CN107261789B - Ammonia desulphurization system and method for high-sulfur flue gas - Google Patents

Ammonia desulphurization system and method for high-sulfur flue gas Download PDF

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CN107261789B
CN107261789B CN201710451972.6A CN201710451972A CN107261789B CN 107261789 B CN107261789 B CN 107261789B CN 201710451972 A CN201710451972 A CN 201710451972A CN 107261789 B CN107261789 B CN 107261789B
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oxidation
flue gas
absorption
main
auxiliary
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CN107261789A (en
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肖文德
李学刚
娄爱娟
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Shanghai Centron Environmental Protection Science & Technology Co ltd
Shanghai Jiaotong University
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Shanghai Centron Environmental Protection Science & Technology Co ltd
Shanghai Jiaotong University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75Multi-step processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/501Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502Sulfur 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/96Regeneration, reactivation or recycling of reactants
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/24Sulfates of ammonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • B01D2251/206Ammonium compounds
    • B01D2251/2062Ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases

Abstract

The invention relates to an ammonia desulphurization system and method for high-sulfur flue gas, which take ammonia, process water and air as raw materials and are characterized by comprising three circulating systems: first circulation system is cooling concentration crystallization system (100), and the second circulation system is main absorption oxidation system (200), and the third circulation system is for assisting absorption oxidation system (300), and the high sulfur flue gas gets into in proper order cooling concentration crystallization system (100), main absorption oxidation system (200) and assist absorption oxidation system (300), and process water gets into in proper order assist absorption oxidation system (300), main absorption oxidation system (200) and cooling concentration crystallization system (100), ammonia and air get into simultaneously main absorption oxidation system (200) and assist absorption oxidation system (300). The raw material high-sulfur flue gas is subjected to cooling pre-washing, main desulfurization and auxiliary desulfurization. Compared with the prior art, the invention has the advantages of high-sulfur flue gas resistance, high desulfurization efficiency, less ammonia escape and aerosol pollution of discharged flue gas, stable and reliable operation and the like.

Description

Ammonia desulphurization system and method for high-sulfur flue gas
Technical Field
The invention belongs to the technical field of chemical industry and environmental protection, and particularly relates to an ammonia desulphurization system and method for high-sulfur flue gas.
Background
The flue gas generated by boilers of power plants or thermal power plants, sintering machines of iron and steel plants or other equipment for burning sulfur-containing fuels contains sulfur dioxide, and SO in the flue gas is determined according to the sulfur content of the fuels2The content is 300-15000mg/Nm3Generally, less than 2000 refers to low sulfur flue gas, 2000-4000 refers to medium sulfur flue gas, and 4000 refers to high sulfur flue gas.
The flue gas desulfurization is a key technology in the field of environmental protection and is also a widely applied technology. However, the flue gas desulfurization apparatus is not only an environmental protection apparatus, but also a production apparatus. Gypsum, magnesium sulfate and ammonium sulfate are obtained from various desulfurization raw materials, such as limestone, magnesium oxide and ammonia, respectively, and are commercially available chemicals. Gypsum can be used as a retarding additive of cement, the dosage can be up to 5%, the market dosage is very large, magnesium sulfate can be used as a magnesium fertilizer, ammonium sulfate is a chemical fertilizer per se, and the gypsum can also be used as a formula of a compound fertilizer, and the market dosage is very large. Therefore, the higher the sulfur content, the more the desulfurization unit can be seen as one production unit.
As a production apparatus, the higher the value of the product, the better. In the flue gas desulfurization technology, China is a large population, grain and chemical fertilizer country, has rich ammonia resources, and has obvious environmental, economic and social significance in developing and popularizing the ammonia desulfurization technology. However, due to the characteristic of easy volatilization of ammonia, the existing ammonia desulphurization technology is mainly suitable for low-sulfur flue gas, ammonia escape and aerosol easily occur in sulfur, especially high-sulfur flue gas, and the problems of low desulphurization efficiency and low ammonia raw material utilization rate are caused, so that the ammonia desulphurization technology is difficult to popularize and apply on a large scale and is especially difficult to enter the field of large-scale thermal power generation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a system and a method for ammonia desulphurization of high-sulfur flue gas, which can realize high-efficiency desulphurization of high-sulfur flue gas and resource recovery of SO 2.
The purpose of the invention can be realized by the following technical scheme: the ammonia desulfurization system for the high-sulfur flue gas takes ammonia, process water and air as raw materials, and is characterized by comprising three circulating systems: the first circulation system is cooling concentration crystallization system, and the second circulation system is main absorption oxidation system, and the third circulation system is supplementary absorption oxidation system, and the high sulfur flue gas gets into in proper order cooling concentration crystallization system, main absorption oxidation system and supplementary absorption oxidation system, process water gets into in proper order supplementary absorption oxidation system, main absorption oxidation system and cooling concentration crystallization system, ammonia and air get into simultaneously main absorption oxidation system and supplementary absorption oxidation system.
The main absorption oxidation system comprises a cylindrical main absorption section and a main oxidation section, a main absorption liquid spraying layer is arranged in the main absorption section, a main air aerator is arranged in the main oxidation section, the outside of the main oxidation section and the outside of the main absorption section are connected with a main absorption liquid circulating pump through a main absorption liquid circulating pipeline, the main oxidation section is connected with an air input pipe, and a raw material ammonia input pipe is further connected onto the main oxidation section or the main absorption liquid circulating pipeline;
the auxiliary absorption oxidation system comprises a cylindrical auxiliary absorption section and an auxiliary oxidation section, an auxiliary absorption liquid spraying layer is arranged in the auxiliary absorption section, an auxiliary air aerator is arranged in the auxiliary oxidation section, the outside of the auxiliary oxidation section and the outside of the auxiliary absorption section are connected with an auxiliary absorption liquid circulating pump through an auxiliary absorption liquid circulating pipeline, the auxiliary oxidation section is connected with an air input pipe, and the auxiliary oxidation section or the auxiliary absorption liquid circulating pipeline is also connected with an input pipe of raw material ammonia;
the concentrated crystallization system of cooling includes the concentrated section of cooling and the crystallizer section of drum type, the inside of the concentrated section of cooling sprays the layer including the thick liquid, the inside agitator of crystallizer section is connected through thick liquid circulating line and thick liquid circulating pump in the outside of crystallizer section and the outside of the concentrated section of cooling the import that is equipped with the high sulphur flue gas between the concentrated section of cooling and the crystallizer section.
And a demister is further arranged in the cooling concentration section, a flushing spraying component is arranged above or below the demister, and the flushing spraying component is connected with the main oxidation section through a liquid pipeline through a flushing pump.
A demister is arranged above the main absorption liquid spraying layer, and a demister is arranged above the auxiliary absorption liquid spraying layer.
Still include the ammonium sulfate and draw circulation system, this ammonium sulfate extraction system includes thick liquid thickener, centrifuge, desiccator and packagine machine, the crystallization tank section pass through discharge circulating pump with the thick liquid thickener of ammonium sulfate extraction system links to each other, the thick liquid mouth of this thick liquid thickener with centrifuge links to each other, centrifuge's solid discharge gate with the desiccator links to each other, the solid discharge gate of desiccator with packagine machine links to each other, the clear liquid mouth of thick liquid thickener and centrifuge's mother liquor discharge gate with the crystallization tank section links to each other.
Still include the electric demister, this electric demister is including discharge cathode ray and dust collection anode tube, the dust collection anode tube is made with the glass steel that has added carbon fiber, the electric demister is connected assist between absorption oxidation system and the chimney.
