CN113694695A - Integrated process for desulfurization and oxidation of waste gas - Google Patents
Integrated process for desulfurization and oxidation of waste gas Download PDFInfo
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Abstract
The invention discloses a waste gas desulfurization and oxidation integrated process, which is characterized in that pretreated waste gas and sulfur dioxide absorption liquid are simultaneously fed into a microporous membrane device, and are synchronously oxidized during desulfurization to generate by-product sulfate, and the temperature of the waste gas to be treated is reduced to 20-60 ℃; simultaneously feeding waste gas with the pressure of 0-100 kpa and absorption liquid with the pressure of 0-100 kpa into a microporous membrane device according to the gas-liquid flow ratio of 10: 1-5000: 1, wherein the gas pressure is not greater than the liquid pressure, and the pressure of the absorption liquid is not greater than the bubble point pressure of the membrane; the waste gas and the absorption liquid are desulfurized and synchronously oxidized in a microporous membrane device by taking a membrane as a contact interface; the treated waste gas reaches the standard and is discharged, and the absorption liquid is circularly absorbed; when the mass concentration of the sulfate in the absorption liquid reaches the standard, partial absorption liquid is discharged outside for resource treatment, the desulfurization effect is efficient and reliable, no waste liquid is discharged, and meanwhile, a high-purity sulfate byproduct can be obtained, so that the method has good economic benefit and environmental benefit.
Description
Technical Field
The patent relates to an atmospheric pollution control method, in particular to a method for removing sulfur dioxide in waste gas and tail gas of coal-fired flue gas, coal chemical industry, coking, petroleum, smelting, steel, cement, glass and the like.
Background
Sulfur dioxide is the most common irritant sulfur oxide and is one of the major atmospheric pollutants. Many industrial processes produce sulfur dioxide, such as coal fired power plants, coal chemical, coking, petroleum, smelting, steel, cement, glass, and the like. Since coal and petroleum generally contain elemental sulfur, sulfur dioxide is produced during combustion, and when dissolved in water, sulfurous acid is formed, and if further oxidized, sulfuric acid, the main component of acid rain, is produced. The national cancer research organization of the world health organization publishes a carcinogen list for preliminary reference arrangement, and sulfur dioxide is in a category 3 carcinogen list.
At present, technologies such as limestone-gypsum desulfurization and ammonia desulfurization are mainly adopted to remove sulfur dioxide in waste gas, and the method has the advantages of wide range of applicable coal types, high desulfurization efficiency, high utilization rate of an absorbent, high equipment operation rate, high working reliability, rich and cheap sources of a desulfurizing agent, namely limestone and ammonia water, and the like. But the method has the problems of step desulfurization and oxidation, low oxidation efficiency or additional addition of an oxidation device and the like.
Patent documents with publication number CN110368816A, published as 2019, 10 and 25 disclose "a method and an apparatus for oxidizing ammonia desulfurization solution", in which an ammonia desulfurization absorption liquid is subjected to oxidation treatment in an oxidation tower, the absorption liquid is conveyed from the ammonia desulfurization absorption tower to the oxidation tower, and the oxidation liquid is conveyed from the oxidation tower to the ammonia desulfurization absorption tower; and in the oxidation process in the oxidation tower, pressurized air is used as oxidation air, and multistage air distribution is adopted to perform forced oxidation on the absorption liquid. Doing so increases equipment investment and operating costs: adding an oxidation device and an oxidation tower; and adding an air pressurizing device additionally to supplement pressurized air.
Publication No. CN103588238A, published as 2014, 2.19 discloses an oxidizing air distributor for calcium desulphurization, which provides an oxidizing air distributor for calcium desulphurization, comprising a main air supply pipe, a plurality of branch air supply pipes and a connecting pipe; the uniform distributor enables the air flow and the air pressure of each air jet hole to be more uniform and stable, thereby improving the oxidation effect of calcium sulfite and the utilization rate of oxidation air. This also adds additional oxidation equipment and components.
