CN111167273B - Flue tail gas desulfurization device and process thereof - Google Patents
Flue tail gas desulfurization device and process thereof Download PDFInfo
- Publication number
- CN111167273B CN111167273B CN201811346750.9A CN201811346750A CN111167273B CN 111167273 B CN111167273 B CN 111167273B CN 201811346750 A CN201811346750 A CN 201811346750A CN 111167273 B CN111167273 B CN 111167273B
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- Prior art keywords
- desulfurization
- tank
- tail gas
- flue
- filter
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 135
- 230000023556 desulfurization Effects 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 44
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000004571 lime Substances 0.000 claims abstract description 27
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 23
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 23
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000008267 milk Substances 0.000 claims abstract description 14
- 235000013336 milk Nutrition 0.000 claims abstract description 14
- 210000004080 milk Anatomy 0.000 claims abstract description 14
- 239000012065 filter cake Substances 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims description 33
- 239000000706 filtrate Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000003546 flue gas Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 35
- 238000001914 filtration Methods 0.000 abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 150000002989 phenols Chemical class 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- SSQNAPWMQSPZRM-UHFFFAOYSA-N benzene-1,4-diol;sodium Chemical compound [Na].OC1=CC=C(O)C=C1 SSQNAPWMQSPZRM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
-
- 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
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/306—Alkali metal compounds of potassium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
-
- 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
Abstract
The invention provides a flue tail gas desulfurization device and a process thereof, comprising the following steps: (1) Introducing flue tail gas into a first desulfurization tank containing a desulfurizing agent and lime milk, carrying out solid-liquid separation after the completion of the stirring desulfurization reaction, filtering slurry into a mixed solution containing the desulfurizing agent and sulfite, transferring the filtered slurry into a liquid storage tank for standby, and obtaining a filter cake of calcium sulfate. The recycling of the desulfurizing agent enables the desulfurizing agent and the sulfite to continuously circulate in the tower, effectively reduces the precipitation and scaling of calcium sulfate in the stirring tank and the pipeline, prevents blockage, ensures that the filtered flue tail gas in the desulfurizing tower has redundant oxygen, enables the sulfite to be oxidized into sulfate, enables sodium sulfate to react with lime, is unfavorable for the promotion of the reaction, adopts organic phenols to neutralize part of alkali in the solution, simultaneously enables gas and the solution to be desulfurized again, promotes the reaction and can maintain continuous balance, effectively improves the reaction efficiency and the production efficiency, thoroughly reduces the emission of waste gas and improves the environmental protection.
Description
Technical Field
The invention relates to the technical field of air pollution control and treatment, in particular to a flue tail gas desulfurization device and a flue tail gas desulfurization process.
Background
At present, flue gas desulfurization is the most effective and widely applied desulfurization technology for controlling SO2 emission in the atmosphere and reducing acid rain hazard. The flue gas desulfurization process is mainly divided into a wet method, a semi-dry method and a dry method. Among them, wet flue gas desulfurization technology is dominant. The wet flue gas desulfurization technology mainly comprises a limestone-lime method, an ammonium method, a double-alkali method and the like. The limestone-lime method has the characteristics of rich raw material resources, low cost, safe and reliable operation, higher desulfurization efficiency, wide application range and the like, and is most applied to wet flue gas desulfurization technology. However, the method also has more problems, and has more prominent defects such as large amount of required raw materials, high energy consumption, low added value of desulfurization byproduct gypsum, large occupied area and the like, so that the limestone-gypsum method is subject to the problem.
Patent number CN106731628A discloses an improved limestone-lime flue gas desulfurization method, which can effectively relieve the problem of tail gas purification cost of enterprises using a limestone-lime method, save energy resources, reduce the production of solid waste, and fully utilize the solid waste in the phosphorus chemical industry to recycle the solid waste. But has the following problems: firstly, lime milk and calcium sulfite scale formation cause blockage of a desulfurization tower and pipelines easily in the desulfurization process by adopting a double-alkali method; secondly, the influence of carbon dioxide in the desulfurization process causes incomplete desulfurization.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a flue tail gas desulfurization device and a flue tail gas desulfurization process capable of preventing a stirring tank and a pipeline from being blocked and thoroughly desulfurizing.
