CN111375271B - Method and device for treating flue gas containing sulfur dioxide - Google Patents

Method and device for treating flue gas containing sulfur dioxide Download PDF

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CN111375271B
CN111375271B CN201811651642.2A CN201811651642A CN111375271B CN 111375271 B CN111375271 B CN 111375271B CN 201811651642 A CN201811651642 A CN 201811651642A CN 111375271 B CN111375271 B CN 111375271B
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adsorption
flue gas
unit
condensation
gas
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CN111375271A (en
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方向晨
赵磊
刘忠生
刘志禹
汪鹏
齐慧敏
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • B01D53/002—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 by condensation
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas

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Abstract

The invention relates to a method for treating flue gas containing sulfur dioxide, which comprises the steps of compressing and condensing the flue gas containing sulfur dioxide in a compression and condensation unit, then feeding the flue gas into a condensation and liquefaction unit, feeding non-condensable gas into an adsorption unit for adsorption, and discharging purified gas which reaches the standard; the adsorption unit adopts an adsorption material which is a modified MIL- (Al) metal organic framework material, desorption is carried out after adsorption penetration, and desorption gas and flue gas to be treated are mixed and enter the compression condensation unit. The invention can realize SO2High-efficiency physical adsorption and recovery, low liquefaction energy consumption and SO2High recovery rate and good operation stability, and the purified gas meets the emission requirement.

Description

Method and device for treating flue gas containing sulfur dioxide
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a method and a device for treating sulfur dioxide-containing flue gas.
Background
Since coal and petroleum generally contain sulfur compounds, SO is formed during combustion2Resulting in SO contained in the exhaust gas2A gas. SO (SO)2The air is colorless and has pungent odor at normal temperature, and is one of main pollutants in the atmosphere. As early as in the fifteen program, SO2Becomes one of the main pollutant emission indexes for national key control of emission. SO in atmospheric pollution emission standard implemented in 7/1 in 20172Is limited to 100mg/m3Some places SO2Is required to be less than 50mg/m3。
Currently, widely used desulfurization techniques can be classified into wet desulfurization techniques and dry desulfurization techniques. The existing desulfurization technology can be divided into three types according to the recycling degree of desulfurization products: the first type is SO2After being removed, the waste water cannot be recycled or is difficult to utilize, such as a gypsum method, a carbide slag method and the like, and the methods generate a large amount of liquid or solid waste and bring secondary pollution. The second type is oxidation by chemical agents or catalytic oxidationAdding SO2Conversion to dilute sulphuric acid or sulphate, e.g. hydrogen peroxide oxidation, ammonia oxidation, wet catalysis with activated carbon, de-SO using hydrogen peroxide as described in patent CN105381699A2Patent CN101085410 describes the treatment of SO in flue gas2A method for converting to ammonium sulfate. The technologies need to consume oxidant or catalyst continuously, and relate to the problems of medicament supply radius and cost, and are inconvenient to use in remote areas. The third type is to use low concentration SO2Absorbing or adsorbing and then desorbing to obtain high-concentration SO2Returning to the acid making section to prepare sulfuric acid. For example, patent CN102743956A describes a process for preparing sulfuric acid by desulfurizing regeneration gas of activated coke. However, activated coke (carbon) is not strictly an adsorbent, it will take part in the reaction to adsorb SO2By oxidation to SO3And is not favorable for subsequent treatment.
CN105251313A discloses an adsorption device for sulfur dioxide, comprising: the device comprises a silica gel drying column, a gas mixer, a pressure swing adsorption bed and a tail gas adsorption column, wherein the silica gel drying column comprises an air silica gel drying column and a sulfur dioxide silica gel drying column; the sulfur dioxide silica gel drying column is connected with the top of the pressure swing adsorption bed through a pipeline, and the air silica gel drying column is connected with the gas mixer and the bottom of the pressure swing adsorption bed through pipelines; the bottom of the pressure swing adsorption bed is additionally connected with a tail gas adsorption column through a pipeline. The invention can concentrate sulfur dioxide while treating sulfur dioxide pollution, the concentrated sulfur dioxide can be used for preparing acid or other purposes, and the active carbon can be recycled. However, when SO is present in the gas2Concentration higher than 0.5%, SO obtained by desorption due to limited adsorption performance of activated carbon2The concentration is not high, and the liquefaction energy consumption is high; and also to make part of SO2Conversion to SO3SO that SO of high purity cannot be obtained2And (5) desorbing gas.
