CN113433263A - Device and method for detecting activity of limestone in wet flue gas desulfurization - Google Patents
Device and method for detecting activity of limestone in wet flue gas desulfurization Download PDFInfo
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000003546 flue gas Substances 0.000 title claims abstract description 202
- 235000019738 Limestone Nutrition 0.000 title claims abstract description 180
- 239000006028 limestone Substances 0.000 title claims abstract description 180
- 230000000694 effects Effects 0.000 title claims abstract description 74
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 51
- 230000023556 desulfurization Effects 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002002 slurry Substances 0.000 claims abstract description 161
- 238000006243 chemical reaction Methods 0.000 claims abstract description 119
- 238000004088 simulation Methods 0.000 claims abstract description 24
- 239000000523 sample Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 80
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- 238000001514 detection method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 abstract description 16
- 238000012360 testing method Methods 0.000 abstract description 14
- 238000013461 design Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000012445 acidic reagent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/162—Determining the equivalent point by means of a discontinuity
- G01N31/164—Determining the equivalent point by means of a discontinuity by electrical or electrochemical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—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
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- 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
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention discloses a device and a method for detecting limestone activity in wet flue gas desulfurization.A flue gas inlet and a first slurry outlet are arranged at the bottom of a reaction tank, and a flue gas outlet is arranged at the upper part of the reaction tank; a smoke outlet of the smoke simulation system is connected with a smoke inlet of the reaction tank through a first smoke pipeline, and a front smoke analyzer is connected into the first smoke pipeline; the inlet of the slurry circulating pump is connected with the first slurry outlet, and the outlet of the slurry circulating pump is connected with the limestone slurry tank; a second slurry outlet is formed in the bottom of the limestone slurry tank, the second slurry outlet is connected with a first slurry pipeline, and an outlet of the first slurry pipeline is formed in the inner top of the reaction tank; the electromagnetic control valve is arranged on the first slurry pipeline; the automatic potentiometric titrator is connected with the electromagnetic control valve, and the probe of the pH electrode is inserted into the reaction tank; and a flue gas outlet of the reaction tank is connected with a second flue gas pipeline, and the rear flue gas analyzer is connected into the second flue gas pipeline. The invention can simulate the actual wet desulphurization process and simply, conveniently and accurately test the limestone activity in the actual desulphurization process.
Description
Technical Field
The invention belongs to the field of energy conservation and environmental protection, and relates to a device and a method for detecting the activity of limestone in wet flue gas desulfurization.
Background
A large amount of coal is combusted, typical coal-smoke type environmental pollution is presented, and the exhaust gas discharged by a coal-fired power plant contains a large amount of sulfide, so that the coal-fired power plant is one of the great causes of atmospheric pollution. In order to deal with the problem of environmental pollution and reduce the emission of pollutants, most coal burning industries are equipped with desulfurization environmental protection facilities. Among them, the limestone-gypsum wet desulphurization process is the most mature and widely applied desulphurization technology in many desulphurization processes because of its advantages of fast reaction speed, high desulphurization efficiency, low cost, etc.
In the wet desulphurization process, the quality of limestone directly affects the running state, desulphurization efficiency, gypsum quality and the like of a wet desulphurization device, and plays a crucial role in the whole desulphurization device, and the selection of limestone is one of the key problems in the design stage of the wet desulphurization device. The activity degree of limestone is a key index for measuring the quality of limestone, and how to quickly and accurately detect the activity degree of the limestone becomes a problem to be solved urgently in the limestone-gypsum wet desulphurization industry.
At present, three limestone activity degree test methods exist:
(1) the national electric power industry standard: the determination of the reaction rate of limestone powder for wet flue gas desulfurization (DL/T943-2005) specifies the determination method of the reaction rate of limestone powder for wet flue gas desulfurization. The method selects limestone powder with fineness of 250 meshes and residual sieve of 5 percent, and titrates 250ml of CaCl by HCl (0.1mol/L) solution under the conditions of controlling temperature at 50 ℃ and pH value at 5.52(0.1mol/L) solution was used as a slurry of limestone (0.150g) in a carrier liquid and the time required for the limestone powder conversion to reach 80% was determined and used as an indicator for characterizing the limestone reaction rate. The method is simple to operate, easy to control and operate and has a certain engineering application value, but the time required for the limestone conversion rate to reach 80% is taken as a quantitative index for judging the limestone activity, so that the method is difficult to be directly applied to the optimization design of wet desulphurization equipment, and the HCl solution and CaCl are added2The difference between the carrier liquid and the environment in the actual desulfurizing tower is large, and the activity of limestone under the actual working condition cannot be reflected.
