CN111359409A - Anion exchange resin desulfurization and denitrification method - Google Patents
Anion exchange resin desulfurization and denitrification method Download PDFInfo
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- CN111359409A CN111359409A CN202010208088.1A CN202010208088A CN111359409A CN 111359409 A CN111359409 A CN 111359409A CN 202010208088 A CN202010208088 A CN 202010208088A CN 111359409 A CN111359409 A CN 111359409A
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- exchange resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a method for desulfurizing and denitrating anion exchange resin, which comprises the following steps: pretreatment: cooling, dedusting and humidifying the industrial flue gas; and (3) oxidation: carrying out oxidation reaction on the pretreated industrial flue gas and ozone in a gas mixing chamber, so that nitric oxide in the industrial flue gas is oxidized into high-valence nitric oxide and at least part of sulfur dioxide is oxidized into sulfur trioxide; and (3) desulfurization and denitrification: and (3) passing the oxidized flue gas through anion exchange resin, so that sulfur dioxide, sulfur trioxide and high-valence nitrogen oxide in the oxidized flue gas are adsorbed by the anion exchange resin through ion exchange reaction, and gas meeting the emission standard is obtained. The desulfurization and denitrification method disclosed by the invention is applied in engineering, the removal efficiency is high, the raw material cost is low, and no secondary pollution is generated.
Description
Technical Field
The disclosure relates to the technical field of flue gas desulfurization and denitration, and particularly relates to a desulfurization and denitration method of anion exchange resin.
Background
The industrial flue gas refers to flue gas and dust generated by combustion of an industrial boiler. Among the pollutants contained in flue gases, sulfur dioxide (SO)2) Nitrogen Oxide (NO)x) In a large proportion. And sulfur dioxide (SO)2) Nitrogen Oxide (NO)x) Is one of the main pollutants causing air pollution, and effectively controlling sulfur dioxide and nitrogen oxide in industrial flue gas is an environmental protection subject which is not slow at present.
The existing flue gas desulfurization and denitration technology mainly combines the flue gas desulfurization technology and the flue gas denitration technology. The flue gas desulfurization treatment technology can be divided into a dry method, a semi-dry method and a wet method according to different phases of the operation process. The dry desulfurization technology is characterized in that a powdery or granular adsorbent is used for absorbing sulfur dioxide in flue gas to a certain degree, and has the advantages of low investment, low energy consumption, convenient treatment of products and no sewage treatment system, but has low desulfurization rate, slow reaction, low reliability and short service life, and is commonly used by an activated carbon adsorption method, an electron beam radiation method, a charged dry absorbent injection method and a metal oxide desulfurization method; the semi-dry desulfurization treatment technology comprises a spray drying method, a semi-dry semi-wet method, a powder-particle spouted bed and flue jet desulfurization. The by-product (desulfurized ash) of the dry/semi-dry flue gas desulfurization technology is different from the fly ash in physical and chemical properties, so that the fly ash can be only utilized at a low level. The wet flue gas desulfurization technology is a gas-liquid reaction, has high reaction speed and high desulfurization efficiency, is generally higher than 90 percent, has mature technology, wide application range and the like. However, the product is liquid or sludge, which is difficult to treat, the equipment is seriously corroded, the energy consumption is high, and the investment and operation cost is high. The system is complex, the water consumption is large, and the one-time investment is high. The common wet flue gas desulfurization techniques include limestone-gypsum wet process, indirect limestone-gypsum process, lemon absorption process, etc. The limestone-gypsum wet method can regularly discharge high-concentration chloride ion wastewater; the indirect limestone-gypsum method has less secondary pollution and high desulfurization efficiency, but the quality of the produced gypsum product is poorer. The lemon absorption method is suitable for low-concentration sulfur dioxide flue gas, but not suitable for high-concentration sulfur dioxide gas absorption, and the application range is narrow.
The flue gas denitration technology comprises a selective catalytic reduction method and a selective non-catalytic reduction method. The selective catalytic reduction denitration technology is mature and reliable, is widely applied in the world at present, particularly developed countries, but has the disadvantages of large investment of process equipment, need of preheating flue gas, expensive catalyst, short service life and high operation cost. The selective non-catalytic reduction needs to inject flue gas at the higher reaction temperature of 930-1090 ℃, the heating cost of the waste gas is high, and the problems of equipment corrosion and the like exist.