The technical scheme of the invention is as follows: the flue tail gas desulfurization device comprises a first desulfurization tank, a second desulfurization tank, a reduction reaction tank, a filter, a slurry pump, a liquid storage tank and a fan, wherein the lower part of the first desulfurization tank is provided with an air inlet and a discharge hole, the upper part of the first desulfurization tank is provided with an air outlet and a feed inlet, the flue tail gas enters the first desulfurization tank from the air inlet through a conveying air pipe, the air outlet is connected with the air inlet of the reduction reaction tank through a conveying air pipe, and the conveying air pipe is provided with the fan; the discharge port is connected with a filter, and the filter is connected with a second desulfurization tank;
and the filtered filtrate of the solution in the second desulfurization tank is pumped into the reduction reaction tank through the slurry pump, the flue tail gas of the first desulfurization tank is treated and then is conveyed to the reduction reaction tank for secondary desulfurization, and the desulfurized solution is transferred into the liquid storage tank and is pumped into the first desulfurization tank for recycling.
Further, the top and the side surfaces of the first desulfurization tank and the reduction reaction tank are respectively provided with an observation hole and an acid-base thermometer.
Further, the first desulfurization tank and the reduction reaction tank are internally provided with a stirring device and a heater.
Further, the rotating speed of the stirring device is 200-1500 rpm.
Further, the heater is a resistive heater or an electromagnetic heater.
Further, a wind flowmeter is arranged on the conveying air pipe.
Further, the rotating speed of the fan is 300-3000 rpm.
Further, the discharge port is connected with the filter through a conveying pipeline, the filter is connected with the second desulfurization tank through a conveying pipeline, and a slurry pump is arranged on the conveying pipeline.
Further, the slurry pump machine is a centrifugal pump, an axial flow pump, a mixed flow pump or a vortex pump.
Further, the upper part of the second desulfurization tank is provided with a stirring reaction chamber, and the lower part of the second desulfurization tank is provided with a filtering device.
A flue tail gas desulfurization device and a process thereof comprise the following steps:
(1) Introducing flue tail gas into a first desulfurization tank containing a desulfurizing agent and lime milk, carrying out solid-liquid separation after the completion of the stirring desulfurization reaction, transferring the filtered slurry into a liquid storage tank for standby, wherein the filter cake is calcium sulfate;
(2) Pumping the slurry in the liquid storage tank into a second desulfurization tank, adding an acidic substance HA, carrying out desulfurization again on the solution, carrying out solid-liquid separation after stirring reaction is completed, transferring filtrate into the liquid storage tank for later use, wherein the filtrate is solution containing A salt and filter cake calcium sulfate;
(3) And (3) introducing the solution containing the salt A into a reduction reaction tank to react with the tail gas treated by the first desulfurization tank in the step (1), and directly transferring the solution into the liquid storage tank after the stirring reaction is finished, and returning the solution to the step (1) for recycling.
Further, the desulfurizing agent is one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate which contain strong alkalinity.
Further, the desulfurizing agent is added to the fresh lime cream slurry in a mass ratio of the desulfurizing agent to lime containing 90% of calcium oxide of-1:4 of 1 to 10M.
Further, the acidic substance HA in the step (2) is one or more of bisphenol a, phenol, cresol, aminophenol, nitrophenol, naphthol and chlorophenol in the organic phenol substance.
Further, the organic phenol substance in the step (2) is bisphenol A, 99.5% of bisphenol A is added according to the mol ratio of 1:5-5:1 of sulfate radical, and the mixture is heated to 50 ℃ and stirred for 1.5 hours.
Further, the molar ratio of the concentration of bisphenol A added to sulfate radical is 1:1.
Further, the tail gas passing through the first desulfurization tank in the step (3) is 1-8L/min, the pH value of the solution is reduced to 7, and the passing through amount of the treated tail gas is reduced or the passing through is stopped.
Further, in the steps (1) to (3), solid-liquid separation is performed by using a membrane filter press.