The membrane desulfurization technology is a technical method which takes a membrane absorber or a membrane absorption tower as an operation unit, utilizes the porous structure of a membrane material to carry out interface isolation on flue gas and absorption liquid, and simultaneously utilizes the gas concentration difference and acid-base neutralization reaction at two sides of the membrane as driving forces to realize the effect of absorbing and removing target components in the flue gas. Compared with the direct contact absorption mode, the membrane absorption for flue gas desulfurization has the following technical advantages: firstly, the membrane material can provide a huge effective contact interface for the flue gas and the absorption liquid, and is beneficial to the full mass transfer of gas-liquid two phases; secondly, the gas phase and the liquid phase are not in direct contact, so that the independent operation and control of the two phases are realized; the absorption liquid does not directly contact with the flue gas, so that the desulfurization by-product with stable quality and high purity can be obtained; and fourthly, according to the actual working condition requirements, different absorption liquids can be replaced for desulfurization.
The patent document with application publication number CN102485320A and publication date of 2012, 6 and 6 discloses a seawater flue gas desulfurization device and process by using a membrane absorption method, wherein seawater is used as an absorbent, gas-liquid two phases form a reaction interface at micropores of a hollow fiber membrane, and SO in flue gas2Reacts with seawater to generate sulfite which is taken away in time, thereby realizing flue gas desulfurization. The process can reduce or avoid the problem of equipment corrosion caused by the entrainment of a large amount of water vapor in the flue gas by the traditional seawater method.
A paper "membrane absorption method seawater flue gas desulfurization pilot-scale research" written by Guanyipeng et al is published in journal of 'membrane science and technology' of No. 5, volume 33, 2013, and the paper indicates that the membrane absorption is a non-direct contact mode, the desulfurization rate can be kept above 90% for a long time, and heavy metals in the flue gas are not in direct contact with seawater, so that heavy metal pollution of absorption liquid can be avoided. Therefore, the impurities in the flue gas can be prevented from entering one side of the absorption liquid by membrane absorption, so that the purity of the absorption liquid is ensured, and the quality of the desulfurization by-product is guaranteed.
Disclosure of Invention
Aiming at the prior art, the invention provides a waste gas desulfurization and oxidation integrated process, which can ensure that sulfur-containing waste gas and high-sulfur-containing waste gas reach the ultralow emission standard after desulfurization, and the adopted absorption liquid can realize 100 percent recovery, prepare high-purity ammonium sulfate salt and realize resource utilization; meanwhile, the desulfurization and the oxidation can be synchronously realized in one set of device, and no oxidation device, part or medicament is required to be additionally arranged or added.
In order to solve the technical problems, the integrated process for desulfurization and oxidation of the waste gas provided by the invention simultaneously feeds the pretreated waste gas and sulfur dioxide absorption liquid into a microporous membrane device, and synchronously oxidizes the waste gas and the sulfur dioxide absorption liquid to generate a byproduct sulfate during desulfurization, and comprises the following steps:
firstly, waste gas pretreatment: reducing the temperature of the waste gas to be treated to 20-60 ℃;
then, integrating desulfurization and oxidation: simultaneously feeding waste gas with pressure of 0-100 kpa and absorption liquid with pressure of 0-100 kpa into a microporous membrane device according to the flow ratio of the waste gas to the absorption liquid of 10: 1-5000: 1, wherein the gas pressure is not more than the liquid pressure, and the pressure of the absorption liquid is not more than the bubble point pressure of the membrane; the waste gas and the absorption liquid are desulfurized and synchronously oxidized in a microporous membrane device by taking a membrane as a contact interface; the treated waste gas reaches the standard and is discharged, and the absorption liquid is circularly absorbed;
while the desulfurization and the oxidation are integrated, the absorption process of the absorption liquid is as follows: and adding alkali liquor into the absorption liquid according to the desulfurization requirement, realizing continuous absorption of the waste gas sulfur dioxide by adjusting the adding amount of the alkali liquor, and discharging part of the absorption liquid for recycling treatment after the mass concentration of the sulfate in the absorption liquid reaches the standard.
In the integrated process for desulfurization and oxidation of waste gas, the adopted microporous membrane device is a hydrophobic membrane device, and the microporous membrane device is selected from one of the following devices: a tubular membrane unit, a column membrane unit, a curtain membrane unit and a tower membrane unit.