Disclosure of Invention
In order to solve at least one of the above technical problems, the present disclosure provides a desulfurization and denitrification method.
According to one aspect of the disclosure, an anion exchange resin desulfurization and denitrification method comprises the following steps:
pretreatment: cooling, dedusting and humidifying the industrial flue gas;
and (3) oxidation: carrying out oxidation reaction on the pretreated industrial flue gas and ozone in a gas mixing chamber, so that nitric oxide in the industrial flue gas is oxidized into high-valence nitric oxide and at least part of sulfur dioxide is oxidized into sulfur trioxide;
and (3) desulfurization and denitrification: and (3) passing the oxidized flue gas through anion exchange resin, so that sulfur dioxide, sulfur trioxide and high-valence nitrogen oxide in the oxidized flue gas are adsorbed by the anion exchange resin through ion exchange reaction, and gas meeting the emission standard is obtained.
According to at least one embodiment of the present disclosure, further comprising regenerating,
and the regeneration uses a regenerant to regenerate the anion exchange resin treated in the desulfurization and denitrification step.
According to at least one embodiment of the present disclosure, the regenerant is one or more of sodium carbonate, sodium hydroxide.
According to at least one embodiment of the present disclosure, the volume ratio of the regenerant to the anion exchange resin is 1.5 to 4:1, wherein half of the amount of regenerant is used for recovery and the other half of the amount of regenerant is used for reuse.
According to at least one embodiment of the present disclosure, the concentration of the regenerant is 5% to 20%.
According to at least one embodiment of the present disclosure, the spatial flow rate of the regenerant is from 1 to 10m3/h/m3。
According to at least one embodiment of the present disclosure, in the pre-treatment step, the molar ratio of ozone to nitric oxide is 1.2 to 3.
According to at least one embodiment of the present disclosure, in the pre-treatment step, the relative humidity of the humidified flue gas is 50 to 80%.
According to at least one embodiment of the present disclosure, the anion exchange resin contains one of quaternary amine functional groups, secondary amine functional groups, primary amine functional groups, or tertiary amine functional groups.
According to at least one embodiment of the present disclosure, the anion exchange resin has an exchange capacity of 3.0 to 7.0 mmol/g. According to at least one embodiment of the present disclosure, the anion exchange resin comprises a macroporous anion exchange resin.
According to at least one embodiment of the present disclosure, the anion exchange resin comprises a styrenic anion exchange resin.
According to at least one embodiment of the present disclosure, the anion exchange resin is a strongly basic or weakly basic anion exchange resin.
According to at least one embodiment of the present disclosure, the anion exchange resin is a D201SC anion exchange resin.
Detailed Description
The present disclosure will be described in further detail with reference to the following embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure.
It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. The present disclosure will be described in detail with reference to embodiments.
The purpose of adopting the ion exchange method to carry out the desulfurization and denitrification cooperative treatment is to effectively remove sulfur dioxide and nitrogen oxide generated in the actual production of a coal-fired boiler and a gas-fired boiler to ensure that the sulfur dioxide and the nitrogen oxide are not higher than 35/50mg/Nm3The double low concentration discharge is realized. The application objects include power plants, steel plants, glass plants, cement plants and other industrial waste gases generated in actual production by using coal-fired and gas-fired boilers.
SO in industrial flue gas2The solubility is not high, belongs to medium solubility, and the solubility of NO is very low, so that the effect of simultaneous desulfurization and denitrification cannot be achieved by completely depending on water dissolution or alkali liquor absorption. SO (SO)2And NO both have reducing properties, SO being present when contacted with a strong oxidizing agent2Will be oxidized to SO3,SO3Very soluble in water to form H2SO4(ii) a And NO is oxidized to NO2And N2O5，NO2And N2O5Very soluble in water to generate HNO3. Whereby SO is simultaneously oxidized with a strong oxidizing agent2And NO, to make it into SO which is very soluble in water3、NO2And N2O5Is a key step for simultaneously desulfurizing and denitrating. The process of desulfurization and denitrification by the ion exchange method is accompanied by a series of oxidation-reduction reactions. Compared with the prior art, the removal efficiency of sulfur dioxide and nitrogen oxide in industrial flue gas of the anion exchange resin desulfurization and denitrification method disclosed by the invention is over 96%, and meanwhile, the gas subjected to desulfurization and denitrification by the ion exchange resin is far lower than the relevant national emission standard. The method has the advantages of simple process, low cost of the anion exchange resin, no generation of waste liquid, no secondary pollution and environmental protection.