(2) A set of large-scale pilot test device is established by the method, named as a limestone activity test method and an analysis system thereof (CN1869685B), and comprises a limestone slurry pool, a slurry pump, an absorption tower, a gas cylinder, a gas flowmeter, a limestone slurry recovery pool and an SO2A concentration analysis system, etc., which is to use limestone slurry and simulated SO2The flue gas directly reacts to simulate the actual flue gas desulfurization process and measure SO2The removal rate of (A) reflects the activity of limestone, SO2The higher the removal rate, the better the limestone activity, SO2The lower the removal rate, the poorer the limestone activity. This method takes into account both the diffusion of the gas in the liquid phase and various surface reactions during the analysis, complicating the overall process. Meanwhile, the mode needs more test equipment and has higher research cost.
(3) Chinese patent named 'test method and test device for limestone activity for wet flue gas desulfurization' (CN10122590B), and the method is used for preparing SO2The ethanol solution (0.05-0.5 mol/L) is used as an acidic reagent and CaCl2(0.1mol/L) limestone slurry with solution as carrier liquid, the testing device of which comprises: acid reagent bottleThe method comprises the steps of dropping an acidic reagent into limestone slurry for reaction, testing the reaction activity, and keeping the pH value at 5.5 in the testing process. Dissolved SO2The ethanol solution is dropped into the limestone slurry, and SO is difficult to dissolve in the slurry2The concentration of ethanol in the slurry is greatly reduced, which can seriously affect the SO caused by ethanol2The dissolving capacity of (B) to cause SO2Spillage, which affects the results of limestone activity tests.
Methods (1) and (3) in the titration Process, CaCl2CaCO formed in the actual wet desulfurization reaction as a readily soluble substance3As insoluble products, CaCO3Easily soluble CaCl which generally affects the reaction rate2There is no such effect, so the limestone activity measured by the methods (1) and (3) is higher than that in the actual desulfurization process.
In conclusion, the existing limestone activity testing technology is difficult to meet the requirements of engineering design of wet desulphurization and desulphurization model optimization. Limestone parameters in the wet desulphurization flue gas desulphurization process are difficult to select, and the design capacity is often too large in order to ensure the desulphurization efficiency, so that the system investment and the operation cost of the desulphurization process are increased. Therefore, it is very urgent to establish a set of test method for limestone reactivity which is relatively simple, convenient to operate and accurate to measure.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the device and the method for detecting the activity of the limestone in the wet flue gas desulfurization.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a limestone activity detection device for wet flue gas desulfurization comprises a flue gas simulation system, a reaction tank, a limestone slurry tank, an electromagnetic control valve, an automatic potentiometric titrator, a slurry circulating pump, a front flue gas analyzer and a rear flue gas analyzer;
the bottom of the reaction tank is provided with a flue gas inlet and a first slurry outlet, and the upper part of the reaction tank is provided with a flue gas outlet;
a smoke outlet of the smoke simulation system is connected with a smoke inlet of the reaction tank through a first smoke pipeline, and a front smoke analyzer is connected into the first smoke pipeline;
an inlet of the slurry circulating pump is connected with the first slurry outlet, and an outlet of the slurry circulating pump is connected with the limestone slurry tank;
a second slurry outlet is formed in the bottom of the limestone slurry tank, the second slurry outlet is connected with a first slurry pipeline, and an outlet of the first slurry pipeline is formed in the inner top of the reaction tank;
the electromagnetic control valve is arranged on the first slurry pipeline;
the automatic potentiometric titrator is connected with the electromagnetic control valve, and a probe of a pH electrode of the automatic potentiometric titrator is inserted into the reaction tank;
and a flue gas outlet of the reaction tank is connected with a second flue gas pipeline, and the rear flue gas analyzer is connected into the second flue gas pipeline.
Preferably, the flue gas simulation system comprises N2Standard gas bottle, O2Standard gas bottle, SO2Standard gas bottle, CO2Standard gas bottle and flow meter, N2Standard gas bottle, O2Standard gas bottle, SO2Target gas bottle and CO2The outlet of the standard gas bottle is communicated with the first flue gas pipeline, the flowmeter is arranged on the first flue gas pipeline, and the front flue gas analyzer is connected to the outlet side of the flowmeter.
Preferably, the flue gas simulation system further comprises a front gas mixing device, the front gas mixing device is arranged on the first flue gas pipeline and is located on the outlet side of the flowmeter and the inlet side of the front flue gas analyzer, and the front gas mixing device has a flue gas temperature control function.