CN103920365A discloses a method for recovering nitrogen and sulfur dioxide in roasted pyrite furnace gas by variable-frequency and variable-pressure adsorption, which comprises the following process steps: after the furnace gas for roasting the pyrite is subjected to dust removal, purification, drying and cooling, removing dust particles and iron rust through a refined sulfuric acid furnace gas filter made of 200-mesh polytetrafluoroethylene; then the deep essence is removed through a fine removal tankAfter dehydration, deoxidation and decarbonation, N is realized by using a variable-frequency variable-pressure adsorption method2With SO2Then obtaining liquid SO by compression or cooling and gas-liquid separation2Separating the separated nitrogen and liquid SO2Bottling for industrial use; SO not separated by liquefaction2Then enters the cycle process of compression or cooling and gas-liquid separation to remove SO in the gas2Continuously separating. Even if a variable-frequency and variable-pressure adsorption method is adopted, SO obtained by desorption is limited in adsorption performance of activated carbon2The concentration is not high, and the liquefaction energy consumption is high; and also to make part of SO2Conversion to SO3SO that SO of high purity cannot be obtained2And (5) desorbing gas.
Penwangwang et al (liquefaction and separation of sulfur dioxide in flue gas desulfurization regeneration tail gas, coal gas and heat power, volume 20, phase 2: 83-87) introduces the basic composition of the regeneration tail gas of the novel coal-fired flue gas desulfurization carbon dry desulfurization, the thermodynamic properties of related gas components and theoretical analysis and experimental summary of the liquefaction effect of sulfur dioxide. The result shows that the liquefaction rate of the sulfur dioxide can reach 80-94 percent when the regeneration tail gas containing the high-concentration sulfur dioxide is purified and dried, pressurized to 2-3MPa and cooled to 0-20 ℃. However, the concentration of sulfur dioxide in the regeneration tail gas is higher than 30%, while the content of sulfur dioxide in the existing industrial waste gas is usually lower than 5%, and an effective adsorption concentration method is not available at present, so that the method is not economical.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a device for treating flue gas containing sulfur dioxide. The invention can realize SO by a combined process of compression condensation, condensation liquefaction and adsorption concentration and combined use of a modified adsorbent2High-efficiency physical adsorption and recovery, low liquefaction energy consumption and SO2High recovery rate and good operation stability, and the purified gas meets the emission requirement.
The invention provides a method for treating flue gas containing sulfur dioxide, which comprises the following steps:
compressing and condensing the flue gas containing sulfur dioxide in a compression and condensation unit, then entering a condensation and liquefaction unit, and allowing the non-condensable gas to enter an adsorption unit for adsorption, wherein the purified gas is discharged after reaching the standard; the adsorption unit adopts an adsorption material which is a modified MIL- (Al) metal organic framework material, desorption is carried out after adsorption penetration, and desorption gas and flue gas to be treated are mixed and enter the compression condensation unit.
In the invention, the flue gas containing sulfur dioxide can be discharged waste gas or flue gas from coal-fired power plants, metallurgical plants, petrochemical plants and the like, such as flue gas of coal-fired or oil-fired boilers, FCC regenerated flue gas, S-zorb adsorbent regenerated flue gas and the like, and SO in the flue gas2The volume concentration of (A) is more than 0.1 percent, generally 0.5 to 10 percent; the volume content of the water is 1-15%. According to the characteristics of the waste gas source, the SO is contained2The flue gas is subjected to pretreatment such as dust removal and cooling before compression and condensation.
In the invention, the compression and condensation unit mainly comprises a compressor, a condenser and the like, and the SO content in the SO-containing gas is reduced2Compressing and condensing the gas, and controlling the gauge pressure to be 0.3-2.0 MPaG, preferably 0.5-1.5 MPaG; the temperature is 0 to 20 ℃, preferably 0 to 10 ℃. The compressed and condensed gas directly enters a condensation liquefaction unit.
