CN111569604A - Low-temperature flue gas adsorption desulfurization method - Google Patents

Low-temperature flue gas adsorption desulfurization method Download PDF

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CN111569604A
CN111569604A CN202010421621.2A CN202010421621A CN111569604A CN 111569604 A CN111569604 A CN 111569604A CN 202010421621 A CN202010421621 A CN 202010421621A CN 111569604 A CN111569604 A CN 111569604A
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flue gas
temperature
adsorption
adsorption desulfurization
low
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汪世清
郜时旺
王绍民
蒋敏华
肖平
黄斌
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Huaneng Clean Energy Research Institute
China Huaneng Group Co Ltd
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Huaneng Clean Energy Research Institute
China Huaneng Group Co Ltd
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Priority to PCT/CN2020/126258 priority patent/WO2021232692A1/en
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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
    • B01D53/02—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
    • B01D53/04—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 with stationary adsorbents
    • 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
    • B01D53/26—Drying gases or vapours
    • 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

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Abstract

The invention discloses a low-temperature flue gas adsorption desulfurization method, which comprises the following steps: containing SO2The flue gas enters a flue gas cooling system, the flue gas is cooled to below room temperature through the flue gas cooling system, moisture in the flue gas is removed through a dehumidification system, then the flue gas is sent into an adsorption desulfurization system, and SO in the flue gas is adsorbed and removed through activated carbon, activated coke or a molecular sieve in the adsorption desulfurization system2Finally, the recovered cold energy is discharged through a chimney or enters an external flue gas purification system for further purification treatment, and the method is used for SO2The adsorption amount is higher, the safety is higher, and meanwhile, the consumption of the adsorbent is lower.

