CN112206641A - Single-tower multistage circulating ammonia/ammonium sulfate method for flue gas desulfurization - Google Patents
Single-tower multistage circulating ammonia/ammonium sulfate method for flue gas desulfurization Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 239000003546 flue gas Substances 0.000 title claims abstract description 132
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 126
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 101
- 230000023556 desulfurization Effects 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 94
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 45
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 149
- 238000005406 washing Methods 0.000 claims abstract description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims description 299
- 238000005507 spraying Methods 0.000 claims description 95
- 238000007254 oxidation reaction Methods 0.000 claims description 87
- 230000003647 oxidation Effects 0.000 claims description 84
- 238000002425 crystallisation Methods 0.000 claims description 45
- 230000008025 crystallization Effects 0.000 claims description 45
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 33
- 239000002002 slurry Substances 0.000 claims description 33
- 239000007921 spray Substances 0.000 claims description 33
- 230000001105 regulatory effect Effects 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 25
- 238000004891 communication Methods 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 210000004911 serous fluid Anatomy 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000000443 aerosol Substances 0.000 abstract description 31
- 239000000243 solution Substances 0.000 description 38
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 25
- 230000001276 controlling effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000001502 supplementing effect Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000001139 pH measurement Methods 0.000 description 5
- 238000004886 process control Methods 0.000 description 5
- 230000009469 supplementation Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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 discloses a flue gas desulfurization method by a single-tower multistage circulating ammonia/ammonium sulfate method. The method comprises the following steps: pre-washing flue gas; step two: desulfurizing flue gas; step three: further desulfurizing the flue gas; step four: removing desulfurization liquid drops from the flue gas; step five: washing the desulfurized flue gas with water; step six: removing fog drops at the outlet of the flue gas; step seven: and (4) concentrating and crystallizing. The invention has the advantage of controlling ammonia escape and aerosol.
Description
Technical Field
The invention relates to the technical field of flue gas desulfurization, in particular to a flue gas desulfurization method by a single-tower multistage circulation ammonia/ammonium sulfate method.
Background
Sulfur dioxide is a main atmospheric pollutant, is directly discharged into the atmosphere, can affect human health, forms acid rain after contacting with water, corrodes buildings, vegetation and the like, and causes great harm to human living environment. SO in China for a long time2The emission amount is always high, and the emission amount becomes the third acid rain area in the world after Europe and America. In order to reduce the emission of sulfur dioxide, the government of China enforces a stricter policy to limit the emission of sulfur dioxide in thermal power plants, and the environmental protection department of China in 2014 proposes an action plan for energy conservation, emission reduction, upgrade and modification of coal and electricity (2014-2020), which proposes an ultra-clean emission target, wherein the action requires that the emission concentration of smoke dust, sulfur dioxide and nitrogen oxides in flue gas of a newly-built coal-fired power generating unit in the eastern region is not more than 10, 35 and 50mg/Nm3 by the end of 2020. In 2015, 12 months, the proposal is to implement ultra-clean discharge in the national region. In order to respond to increasingly strict environmental protection policies and relieve environmental pressure, it is imperative to continuously improve the existing environmental protection technology of coal-fired power plants and to develop new environmental protection technology of coal-fired power plants.
Up to now, hundreds of technologies for controlling sulfur dioxide in coal burning process have been developed in various countries, and among them, the wet desulphurization process is most widely used. The wet desulfurization techniques are classified into calcium desulfurization, magnesium desulfurization, ammonia desulfurization, seawater desulfurization, and the like, according to the kind of the absorbent. The ammonia desulfurization method can absorb sulfur dioxide in flue gas to produce ammonium sulfate fertilizer, can realize resource recycling, especially can utilize waste ammonia water in chemical industry, greatly reduces energy consumption, and has unique advantages. Meanwhile, the ammonia desulphurization device has strong adaptability to unit load change and can adapt to modes such as quick start, cold start, warm start, hot start and the like.
However, with the stricter emission limit of the coal-fired flue gas pollutants, new challenges are also provided for the ammonia desulphurization technology. For a long time, the problems of excessive ammonia escape and ammonium sulfate aerosol exist in ammonia desulphurization, and the flue gas flow at the inlet of an absorption tower and SO in the flue gas can be caused by the change of boiler coal during the actual operation process2The quality concentration changes frequently, so the ammonia supplementing quantity added into the absorption tower needs to be correspondingly adjusted in real time, and the traditional adjusting valve is difficult to realize accurate and continuous ammonia supplementing quantity control. At present, many technologies focus on how to capture aerosol generated in the absorption process, rather than inhibiting or reducing the generation of aerosol in the absorption process from the source, which results in large system investment, high operation cost and unstable operation.
The prior patent CN204735109U, "an ammonia desulfurization device for controlling ammonia escape", discloses an ammonia desulfurization device for controlling ammonia escape, which optimizes the process flow and device to a certain extent, but does not solve the problem from the source, and is mainly embodied in the following aspects:
(1) the patent does not set chain feedback for ammonia addition, and the control of ammonia water regulation is a difficult point along with fluctuation of flue gas load in actual engineering; in the prior art, the ammonia adding amount is generally regulated and controlled according to the detection result of the clean flue gas at the outlet of the absorption tower, but the delay time of the mode is long, so that the ammonia adding regulation is not timely, and the desulfurization efficiency cannot be reached or the ammonia escape exceeds the standard;
(2) the means of this patent control ammonia escape and aerosol is complicated, does not control at the absorption section, and the height of tower is increased more to the subsequent processing technology, for example the defogging section is equipped with electric demister, washs and sprays layer, grid packing layer, folded plate formula defroster from top to bottom in proper order. However, the methods are not based on the source of aerosol and ammonia escape in the absorption process, and only concern about how to eliminate the ammonia and the aerosol escaping in the absorption process, so that the number of stages of the tower is more and more, the system is more complex, the treatment effect is poor, and the investment and operation cost is greatly increased;
(3) the patent does not determine the specific composition, concentration, absorption temperature and pH of the absorption solution, does not monitor corresponding data in the process flow, can not realize the cooperative control of absorption, oxidation and concentration, can not completely control ammonia escape and aerosol generation from the swimming head, and the flue gas after simple washing and demisting can not meet the requirement of the current ultralow emission standard or higher.
Therefore, the problem of aerosol and ammonia escape is solved from the source of aerosol and ammonia escape in the absorption process, and the problem becomes the difficulty of realizing ultralow emission in ammonia desulphurization. There is a need to develop a desulfurization method that solves the problem of aerosol and ammonia escape during absorption from the source.
Disclosure of Invention
The invention aims to provide the single-tower multistage circulation ammonia/ammonium sulfate method for flue gas desulfurization, which solves the problem of aerosol and ammonia escape from the source of aerosol and ammonia escape in the absorption process, and has the advantages of high automation degree, simple operation, low operation cost and high desulfurization efficiency.