In the invention, the condensation liquefaction unit mainly comprises a condensation tank and liquid SO2And (4) storage tank. The condensation tank can be an empty tank or can be filled with inert porous medium materials, such as at least one of ceramic porous medium materials, foam porous medium materials, activated carbon, glass fibers and the like, and the pore size distribution is 1-200 nm, preferably 2-100 nm. Production of SO-containing by a condensed liquefaction unit2The mixture with water can be separated by flash evaporation and the like to collect SO2And a sulfurous acid solution, wherein the flash evaporation temperature is controlled to be 0-20 ℃, preferably 2-10 ℃, and the absolute vacuum degree is 20-80 KPa, preferably 30-60 KPa. And the non-condensable gas discharged from the condensation liquefaction unit enters the adsorption unit.
In the invention, the adsorption unit consists of two or more than two adsorption towers and can alternately operate. The adsorption conditions were: the adsorption temperature is-10 to 40 ℃, the preferred temperature is 5 to 30 ℃, and the space velocity of the adsorption volume is 100 to 1000h-1The adsorption pressure is 0.1-1.0 MPa.
In the present invention, the adsorption outlet concentration is setThe degree is not higher than 50mg/m3The time is the penetration time, desorption is carried out after adsorption penetration, and the desorption can adopt methods such as heating regeneration, vacuum heat regeneration and the like, and preferably adopts the combination of vacuum regeneration and regular vacuum heat regeneration. The final absolute pressure of the regenerated adsorption tower is 3-8 KPa, the regeneration time is 0.5-6 hours, and the maximum absolute pressure does not exceed 70% of the adsorption time. After the adsorption tower is subjected to multiple times of adsorption-desorption, when the adsorption quantity of the adsorbent is reduced to be below 85% of the initial adsorption quantity, the adsorption tower is subjected to vacuum thermal regeneration, nitrogen is used as a gas source, the absolute pressure of regeneration is 10-50 KPa, and the temperature is 80-300 ℃. Desorbed SO2And the gas is mixed with the flue gas to be treated and then enters the compression and condensation unit.
In the invention, the modified MIL- (Al) metal organic framework material takes the MIL- (Al) metal organic framework material as a matrix, and is subjected to carbonization, acid cleaning, filtering, drying, then placing in an ethylenediamine aqueous solution, and adding N2Existing, and processed at 500-800 deg.C.
In the invention, the MIL- (Al) metal-organic framework material is MIL-53(Al) or/and MIL-100(Al), and preferably MIL-100 (Al). The specific surface area of the metal organic framework material is 1100-1250m2Per g, pore volume of 0.45-0.65cm3(ii) in terms of/g. The carbonization condition is N2Carbonizing at 600-1000 deg.C for 6-12 hr. The acid cleaning is carried out by adopting at least one of inorganic acid solutions such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like, and the mass concentration of the acid solution is 10-20%. Filtering by suction filtration or other filtration methods, washing with deionized water, and drying at 100-120 deg.C for 6-12 hr.
In the present invention, the volume concentration of the ethylenediamine aqueous solution is 5% to 50%, preferably 20% to 30%. In N2Modifying at 500-800 deg.c for 0.5-2 hr in the presence of alkali. Furthermore, acrylonitrile with the volume concentration of 10% -20% is added into the ethylenediamine aqueous solution, so that the adsorption performance of the adsorption material is further improved. The adsorption saturation capacity of the modified MIL- (Al) metal organic framework material is more than 1.8 times of that of the commercial active carbon.
The invention also provides a treatment device for treating the flue gas containing sulfur dioxide, which mainly comprises a compression condensation unit, a condensation liquefaction unit and an absorption unitAn additional unit and a regeneration unit, wherein the compression and condensation unit mainly comprises a compressor and a condenser and is used for containing SO2Compressing and condensing the flue gas; the condensation liquefaction unit mainly comprises a condensation tank, a flash tower and SO2The storage tank or the gas holder is used for condensing and liquefying the compressed and condensed flue gas; the adsorption unit mainly comprises two or more than two adsorption towers filled with modified MIL- (Al) metal organic framework materials; the regeneration unit mainly comprises a vacuum pump, a nitrogen heater and the like and is used for desorption regeneration of the adsorption unit.
