CN115646181A - Limestone-gypsum wet flue gas desulfurization composite synergist and desulfurization method thereof - Google Patents
Limestone-gypsum wet flue gas desulfurization composite synergist and desulfurization method thereof Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 131
- 230000023556 desulfurization Effects 0.000 title claims abstract description 131
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003546 flue gas Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000010440 gypsum Substances 0.000 title claims abstract description 64
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 20
- 150000007524 organic acids Chemical class 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 239000012190 activator Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000010953 base metal Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 50
- 235000019738 Limestone Nutrition 0.000 claims description 39
- 239000006028 limestone Substances 0.000 claims description 39
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 24
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 24
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 22
- 239000000700 radioactive tracer Substances 0.000 claims description 22
- 239000011268 mixed slurry Substances 0.000 claims description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 13
- 239000005711 Benzoic acid Substances 0.000 claims description 12
- 235000010233 benzoic acid Nutrition 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 229940074404 sodium succinate Drugs 0.000 claims description 10
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 10
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 9
- 235000010234 sodium benzoate Nutrition 0.000 claims description 9
- 239000004299 sodium benzoate Substances 0.000 claims description 9
- 239000004280 Sodium formate Substances 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- -1 organic acid alkali metal salt Chemical class 0.000 claims description 8
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 8
- 235000019254 sodium formate Nutrition 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 30
- 239000011593 sulfur Substances 0.000 abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 abstract description 30
- 239000003245 coal Substances 0.000 abstract description 18
- 230000009466 transformation Effects 0.000 abstract description 12
- 230000005611 electricity Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 description 32
- 239000000203 mixture Substances 0.000 description 16
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- 230000003044 adaptive effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
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- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
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- 239000011575 calcium Substances 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 238000005299 abrasion Methods 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
The invention belongs to the technical field of flue gas desulfurization of thermal power plants, and particularly relates to a limestone-gypsum wet flue gas desulfurization composite synergist and a desulfurization method thereof. The composite synergist provided by the invention comprises the following components in parts by mass: 30-80 parts of organic acid synergist, 15-55 parts of organic acid-base metal salt synergist, 5-35 parts of solid-liquid interface activator and 1-20 parts of oxidation catalyst. The composite synergist provided by the invention can adapt to the working condition of flue gas desulfurization generated by coal types with the sulfur content of 20-30% higher than the designed sulfur content on the premise of not performing capacity-increasing transformation on the original desulfurization equipment, obviously improves the adaptability of the conventional desulfurization device to the sulfur content of the coal types, and meets the requirements of desulfurization efficiency and clean flue gas SO 2 Emission concentration requirements; simultaneously can reduce the power consumption of the desulphurization plant by 0.15 to 0.25 percent and save electricity per hourThe electricity is about 1000-1800 kW, the operation cost of desulfurization is reduced, and the operation rate and the availability of the desulfurization device are improved.
Description
Technical Field
The invention belongs to the technical field of flue gas desulfurization of thermal power plants, and particularly relates to a limestone-gypsum wet flue gas desulfurization composite synergist and a desulfurization method thereof.
Background
The limestone-gypsum wet flue gas desulfurization process is widely adopted due to the characteristics of mature technology, high desulfurization efficiency, rich absorbent source, low price, available byproducts and the like, and becomes the most widely applied method for flue gas desulfurization of coal-fired power plants at present. The limestone-gypsum wet flue gas desulfurization process principle is as follows: limestone powder is prepared into slurry which is used as a desulfurization absorbent and is contacted and mixed with flue gas entering an absorption tower after being cooled, and sulfur dioxide in the flue gas, calcium carbonate in the slurry and added air are subjected to chemical reaction to generate dihydrate gypsum.
However, the problems of high energy consumption and operation cost, poor adaptability to coal sulfur and the like generally exist in the operation of limestone-gypsum wet flue gas desulfurization devices of thermal power plants in China at present. Along with the shortage and instability of coal resources, a plurality of power plants burn fire coal which exceeds the designed sulfur for a long time, so that a desulfurization system cannot normally operate, and along with the implementation of more and more strict environmental emission standards, a plurality of desulfurization devices (absorption towers) are forced to perform capacity-increasing transformation work.
