CN111375270B - Containing SO2Flue gas treatment method and device - Google Patents
Containing SO2Flue gas treatment method and device Download PDFInfo
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- CN111375270B CN111375270B CN201811651639.0A CN201811651639A CN111375270B CN 111375270 B CN111375270 B CN 111375270B CN 201811651639 A CN201811651639 A CN 201811651639A CN 111375270 B CN111375270 B CN 111375270B
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Classifications
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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
Abstract
The invention relates to a method for preparing a sulfur-containing organic compound2The method and device for treating flue gas contain SO2The gas is compressed and condensed in the compression and condensation unit, then enters the condensation and liquefaction unit, the non-condensable gas enters the adsorption unit for adsorption, and the purified gas is discharged after reaching the standard; the adsorbent adopted by the adsorption unit is a modified zinc-based metal organic framework material, desorption is carried out after adsorption penetration, and desorption gas and SO-containing gas to be treated are obtained2The flue gas is mixed and then enters a compression condensing unit. The invention can realize SO2High-efficiency physical adsorption and liquefaction recovery, and reduces the liquefaction energy consumption and SO2High recovery rate and good operation stability, and the purified gas meets the emission requirement.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a sulfur dioxide (SO) -containing catalyst2A method and a device for treating 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。
At present, the desulfurization technology is widely appliedThe technical classification can be wet desulphurization technology and dry desulphurization technology. 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 is the oxidation of SO by chemical agents or catalytic oxidation2Conversion 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 N is realized by a method of frequency conversion and pressure swing adsorption after deep fine dehydration, deoxidation and decarbonation of a fine dehydration tank2With 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. However, even if the variable-frequency and variable-pressure adsorption method is adopted, the SO obtained by desorption is limited due to the adsorption performance of the active 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 catalyst containing SO2A method and a device for treating flue gas. 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 liquefaction recoveryLow energy consumption for liquefaction, SO2High recovery rate and good operation stability, and the purified gas meets the emission requirement.
The invention provides a process for preparing a compound containing SO2The gas treatment method comprises the following steps:
will contain SO2The gas is compressed and condensed in the compression and condensation unit, then enters the condensation and liquefaction unit, the non-condensable gas enters the adsorption unit for adsorption, and the purified gas is discharged after reaching the standard; the adsorbent adopted by the adsorption unit is a modified zinc-based metal organic framework material, desorption is carried out after adsorption penetration, and desorption gas and SO-containing gas to be treated are obtained2The flue gas is mixed and then enters a compression condensing unit.
In the invention, the modified zinc-based metal organic framework material is prepared by treating a zinc-based MOFs material at 850-1150 ℃ for 5-10 hours in the presence of nitrogen. The zinc-based metal organic framework material can be at least one of MOFs-5, MOFs-74, ZIF series and the like, the ZIF series material can be at least one of ZIF-8, ZIF-20, ZIF-21 and the like, and MOFs-5 is preferable. The specific surface area of the zinc-based metal organic framework material is 850-1660 m2A pore volume of 0.8 to 1.15 cm/g3(ii) in terms of/g. Furthermore, before the treatment, a certain amount of basic amino acid is doped for modification, such as at least one of lysine, arginine, histidine and the like, preferably histidine. The dosage of the amino acid is 0.01-5.0 percent of the mass of the metal organic framework material, and preferably 0.1-2.0 percent. The adsorption saturation capacity of the modified zinc-based metal organic framework material is more than 2 times of that of the commercial active carbon.
In the present invention, the SO-containing compound2The flue gas can be from the exhaust gas or flue gas of coal-fired power plants, metallurgical plants, petrochemical plants and the like, such as the 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 0.5%, generally 0.5% -15%. According to the characteristics of the waste gas source, the SO is contained2The flue gas is pretreated by dedusting, cooling, dehydrating, drying and the like before compression and condensation.
In the invention, the compression and condensation unit mainly comprises a compressor, a refrigerating unit and the like and is used for treating SO-containing gas2Compressing and condensing the gas, and controlling the gauge pressure to be 0.3-3.0 MPaG, preferably 0.5-2.0 MPaG; the temperature is-20 to 10 ℃, preferably-15 to 0 ℃. 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, and is preferably filled with an inert porous medium material, such as at least one of a ceramic porous medium material, a foam porous medium material, activated carbon, glass fiber and the like, and the pore size distribution is 1-200 nm, preferably 2-100 nm. SO (SO)2Condensing and liquefying in a condensing tank to obtain liquid SO2. 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 ℃, preferably 5 to 30 ℃, and the volume space velocity is 100 to 1000h-1The adsorption pressure is 0.1-1.0 MPa.
In the present invention, the concentration of the adsorption outlet is set to 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 h, 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.