In order to achieve the purpose, the technical scheme of the invention is as follows: the single-tower multistage circulating ammonia/ammonium sulfate method for flue gas desulfurization is characterized in that: comprises the following steps of (a) carrying out,
the method comprises the following steps: pre-washing flue gas;
the flue gas to be treated enters the absorption tower from a flue gas inlet, and is pre-washed and cooled through a flue gas pre-washing spray layer, so that the temperature of the flue gas is reduced to below 70 ℃;
step two: desulfurizing flue gas;
the pre-washed flue gas is desulfurized through a primary absorption circulating system, and the desulfurization method of the primary absorption circulating system comprises the following steps:
the first-stage absorption circulating pump sends the liquid on the upper part of the oxidation tank into the first-stage absorption spraying layer, and SO in the flue gas is sprayed by the first-stage absorption spraying layer2Is absorbed by the spraying liquid in the first-stage absorption spraying layerCollecting and removing, wherein at the moment, the desulfurization spray liquid is converged into a second liquid collector, and the desulfurization spray liquid in the second liquid collector returns to the oxidation tank from the top of the oxidation tank through a communication pipeline;
the primary absorption circulation A pump and the primary absorption circulation B pump out the solution from different heights of the oxidation tank and respectively pump out the solution to the primary absorption spraying layer A and the primary absorption spraying layer B to form solution gradient distribution; meanwhile, the ammonia water conveying device adds ammonia to the spray liquid input into the primary absorption spray layer through a communication pipeline, so that the PH and the oxidation rate of the slurry sprayed out of the spray layers with different heights of the absorption section form difference;
step three: further desulfurizing the flue gas;
and (3) further desulfurizing the flue gas treated in the second step by using a secondary absorption circulating system, wherein the desulfurization method of the secondary absorption circulating system comprises the following steps:
the liquid at the lower part of the oxidation tank is sent into a secondary absorption spraying layer by a secondary absorption circulating pump, and SO in the flue gas is sprayed by the secondary absorption spraying layer2The desulfurization spraying liquid in the second liquid collector returns to the oxidation tank from the top of the oxidation tank through a communicating pipeline;
meanwhile, the oxidizing air device is used for introducing oxygen to the bottom of the oxidizing tank through an oxidizing air distribution pipe;
step four: removing desulfurization liquid drops from the flue gas;
the absorption demisting section absorbs the desulfurization liquid drops and controls the liquid drops entering the water washing section;
pumping the slurry at the bottom of the oxidation tank into a concentration crystallization section through a secondary absorption circulating pump, and controlling the pumping flow through a regulating valve;
step five: washing the desulfurized flue gas with water;
the water washing circulating system washes the desulfurized flue gas, and the specific water washing method comprises the following steps:
the water washing circulating pump inputs the process water in the water washing circulating tank into the water washing circulating spraying layer, and the water washing circulating spraying layer sprays flue gas, so that the concentration of ammonium sulfate carried by liquid drops at an outlet is reduced, and the escape of ammonia is reduced; at the moment, the washing liquid is collected into the first liquid collector, and the washing liquid in the first liquid collector returns to the washing circulation tank from the top of the washing circulation tank through a communication pipeline;
step six: removing fog drops at the outlet of the flue gas;
the flue gas after washing absorbs fog drops at an outlet through a washing demisting section and then is discharged to a chimney from the top end of the absorption tower;
step seven: concentrating and crystallizing;
the concentration circulating pump pumps the circulating liquid in the concentration crystallization section into a concentration spraying layer to pre-wash and cool the flue gas, and the residual temperature of the pre-washed slurry is utilized to concentrate the slurry and promote the crystallization of the slurry;
the pump is disturbed to circulate the serous fluid in the concentrated crystallization section, promote the internal circulation of the serous fluid in the concentrated crystallization section and improve the uniformity of the serous fluid in the concentrated crystallization section;
when the density of the slurry in the concentrated crystallization section is more than 1285kg/m3And when the slurry is processed, the ammonium sulfate is discharged by an ammonium sulfate discharge pump and sent to an ammonium sulfate post-processing working section.
In the technical scheme, the first interlocking ammonia water pipeline regulating valve and the second interlocking ammonia water pipeline regulating valve are automatic regulating valves; and the signal fed back by the second pH meter controls the first interlocking ammonia water pipeline regulating valve in an interlocking manner, and the signal fed back by the first pH meter controls the second interlocking ammonia water pipeline regulating valve in an interlocking manner.
In the technical scheme, a second pH meter is arranged at the outlet of the first-stage absorption circulating pump A; a first pH meter is arranged at the outlet of the second liquid collector;
a temperature sensor is arranged between the accident spraying system and the primary absorption section;
the washing circulation tank is connected with the absorption demisting section through a washing circulation pump and a communication pipeline;
the densimeter is arranged on a communicating pipeline between the primary absorption circulating C pump and the secondary absorption spraying layer.
In the technical scheme, the washing demisting section is a three-stage ridge type efficient demister; the concentration of fog drops at the outlet of the water-washing demisting section is less than or equal to 20mg/Nm3。
In the technical scheme, in the second step, the temperature of the primary absorption section is 40-60 ℃, and the pH value is 5.5-6.5;
in the third step, the temperature of the second-stage absorption section is 30-50 ℃, and the pH value is 3.5-5.5;
in the seventh step, the temperature of the concentrated crystallization section is 50-60 ℃, and the pH is 2-3.5.
The invention has the following advantages:
(1) the single tower is provided with the multi-stage circulating partition through the liquid collector, so that the degree of automation is high, the operation is simple, the operation cost is low, and the desulfurization efficiency is high;
(2) the single-tower multistage circulation ammonia/ammonium sulfate method flue gas desulfurization system is provided with the external oxidation tank, so that the height of the absorption tower can be reduced compared with the internal oxidation of the absorption tower, the energy consumption of absorption circulation operation is reduced, and meanwhile, the oxidation is independently controlled, so that the oxidation rate of more than 98.5 percent can be ensured; in the whole oxidation process, the required oxygen is provided by a bottom aeration system (namely, an oxidation air device and an oxidation air distribution pipe), and the oxidation air distribution pipe in the aeration system is formed by arranging a hose in a spiral shape; in addition, the stirrer arranged on the side wall of the tower can effectively ensure that oxygen and solution are fully contacted and mixed, further accelerates the oxidation process, and is more favorable for cooperatively controlling the desulfurization efficiency and the problem of ammonia escape;
(3) the system is characterized in that the concentration and crystallization in the tower and the pre-washing and cooling of the flue gas are carried out, the residual temperature concentrated slurry is utilized to promote the crystallization of the flue gas, the temperature of the flue gas is reduced to be below 60 ℃, the absorption of sulfur dioxide is facilitated, the ammonia escape is not facilitated, the slurry at the bottom of the tower is washed into a saturated solution, the concentration and pH value in the tower is controlled to be below 3, the temperature and pH value condition is the most favorable condition for the crystallization and dehydration of the solution, and the system is not interfered by the solution of an absorption circulating system and has high concentration of a defogging flushing solution, so the system is completely capable of manufacturing and maintaining the favorable environment; compared with a single-tower system in the prior art, the invention completely solves the problem of difficult crystallization of the solution, reasonably utilizes the heat of the flue gas to reduce the energy consumption, and conforms to the concept of circular economy;
(4) the primary function of the primary absorption cycle system in the invention is to carry out (NH) pair4)2SO3-NH4HSO3The mixed liquid is continuously circulated to absorb SO in the flue gas2And (NH)4)2SO3To SO2Has better absorption capacity, and new ammonia water continuously compensated is high-efficiency SO in the absorption flue gas2Providing favorable environments and conditions; the circulating absorption liquid is unsaturated solution, is provided by an oxidation tank, is added with ammonia in a tower inlet pipeline and is used as primary absorption circulating liquid, and the pH value is controlled to be 5.5-6.5; the first-stage absorption circulating liquid in the invention enters an oxidation tank to ensure that the oxidation rate is more than 98.5 percent, and most of the solution is (NH)4)2SO4A lower pH of the circulating solution may be maintained to control ammonium sulfite decomposition and ammonia slip; the primary absorption circulation system and the secondary absorption circulation system are relatively independent, the slurry concentration and the pH value are maintained in respective required ranges, and the absorption efficiency can be completely maintained above 98%;
(5) the invention adopts a mode of adding ammonia into a tower pipeline by primary circulating absorption, achieves the aim of independent ammonia adding oxidation, saves an ammonia adding groove and reduces equipment investment;
(6) according to the invention, by a process control method, the temperature of the absorption section and the solution composition of the absorption circulating liquid are controlled by adjusting process water supplement and ammonia addition amount by using a method of feeding back the state of the system in time by using test results of a densimeter, a temperature sensor and pH measurement, so that the problem of delay of ammonia addition control is solved, and the maximization of desulfurization efficiency is ensured while ammonia escape is controlled to reach the standard;
(7) the invention can set a plurality of stages of water washing spray layers according to the actual smoke situation to reduce the concentration of ammonium sulfate carried by liquid drops at the outlet, thereby reducing the generation of smoke tailing phenomenon to the maximum extent.