The ammonia desulphurization method for the high-sulfur flue gas by adopting any one of the systems is characterized by comprising the following steps of:
(1) cooling and pre-washing flue gas: the high-sulfur flue gas enters a flue gas inlet of a cooling, concentrating and crystallizing system, flows upwards, is contacted with ammonium sulfate slurry sprayed from a slurry spraying layer, and has mass and heat transfer, the temperature of the high-sulfur flue gas is reduced, the humidity of the high-sulfur flue gas is increased, and dust and strong acid gas in the high-sulfur flue gas are washed and enter the slurry;
(2) ammonium sulfate crystallization: the ammonium sulfate slurry flows through the slurry circulating pipeline in the crystallization tank section through the slurry circulating pump, is circularly conveyed to the slurry spraying layer, is changed into liquid drops through an atomizing nozzle of the slurry spraying layer, flows downwards, is in countercurrent contact with high-temperature hot flue gas, transfers heat and mass, is concentrated to enable the concentration of ammonium sulfate in the slurry to exceed the solubility, and further crystallizes and separates out ammonium sulfate crystals to obtain slurry containing ammonium sulfate solids, wherein the ammonium sulfate content of the slurry is not less than 50%, and the pH value is not more than 4.5;
(3) flue gas main desulfurization: the flue gas obtained from the step (1) leaves the temperature reduction concentration section and enters a main absorption section of the main absorption oxidation system, flows upwards, and is in countercurrent contact with liquid drops sprayed from the main absorption liquid spraying layer to absorb SO by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the main oxidation section, is oxidized into ammonium sulfate by the air blown by the main air aerator, simultaneously, the desulfurization raw material ammonia is added to maintain the pH value of the absorption liquid, and then is circularly conveyed to the main absorption liquid spraying layer by the main absorption liquid circulating pump through the main absorption liquid circulating pipeline for continuous desulfurization, and the ammonium sulfate in the absorption liquid contains ammonium sulfateThe amount is between 15 and 45 percent, the pH value is less than or equal to 6.0, and the desulfurization efficiency of the main absorption oxidation system is more than 90 percent;
(4) and (3) auxiliary desulfurization of flue gas: the flue gas obtained from the step (3) leaves the main absorption section, enters an auxiliary absorption section of the auxiliary absorption oxidation system, flows upwards, and is in countercurrent contact with liquid drops sprayed from the auxiliary absorption liquid spraying layer, SO that SO is absorbed by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the auxiliary oxidation section, the air blown by the auxiliary air aerator is oxidized into ammonium sulfate, simultaneously, desulfurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the auxiliary absorption liquid spraying layer through the auxiliary absorption liquid circulating pipe by the auxiliary absorption liquid circulating pump to be continuously desulfurized, wherein the ammonium sulfate content in the absorption liquid is less than or equal to 10 percent, and the pH value is less than or equal to 5.5; SO in the flue gas after passing through the auxiliary absorption oxidation system2Content ≦ 100mg/Nm3Dust content ≦ 30mg/Nm3
(5) Water balance control: controlling the liquid levels of the crystallization tank section, the main oxidation section and the auxiliary oxidation section to maintain the water balance of the high-sulfur flue gas ammonia desulphurization system; the liquid level of the crystallization tank section is controlled by the flow regulation of the ammonium sulfate solution conveyed by the main oxidation section through the liquid pipeline and the flushing pump; the liquid level of the main oxidation section is controlled by adjusting the flow of the ammonium sulfate solution conveyed to the main absorption oxidation system by the auxiliary oxidation section; the liquid level of the secondary oxidation section is controlled by the flow regulation of the process water added into the secondary oxidation section;
(6) ammonium sulfate extraction: conveying the slurry containing ammonium sulfate solids obtained in the step (2) to the ammonium sulfate extraction circulating system through the discharge circulating pump, and sequentially passing through the slurry thickener, the centrifuge, the dryer and the packaging machine to obtain an ammonium sulfate product; and returning the clear liquid of the slurry thickener and the mother liquid of the centrifuge to the crystallization pool section, and concentrating and crystallizing.
And (3) a flue gas ultra-clean dedusting step, wherein the desulfurized flue gas obtained in the step (4) enters the electric demister, and ultra-fine acid mist particles in the flue gas are removed through high-voltage discharge treatment, so that the dust content in the purified flue gas is less than or equal to 10mg/Nm3And then discharged through the chimney.
The pH values of the ammonium sulfate solutions in the crystallization pond section, the main oxidation section and the auxiliary oxidation section are respectively between 3.5 and 4.5, 5.2 and 6.0 and 4.0 and 6.0.
The purified flue gas is discharged via the chimney, SO2Content ≦ 35mg/Nm3Dust content ≦ 5mg/Nm3
Compared with the prior art, the invention has the beneficial effects that the high-sulfur flue gas sequentially passes through three circulating systems of cooling, concentration and crystallization, main absorption and oxidation and auxiliary absorption and oxidation to realize SO2The high-efficiency desorption and the reduction of ammonia escape and the pollution of the exhausted aerosol, and the system has stable and reliable operation.
Drawings
FIG. 1 is a schematic view of a first process flow of the present invention;
FIG. 2 is a schematic view of a second process flow of the present invention;
FIG. 3 is a schematic view of a third process flow of the present invention;
FIG. 4 is a schematic view of a fourth process flow of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
One thermal power plant and two 300MW units, the sulfur content of the fire coal is 2 percent, and the flow rate of each flue gas is 120 ten thousand Nm3Hr, smoke sulfur content of 4800mg/Nm3The flue gas temperature is 130 ℃, the desulfurization system is a furnace and a line, the high-sulfur flue gas ammonia desulfurization system shown in figure 1 is adopted, ammonia is used as a desulfurizing agent, process water and air are used as auxiliary materials, and the system comprises three circulating systems: the first circulating system is a cooling, concentrating and crystallizing system 100, the second circulating system is a main absorption and oxidation system 200, the third circulating system is an auxiliary absorption and oxidation system 300, and the three circulating systems are respectively and independently arranged;
wherein: the main absorption oxidation system 200 comprises a cylindrical main absorption section 210 and a main oxidation section 220, wherein the main absorption section 210 comprises a main absorption liquid spraying layer 211 inside, the main oxidation section 220 comprises a main air aerator 221 inside, the outside of the main oxidation section 220 and the outside of the main absorption section 210 are connected with a main absorption liquid circulating pump 250 through a main absorption liquid circulating pipeline 240, the main oxidation section 220 is connected with an air input pipe, and the main oxidation section 220 is also connected with an input pipe of raw material ammonia; a demister is disposed above the main absorption liquid spray layer 211 inside the main absorption section 210 in order to eliminate mist generated by spraying of the main absorption liquid spray layer 211.
The auxiliary absorption oxidation system 300 comprises a cylindrical auxiliary absorption section 310 and an auxiliary oxidation section 320, wherein an auxiliary absorption liquid spraying layer 311 is arranged in the auxiliary absorption section 310, an auxiliary air aerator 321 is arranged in the auxiliary oxidation section 220, the outside of the auxiliary oxidation section 320 and the outside of the auxiliary absorption section 310 are connected with an auxiliary absorption liquid circulating pump 350 through an auxiliary absorption liquid circulating pipeline 340, the auxiliary oxidation section 320 is connected with an air input pipe, and the auxiliary oxidation section 320 is also connected with an input pipe of raw material ammonia; a demister is also provided above the auxiliary absorbing liquid spraying layer 311 inside the auxiliary absorbing section 310 in order to eliminate mist generated by spraying of the auxiliary absorbing liquid spraying layer 311.
The cooling concentration crystallization system 100 comprises a cylindrical cooling concentration section 110 and a crystallization tank section 120, the inside of the cooling concentration section 110 comprises a slurry spraying layer 111, the inside of the crystallization tank section 120 comprises a stirrer 121, the outside of the crystallization tank section 120 and the outside of the cooling concentration section 110 are connected with a slurry circulating pump 150 through a slurry circulating pipeline 140, and an inlet 130 for high-sulfur flue gas is arranged between the cooling concentration section 110 and the crystallization tank section 120. In the temperature reduction concentration section 110, a demister is further provided, a flushing spray member is provided above the demister, and the liquid of the flushing spray member comes from the main oxidation section.
The system further comprises an ammonium sulfate extraction circulating system 600, the ammonium sulfate extraction system 600 comprises a slurry thickener, a centrifugal machine, a drying machine and a packaging machine, the crystallization tank section 120 is connected with the slurry thickener of the ammonium sulfate extraction system 600 through a discharge circulating pump 610, a thick liquid port of the slurry thickener is connected with the centrifugal machine, a solid discharge port of the centrifugal machine is connected with the drying machine, a solid discharge port of the drying machine is connected with the packaging machine, and a clear liquid port of the slurry thickener and a mother liquid discharge port of the centrifugal machine are connected with the crystallization tank section 120.