The invention has the following characteristics:
1. the flue tail gas filtered out of the desulfurizing tower is provided with redundant oxygen, so that sulfite is oxidized into sulfate, sodium sulfate reacts with lime, the regeneration effect is poor, the regenerated alkali concentration is low, the promotion of the reaction is unfavorable, acidic substance HA is adopted to neutralize part of alkali in the solution, gas and the solution are desulfurized again, after desulfurization, organic phenol substances are regenerated, the desulfurizing effect of the flue tail gas is effectively improved, the reaction is promoted, the continuous balance can be maintained, the reaction efficiency and the production efficiency are effectively improved, and the flue tail gas is desulfurized thoroughly.
2. The recycling of the desulfurizing agent enables the desulfurizing agent and the sulfite to continuously circulate in the tower, effectively reduces the precipitation and scaling of calcium sulfate in the stirring tank and the pipeline, prevents the blockage, improves the production efficiency and improves the desulfurizing purity.
3. The invention has ingenious design, the recycling of the desulfurizing agent and the organic phenol substances, effectively reduces the emission of waste gas, improves the environmental protection, reduces the consumption of raw materials, and improves the thorough purification efficiency of flue tail gas desulfurization.
The detailed structure of the present invention is further described below with reference to the accompanying drawings and detailed description.
Drawings
FIG. 1-is a process flow diagram of example 1 of the present invention;
FIG. 2-is a schematic diagram of a flue gas desulfurization apparatus according to example 1;
1-flue tail gas, 2-fans, 3-air flow meters, 4-first desulfurization tanks, 5-stirring devices, 6-acid-base thermometer, 7-slurry pump, 8-filter residue outlets, 9-filter observation holes, 10-filter feed inlets, 11-reduction reaction tank feed inlets, 12-reduction reaction tank air outlets, 13-observation holes, 14-reduction reaction tanks, 15-filters, 16-second desulfurization tanks and 17-liquid storage tanks.
Detailed Description
Examples
As shown in fig. 1-2, a flue tail gas 1 desulfurization device comprises a first desulfurization tank 4, a second desulfurization tank 16, a reduction reaction tank 14, a filter 15, a slurry pump 7, a liquid storage tank 17 and a fan 2, wherein the lower part of the first desulfurization tank 4 is provided with an air inlet and a discharge hole, and the upper part is provided with an air outlet, a feed inlet and an observation hole 13.
The lower part of the reduction reaction tank 14 is provided with a reduction reaction tank air inlet and a reduction reaction tank discharge outlet, and the upper part is provided with a reduction reaction tank air outlet, a reduction reaction tank feed inlet and an observation hole 13.
The flue tail gas 1 enters a first desulfurization tank 4 filled with a desulfurizing agent and lime milk from an air inlet of the first desulfurization tank 4 by using a fan 2 to drive gas through a conveying air pipe, an air outlet is connected with an air inlet of a reduction reaction tank 14 through the conveying air pipe, and the conveying air pipe is provided with the fan 2 and an airflow meter 3; the stirring device 5 is arranged in the first desulfurization tank 4, and the flue tail gas 1 is introduced while stirring, so that the area of the flue tail gas 1 which can be relieved with the solution of the first desulfurization tank 4 in the process of rising from the lower part of the first desulfurization tank 4 is more sufficient, and the desulfurization of the flue tail gas 1 is more thorough.
The filter 15 upper portion is equipped with filter observation hole 9 and filter feed inlet 10, and its lower part side is equipped with filter residue export 8, and its bottom is equipped with the filtrate export, can add other materials in filter 15 through filter feed inlet 10, and filter observation hole 9 is used for observing the inside filtrate filtering condition of filter 15, and filter residue export 8 is used for discharging the filter residue, and the filtrate export is used for discharging the filtrate, is equipped with sealed detachable sealed lid on the filter feed inlet 10.
The discharge gate of first digester 4 passes through pipeline connection with filter 15, shifts into the reservoir 17 through the discharge gate of filter 15 with the solution and is used, carries the solution in the reservoir 17 to second digester 16 again, all is equipped with thick liquid pump 7 on the pipeline, and pipeline is used for carrying the filter pulp after the filtration, and the filter residue after the filtration is discharged from filter residue export 8 of filter 15, collects.