Preferably, a flue gas spray hole or a flue gas nozzle connected with a flue gas inlet of the reaction tank is arranged in the reaction tank, and the flue gas spray hole or the flue gas nozzle can blow flue gas on the whole section of the inner cavity of the reaction tank;
the first slurry outlet is arranged above the flue gas jet holes or the flue gas nozzles, the first slurry pipeline outlet is provided with the slurry nozzles, and the slurry nozzles can jet slurry to the whole section of the inner cavity of the reaction tank.
Preferably, the outlet of the slurry circulating pump is connected with the top of the limestone slurry tank, and a stirrer which never stirs limestone slurry is arranged in the limestone slurry tank.
Preferably, the second flue gas pipeline is also connected with a rear gas mixing device, and the rear gas mixing device is positioned at the upstream of the rear flue gas analyzer.
Preferably, the outlet of the second flue gas pipeline is connected with a gas washing device.
Preferably, the apparatus for detecting activity of limestone in wet flue gas desulfurization further comprises a constant temperature water device, wherein the constant temperature water device comprises a constant temperature water bath container, and the reaction tank is inserted into the constant temperature water bath container.
The invention also provides a method for detecting the activity of the limestone in wet flue gas desulfurization, which is carried out by adopting the device for detecting the activity of the limestone in wet flue gas desulfurization, and comprises the following steps:
adding the prepared limestone slurry into a reaction tank and a limestone slurry box, and immersing a probe of a pH electrode into the limestone slurry in the reaction tank;
introducing simulated flue gas configured by a flue gas simulation system into a reaction tank to react with limestone slurry in the reaction tank; starting a slurry circulating pump and controlling the circulating flow of the slurry; starting an automatic potentiometric titrator, wherein the automatic potentiometric titrator controls an electromagnetic control valve through the pH value measured by a pH electrode, adjusts the slurry supplementing amount of limestone slurry, and maintains the pH value of the limestone slurry in the reaction tank to be a preset value;
respectively measuring SO in the first flue gas pipeline and the second flue gas pipeline by the front flue gas analyzer and the rear flue gas analyzer2Concentration, SO measured by front and rear flue gas analyzers2And calculating the desulfurization efficiency according to the concentration, and evaluating the activity of the limestone in the wet flue gas desulfurization according to the desulfurization efficiency.
Preferably:
in the prepared limestone slurry: the solid content is 3-5%, and the particle size of limestone powder adopted in preparation is 250 +/-20 meshes;
the concentration of sulfur dioxide in the simulated flue gas is 5000-6000 mg/m3The volume concentration of oxygen is 5-8%, and the volume concentration of carbon dioxide is 8-13%;
the reaction temperature of the reaction tank is maintained at 47-55 ℃;
the pH value of limestone slurry in the reaction tank is maintained at 5.2-5.8.
The invention has the following beneficial effects:
the invention can simulate the flue gas with the same components as the flue gas by utilizing a flue gas simulation system, can realize the updating circulation of limestone slurry in the reaction tank by utilizing the reaction tank, the limestone slurry tank, the first slurry pipeline and the slurry circulating pump, can control the pH value of the limestone slurry in the reaction tank to be maintained in a preset range value by an electromagnetic control valve and an automatic potentiometric titrator, and meets the measurement requirement; preceding flue gas analyzer and back flue gas analyzer can measure the concentration of sulfur dioxide in the simulation flue gas of business turn over retort, just can calculate out desulfurization efficiency according to the concentration of sulfur dioxide in the simulation flue gas of play retort, can efficiency evaluation wet flue gas desulfurization limestone activity through the desulfurization. In conclusion, the limestone activity detection device for wet flue gas desulfurization can control the reaction conditions and working conditions to be quite close to those of the actual wet desulfurization process, and can truly reflect the activity of limestone under the actual condition; the invention can simulate the activity of the limestone under the actual wet desulphurization working condition, and can research the influence of various factors on a desulphurization system while researching the activity of the limestone. Meanwhile, the limestone activity detection device for wet flue gas desulfurization has a simple structure, can be realized under laboratory conditions, can correctly evaluate the activity of limestone to a certain extent, and provides a basis for the optimal design of a wet flue gas desulfurization process.
Further, through setting up preceding gas mixing device, can be so that each composition misce bene in the simulation flue gas, the temperature that can also control the simulation flue gas simultaneously reaches the experimental requirement, and flue gas analyzer can accurately detect out the sulfur dioxide concentration in the simulation flue gas before still being favorable to in addition, and then improves the accuracy of testing result.