The system further comprises an electric demister 400, wherein the electric demister 400 comprises a discharge cathode wire and a dust collection anode tube, the anode tube is made of glass fiber reinforced plastic added with carbon fibers, and the electric demister 400 is connected between the auxiliary absorption oxidation system 300 and the chimney 500.
The high-sulfur flue gas sequentially enters a cooling, concentrating and crystallizing system 100, a main absorption and oxidation system 200 and an auxiliary absorption and oxidation system 300, process water sequentially enters the auxiliary absorption and oxidation system 300, the main absorption and oxidation system 200 and the cooling, concentrating and crystallizing system 100, and ammonia and air simultaneously enter the main absorption and oxidation system 200 and the auxiliary absorption and oxidation system 300; the high-sulfur flue gas is sequentially subjected to three circulating systems of cooling, concentration and crystallization, main absorption and oxidation and auxiliary absorption and oxidation to realize SO2The high-efficiency removal and the reduction of ammonia escape and smoke-exhaust aerosol pollution, the specific application of the system for high-sulfur flue gas ammonia desulphurization comprises the following steps:
(1) cooling and pre-washing flue gas: raw material high-sulfur flue gas enters a flue gas inlet 130 of the cooling concentration crystallization system 100, flows upwards, contacts with ammonium sulfate slurry sprayed from the slurry spraying layer 111, transfers heat and mass, reduces the temperature of the flue gas, increases the humidity, and washes dust and strong acid gas in the flue gas to enter the slurry;
(2) ammonium sulfate crystallization: the crystallization tank section 120 is provided with ammonium sulfate slurry which is obtained by spraying liquid from a slurry spraying layer 111 to contact with high-sulfur flue gas in a countercurrent manner to obtain ammonium sulfate slurry liquid flowing to the crystallization tank section 120, and fluid left after being input into a washing and spraying component 113 at the top of the cooling and concentrating crystallization system 100 from a main oxidation section 220 through a liquid pipeline 21 and a washing pump 22 is demisted by a demister 112 and contacts with the high-sulfur flue gas flowing in an inlet 130 in a countercurrent manner to obtain ammonium sulfate slurry liquid flowing to the crystallization tank section 120, the ammonium sulfate slurry in the crystallization tank section 120 passes through a slurry circulating pump 150, flows through a slurry circulating pipeline 140 and is circularly conveyed to the slurry spraying layer 111, is changed into liquid drops through an atomizing nozzle of the slurry spraying layer 111, flows downwards to contact with the high-temperature hot flue gas in a countercurrent manner, and is subjected to heat and mass transfer, and is concentrated to ensure that the concentration of ammonium sulfate in the slurry exceeds the solubility, further crystallizing to precipitate ammonium sulfate crystal, to obtain slurry containing ammonium sulfate solid, wherein the slurry has ammonium sulfate content of 50% and pH of 4.5;
(3) flue gas main desulfurization: the flue gas obtained from the step (1) leaves the temperature reduction concentration section 110 and enters the main absorption section 210 of the main absorption oxidation system 200, flows upwards, and is in countercurrent contact with the absorption liquid droplets sprayed from the main absorption liquid spraying layer 211 to absorb SO by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the main oxidation section 220, is oxidized into ammonium sulfate by the air blown in by the main air aerator 221, and simultaneously, a desulfurization raw material ammonia is added to maintain the pH value of the absorption liquid, and is circularly conveyed to the main absorption liquid spraying layer 211 by the main absorption liquid circulating pump 250 through the main absorption liquid circulating pipeline 240 to perform continuous desulfurization, wherein the content of ammonium sulfate in the absorption liquid is 20%, the pH value is 5.5, and the desulfurization efficiency of the main absorption oxidation system is 91%;
(4) and (3) auxiliary desulfurization of flue gas: the flue gas obtained from the step (3) leaves the main absorption section 210, enters the auxiliary absorption section 310 of the auxiliary absorption oxidation system 300, flows upwards, and is in countercurrent contact with absorption liquid droplets sprayed from the auxiliary absorption liquid spraying layer 311, SO as to carry out mass transfer absorption on SO2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the auxiliary oxidation section 320, is oxidized into ammonium sulfate by the air blown by the auxiliary air aerator 321, is added with desulfurization raw material ammonia to maintain the pH value of the absorption liquid, and is circularly conveyed to the auxiliary absorption liquid spraying layer 311 by the auxiliary absorption liquid circulating pump 350 through the auxiliary absorption liquid circulating pipeline 340 to be continuously desulfurized, wherein the content of ammonium sulfate in the absorption liquid is 9 percent, and the pH value is 5.0; after passing through the auxiliary absorption oxidation system 300, SO in the flue gas2The content is 33.6mg/Nm3The dust content is 25mg/Nm3The following;
(5) water balance control: controlling the liquid levels of the crystallization tank section 120, the main oxidation section 220 and the auxiliary oxidation section 320 to maintain the water balance of the high-sulfur flue gas ammonia desulfurization system; the liquid level of the crystallization tank section 120 is controlled by adjusting the flow rate of the ammonium sulfate solution conveyed by the main oxidation section 220 through the liquid pipeline 21 and the flushing pump 22; the liquid level of the main oxidation section 220 is controlled by the flow regulation of the ammonium sulfate solution conveyed to the main absorption oxidation system 200 by the auxiliary oxidation section 320; the liquid level of the secondary oxidation stage 320 is controlled by the flow regulation of the process water fed to the secondary oxidation stage 320;
(6) ammonium sulfate extraction: sending the ammonium sulfate slurry containing ammonium sulfate solids obtained in the step (2) to the ammonium sulfate extraction circulation system 600 through the discharge circulation pump 610, and sequentially passing through the slurry thickener, the centrifuge, the dryer and the packaging machine to obtain an ammonium sulfate product; and the clear liquid of the slurry thickener and the mother liquid of the centrifuge flow back to the crystallization pool section 120, and are concentrated and crystallized.
The desulfurization method also comprises a flue gas ultra-clean dedusting step, wherein the desulfurized flue gas obtained in the step (4) enters the electric demister 400, and is subjected to high-voltage discharge treatment to remove superfine acid mist particles in the flue gas, so that the dust content in the purified flue gas is reduced to 4.3mg/Nm3And then discharged through the stack 500.
By applying the high-sulfur flue gas ammonia desulphurization system and method, the flue gas SO at the outlet of the chimney 500 can be realized2The content is 33.6mg/Nm3Dust content 4.3mg/Nm3The yield of the emission target of (1) is 23.83 tons/hr of ammonium sulfate, 6000 hours of electricity generation are carried out in the whole year, and the annual output of the ammonium sulfate is 14.3 ten thousand tons.
Example 2
A thermal power plant, two 600MW units, the coal-fired sulfur content is 3.5%, each flue gas flow is 225 ten thousand Nm3/hr, the flue gas sulfur content is 9200mg/Nm3, the flue gas temperature is 135 ℃, the desulfurization system is a stove and a line, adopt the high-sulfur flue gas ammonia desulfurization system shown in figure 2, use ammonia as desulfurizer, assisted by water and air, including three circulation systems: the first circulation system is a cooling, concentrating and crystallizing system 100, the second circulation system is a main absorption and oxidation system 200, and the third circulation system is an auxiliary absorption and oxidation system 300. Unlike embodiment 1, the cylindrical main absorption section 210 of the main absorption oxidation system 200 in this embodiment shares one tower with the temperature-reducing concentration crystallization system 100, and the cylindrical main absorption section 210 of the main absorption oxidation system 200 is above the temperature-reducing concentration crystallization system 100 and is separated by a hood partition plate.
The main absorption oxidation system 200 comprises a cylindrical main absorption section 210 and a main oxidation section 220, wherein the main absorption section 210 comprises a main absorption liquid spraying layer 211, the main oxidation section 220 comprises a main air aerator 221, the outside of the main oxidation section 220 and the outside of the main absorption section 210 are connected with a main absorption liquid circulating pump 250 through a main absorption liquid circulating pipeline 240, the main oxidation section 220 is connected with an air input pipe, and the main absorption liquid circulating pipeline 240 is also connected with an input pipe of raw material ammonia; a demister is disposed above the main absorbing liquid spraying layer 211 in the main absorbing stage 210, and a demister is disposed above the auxiliary absorbing liquid spraying layer 311 in the auxiliary absorbing stage 310.