According to a first embodiment of the present disclosure, there is provided an anion exchange resin desulfurization and denitrification method, including: pretreatment: cooling, dedusting and humidifying the industrial flue gas; and (3) oxidation: carrying out oxidation reaction on the pretreated industrial flue gas and ozone in a gas mixing chamber, so that nitric oxide in the industrial flue gas is oxidized into high-valence nitric oxide and at least part of sulfur dioxide is oxidized into sulfur trioxide; and (3) desulfurization and denitrification: and (3) passing the oxidized flue gas through anion exchange resin, so that sulfur dioxide, sulfur trioxide and high-valence nitrogen oxide in the oxidized flue gas are adsorbed by the anion exchange resin through ion exchange reaction, and gas meeting the emission standard is obtained.
Optionally, when the industrial flue gas is pretreated, because the temperature of the industrial flue gas is high, the temperature of the flue gas needs to be reduced to 40-90 ℃, preferably 50-70 ℃ by using heat exchange equipment, so that the anion exchange resin can reach the optimal use state when ion exchange is carried out. Optionally, the pretreatment of the industrial flue gas also comprises dust removal treatment, and the industrial flue gas contains a large amount of dust particles which can block gaps in the resin layer, so that the working exchange capacity of the anion exchange resin is reduced, and the desulfurization and denitrification effects in the subsequent process are easily reduced. Optionally, the pretreatment of the industrial flue gas further comprises a humidification treatment, the relative humidity of the humidified industrial flue gas is 50-90%, optionally 50-80%, optionally 50-70%, and on the one hand, the increase of the relative humidity can oxidize nitrogen oxides and sulfur dioxide in a strong oxidant (such as ozone) so that at least part or all of the sulfur dioxide is oxidized into sulfur trioxide which is very soluble in water, and the nitrogen monoxide is oxidized into nitrogen oxides with high valence state, such as NO2、N2O5、N2O3、N2O4The like, thereby ensuring that sulfur dioxide and nitrogen oxide in the flue gas are removed in the subsequent treatment process; on the other hand, the relative humidity is also increasedThe method is beneficial to the reaction process of the anion exchange resin during ion exchange, and the effect of maximizing the removal efficiency is achieved.
Optionally, the molar ratio of ozone to nitric oxide in the industrial flue gas is 1.2-3, optionally 1.5-2, during oxidation with a strong oxidant. Under this proportion and the above-mentioned temperature and humidity condition, ozone can make more than 98% low valence state nitrogen oxide oxidize into the high valence state nitrogen oxide that easily dissolves in the water to improve the desorption rate of nitrogen oxide, if the quantity of ozone is too big, exceed above-mentioned proportion, the ozone that does not participate in the reaction is in the device ineffective circulation, increase the operation cost, and the ozone quantity is few, then can not reach due proportion to the oxidation of sulfur dioxide and nitrogen oxide in the flue gas, make the desorption rate of sulfur dioxide and nitrogen oxide reduce, exceed national emission standard.
In the desulfurization and denitrification step, the treatment is generally carried out in an ion exchange tower or an ion exchange column, and optionally, a plurality of ion exchange towers are adopted for treatment, so that the treatment capacity can be improved, meanwhile, part of anion exchange resin in the ion exchange towers can be subjected to ion exchange, and the rest of the ion exchange towers are subjected to a regeneration process on the anion exchange resin which is saturated in adsorption. Specifically, anion exchange resin is loaded into an ion exchange tower or an ion exchange column according to a specified amount, and optionally, the anion exchange resin is subjected to humidification treatment according to actual needs so as to improve the adsorption rate of the anion exchange resin to the industrial flue gas. Anion exchange resin contains a large number of hydrophilic groups, and the volume of the resin is increased by water contact, namely water absorption expansion, and when an ion exchange device is designed, the expansion degree of the resin must be considered so as to adapt to the volume change of the resin generated by ion exchange in the resin during production and operation.