Furthermore, a flue gas spray hole or a flue gas nozzle connected with a flue gas inlet of the reaction tank is arranged in the reaction tank, and the simulated flue gas can fully blow the limestone slurry and react by utilizing the flue gas spray hole or the flue gas nozzle, so that the accuracy of a detection result is facilitated; the slurry nozzle is arranged at the outlet of the first slurry pipeline, so that supplemented limestone slurry can continuously react with sulfur dioxide in simulated flue gas after the limestone slurry reacts with the limestone slurry at the lower part of the reaction tank by using the slurry nozzle, and the accuracy of a detection result is improved.
Furthermore, the rear gas mixing device is arranged, so that the temperature of the simulated flue gas can be controlled to meet the detection requirement of the rear flue gas analyzer.
Furthermore, through setting up the gas washing device, can prevent experimental tail gas contaminated air.
Furthermore, by arranging the constant temperature water device, the temperature in the reaction tank can be stable, and the reaction at different temperatures can be simulated.
Drawings
Fig. 1 is a schematic diagram of a limestone activity detection device for wet flue gas desulfurization according to the present invention.
Wherein 1 is N22 is O as standard gas2Standard gas, 3 is CO2Standard gas, 4 is SO2Standard gas, 5 a flowmeter, 6 a front gas mixing device, 7 a stirrer, 8 a limestone slurry tank, 9 an electromagnetic control valve, 10 an automatic potentiometric titrator, 11 a reaction tank, 11-1 a flue gas outlet measuring hole, 12 a pH electrode, 13 a slurry circulating pump, 14 a front flue gas analyzer, 15 a constant temperature water device, 16 a rear flue gas analyzer, 17 a rear gas mixing device and 18 a gas washing bottle.
Detailed Description
The invention is further described below with reference to the figures and examples.
The limestone activity test method is to mix limestone slurry with SO2The flue gas is directly subjected to contact reaction in a bubbling mode, the working process of the actual desulfurization process can be fully simulated, and the SO at the inlet and the outlet of the reaction tank 11 is measured2Concentration, calculating SO2Evaluation of limestone Activity by removal Rate, SO2The higher the removal rate, the better the limestone activity, and conversely,SO2the lower the removal rate, the poorer the limestone activity.
Referring to fig. 1, the apparatus for detecting limestone activity in wet flue gas desulfurization of the present invention comprises a flue gas simulation system, a reaction tank 11, a limestone slurry tank 8, an electromagnetic control valve 9, an automatic potentiometric titrator 10, a slurry circulating pump 13, a front flue gas analyzer 14 and a rear flue gas analyzer 16; a flue gas inlet and a first slurry outlet are formed in the bottom of the reaction tank 11, and a flue gas outlet is formed in the upper part of the reaction tank 11; a flue gas outlet of the flue gas simulation system is connected with a flue gas inlet of the reaction tank 11 through a first flue gas pipeline, and the front flue gas analyzer 14 is connected into the first flue gas pipeline; the inlet of the slurry circulating pump 13 is connected with the first slurry outlet, and the outlet of the slurry circulating pump 13 is connected with the limestone slurry tank 8; a second slurry outlet is formed in the bottom of the limestone slurry tank 8 and connected with a first slurry pipeline, and an outlet of the first slurry pipeline is formed in the inner top of the reaction tank 11; the electromagnetic control valve 9 is arranged on the first slurry pipeline; the automatic potentiometric titrator 10 is connected with the electromagnetic control valve 9, and a probe of a pH electrode 12 of the automatic potentiometric titrator 10 is inserted into a reaction tank 11; the flue gas outlet of the reaction tank 11 is connected with a second flue gas pipeline, and the rear flue gas analyzer 16 is connected to the second flue gas pipeline.
As a preferred embodiment of the present invention, the flue gas simulation system comprises N2 Standard gas bottle 1, O2Standard gas bottle 2, SO2Standard gas bottle 3, CO2A sample bottle 4 and a flow meter 5, N2 Standard gas bottle 1, O2Standard gas bottle 2, SO2Target gas bottle 3 and CO2The outlet of the standard gas bottle 4 is communicated with the first flue gas pipeline, the flowmeter 5 is arranged on the first flue gas pipeline, and the front flue gas analyzer 14 is connected to the outlet side of the flowmeter 5.
As a preferred embodiment of the present invention, the flue gas simulation system further includes a front gas mixing device 6, the front gas mixing device 6 is disposed on the first flue gas pipeline and is located on the outlet side of the flow meter 5 and the inlet side of the front flue gas analyzer 14, and the front gas mixing device 6 has a flue gas temperature control function.