The invention can realize SO by a combined process of compression condensation, condensation liquefaction and adsorption concentration and combined use of a modified adsorbent2High-efficiency physical adsorption and desorption, and can obtain high-purity SO2Gas and sulfurous acid solution, SO2The recovery rate is high; and the liquefaction energy consumption is obviously reduced, the operation stability is good, the treatment cost is reduced while the standard emission of the exhaust gas is realized, and the environment-friendly and economic benefits are good.
The invention adopts the modified metal organic framework material as the adsorption material, on one hand, SO can be avoided2Oxidation to SO3Realization of SO2Exhibits more excellent SO compared with commercial activated carbon2Physical adsorption property. On the other hand, the modified MIL- (Al) metal-organic framework material has SO under the condition of 0.1-0.3 MPa in the penetration time2The adsorption capacity is more than 1.8 times of that of commercial activated carbon and more than 1.5 times of that of an MIL-100(Al) material, so that the number and scale of the adsorption towers can be reduced, and the treatment cost is reduced.
The modified MIL- (Al) metal organic framework material prepared by the invention is beneficial to SO2High-efficiency physical adsorption and rapid desorption of SO2After multiple times of adsorption-desorption, the adsorption capacity can be stabilized to be more than 85% of the initial adsorption capacity, and the adsorption stability is good.
Drawings
FIG. 1 is a schematic flow diagram of the treatment process of the present invention; wherein: 1-compressor, 2-condenser, 3-condensation tank, 4-flash column, 5-SO2Storage tank or gas holder, 6-adsorption tower set, 7-SO2An online detector, 8-desorption vacuum pump, 9-heater and 10-heat regeneration vacuum pump.
Detailed Description
The treatment method and the treatment effect of the present invention will be further described below by way of examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
The content of the metal element of the present invention was analyzed by the ICP method. SO in gas2The content was analyzed by an instrument (Emerson X-STREAM). The concentration of the adsorption outlet was set to 50mg/m3Time being the breakthrough time, SO on the adsorbent material2The adsorption capacity is calculated by the following formula:
Figure DEST_PATH_IMAGE002
in the formula: q is sulfur capacity, mg/g; q is the total flow of the mixed gas at the inlet, mL/min; c0Is an inlet SO2Concentration, mg/L; ciIs the ith sampling outlet SO2Concentration, mg/L; t is the ith sampling time, min; n is the sampling times when the adsorption reaches saturation or within a specified time; m is the loading of the adsorbent material, g.
The treatment device mainly comprises a compression condensing unit, a condensation liquefying unit, an adsorption unit and a regeneration unit as shown in figure 1, wherein the compression condensing unit mainly comprises a compressor 1 and a condenser 2, and the condensation liquefying unit mainly comprises a condensation tank 3, a flash tower 4 and SO2A storage tank or gas cabinet 5; the adsorption unit mainly comprises two or more than two adsorption tower groups 6, each adsorption tower is filled with modified MIL- (Al) metal organic framework material, and SO is arranged at the outlet of the adsorption tower2An online detector 7; the regeneration unit mainly comprises a desorption vacuum pump 8, a heater 9 and a heat regeneration vacuum pump10. Firstly, removing particles and cooling to obtain a product containing high-concentration SO2The wet flue gas is compressed by a compressor and then enters a condenser for condensation, and then enters a condensation tank 3 to generate SO-containing flue gas2The mixture with water enters a flash tower 4, and high-purity SO flashed out2Entering a storage tank or a gas holder 5 for storage, entering non-condensable gas into an adsorption tower group 6, switching operation by a plurality of adsorption towers, and entering adsorbed flue gas into SO2An on-line detector 7 for controlling the purified gas SO2The concentration is not higher than 50mg/m3When purifying the gas SO2When the concentration reaches the control index, the adsorption-desorption switching is carried out, the desorption vacuum pump 8 is used for vacuumizing for vacuum regeneration, and the desorption gas and the pretreated gas contain high-concentration SO2The flue gas is mixed and then enters a compression condensing unit. After the adsorption tower is subjected to multiple adsorption-desorption operations, when the adsorption capacity is reduced to below 85% of the initial adsorption capacity, performing vacuum thermal regeneration once, and under the action of a thermal regeneration vacuum pump 10, performing N2Heated by a heater 9, circularly heated in an adsorption tower, and discharged partial thermal regeneration gas and SO-containing gas2And mixing the flue gas and cooling.