The auxiliary absorption oxidation system 300 comprises a cylindrical auxiliary absorption section 310 and an auxiliary oxidation section 320, wherein an auxiliary absorption liquid spraying layer 311 is arranged inside the auxiliary absorption section 310, an auxiliary air aerator 321 is arranged inside the auxiliary oxidation section 220, the outside of the auxiliary oxidation section 320 and the outside of the auxiliary absorption section 310 are connected with an auxiliary absorption liquid circulating pump 350 through an auxiliary absorption liquid circulating pipeline 340, the auxiliary oxidation section 320 is connected with an air input pipe, and the auxiliary absorption liquid circulating pipeline 340 is also connected with an input pipe of raw material ammonia;
the cooling concentration crystallization system 100 comprises a cylindrical cooling concentration section 110 and a crystallization tank section 120, the inside of the cooling concentration section 110 comprises a slurry spraying layer 111, the inside of the crystallization tank section 120 comprises a stirrer 121, the outside of the crystallization tank section 120 and the outside of the cooling concentration section 110 are connected with a slurry circulating pump 150 through a slurry circulating pipeline 140, and an inlet 130 of high-sulfur flue gas is arranged between the cooling concentration section 110 and the crystallization tank section 120. In the temperature reduction concentration section 110, a demister is further provided, a flushing spray member is provided above the demister, and the required flushing spray liquid comes from the main oxidation section 220.
The system also comprises an ammonium sulfate extraction circulation system 600, the ammonium sulfate extraction system 600 comprises a slurry thickener, a centrifuge, a dryer and a packing machine, the crystallization tank section 120 is connected with the slurry thickener of the ammonium sulfate extraction system 600 through a discharge circulation pump 610, a thick liquid port of the slurry thickener is connected with the centrifuge, a solid discharge port of the centrifuge is connected with the dryer, a solid discharge port of the dryer is connected with the packing machine, and a clear liquid port of the slurry thickener and a mother liquid discharge port of the centrifuge are connected with the crystallization tank section 12).
The system further comprises an electric demister 400, wherein the electric demister 400 comprises a discharge cathode wire and a dust collection anode tube, the anode tube is made of glass fiber reinforced plastic added with carbon fibers, and the electric demister 400 is connected between the auxiliary absorption oxidation system 300 and the chimney 500.
The high-sulfur flue gas sequentially enters a cooling, concentrating and crystallizing system 100, a main absorption and oxidation system 200 and an auxiliary absorption and oxidation system 300, process water sequentially enters the auxiliary absorption and oxidation system 300, the main absorption and oxidation system 200 and the cooling, concentrating and crystallizing system 100, and ammonia and air simultaneously enter the main absorption and oxidation system 200 and the auxiliary absorption and oxidation system 300; the high-sulfur flue gas is sequentially subjected to three circulating systems of cooling, concentration and crystallization, main absorption and oxidation and auxiliary absorption and oxidation to realize SO2The high-efficiency removal and the reduction of ammonia escape and smoke-exhaust aerosol pollution, the specific application of the system for high-sulfur flue gas ammonia desulphurization comprises the following steps:
(1) cooling and pre-washing flue gas: raw material high-sulfur flue gas enters a flue gas inlet 130 of the cooling concentration crystallization system 100, flows upwards, contacts with ammonium sulfate slurry sprayed from the slurry spraying layer 111, transfers heat and mass, reduces the temperature of the flue gas, increases the humidity, and washes dust and strong acid gas in the flue gas to enter the slurry;
(2) ammonium sulfate crystallization: the ammonium sulfate slurry flows through the slurry circulating pipeline 140 in the crystallization tank section 120 through the slurry circulating pump 150, is circularly conveyed to the slurry spraying layer 111, is changed into liquid drops through an atomizing nozzle of the slurry spraying layer 111, flows downwards, is in countercurrent contact with high-temperature hot flue gas, transfers heat and mass, is concentrated to enable the concentration of ammonium sulfate in the slurry to exceed the solubility, and further crystallizes and separates out crystal ammonium sulfate to obtain slurry containing ammonium sulfate solids, wherein the ammonium sulfate content of the slurry is 50%, and the pH value of the slurry is 4.5;
(3) flue gas main desulfurization: the flue gas obtained from the step (1) leaves the temperature-reducing concentration section 110, enters the main absorption section 210 of the main absorption oxidation system 200, flows upwards and is sprayed with the main absorption liquidLiquid drops sprayed from the spraying layer 211 are in countercurrent contact, and SO is absorbed by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the main oxidation section 220, is oxidized into ammonium sulfate by the air blown in by the main air aerator 221, is added with desulphurization raw material ammonia at the same time, maintains the pH value of the absorption liquid, and is circularly conveyed to the main absorption liquid spraying layer 211 by the main absorption liquid circulating pump 250 through the main absorption liquid circulating pipeline 240 to be continuously desulfurized, the content of ammonium sulfate in the absorption liquid is 30 percent, the pH value is 5.0, and the desulphurization efficiency of the main absorption oxidation system is 90 percent;
(4) and (3) auxiliary desulfurization of flue gas: the flue gas obtained from the step (3) leaves the main absorption section 210, enters the auxiliary absorption section 310 of the auxiliary absorption oxidation system 300, flows upwards, and is in countercurrent contact with liquid drops sprayed from the auxiliary absorption liquid spraying layer 311, SO as to carry out mass transfer absorption on SO2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the auxiliary oxidation section 320, the air blown by the auxiliary air aerator 321 is oxidized into ammonium sulfate, simultaneously, desulphurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the auxiliary absorption liquid spraying layer 311 by the auxiliary absorption liquid circulating pump 350 through the auxiliary absorption liquid circulating pipeline 340 for continuous desulphurization, wherein the ammonium sulfate content in the absorption liquid is 8%, and the pH value is 5.5; after passing through the auxiliary absorption oxidation system 300, SO in the flue gas2The content is 46mg/Nm3The dust content is 20mg/Nm3The following;
(5) water balance control: controlling the liquid levels of the crystallization tank section 120, the main oxidation section 220 and the auxiliary oxidation section 320 to maintain the water balance of the high-sulfur flue gas ammonia desulfurization system; the liquid level of the crystallization tank section 120 is controlled by adjusting the flow rate of the ammonium sulfate solution conveyed by the main oxidation section 220 through the liquid pipeline 21 and the flushing pump 22; the liquid level of the main oxidation section 220 is controlled by the flow regulation of the ammonium sulfate solution conveyed to the main absorption oxidation system 200 by the auxiliary oxidation section 320; the liquid level of the secondary oxidation stage 320 is controlled by the flow regulation of the process water fed to the secondary oxidation stage 320;
(6) ammonium sulfate extraction: the ammonium sulfate slurry containing ammonium sulfate solids obtained in the step (2) is conveyed to the ammonium sulfate extraction circulation system 600 through the slurry conveying pump, and sequentially passes through the slurry thickener, the centrifuge, the dryer and the packaging machine to obtain an ammonium sulfate product; and the clear liquid of the slurry thickener and the mother liquid of the centrifuge flow back to the crystallization pool section 120, and are concentrated and crystallized.
The desulfurization method also comprises a flue gas ultra-clean dedusting step, wherein the desulfurized flue gas obtained in the step (4) enters the electric demister 400, and is subjected to high-voltage discharge treatment to remove superfine acid mist particles in the flue gas, so that the dust content in the purified flue gas is reduced to 8.1mg/Nm3And then discharged through the stack 500.
By adopting the ammonia desulphurization system and method for the high-sulfur flue gas, the SO of the flue gas at the outlet of the chimney 500 can be realized2Content 46mg/Nm3Dust content 8.1mg/Nm3The yield of the emission target of (1) is 85.82 tons/hr of ammonium sulfate, 6000 hours of electricity generation are carried out in the whole year, and the yield of the ammonium sulfate in the whole year is 51.49 ten thousand tons.