As a preferred embodiment of the present invention, a flue gas nozzle or a flue gas nozzle connected to a flue gas inlet of the reaction tank 11 is disposed inside the reaction tank 11, and the flue gas nozzle or the flue gas nozzle can blow flue gas on the whole cross section of the inner cavity of the reaction tank 11;
the first slurry outlet is arranged above the flue gas spray holes or the flue gas nozzles, the first slurry pipeline outlet is provided with the slurry nozzles, and the slurry nozzles can spray slurry on the whole section of the inner cavity of the reaction tank 11.
As a preferred embodiment of the present invention, an outlet of the slurry circulation pump 13 is connected to the top of the limestone slurry tank 8, and the limestone slurry tank 8 is provided therein with a stirrer 7 which never stirs the limestone slurry.
As a preferred embodiment of the present invention, a post gas mixing device 17 is further connected to the second flue gas pipeline, and the post gas mixing device 17 is located upstream of the post flue gas analyzer 16.
As a preferred embodiment of the present invention, the outlet of the second flue gas pipeline is connected with a gas washing device.
As a preferred embodiment of the invention, the limestone activity detection device by wet flue gas desulfurization further comprises a constant temperature water device 15, wherein the constant temperature water device 15 comprises a constant temperature water bath container, and the reaction tank 11 is inserted into the constant temperature water bath container.
The invention also provides a method for detecting the activity of the limestone in wet flue gas desulfurization, which is carried out by adopting the device for detecting the activity of the limestone in wet flue gas desulfurization, and comprises the following steps:
adding prepared limestone slurry into a reaction tank 11 and a limestone slurry tank 8, and immersing a probe of a pH electrode 12 into the limestone slurry in the reaction tank 11;
introducing simulated flue gas configured by a flue gas simulation system into the reaction tank 11 to react with limestone slurry in the reaction tank 11; starting a slurry circulating pump 13 to control the circulating flow of the slurry; starting the automatic potentiometric titrator 10, wherein the automatic potentiometric titrator 10 controls the electromagnetic control valve 9 through the pH value measured by the pH electrode 12, adjusts the slurry supplementing amount of limestone slurry, and maintains the pH value of the limestone slurry in the reaction tank 11 to be a preset value;
SO in the first flue gas duct and the second flue gas duct is measured by a front flue gas analyzer 14 and a rear flue gas analyzer 16, respectively2Concentration, through front flue gas analyzer14 and measured by post flue gas analyzer 162And calculating the desulfurization efficiency according to the concentration, and evaluating the activity of the limestone in the wet flue gas desulfurization according to the desulfurization efficiency. Wherein, in the prepared limestone slurry: the solid content is 3-5%, and the particle size of limestone powder adopted in preparation is 250 +/-20 meshes; the concentration of sulfur dioxide in the simulated flue gas is 5000-6000 mg/m3The volume concentration of oxygen is 5-8%, and the volume concentration of carbon dioxide is 8-13%; the reaction temperature of the reaction tank 11 is maintained at 47-55 ℃; the pH value of limestone slurry in the reaction tank 11 is maintained at 5.2-5.8.
The invention can truly reflect the activity of limestone under the actual condition, and the analysis of the activity of the limestone by adopting the invention is not only beneficial to selecting proper absorbent in the WFGD system design stage, but also can determine the optimal operation parameter in the operation stage, thereby reducing the operation cost of wet desulphurization.
Examples
As shown in fig. 1, the apparatus for detecting limestone activity in wet flue gas desulfurization of the present embodiment includes a flue gas simulation system, a limestone slurry circulation system, a reaction tank, and a flue gas component detection apparatus, where the flue gas simulation system includes N2Standard gas bottle 1, O2Standard gas bottle 2, SO2Standard gas bottle 3, CO2A standard gas bottle 4, a flow meter 5 and a front gas mixing device 6, N2Standard gas bottle 1, O2Standard gas bottle 2, SO2Standard gas bottle 3, CO2The standard gas bottle 4 is connected with the inlet of the front gas mixing device 6 after being connected in parallel, and the front gas mixing device 6 can mix N2、O2、SO2、CO2Uniformly mixing, wherein the gas after uniform mixing reaches certain SO2Concentration (C)SO2-in＝5500mg/m3) And then, the mixed gas enters the reaction tank 11 from the bottom of the reaction tank 11, the upper side surface and the lower side surface of the reaction tank 11 are both provided with holes, the mixed gas is uniformly blown out from the cross section of the reaction tank 11 after entering the reaction tank 11, and a front flue gas analyzer 14 is connected between a side hole of a flue gas inlet at the lower part of the reaction tank 11 and the front gas mixing device 6. Inverse directionThe smoke outlet measuring hole 11-1 at the upper part of the reaction tank 11 is connected with a rear gas mixing device 17, the outlet of the rear gas mixing device 17 is connected with a gas washing bottle 18, and a rear smoke analyzer 16 is connected between the rear gas mixing device 17 and the gas washing bottle 18.