Example 1
Containing SO2The gas is S-zorb adsorbent regeneration flue gas, and is subjected to dust removal and cooling pretreatment before compression and condensation, and SO in the treated waste gas2The volume concentration of (A) is 2-5%, the volume content of water is 2.2-2.6%, and O is2The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 500Nm3/h。
Preparation of modified MIL- (Al) metal organic framework material: MIL-100(Al) is taken as a substrate, and the specific surface area is 1180m2Per g, pore volume of 0.64cm3The Al content is 15.2 percent per gram. Carbonizing at 800 deg.C for 6 hr in the presence of nitrogen, soaking in 10% hydrochloric acid solution, stirring for 12 hr for acid washing, filtering, and drying at 100 deg.C for 8 hr. The materials are put into an ethylenediamine aqueous solution with the volume concentration of 30 percent, and are modified for 1 hour at 600 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is detected to be 2150m2Per g, pore volume 2.55cm3(ii)/g, containing no metal element.
Will contain SO2The flue gas is compressed and condensed, the gauge pressure is controlled to be 1.0MPaG, and the temperature is about 3 ℃. After compression and condensation, the condensed liquid enters a condensation liquefaction unit, and a condensation tank is an empty tank to obtain the liquid containing SO2And water. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified MIL- (Al) metal organic framework material. The adsorption conditions were: the adsorption temperature is 5-30 ℃, and the volume space velocity is about 200h-1The adsorption pressure is 0.2-0.3 MPa. The concentration of an adsorption outlet is 40mg/m3Is taken as the penetration time by SO2And (3) detecting the exhaust gas on line, controlling the switching among the adsorption towers on line, and ensuring that the penetration time of a single adsorption tower is about 1-2 h. And (3) carrying out vacuum desorption after the adsorption tower penetrates through the adsorption tower, wherein the final absolute pressure of the adsorption tower is 3-5 KPa, and the desorption time is 60% of the adsorption time. Desorbed gaseous SO2Entering a compression condensation unit and then entering a condensation liquefaction unit to obtain SO2The water mixture enters a flash tower, the flash temperature is controlled to be 10-15 ℃, the absolute vacuum degree is 30KPa, and the SO flashed out is collected2Gas and obtaining a sulfurous acid solution. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3And when the adsorption capacity is reduced to below 85% of the initial adsorption capacity, carrying out primary vacuum thermal regeneration, wherein hot nitrogen is used as a gas source, the regeneration temperature is 150-180 ℃, and the regeneration absolute pressure is 20-30 KPa.
Running for 1 month and obtaining SO cumulatively2About 27 tons of gas and about 6 tons of sulfurous acid solution, the adsorption capacity of the adsorbent can be stabilized at 85% or more of the initial adsorption capacity.
Example 2
Containing SO2The gas is S-zorb adsorbent regeneration flue gas, and is subjected to dust removal and cooling pretreatment before compression and condensation, and SO in the treated waste gas2The volume concentration of (A) is 2-5%, the volume content of water is 2.2-2.6%, and O is2The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 500Nm3/h。
Preparation of modified MIL- (Al) metal organic framework material: MIL-100(Al) is taken as a substrate, and the specific surface area is 1180m2Per g, pore volume of 0.64cm3The Al content is 15.2 percent per gram. In the presence of nitrogen at 800Carbonizing at 6 deg.C for 6 hr, soaking in 10% hydrochloric acid solution, stirring for 12 hr, acid washing, filtering, and drying at 100 deg.C for 8 hr. The materials are put into an ethylenediamine aqueous solution with the volume concentration of 30 percent, and are modified for 1 hour at 600 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is detected to be 2150m2Per g, pore volume 2.55cm3(ii)/g, containing no metal element.