Drawings
FIG. 1 is a schematic view of the structure of the present invention.
In fig. 1, a represents process water; b represents an ammonium sulfate post-treatment section; and C represents an accident spray system.
In the figure, 1-absorption tower, 1.1-concentrated crystallization section, 1.2-primary absorption section, 1.21-primary absorption spray layer, 1.3-secondary absorption section, 1.31-secondary absorption spray layer, 1.4-absorption demisting section, 1.5-washing circulation section, 1.51-washing circulation spray layer, 1.6-washing demisting section, 1.7-flue gas inlet, 2-oxidation tank, 3-washing circulation tank, 4-circulation pump, 4.1-primary absorption circulation pump, 4.11-primary absorption circulation pump A, 4.12-primary absorption circulation pump B, 4.13-primary absorption circulation pump C, 4.2-secondary absorption circulation pump, 4.3-washing circulation pump, 5-liquid collector, 5.1-first liquid collector, 5.2-second liquid collector, 6-ammonia water conveying device, 6.1-ammonia injection pump, 7-oxidation air device, 8-disturbance pump, 9-concentration circulating pump, 10-ammonium sulfate discharge pump, 11-flue gas prewashing spraying layer, 12-first interlocking ammonia water pipeline regulating valve, 13-liquid level meter, 14-first-stage absorption circulating system, 15-second-stage absorption circulating system, 16-pH value testing device, 16.1-first pH meter, 16.2-second pH meter, 17-chimney, 18-second interlocking ammonia water pipeline regulating valve, 19-water washing circulating system, 20-oxidation air distribution pipe, 21-temperature sensor, 22-densimeter and 23-concentration circulating system.
Detailed Description
The embodiments of the present invention will be described in detail with reference to the accompanying drawings, which are not intended to limit the present invention, but are merely exemplary. While the advantages of the invention will be clear and readily understood by the description.
With reference to the accompanying drawings: the flue gas desulfurization method by the single-tower multistage circulating ammonia/ammonium sulfate method comprises the following steps,
the method comprises the following steps: pre-washing flue gas;
the flue gas to be treated enters the absorption tower 1 from a flue gas inlet 1.7, and is pre-washed and cooled through a flue gas pre-washing spray layer 11, so that the temperature of the flue gas is reduced to below 70 ℃;
step two: desulfurizing flue gas;
the pre-washed flue gas is desulfurized through the primary absorption cycle system 14, and the desulfurization method of the primary absorption cycle system 14 is as follows:
the first-stage absorption circulating pump 4.1 sends the liquid on the upper part of the oxidation tank 2 into the first-stage absorption spraying layer 1.21, and SO in the flue gas is sprayed by the first-stage absorption spraying layer 1.212Is absorbed and removed by the spray liquid in the first-stage absorption spray layer 1.21, at the moment, the desulfurization spray liquid is converged into the second liquid collector 5.2, and the desulfurization spray liquid in the second liquid collector 5.2 is discharged from the oxygen through a communicating pipelineThe top of the chemical tank 2 returns to the oxidation tank 2;
the first-stage absorption circulation A pump 4.11 and the first-stage absorption circulation B pump 4.12 pump out the solution from different heights of the oxidation tank 2 and respectively pump out the solution to the first-stage absorption spraying layer A1.211 and the first-stage absorption spraying layer B1.212, so that reasonable solution gradient distribution is formed, and the absorption efficiency of a desulfurization system and the inhibition effect on ammonia escape are improved;
the primary absorption circulating pump 4.1 and the secondary absorption circulating pump 4.2 pump out the solution from the oxidation tank 2 at different heights and pump out the solution to the primary absorption section 1.2 and the secondary absorption section 1.3 to form reasonable gradient distribution; meanwhile, the ammonia water conveying device 6 adds ammonia to the spray liquid input into the primary absorption spray layer 1.21 through a communication pipeline, so that the PH and the oxidation rate of the slurry sprayed out of the spray layers with different heights in the absorption section form differences, and the absorption efficiency of the desulfurization system and the inhibition effect on ammonia escape are improved;
circulating a primary absorption liquid (namely, an upper layer liquid in the oxidation tank 2) from the oxidation tank 2 to a primary absorption spraying layer 1.21 of the absorption tower 1, adopting a mode of adding ammonia into a tower pipeline by primary circulation absorption, ensuring the desulfurization efficiency by using a high-pH circulation solution, and solving the problems of insufficient desulfurization efficiency or ammonia escape caused by delay of ammonia adding control by monitoring the pH linkage control ammonia adding amount of the circulation liquid in real time so as to control the generation of aerosol in the desulfurization process from the source;
step three: further desulfurizing the flue gas;
the secondary absorption circulation system 15 further desulfurizes the flue gas treated in the second step, and the desulfurization method of the secondary absorption circulation system 15 is as follows:
the second-stage absorption circulating pump 4.2 sends the liquid at the lower part of the oxidation tank 2 into the second-stage absorption spraying layer 1.31, and SO in the flue gas is sprayed by the second-stage absorption spraying layer 1.312The desulfurization spraying liquid in the second-stage absorption spraying layer 1.31 is absorbed and removed, at the moment, the desulfurization spraying liquid is converged into the second liquid collector 5.2, and the desulfurization spraying liquid in the second liquid collector 5.2 returns to the oxidation tank 2 from the top of the oxidation tank 2 through a communication pipeline;
meanwhile, the oxidizing air device 7 feeds oxygen to the bottom of the oxidizing tank 2 through an oxidizing air distribution pipe 20;
the secondary absorption liquid circulates from the oxidation tank to the secondary spraying layer of the absorption tower, and the decomposition of the ammonium sulfite in the flue gas, ammonia escape and aerosol are controlled by regulating the concentration, temperature and oxidation rate of the solution and utilizing the circulating solution with lower pH value while further desulfurization, so that the standard of ultralow emission is achieved;
step four: removing desulfurization liquid drops from the flue gas;
the absorption demisting section 1.4 absorbs the desulfurization liquid drops, and the liquid drops entering the water washing section are controlled, so that the total dust (containing ammonium salt) at the outlet can meet the ultra-low requirement, and the generation of aerosol is reduced;
the slurry at the bottom of the oxidation tank 2 is pumped into a concentrated crystallization section 1.1 through a secondary absorption circulating pump 4.2, and the pumping flow is controlled through a regulating valve;
step five: washing the desulfurized flue gas with water;
the water washing circulation system 19 washes the desulfurized flue gas, and the specific water washing method is as follows:
