CN113491945A - Absorption recovery system and process for sulfur dioxide flue gas - Google Patents

Absorption recovery system and process for sulfur dioxide flue gas Download PDF

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Publication number
CN113491945A
CN113491945A CN202010270814.2A CN202010270814A CN113491945A CN 113491945 A CN113491945 A CN 113491945A CN 202010270814 A CN202010270814 A CN 202010270814A CN 113491945 A CN113491945 A CN 113491945A
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China
Prior art keywords
flue gas
water
absorption
tank
sulfur dioxide
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杨继
毛松柏
郭本帅
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants
    • B01D2255/702—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention relates to the field of gas purification, in particular to a system and a process for absorbing and recovering sulfur dioxide flue gas. The invention provides a novel absorption and recovery system and a novel absorption and recovery process for sulfur dioxide flue gas, aiming at solving the problems that a disposable and irreversible absorbent is used in the traditional sulfur dioxide absorption process, and the added value of the generated product is low; the absorbent adopted in the absorption process has stable performance, can be regenerated, has low energy consumption and higher desulfurization efficiency which reaches more than 99.5 percent, and the regenerated desulfurizer can also reach similar efficiency.

Description

Absorption recovery system and process for sulfur dioxide flue gas
Technical Field
The invention relates to the field of gas purification, in particular to a system and a process for absorbing and recovering sulfur dioxide flue gas.
Background
Although the economic development of China is rapid and the industrialization level is continuously improved, the condition of air pollution is increasingly serious. On the one hand, coal resources play an important role in the global energy consumption structure. And all aspects of economic development need to depend on coal resources, high-sulfur coal occupies one third of the coal resources, and the combustion of the high-sulfur coal can release a large amount of SO2 gas, thereby causing serious harm to the environment. On the other hand, the yield of sulfuric acid in China is large, and a large amount of SO2 gas is discharged in the production process of sulfuric acid. Meanwhile, in the ultralow emission standard which needs to be realized in 2020, SO2 in the treated flue gas is lower than 50 mg/Nm3, and in some sensitive areas, SO2 is lower than 355 mg/Nm 3.
The traditional common sulfur dioxide removal method comprises a limestone absorption method and an ammonia gas method. Although the lime method desulfurization has low absorption cost, a large amount of gypsum is generated, the economic value is low, and if no proper place is provided, the lime method desulfurization belongs to solid waste; if the gypsum is made into lime slurry, the problems of large equipment volume, complex manufacturing method, high investment and high water consumption are encountered. The ammonia desulphurization is also called ammonia desulphurization, the value of the ammonia is high, the added value of the byproduct ammonium sulfate generated after desulphurization is low, and meanwhile, the phenomenon of ammonia escape exists in the process of sulfur dioxide removal, and aerosol is formed to cause pollution.
The two common sulfur dioxide removal methods have certain limitations, a new absorption and recovery system and a new absorption and recovery process can be recycled, and the low cost is the technical key for solving the problem at the present stage.
Disclosure of Invention
The invention relates to the field of gas purification, in particular to a system and a process for absorbing and recovering sulfur dioxide flue gas.
The invention provides a novel absorption and recovery system and a novel absorption and recovery process for sulfur dioxide flue gas, aiming at solving the problems that a disposable and irreversible absorbent is used in the traditional sulfur dioxide absorption process, and the added value of the generated product is low; the absorbent adopted in the absorption process has stable performance, can be regenerated, has low energy consumption and higher desulfurization efficiency which reaches more than 99.5 percent, and the regenerated desulfurizer can also reach similar efficiency.
The invention realizes the above effects through the following scheme:
the invention provides an absorption and recovery system for sulfur dioxide flue gas, which mainly comprises a water supplementing system, an absorption system, a regeneration system and a sulfuric acid recovery system; the water supplementing system is provided with a first flue gas inlet and a first flue gas flowmeter; the water replenishing system is also provided with an oxygen inlet and an oxygen inlet flowmeter; the water supplementing system is also provided with a smoke buffer tank, a second smoke inlet, a water supplementing tank and electric heating; the flue gas enters the buffer tank through the first flue gas inlet and enters the water supplementing tank through the second flue gas inlet, and the water supplementing tank is electrically heated to ensure that the flue gas takes away enough water vapor for subsequent absorption catalysis; the absorption system comprises an absorption tower, an absorbent, an upper flange of the absorption tower, a lower flange of the absorption tower, a purifier outlet and lower evacuation of the absorption tower; the gas inlet in the absorption system is arranged at the bottom of the absorption tower, and the purified gas outlet is arranged at the top of the absorption tower; the regeneration system comprises a regeneration water tank, regeneration water, a regeneration water pump and a regeneration water flowmeter; the sulfuric acid recovery system comprises a sulfuric acid pipeline, a sulfuric acid tank, sulfuric acid and a sulfuric acid tank emptying device.