The upper part of the second desulfurization tank 16 is a stirring reaction chamber, and the lower part thereof is a filtering device; the stirring reaction chamber and the filtration are integrally arranged, the stirring reaction chamber is internally provided with a stirring device 5 for accelerating full reaction, simultaneously preventing slurry from solidifying and precipitating, saving equipment setting cost, improving working efficiency, the stirring reaction chamber is internally provided with the stirring device 5, and the stirring reaction chamber is added with organic phenolic substances.
The filtrate of the second desulfurization tank 16 is pumped into the liquid storage tank 17 through a conveying pipeline and a slurry pump 7 on the conveying pipeline, then the filtrate is conveyed into the reduction reaction tank 14, the flue tail gas 1 of the first desulfurization tank 4 is treated and then conveyed into the reduction reaction tank 14 for secondary desulfurization, and the desulfurized slurry is directly pumped into the liquid storage tank 17 through the slurry pump 7 to be transferred into the first desulfurization tank for recycling.
The purified flue tail gas 1 is discharged from the top gas outlet of the reduction reaction tank 14 or is directly used in industry, the purified gas is mainly carbon dioxide-containing gas, and the purified gas can be directly used in industry with relatively more application of carbon dioxide.
The first desulfurization tank 4 and the reduction reaction tank 14 are also provided with an acid-base thermometer 6 for observing the temperature and the pH value thereof, and simultaneously adjusting the inlet amount of the flue tail gas 1 according to the values.
The filter residues of the filter 15 and the second desulfurization tank 16 can be collected, so that the value can be created for sale, and the cost can be saved.
The first desulfurization tank 4 and the reduction reaction tank 14 are both provided with a temperature heater and a stirring device 5, wherein the heater is a resistance heater, and also can be an electromagnetic heater. The rotation speed of the stirring device 5 is 200-1500 rpm.
The rotating speed of the fan 2 is 300-3000 rpm; the slurry pump 7 is a centrifugal pump, an axial flow pump, a mixed flow pump or a vortex pump.
The flue tail gas desulfurization device treats flue tail gas, and comprises the following treatment processes:
the flue tail gas is coal-fired tail gas of a certain thermal power plant, and contains 25% of SO2, 20% of CO2,2% of CO,40% of N2, 12% of H2O and 1% of O2.
(1) Introducing flue tail gas into a first desulfurization tank 4 containing fresh lime milk slurry according to the mass ratio of 1:3 of lime containing 5M sodium hydroxide and 90% of calcium oxide, wherein the introducing amount of the flue tail gas is 4L/min, the pH value of the solution is reduced to 8, the introducing amount is reduced or the introducing is stopped, the temperature is increased to 50 ℃, stirring is carried out for 2 hours, after the reaction is finished, the pH value is controlled, a diaphragm filter press is adopted for solid-liquid separation, the slurry is a mixed solution containing sodium hydroxide and sodium sulfite, and the mixed solution is pumped into a liquid storage tank 17 for standby, and the filter cake is calcium sulfate.
(2) Pumping the filtered slurry in the liquid storage tank 17 into a second desulfurization tank 16, adding hydroquinone, adding 99.5% hydroquinone according to the mol ratio of 1:1 of sulfate radical, heating to 50 ℃ and stirring for 1.5 hours. After the solution is desulfurized again and the stirring reaction is completed, solid-liquid separation is carried out by adopting a membrane filter press, filtrate is a solution containing sodium hydroquinone and filter cake calcium sulfate, and the filtrate is transferred into a liquid storage tank 17 for standby.
(3) Introducing the filtrate in the liquid storage tank 17 in the step (2) into a reduction reaction tank to react with the tail gas treated by the first desulfurization tank in the step (1), performing desulfurization again, introducing the tail gas treated by the first desulfurization tank to 3L/min, reducing the pH value of the solution to 7, reducing the introducing amount of the treated tail gas or stopping introducing, stirring, and transferring the solution into the liquid storage tank 17 to be returned to the first desulfurization tank 4 for recycling after the stirring reaction is completed.
Through detection analysis, the content of sulfur in the flue tail gas is 23ppm, the content of CO2 is 15%, and the content of O2 is 0.21%; the result shows that the sulfur content in the flue tail gas is very low, the desulfurization is thorough, and the carbon dioxide is purified, so that the flue tail gas can be further used for industrial application, the consumption of raw materials is effectively reduced, the purification efficiency is improved, meanwhile, the problems of blocking a pipeline by lime milk and calcium sulfate and incomplete desulfurization are effectively solved, and the cost is saved.