But the capacity-increasing transformation of the desulfurization device consumes tens of millions of capital frequently, the construction period of transformation after desulfurization stop is generally 3-4 months, and unprecedented economic and environmental protection pressure is brought to a power plant.
Disclosure of Invention
The invention aims to provide a limestone-gypsum wet flue gas desulfurization composite synergist and a desulfurization method thereof, the composite synergist provided by the invention can adapt to the working condition of flue gas desulfurization generated by coal which exceeds the designed sulfur (the maximum adaptive amount of the sulfur designed when a desulfurization absorption tower of a desulfurization device is built) by 20-30 wt% on the premise of not carrying out capacity-increasing transformation on the original desulfurization equipment (absorption tower), obviously improve the adaptive capacity of the conventional desulfurization device to the sulfur of the coal, and meet the requirements of desulfurization efficiency and clean flue gas SO 2 Emission concentration requirements.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a limestone-gypsum wet flue gas desulfurization composite synergist which comprises the following components in parts by mass:
30-80 parts of organic acid synergist, 15-55 parts of organic acid-base metal salt synergist, 5-35 parts of solid-liquid interface activator and 1-20 parts of oxidation catalyst.
Preferably, the kit also comprises 1-10 parts of a tracer.
Preferably, the organic acid synergist comprises one or more of benzoic acid, succinic acid, adipic acid and citric acid.
Preferably, the organic acid alkali metal salt synergist comprises one or more of sodium succinate, sodium formate and sodium benzoate.
Preferably, the solid-liquid interface activator comprises formamide and/or polyethylene glycol.
Preferably, the oxidation catalyst comprises one or more of iron trichloride, manganese sulfate and vanadium pentoxide.
Preferably, the tracer comprises sodium bromide and/or potassium bromide.
The invention provides a limestone-gypsum wet flue gas desulfurization method, which comprises the following steps:
mixing the composite synergist and limestone slurry to obtain mixed slurry;
and (3) contacting and mixing the mixed slurry with flue gas, and performing wet reaction desulfurization in the atmosphere of air.
Preferably, the mass percentage content of the composite synergist in the mixed slurry is 500-1000 ppm.
Preferably, the limestone slurry has a pH of 5.2 to 5.8 and a density of 1100 to 1160kg/m 3 。
The invention provides a limestone-gypsum wet flue gas desulfurization composite synergist which comprises the following components in parts by mass: 30-80 parts of organic acid synergist, 15-55 parts of organic acid-base metal salt synergist, 5-35 parts of solid-liquid interface activator and 1-20 parts of oxidation catalyst. In the invention, the organic acid synergist and the organic acid alkali metal salt synergist provide a buffer pair in the limestone slurry, accelerate the mass transfer process between the flue gas film and the limestone slurry liquid film and improve the wet reaction speed; the solid-liquid interface activator can improve the wettability of the solid-liquid interface, reduce the resistance of a liquid film between a solid phase and a liquid phase and improve the mass transfer efficiency of the solid-liquid interface; in the range of the mass parts, the organic acid synergist, the organic acid alkali metal salt synergist, the solid-liquid interface activator and the oxidation catalyst are compounded in a synergistic way, so that the limestone can be preparedThe half dissolving time is shortened by more than 40 percent, and the dissolving speed of the limestone is greatly accelerated, thereby greatly improving the reaction activity of the limestone and sulfur dioxide and leading the excess CaCO in the gypsum 3 The utilization rate of limestone is greatly reduced; the composite synergist provided by the invention can reduce the circulating strength of limestone slurry by one third to one half under the working condition of sulfur design, so that part of pumps can be stopped to operate (for example, 4 pumps can be stopped and one pump can be operated by 3 pumps); the liquid-gas ratio of the desulfurization system is reduced, the resistance of the desulfurization system is reduced, and the energy consumption of the desulfurization system is obviously reduced; at the same time, the invention reduces the excessive CaCO in the gypsum 3 And the scaling and blocking