the water washing circulating pump 4.3 inputs the process water in the water washing circulating tank 3 into the water washing circulating spraying layer 1.51, the water washing circulating spraying layer 1.51 sprays flue gas, the concentration of ammonium sulfate carried by liquid drops at an outlet is reduced, and the escape of ammonia is reduced; at the moment, the washing liquid is collected into the first liquid collector 5.1, and the washing liquid in the first liquid collector 5.1 returns to the washing circulating tank 3 from the top of the washing circulating tank 3 through a communication pipeline;
step six: removing fog drops at the outlet of the flue gas;
the flue gas after washing absorbs fog drops at an outlet through a washing demisting section 1.6, and then is discharged to a chimney 17 from the top end of the absorption tower 1;
step seven: concentrating and crystallizing;
the concentration circulating pump 9 pumps the circulating liquid in the concentration crystallization section 1.1 into the concentration spraying layer 11 to pre-wash and cool the flue gas, and the residual temperature of the pre-washed serous fluid is utilized to concentrate the serous fluid and promote the serous fluid to crystallize;
the disturbance pump 8 enables the slurry to circulate in the concentrated crystallization section 1.1, promotes the internal circulation of the slurry in the concentrated crystallization section 1.1, and improves the uniformity of the slurry in the concentrated crystallization section 1.1;
when the density of the slurry in the concentrated crystallization section 1.1 is more than 1285kg/m3, the ammonium sulfate discharge pump 10 sends the slurry to an ammonium sulfate post-treatment section for filtration and drying to obtain the finished product of ammonium sulfate.
Further, the first interlocking ammonia water pipeline regulating valve 12 and the second interlocking ammonia water pipeline regulating valve 18 are both automatic regulating valves; the first interlocking ammonia water pipeline regulating valve 12 is controlled in an interlocking mode through a signal fed back by the second pH meter 16.2, and the second interlocking ammonia water pipeline regulating valve 18 is controlled in an interlocking mode through a signal fed back by the first pH meter 16.1, SO that ammonia supplementation amount of the primary absorption section 1.2 inlet is controlled, and the ammonia supplementation amount of the absorption tower is correspondingly adjusted in real time due to the fact that boiler coal burning change can cause the smoke flow of the absorption tower inlet and frequent change of SO2 mass concentration in the smoke in the actual operation process, and the traditional regulating valve is difficult to accurately and continuously control the ammonia supplementation amount. Therefore, the absorption tower is supplied with ammonia by adopting a variable frequency controller, the aim of controlling the ammonia supply amount is achieved by controlling the frequency of the ammonia injection pump, the adjustment has obvious effects of saving ammonia, saving electricity and having quick response compared with the method of controlling the ammonia supply amount by generally adopting an adjusting valve, and the desulfurization efficiency reaches the emission standard and runs stably;
the first interlocking ammonia water pipeline regulating valve 12 controls the frequency of the ammonia injection pump so as to control the ammonia supplementing amount of the inlet 1.2 of the primary absorption section;
the second interlocking ammonia water pipeline regulating valve 18 controls the frequency of the ammonia injection pump so as to control the ammonia supplementing amount of the outlet of the second liquid collector 5.2 in the primary absorption cycle system 14;
the ammonia supplementing mode can be realized by adopting an automatic frequency conversion control system; because the change of the boiler coal causes the frequent change of the flue gas flow at the inlet of the absorption tower and the SO2 mass concentration in the flue gas in the actual operation process, the ammonia supplementing amount added into the absorption tower needs to be correspondingly adjusted in real time, and the traditional adjusting valve is difficult to accurately and continuously control the ammonia supplementing amount. Therefore, the absorption tower is supplemented with ammonia by adopting a variable frequency controller, the aim of controlling the ammonia supplementation amount is achieved by controlling the frequency of the ammonia injection pump, the adjustment has obvious effects of saving ammonia, saving electricity and having quick response compared with the method of controlling the ammonia supplementation amount by generally adopting an adjusting valve, and the desulfurization efficiency reaches the emission standard and runs stably.
Further, a second pH meter 16.2 is arranged at the outlet of the first-stage absorption circulation A pump 4.11; a first pH meter 16.1 is arranged at an outlet of the second liquid collector 5.2, and a pH value testing device monitors the pH value of the circulating liquid in real time, controls the amount of added ammonia water and prevents excessive ammonia;
a temperature sensor 21 is arranged between the accident spraying system and the primary absorption section 1.2;
the water washing circulating tank 3 is connected with the absorption demisting section 1.4 through a water washing circulating pump 4.3 and a communicating pipeline;
a densimeter 23 is arranged on a communicating pipeline between the primary absorption circulating C pump 4.13 and the secondary absorption spraying layer 1.31, and the temperature of the absorption section and the solution composition of the absorption circulating liquid can be adjusted by a method of feeding back the state of the system in time by using a densimeter, a temperature sensor and pH measurement control through a process control method, so that the temperature and the pH value of the absorption section are controlled.
Further, washing defogging section 1.6 is the high-efficient defroster of tertiary ridge formula, has set up the high-efficient defroster of tertiary ridge formula above washing, and export fog droplet concentration reaches 20mg/Nm3In the following, the generation of the smoke tailing phenomenon is reduced to the maximum extent.
Further, in the second step, the temperature of the first-stage absorption section 1.2 is 40-60 ℃, and the pH value is 5.5-6.5;
in the third step, the temperature of the second-stage absorption section 1.3 is 30-50 ℃, and the pH value is 3.5-5.5;
in the seventh step, the temperature of the concentrated crystallization section 1.1 is 50-60 ℃, and the pH is 2-3.5; by a process control method, the temperature of the absorption section and the solution components of the absorption circulating liquid can be adjusted by a method of feeding back the state of the system in time by utilizing the control of a densimeter, a temperature sensor and pH measurement, the temperature of the absorption section is controlled to be 40-60 ℃, the pH of the primary absorption is controlled to be 5.5-6.5, the pH of the secondary absorption is controlled to be 3.5-5.5, the temperature of the concentration crystallization is controlled to be 50-60 ℃, the pH of the concentration crystallization section is controlled to be 2-3.5, the whole absorption tower is in a balanced state which is beneficial to absorbing sulfur dioxide, and the maximization of the desulfurization efficiency is ensured while the ammonia escape is controlled to.
