CN110856778A - Separation and recovery technology for solid waste in flue gas desulfurization - Google Patents
Separation and recovery technology for solid waste in flue gas desulfurization Download PDFInfo
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- CN110856778A CN110856778A CN201810960974.2A CN201810960974A CN110856778A CN 110856778 A CN110856778 A CN 110856778A CN 201810960974 A CN201810960974 A CN 201810960974A CN 110856778 A CN110856778 A CN 110856778A
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- solid waste
- flue gas
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- 239000002910 solid waste Substances 0.000 title claims abstract description 27
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 25
- 230000023556 desulfurization Effects 0.000 title claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000003546 flue gas Substances 0.000 title claims abstract description 18
- 238000000926 separation method Methods 0.000 title claims description 5
- 238000011084 recovery Methods 0.000 title claims description 4
- 238000005516 engineering process Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 17
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 17
- 239000012452 mother liquor Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000010587 phase diagram Methods 0.000 claims abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000004043 dyeing Methods 0.000 claims abstract description 6
- 238000007639 printing Methods 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 3
- 230000007363 regulatory process Effects 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000003517 fume Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 241000565357 Fraxinus nigra Species 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002956 ash Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003712 decolorant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
- B01D36/003—Filters in combination with devices for the removal of liquids
-
- 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
- B01D53/73—After-treatment of removed components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a new technology for treating and recycling flue gas desulfurization solid waste, which is a new process for treating the solid waste developed by taking the solid waste of flue gas desulfurization by a soda ash semidry method as a raw material, taking a water-salt system phase diagram as guidance and taking a special inorganic salt additive and a printing and dyeing auxiliary agent as target products. The process comprises the following steps: firstly, dissolving black ash and removing impurities to prepare a solution containing 15-30% of salt; adding a decolorizing agent according to the mass ratio of the clear liquid of 0.1-0.8%; evaporating the decolorized solution at 90-120 deg.C for one period, and controlling the mother liquor composition: 0.5 to 1.0 percent of sodium carbonate, 4.0 to 5.0 percent of sodium sulfate and 24.5 to 26.5 percent of sodium chloride; after the first-stage evaporation mother liquor is subjected to acid adjustment treatment, the second-stage evaporation is continued, the pH value is controlled to be 6-8, and the evaporation temperature is 100-. At present, most of desulfurization solid wastes are difficult to effectively treat, so that new pollution is caused to the environment, the technology well solves the problem of resource utilization of the soda semi-dry desulfurization solid wastes, and the method has good economic benefit.
Description
Technical Field
The invention belongs to a treatment and recovery production process of flue gas desulfurization solid waste, in particular to Na2CO3-Na2SO4-NaCl-H2The O quaternary water salt system phase diagram is used as a guide, and the special inorganic salt additive and the printing and dyeing auxiliary agent are used as target products to develop a new process for treating solid waste. So as to achieve the purpose of recycling the solid wastes.
Background
Flue gas desulfurization is an effective desulfurization method applied in large scale in industrial industry, and the desulfurization technology can be divided into a dry method, a semi-dry method and a wet method according to the forms of sulfide absorbents and byproducts. The dry desulfurization process has the advantages of no waste water discharge in treatment and the disadvantages of low desulfurization efficiency and huge equipment. The wet desulphurization efficiency is high, but the flue gas temperature after desulphurization is lower, and the corrosion of equipment is more serious than that of a dry method. The semi-dry desulfurization technology has the advantages of dry method and wet method, while the soda semi-dry desulfurization technology is a more advanced flue gas treatment technology recommended by the industry and the association, but new solid waste desulfurization ash can be generated in the production process by applying the technology. The desulfurized fly ash is a mixture composed of sodium carbonate, sodium chloride, sodium sulfate and the like, is easy to dissolve in water, and can generate certain damage to soil, underground water, water areas and the like when entering the water areas through rainwater dripping and permeating the soil or scouring. Therefore, the development of key technologies for efficient emission reduction and high-value utilization of solid wastes is particularly urgent and important for the bottleneck problems of difficult effective utilization, high pollution and the like of the solid waste desulfurized ash generated by the flue gas of the soda semi-dry method.
Disclosure of Invention
The invention aims to provide a method for separating and recycling flue gas desulfurization solid waste. The present invention utilizes Na2CO3-Na2SO4-NaCl-H2The novel solid waste treatment technology is developed by using an O quaternary water salt system phase diagram and the requirement characteristics of certain industries on inorganic salt additives.