Example 3
A coalification plant comprises 4 260 tons of thermoelectric boilers, 3 boilers and 1 boiler, the sulfur content of fire coal is 5.0 percent, the flow rate of each flue gas is 33 ten thousand Nm3/hr, the sulfur content of the flue gas is 12600mg/Nm3, the temperature of the flue gas is 145 ℃, a desulfurization system is a three-furnace one-line, a high-sulfur flue gas ammonia desulfurization system shown in figure 3 is adopted, ammonia is used as a desulfurizing agent, water and air are used as auxiliary materials, and the coalification plant comprises three circulating systems: the first circulation system is a temperature reduction concentration crystallization system 100, the second circulation system is a main absorption oxidation system 200, and the third circulation system is an auxiliary absorption oxidation system 300. Unlike embodiment 1 or 2, the cylindrical secondary absorption section 310 of the secondary absorption oxidation system 300, the cylindrical primary absorption section 210 of the primary absorption oxidation system 200 and the temperature-reducing concentrated crystallization system 100 in this embodiment share one tower, and the cylindrical secondary absorption section 310 of the secondary absorption oxidation system 300 is above the cylindrical primary absorption section 210 of the primary absorption oxidation system 200, and the cylindrical primary absorption section 210 of the primary absorption oxidation system 200 is above the temperature-reducing concentrated crystallization system 100, which are separated by a hood partition.
The main absorption oxidation system 200 comprises a cylindrical main absorption section 210 and a main oxidation section 220, wherein the main absorption section 210 comprises a main absorption liquid spraying layer 211 inside, the main oxidation section 220 comprises a main air aerator 221 inside, the outside of the main oxidation section 220 and the outside of the main absorption section 210 are connected with a main absorption liquid circulating pump 250 through a main absorption liquid circulating pipeline 240, the main oxidation section 220 is connected with an air input pipe, and the main oxidation section 220 is also connected with an input pipe of raw material ammonia;
the auxiliary absorption oxidation system 300 comprises a cylindrical auxiliary absorption section 310 and an auxiliary oxidation section 320, wherein an auxiliary absorption liquid spraying layer 311 is arranged in the auxiliary absorption section 310, an auxiliary air aerator 321 is arranged in the auxiliary oxidation section 220, the outside of the auxiliary oxidation section 320 and the outside of the auxiliary absorption section 310 are connected with an auxiliary absorption liquid circulating pump 350 through an auxiliary absorption liquid circulating pipeline 340, the auxiliary oxidation section 320 is connected with an air input pipe, and the auxiliary oxidation section 320 is also connected with an input pipe of raw material ammonia;
the cooling concentration crystallization system 100 comprises a cylindrical cooling concentration section 110 and a crystallization tank section 120, the inside of the cooling concentration section 110 comprises a slurry spraying layer 111, the inside of the crystallization tank section 120 comprises a stirrer 121, the outside of the crystallization tank section 120 and the outside of the cooling concentration section 110 are connected with a slurry circulating pump 150 through a slurry circulating pipeline 140, and an inlet 130 of high-sulfur flue gas is arranged between the cooling concentration section 110 and the crystallization tank section 120.
The system further comprises an ammonium sulfate extraction circulating system 600, the ammonium sulfate extraction system 600 comprises a slurry thickener, a centrifugal machine, a drying machine and a packaging machine, the crystallization tank section 120 is connected with the slurry thickener of the ammonium sulfate extraction system 600 through a discharge circulating pump 610, a thick liquid port of the slurry thickener is connected with the centrifugal machine, a solid discharge port of the centrifugal machine is connected with the drying machine, a solid discharge port of the drying machine is connected with the packaging machine, and a clear liquid port of the slurry thickener and a mother liquid discharge port of the centrifugal machine are connected with the crystallization tank section 120.
The system further comprises an electric demister 400, wherein the electric demister 400 comprises a discharge cathode wire and a dust collection anode tube, the anode tube is made of glass fiber reinforced plastic added with carbon fibers, and the electric demister 400 is connected between the auxiliary absorption oxidation system 300 and the chimney 500.
The high-sulfur flue gas sequentially enters a cooling, concentrating and crystallizing system 100 and is subjected to main absorption and oxidationThe system comprises a system 200 and an auxiliary absorption oxidation system 300, wherein process water sequentially enters the auxiliary absorption oxidation system 300, a main absorption oxidation system 200 and a cooling concentration crystallization system 100, and ammonia and air simultaneously enter the main absorption oxidation system 200 and the auxiliary absorption oxidation system 300; the high-sulfur flue gas is sequentially subjected to three circulating systems of cooling, concentration and crystallization, main absorption and oxidation and auxiliary absorption and oxidation to realize SO2The high-efficiency removal and the reduction of ammonia escape and smoke-exhaust aerosol pollution, the specific application of the system for high-sulfur flue gas ammonia desulphurization comprises the following steps:
(1) cooling and pre-washing flue gas: raw material high-sulfur flue gas enters a flue gas inlet 130 of the cooling concentration crystallization system 100, flows upwards, contacts with ammonium sulfate slurry sprayed from the slurry spraying layer 111, transfers heat and mass, reduces the temperature of the flue gas, increases the humidity, and washes dust and strong acid gas in the flue gas to enter the slurry;
(2) ammonium sulfate crystallization: the ammonium sulfate slurry flows through the slurry circulating pipeline 140 in the crystallization tank section 120 through the slurry circulating pump 150, is circularly conveyed to the slurry spraying layer 111, is changed into liquid drops through an atomizing nozzle of the spraying layer 110, flows downwards, is in countercurrent contact with high-temperature hot flue gas, transfers heat and mass, is concentrated to enable the concentration of ammonium sulfate in the slurry to exceed the solubility, and further crystallizes and separates out crystal ammonium sulfate to obtain slurry containing ammonium sulfate solids, wherein the ammonium sulfate content of the slurry is 50%, and the pH value of the slurry is 4.5;
(3) flue gas main desulfurization: the flue gas obtained from the step (1) leaves the temperature reduction concentration section 110 and enters the main absorption section 210 of the main absorption oxidation system 200, flows upwards, and is in countercurrent contact with liquid drops sprayed from the main absorption liquid spraying layer 211 to absorb SO by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the main oxidation section 220, the air blown by the main air aerator 221 is oxidized into ammonium sulfate, simultaneously, desulfurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the main absorption liquid spraying layer 211 by the main absorption liquid circulating pump 250 through the main absorption liquid circulating pipeline 240 for continuous desulfurization, wherein the content of ammonium sulfate in the absorption liquid is 30 percent, the pH value is 5.0, and the absorption liquid is continuously desulfurizedThe desulfurization efficiency of the main absorption oxidation system is 90 percent;
(4) and (3) auxiliary desulfurization of flue gas: the flue gas obtained from the step (3) leaves the main absorption section 210, enters the auxiliary absorption section 310 of the auxiliary absorption oxidation system 300, flows upwards, and is in countercurrent contact with liquid drops sprayed from the auxiliary absorption liquid spraying layer 311, SO as to carry out mass transfer absorption on SO2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the auxiliary oxidation section 320, the air blown by the auxiliary air aerator 321 is oxidized into ammonium sulfate, simultaneously, desulphurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the auxiliary absorption liquid spraying layer 311 by the auxiliary absorption liquid circulating pump 340 through the auxiliary absorption liquid circulating pipeline 330 for continuous desulphurization, wherein the ammonium sulfate content in the absorption liquid is 8%, and the pH value is 5.5; after passing through the auxiliary absorption oxidation system 300, SO in the flue gas2The content is 63mg/Nm3The dust content is 30mg/Nm3The following;
(5) water balance control: controlling the liquid levels of the crystallization tank section 120, the main oxidation section 220 and the auxiliary oxidation section 320 to maintain the water balance of the high-sulfur flue gas ammonia desulfurization system; the liquid level of the crystallization tank section 120 is controlled by adjusting the flow rate of the ammonium sulfate solution conveyed by the main oxidation section 220 through the liquid pipeline 21 and the flushing pump 22; the liquid level of the main oxidation section 220 is controlled by the flow regulation of the ammonium sulfate solution conveyed to the main absorption oxidation system 200 by the auxiliary oxidation section 320; the liquid level of the secondary oxidation stage 320 is controlled by the flow regulation of the process water fed to the secondary oxidation stage 320;
(6) ammonium sulfate extraction: the ammonium sulfate slurry containing ammonium sulfate solids obtained in the step (2) is conveyed to the ammonium sulfate extraction circulation system 600 through the slurry conveying pump, and sequentially passes through the slurry thickener, the centrifuge, the dryer and the packaging machine to obtain an ammonium sulfate product; and the clear liquid of the slurry densifier and the mother liquid of the centrifuge flow back to the crystallization pool section 120, and are concentrated and crystallized.