Wherein the material of the membrane is selected from one or more of the following: polyethylene film, polypropylene film, polyvinylidene fluoride film, polytetrafluoroethylene film, polystyrene film, ceramic film;
the membrane is a hydrophobic membrane, a hydrophobic modified membrane, a super-hydrophobic modified membrane or a super-hydrophobic oleophobic modified membrane; the membrane is in the form of a hollow fiber membrane, a flat sheet membrane or a tubular membrane; the structure of the membrane is a porous membrane, a composite membrane or a compact membrane; the porosity of the membrane is 10-90%
The absorption liquid is selected from one or more of the following solutions: water, seawater, concentrated seawater, sodium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia water, ammonium sulfite, ammonium bisulfite, ammonium sulfate, ammonium bisulfate. As for the concentration of each solution and when it is a plurality of solutions, the ratio or concentration relationship between each other is not limited.
The temperature of the absorption liquid is 20-60 ℃.
In the invention, the smoke content in the waste gas to be treated is higher than 100mg/m3Performing dust removal treatment on the waste gas, and controlling the content of smoke dust to be not more than 100mg/m3. In the waste gas to be treated: the mass volume concentration of the sulfur dioxide is 0-100000 mg/m3The smoke content is not more than 100mg/m3The volume percentage of the oxygen is not less than 0.5 percent, and the mol ratio of the oxygen to the sulfur dioxide is not less than 1: 2. The content of sulfur dioxide in the waste gas treated in the second step is 0-35 mg/m3。
Compared with the prior art, the invention has the beneficial effects that:
(1) the desulfurization and the sulfite oxidation are integrated, and an oxidation device, a part, a pipeline or a medicament does not need to be additionally or additionally added, so that the investment and the operation cost are reduced;
(2) the sulfur dioxide is removed by adopting a hydrophobic membrane and a device, and the sulfite in the absorption liquid can be oxidized into sulfate by utilizing the specific porous structure and the huge gas-liquid contact area of the hydrophobic membrane and the oxygen stored in the waste gas under the condition of proper working conditions during the process operation.
(3) The concentration of the treated waste gas can reach 100000mg/m3The method has universality for waste gases with different sulfur-containing concentrations.
(4) After desulfurization treatment, the concentration of sulfur dioxide at the outlet can realize ultralow discharge and even zero discharge, and the actually measured concentration of sulfur dioxide at the outlet is 0-35 mg/m3；
(5) Impurities in the waste gas cannot enter the absorption liquid, and the sulfate byproduct has high purity and accords with the circular economy concept;
(6) the absorption liquid is circularly absorbed, the used absorption liquid is small in amount, no wastewater is discharged in the whole process, and the environment is protected;
(7) when ammonia water is used as the absorption liquid, the concentration of the outlet ammonia is 0-35 mg/m3。
Drawings
FIG. 1 is a flow chart of the integrated process based on desulfurization and oxidation of exhaust gas according to the present invention;
FIG. 2-1 is a schematic view of a membrane unit configuration employed in the treatment process of the present invention;
fig. 2-2 are schematic views of alternative membrane arrangements for use in the treatment process of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
The invention provides a waste gas desulfurization and oxidation integrated process, which mainly comprises the following steps: the waste gas pretreatment, desulfurization and oxidation are integrated and the absorption process is adopted, the process is adopted for desulfurization and oxidation of the waste gas, and the mass volume concentration of sulfur dioxide in the waste gas to be treated can reach 100000mg/m3If the content of smoke dust in the waste gas to be treated exceeds 100mg/m3The waste gas is dedusted in advance, and the smoke content is controlled to be not more than 100mg/m3(ii) a In addition, the volume percentage of oxygen in the waste gas to be treated is not less than 0.5 percent, and meanwhile, the molar ratio of the oxygen to sulfur dioxide is not less than 1: 2; and simultaneously feeding the pretreated waste gas and the sulfur dioxide absorption liquid into a microporous membrane device, wherein the sulfur dioxide is absorbed by the absorption liquid through micropores of the membrane, and the generated sulfite is simultaneously oxidized into sulfate by oxygen in the waste gas. In the integrated desulfurization and oxidation process, the sulfur dioxide absorption solution is selected from one or more of the following solutions: water,Seawater, concentrated seawater, sodium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia water, ammonium sulfite, ammonium bisulfite, ammonium sulfate, ammonium bisulfate, etc.; the absorption liquid is unsaturated, and the temperature is 20-60 ℃. The absorption liquid and the pretreated waste gas are simultaneously fed into a microporous membrane device, the absorption liquid and the pretreated waste gas are simultaneously oxidized during desulfurization, a byproduct sulfate is generated, and the concentration of sulfur dioxide in the treated waste gas can reach the ultra-low emission standard (0-35 mg/m)3) And the absorption liquid is recovered to an absorption liquid collecting tank, and finally, a high-purity sulfate byproduct can be obtained through an absorption process. The process of the invention is adopted to treat the waste gas, the desulfurization effect is efficient and reliable, no waste liquid is discharged, and meanwhile, high-quality byproducts are obtained, thus having good economic benefit and environmental benefit.