Examples
The present invention will now be described in detail by way of examples.
The single-tower multi-stage circulation ammonia/ammonium sulfate method flue gas desulfurization method in the embodiment adopts a single-tower multi-stage circulation ammonia/ammonium sulfate method flue gas desulfurization system, ammonia escape and aerosol are controlled, the ultra-low emission standard is achieved, and the method is an economic, energy-saving, green and environment-friendly desulfurization system.
With reference to the accompanying drawings: the single-tower multistage circulating ammonia/ammonium sulfate method flue gas desulfurization method in the embodiment adopts a single-tower multistage circulating ammonia/ammonium sulfate method flue gas desulfurization system, which comprises an absorption tower 1, an oxidation tank 2, a water washing circulating tank 3 and a circulating pump 4; the oxidation tank 2 and the water washing circulation tank 3 are both arranged outside the absorption tower 1; the single-tower multi-stage circulation ammonia/ammonium sulfate method flue gas desulfurization technology is provided with an external oxidation tank of the tower, the single tower is provided with a multi-stage circulation subarea through a liquid collector, concentration and crystallization in the tower are carried out, flue gas is pre-washed and cooled, the absorption temperature is controlled in a proper range, and meanwhile, through reasonable design, the pH, the solution concentration and the oxidation rate of slurry sprayed out of spraying layers with different heights in an absorption section form differences and are reasonably distributed in a gradient manner, so that the desulfurization efficiency can be ensured, ammonia escape and aerosol can be reduced, the flue gas heat is reasonably utilized, the energy consumption is reduced, and the circular economy concept is met;
the liquid collector 5 is arranged in the absorption tower 1; the liquid collectors 5 are multiple and comprise a first liquid collector 5.1 and a second liquid collector 5.2; the first liquid collector 5.1 and the second liquid collector 5.2 are arranged at intervals;
the interior of the absorption tower 1 is divided into a multi-stage circulation subarea by a liquid collector 5, and the multi-stage circulation subarea sequentially comprises a concentrated crystallization section 1.1, a first-stage absorption section 1.2, a second-stage absorption section 1.3, an absorption demisting section 1.4, a water washing circulation section 1.5 and a water washing demisting section 1.6 from bottom to top;
the flue gas inlet 1.7 is arranged in the middle of the absorption tower 1; the primary absorption section 1.2, the secondary absorption section 1.3, the absorption demisting section 1.4, the water washing circulation section 1.5, the water washing demisting section 1.6 and the liquid collector 5 are all positioned above the flue gas inlet 1.7;
the water washing demisting section 1.6 is arranged at the top of the absorption tower 1;
the water washing circulation section 1.5 is arranged between the water washing demisting section 1.6 and the first liquid collector 5.1; the water washing circulation section 1.5 and the first liquid collector 5.1 are respectively connected with the water washing circulation tank 3 through a communication pipeline; the water washing circulation section 1.5, the first liquid collector 5.1 and the water washing circulation tank 3 form a water washing circulation system 19 through a communication pipeline;
the primary absorption section 1.2 and the secondary absorption section 1.3 are arranged above the second liquid collector 5.2 at intervals and below the absorption demisting section 1.4; an absorption section demister is arranged above the absorption section, so that the load of liquid drops entering the water washing section is reduced; because more ammonium sulfate is dissolved in the absorption liquid of the absorption section, the liquid drops entering the water washing section are strictly controlled, so that the total dust (containing ammonium salt) at the outlet can meet the ultra-low requirement, and the generation of aerosol is reduced;
the second liquid collector 5.2 is connected with the oxidation tank 2 through a communication pipeline;
the oxidation tank 2 is respectively connected with the primary absorption section 1.2 and the secondary absorption section 1.3;
the pH value testing device 16 is arranged outside the absorption tower 1; the pH value testing device 16 comprises a first pH meter 16.1 and a second pH meter 16.2; the first pH meter 16.1 is connected to a communicating pipeline between the oxidation tank 2 and the primary absorption section 1.2; the second pH meter 16.2 is connected to a communication pipeline between the second liquid collector 5.2 and the oxidation tank 2;
the ammonia water conveying device 6 and the first interlocking ammonia water pipeline regulating valve 12 are respectively connected to a communicating pipeline of the oxidation tank 2 and the primary absorption section 1.2;
the first interlocking ammonia water pipeline regulating valve 12 and the second pH meter 16.2 are arranged in interlocking control;
a second ammonia interlocking pipeline regulating valve 18 is connected to a communicating pipeline between the oxidation tank 2 and the second liquid collector 5.2;
the second interlocking ammonia water pipeline regulating valve 18 and the first pH meter 16.1 are arranged in interlocking control;
the primary absorption section 1.2 is connected to the upper part of the oxidation tank 2; the primary absorption section 1.2, the oxidation tank 2, the second liquid collector 5.2 and the ammonia water conveying device 6 are connected into a primary absorption circulating system 14 through a communicating pipeline;
the secondary absorption section 1.3 is connected to the lower part of the oxidation tank 2; the secondary absorption section 1.3, the oxidation tank 2, the second liquid collector 5.2 and the communication pipeline are connected to form a secondary absorption circulation system 15;
the sulfur dioxide absorption section is provided with a first-stage absorption cycle and a second-stage absorption cycle: the primary absorption liquid circulates from the oxidation tank to the primary spraying layer of the absorption tower, a mode of adding ammonia into a tower pipeline by primary circulating absorption is adopted, the desulfurization efficiency is ensured by using a high-pH circulating solution, the ammonia adding amount is controlled by monitoring the pH linkage of the circulating liquid in real time, the problem of insufficient desulfurization efficiency or ammonia escape caused by delay of ammonia adding control is solved, and the generation of aerosol in the desulfurization process is controlled from the source; the secondary absorption liquid circulates from the oxidation tank to the secondary spraying layer of the absorption tower, and the decomposition of the ammonium sulfite in the flue gas, ammonia escape and aerosol are controlled by regulating the concentration, temperature and oxidation rate of the solution and utilizing the circulating solution with lower pH value while further desulfurization, so that the standard of ultralow emission is achieved;
the oxidation air distribution pipe 20 is arranged at the bottom of the oxidation tank 2; the oxidizing air distribution pipe 20 is connected with the oxidizing air device 7; the mechanism of aerosol formation can be analyzed to derive two requirements for aerosol appearance: excess ammonia and high concentration solution; the ammonia addition and the oxidation are independently controlled, so that the high-efficiency desulfurization can be ensured, the ammonia water amount is strictly controlled, and the excessive ammonia is prevented; on the other hand, the liquid for flushing the secondary demister of the system is process water, the circulating liquid is continuously diluted, secondary absorption circulation of ammonium sulfite solids generated by saturated crystallization of the circulating liquid, which is provided with the oxidizing air distribution pipe 20 and the oxidizing air device 7, has good effect on preventing the problems of excessive ammonia, crystallization of the circulating liquid and the like, and aerosol is naturally difficult to occur;
the water washing circulating tank 3, the water washing circulating pump 4.3 and the water washing circulating section 1.5 are connected through a communicating pipeline to form a water washing circulating system 19;
a disturbance pump 8, a concentration circulating pump 9 and an ammonium sulfate discharge pump 10 are arranged at a concentration crystallization section 1.1 at the bottom of the absorption tower 1;
the concentration and crystallization section 1.1, the flue gas prewashing spray layer 11 and the concentration circulating pump 9 form a concentration circulating system 23 through a communicating pipeline;
the flue gas prewashing spraying layer 11 is positioned above the flue gas inlet 1.7;
the disturbance pump 8 is connected to the side wall of the absorption tower 1 and is positioned below the flue gas inlet 1.7;
the ammonium sulfate discharge pump 10 is connected to the bottom of the absorption tower 1 and is located below the concentration circulating pump 9.