Examples
A flue tail gas desulfurization device and a process thereof, wherein the flue tail gas is coal-fired tail gas of a certain thermal power plant, and contains 21% of SO2, 22% of CO2,2% of CO,42% of N2, 11% of H2O,1% of O2 and 1% of impurities; the method comprises the following processing steps:
(1) Introducing flue tail gas into a first desulfurization tank 4 containing fresh lime milk slurry according to the mass ratio of 1:2 of lime containing 6M sodium hydroxide and 90% of calcium oxide, wherein the introducing amount of the flue tail gas is 3L/min, the pH value of the solution is reduced to 8, the introducing amount is reduced or the introducing is stopped, the temperature is increased to 50 ℃, stirring is carried out for 2 hours, after the reaction is finished, the pH value is controlled, a diaphragm filter press is adopted for solid-liquid separation, the slurry is a mixed solution containing sodium hydroxide and sodium sulfite, and the mixed solution is pumped into a liquid storage tank 17 for standby, and a filter cake is calcium sulfate.
(2) Pumping the filtered slurry in the liquid storage tank into a second desulfurization tank 16, adding hydroquinone, adding 99.5% hydroquinone according to the mol ratio of 1:1 of sulfate radical, heating to 50 ℃ and stirring for 1.5 hours. After the solution is desulfurized again and the stirring reaction is completed, solid-liquid separation is carried out by adopting a membrane filter press, filtrate is a solution containing sodium hydroquinone and filter cake calcium sulfate, and the filtrate is transferred into a liquid storage tank 17 for standby.
(3) Introducing the filtrate in the liquid storage tank 17 in the step (2) into a reduction reaction tank to react with the tail gas treated by the first desulfurization tank in the step (1), performing desulfurization again, introducing the tail gas treated by the first desulfurization tank to an introducing amount of 2.5L/min, reducing the pH value of the solution to 7 to reduce the introducing amount of the treated tail gas or stopping introducing, stirring, and transferring the solution into the liquid storage tank 17 after the reaction is completed to be returned to the first desulfurization tank for recycling.
Through detection analysis, the sulfur content in the flue tail gas is 20ppm, the CO2 content is 18%, and the O2 content is 0.25%; the result shows that the sulfur content in the flue tail gas is very low, the desulfurization is thorough, and the carbon dioxide is purified, so that the flue tail gas can be further used for industrial application, the consumption of raw materials is effectively reduced, the purification efficiency is improved, meanwhile, the problems of blocking a pipeline by lime milk and calcium sulfate and incomplete desulfurization are effectively solved, and the cost is saved.
Examples
A flue tail gas desulfurization device and a process thereof, wherein the flue tail gas is coal-fired tail gas of a metal smelting plant, and contains 19% of SO2, 25% of CO2,2% of CO,41% of N2, 11% of H2O,1% of O2 and 1% of impurities; the method comprises the following processing steps:
(1) Introducing flue tail gas into a first desulfurization tank 4 containing fresh lime milk slurry according to the mass ratio of 1:2 of lime containing 6M sodium hydroxide and 90% of calcium oxide, wherein the introducing amount of the flue tail gas is 3L/min, the pH value of the solution is reduced to 8 to reduce the introducing amount or stop introducing, heating to 50 ℃, stirring for 2 hours, controlling the pH value after the reaction is completed, performing solid-liquid separation by adopting a diaphragm filter press, transferring the slurry into a liquid storage tank 17 for later use, wherein the filter cake is calcium sulfate.
(2) The slurry in the reservoir 17 was pumped into the second desulfurization tank 16, catechol was added, bisphenol A was added at a ratio of 1:1 molar amount of sulfate, 99.5%, and the mixture was heated to 50℃and stirred for 1.5 hours. After the solution is desulfurized again and the stirring reaction is completed, solid-liquid separation is carried out by adopting a membrane filter press, filtrate is a solution containing sodium catechol and filter cake calcium sulfate, and the filtrate is pumped into a liquid storage tank 17 for standby.