As shown in FIG. 1, the process of the invention comprises the following specific steps:
firstly, exhaust gas pretreatment is carried out: reducing the temperature of the waste gas to be treated to 20-60 ℃, if the content of smoke dust in the waste gas to be treated is higher than 100mg/m3Firstly, the waste gas is dedusted, and the content of smoke dust in the waste gas is controlled not to exceed 100mg/m3The cooling of the exhaust gas can be carried out by the following methods: spraying direct cooling, cooling by a heat exchanger, cooling by cold air directly, and collecting condensate generated in the cooling process to an absorption liquid collecting tank.
Then, integrating desulfurization and oxidation: simultaneously feeding waste gas with the pressure of 0-100 kpa and absorption liquid with the pressure of 10-100 kpa into a membrane device according to the flow ratio of the waste gas to the absorption liquid of 10: 1-5000: 1, wherein the pressure of the absorption liquid is not lower than the gas pressure but not higher than the bubble point pressure of the membrane; the waste gas and the absorption liquid are desulfurized and oxidized in the membrane device by taking the membrane as a contact interface. The membrane device is a hydrophobic membrane device and can be a tubular membrane device, a column type membrane device, a curtain type membrane device, a tower type membrane device and the like. The membrane is a hydrophobic membrane selected from one or more of the following: polyethylene films, polypropylene films, polyvinylidene fluoride films, polytetrafluoroethylene films, polystyrene films, ceramic films and the like, particularly hydrophobic modified, super-hydrophobic modified or super-hydrophobic oleophobic modified films; the membrane form can be a hollow fiber membrane, a flat membrane or a tubular membrane; the membrane structure is a porous membrane, a composite membrane or a compact membrane; the porosity of the film is 10-90%. The absorption liquid can be one or more of water, seawater, concentrated seawater, sodium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia water, ammonium sulfite, ammonium bisulfite, ammonium sulfate or ammonium bisulfate, and the like, taking ammonia water as an example, the chemical reaction generated in the process is as follows:
(NH4)2SO3+SO2+O2+H2O＝2NH4HSO4
the content range of sulfur dioxide in the waste gas treated in the second step is 0-35 mg/m3And the treated waste gas reaches the standard and is discharged, and the absorption liquid is recovered to an absorption liquid collecting tank.
While the desulfurization and the oxidation are integrated, the absorption process of the absorption liquid is as follows: and adding alkali liquor into the absorption liquid according to the desulfurization requirement, realizing continuous absorption of the waste gas sulfur dioxide by adjusting the adding amount of the alkali liquor, and discharging part of the absorption liquid for recycling treatment after the mass concentration of the sulfate in the absorption liquid reaches the standard. Taking the example of adding ammonia water, the chemical reaction is as follows:
SO2+NH3+H2O＝NH4HSO3
SO2+2NH3+H2O＝(NH4)2SO3
NH4HSO3+NH3＝(NH4)2SO3
(NH4)2SO3+O2＝(NH4)2SO4
2NH4HSO3+O2＝2NH4HSO4
NH4HSO4+NH3＝(NH4)2SO4
the absorption liquid with a certain concentration meets the requirement of emission concentration index, and is discharged for resource crystallization treatment to obtain a high-purity byproduct ammonium sulfate.