Will contain SO2The flue gas is compressed and condensed, the gauge pressure is controlled to be 0.5MPaG, and the temperature is about 3 ℃. Compressing, condensing, introducing into a condensing and liquefying unit, filling activated carbon in a condensing tank with aperture of 100-150nm to obtain SO-containing solution2And water. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified MIL- (Al) metal organic framework material under the following adsorption conditions: the adsorption temperature is 5-30 ℃, and the volume space velocity is about 200h-1The adsorption pressure is 0.2-0.3 MPa. The concentration of an adsorption outlet is 40mg/m3Is taken as the penetration time by SO2And (3) detecting the exhaust gas on line, controlling the switching among the adsorption towers on line, and ensuring that the penetration time of a single adsorption tower is about 1-2 h. And (3) carrying out vacuum desorption after the adsorption tower penetrates through the adsorption tower, wherein the final absolute pressure of the adsorption tower is 3-5 KPa, and the desorption time is 60% of the adsorption time. Desorbed gaseous SO2Entering a compression condensation unit and then entering a condensation liquefaction unit to obtain SO2The mixture with water enters a flash tower, the flash temperature is controlled to be 10-15 ℃, the absolute vacuum degree is 30KPa, and the SO flashed out is collected2Gas and obtaining a sulfurous acid solution. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3And when the adsorption capacity is reduced to below 85% of the initial adsorption capacity, carrying out primary vacuum thermal regeneration, wherein hot nitrogen is used as a gas source, the regeneration temperature is 150-180 ℃, and the regeneration absolute pressure is 20-30 KPa.
Running for 1 month and obtaining SO cumulatively2About 26.5 tons of gas and about 6.1 tons of sulfurous acid solution, the adsorption capacity of the adsorbent can be stabilized at 85% or more of the initial adsorption capacity.
Example 3
Containing SO2The gas is catalytic cracking regeneration flue gas inDedusting and cooling pretreatment are carried out before compression, and SO in treated waste gas2The volume concentration of (A) is 0.05-0.2%, the volume content of water is about 8-10%, and O2The volume concentration of the flue gas is 3-5 percent, and the flue gas treatment capacity is 1000Nm3/h。
Preparation of modified MIL- (Al) metal organic framework material: MIL-100(Al) is taken as a substrate, and the specific surface area is 1180m2Per g, pore volume of 0.64cm3The Al content is 15.2 percent per gram. Carbonizing at 800 deg.C for 6 hr in the presence of nitrogen, soaking in 10% hydrochloric acid solution, stirring for 12 hr for acid washing, filtering, and drying at 100 deg.C for 8 hr. The materials are put into an ethylenediamine aqueous solution with the volume concentration of 30 percent, and are modified for 1 hour at 600 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is detected to be 2150m2Per g, pore volume 2.55cm3(ii)/g, containing no metal element.
Will contain SO2The flue gas is compressed and condensed, the gauge pressure is controlled to be 0.5MPaG, and the temperature is about 3 ℃. The mixture enters a condensation liquefaction unit after being compressed and condensed, a condensation tank is filled with active carbon, the aperture is 30-100 nm, and SO is obtained2And water. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified MIL- (Al) metal organic framework material under the following adsorption conditions: the adsorption temperature is 5-30 ℃, and the volume space velocity is about 1000h-1The adsorption pressure is 0.2-0.3 MPa. The concentration of an adsorption outlet is 40mg/m3Is taken as the penetration time by SO2And (3) online detection of exhaust gas, online control of switching among adsorption towers, and penetration time of a single adsorption tower about 50-80 h. And (3) carrying out vacuum desorption after the adsorption tower penetrates through the adsorption tower, wherein the final absolute pressure of the adsorption tower is 3-5 KPa, and the desorption time is 3-8 hours. Desorbed gaseous SO2Entering a compression condensation unit and then entering a condensation liquefaction unit to obtain a sulfurous acid solution. And when the adsorption capacity is reduced to below 85 percent of the initial adsorption capacity, carrying out primary vacuum thermal regeneration, wherein hot nitrogen is used as a gas source, the regeneration temperature is 150-180 ℃, and the regeneration absolute pressure is 20-30 KPa.