Description

Low-temperature flue gas adsorption desulfurization method
Technical Field
The invention belongs to the technical field of dry flue gas desulfurization, and relates to a low-temperature flue gas adsorption desulfurization method.
Background
The flue gas generated by burning coal contains a large amount of SO2It is one of the main causes of air pollution. At present, the mainstream desulfurization technology of coal-fired flue gas is limestone-gypsum wet desulfurization technology, and SO is subjected to wet desulfurization2And reacting with limestone slurry to generate insoluble calcium sulfate (gypsum) for removal. The wet desulphurization uses a large amount of limestone as a desulfurizer, the serious mountain destruction is caused by the large amount of exploitation of the limestone, and the treatment problem of a power plant is also brought by the generation of a large amount of desulphurization wastewater.
In addition, the dry active coke (charcoal) desulfurization technology is one of the mature desulfurization technologies at present, and is widely applied in japan, germany and our country. The operation temperature of the active coke (carbon) dry desulfurization technology is generally 100-150 ℃ for adsorption, and the SO is absorbed at the temperature2With H in the flue gas2O and O2Reaction to form H2SO4Thus SO2By chemisorption with H2SO4The form of (2) realizes adsorption. Adsorbed H2SO4Heating for regeneration to generate high-concentration SO2To prepare products such as sulfuric acid or sulfur; or by washing with water and regenerating2SO4And (6) washing to obtain the finished product.
The adsorption and heating regeneration mechanism of the dry desulfurization of the activated coke (carbon) is as follows:
and (3) adsorption reaction: SO (SO)2+H2O+1/2O2＝H2SO4
Heating and regenerating reaction: 2H2SO4+C→CO2+2SO2+2H2O (350-450 ℃ main reaction)
H2SO4+C→CO+SO2+H2O (main reaction at 450 ℃ C. or higher)
The dry active coke (charcoal) desulfurization technique has the following disadvantages:
1. sulfur capacity (SO)2Amount of adsorption) Low, generally lower than 30mg/g, large loading of active coke (carbon) and large adsorption equipment;
2. the heating regeneration temperature is high, generally higher than 350 ℃, the heat consumption is large, and the spontaneous combustion of the active coke (carbon) is easy to generate, so the contact with oxygen is prevented in the regeneration process, and the safety is poor;
3. in the heating regeneration process, active coke (carbon) participates in the reaction, and the consumption of the adsorbent is large.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a low-temperature adsorption desulfurization method for flue gas, which is used for SO2The adsorption amount is higher, the safety is higher, and meanwhile, the consumption of the adsorbent is lower.
In order to achieve the aim, the low-temperature flue gas adsorption desulfurization method comprises the following steps:
containing SO2The flue gas enters a flue gas cooling system, the flue gas is cooled to below room temperature through the flue gas cooling system, moisture in the flue gas is removed through a dehumidification system, then the flue gas is sent into an adsorption desulfurization system, and SO in the flue gas is adsorbed and removed through activated carbon, activated coke or a molecular sieve in the adsorption desulfurization system2And finally, the cold energy is recovered and then is discharged through a chimney or enters an external flue gas purification system for further purification treatment.
Further comprising: SO is adsorbed by adopting a heating regeneration mode or a vacuumizing regeneration mode2The activated carbon, the activated coke and the molecular sieve are regenerated.
Cooling the flue gas to-100-25 ℃ by a flue gas cooling system.
When the regeneration is carried out by adopting a heating regeneration mode, the regeneration temperature is 100-350 ℃.
The invention has the following beneficial effects:
during the specific operation of the low-temperature flue gas adsorption desulfurization method, the flue gas is cooled to below room temperature, the moisture in the flue gas is removed through the dehumidification system, and then the SO in the flue gas is adsorbed and removed through the activated carbon, the activated coke or the molecular sieve in the adsorption desulfurization system2The temperature of the flue gas is reduced to remove moisture in the flue gas and inhibit chemical adsorption (SO)2Conversion to H2SO4Adsorption), the adsorption capacity and the adsorption rate are far higher than those of the conventional activated coke (carbon) chemical adsorption desulfurization method, the method can be widely applied to coal-fired flue gas such as power plant flue gas, steel plant sintering flue gas, coke oven flue gas and the like, simultaneously, the activated carbon, the activated coke or the molecular sieve are regenerated by adopting a heating regeneration mode or a vacuum suction regeneration mode, the regeneration temperature is lower than that of the conventional activated coke (carbon) dry desulfurization regeneration process, and the safety is higher. In addition, SO2The desorption process is physical desorption without consumption of adsorbent, and the consumption of adsorbent is lower compared with the conventional active coke (carbon) dry desulfurization regeneration mechanism.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a graph showing the relationship between sulfur capacity and adsorption temperature of activated carbon.
Wherein, 1 is a flue gas cooling system, and 2 is an adsorption desulfurization system.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, the flue gas low-temperature adsorption desulfurization method of the present invention comprises the following steps:
containing SO2The flue gas enters a flue gas cooling system 1, the flue gas is cooled to-100-25 ℃ through the flue gas cooling system 1, then the moisture in the flue gas is removed through a dehumidification system, then the flue gas is sent into an adsorption desulfurization system 2, and the SO in the flue gas is adsorbed and removed through activated carbon, activated coke or molecular sieve in the adsorption desulfurization system 22And finally, the cold energy is recovered and then is discharged through a chimney or enters an external flue gas purification system for further purification treatment.
The invention also includes: SO is adsorbed by adopting a heating regeneration mode or a vacuumizing regeneration mode2The activated carbon, the activated coke and the molecular sieve are regenerated and then reused, wherein when the regeneration is carried out by adopting a heating regeneration mode, the regeneration temperature is 100-350 ℃, and in addition, high-concentration SO is obtained by regeneration2System ofTaking liquid SO2High value-added sulfur products such as sulfuric acid, sulfur, sulfate and the like.
The flue gas cooling system 1 and the adsorption desulfurization system 2 are both arranged in a cold insulation mode, and the loss of low-temperature flue gas cold energy is reduced.
The smoke parameters in the examples and comparative examples were: flue gas composition before desulfurization: SO (SO)2：3000mg/Nm3，CO2：12％，O2：6％，H2O: 5 percent. Flue gas flow rate: 1L/min.
Examples
Cooling the flue gas to-30 deg.C, removing condensed water, passing through 5g of active carbon with particle size of 30-40 meshes, passing through active carbon bed layer, and collecting SO2The content is detected by a flue gas analyzer, SO2The penetration time and the saturated adsorption amount are shown in table 1.
SO2Respectively heating the activated carbon after adsorption saturation to 100 ℃, 200 ℃, 300 ℃ and 400 ℃ for regeneration, and measuring the residual SO in the activated carbon by a total sulfur meter2Content, calculating SO2The desorption rate is shown in Table 2.
Comparative example:
the flue gas is heated to 100 ℃, and other processes are the same as the embodiment.
TABLE 1
Examples Comparative examples
Adsorption temperature -20℃ 100℃
Penetration duration 300 minutes 37 minutes
SO2Amount of adsorption 180mg/g 22mg/g
TABLE 2
Figure BDA0002497177720000041
Figure BDA0002497177720000051
The analysis results of examples and comparative examples show that the SO content is better at low temperature2Adsorption Effect, SO2The adsorption capacity at the smoke temperature of 20 ℃ below zero is 8 times of that at the smoke temperature of 100 ℃; adsorption in low temperature environment, SO due to less water content2Mainly adopts physical adsorption, is easy to desorb, and SO is absorbed when the temperature is heated to 100 DEG C2The desorption rate is close to 80 percent; when the adsorbent is adsorbed at a high temperature of 100 ℃, SO is generated due to more water2Mainly by H2SO4The form of adsorption (chemical adsorption) is difficult to desorb, and the desorption can be effectively carried out only by heating to about 400 ℃. Therefore, the low-temperature adsorption desulfurization method disclosed by the invention has more advantages than the conventional adsorption desulfurization method.