In the invention, the membrane and the membrane device can adopt a novel low-air-resistance box-type gas-liquid contact membrane absorption unit disclosed in patent document No. 201020641559.X, the basic structure of the membrane and the membrane device is shown in figure 2-1 and comprises a plurality of sheet curtain type hydrophobic hollow fiber membrane elements, a membrane cleaning component and a box body, wherein the curtain type membrane elements are uniformly distributed in the box body at a certain membrane filling density and form a grid-shaped network structure along the gas phase flowing direction so as to ensure that the gas phase uniformly flows through the outer surface of the hollow fiber membrane along the direction vertical to the hollow fiber membrane axis. The formed membrane absorption device has low air resistance, large flow of treated gas and high efficiency; the gas phase and the liquid phase are uniformly distributed, the effective contact area is large, and the mass transfer rate is high; the gas-liquid two-phase flow rate is independently controlled, and the operation can be carried out in a wider range.
The membrane absorption device can also adopt a novel high-efficiency single-stage or multi-stage tank type gas-liquid contact membrane absorption unit disclosed in patent document with the patent number of 201020641558.5, the basic structure of which is shown in figure 2-2 and comprises a plurality of groups of column type hydrophobic hollow fiber membrane elements, a tank type shell and a membrane cleaning part horizontally arranged in the tank type shell; the hollow fiber membranes in each group of the column-type hydrophobic hollow fiber membrane elements are woven by yarns and then rolled into a column shape, the two ends of the hollow fiber membranes are sealed and cast, each group of the column-type hydrophobic hollow fiber membrane elements are relatively independent, and the upper ends and the lower ends of a plurality of groups of the column-type hydrophobic hollow fiber membrane elements are provided with guide supports or support structures of the column-type hydrophobic hollow fiber membrane elements; the membrane cleaning component comprises a plurality of cleaning pipes, a plurality of nozzles are arranged on the pipe walls of the cleaning pipes, and the cleaning pipes are integrally connected to the water supply pipe. The gas phase flows back and forth freely from the pipe wall hole of the central pipe, the gas resistance is low, the flow of the treated gas is large, and the efficiency is high; the column type membrane elements are uniformly distributed in the tank type shell at a certain filling density; the gas phase and the liquid phase are uniformly distributed, the effective contact area is large, and the mass transfer rate is high; the gas-liquid two-phase flow rate is independently controlled, and the operation can be carried out in a wider range.
The desulfurization waste gas comprises at least one of coal-fired flue gas, coal chemical industry, coking, petroleum, smelting, steel, cement, glass, brick kiln and other sulfur-containing waste gases, wherein sulfide is mainly sulfur dioxide; the following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claimed invention.
Example 1:
the example of the embodiment is to treat sulfur-containing waste gas of a coal-fired power plant, the temperature of the sulfur-containing waste gas is 160 ℃, and the flow rate of the sulfur-containing waste gas is 20000m3H, pressure of 3kpa, and sulfur dioxide concentration of 800-3000 mg/m3And the oxygen content is 6.6-7.5%. The waste gas desulfurization process of the present invention as shown in fig. 1 is adopted, and the process is as follows:
step one, waste gas pretreatment: cooling the sulfur-containing waste gas with the temperature of 160 ℃ to 40 ℃ through a quenching tower;
step two, integration of desulfurization and oxidation: desulfurizing the sulfur-containing waste gas with the temperature reduced by using the membrane absorption device shown in FIG. 2-1 at a flow rate of 20000m3And h, the pressure is 3kpa, the sulfur dioxide enters the membrane absorption device, and the sulfur dioxide concentration is detected at the inlet and outlet positions of the membrane absorption device simultaneously. Starting an absorption liquid pump, feeding waste gas into a membrane device, feeding the absorption liquid into the membrane absorption device, wherein an absorption liquid collecting tank contains 3000L of absorption liquid, wherein the weight percentage of ammonium sulfite is 0.5 percent, the weight percentage of ammonium sulfate is 16 percent, the temperature is 40 ℃, and the flow of the absorption liquid entering the membrane absorption device is 60m3The pressure is 25kpa, the gas-liquid ratio is 333:1, and the concentration of sulfur dioxide in the desulfurized waste gas is 35mg/m3The ammonia escape concentration in the exhaust gas is 0.52mg/m3。
Step three, an absorption process: and (4) refluxing the desulfurized absorption liquid to an absorption liquid collecting tank through a pipeline, and adding ammonia water into the reflux pipeline by using a metering pump for 50L/h. Discharging 50L/h of absorption liquid from the absorption liquid collecting tank by using a liquid discharge pump, and performing evaporative crystallization and resource treatment through a pipeline to obtain a byproduct ammonium sulfate with the purity of 21.2%.