The invention also provides a method for treating the SO-containing gas2The flue gas treatment device mainly 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 refrigerating unit and is used for treating SO-containing gas2Compressing and condensing the flue gas; the condensation liquefaction unit mainly comprises a condensation tank and liquid SO2The storage tank 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 zinc-based 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 liquid SO with higher purity2，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 zinc-based metal organic framework material has SO in the penetration time under the condition of 0.1-0.3 MPa2The adsorption capacity of the adsorption tower is more than 2 times that of commercial activated carbon and more than 1.6 times that of MOFs materials, so that the number and scale of the adsorption towers can be reduced, and the treatment cost is reduced. Adopts amino acid modified zinc-based metal organic framework material, is beneficial to SO2High-efficiency physical adsorption and rapid desorption of SO2After multiple times of cyclic adsorption-desorption, the adsorption capacity can still be stabilized to more than 85% of the initial adsorption capacity, and the adsorption stability is good.
Drawings
FIG. 1 is a schematic flow diagram of an adsorption process of the present invention; wherein: 1-compressor, 2-refrigerating unit, 3-condensate tank, 4-liquid SO2Storage tank, 5-adsorption tower set, 6-SO2An online detector, 7-desorption vacuum pump, 8-heater, 9-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:
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, wherein the compression condensing unit mainly comprises a compressor 1 and a refrigerating unit 2, and the condensation liquefying unit mainly comprises a condensation tank 3 and liquid SO (SO)2A storage tank 4; the adsorption unit mainly comprises two or more than two adsorption tower groups 5, each adsorption tower is filled with modified zinc-based metal organic framework materials, and an SO is arranged at the outlet of the adsorption tower2An online detector 6; the regeneration unit mainly comprises a desorption vacuum pump 7, a heater 8 and a heat regeneration vacuum pump 9. Firstly, removing particles, dehydrating and cooling to obtain the product containing high-concentration SO2The flue gas is compressed by a compressor and then enters a refrigerating unit for condensation, and then enters a condensation tank 3, and the generated liquid SO2Into liquid SO2The non-condensable gas in the storage tank 4 enters the adsorption tower group 5 and is switched by a plurality of adsorption towers,the adsorbed flue gas enters SO2An on-line detector 6 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 7 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 9, performing N regeneration2Heated by a heater 8, 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, cooling, dehydration and drying pretreatment before compression and condensation, and SO in the treated waste gas2The volume concentration of (A) is 2-5%, O2The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 500Nm3/h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m2G, pore volume of 1.13cm3G, Zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO2The flue gas is compressed and condensed, the gauge pressure is controlled to be 2.0MPaG, and the temperature is controlled to be minus 10 ℃. After compression and condensation, the condensed liquid enters a condensation liquefaction unit, and a condensation tank is an empty tank to obtain liquid SO2. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified zinc-based metal organic framework material. The adsorption conditions were: the adsorption temperature is 5-30 ℃, and the volume space velocity is about 300h-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 1-3 h. Vacuum desorption is adopted after the adsorption tower penetrates through the adsorption tower, the final absolute pressure of the adsorption tower is 3-5 KPa, and desorption is carried outThe time was 60% of the adsorption time. Desorbed gaseous SO2Entering a compression condensation unit and then entering a condensation liquefaction unit to obtain liquid SO2Entering a storage tank for storage. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3When the adsorption capacity is reduced to below 85% of the initial adsorption capacity, performing one-time 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 1 month of operation, accumulating to obtain liquid SO2About 30 tons, the adsorption capacity of the adsorbent can be stabilized to 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, cooling, dehydration and drying pretreatment before compression and condensation, and SO in the treated waste gas2The volume concentration of (A) is 3-10%, O2The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 1000Nm3/h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m2G, pore volume of 1.13cm3G, Zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO2Compressing and condensing the flue gas, controlling the gauge pressure to be 2.0MPaG and the temperature to be-15 ℃. After compression and condensation, the condensed liquid enters a condensation liquefaction unit, and a condensation tank is an empty tank to obtain liquid SO2. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified zinc-based 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 0.3-0.4 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 1-3 h. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 45mg/m3. Vacuum desorption is adopted after the adsorption tower penetrates through the adsorption tower, the final absolute pressure of the adsorption tower is 3-5 KPa, and the desorption time is60% of the adsorption time. Desorbed gaseous SO2Entering a compression condensation unit and then entering a condensation liquefaction unit to obtain liquid SO2Entering a storage tank for storage. When the adsorption capacity is reduced to below 85% of the initial adsorption capacity, performing one-time 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 1 month of operation, accumulating to obtain liquid SO2About 100 tons, the adsorption capacity of the adsorbent can be stabilized to 85% or more of the initial adsorption capacity.