Claims (4)

1. A low-temperature adsorption desulfurization method for flue gas is characterized by comprising the following steps:
containing SO2The flue gas enters a flue gas cooling system (1), the flue gas is cooled to below room temperature through the flue gas cooling system (1), moisture in the flue gas is removed through a dehumidification system, then the flue gas is sent into an adsorption desulfurization system (2), and SO in the flue gas is adsorbed and removed through activated carbon, activated coke or molecular sieves in the adsorption desulfurization system (2)2Finally go intoAnd the recovered cold energy is discharged through a chimney or enters an external flue gas purification system for further purification treatment.
2. The method for low-temperature adsorption desulfurization of flue gas according to claim 1, further comprising: SO is adsorbed by adopting a heating regeneration mode or a vacuumizing regeneration mode2The activated carbon, the activated coke and the molecular sieve are regenerated.
3. The low-temperature flue gas adsorption desulfurization method according to claim 1, characterized in that the flue gas is cooled to-100 ℃ to 25 ℃ by the flue gas cooling system (1).
4. The method for low-temperature flue gas adsorption desulfurization according to claim 2, wherein the regeneration is carried out by heating regeneration at a temperature of 100 ℃ to 350 ℃.
CN202010421621.2A 2020-05-18 2020-05-18 Low-temperature flue gas adsorption desulfurization method Pending CN111569604A (en)

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WO2021232692A1 (en) * 2020-05-18 2021-11-25 中国华能集团有限公司 Method for low temperature adsorption and desulfurization of flue gas
WO2021232693A1 (en) * 2020-05-18 2021-11-25 中国华能集团有限公司 Flue gas integrated desulfurization and denitration method based on low-temperature adsorption principle
CN113769636A (en) * 2021-09-22 2021-12-10 天津汇能朗天环保设备有限公司 Method for mixing chemical powder and flue gas in dry desulfurization purifier
WO2022032860A1 (en) * 2020-08-14 2022-02-17 中国华能集团清洁能源技术研究院有限公司 Near-zero emission-type flue gas multi-pollutant integrated removal system and method
WO2023050896A1 (en) * 2021-09-28 2023-04-06 中国华能集团清洁能源技术研究院有限公司 Low-temperature desulfurization and denitrification system for flue gas of biomass power plant

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WO2021232692A1 (en) * 2020-05-18 2021-11-25 中国华能集团有限公司 Method for low temperature adsorption and desulfurization of flue gas
WO2021232693A1 (en) * 2020-05-18 2021-11-25 中国华能集团有限公司 Flue gas integrated desulfurization and denitration method based on low-temperature adsorption principle
WO2022032860A1 (en) * 2020-08-14 2022-02-17 中国华能集团清洁能源技术研究院有限公司 Near-zero emission-type flue gas multi-pollutant integrated removal system and method
CN113769636A (en) * 2021-09-22 2021-12-10 天津汇能朗天环保设备有限公司 Method for mixing chemical powder and flue gas in dry desulfurization purifier
WO2023050896A1 (en) * 2021-09-28 2023-04-06 中国华能集团清洁能源技术研究院有限公司 Low-temperature desulfurization and denitrification system for flue gas of biomass power plant

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