After 2 months of operation, about 100 tons of sulfurous acid solution is obtained (4-6%), and the adsorption capacity of the adsorbent can be stabilized to be more than 85% of the initial adsorption capacity.
Example 4
The difference from example 1 is that: preparation of modified MIL- (Al) metal organic framework material: MIL-53(Al) is taken as a substrate, and the specific surface area is 1135 m2Per g, pore volume of 0.54 cm3In terms of/g, the Al content was 20.5%. Carbonizing at 800 deg.C for 6 hr in the presence of nitrogen, soaking in 10% hydrochloric acid solution, stirring for 12 hr for acid washing, filtering, and drying at 100 deg.C for 8 hr. The materials are put into an ethylenediamine aqueous solution with the volume concentration of 30 percent, and are modified for 1 hour at 600 ℃ in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is detected to be 1895m2Per g, pore volume of 2.37cm3(ii)/g, containing no metal element.
The volume space velocity is required to be reduced to 150h-1The penetration time of a single adsorption tower is 1-2 h. Accumulating to obtain SO after 1 month of adsorption-desorption cycle2About 26 tons of gas and about 6 tons of sulfurous acid solution, and the adsorption capacity of the adsorbent can be stabilized at more than 85% of the initial adsorption capacity.
Example 5
The difference from example 1 is that: preparation of modified MIL- (Al) metal organic framework material: MIL-100(Al) is taken as a substrate, and the specific surface area is 1180m2Per g, pore volume of 0.64cm3The Al content is 15.2 percent per gram. Carbonizing at 800 deg.C for 6 hr in the presence of nitrogen, soaking in 10% hydrochloric acid solution, stirring for 12 hr for acid washing, filtering, and drying at 100 deg.C for 8 hr. Placing the materials into an ethylenediamine aqueous solution with the volume concentration of 30%, adding acrylonitrile with the volume concentration of 10% into the ethylenediamine aqueous solution, and modifying at 600 ℃ for 1 hour in the presence of nitrogen to obtain SO2Adsorbing the material. The specific surface area of the prepared material is 2335 m2Per g, pore volume of 2.61 cm3(ii)/g, containing no metal element.
The penetration time of a single adsorption tower is 1.5-3 h, and SO is obtained through accumulation after 1 month of adsorption-desorption circulation2About 27.5 tons of gas and about 6 tons of sulfurous acid solution, the adsorption capacity of the adsorbent can be stabilized at the initial stageThe adsorption capacity is more than 85%.
Comparative example 1
The difference from example 1 is that activated carbon was used as the adsorbent. The volume space velocity needs to be controlled at 80h-1In addition, since the desorption time is too long, it is necessary to additionally provide an adsorption column.
Comparative example 2
The same as example 1, except that MIL-100(Al) metal organic framework material was used as the adsorbent. The volume space velocity needs to be reduced to 150h-1And O in the exhaust gas due to the catalytic action of the material itself2Adding SO2By oxidation to SO3Affecting the solution purity.
Comparative example 3
The difference from example 1 is that condensation liquefaction is not used, and the adsorption is directly removed after compression condensation. Water will react with SO2Competitive adsorption, increased adsorbent consumption, and desorption gas with water and SO2Separation of (4).

Claims (17)

1. A method for treating flue gas containing sulfur dioxide is characterized by comprising the following steps: compressing and condensing the flue gas containing sulfur dioxide in a compression and condensation unit, then entering a condensation and liquefaction unit, and allowing the non-condensable gas to enter an adsorption unit for adsorption, wherein the purified gas is discharged after reaching the standard; the adsorption unit adopts an adsorption material which is a modified MIL-Al metal organic framework material, desorption is carried out after adsorption penetration, and desorption gas and the flue gas to be treated are mixed and enter the compression condensation unit; the modified MIL-Al metal organic framework material takes MIL-Al metal organic framework material as a matrix, and is subjected to carbonization, acid cleaning, filtering, drying, then placing in ethylenediamine aqueous solution, and adding N2Existing, and processed at 500-800 deg.C.