Further, a primary absorption spraying layer 1.21 is arranged on the primary absorption section 1.2; the primary absorption spraying layer 1.21 has a plurality of layers;
a secondary absorption spraying layer 1.31 is arranged on the secondary absorption section 1.3; the number of the secondary absorption spraying layers 1.31 is more than or equal to 1;
a water washing circulating spraying layer 1.51 is arranged on the water washing circulating section 1.5; adopt multistage washing technique in absorption section defroster top, spray the layer through setting up three-layer washing and reduce the concentration of ammonium sulfate in the export liquid drop carries to reduced ammonia escape, set up the high-efficient defroster of tertiary ridge formula above the washing at last, export fog drop concentration reaches 20mg/Nm3In the following, the generation of the smoke tailing phenomenon is reduced to the maximum extent.
Further, the circulating pump 4 comprises a first-stage absorption circulating pump 4.1, a second-stage absorption circulating pump 4.2 and a water washing circulating pump 4.3;
the primary absorption circulating pump 4.1 is positioned on the primary absorption circulating system 14 and is arranged at an outlet at the upper part of the oxidation tank 2;
the secondary absorption circulating pump 4.2 is positioned on the secondary absorption circulating system 15 and is arranged at the outlet at the lower part of the oxidation tank 2;
the primary absorption circulating pump 4.1 and the secondary absorption circulating pump 4.2 can be mutually standby;
the water washing circulation pump 4.3 is located on the water washing circulation system 19 and is disposed at the lower outlet of the water washing circulation tank 3.
Furthermore, a plurality of first-stage absorption circulating pumps 4.1 are provided, and each first-stage absorption circulating pump 4.1 comprises a first-stage absorption circulating pump A4.11, a first-stage absorption circulating pump B4.12 and a first-stage absorption circulating pump C4.13; three pumps of the primary absorption circulating pump 4.1 are mutually standby; meanwhile, the pump C of 4.1 can be used as a second-stage absorption circulating pump 4.2 for standby;
the first-stage absorption spraying layer 1.21 comprises a first-stage absorption spraying layer A1.211 and a first-stage absorption spraying layer B1.212; the first-stage absorption spraying A layer 1.211 is positioned above the second liquid collector 5.2; the primary absorption spraying B layer 1.212 is positioned above the primary absorption spraying A layer 1.211;
the first-stage absorption circulating A pump 4.11 is connected with the first-stage absorption spraying A layer 1.211; the second pH meter 16.2 is connected to a communicating pipeline between the primary absorption circulation A pump 4.11 and the primary absorption spraying A layer 1.211;
the primary absorption circulating B pump 4.12 is connected with the primary absorption spraying B layer 1.212;
the primary absorption circulating pump C4.13 is respectively connected with the primary absorption spraying layer B1.212 and the secondary absorption spraying layer 1.31;
the ammonia water conveying device 6 is respectively connected to a communicating pipeline between the primary absorption circulation A pump 4.11 and the primary absorption spraying layer A1.211 and a communicating pipeline between the primary absorption circulation B pump 4.12 and the primary absorption spraying layer B1.212;
an ammonia injection pump 6.1 is arranged at the outlet of the ammonia water conveying device 6.
Further, the oxidation tank 2 is connected with the bottom of the absorption tower 1 through a communication pipeline;
the secondary absorption circulating pump 4.2 is arranged on a communicating pipeline between the oxidation tank 2 and the absorption tower 1;
the second liquid collector 5.2 is connected to the upper part of the oxidation tank 2 through a communication pipeline;
the first liquid collector 5.1 is connected to the upper part of the water washing circulation tank 3 through a communication pipeline.
The flue gas desulfurization method by the single-tower multistage circulation ammonia/ammonium sulfate method in the embodiment comprises the following steps,
the method comprises the following steps: pre-washing flue gas;
the flue gas to be treated enters the absorption tower 1 from a flue gas inlet 1.7, and is pre-washed and cooled through a flue gas pre-washing spray layer 11, so that the temperature of the flue gas is reduced to below 70 ℃;
step two: desulfurizing flue gas;
the pre-washed flue gas is desulfurized through the primary absorption cycle system 14, and the desulfurization method of the primary absorption cycle system 14 is as follows:
the first-stage absorption circulating pump 4.1 sends the liquid on the upper part of the oxidation tank 2 into the first-stage absorption spraying layer 1.21, and SO in the flue gas is sprayed by the first-stage absorption spraying layer 1.212Is sprayed in the primary absorption spraying layer 1.21The spraying liquid is absorbed and removed, at the moment, the desulfurization spraying liquid is converged into the second liquid collector 5.2, and the desulfurization spraying liquid in the second liquid collector 5.2 returns to the oxidation tank 2 from the top of the oxidation tank 2 through a communication pipeline;
the first-stage absorption circulation A pump 4.11 and the first-stage absorption circulation B pump 4.12 pump out the solution from different heights of the oxidation tank 2 and respectively pump out the solution to the first-stage absorption spraying layer A1.211 and the first-stage absorption spraying layer B1.212, so that reasonable solution gradient distribution is formed, and the absorption efficiency of a desulfurization system and the inhibition effect on ammonia escape are improved; a second pH meter 16.2 is arranged at the outlet of the first-stage absorption circulation A pump 4.11; a first pH meter 16.1 is arranged at an outlet of the second liquid collector 5.2, and a pH value testing device monitors the pH value of the circulating liquid in real time, controls the amount of added ammonia water and prevents excessive ammonia;
the temperature of the first-stage absorption section 1.2 is 40-60 ℃, and the pH value is 5.5-6.5;
a temperature sensor 21 is arranged between the accident spraying system and the primary absorption section 1.2;
the water washing circulating tank 3 is connected with the absorption demisting section 1.4 through a water washing circulating pump 4.3 and a communicating pipeline;
a densimeter 23 is arranged on a communicating pipeline between the primary absorption circulating C pump 4.13 and the secondary absorption spraying layer 1.31, and the temperature of the absorption section and the solution composition of the absorption circulating liquid can be adjusted by a method of feeding back the state of the system in time by using a densimeter, a temperature sensor and pH measurement control through a process control method, so that the temperature and the pH value of the absorption section are controlled;
the primary absorption circulating pump 4.1 and the secondary absorption circulating pump 4.2 pump out the solution from the oxidation tank 2 at different heights and pump out the solution to the primary absorption section 1.2 and the secondary absorption section 1.3 to form reasonable gradient distribution; meanwhile, the ammonia water conveying device 6 adds ammonia to the spray liquid input into the primary absorption spray layer 1.21 through a communication pipeline, so that the PH and the oxidation rate of the slurry sprayed out of the spray layers with different heights in the absorption section form differences, and the absorption efficiency of the desulfurization system and the inhibition effect on ammonia escape are improved;