The desulfurization method also comprises a flue gas ultra-clean dedusting step, wherein the desulfurized flue gas obtained in the step (4) enters the electric demister 400, and is subjected to high-voltage discharge treatment to remove superfine acid mist in the flue gasGranulating to reduce dust content in the purified flue gas to 15.8mg/Nm3And then discharged through the stack 500.
By adopting the high-sulfur flue gas ammonia desulphurization system and method, the outlet flue gas SO can be realized2Content 63mg/Nm3Dust content 15.8mg/Nm3The yield of the emission target of (1) is 25.86 tons/hr of ammonium sulfate, the annual operation is calculated according to 8400 hours, and the annual output of the ammonium sulfate is 21.72 ten thousand tons.
Example 4
One iron and steel plant with 1 station of 360m2The flue gas flow of the sintering machine is 120 ten thousand Nm3Hr, smoke sulfur content of 5500mg/Nm3The flue gas temperature is 150 ℃, a high-sulfur flue gas ammonia desulphurization system shown in figure 4 is adopted, ammonia is used as a desulfurizer, water and air are used as auxiliary materials, and the system comprises three circulating systems: the first circulation system is a cooling, concentrating and crystallizing system 100, the second circulation system is a main absorption and oxidation system 200, and the third circulation system is an auxiliary absorption and oxidation system 300. Unlike embodiment 1, 2 or 3, the cylindrical secondary absorption section 310 of the secondary absorption oxidation system 300 in the present embodiment shares one tower with the primary absorption oxidation system 200, and the cylindrical secondary absorption section 310 of the secondary absorption oxidation system 300 is separated above the primary absorption oxidation system 200 by a hood partition.
The main absorption oxidation system 200 comprises a cylindrical main absorption section 210 and a main oxidation section 220, wherein the main absorption section 210 comprises a main absorption liquid spraying layer 211 inside, the main oxidation section 220 comprises a main air aerator 221 inside, the outside of the main oxidation section 220 and the outside of the main absorption section 210 are connected with a main absorption liquid circulating pump 250 through an absorption liquid circulating pipeline 240, the main oxidation section 220 is connected with an air input pipe, and the main oxidation section 220 is also connected with an input pipe of raw material ammonia;
the auxiliary absorption oxidation system 300 comprises a cylindrical auxiliary absorption section 310 and an auxiliary oxidation section 320, wherein an auxiliary absorption liquid spraying layer 311 is arranged in the auxiliary absorption section 310, an auxiliary air aerator 321 is arranged in the auxiliary oxidation section 220, the outside of the auxiliary oxidation section 320 and the outside of the auxiliary absorption section 310 are connected with an auxiliary absorption liquid circulating pump 350 through an auxiliary absorption liquid circulating pipeline 340, the auxiliary oxidation section 320 is connected with an air input pipe, and the auxiliary oxidation section 320 is also connected with an input pipe of raw material ammonia;
the cooling concentration crystallization system 100 comprises a cylindrical cooling concentration section 110 and a crystallization tank section 120, the inside of the cooling concentration section 110 comprises a slurry spraying layer 111, the inside of the crystallization tank section 120 comprises a stirrer 121, the outside of the crystallization tank section 120 and the outside of the cooling concentration section 110 are connected with a slurry circulating pump 150 through a slurry circulating pipeline 140, and an inlet 130 of high-sulfur flue gas is arranged between the cooling concentration section 110 and the crystallization tank section 120.
The system further comprises an ammonium sulfate extraction circulating system 600, the ammonium sulfate extraction system 600 comprises a slurry thickener, a centrifugal machine, a drying machine and a packaging machine, the crystallization tank section 120 is connected with the slurry thickener of the ammonium sulfate extraction system 600 through a discharge circulating pump 610, a thick liquid port of the slurry thickener is connected with the centrifugal machine, a solid discharge port of the centrifugal machine is connected with the drying machine, a solid discharge port of the drying machine is connected with the packaging machine, and a clear liquid port of the slurry thickener and a mother liquid discharge port of the centrifugal machine are connected with the crystallization tank section 120.
The system further comprises an electric demister 400, wherein the electric demister 400 comprises a discharge cathode wire and a dust collection anode tube, the anode tube is made of glass fiber reinforced plastic added with carbon fibers, and the electric demister 400 is connected between the auxiliary absorption oxidation system 300 and the chimney 500.
The high-sulfur flue gas sequentially enters a cooling, concentrating and crystallizing system 100, a main absorption and oxidation system 200 and an auxiliary absorption and oxidation system 300, process water sequentially enters the auxiliary absorption and oxidation system 300, the main absorption and oxidation system 200 and the cooling, concentrating and crystallizing system 100, and ammonia and air simultaneously enter the main absorption and oxidation system 200 and the auxiliary absorption and oxidation system 300; the high-sulfur flue gas is sequentially subjected to three circulating systems of cooling, concentration and crystallization, main absorption and oxidation and auxiliary absorption and oxidation to realize SO2The high-efficiency removal and the reduction of ammonia escape and smoke-exhaust aerosol pollution, the specific application of the system for high-sulfur flue gas ammonia desulphurization comprises the following steps:
(1) cooling and pre-washing flue gas: raw material high-sulfur flue gas enters a flue gas inlet 130 of the cooling concentration crystallization system 100, flows upwards, contacts with ammonium sulfate slurry sprayed from the slurry spraying layer 111, transfers heat and mass, reduces the temperature of the flue gas, increases the humidity, and washes dust and strong acid gas in the flue gas to enter the slurry;
(2) ammonium sulfate crystallization: the ammonium sulfate slurry flows through the slurry circulating pipeline 140 in the crystallization tank section 120 through the slurry circulating pump 150, is circularly conveyed to the slurry spraying layer 111, is changed into liquid drops through an atomizing nozzle of the spraying layer 110, flows downwards, is in countercurrent contact with high-temperature hot flue gas, transfers heat and mass, is concentrated to enable the concentration of ammonium sulfate in the slurry to exceed the solubility, and further crystallizes and separates out crystal ammonium sulfate to obtain slurry containing ammonium sulfate solids, wherein the ammonium sulfate content of the slurry is 50%, and the pH value of the slurry is 4.5;
(3) flue gas main desulfurization: the flue gas obtained from the step (1) leaves the temperature reduction concentration section 110 and enters the main absorption section 210 of the main absorption oxidation system 200, flows upwards, and is in countercurrent contact with liquid drops sprayed from the main absorption liquid spraying layer 211 to absorb SO by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the main oxidation section 220, the air blown in by the main air aerator 221 is oxidized into ammonium sulfate, simultaneously, a desulfurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the main absorption liquid spraying layer 211 by the main absorption liquid circulating pump 250 through the main absorption liquid circulating pipeline 240 to be continuously desulfurized, wherein the content of ammonium sulfate in the absorption liquid is 30%, the pH value is 5.0, and the desulfurization efficiency of the main absorption oxidation system is 90%;
(4) and (3) auxiliary desulfurization of flue gas: the flue gas obtained from the step (3) leaves the main absorption section 210, enters the auxiliary absorption section 310 of the auxiliary absorption oxidation system 300, flows upwards, and is in countercurrent contact with liquid drops sprayed from the auxiliary absorption liquid spraying layer 311, SO as to carry out mass transfer absorption on SO2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the auxiliary oxidation section 320, the air blown by the auxiliary air aerator 321 is oxidized into ammonium sulfate, simultaneously, desulphurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the auxiliary absorption liquid spraying layer 311 by the auxiliary absorption liquid circulating pump 340 through the auxiliary absorption liquid circulating pipeline 330 for continuous desulphurization, wherein the content of ammonium sulfate in the absorption liquid is 8% pH 5.5; after passing through the auxiliary absorption oxidation system 300, SO in the flue gas2The content is 27.5mg/Nm3The dust content is 20mg/Nm3The following;
(5) water balance control: controlling the liquid levels of the crystallization tank section 120, the main oxidation section 220 and the auxiliary oxidation section 320 to maintain the water balance of the high-sulfur flue gas ammonia desulfurization system; the liquid level of the crystallization tank section 120 is controlled by adjusting the flow rate of the ammonium sulfate solution conveyed by the main oxidation section 220 through the liquid pipeline 21 and the flushing pump 22; the liquid level of the main oxidation section 220 is controlled by the flow regulation of the ammonium sulfate solution conveyed to the main absorption oxidation system 200 by the auxiliary oxidation section 320; the liquid level of the secondary oxidation stage 320 is controlled by the flow regulation of the process water fed to the secondary oxidation stage 320;
(6) ammonium sulfate extraction: the ammonium sulfate slurry containing ammonium sulfate solids obtained in the step (2) is conveyed to the ammonium sulfate extraction circulation system 600 through the slurry conveying pump, and sequentially passes through the slurry thickener, the centrifuge, the dryer and the packaging machine to obtain an ammonium sulfate product; and the clear liquid of the slurry densifier and the mother liquid of the centrifuge flow back to the crystallization pool section 120, and are concentrated and crystallized.