(3) Introducing the filtrate in the liquid storage tank 17 in the step (2) into a reduction reaction tank to react with the tail gas treated by the first desulfurization tank in the step (1), desulfurizing again, reducing the tail gas introducing amount treated by the first desulfurization tank to 2.5L/min, reducing the pH value of the solution to 7, reducing the tail gas introducing amount treated or stopping introducing, and transferring the solution into the liquid storage tank 17 after the stirring reaction is completed to be returned to the first desulfurization tank for recycling.
Through detection analysis, the content of sulfur in the flue tail gas is 18ppm, the content of CO2 is 20%, and the content of O2 is 0.22%; the result shows that the sulfur content in the flue tail gas is very low, the desulfurization is thorough, and the carbon dioxide is purified, so that the flue tail gas can be further used for industrial application, the consumption of raw materials is effectively reduced, the purification efficiency is improved, meanwhile, the problems of blocking a pipeline by lime milk and calcium sulfate and incomplete desulfurization are effectively solved, and the cost is saved.
Examples
As shown in fig. 2, a flue tail gas desulfurization device and a process thereof, wherein the flue tail gas is coal-fired tail gas of a metal smelting plant, and contains 19% of SO2, 25% of CO2,2% of CO,41% of N2, 11% of H2O,1% of O2 and 1% of impurities; the method comprises the following processing steps:
(1) Introducing flue tail gas into a first desulfurization tank 4 containing fresh lime milk slurry according to the mass ratio of 1:3 of lime containing 6M potassium hydroxide and 90% of calcium oxide, wherein the introducing amount of the flue tail gas is 4L/min, the pH value of the solution is reduced to 8, the introducing amount is reduced or the introducing is stopped, the temperature is increased to 50 ℃, stirring is carried out for 2 hours, after the reaction is finished, the pH value is controlled, a diaphragm filter press is adopted for solid-liquid separation, the filter slurry is a mixed liquid containing potassium hydroxide and potassium sulfite and is pumped into a liquid storage tank 17 for standby, and the filter cake is calcium sulfate.
(2) Pumping the filter pulp in the liquid storage tank 17 into a second desulfurization tank 16, adding phenol, adding 99.5% of phenol according to the molar ratio of 1:1 of sulfate radical, heating to 65 ℃ and stirring for 1.5 hours. After the solution is desulfurized again and the stirring reaction is completed, solid-liquid separation is carried out by adopting a membrane filter press, filtrate is solution containing potassium phenoxide and filter cake calcium sulfate, and the filtrate is pumped into a liquid storage tank 17 for standby.
(3) Introducing the filtrate in the liquid storage tank 17 in the step (2) into a reduction reaction tank to react with the tail gas treated by the first desulfurization tank in the step (1), performing desulfurization again, introducing the tail gas treated by the first desulfurization tank to an introducing amount of 2.5L/min, reducing the pH value of the solution to 7 to reduce the introducing amount of the treated tail gas or stopping introducing, stirring, and pumping the filtrate into the liquid storage tank 17 after the completion of the stirring reaction, and returning the filtrate to the first desulfurization tank 4 for recycling.
Through detection analysis, the content of sulfur in the flue tail gas is 19ppm, the content of CO2 is 19%, and the content of O2 is 0.19%; the result shows that the sulfur content in the flue tail gas is very low, the desulfurization is thorough, and the carbon dioxide is purified, so that the flue tail gas can be further used for industrial application, the consumption of raw materials is effectively reduced, the purification efficiency is improved, meanwhile, the problems of blocking a pipeline by lime milk and calcium sulfate and incomplete desulfurization are effectively solved, and the cost is saved.
The preferred embodiments of the present invention have been described in detail above, but it is apparent that the present invention is not limited to the above-described embodiments. Within the scope of the technical idea of the invention, various equivalent modifications can be made to the technical solution of the invention, which all belong to the protection scope of the invention. In addition, the technical features described in the above-described specific embodiments may be combined separately and independently as long as they are within the technical concept of the present invention.