effects on the subsequent equipment are reduced to a certain extent. In conclusion, the composite synergist provided by the invention improves the processing capacity of limestone slurry on sulfur dioxide in flue gas by improving the reaction activity of limestone, oxygen and sulfur dioxide on the premise of not performing capacity increase transformation on the original desulfurization equipment (absorption tower), thereby realizing that: the pump is stopped to save energy, the operation is carried out or the coal quality condition which exceeds the design capability within a certain range can be processed (for example, the working condition of flue gas desulfurization generated by coal types with the sulfur content exceeding 20 to 30 percent of the design sulfur content can be adapted), the adaptability of the existing desulfurization device to the sulfur content of the coal types is obviously improved, and the desulfurization efficiency and the clean flue gas SO are met 2 Emission concentration requirements; meanwhile, the power consumption of the desulfurization plant can be reduced by 0.15-0.25%, electricity can be saved by 1000-1800 kW per hour, the operation cost of desulfurization is greatly reduced, and the commissioning rate and the availability of a desulfurization device are obviously improved.
Further, the invention also comprises 1-10 parts of tracer. In the present invention, the tracer is used for tracking and monitoring the concentration of the desulfurization synergist in the limestone slurry of the absorption tower. In the present invention, if the following four situations occur in the operation of the desulfurization system: (1) When the desulfurization synergist is not continuously supplemented every day according to the amount as required after the background concentration of the desulfurization synergist is established; (2) When the slurry throwing condition occurs and the slurry throwing amount cannot be determined; (3) discharging a large amount of desulfurization wastewater; (4) when filtrate water of the desulfurization system is public and cannot be distinguished; when the four situations occur in the operation of the desulfurization system, the concentration of the synergist in the slurry of the absorption tower needs to be analyzed and tested by adopting an analysis method of the tracer in the desulfurization synergist, and the amount of the desulfurization synergist to be supplemented is calculated according to test data. According to the invention, a quantitative tracer is added into the desulfurization composite synergist, the concentration of the desulfurization synergist in the slurry of the absorption tower can be converted by analyzing the concentration of the tracer, and the daily supplement amount of the desulfurization synergist is calculated according to the test concentration.
The invention provides a limestone-gypsum wet flue gas desulfurization method, which comprises the following steps: mixing the composite synergist and limestone slurry to obtain mixed slurry; and (3) contacting and mixing the mixed slurry with flue gas, and performing wet reaction desulfurization in an air oxidation atmosphere. On the reaction mechanism of a limestone-gypsum wet desulphurization method, the composite synergist of the technical scheme is utilized to accelerate limestone dissolution, obviously improve limestone activity, improve desulphurization reaction speed so as to shorten the contact time of flue gas and slurry reaching the designed desulphurization efficiency, improve the utilization efficiency of air, improve the quality of desulfurized gypsum and reduce the Ca/S ratio of a system so as to improve the utilization efficiency of limestone, prevent equipment from scaling and blocking, reduce abrasion and buffer the fluctuation of the pH value of slurry, so that the limestone-gypsum wet desulphurization method can adapt to coal types with the sulfur content about 20-30% higher than the designed sulfur content, reduce the energy loss of the system and bring good economic and social benefits to a power plant.
Detailed Description
The invention provides a limestone-gypsum wet flue gas desulfurization composite synergist which comprises the following components in parts by mass:
30-80 parts of organic acid synergist, 15-55 parts of organic acid-base metal salt synergist, 5-35 parts of solid-liquid interface activator and 1-20 parts of oxidation catalyst.
In the present invention, all the preparation starting materials/components are commercially available products well known to those skilled in the art, unless otherwise specified.