Optionally, the anion exchange resin needs to be replaced when the anion exchange resin reaches adsorption saturation, and the anion exchange resin of the present disclosure is selected to be regenerative, so that the anion exchange resin can be regenerated, and thus the next ion adsorption cycle can be continued, which saves cost, and the regeneration process does not produce pollution of waste liquid, and the regenerant is generally selected to be one of sodium carbonate or sodium hydroxide according to actual needs, so that the anion exchange resin has strong basicity or weak basicity again. Optionally, the regeneration process can be performed in one ion exchange tower, anion exchange resin which is not adsorbed and saturated in other ion exchange towers in the equipment is subjected to ion exchange synchronously, the ion exchange tower after the regeneration process is completed participates in the ion exchange, and the regeneration-ion exchange process performed by a plurality of ion exchange towers circularly can ensure that the flue gas treatment process is not interrupted, improve the efficiency of flue gas desulfurization and denitration, and save the cost of the anion exchange resin and the regenerant. The regeneration period of the ion exchange resin is 48-72 hours, and the operation and maintenance cost of the regenerant is saved due to the long period.
Optionally, the volume ratio of the regenerant to the anion exchange resin is from 1.5 to 4:1, further optionally from 1.5 to 3:1, preferably 2:1, wherein the amount of regenerant is recovered in the same amount as the volume of the ion exchange material and another amount of regenerant in the same volume as the volume of the ion exchange material is recycled. The experimental results show that: in the regeneration process, the efficiency of the previous time of regeneration liquid is very high, the regeneration efficiency can reach more than 60 percent, and the concentration of the recovered sulfate radicals and nitrate radicals is higher; the regeneration efficiency of the latter one-time regeneration liquid is low, the average regeneration efficiency is about 20 percent, the concentration of the recovered sulfate radicals and nitrate radicals is low, and the recovery liquid still contains a large amount of Na2CO3Ingredients, therefore, in order to save regenerant and reduce the amount of regeneration waste liquid, the present disclosure employs a novel regeneration process of "recovery in the first time, reuse in the latter time".
Optionally, the concentration of the regenerant is 5% to 20%, optionally 5% to 15%, preferably 8% to 10%, the concentration of the regenerant exceeds 20%, the utilization rate for the regenerant is not high, and the concentration of the regenerant is too low, the purpose of regenerating the anion exchange resin is not achieved.
Optionally, the regenerant has a spatial flow rate of 1-10m3/h/m3Alternatively 1-5m3/h/m3And optionally 2-3m3/h/m3The space flow rate of the regenerant exceeds 10m3/h/m3If the utilization rate of the regenerant is not high and the space flow rate of the regenerant is too low, the regeneration rate is reachedThe purpose of regenerating the anion exchange resin is not achieved.
Alternatively, the anion exchange resin comprises a styrenic anion exchange resin, which may also be an acrylic anion exchange resin, and which has a stronger ion adsorption capacity and is more easily eluted with the eluate.
Alternatively, the particle size of the anion exchange resin is 0.4-1.5mm, alternatively 0.6-1.25mm, and optionally 0.7-1mm, the anion exchange resin is usually made into small spherical particles, the resin particles are smaller, the reaction speed is high, but the resin particles have larger gas passing resistance and need higher working pressure, and if the resin particles are too large, the interval between the particles is too large, and the ion exchange capacity for the gas is reduced, so the size of the anion exchange resin particles should be properly selected, otherwise the gas flow and the production capacity are obviously reduced.
Optionally, the water content of the anion exchange resin is 40-90%, optionally 50-70%, and optionally 50-60%, and the water in the anion exchange resin is favorable for exchanging ions in the industrial flue gas, so as to achieve the purpose of desulfurization and denitrification.
Alternatively, the anion exchange resin comprises a macroporous anion exchange resin, and the macroporous anion exchange resin is prepared by adding a pore-forming agent during polymerization reaction to form a skeleton with a porous sponge-like structure, wherein a large number of permanent micropores are formed inside the skeleton, and then introducing exchange groups. The composite material has micro-pores and large meshes, the pore diameter of the wetting resin reaches 100-500 nm, and the size and the number of the wetting resin can be controlled during manufacturing. The surface area of the channels may be increased to over 1000m2(ii) in terms of/g. The method not only provides good contact conditions for ion exchange, shortens the ion diffusion path, has quick action and high efficiency in use, but also increases a plurality of chain active centers, generates molecular adsorption through the Van der Waals attractive force between molecules, and can adsorb various nonionic substances like activated carbon to expand the functions of the nonionic substances.