In the invention, the first flue gas flowmeter is used for controlling the gas flow of the raw material gas.
In the invention, the oxygen inlet flow meter is used for controlling the gas flow of the oxygen inlet.
In the invention, the first flue gas inlet is used for containing SO2The flue gas is sent into a buffer tank.
In the invention, the buffer tank is used for mixing the raw material gas and the oxygen.
In the invention, the liquid of the water replenishing tank is provided with a water inlet of the water replenishing tank, and the water inlet of the water replenishing tank is used for maintaining the liquid level of the water replenishing tank.
In the invention, the water replenishing tank is provided with a thermocouple, and the thermocouple is used for measuring the temperature of water in the water replenishing tank.
In the invention, the water replenishing tank is provided with a transformer, and the transformer is used for adjusting the power of the heating wire of the water replenishing tank.
In the invention, the second flue gas inlet is arranged at the upper part of the liquid level of the water replenishing tank and is used for humidifying flue gas.
In the invention, the smoke outlet of the water replenishing tank is arranged at the top of the water replenishing tank.
In the invention, the absorption system also comprises absorption tower circulating water, an absorption tower circulating water flowmeter, an absorption tower circulating water pump and an absorption tower circulating water constant temperature water tank, and the part can be replaced by electric heating and heat preservation.
In the invention, the gas inlet in the absorption system is arranged at the bottom of the absorption tower.
In the invention, the upper flange and the lower flange of the absorption tower are used for facilitating the replacement and the maintenance of the absorbent in the absorption tower.
In the invention, the absorption tower is used for contacting the humidified flue gas with the absorbent, so that the sulfur dioxide and water in the flue gas are absorbed and catalyzed by the absorbent.
In the absorption system, the purified gas outlet is arranged at the top of the absorption tower.
In the invention, the lower discharge liquid of the absorption tower of the absorption system is used for discharging the redundant liquid in the absorption process.
In the invention, the circulating water of the absorption system is provided with a thermocouple and electric heating, and the thermocouple and the electric heating are used for controlling the temperature of the circulating water of the absorption system.
In the present invention, the regeneration water is normal temperature water.
In the invention, the regeneration water flow meter is used for controlling the flow of the regeneration water.
The sulfuric acid recovery system comprises a sulfuric acid pipeline, a sulfuric acid tank, sulfuric acid and a sulfuric acid tank emptying device.
In the invention, the sulfuric acid pipeline is used for removing the regeneration by-product sulfuric acid.
In the invention, the emptying of the sulfuric acid tank is used for recovering the regeneration byproduct sulfuric acid.
The invention also provides an absorption and recovery process for the sulfur dioxide flue gas, which comprises the following steps:
(1) the flow of the flue gas containing sulfur dioxide and oxygen is controlled by the first flue gas flowmeter and the oxygen inlet flowmeter, the flue gas and the oxygen enter a buffer tank to be mixed, then the flue gas and the oxygen enter a water supplementing tank through a second flue gas inlet, and wet flue gas with the temperature of above 40 ℃ is obtained after water supplementing and heating;
(2) the wet flue gas is contacted with an absorbent in an absorption tower, and clean tail gas is obtained through catalytic absorption;
(3) the absorption tower is regenerated through a regeneration system, normal-temperature water is sprayed into the absorption tower for regeneration, and regenerated liquid is recycled through the sulfuric acid pipeline;
(4) the regenerated absorbent can be used for catalyzing and absorbing sulfur dioxide.
Further, in the step (1), the maximum sulfur dioxide content of the sulfur dioxide concentration in the sulfur dioxide-containing flue gas may be 10000 mg/Nm3。
In the step (1), the optimal temperature of the heated wet flue gas is 40-85 ℃, for example, 40 ℃.
In the step (1), the pressure of the buffer tank is the conventional operation pressure in the field, and is preferably 101 to 110 kPa, such as 105 kPa.
In the step (2), the raw material gas is heated and humidified and then enters an absorption tower to be absorbed within the range of 40-95 ℃, for example, the temperature is 80 ℃.
In the step (2), the absorbent is activated carbon modified by one or more metal oxides, and the oxide of the activated carbon can be one or more of Cu, Cr, Fe, Ni, Co and Ce.