The limestone-gypsum wet flue gas desulfurization composite synergist comprises, by mass, 30-80 parts of an organic acid synergist, preferably 40-50 parts.
In the present invention, the organic acid synergist comprises one or more of benzoic acid, succinic acid, adipic acid and citric acid. In the invention, when the organic acid synergist comprises two of benzoic acid, succinic acid, adipic acid and citric acid, the organic acid synergist is specifically a mixture of benzoic acid and adipic acid or a mixture of succinic acid and citric acid. In the present invention, the mass ratio of benzoic acid to adipic acid in the mixture of benzoic acid and adipic acid is preferably 4:1. the invention has no special requirement on the mass ratio of the succinic acid to the citric acid in the mixture of the succinic acid and the citric acid.
Based on the mass parts of the organic acid synergist, the limestone-gypsum wet flue gas desulfurization composite synergist provided by the invention comprises 15-55 parts of organic acid-base metal salt synergist, preferably 25-35 parts.
In the present invention, the organic acid alkali metal salt synergist preferably comprises one or more of sodium succinate, sodium formate and sodium benzoate. In the present invention, when the organic acid alkali metal salt includes two of sodium succinate, sodium formate and sodium benzoate, it is specifically a mixture of sodium formate and sodium benzoate or a mixture of sodium succinate and sodium benzoate. In the present invention, when the organic acid alkali metal salt synergist is preferably the two above substances, the present invention has no special requirement on the mass ratio of any two organic acid alkali metal salt synergists.
Based on the mass portion of the organic acid synergist, the limestone-gypsum wet flue gas desulfurization composite synergist provided by the invention comprises 5-35 parts of a solid-liquid interface activator, preferably 15-20 parts.
In the present invention, the solid-liquid interface activator includes formamide and/or polyethylene glycol. In the present invention, when the solid-liquid interface activator is preferably the above two substances, the present invention does not require a specific mass ratio of any two solid-liquid interface activators.
Based on the mass portion of the organic acid synergist, the limestone-gypsum wet flue gas desulfurization composite synergist provided by the invention comprises 1-20 parts of oxidation catalyst, preferably 5-10 parts.
In the present invention, the oxidation catalyst comprises one or more of iron trichloride, manganese sulfate and vanadium pentoxide. In the present invention, the oxidation catalyst preferably includes two of ferric trichloride, manganese sulfate and vanadium pentoxide, specifically, a mixture of ferric trichloride and manganese sulfate. In the present invention, when the oxidation catalyst is preferably the above two substances, the present invention does not particularly require the mass ratio of any two oxidation catalysts.
Based on the mass portion of the organic acid synergist, the limestone-gypsum wet flue gas desulfurization composite synergist also comprises 1-10 parts of a tracer, preferably 1 part.
The concentration of the tracer agent is preferably measured and can be converted into the concentration of the desulfurization composite synergist, so that the use condition of the desulfurization composite synergist can be conveniently obtained.
In the present invention, the tracer comprises sodium bromide and/or potassium bromide. In the present invention, when the tracers are preferably the above two substances, the present invention has no particular requirement on the mass ratio of the above two tracers.
The preparation method of the limestone-gypsum wet flue gas desulfurization composite synergist has no special requirements, and the components are uniformly mixed.
The invention provides a limestone-gypsum wet flue gas desulfurization method, which comprises the following steps:
mixing the composite synergist and limestone slurry to obtain mixed slurry;
and (3) contacting and mixing the mixed slurry with flue gas, and performing wet reaction desulfurization in the atmosphere of air.
The composite synergist in the technical scheme is mixed with limestone slurry to obtain mixed slurry.
In the invention, the pH value of the limestone slurry is 5.2-5.8, and the density of the limestone slurry is 1100-1160 kg/m 3 。
In the invention, the mass percentage content of the composite synergist in the mixed slurry is preferably 500-1000 ppm.
In the invention, when the composite synergist is firstly mixed with limestone slurry, the mass percentage content of the composite synergist in the obtained firstly mixed slurry is preferably 500-1000 ppm.