Example 3
Containing SO2The gas is S-zorb adsorbent regeneration flue gas, and is subjected to dust removal, cooling, dehydration and drying pretreatment before compression and condensation, and SO in the treated waste gas2The volume concentration of (A) is 2-5%, O2The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 500Nm3/h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m2G, pore volume of 1.13cm3G, Zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO2Compressing and condensing the flue gas, controlling the gauge pressure to be 1.0MPaG and the temperature to be-15 ℃. After compression and condensation, the condensed liquid enters a condensation liquefaction unit, and a condensation tank is an empty tank to obtain liquid SO2. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified zinc-based 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 0.3-0.4 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. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3. 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 SO2The mixture enters a compression and condensation unit,then enters a condensation liquefaction unit to obtain liquid SO2Entering a storage tank for storage. When the adsorption capacity is reduced to below 85% of the initial adsorption capacity, performing one-time 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 1 month of operation, accumulating to obtain liquid SO2About 28.5 tons, the adsorption capacity of the adsorbent can be stabilized to 85% or more of the initial adsorption capacity.
Example 4
Containing SO2The gas is S-zorb adsorbent regeneration flue gas, and is subjected to dust removal, cooling, dehydration and drying pretreatment before compression and condensation, and SO in the treated waste gas2The volume concentration of (A) is 2-5%, O2The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 500Nm3/h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m2G, pore volume of 1.13cm3G, Zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO2The flue gas is compressed and condensed, the gauge pressure is controlled to be 0.6MPaG, and the temperature is controlled to be-5 ℃. Compressing, condensing, introducing into a condensing and liquefying unit, filling activated carbon with main pore diameter distribution of 1-60nm in a condensing tank to obtain liquid SO2. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified zinc-based metal organic framework material. The adsorption conditions were: the adsorption temperature is 5-30 ℃, and the volume space velocity is about 300h-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 1-3 h. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 40mg/m3. 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 a liquid stateSO2Entering a storage tank for storage. When the adsorption capacity is reduced to below 85% of the initial adsorption capacity, performing one-time 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 1 month of operation, accumulating to obtain liquid SO2About 31 tons, the adsorption capacity of the adsorbent can be stabilized to 85% or more of the initial adsorption capacity.
Example 5
Containing SO2The gas is S-zorb adsorbent regeneration flue gas, and is subjected to dust removal, cooling, dehydration and drying pretreatment before compression and condensation, and SO in the treated waste gas2The volume concentration of (A) is 2-5%, O2The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 500Nm3/h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m2G, pore volume of 1.13cm3G, Zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO2The flue gas is compressed and condensed, the gauge pressure is controlled to be 1.0MPaG, and the temperature is controlled to be-5 ℃. Compressing and condensing the mixture, introducing the condensed mixture into a condensation liquefaction unit, filling a condensation tank with a ceramic porous medium material with a main pore diameter of 30-100nm to obtain liquid SO2. The non-condensable gas discharged from the condensation tank enters an adsorption unit, and the adsorption unit is filled with the modified zinc-based metal organic framework material. The adsorption conditions were: the adsorption temperature is 5-30 ℃, and the volume space velocity is about 300h-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 1-3 h. SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3. 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 liquid SO2Entering a storage tank for storage.When the adsorption capacity is reduced to below 85% of the initial adsorption capacity, performing one-time vacuum thermal regeneration, wherein hot nitrogen is used as a gas source, the regeneration temperature is 150-.
After 1 month of operation, accumulating to obtain liquid SO2About 31.5 tons, the adsorption capacity of the adsorbent can be stabilized to 85% or more of the initial adsorption capacity.
Example 6
The difference from example 1 is that: the preparation of the modified zinc-based metal organic framework material comprises the following steps: taking MOF-5 as a matrix, the specific surface area is 1655m2G, pore volume of 1.13cm3G, Zn content 31.2%. And (3) doping lysine accounting for 1.0% of the MOF-5 by mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
The volume space velocity needs to be controlled at 250h-1The penetration time of a single adsorption tower is about 1-3 h, and SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3. After 1 month of operation, accumulating to obtain liquid SO2About 29.2 tons, the adsorption capacity of the adsorbent can be stabilized to 85% or more of the initial adsorption capacity.
Example 7
The difference from example 1 is that: the preparation of the modified zinc-based metal organic framework material comprises the following steps: taking MOF-5 as a matrix, the specific surface area is 1655m2G, pore volume of 1.13cm3G, Zn content 31.2%. Doping arginine accounting for 1.0 percent of the MOF-5 by mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
The volume space velocity is still controlled to be 300h-1The penetration time of a single adsorption tower is about 0.5-2 h, and SO in the exhaust gas of the adsorption tower2The concentration is always lower than 50mg/m3. After 1 month of operation, accumulating to obtain liquid SO2About 27 tons, the adsorption capacity of the adsorbent can be stabilized to 85% or more of the initial adsorption capacity.