The production process comprises the following steps:
1. firstly, dissolving black ash and removing impurities, specifically, mixing desulfurization solid waste and water according to a certain proportion to prepare a solution containing 15-30% of salt, mixing and stirring, and then carrying out filter pressing to obtain a clear liquid for later use, wherein insoluble impurities enter a slag storage field.
2. The clear liquid is decolorized by adding a decolorizing agent according to the mass ratio of 0.1-0.8% of the clear liquid, wherein the decolorizing temperature is controlled at 50-80 ℃, the stirring speed is 20-80r/min, and the stirring time is 20-100 min.
3. The solution after impurity removal and decoloration treatment enters a first-stage steamingEvaporating with Na in hair-dryer2CO3-Na2SO4-NaCl-H2And controlling the first-stage evaporation temperature to be 90-120 ℃ and the composition of the first-stage evaporation end mother liquor by taking an O quaternary water-salt system phase diagram as a guide: 0.5 to 1.0 percent of sodium carbonate, 4.0 to 5.0 percent of sodium sulfate and 24.5 to 26.5 percent of sodium chloride. And drying the solid subjected to the centrifugal separation of the first-stage evaporation finished liquid by a fluidized bed to obtain a target product I.
4. And (4) carrying out acid adjustment treatment on the first-stage evaporation end mother liquor, and controlling the pH value of the mother liquor to be 6-8. The mother liquor after the acid adjustment is continuously evaporated in two stages to obtain a second target product, and the evaporation temperature is controlled at 100-130 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the phase diagram and the requirement characteristics of certain industries on the inorganic salt additive are skillfully utilized, so that the resource utilization of solid wastes is realized;
(2) except for about 5 percent of water-insoluble substances in the desulfurized solid waste, all the rest inorganic salts are recycled, and the utilization rate is far higher than the same industrial level.
Description of the drawings: FIG. 1 is a process flow diagram of a method for separating and recovering flue gas desulfurization solid waste.
The specific implementation scheme is as follows:
example 1
1000 g of solid waste of flue gas desulfurization by a soda ash method is added with 3500 ml of water for dissolution, and filtration is carried out after the dissolution is completed, thus obtaining 3670 ml of clear liquid with 21.2 percent of salt content and 48 g of insoluble impurities. 8 g of decolorant is added for decoloration treatment, the temperature of decoloration is controlled to be 60 ℃, the stirring speed is 30r/min, and the stirring time is 40 min. The decolorized solution enters a first-stage evaporator to be evaporated, 855 g of special inorganic salt additive with the main content of 99.1 percent is obtained, the composition of the special inorganic salt additive is 253 ml of mother liquor containing 0.75 percent of sodium carbonate, 4.68 percent of sodium sulfate and 25.2 percent of sodium chloride, 4 ml of 37 percent hydrochloric acid is added to adjust the pH value of the mother liquor to be 7.0, the mother liquor after acid adjustment is continuously evaporated, and 97 g of printing and dyeing auxiliary agent containing 15.4 percent of sodium sulfate and 84.6 percent of sodium chloride is obtained.
Example 2
And adding 8000 ml of water into 2500 g of solid waste generated by flue gas desulfurization by a soda ash method for dissolving, and filtering after stirring and dissolving to obtain 8536 ml of clear liquid with the salt content of 22.9 percent and 121 g of insoluble impurities. Adding 25 g of decolorizing agent for decolorizing treatment, controlling the decolorizing temperature to 65 ℃, and stirring at the rotating speed of 50r/min for 30 min. The decolorized solution enters a first-stage evaporator for evaporation to obtain 2118 g of special inorganic salt additive with the main content of 99.3 percent, which comprises 0.82 percent of sodium carbonate, 4.95 percent of sodium sulfate and 698 ml of mother liquor with the content of 24.6 percent of sodium chloride, 11.9 ml of 37 percent hydrochloric acid is added to adjust the pH value of the mother liquor to be 7.2, and the mother liquor after acid adjustment is continuously evaporated to obtain 260 g of printing and dyeing auxiliary agent with the content of 16.3 percent of sodium sulfate and 83.7 percent of sodium chloride.