Alternatively, the anion exchange resin is a strongly basic or weakly basic anion exchange resin, wherein the strongly basic anion exchange resin is capable of dissociating OH-in water to form a strongly basic anion exchange resinThe resin is very dissociative and works normally at different pH, e.g. containing quaternary amine groups-NR3OH (R is a hydrocarbon group). Alternatively, weakly basic anion exchange resins, e.g. containing primary amino-NH groups2Secondary amino-NHR, or tertiary amino-NR2They can dissociate OH-in water to be alkalescent, and the positive group of alkalescent anion exchange resin can be adsorbed and combined with anion in solution, so as to produce anion exchange action. In most cases, the resin will adsorb the entire acid molecule to the resin and will only work under neutral or acidic conditions (e.g., pH 1-9).
Alternatively, the ion exchange resin can be subjected to an ion exchange reaction in the presence of an ion exchange capacity of 3.0 to 7.0mmol/g, alternatively 3.5 to 5.0mmol/g, and further alternatively 3.7 to 4mmol/g, to ensure desulfurization and denitrification of the anion exchange resin.
The method for desulfurizing and denitrating anion exchange resin disclosed by the invention comprises the following chemical reactions in the process from ozone oxidation of flue gas to adsorption of the anion exchange resin and the regeneration process of the anion exchange resin:
and (3) oxidation reaction:
ozone with a certain molar ratio is added into the flue gas, the reaction rate of the gas is fast, and nitric oxide and partial sulfur dioxide in the flue gas are rapidly oxidized into nitrogen dioxide, dinitrogen pentoxide and sulfur trioxide.
NO+O3→NO2+O2
NO2+O3→NO3+O2
NO3+NO2→N2O5
NO2+NO2→N2O4
N2O4+O3→N2O5+O2
SO2+O3→SO3+O2
Water and reaction:
sulfur dioxide, sulfur trioxide, nitrogen dioxide and dinitrogen pentoxide are dissolved in water to generate sulfurous acid, sulfuric acid and nitric acid; gaseous sulfur dioxide, sulfur trioxide, nitrogen dioxide and dinitrogen pentoxide, water-soluble water and the reaction are reversible.
Ion exchange reaction:
the sulfite, sulfate and nitrate generated by the water and the reaction are continuously adsorbed by the strong base type ion exchange material and generate ion exchange reaction with carbonate ions on the anion exchange resin, thereby achieving the aim of simultaneously desulfurizing and denitrating.
R2CO3+SO3 2-+2H+→R2SO3+CO2↑+H2O
R2CO3+SO4 2-+2H+→R2SO4+CO2↑+H2O
R2CO3+2NO3 1-+2H+→2RNO3+CO2↑+H2O
Regeneration of anion exchange resins
When the anion exchange resin reached saturation, 10% Na was used2CO3And (4) regenerating, and then continuously using the anion exchange resin.
R2SO3+Na2CO3→R2CO3+Na2SO3
R2SO4+Na2CO3→R2CO3+Na2SO4
2RNO3+Na2CO3→R2CO3+2NaNO3
Through the chemical reaction process, sulfur dioxide and nitrogen oxide in industrial flue gas can be effectively removed, the removal rate can reach more than 95%, and the emission is far lower than the national emission standard. The anion exchange resin is adopted as the ion exchange material for removing sulfur dioxide and nitrogen oxide in industrial flue gas, which belongs to the pioneering technology in practice, and the anion exchange resin completely reaches the national emission standard through strict detection, and the emission concentration of the sulfur dioxide and the nitrogen oxide can reach not higher than 35/50mg/Nm through laboratory tests, pilot scale tests, and test production in actual fields3The national standard of (2) realizes double low concentration discharge. Meanwhile, the anion exchange resin is adopted as the ion exchange material for removing the sulfur dioxide and the nitrogen oxide in the industrial flue gas, and the characteristic of large treatment capacity is also realized, for example, the flow of treating the industrial flue gas is 300m by using related technical equipment3The total amount of the industrial flue gas to be treated is 1.2 ten thousand cubic meters, and the industrial flue gas emission treatment requirement of a small-sized factory is completely met. Meanwhile, the market price of the anion exchange resin is 5-20 yuan/kg, taking a steel mill as an example, the operation and maintenance cost (water content, electric charge and ozone cost) of the anion exchange resin is 19 yuan/ton ore, the investment and regeneration cost of the used anion exchange resin accounts for the investment cost of the desulfurization and denitrification treatment equipment, and the method has high economic benefit. 5000m3Investment cost per hour of processing capacity includes equipment costs in the order of millions, 3 ten thousand meters3Investment costs of/h processing capacity include equipment costs around 300 ten thousand yuan.