circulating a primary absorption liquid (namely, an upper layer liquid in the oxidation tank 2) from the oxidation tank 2 to a primary absorption spraying layer 1.21 of the absorption tower 1, adopting a mode of adding ammonia into a tower pipeline by primary circulation absorption, ensuring the desulfurization efficiency by using a high-pH circulation solution, and solving the problems of insufficient desulfurization efficiency or ammonia escape caused by delay of ammonia adding control by monitoring the pH linkage control ammonia adding amount of the circulation liquid in real time so as to control the generation of aerosol in the desulfurization process from the source;
step three: further desulfurizing the flue gas;
the secondary absorption circulation system 15 further desulfurizes the flue gas treated in the second step, and the desulfurization method of the secondary absorption circulation system 15 is as follows:
the second-stage absorption circulating pump 4.2 sends the liquid at the lower part of the oxidation tank 2 into the second-stage absorption spraying layer 1.31, and SO in the flue gas is sprayed by the second-stage absorption spraying layer 1.312The desulfurization spraying liquid in the second-stage absorption spraying layer 1.31 is absorbed and removed, at the moment, the desulfurization spraying liquid is converged into the second liquid collector 5.2, and the desulfurization spraying liquid in the second liquid collector 5.2 returns to the oxidation tank 2 from the top of the oxidation tank 2 through a communication pipeline;
the temperature of the secondary absorption section 1.3 is 30-50 ℃, and the pH is 3.5-5.5;
meanwhile, the oxidizing air device 7 feeds oxygen to the bottom of the oxidizing tank 2 through an oxidizing air distribution pipe 20;
the secondary absorption liquid circulates from the oxidation tank to the secondary spraying layer of the absorption tower, and the decomposition of the ammonium sulfite in the flue gas, ammonia escape and aerosol are controlled by regulating the concentration, temperature and oxidation rate of the solution and utilizing the circulating solution with lower pH value while further desulfurization, so that the standard of ultralow emission is achieved;
step four: removing desulfurization liquid drops from the flue gas;
the absorption demisting section 1.4 absorbs the desulfurization liquid drops, and the liquid drops entering the water washing section are controlled, so that the total dust (containing ammonium salt) at the outlet can meet the ultra-low requirement, and the generation of aerosol is reduced;
the slurry at the bottom of the oxidation tank 2 is pumped into a concentrated crystallization section 1.1 through a secondary absorption circulating pump 4.2, and the pumping flow is controlled through a regulating valve;
step five: washing the desulfurized flue gas with water;
the water washing circulation system 19 washes the desulfurized flue gas, and the specific water washing method is as follows:
the water washing circulating pump 4.3 inputs the process water in the water washing circulating tank 3 into the water washing circulating spraying layer 1.51, the water washing circulating spraying layer 1.51 sprays flue gas, the concentration of ammonium sulfate carried by liquid drops at an outlet is reduced, and the escape of ammonia is reduced; at the moment, the washing liquid is collected into the first liquid collector 5.1, and the washing liquid in the first liquid collector 5.1 returns to the washing circulating tank 3 from the top of the washing circulating tank 3 through a communication pipeline;
step six: removing fog drops at the outlet of the flue gas;
the flue gas after washing absorbs fog drops at an outlet through a washing demisting section 1.6, and then is discharged to a chimney 17 from the top end of the absorption tower 1; the washing demisting section 1.6 is a three-stage ridge type high-efficiency demister, the three-stage ridge type high-efficiency demister is arranged above the washing, and the concentration of outlet fog drops reaches 20mg/Nm3The generation of the smoke trailing phenomenon is reduced to the maximum extent;
step seven: concentrating and crystallizing;
the concentration circulating pump 9 pumps the circulating liquid in the concentration crystallization section 1.1 into the concentration spraying layer 11 to pre-wash and cool the flue gas, and the residual temperature of the pre-washed serous fluid is utilized to concentrate the serous fluid and promote the serous fluid to crystallize;
the disturbance pump 8 enables the slurry to circulate in the concentrated crystallization section 1.1, promotes the internal circulation of the slurry in the concentrated crystallization section 1.1, and improves the uniformity of the slurry in the concentrated crystallization section 1.1;
when the density of the slurry in the concentrated crystallization section 1.1 is more than 1285kg/m3, an ammonium sulfate discharge pump 10 sends the slurry to an ammonium sulfate post-treatment section for filtering and drying to obtain a finished product of ammonium sulfate;
the temperature of the concentration crystallization section 1.1 is 50-60 ℃, and the pH value is 2-3.5; by a process control method, the temperature of the absorption section and the solution components of the absorption circulating liquid can be adjusted by a method of feeding back the state of the system in time by utilizing the control of a densimeter, a temperature sensor and pH measurement, the temperature of the absorption section is controlled to be 40-60 ℃, the pH of the primary absorption is controlled to be 5.5-6.5, the pH of the secondary absorption is controlled to be 3.5-5.5, the temperature of the concentration crystallization is controlled to be 50-60 ℃, the pH of the concentration crystallization section is controlled to be 2-3.5, the whole absorption tower is in a balanced state which is beneficial to absorbing sulfur dioxide, and the maximization of the desulfurization efficiency is ensured while the ammonia escape is controlled to.
And (4) conclusion: the embodiment is generated from aerosol and ammonia escape in the absorption processThe problem of aerosol and ammonia escape is solved from the source, the desulfurization efficiency is high (more than 98.5%), the ammonia adding amount is controlled in a linkage manner by monitoring the pH value of the circulating liquid in real time, the problem of insufficient desulfurization efficiency or ammonia escape caused by delay of ammonia adding control is solved, the aerosol in the desulfurization process is controlled from the source, and the generation of a flue gas tailing phenomenon is reduced to the greatest extent; in the embodiment, the three-stage ridge type high-efficiency demister is arranged above the water washing, and the concentration of fog drops at the outlet reaches 20mg/Nm3The method has the advantages that the generation of a flue gas tailing phenomenon is reduced to the greatest extent, the maximization of the desulfurization efficiency can be ensured, the ammonia escape is controlled to reach the standard at the same time, and the operation cost is low.