In the invention, in the subsequent operation process of the limestone-gypsum wet flue gas desulfurization, when the composite synergist is mixed with the limestone slurry again, the mass percentage content of the composite synergist in the obtained mixed slurry during operation is preferably 600-800 ppm.
In the invention, when the composite synergist is firstly mixed with the limestone slurry, the composite synergist is preferably directly pumped into the absorption tower from a pit of the absorption tower through a pit pump to be firstly mixed with the limestone slurry.
In the invention, in the subsequent operation process of the limestone-gypsum wet flue gas desulfurization, the composite synergist is preferably directly added into the limestone slurry tank to be mixed with the limestone slurry again.
In the invention, when the slurry is mixed again, the mass percentage of the composite synergist in the obtained mixed slurry during operation is preferably supplemented according to a material balance, wherein the material balance comprises the steps of gypsum carrying water, desulfurization wastewater discharge, flue gas carrying water loss and the attenuation condition of an absorption tower.
After the mixed slurry is obtained, the mixed slurry is contacted and mixed with the flue gas, and wet reaction desulfurization is carried out in the atmosphere of air.
In the invention, when the flue gas is generated by coal types with 20-30% of over designed sulfur, in order to keep the pH value of the limestone slurry in the absorption tower at 5.2-5.8, the density of the limestone slurry is 1100-1160 kg/m 3 The present invention preferably modifies the slurry supply and gypsum discharge system of the absorption tower to meet the requirements of the pH value of the limestone slurry and the slurry density of the absorption tower within the above ranges to maintain the desulfurization reaction in the absorption tower in normal operation. The invention preferably modifies the feeding pump and the slurry discharging system according to the material balance calculation in the limestone-gypsum wet flue gas desulfurization process.
In the invention, because the composite synergist has a certain amount of loss due to the links of water carrying outside gypsum, desulfurization wastewater, flue gas carrying and the like, the composite synergist is preferably supplemented with a certain amount of composite synergist periodically according to the operation condition of a desulfurization device (absorption tower) (the emission condition of sulfur content in desulfurization wastewater). In the invention, the composite synergist is preferably supplemented by 50-200 kg per day for the emission of sulfur content in the desulfurization wastewater.
When the limestone-gypsum wet flue gas desulfurization composite synergist provided by the invention is preferably applied to a desulfurization device with the sulfur content of the fire coal within the designed sulfur content, the desulfurization composite synergist provided by the invention can reduce the circulating strength of limestone slurry by one third to one half, reduce the liquid-gas ratio of a desulfurization system, and reduce the resistance of an absorption tower part, thereby obviously reducing the energy consumption of the desulfurization system, improving the utilization efficiency of the limestone, improving the quality of the desulfurization gypsum, reducing the Ca/S ratio of the system, and reducing the scaling and blockage of slurry liquid drops of the absorption tower brought out by the flue gas on a later-stage device.
When the limestone-gypsum wet flue gas desulfurization composite synergist provided by the invention is preferably applied to a desulfurization device with the coal sulfur content exceeding about 20-30% of the designed sulfur content, the utilization efficiency of air can be improved by using the desulfurization composite synergist provided by the invention SO as to meet the normal operation of a desulfurization system, the air utilization rate can be improved by about 50-60%, the oxidation effect of the coal sulfur content exceeding 20-30% of the designed value can be met on the basis of no transformation of the original oxidation system, and the desulfurization efficiency and SO required by environmental protection are achieved 2 The discharge concentration of (d); however, the premise for achieving the expected effect is that the pH value of the slurry of the absorption tower and the density of the slurry of the absorption tower must be controlled within a normal operation range, under the working condition that the designed sulfur content is about 20-30%, the normal operation level of the slurry of the absorption tower cannot be ensured by the original slurry supply and dehydration system of the desulfurization device, necessary capacity increasing transformation needs to be carried out on a slurry supply and gypsum discharge system, the transformation work change engineering amount and the transformation cost of the part are small, the transformation work can be carried out under the condition that the normal operation of the desulfurization device is not influenced, and the operability is very strong.