2. The method of claim 1, wherein: the flue gas containing sulfur dioxide is flue gas discharged from coal-fired power plants, metallurgical plants and petrochemical plants, specifically at least one of flue gas of coal-fired or oil-fired boilers, FCC regenerated flue gas and S-zorb adsorbent regenerated flue gas, and SO in the flue gas2Volume concentration ofMore than 0.1 percent and the volume content of water is 1 to 15 percent.
3. The method according to claim 1 or 2, characterized in that: according to the characteristics of the waste gas source, the SO is contained2The flue gas needs to be subjected to dust removal and cooling pretreatment before compression and condensation.
4. The method of claim 1, wherein: in the compression condensing unit, the gauge pressure is controlled to be 0.3-2.0 MPaG, and the temperature is controlled to be 0-20 ℃.
5. The method of claim 1, wherein: the condensation liquefaction unit mainly comprises a condensation tank and SO2And the storage tank, wherein the coagulation tank is filled with inert porous medium materials, and the pore diameter distribution is 1-200 nm.
6. The method of claim 5, wherein: the inert porous medium material is at least one of a ceramic porous medium material, a foam porous medium material, activated carbon and glass fiber, and the pore size distribution is 2-100 nm.
7. The method of claim 1, 5 or 6, wherein: production of SO-containing by a condensed liquefaction unit2Collecting SO from the mixture with water by flash evaporation2And a sulfurous acid solution, wherein the flash evaporation temperature is controlled to be 0-20 ℃, and the absolute vacuum degree is controlled to be 20-80 KPa.
8. The method of claim 1, wherein: the adsorption unit consists of more than two adsorption towers and alternately operates; the adsorption conditions were: the adsorption temperature is-10 to 40 ℃, and the space velocity of the adsorption volume is 100 to 1000h-1The adsorption pressure is 0.1-1.0 MPa.
9. The method of claim 1, wherein: setting the concentration of the adsorption outlet not higher than 50mg/m3Desorbing after penetrating the adsorption, wherein the desorption adopts heating regeneration,At least one of vacuum regeneration and vacuum thermal regeneration.
10. The method of claim 9, wherein: the final absolute pressure of the vacuum regenerated adsorption tower is 3-8 KPa, the regeneration time is 0.5-6 hours, and the maximum absolute pressure does not exceed 70% of the adsorption time.
11. The method of claim 1, 9 or 10, wherein: after the adsorption tower is subjected to multiple times of adsorption-desorption, when the adsorption quantity of the adsorbent is reduced to be below 85% of the initial adsorption quantity, the adsorption tower is subjected to vacuum thermal regeneration, nitrogen is used as a gas source, the absolute pressure of regeneration is 10-50 KPa, and the temperature is 80-300 ℃.
12. The method of claim 1, wherein: the MIL-Al metal organic framework material is MIL-53Al or/and MIL-100 Al.
13. The method according to claim 1 or 12, characterized in that: the carbonization is in N2Carbonizing at 600-1000 deg.C for 6-12 hr.
14. The method of claim 1, wherein: the acid cleaning adopts at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid solution, and the mass concentration of the acid solution is 10-20%.
15. The method of claim 1, wherein: the volume concentration of the ethylenediamine aqueous solution is 5-50%.
16. The method of claim 15, wherein: adding acrylonitrile with the volume concentration of 10-20% into the ethylene diamine aqueous solution.
17. A treatment plant for the treatment process of a sulphur dioxide containing flue gas according to any of claims 1 to 16, characterized in that it essentially comprises a compression and condensation unit, a condensation and liquefaction unit, an adsorption unit and a regeneration unit,wherein the compression and condensation unit mainly comprises a compressor and a condenser and is used for containing SO2Compressing and condensing the flue gas; the condensation liquefaction unit mainly comprises a condensation tank, a flash tower and SO2The storage tank is used for condensing and liquefying the compressed and condensed flue gas; the adsorption unit mainly comprises more than two adsorption towers filled with modified MIL-Al metal organic framework materials; the regeneration unit mainly comprises a vacuum pump and a nitrogen heater and is used for desorption regeneration of the adsorption unit.
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