Example 2:
in this embodiment, the sulfur-containing waste gas of a certain coking plant is treated, the temperature of the sulfur-containing waste gas is 160 ℃, and the flow rate is 100m3The pressure is 10kpa, the concentration of sulfur dioxide is 300-800 mg/m3And 4.5% of oxygen. The waste gas desulfurization process of the present invention as shown in fig. 1 is adopted, and the process is as follows:
step one, waste gas pretreatment: cooling the sulfur-containing waste gas with the temperature of 160 ℃ to 60 ℃ by a quenching tower;
step two, integration of desulfurization and oxidation: the membrane absorption device shown in figure 2-1 is adopted for desulfurization treatment, and the flow rate of the cooled waste gas is 100m3And/h, the pressure is 10kpa, the sulfur dioxide enters the membrane absorption device, and the sulfur dioxide concentration is detected at the inlet and outlet positions of the membrane absorption device simultaneously. Starting an absorption liquid pump, feeding waste gas into a membrane absorption device, feeding the absorption liquid into the membrane absorption device, wherein an absorption liquid collection tank contains 200L of absorption liquid, wherein the weight percentage of ammonium sulfite is 3.5 percent, the weight percentage of ammonium sulfate is 25 percent, the temperature is 40 ℃, and the flow of the absorption liquid entering the membrane absorption device is 1m3The pressure is 25kpa, the gas-liquid ratio is 100:1, and the concentration of sulfur dioxide in the desulfurized waste gas is 13mg/m3The escape concentration of ammonia in the waste gas is 2.2mg/m3。
Step three, an absorption process: and (3) refluxing the desulfurized absorption liquid to the absorption liquid collecting tank through a pipeline, and adding 0.5L/h of ammonia water into the reflux pipeline by using a metering pump. 0.5L/h of absorption liquid is extracted from the absorption liquid collecting tank by a metering pump, and enters evaporation crystallization through a pipeline for recycling treatment to obtain a byproduct ammonium sulfate with the purity of 21.2 percent.