In the invention, the designed sulfur content of the absorption tower is the maximum adaptive amount of the sulfur content designed when the desulfurization absorption tower of the desulfurization device is built.
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the invention obviously improves the adaptability of the existing desulfurization device to the sulfur content of coal. The power consumption of the desulphurization plant can be reduced by 0.15-0.25%, electricity can be saved by about 1000-1800 kW per hour, the running cost of desulphurization is greatly reduced, and the commissioning rate and the availability of the desulphurization device are obviously improved.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 40% of organic acid synergist benzoic acid, 35% of organic salt synergist sodium succinate, 15% of efficient activator formamide, 9% of oxidation catalyst ferric trichloride, and 1% of tracer sodium bromide.
Example 2
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 50% of organic acid synergist succinic acid, 25% of organic salt synergist sodium formate, 17% of efficient activator polyethylene glycol, 7% of oxidation catalyst manganese sulfate and 1% of tracer potassium bromide.
Example 3
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 41% of organic acid synergist, namely, phthalic acid, 28% of organic salt synergist, namely, sodium benzoate, 20% of a mixture of efficient activator, namely, formamide and polyethylene glycol, 10% of oxidation catalyst, namely, vanadium pentoxide, and 1% of a mixture of tracer, namely, sodium bromide and potassium bromide.
Example 4
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 46% of a mixture of organic acid synergists benzoic acid and adipic acid, 30% of a mixture of organic salt synergists sodium succinate and sodium formate, 18% of a high-efficiency activator formamide, 5% of a mixture of oxidation catalysts ferric trichloride and manganese sulfate, and 1% of a tracer sodium bromide.
Example 5
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 43% of a mixture of organic acid synergists, namely succinic acid and citric acid, 32% of a mixture of organic salt synergists, namely sodium formate and sodium benzoate, 16% of a mixture of efficient activators, namely formamide and polyethylene glycol, and 8% of oxidation catalyst, namely vanadium pentoxide, and 1% of a mixture of tracer, namely sodium bromide and potassium bromide.
Example 6
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 48% of an organic acid synergist citric acid, 26% of an organic salt synergist sodium benzoate, 19% of a high-efficiency activator formamide, 6% of an oxidation catalyst ferric trichloride and 1% of a tracer sodium bromide.
Comparative example 1
The limestone-gypsum wet flue gas desulfurization composite synergist comprises 61.53% of organic acid synergist benzoic acid, 23.08% of high-efficiency activator formamide, 13.85% of oxidation catalyst ferric trichloride and 1.54% of tracer sodium bromide in percentage by mass.
Comparative example 2
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 58.33% of an organic salt synergist sodium succinate, 25% of a high-efficiency activator formamide, 15% of an oxidation catalyst ferric trichloride, and 1.67% of a tracer sodium bromide.
Comparative example 3
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 47.06% of organic acid synergist benzoic acid, 41.18% of organic salt synergist sodium succinate, 10.59% of oxidation catalyst ferric trichloride and 1.17% of tracer sodium bromide.
Comparative example 4
The limestone-gypsum wet flue gas desulfurization composite synergist provided by the embodiment comprises, by mass, 43.96% of organic acid synergist benzoic acid, 38.46% of organic salt synergist sodium succinate, 16.48% of efficient activator formamide and 1.1% of tracer sodium bromide.