The slurry outlet at the lower part of the reaction tank 11 is connected with a slurry circulating pump 13, the outlet of the slurry circulating pump 13 is communicated with the top of a limestone slurry tank 8, a stirrer 7 is installed at the top of the limestone slurry tank 8, a stirring impeller of the stirrer 7 is immersed in limestone slurry, an electromagnetic control valve 9 is installed at the limestone slurry outlet at the bottom of the limestone slurry tank 8, the opening and closing of the electromagnetic valve 9 are controlled by an automatic point-position titrator 10, the limestone slurry in the limestone slurry tank enters the reaction tank 11 through a first slurry pipeline, a slurry nozzle is arranged at the outlet of the first slurry pipeline, so that the limestone slurry is uniformly sprayed on the cross section of the whole reaction tank 11, a pH electrode 12 of the automatic potential titrator 10 is inserted into the reaction tank 11 from the top of the reaction tank 11, and a pH electrode 12 probe is immersed in the limestone slurry in the reaction tank 11.
The reaction tank 11 is inserted into a thermostatic waterbath container, the bottom of which is provided with a water inlet and a water outlet, and a connecting pipe of the water inlet and the water outlet is connected to a thermostatic water device 15.
The front gas mixing device 6 has a flue gas temperature control function.
The limestone slurry used for the test had a solids content of 5% with a solids composition of 90% CaSO4And 10% CaSO3。
The concentration of sulfur dioxide of the simulated flue gas is 5500mg/m3The volume concentration of oxygen was 6% and the volume concentration of carbon dioxide was 11%.
The process for detecting the activity of the limestone by using the limestone activity detection device for wet desulphurization of the embodiment comprises the following steps:
(1) preparing limestone slurry: limestone powder is required to have a particle size fluctuation range within 20 meshes, 250-mesh limestone particles are screened from the limestone powder, and the limestone powder is mixed with water to prepare limestone slurry with the solid content of 5%;
(2) configuring simulated smoke: by adjusting N2 Standard gas bottle 1, O2Standard gas bottle 2, SO2Standard gas bottle 3, CO2Standard gas bottleThe pressure reducing valve on 4 ensures the concentration C of sulfur dioxide of the simulated flue gas according to the test data of the front flue gas analyzer 15SO2-inIs 5500mg/m3The volume concentration of oxygen was 6% and the volume concentration of carbon dioxide was 11%.
(3) Adding the prepared limestone slurry into a reaction tank 11 and a limestone slurry tank 9, and starting a constant temperature water device 16 to keep the constant temperature water bath temperature at 50 ℃;
(4) starting a slurry circulating pump 14, controlling the circulating flow of slurry, starting an automatic potentiometric titrator 11, adjusting the slurry supplementing amount of limestone slurry by controlling an electromagnetic control valve 10, maintaining the pH value of the limestone slurry in the reaction tank to be 5.5, starting a flue gas analyzer 17 after starting, and recording SO2Concentration CSO2-out. The activity of limestone is evaluated by calculating the desulfurization efficiency η:
the limestone activity detection method can simulate the actual wet desulphurization process, can accurately measure the limestone activity, and can provide a powerful basis for the design of wet desulphurization.
Containing SO2The whole reaction process of the flue gas and the limestone solution is as follows:
dissolution rate of limestone with reaction temperature, p-value and unreacted CaCO3Concentration-related, limestone ablation reactions are controlled by fluid diffusion and surface chemistry at a given pH and temperature, and the reaction rate per unit surface of particles per unit time can be expressed as:
wherein: q. q.smIs a unit surface of a particleThe amount of reactant consumed, mol. s-1·m-2；C1Is the concentration of the reactant in the liquid phase, mol. m-3；k1Is the liquid phase mass transfer coefficient, m.s-1；krIs a chemical reaction rate constant, m.s-1。
The limestone particle dissolution rate (per surface) is:
where ρ ismAs CaCO in solids3Molar concentration of (1), mol. m-3(ii) a r is the radius of the solid particles, m; t is the reaction time, s.