In order to more clearly illustrate the advantages of the flue gas desulfurization method by using single-tower multistage circulation ammonia/ammonium sulfate method in the invention compared with the prior art, the two technical schemes are compared by workers, and the comparison results are as follows:
as can be seen from the above table, compared with the prior art, the single-tower multistage circulation ammonia/ammonium sulfate method for flue gas desulfurization has the advantages of high desulfurization efficiency, low probability of generating aerosol, furthest reduction of the generation of a flue gas tailing phenomenon, capability of ensuring that the desulfurization efficiency is maximized and controlling ammonia escape to reach the standard at the same time, and low operation cost.
Other parts not described belong to the prior art.
Claims (5)
1. A single-tower multi-stage circulating ammonia/ammonium sulfate method for flue gas desulfurization is characterized in that: comprises the following steps of (a) carrying out,
the method comprises the following steps: pre-washing flue gas;
the flue gas to be treated enters the absorption tower (1) from a flue gas inlet (1.7), and is pre-washed and cooled through a flue gas pre-washing spraying layer (11), so that the temperature of the flue gas is reduced to below 70 ℃;
step two: desulfurizing flue gas;
the pre-washed flue gas is desulfurized through the primary absorption circulating system (14), and the desulfurization method of the primary absorption circulating system (14) is as follows:
the first-stage absorption circulating pump (4.1) sends the liquid on the upper part of the oxidation tank (2) into the first-stage absorption spraying layer (1.21), and SO in the flue gas is sprayed by the first-stage absorption spraying layer (1.21)2The desulfurization spraying liquid in the first-stage absorption spraying layer (1.21) is absorbed and removed, at the moment, the desulfurization spraying liquid is converged into a second liquid collector (5.2), and the desulfurization spraying liquid in the second liquid collector (5.2) returns to the oxidation tank (2) from the top of the oxidation tank (2) through a communicating pipeline;
the primary absorption circulation A pump (4.11) and the primary absorption circulation B pump (4.12) pump out the solution from different heights of the oxidation tank (2) and respectively pump out the solution to the primary absorption spraying layer A (1.211) and the primary absorption spraying layer B (1.212) to form solution gradient distribution; meanwhile, the ammonia water conveying device (6) adds ammonia to the spray liquid input into the primary absorption spray layer (1.21) through a communication pipeline, so that the PH and the oxidation rate of the slurry sprayed out of the spray layers with different heights in the absorption section form difference;
step three: further desulfurizing the flue gas;
the secondary absorption circulation system (15) further desulfurizes the flue gas treated in the step two, and the desulfurization method of the secondary absorption circulation system (15) is as follows:
the second-stage absorption circulating pump (4.2) sends the liquid at the lower part of the oxidation tank (2) into the second-stage absorption spraying layer (1.31), and SO in the flue gas is sprayed by the second-stage absorption spraying layer (1.31)2The desulfurization spraying liquid in the second-stage absorption spraying layer (1.31) is absorbed and removed, at the moment, the desulfurization spraying liquid is converged into a second liquid collector (5.2), and the desulfurization spraying liquid in the second liquid collector (5.2) returns to the oxidation tank (2) from the top of the oxidation tank (2) through a communicating pipeline;
meanwhile, the oxidizing air device (7) is used for introducing oxygen to the bottom of the oxidizing tank (2) through an oxidizing air distribution pipe (20);
step four: removing desulfurization liquid drops from the flue gas;
the absorption demisting section (1.4) absorbs the desulfurization liquid drops and controls the liquid drops entering the water washing section;
the slurry at the bottom of the oxidation tank (2) is pumped into a concentration crystallization section (1.1) through a secondary absorption circulating pump (4.2), and the pumping flow is controlled through a regulating valve;
step five: washing the desulfurized flue gas with water;
the water washing circulating system (19) washes the desulfurized flue gas, and the specific water washing method comprises the following steps:
the water washing circulating pump (4.3) inputs the process water in the water washing circulating tank (3) into the water washing circulating spraying layer (1.51), the water washing circulating spraying layer (1.51) sprays flue gas, the concentration of ammonium sulfate carried by liquid drops at an outlet is reduced, and the escape of ammonia is reduced; at the moment, the washing liquid is collected into the first liquid collector (5.1), and the washing liquid in the first liquid collector (5.1) returns to the washing circulating tank (3) from the top of the washing circulating tank (3) through a communicating pipeline;
step six: removing fog drops at the outlet of the flue gas;
the flue gas after washing absorbs fog drops at an outlet through a washing demisting section (1.6), and then is discharged to a chimney (17) from the top end of the absorption tower (1);
step seven: concentrating and crystallizing;
the concentration circulating pump (9) pumps the circulating liquid in the concentration crystallization section (1.1) into the concentration spraying layer (11) to pre-wash and cool the flue gas, and the residual heat of the pre-washed serous fluid is utilized to concentrate the serous fluid and promote the serous fluid crystallization;
the disturbance pump (8) enables the slurry to circulate in the concentrated crystallization section (1.1), promotes the internal circulation of the slurry in the concentrated crystallization section (1.1), and improves the uniformity of the slurry in the concentrated crystallization section (1.1);
when the density of the slurry in the concentrated crystallization section (1.1) is more than 1285kg/m3When the slurry is processed, the ammonium sulfate discharge pump (10) sends the slurry to an ammonium sulfate post-processing section.
2. The single-tower multistage circulation ammonia/ammonium sulfate method flue gas desulfurization method according to claim 1, characterized in that: the first interlocking ammonia water pipeline regulating valve (12) and the second interlocking ammonia water pipeline regulating valve (18) are both automatic regulating valves; the first interlocking ammonia water pipeline regulating valve (12) is controlled in an interlocking mode through a signal fed back by the second pH meter (16.2), and the second interlocking ammonia water pipeline regulating valve (18) is controlled in an interlocking mode through a signal fed back by the first pH meter (16.1).
3. The single-tower multistage circulation ammonia/ammonium sulfate method flue gas desulfurization method according to claim 2, characterized in that: a second pH meter (16.2) is arranged at the outlet of the first-stage absorption circulation A pump (4.11); a first pH meter (16.1) is arranged at the outlet of the second liquid collector (5.2);
a temperature sensor (21) is arranged between the accident spraying system and the primary absorption section (1.2);
the water washing circulating tank (3) is connected with the absorption demisting section (1.4) through a water washing circulating pump (4.3) and a communicating pipeline;
the densimeter (23) is arranged on a communicating pipeline between the primary absorption circulating C pump (4.13) and the secondary absorption spraying layer (1.31).
4. The single-tower multistage circulation ammonia/ammonium sulfate method flue gas desulfurization method according to claim 3, characterized in that: the washing demisting section (1.6) is a three-stage ridge type high-efficiency demister; the concentration of fog drops at the outlet of the water-washing demisting section (1.6) is less than or equal to 20mg/Nm3。
5. The single-tower multistage circulation ammonia/ammonium sulfate method flue gas desulfurization method according to claim 4, characterized in that: in the second step, the temperature of the first-stage absorption section (1.2) is 40-60 ℃, and the pH value is 5.5-6.5;
in the third step, the temperature of the second-stage absorption section (1.3) is 30-50 ℃, and the pH value is 3.5-5.5;
in the seventh step, the temperature of the concentrated crystallization section (1.1) is 50-60 ℃, and the pH is 2-3.5.
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