The above-mentioned method for removing sulfur dioxide and nitrogen oxides from industrial flue gas using anion exchange resin as an ion exchange material will be described in detail with reference to specific examples.
Example one
The present disclosure provides a method for desulfurization and denitrification by anion exchange resin, specifically, the concentration of sulfur dioxide in the smoke components generated by a certain factory is 500-1000mg/m3The concentration of nitrogen oxide is 300-500mg/m3. The method for synchronously desulfurizing and denitrating industrial flue gas by using anion exchange resin comprises the following steps:
1. 500ml of D201SC anion exchange resin is filled into an ion exchange column;
2. cooling the industrial flue gas to 60 ℃, and performing dust removal treatment and humidification treatment in a pretreatment chamber to ensure that the relative humidity of the industrial flue gas is 75%;
3. pressurizing by a booster pump, injecting the industrial flue gas treated in the step 2 into a gas mixing chamber at a flow rate of 504L/h, introducing ozone for reaction, and controlling the molar ratio of the ozone to the nitric oxide to be 1.5;
4. and (3) introducing the industrial flue gas treated in the step (3) into the ion exchange column treated in the step (1), continuously monitoring the gas components at the outlet to remove sulfur dioxide and nitrogen oxides, wherein the total amount of the treated flue gas is 12000L, and the adsorption condition of the ion exchange resin on the sulfur dioxide and the nitrogen oxides in the industrial flue gas is shown in Table 1.
TABLE 1 treatment of SO in Industrial flue gas2、NOxAdsorption condition (unit: mg/m)3)
As can be seen from Table 1, in the treatment method of the present embodiment, the removal efficiency of sulfur dioxide in the industrial flue gas is 96.5%, the removal efficiency of nitrogen oxide is 99.5%, and the emission concentration of sulfur dioxide in the industrial flue gas after the denitration and desulfurization method is 24mg/m3Nitrogen oxide of 1.3mg/m3Far below the national emission standards.
Example two
The present disclosure provides a method for desulfurization and denitrification by anion exchange resin, specifically, the concentration of sulfur dioxide in the smoke components generated by a certain factory is 500-1000mg/m3The concentration of nitrogen oxide is 300-500mg/m3. The synchronous desulfurization and denitrification method comprises the following steps:
1. loading 300L D201SC anion exchange resin into ion exchange column, and regenerating the resin with 600L 10% sodium carbonate solution;
2. cooling the industrial flue gas to 60 ℃, and performing dust removal treatment and humidification treatment in a pretreatment chamber to ensure that the relative humidity of the industrial flue gas is 75%;
3. through a draught fan, the industrial flue gas treated in the step 2 is 300m3Injecting the flow of the mixture into a gas mixing chamber at a flow rate of/h, introducing ozone for reaction, and controlling the molar ratio of the ozone to the nitric oxide to be 1.5;
4. introducing the industrial flue gas treated in the step 3 into the ion exchange column treated in the step 1, continuously monitoring the gas components at an outlet to remove sulfur dioxide and nitrogen oxides, wherein the total amount of the treated flue gas is 12000m3The adsorption of sulfur dioxide and nitrogen oxides in industrial flue gas by ion exchange resin is shown in table 2.