The desulfurization method also comprises a flue gas ultra-clean dedusting step, wherein the desulfurized flue gas obtained in the step (4) enters the electric demister 400, and is subjected to high-voltage discharge treatment to remove superfine acid mist particles in the flue gas, so that the dust content in the purified flue gas is reduced to 3.8mg/Nm3And then discharged through the stack 500.
By adopting the high-sulfur flue gas ammonia desulphurization system and method, the outlet flue gas SO can be realized2The content is 27.5mg/Nm3Dust content 3.8mg/Nm3The yield of the emission target of (1) is 13.68 tons/hr of ammonium sulfate, the annual operation is calculated according to 8400 hours, and the annual output of the ammonium sulfate is 11.49 ten thousand tons.
Example 5
The production capacity of a carbon plant is 20 ten thousand tons per year of carbon, high-sulfur petroleum coke is used as a raw material, and the flue gas flow is 50 ten thousand Nm3Hr, flue gas sulfur content of 8000mg/Nm3The temperature of the flue gas is 160 ℃, and the method adopts the following chartThe high-sulfur flue gas ammonia desulfurization system shown in 1 takes ammonia as a desulfurizer and is assisted by water and air, and comprises three circulating systems: the first circulation system is a cooling, concentrating and crystallizing system 100, the second circulation system is a main absorption and oxidation system 200, the third circulation system is an auxiliary absorption and oxidation system 300, and the three circulation systems are respectively and independently arranged.
The main absorption oxidation system 200 comprises a cylindrical main absorption section 210 and a main oxidation section 220, wherein the main absorption section 210 comprises a main absorption liquid spraying layer 211 inside, the main oxidation section 220 comprises a main air aerator 221 inside, the outside of the main oxidation section 220 and the outside of the main absorption section 210 are connected with a main absorption liquid circulating pump 250 through an absorption liquid circulating pipeline 240, the main oxidation section 220 is connected with an air input pipe, and the main oxidation section 220 is also connected with an input pipe of raw material ammonia;
the auxiliary absorption oxidation system 300 comprises a cylindrical auxiliary absorption section 310 and an auxiliary oxidation section 320, wherein an auxiliary absorption liquid spraying layer 311 is arranged in the auxiliary absorption section 310, an auxiliary air aerator 321 is arranged in the auxiliary oxidation section 220, the outside of the auxiliary oxidation section 320 and the outside of the auxiliary absorption section 310 are connected with an auxiliary absorption liquid circulating pump 350 through an auxiliary absorption liquid circulating pipeline 340, the auxiliary oxidation section 320 is connected with an air input pipe, and the auxiliary oxidation section 320 is also connected with an input pipe of raw material ammonia;
the cooling concentration crystallization system 100 comprises a cylindrical cooling concentration section 110 and a crystallization tank section 120, the inside of the cooling concentration section 110 comprises a slurry spraying layer 111, the inside of the crystallization tank section 120 comprises a stirrer 121, the outside of the crystallization tank section 120 and the outside of the cooling concentration section 110 are connected with a slurry circulating pump 150 through a slurry circulating pipeline 140, and an inlet 130 of high-sulfur flue gas is arranged between the cooling concentration section 110 and the crystallization tank section 120.
The system further comprises an ammonium sulfate extraction circulating system 600, the ammonium sulfate extraction system 600 comprises a slurry thickener, a centrifugal machine, a drying machine and a packaging machine, the crystallization tank section 120 is connected with the slurry thickener of the ammonium sulfate extraction system 600 through a discharge circulating pump 610, a thick liquid port of the slurry thickener is connected with the centrifugal machine, a solid discharge port of the centrifugal machine is connected with the drying machine, a solid discharge port of the drying machine is connected with the packaging machine, and a clear liquid port of the slurry thickener and a mother liquid discharge port of the centrifugal machine are connected with the crystallization tank section 120.
The system further comprises an electric demister 400, wherein the electric demister 400 comprises a discharge cathode wire and a dust collection anode tube, the anode tube is made of glass fiber reinforced plastic added with carbon fibers, and the electric demister 400 is connected between the auxiliary absorption oxidation system 300 and the chimney 500.
The high-sulfur flue gas sequentially enters a cooling, concentrating and crystallizing system 100, a main absorption and oxidation system 200 and an auxiliary absorption and oxidation system 300, process water sequentially enters the auxiliary absorption and oxidation system 300, the main absorption and oxidation system 200 and the cooling, concentrating and crystallizing system 100, and ammonia and air simultaneously enter the main absorption and oxidation system 200 and the auxiliary absorption and oxidation system 300; the high-sulfur flue gas is sequentially subjected to three circulating systems of cooling, concentration and crystallization, main absorption and oxidation and auxiliary absorption and oxidation to realize SO2The high-efficiency removal and the reduction of ammonia escape and smoke-exhaust aerosol pollution, the specific application of the system for high-sulfur flue gas ammonia desulphurization comprises the following steps:
(1) cooling and pre-washing flue gas: raw material high-sulfur flue gas enters a flue gas inlet 130 of the cooling concentration crystallization system 100, flows upwards, contacts with ammonium sulfate slurry sprayed from the slurry spraying layer 111, transfers heat and mass, reduces the temperature of the flue gas, increases the humidity, and washes dust and strong acid gas in the flue gas to enter the slurry;
(2) ammonium sulfate crystallization: the ammonium sulfate slurry flows through the slurry circulating pipeline 140 in the crystallization tank section 120 through the slurry circulating pump 150, is circularly conveyed to the slurry spraying layer 111, is changed into liquid drops through an atomizing nozzle of the spraying layer 110, flows downwards, is in countercurrent contact with high-temperature hot flue gas, transfers heat and mass, is concentrated to enable the concentration of ammonium sulfate in the slurry to exceed the solubility, and further crystallizes and separates out crystal ammonium sulfate to obtain slurry containing ammonium sulfate solids, wherein the ammonium sulfate content of the slurry is 60%, and the pH value of the slurry is 4.0;
(3) flue gas main desulfurization: the flue gas obtained from the step (1) leaves the temperature reduction concentration section 110 and enters the main absorption section 210 of the main absorption oxidation system 200, flows upwards, and is in countercurrent contact with liquid drops sprayed from the main absorption liquid spraying layer 211 for mass transferAbsorption of SO2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the main oxidation section 220, the air blown in by the main air aerator 221 is oxidized into ammonium sulfate, simultaneously, a desulfurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the main absorption liquid spraying layer 211 by the main absorption liquid circulating pump 250 through the main absorption liquid circulating pipeline 240 to be continuously desulfurized, wherein the content of ammonium sulfate in the absorption liquid is 30%, the pH value is 5.0, and the desulfurization efficiency of the main absorption oxidation system is 94%;
(4) and (3) auxiliary desulfurization of flue gas: the flue gas obtained from the step (3) leaves the main absorption section 210, enters the auxiliary absorption section 310 of the auxiliary absorption oxidation system 300, flows upwards, and is in countercurrent contact with liquid drops sprayed from the auxiliary absorption liquid spraying layer 311, SO as to carry out mass transfer absorption on SO2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the auxiliary oxidation section 320, the air blown by the auxiliary air aerator 321 is oxidized into ammonium sulfate, simultaneously, desulphurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to the auxiliary absorption liquid spraying layer 311 by the auxiliary absorption liquid circulating pump 340 through the auxiliary absorption liquid circulating pipeline 330 for continuous desulphurization, wherein the ammonium sulfate content in the absorption liquid is 8%, and the pH value is 4.0; after passing through the auxiliary absorption oxidation system 300, SO in the flue gas2The content is 40.0mg/Nm3The dust content is 20mg/Nm3The following;
(5) water balance control: controlling the liquid levels of the crystallization tank section 120, the main oxidation section 220 and the auxiliary oxidation section 320 to maintain the water balance of the high-sulfur flue gas ammonia desulfurization system; the liquid level of the crystallization tank section 120 is controlled by adjusting the flow rate of the ammonium sulfate solution conveyed by the main oxidation section 220 through the liquid pipeline 21 and the flushing pump 22; the liquid level of the main oxidation section 220 is controlled by the flow regulation of the ammonium sulfate solution conveyed to the main absorption oxidation system 200 by the auxiliary oxidation section 320; the liquid level of the secondary oxidation stage 320 is controlled by the flow regulation of the process water fed to the secondary oxidation stage 320;
(6) ammonium sulfate extraction: the ammonium sulfate slurry containing ammonium sulfate solids obtained in the step (2) is conveyed to the ammonium sulfate extraction circulation system 600 through the slurry conveying pump, and sequentially passes through the slurry thickener, the centrifuge, the dryer and the packaging machine to obtain an ammonium sulfate product; and the clear liquid of the slurry thickener and the mother liquid of the centrifuge flow back to the crystallization pool section 120, and are concentrated and crystallized.