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 150h-1Following, and due to too long desorption timeLong, the need to add an adsorption column.
Comparative example 2
The difference from example 1 is that MOF-5 is used as the adsorbent material. The volume space velocity needs to be reduced to 200h-1Following, and due to the catalytic action of MOF-5 itself, small amounts of O in the exhaust gas2Adding SO2By oxidation to SO3Resulting in the final formation of liquid SO2Containing a small amount of SO3。
Comparative example 3
The difference from example 1 is that condensation liquefaction is not used, and the adsorption is directly removed after compression condensation. Require adsorption of regenerated SO2And a compression condensing system is additionally arranged, so that the equipment investment and the operation energy consumption are improved.
Claims (19)
1. Containing SO2The method for treating the flue gas is characterized by comprising the following steps: will contain SO2The gas is compressed and condensed in the compression and condensation unit, then enters the condensation and liquefaction unit, the non-condensable gas enters the adsorption unit for adsorption, and the purified gas is discharged after reaching the standard; the adsorbent adopted by the adsorption unit is a modified zinc-based metal organic framework material, the modified zinc-based metal organic framework material is prepared by treating the zinc-based metal organic framework material at 850-1150 ℃ for 5-10 hours in the presence of nitrogen, and doping a certain amount of basic amino acid before treatment for modification, wherein the basic amino acid is at least one of lysine, arginine and histidine; the zinc-based metal organic framework material is at least one of MOFs-5, MOFs-74 and ZIF series; desorbing after the adsorption penetration, and desorbing the gas containing SO to be treated2The flue gas is mixed and then enters a compression condensing unit.
2. The method of claim 1, wherein: the zinc-based metal organic framework material is MOFs-5.
3. The method of claim 1, wherein: the basic amino acid is histidine.
4. The method of claim 1, wherein: the dosage of the basic amino acid is 0.01 to 5.0 percent of the mass of the zinc-based metal organic framework material.
5. The method of claim 4, wherein: the dosage of the basic amino acid is 0.1 to 2.0 percent of the mass of the zinc-based metal organic framework material.
6. The method of claim 1, wherein: said SO-containing2The flue gas is from waste gas or 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 gas2The volume concentration of (a) is 0.5% or more.
7. The method of claim 6, wherein: SO in flue gas2The volume concentration of (A) is 0.5-15%.
8. The method of claim 1, 6 or 7, wherein: according to the characteristics of the waste gas source, the SO is contained2The flue gas is subjected to dust removal, cooling, dehydration and drying pretreatment before compression and condensation.
9. The method of claim 1, wherein: in the compression condensing unit, the gauge pressure is controlled to be 0.3-3.0 MPaG, and the temperature is controlled to be-20-10 ℃.
10. The method of claim 9, wherein: the gauge pressure is controlled to be 0.5-2.0 MPaG, and the temperature is controlled to be-15-0 ℃.
11. The method of claim 1, wherein: the condensation liquefaction unit mainly comprises a condensation tank and liquid SO2A storage tank, wherein the coagulation tank is an empty tank.
12. The method of claim 1The method is characterized in that: the condensation liquefaction unit mainly comprises a condensation tank and liquid SO2And the agglomeration tank is filled with an inert porous medium material, and the pore size distribution is 1-200 nm.
13. The method of claim 12, wherein: the porous medium material is at least one of ceramic porous medium material, foam porous medium material, activated carbon and glass fiber, and the pore size distribution is 2-100 nm.
14. The method of claim 1, wherein: the adsorption unit consists of two or more adsorption towers and alternately operates; the adsorption conditions were: the adsorption temperature is-10 to 40 ℃, and the volume space velocity is 100 to 1000h-1The adsorption pressure is 0.1-1.0 MPa.
15. The method of claim 1, wherein: setting the concentration of the adsorption outlet not higher than 50mg/m3Desorbing after the adsorption penetration, wherein the desorption adopts heating regeneration, vacuum regeneration or vacuum thermal regeneration.
16. The method of claim 1, wherein: the desorption adopts the combination of vacuum regeneration and periodic vacuum thermal regeneration.
17. The method according to claim 15 or 16, characterized in that: the final absolute pressure of the vacuum regenerated adsorption tower is 3-8 KPa, the regeneration time is 0.5-6 h, and the maximum absolute pressure does not exceed 70% of the adsorption time.
18. The method of claim 1, 15 or 16, 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 ℃.
19. For use in claim 1-18 any of said SO-containing compounds2The treatment device of the flue gas treatment method is characterized by mainly comprising 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 refrigerating unit and is used for treating SO-containing gas2Compressing and condensing the flue gas; the condensation liquefaction unit mainly comprises a condensation tank and liquid SO2The storage tank 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 zinc-based 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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Effective date of registration: 20231016 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
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