From the above two equations, it can be derived:
can make
Scale kmAs overall reaction constant, then:
wherein r is0Is the initial radius of the solid particles, m;
reissue to order
K can be called the overall chemical reaction coefficient and contains all factors that influence the dissolution of solid particles. The dissolution of a single solid particle can be expressed as:
wherein D is0Is the initial diameter of the solid particles, m.
The particle size of limestone selected by the invention is about 250 meshes, the particle size fluctuation range of limestone powder is within 20 meshes, so the limestone dissolution model can be selected to evaluate the activity of the limestone, the limestone dissolution rate of the model is determined by a comprehensive reaction coefficient k and initial particle size distribution, and k is related to reaction conditions and limestone particle characteristics. In the actual reaction, kmRelated to the diffusion capacity of the reactants and the chemical reaction. Comprehensive reaction coefficient k and integral reaction constant k in the modelmAll can be estimated by the wet desulphurization limestone activity testing device.
The model can obtain limestone dissolution amounts at different times under certain pH and slurry circulation amount through an x-t curve obtained by a limestone reaction activity test system, can evaluate limestone activity, and indicates that the more limestone particles are dissolved in the same time, the higher the limestone activity is, and conversely, the less the limestone particles are dissolved in the same time, the worse the limestone activity is.
After the scheme is adopted, the limestone detection method is simple in structure, can overcome the defects of the existing manual titration, can be realized under laboratory conditions, can correctly evaluate the activity of limestone to a certain extent, and provides a basis for the optimal design of a wet desulphurization process; the reaction conditions and working conditions of the invention are quite close to those of the actual wet desulphurization process, and the activity of limestone under the actual condition can be truly reflected; by adopting the method to analyze the limestone activity, the method is not only beneficial to selecting a proper absorbent in the WFGD system design stage, but also can determine the optimal operation parameters in the operation stage, thereby reducing the operation cost of wet desulphurization; the invention can simulate the activity of the limestone under the actual wet desulphurization working condition, and can research the influence of various factors on a desulphurization system while researching the activity of the limestone.
Claims (10)
1. A limestone activity detection device for wet flue gas desulfurization is characterized by comprising a flue gas simulation system, a reaction tank (11), a limestone slurry tank (8), an electromagnetic control valve (9), an automatic potentiometric titrator (10), a slurry circulating pump (13), a front flue gas analyzer (14) and a rear flue gas analyzer (16);
a flue gas inlet and a first slurry outlet are formed in the bottom of the reaction tank (11), and a flue gas outlet is formed in the upper part of the reaction tank (11);
a flue gas outlet of the flue gas simulation system is connected with a flue gas inlet of the reaction tank (11) through a first flue gas pipeline, and a front flue gas analyzer (14) is connected to the first flue gas pipeline;
an inlet of the slurry circulating pump (13) is connected with the first slurry outlet, and an outlet of the slurry circulating pump (13) is connected with the limestone slurry tank (8);
a second slurry outlet is formed in the bottom of the limestone slurry tank (8), the second slurry outlet is connected with a first slurry pipeline, and an outlet of the first slurry pipeline is arranged at the inner top of the reaction tank (11);
the electromagnetic control valve (9) is arranged on the first slurry pipeline;
the automatic potentiometric titrator (10) is connected with the electromagnetic control valve (9), and a probe of a pH electrode (12) of the automatic potentiometric titrator (10) is inserted into the reaction tank (11);
the flue gas outlet of the reaction tank (11) is connected with a second flue gas pipeline, and the rear flue gas analyzer (16) is connected to the second flue gas pipeline.
2. The apparatus for detecting limestone activity in wet flue gas desulfurization according to claim 1, wherein the flue gas simulation system comprises N2Standard gas bottle (1), O2Standard gas bottle (2), SO2A standard gas bottle (3), CO2A standard gas bottle (4) and a flow meter (5), N2Standard gas bottle (1), O2Standard gas bottle (2), SO2A standard gas bottle (3) and CO2The outlet of the standard gas bottle (4) is communicated with the first flue gas pipeline, the flowmeter (5) is arranged on the first flue gas pipeline, and the front flue gas analyzer (14) is connected to the outlet side of the flowmeter (5).
3. The apparatus for detecting activity of limestone through wet flue gas desulfurization according to claim 2, wherein the flue gas simulation system further comprises a front gas mixing device (6), the front gas mixing device (6) is disposed on the first flue gas pipeline and is located at an outlet side of the flowmeter (5) and an inlet side of the front flue gas analyzer (14), and the front gas mixing device (6) has a flue gas temperature control function.