The desulfurization method also comprises a flue gas ultra-clean dedusting step, wherein the desulfurized flue gas obtained in the step 4 enters the electric demister 400, and is subjected to high-pressure discharge treatment to remove ultrafine acid mist particles in the flue gas, so that the dust content in the purified flue gas is reduced to 8.5mg/Nm3And then discharged through the stack 500.
By adopting the system and the method of the invention, the outlet flue gas SO can be realized2The content is 40.0mg/Nm3Dust content 8.5mg/Nm3The yield of the emission target of (1) is 8.29 tons/hr of ammonium sulfate, the annual operation is calculated according to 8400 hours, and the annual output of the ammonium sulfate is 6.965 ten thousand tons.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims (3)

1. The ammonia desulphurization method of the high-sulfur flue gas is characterized by comprising the following steps of:
(1) cooling and pre-washing flue gas: the high-sulfur flue gas enters a flue gas inlet (130) of a cooling concentration crystallization system (100), flows upwards, is contacted with ammonium sulfate slurry sprayed by a slurry spraying layer (111), and has mass and heat transfer, the temperature of the high-sulfur flue gas is reduced, the humidity of the high-sulfur flue gas is increased, and dust and strong acid gas in the high-sulfur flue gas are washed and enter the slurry;
(2) ammonium sulfate crystallization: ammonium sulfate slurry flows through a slurry circulating pipeline (140) in a crystallization tank section (120) through a slurry circulating pump (150), is circularly conveyed to a slurry spraying layer (111), is changed into liquid drops through an atomizing nozzle of the slurry spraying layer (111), flows downwards, is in countercurrent contact with high-temperature hot flue gas, conducts heat and mass, is concentrated to enable the concentration of ammonium sulfate in the slurry to exceed the solubility, and further is crystallized to separate out crystal ammonium sulfate to obtain slurry containing ammonium sulfate solid, wherein the ammonium sulfate content of the slurry is not less than 50%, and the pH value is not less than 4.5;
(3) flue gas main desulfurization: the flue gas obtained from the step (1) leaves the temperature reduction concentration section (110) and enters a main absorption section (210) of a main absorption oxidation system (200), flows upwards, and is in countercurrent contact with liquid drops sprayed from a main absorption liquid spraying layer (211) to absorb SO by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to the main oxidation section (220), air blown by a main air aerator (221) is oxidized into ammonium sulfate, simultaneously, desulfurization raw material ammonia is added to maintain the pH value of the absorption liquid, and the absorption liquid is circularly conveyed to a main absorption liquid spraying layer (211) by a main absorption liquid circulating pump (250) through a main absorption liquid circulating pipeline (240) to be continuously desulfurized, wherein the content of ammonium sulfate in the absorption liquid is between 15 and 45 percent, the pH value is less than or equal to 6.0, and the desulfurization efficiency of the main absorption oxidation system is more than 90 percent;
(4) and (3) auxiliary desulfurization of flue gas: the flue gas obtained from the step (3) leaves the main absorption section (210) and enters the auxiliary absorption section (310) of the auxiliary absorption oxidation system (300) to flow upwards and contact with liquid drops sprayed from the auxiliary absorption liquid spraying layer (311) in a countercurrent manner, SO is absorbed by mass transfer2To obtain ammonium sulfite which enters absorption liquid; the absorption liquid flows back to an auxiliary oxidation section (320), air blown by an auxiliary air aerator (321) is oxidized into ammonium sulfate, simultaneously, desulfurization raw material ammonia is added, the pH value of the absorption liquid is maintained, and the absorption liquid is circularly conveyed to an auxiliary absorption liquid spraying layer (311) by an auxiliary absorption liquid circulating pump (350) through an auxiliary absorption liquid circulating pipeline (340), so that continuous desulfurization is carried out, wherein the content of ammonium sulfate in the absorption liquid is less than or equal to 10%, and the pH value is less than or equal to 5.5; SO in the flue gas passes through the auxiliary absorption oxidation system (300)2Content ≦ 100mg/Nm3Dust content ≦ 30mg/Nm3(ii) a The desulfurized flue gas obtained in the step (4) enters an electric demister (400), and superfine acid mist particles in the flue gas are removed through high-voltage discharge treatment, so that the dust content in the purified flue gas is less than or equal to 10mg/Nm3Then discharged through a chimney (500);
(5) water balance control: controlling the liquid levels of the crystallization tank section (120), the main oxidation section (220) and the auxiliary oxidation section (320) to maintain the water balance of the high-sulfur flue gas ammonia desulphurization system; the liquid level of the crystallization tank section (120) is controlled by the flow regulation of the ammonium sulfate solution conveyed by the main oxidation section (220) through a liquid pipeline (21) and a flushing pump (22); the liquid level of the main oxidation section (220) is controlled by the flow regulation of the ammonium sulfate solution conveyed to the main absorption oxidation system (200) by the auxiliary oxidation section (320); the liquid level of the secondary oxidation section (320) is controlled by the flow regulation of the process water fed to the secondary oxidation section (320);
(6) ammonium sulfate extraction: sending the slurry containing ammonium sulfate solids obtained in the step (2) to an ammonium sulfate extraction circulating system (600) through a discharge circulating pump (610), and sequentially passing through a slurry thickener, a centrifuge, a dryer and a packaging machine to obtain an ammonium sulfate product; the clear liquid of the slurry thickener and the mother liquid of the centrifuge return to the crystallization pool section (120) and are concentrated and crystallized again.
2. The method for ammonia desulphurization of high sulfur flue gas according to claim 1, wherein the pH values of the ammonium sulfate solutions in the crystallization pond section (120), the main oxidation section (220) and the auxiliary oxidation section (320) are between 3.5-4.5, 5.2-6.0 and 4.0-6.0, respectively.
3. The method for ammonia desulfurization of high sulfur flue gas according to claim 1, wherein the cleaned flue gas is discharged via the stack (500), SO2Content ≦ 35mg/Nm3Dust content ≦ 5mg/Nm3
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