Application example 1
Controlling the pH value of limestone slurry in the absorption tower to be between 5.2 and 5.8, and controlling the density of the limestone slurry to be between 1100 and 1160kg/m 3 Then, dissolving the limestone-gypsum wet flue gas desulfurization composite synergist provided in the embodiment 1 in water to prepare a solution, directly pumping the solution into an absorption tower from a pit of the absorption tower through a pit pump, mixing the solution with limestone slurry for the first time, and adding the limestone-gypsum wet flue gas desulfurization composite synergist provided in the embodiment 1 in the first mixed slurry obtained by mixing the solution for the first time to the limestone slurry in an amount of 500 to 1000ppm by mass (when adding the limestone-gypsum wet flue gas desulfurization composite synergist provided in the embodiment 1 in a supplementary manner in a later period, directly adding the limestone-gypsum wet flue gas desulfurization composite synergist provided in the embodiment 1 into a limestone slurry tank, and maintaining the limestone-gypsum wet flue gas desulfurization composite synergist provided in the embodiment 1 in the mixed slurry in an amount of 600 to 800ppm by mass); and introducing flue gas generated by coal with the sulfur content of 20-30 wt% higher than the designed sulfur content, and performing continuous reaction desulfurization in an oxidizing gas atmosphere. The structure of the absorption tower does not need to be changed, and only the absorption tower slurry supply and gypsum discharge system needs to be subjected to capacity expansion transformation according to the material balance so as to meet the normal operation requirements of the pH value of the absorption tower slurry and the density of the absorption tower slurry. The modification work has small modification work amount and modification cost, can be carried out under the condition of not influencing the normal operation of the desulfurization device (absorption tower), and has strong operability.
The application example can reduce the power consumption of the desulphurization plant by 0.15-0.25%, save electricity by 1000-1800 kW per hour, greatly reduce the operation cost of desulphurization, and remarkably improve the commissioning rate and the availability of the desulphurization device.
The limestone-gypsum wet flue gas desulfurization composite synergist provided in the embodiments 2 to 6 is basically the same as that of the limestone-gypsum wet flue gas desulfurization composite synergist provided in the embodiment 1.
Application example 2
When the limestone-gypsum wet flue gas desulfurization composite synergist provided in the comparative examples 1-4 is used for wet desulfurization, the absorption tower needs to be modified so as to realize standard desulfurization of flue gas generated by coal with the sulfur content of 20-30 wt% higher than the designed sulfur content.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The limestone-gypsum wet flue gas desulfurization composite synergist is characterized by comprising the following components in parts by mass:
30-80 parts of organic acid synergist, 15-55 parts of organic acid-base metal salt synergist, 5-35 parts of solid-liquid interface activator and 1-20 parts of oxidation catalyst.
2. The limestone-gypsum wet flue gas desulfurization composite synergist according to claim 1, characterized by further comprising 1-10 parts of a tracer.
3. The limestone-gypsum wet flue gas desulfurization composite synergist according to claim 1 or 2, wherein the organic acid synergist comprises one or more of benzoic acid, succinic acid, adipic acid, and citric acid.
4. The limestone-gypsum wet flue gas desulfurization composite synergist according to claim 1 or 2, wherein the organic acid alkali metal salt synergist comprises one or more of sodium succinate, sodium formate and sodium benzoate.
5. The limestone-gypsum wet flue gas desulfurization composite synergist according to claim 1 or 2, wherein the solid-liquid interface activator comprises formamide and/or polyethylene glycol.
6. The limestone-gypsum wet flue gas desulfurization composite synergist according to claim 1 or 2, wherein the oxidation catalyst comprises one or more of ferric trichloride, manganese sulfate, and vanadium pentoxide.
7. The limestone-gypsum wet flue gas desulfurization composite synergist according to claim 2, wherein the tracer comprises sodium bromide and/or potassium bromide.
8. A limestone-gypsum wet flue gas desulfurization method is characterized by comprising the following steps:
mixing the composite synergist of any one of claims 1-7 with limestone slurry to obtain mixed slurry;
and (3) contacting and mixing the mixed slurry with flue gas, and performing wet reaction desulfurization in the atmosphere of air.
9. The method according to claim 8, wherein the composite synergist is contained in the mixed slurry in an amount of 500 to 1000ppm by mass.
10. The method according to claim 8 or 9, wherein the limestone slurry has a pH value of 5.2 to 5.8 and a density of 1100 to 1160kg/m 3 。
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