Claims (6)
1. By using Na2CO3-Na2SO4-NaCl-H2The production process of separating and recovering solid waste from semi-dry fume desulfurization with soda ash features that the solid waste is first dissolved to eliminate impurity, the clear liquid is decolorized, the decolorized solution is first evaporated to obtain the special inorganic salt additive as the target product, and the mother liquid after solid-liquid separation is then acid regulated and second evaporated to obtain the second printing and dyeing assistant as the target product.
2. According to the claim 1, the process of dissolving and removing impurities in the production process of separating and recovering solid waste of flue gas desulfurization by a sodium carbonate semidry method by using a water-salt system phase diagram is characterized in that: mixing the desulfurized solid waste and water according to a certain proportion to prepare a solution containing 15-30% of salt, mixing and stirring, and then carrying out filter pressing to obtain clear liquid for later use, wherein insoluble impurities enter a slag storage field.
3. According to the method disclosed by claim 1, the clear liquid decoloring procedure in the production process for separating and recovering solid waste of flue gas desulfurization by a soda semi-dry method by using a water-salt system phase diagram is characterized in that: adding a decoloring agent according to the mass ratio of the clear liquid of 0.1-0.8%, controlling the decoloring temperature at 50-80 ℃, stirring at the rotating speed of 20-80r/min, and stirring for 20-100min, which is a key step for ensuring the product quality.
4. The method comprises the following steps of utilizing a water-salt system phase diagram to desulfurize flue gas by a soda ash semi-dry methodThe characteristic of one section of evaporation process in the waste separation and recovery production process is as follows: the solution after impurity removal and decoloration treatment enters an evaporator for evaporation, and Na is added2CO3-Na2SO4-NaCl-H2And controlling the first-stage evaporation temperature to be 90-120 ℃ and the composition of the first-stage evaporation end mother liquor by taking an O quaternary water-salt system phase diagram as a guide: 0.5-1.0% of sodium carbonate, 4.0-5.0% of sodium sulfate and 24.5-26.5% of sodium chloride, wherein the target product is obtained by first-stage evaporation: the main content is more than 99 percent, and the chloride ion is less than 0.5 percent.
5. According to the method disclosed by claim 1, the acid regulating process in the production process for separating and recovering the solid waste of flue gas desulfurization by the soda semi-dry method by using a water-salt system phase diagram is characterized in that: and (4) carrying out acid adjustment treatment on the first-stage evaporation end mother liquor, and controlling the pH value of the mother liquor to be 6-8.
6. According to the method disclosed by claim 1, the two-stage evaporation process in the production process for separating and recovering the flue gas desulfurization solid waste by the soda semi-dry method is characterized by comprising the following steps of: the mother liquor after the acid regulating process is continuously evaporated, the second-stage evaporation temperature is controlled to be 100-: the components conforming to the enterprise standard are 15-20% of sodium sulfate and 80-85% of sodium chloride as printing and dyeing auxiliary agents.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111422885A (en) * | 2020-04-21 | 2020-07-17 | 山西焦化股份有限公司 | Mixed salt based on coke oven flue gas desulfurization ash, preparation method and application |
| CN112264424A (en) * | 2020-09-01 | 2021-01-26 | 湖南博一环保科技有限公司 | High-added-value soda ash desulfurization and dedusting treatment process |
| CN112919499A (en) * | 2021-02-02 | 2021-06-08 | 自然资源部天津海水淡化与综合利用研究所 | Method for recycling sodium bicarbonate dry-process desulfurized fly ash |
| CN113800542A (en) * | 2020-06-16 | 2021-12-17 | 南风化工集团股份有限公司 | High-efficiency resource utilization technology for coking desulfurization ash |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111422885A (en) * | 2020-04-21 | 2020-07-17 | 山西焦化股份有限公司 | Mixed salt based on coke oven flue gas desulfurization ash, preparation method and application |
| CN113800542A (en) * | 2020-06-16 | 2021-12-17 | 南风化工集团股份有限公司 | High-efficiency resource utilization technology for coking desulfurization ash |
| CN112264424A (en) * | 2020-09-01 | 2021-01-26 | 湖南博一环保科技有限公司 | High-added-value soda ash desulfurization and dedusting treatment process |
| CN112919499A (en) * | 2021-02-02 | 2021-06-08 | 自然资源部天津海水淡化与综合利用研究所 | Method for recycling sodium bicarbonate dry-process desulfurized fly ash |
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