Example 3:
in this example, the sulfur-containing waste gas is treated in a laboratory, the temperature of the sulfur-containing waste gas is 35 ℃, and the flow rate is 30m3H, pressure of 8kpa, sulfur dioxide concentration of 30000mg/m3And the oxygen content is 20.8%. The membrane absorption device shown in the figure 2-2 is adopted for desulfurization treatment, and because the sulfur-containing waste gas is the distribution of sulfur dioxide and air, pretreatment is not needed, and the flow rate of the waste gas is 30m3And h, directly entering the membrane absorption device at the pressure of 8kpa, and simultaneously detecting the concentration of sulfur dioxide at the inlet and outlet positions of the membrane absorption device. Starting an absorption liquid pump, feeding waste gas into a membrane absorption device, feeding the absorption liquid into the membrane absorption device, wherein an absorption liquid collecting tank contains 150L of absorption liquid, wherein the weight percentage of ammonium sulfite is 2.2 percent, the weight percentage of ammonium sulfate is 9 percent, the temperature is 36 ℃, and the flow of the absorption liquid entering the membrane absorption device is 1m3The pressure is 20kpa, the gas-liquid ratio is 30:1, and the concentration of sulfur dioxide in the desulfurized waste gas is 20mg/m3The escape concentration of ammonia in the exhaust gas is 0mg/m3. The absorption liquid after desulfurization flows back to the absorption liquid collecting tank through a pipeline,and 0.1L/h of ammonia water is added into the reflux pipeline by a metering pump. And discharging 0.1L/h of absorption liquid from the absorption liquid collecting tank by using a liquid discharge pump, and performing resource treatment to obtain a by-product ammonium sulfate with the purity of 21.0%.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (8)
1. An integrated process for desulfurization and oxidation of waste gas is characterized in that: simultaneously sending the pretreated waste gas and sulfur dioxide absorption liquid into a microporous membrane device, and synchronously oxidizing while desulfurizing to generate a byproduct sulfate, wherein the method comprises the following steps:
firstly, waste gas pretreatment: reducing the temperature of the waste gas to be treated to 20-60 ℃;
then, integrating desulfurization and oxidation: simultaneously feeding waste gas with pressure of 0-100 kpa and absorption liquid with pressure of 0-100 kpa into a microporous membrane device according to the flow ratio of the waste gas to the absorption liquid of 10: 1-5000: 1, wherein the gas pressure is not more than the liquid pressure, and the pressure of the absorption liquid is not more than the bubble point pressure of the membrane; the waste gas and the absorption liquid are desulfurized and synchronously oxidized in a microporous membrane device by taking a membrane as a contact interface; the treated waste gas reaches the standard and is discharged, and the absorption liquid is circularly absorbed;
while the desulfurization and the oxidation are integrated, the absorption process of the absorption liquid is as follows: and adding alkali liquor into the absorption liquid according to the desulfurization requirement, realizing continuous absorption of the waste gas sulfur dioxide by adjusting the adding amount of the alkali liquor, and discharging part of the absorption liquid for recycling treatment after the mass concentration of the sulfate in the absorption liquid reaches the standard.
2. The integrated desulfurization and oxidation process of claim 1, wherein the microporous membrane device is a hydrophobic membrane device, optionally selected from one of the following: a tubular membrane unit, a column membrane unit, a curtain membrane unit and a tower membrane unit.
3. The integrated desulfurization and oxidation process of claim 2, wherein the membrane is as follows:
the material of the membrane is selected from one or more of the following: polyethylene film, polypropylene film, polyvinylidene fluoride film, polytetrafluoroethylene film, polystyrene film, ceramic film;
the membrane is a hydrophobic membrane, a hydrophobic modified membrane, a super-hydrophobic modified membrane or a super-hydrophobic oleophobic modified membrane;
the membrane is in the form of a hollow fiber membrane, a flat sheet membrane or a tubular membrane;
the structure of the membrane is a porous membrane, a composite membrane or a compact membrane;
the porosity of the membrane is 10-90%.
4. The integrated desulfurization and oxidation process of claim 1, wherein the absorption liquid is selected from one or more of the following solutions:
water, seawater, concentrated seawater, sodium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia water, ammonium sulfite, ammonium bisulfite, ammonium sulfate, ammonium bisulfate.
5. The integrated desulfurization and oxidation process for exhaust gas as claimed in claim 1, wherein the temperature of the absorption liquid is 20-60 ℃.
6. The integrated desulfurization and oxidation process of flue gas according to claim 1, wherein the flue gas to be treated has a soot content higher than 100mg/m3Performing dust removal treatment on the waste gas, and controlling the content of smoke dust to be not more than 100mg/m3。
7. The integrated desulfurization and oxidation process according to claim 1 or 6, wherein: the mass volume concentration of the sulfur dioxide is 0-100000 mg/m3The smoke content is not more than 100mg/m3Volume of oxygen gasThe percentage is not less than 0.5 percent, and the mol ratio of oxygen to sulfur dioxide is not less than 1: 2.
8. The integrated process for desulfurization and oxidation of exhaust gas according to claim 1, wherein the sulfur dioxide content in the exhaust gas treated in the second step is in the range of 0-35 mg/m3。
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