Claims (12)
1. The flue tail gas desulfurization device comprises a first desulfurization tank, a second desulfurization tank, a reduction reaction tank, a filter, a slurry pump, a liquid storage tank and a fan, wherein the lower part of the first desulfurization tank is provided with an air inlet and a discharge hole, the upper part of the first desulfurization tank is provided with an air outlet and a feed inlet, the flue tail gas enters the first desulfurization tank from the air inlet through a conveying air pipe, the air outlet is connected with the air inlet of the reduction reaction tank through a conveying air pipe, and the conveying air pipe is provided with the fan; the discharge port is connected with a filter, and the filter is connected with a second desulfurization tank; the method is characterized in that: and the filtered filtrate of the solution in the second desulfurization tank is pumped into the reduction reaction tank through the slurry pump, the flue tail gas of the first desulfurization tank is treated and then is conveyed to the reduction reaction tank for secondary desulfurization, and the desulfurized solution is transferred into the liquid storage tank and is pumped into the first desulfurization tank for recycling.
2. The flue gas desulfurization device according to claim 1, wherein the top and the side surfaces of the first desulfurization tank and the reduction reaction tank are respectively provided with an observation hole and an acid-base thermometer; and stirring devices and heaters are arranged in the first desulfurization tank and the reduction reaction tank.
3. The flue gas desulfurization device of claim 2, wherein the heater is a resistive heater or an electromagnetic heater; the air flow meter is arranged on the conveying air pipe; the rotating speed of the fan is 300-3000 rpm.
4. The flue gas desulfurization device according to claim 1, wherein the discharge port is connected with a filter through a conveying pipeline, the filter is connected with a second desulfurization tank through a conveying pipeline, and slurry pumps are arranged on the conveying pipelines; the slurry pump machine is a centrifugal pump, an axial flow pump, a mixed flow pump or a vortex pump.
5. The flue gas desulfurization apparatus according to any one of claims 1 to 4, wherein the second desulfurization tank has an upper portion of a stirring reaction chamber and a lower portion of a filter device.
6. The flue tail gas desulfurization process is characterized by comprising the following steps of:
(1) Introducing flue tail gas into a first desulfurization tank containing a desulfurizing agent and lime milk, carrying out solid-liquid separation after the completion of the stirring desulfurization reaction, transferring the filtered slurry into a liquid storage tank for standby, wherein the filter cake is calcium sulfate;
(2) Pumping the slurry in the liquid storage tank into a second desulfurization tank, adding an acidic substance HA, carrying out desulfurization again on the solution, carrying out solid-liquid separation after stirring reaction is completed, transferring filtrate into the liquid storage tank for later use, wherein the filtrate is solution containing A salt and filter cake calcium sulfate;
(3) And (3) introducing the solution containing the salt A into a reduction reaction tank to react with the tail gas treated by the first desulfurization tank in the step (1), stirring, directly transferring the solution into the liquid storage tank after the reaction is completed, and returning the solution to the step (1) for recycling.
7. The flue gas desulfurization process of claim 6, wherein the desulfurizing agent is one or more of sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate, which contain strong alkalinity; the desulfurizing agent is added into the fresh lime milk slurry according to the mass ratio of the desulfurizing agent to lime containing 90% of calcium oxide of 1 to 10M of 1:4.
8. The flue gas desulfurization process according to claim 6, wherein the acidic material HA in the step (2) is one or more of bisphenol a, phenol, cresol, aminophenol, nitrophenol, naphthol and chlorophenol in the organic phenol material.
9. The flue gas desulfurization process according to claim 8, wherein the organic phenol is bisphenol a, and 99.5% of bisphenol a is added in a molar ratio of 1:5-5:1 of sulfate radical, and the mixture is heated to 50 ℃ and stirred for 1.5 hours.
10. The flue gas desulfurization process of claim 9, wherein the bisphenol a is added at a molar ratio of 1:1 to sulfate.
11. The flue gas desulfurization process according to claim 6, wherein the amount of the treated tail gas introduced into the first desulfurization tank in the step (3) is 1-8L/min, and the pH value of the solution is reduced to 7 to reduce the amount of the treated tail gas introduced or stop the introduction.
12. The flue gas desulfurization process according to any one of claims 6 to 11, wherein the solid-liquid separation in steps (1) to (3) is performed by a membrane filter press.
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