TABLE 2 treatment of SO in Industrial flue gas2、NOxAdsorption condition (unit: mg/m)3)
| Sampling location | Sulfur dioxide | Nitrogen oxides |
| Air inlet | 953 | 264 |
| Air outlet | 26 | 0.8 |
| Efficiency of removal | 97.2％ | 99.7％ |
As can be seen from Table 2, in the treatment method of this example, the removal efficiency of sulfur dioxide in the industrial flue gas was 97.2%, and the removal efficiency of nitrogen oxide was 99.7%, and the emission concentration of sulfur dioxide in the industrial flue gas after the denitration and desulfurization method was 26mg/m3Nitrogen oxide of 0.8mg/m3Far below the national emission standards. Meanwhile, the flow rate of the introduced industrial flue gas is 300m3The treatment method can meet the treatment requirement of desulfurization and denitrification of industrial flue gas discharged by a common factory by adopting the production process of anion exchange resin in ion exchange and the regeneration and circulation process of other ion exchange columns, and meanwhile, no waste liquid is generated and no secondary pollution is caused by regeneration of a regenerant.
EXAMPLE III
The present disclosure provides a method for desulfurization and denitrification by anion exchange resin, specifically, the concentration of sulfur dioxide in the smoke components generated by a certain factory is 500-1000mg/m3The concentration of nitrogen oxide is 300-500mg/m3. The method for synchronously desulfurizing and denitrating industrial flue gas by using anion exchange resin comprises the following steps:
1. 500ml of D201SC anion exchange resin is filled into an ion exchange column, and 1L of 10% sodium carbonate solution is used for regenerating the anion exchange resin;
2. cooling the industrial flue gas to 60 ℃, and performing dust removal treatment and humidification treatment in a pretreatment chamber to ensure that the relative humidity of the industrial flue gas is 60%;
3. pressurizing by a booster pump, injecting the industrial flue gas treated in the step 2 into a gas mixing chamber at a flow rate of 504L/h, introducing ozone for reaction, and controlling the molar ratio of the ozone to the nitric oxide to be 1.3;
4. and (3) introducing the industrial flue gas treated in the step (3) into the ion exchange column treated in the step (1), continuously monitoring the gas components at the outlet to remove sulfur dioxide and nitrogen oxides, wherein the total amount of the treated flue gas is 12000L, and the adsorption condition of the ion exchange resin on the sulfur dioxide and the nitrogen oxides in the industrial flue gas is shown in Table 3.
TABLE 3 treatment of SO in Industrial flue gas2、NOxAdsorption condition (unit: mg/m)3)
| Sampling location | Sulfur dioxide | Nitrogen oxides |
| Air inlet | 711 | 351 |
| Air outlet | 32 | 20 |
| Efficiency of removal | 95.5％ | 94.3％ |
Example four
The present disclosure provides a method for desulfurizing and denitrating anion exchange resin, in particular, it relates to flue gas produced by a certain factoryIn the components, the concentration of the sulfur dioxide is 500-1000mg/m3The concentration of nitrogen oxide is 300-500mg/m3. The synchronous desulfurization and denitrification method comprises the following steps:
1. filling 300L of D201SC anion exchange resin into an ion exchange column;
2. cooling the industrial flue gas to 60 ℃, and performing dust removal treatment and humidification treatment in a pretreatment chamber to ensure that the relative humidity of the industrial flue gas is 65%;
3. through a draught fan, the industrial flue gas treated in the step 2 is 300m3Injecting the flow of the mixture into a gas mixing chamber at a flow rate of/h, introducing ozone for reaction, and controlling the molar ratio of the ozone to the nitric oxide to be 1.8;
4. introducing the industrial flue gas treated in the step 3 into the ion exchange column treated in the step 1, continuously monitoring the gas components at an outlet to remove sulfur dioxide and nitrogen oxides, wherein the total amount of the treated flue gas is 12000m3The adsorption of sulfur dioxide and nitrogen oxides in industrial flue gas by ion exchange resin is shown in table 4.