4. The apparatus for detecting the activity of limestone through wet flue gas desulfurization according to claim 1, wherein the reaction tank (11) is internally provided with flue gas spray holes or flue gas nozzles connected with the flue gas inlet of the reaction tank (11), and the flue gas spray holes or the flue gas nozzles can blow flue gas on the whole section of the inner cavity of the reaction tank (11);
the first slurry outlet is arranged above the flue gas spray holes or the flue gas nozzles, the first slurry pipeline outlet is provided with the slurry nozzles, and the slurry nozzles can spray slurry on the whole section of the inner cavity of the reaction tank (11).
5. The apparatus for detecting the activity of limestone in wet flue gas desulfurization according to claim 1, wherein the outlet of the slurry circulating pump (13) is connected with the top of the limestone slurry tank (8), and the limestone slurry tank (8) is internally provided with a stirrer (7) which never stirs limestone slurry.
6. The apparatus for detecting activity of limestone through wet flue gas desulfurization according to claim 1, wherein a post gas mixing device (17) is further connected to the second flue gas pipeline, and the post gas mixing device (17) is located upstream of the post flue gas analyzer (16).
7. The apparatus for detecting the activity of limestone through wet flue gas desulfurization according to claim 1 or 6, wherein an outlet of the second flue gas pipeline is connected with a scrubber.
8. The apparatus for detecting the activity of limestone in wet flue gas desulfurization according to claim 1, further comprising a thermostatic water device (15), wherein the thermostatic water device (15) comprises a thermostatic water bath container, and the reaction tank (11) is inserted into the thermostatic water bath container.
9. A method for detecting the activity of limestone in wet flue gas desulfurization, which is characterized by being carried out by adopting the device for detecting the activity of limestone in wet flue gas desulfurization according to any one of claims 1 to 8, and comprising the following steps of:
adding prepared limestone slurry into a reaction tank (11) and a limestone slurry tank (8), and immersing a probe of a pH electrode (12) into the limestone slurry in the reaction tank (11);
introducing simulated flue gas configured by a flue gas simulation system into a reaction tank (11) to react with limestone slurry in the reaction tank (11); starting a slurry circulating pump (13) to control the circulating flow of the slurry; starting the automatic potentiometric titrator (10), wherein the automatic potentiometric titrator (10) controls the electromagnetic control valve (9) through the pH value measured by the pH electrode (12), adjusts the slurry supplementing amount of limestone slurry, and maintains the pH value of the limestone slurry in the reaction tank (11) to be a preset value;
SO in the first flue gas pipeline and SO in the second flue gas pipeline are respectively measured by a front flue gas analyzer (14) and a rear flue gas analyzer (16)2Concentration, SO measured by a front flue gas analyzer (14) and a rear flue gas analyzer (16)2And calculating the desulfurization efficiency according to the concentration, and evaluating the activity of the limestone in the wet flue gas desulfurization according to the desulfurization efficiency.
10. The method for detecting the activity of the limestone in the wet flue gas desulfurization process according to claim 9, wherein the method comprises the following steps:
in the prepared limestone slurry: the solid content is 3-5%, and the particle size of limestone powder adopted in preparation is 250 +/-20 meshes;
the concentration of sulfur dioxide in the simulated flue gas is 5000-6000 mg/m3The volume concentration of oxygen is 5-8%, and the volume concentration of carbon dioxide is 8-13%;
the reaction temperature of the reaction tank (11) is maintained at 47-55 DEG C
The pH value of limestone slurry in the reaction tank (11) is maintained at 5.2-5.8.
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| CN115708993A (en) * | 2022-11-21 | 2023-02-24 | 西安热工研究院有限公司 | Semi-continuous gas-solid-liquid three-phase reaction device and using method thereof |
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| CN215415268U (en) * | 2021-07-19 | 2022-01-04 | 西安热工研究院有限公司 | Active detection device of wet flue gas desulfurization lime stone |
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| CN1869685A (en) * | 2006-05-18 | 2006-11-29 | 重庆大学 | Investigating method for lime activity and its analysing system |
| CN215415268U (en) * | 2021-07-19 | 2022-01-04 | 西安热工研究院有限公司 | Active detection device of wet flue gas desulfurization lime stone |
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| CN115708993A (en) * | 2022-11-21 | 2023-02-24 | 西安热工研究院有限公司 | Semi-continuous gas-solid-liquid three-phase reaction device and using method thereof |
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