentration of the solution is 26-28%, then, the solution is subjected to pressure filtration by using a pressure filter to obtain filtrate (called raw material solution) and insoluble filter residue, and the filter residue is used for coal blending and coking after being accumulated;
wherein Na is at 100 ℃ 2 CO 3 -Na 2 SO 4 -NaCl- H 2 The phase diagram of the O quaternary water salt system is shown in figure 2, wherein the point a in the diagram is the system point which is positioned in the saltcake (2 Na) 2 SO 4 •Na 2 CO 3 ) The crystallization area of (1) is that the crystallization line of the salt is a-b-E5, the section a-b is the crystallization line of pure glauber's salt, the section b-E5 is the eutectoid section of the glauber's salt and sodium sulfate, that is, the pure single salt is impossible to obtain by evaporation crystallization in the system, and the single salt exists in the form of double salt and mixed salt;
(3) The raw material liquid obtained in the step (2) is numbered as No. 1, the test adopts that 2000 ml of solution is taken to be heated and rotated in a rotary evaporator to evaporate salt, evaporated water vapor is cooled into liquid water after heat exchange, the liquid water is recycled in the technology, when the solution is evaporated to 1250 ml and is subjected to filter pressing, a solid No. 1 sample and a solid No. 2 mother solution are obtained, about 1000 ml of the solid No. 2 mother solution is obtained, the stock solution is added to 2000 ml to be evaporated and evaporated to 1250 ml, a solid No. 2 sample and a solid No. 3 mother solution are obtained, the solid samples are sequentially circulated for multiple times, multiple solid samples and corresponding mother solutions are obtained, the solid samples are dried for 4 hours at 105 ℃, finally 1000 ml of the final mother solution is remained, the circulating feeding times are determined by judging whether the content of chloride ions in mixed salt exceeds 2 percent and the whiteness of the mixed salt is larger than two indexes of 86 percent, whether tail solution is discharged or not, and the experiment shows that: 1) (controlling the content of sodium chloride in the product mixed salt to be less than or equal to 2%) and the extraction rate of the mixed salt in the desulfurized fly ash to reach 89.3%, wherein the content of the sodium chloride in the mixed salt is close to but still meets the standard requirement of washing powder (the content of the sodium chloride is less than or equal to 1%); 2) The whiteness of the product is not influenced by the cycle number at all, and meets 86% of the standard requirement of the washing powder; 3) The discharged tail liquid contains sodium chloride as main component, and can be used for preparing industrial salt by evaporating and salting out when the tail liquid is accumulated to a certain amount.
The desulfurized fly ash is converted into the ingredient mixed salt of the washing powder for analysis and detection, and other ions are not detected, the arsenic content is only 1ppm, and the use is not influenced at all, namely toxic substances (cyanide, thiocyanide, heavy metal lead and arsenic) in the desulfurized fly ash are not introduced into the product mixed salt, so that the safe use of the product washing powder is ensured.
The sodium sulfate and sodium carbonate in the washing powder are replaced by the mixed salt which is qualified by analysis, the washing powder is prepared by pulping and drying with other ingredients, and the whole process flow is shown in figure 1.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
Claims (1)
1. The mixed salt for preparing washing powder based on coke oven flue gas desulfurization ash is characterized by being mixed salt of sodium sulfate and glauber's salt, and the desulfurization ash is added at a temperature of more than or equal to 600 DEG o Calcining at high temperature for 2 hours, dissolving in deionized water, and heating while stirring to form Na with a mass solution of 26-28% 2 CO 3 -Na 2 SO 4 -NaCl- H 2 Filtering the O quaternary water salt system, evaporating and crystallizing at the temperature of less than 100 ℃ to obtain the mixed salt of sodium sulfate and sodium sulfate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2203510C (en) * | 1994-11-28 | 2000-07-18 | Itzhak Efraim | Co-production of potassium sulfate, sodium sulfate and sodium chloride |
| CN1055065C (en) * | 1996-08-29 | 2000-08-02 | 内蒙古伊克昭化工研究设计院 | Production of crystal anhydrous sodium sulphate from nitrate containing brine |
| CN101336207A (en) * | 2005-12-21 | 2008-12-31 | Fmc有限公司 | Production of sodium sesquicarbonate and sodium carbonate monohydrate |
| CN110856778A (en) * | 2018-08-22 | 2020-03-03 | 南风化工集团股份有限公司 | Separation and recovery technology for solid waste in flue gas desulfurization |
| CN110451532A (en) * | 2019-08-28 | 2019-11-15 | 淮阴工学院 | A kind of sodium method Desulphurization recycling processing method |
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