TABLE 4 treatment of SO in Industrial flue gas2、NOxAdsorption condition (unit: mg/m)3)
| Sampling location | Sulfur dioxide | Nitrogen oxides |
| Air inlet | 1010 | 340 |
| Air outlet | 34 | 22 |
| Efficiency of removal | 96.6％ | 93.5％ |
Therefore, compared with the prior art, the removal efficiency of removing sulfur dioxide and nitrogen oxides in the industrial flue gas by adopting the ion exchange resin is greatly improved, the highest removal efficiency of the anion exchange resin can reach more than 99%, and the emission concentration of the sulfur dioxide and the nitrogen oxides in the industrial flue gas after the denitration and desulfurization method is far lower than the national emission standard. Compared with the prior art, the treatment method has lower maintenance cost and operation cost, can meet the treatment requirement of desulfurization and denitrification of industrial flue gas discharged by a common factory, and can not generate waste liquid and cause secondary pollution through regeneration of the regenerant.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.
Claims (10)
1. The method for desulfurizing and denitrating anion exchange resin is characterized by comprising the following steps:
pretreatment: cooling, dedusting and humidifying the industrial flue gas;
and (3) oxidation: carrying out oxidation reaction on the pretreated industrial flue gas and ozone in a gas mixing chamber, so that nitric oxide in the industrial flue gas is oxidized into high-valence nitric oxide and at least part of sulfur dioxide is oxidized into sulfur trioxide;
and (3) desulfurization and denitrification: and (3) passing the oxidized flue gas through anion exchange resin, so that sulfur dioxide, sulfur trioxide and high-valence nitrogen oxide in the oxidized flue gas are adsorbed by the anion exchange resin through ion exchange reaction, and gas meeting the emission standard is obtained.
2. The method of claim 1, further comprising regenerating the anion exchange resin,
and the regeneration uses a regenerant to regenerate the anion exchange resin treated in the desulfurization and denitrification step.
3. The method for desulfurization and denitrification of anion exchange resin according to claim 2, wherein the regenerant is one or more of sodium carbonate and sodium hydroxide.
4. The method for desulfurization and denitrification of anion exchange resin according to claim 3, wherein the volume ratio of the regenerant to the anion exchange resin is 1.5-4:1, wherein half of the dosage of the regenerant is used for recovery and the other half of the dosage of the regenerant is used for recycling.
5. The method for desulfurization and denitrification of anion exchange resin according to claim 4, wherein the concentration of the regenerant is 5 to 20%.
6. The method of claim 4, wherein the regenerant has a space flow rate of 1-10m3/h/m3。
7. The method for desulfurization and denitrification with anion exchange resin according to claim 1, wherein the molar ratio of ozone to nitric oxide in the pretreatment step is 1.2 to 3.
8. The method for desulfurization and denitrification by anion exchange resin according to claim 1, wherein in the pretreatment step, the relative humidity of the flue gas after humidification treatment is 50 to 80%.
9. The method of claim 1, wherein the anion exchange resin comprises one of quaternary amine functional groups, secondary amine functional groups, primary amine functional groups, or tertiary amine functional groups.
10. The method for desulfurization and denitrification of an anion exchange resin according to claim 1, wherein the anion exchange resin has an exchange capacity of 3.0 to 7.0 mmol/g.
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| CN112957872A (en) * | 2021-03-17 | 2021-06-15 | 西北大学 | Purifying CO2Removal of SO2In a semiconductor device |
| CN113368676A (en) * | 2021-07-06 | 2021-09-10 | 深圳前海中盛环保科技有限公司 | Flue gas desulfurization and denitrification integrated treatment method |
| CN113413723A (en) * | 2021-07-13 | 2021-09-21 | 深圳前海中盛环保科技有限公司 | Method for treating waste gas by using ion exchange resin |
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| CN113368676A (en) * | 2021-07-06 | 2021-09-10 | 深圳前海中盛环保科技有限公司 | Flue gas desulfurization and denitrification integrated treatment method |
| CN113368676B (en) * | 2021-07-06 | 2022-09-23 | 深圳灏权环保有限公司 | Flue gas desulfurization and denitrification integrated treatment method |
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| CN113413723A (en) * | 2021-07-13 | 2021-09-21 | 深圳前海中盛环保科技有限公司 | Method for treating waste gas by using ion exchange resin |
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| CN113413723B (en) * | 2021-07-13 | 2022-09-27 | 深圳灏权环保有限公司 | Method for treating waste gas by using ion exchange resin |
| CN113413929B (en) * | 2021-07-13 | 2023-09-15 | 深圳前海中盛环保科技有限公司 | Method for purifying flue gas by ion exchange fiber and simultaneously partially regenerating |
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