In the step (2), the absorbent is cylindrical or spherical, and the filling density is 0.45-0.85 g/cm3E.g. columnar, packing density of 0.75 g/cm3。
In the step (3), the reclaimed water is desalted water, and the temperature is normal temperature, preferably 10-30 ℃, such as 25 ℃.
In the step (4), the regenerated absorbent can be directly used for catalyzing and absorbing sulfur dioxide.
The above conditions may be combined arbitrarily to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The starting materials and reagents required for the present invention are commercially available.
The invention discloses a new absorption recovery system and a new absorption recovery process, wherein the system and an absorbent can be recycled, and the cost is low; the absorbent adopted by the absorption process has stronger absorption capacity to sulfur dioxide and high desulfurization efficiency, and can absorb 1000 mg/Nm sulfur dioxide3The desulfurization efficiency of the raw material gas reaches more than 99.5 percent.
Drawings
FIG. 1 is a schematic view of an absorption recovery system in an embodiment of the present invention.
Description of reference numerals:
first flue gas inlet 1
First flue gas flowmeter 2
Flue gas buffer tank 3
Second flue gas inlet 4
Water replenishing tank 5
Schematic of make-up water 6
Electric heating wire 7
Absorption tower 8
Absorbent 9
Absorption tower upper flange 10
Absorb the lower flange 11 of the other
Purifier outlet 12
Circulating water 13 of the absorption tower
Circulating water flow meter 14 of absorption tower
Absorption tower circulating water pump 15
Circulating water constant temperature water tank 16 of absorption tower
Regeneration water tank 17
Regeneration water 18
Regeneration water pump 19
Regeneration water flowmeter 20
Sulfuric acid line 21
Sulfuric acid tank 22
Sulfuric acid 23
Sulfuric acid tank emptying 24
Lower column evacuation 25
Oxygen inlet 26
An oxygen inlet flow meter 27.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
The method of the embodiment has the following steps:
(1) preparation of the absorbent: the activated carbon used in this example was self-made and was activated mainly by physical activation. The preparation method comprises the following steps: weighing certain pretreated coconut shell carbonized material, putting into an activated carbon activator, introducing nitrogen, heating to about 900 deg.C, and introducing steam or CO respectively2Activating, cooling, regulating the pH value of the activated carbon to 7, and finally drying to obtain the required activated carbon.
(2) Referring to fig. 1, the absorption process flow is as follows: the gas containing sulfur dioxide enters the absorption tower from the bottom of the tower after being humidified, and is absorbed and purified by the heat-insulated absorbent zone in the absorption tower and then is discharged from the gas outlet at the top of the absorption tower. After a certain period of time of absorption, the regenerated water flows in from the top of the tower to regenerate the active carbon.
(3) The experimental conditions were: gas composition: oxygen 7.26% (nitrogen), sulfur dioxide content 10000 mg/Nm3And the balance of nitrogen. Gas flow rate 97 m3H, space velocity 600 h-1And the heat preservation temperature of the absorbent is 80 ℃. The measured sulfur dioxide concentration of the purified gas was 35 mg/Nm3About 50 mg/Nm of purified gas3The effective absorption capacity of the inner absorbent is 22.4 mg/mL.
Example 2
Gas composition: oxygen 7.26% (nitrogen), sulfur dioxide content 10000 mg/Nm3And the balance of nitrogen. Gas flow rate 97 m3H, space velocity 600 h-1And the heat preservation temperature of the absorbent is 40 ℃. The measured sulfur dioxide concentration of the purified gas was 370 mg/Nm3Left and right.
Example 3
Gas composition: oxygen 7.26% (nitrogen), sulfur dioxide content 10000 mg/Nm3And the balance of nitrogen. Gas flow rate 97 m3H, space velocity 600 h-1And the heat preservation temperature of the absorbent is 60 ℃. The measured sulfur dioxide concentration of the purified gas was 95 mg/Nm3Left and right.
Example 4
Gas composition: oxygen 7.26% (nitrogen), sulfur dioxide content 10000 mg/Nm3And the balance of nitrogen. Gas flow rate 97 m3H, space velocity 600 h-1And the heat preservation temperature of the absorbent is 70 ℃. The measured sulfur dioxide concentration of the purified gas was 65 mg/Nm3Left and right.
Example 5
Gas composition: oxygen 7.26% (nitrogen), sulfur dioxide content 10000 mg/Nm3And the balance of nitrogen. Gas flow rate 97 m3H, space velocity 600 h-1And the heat preservation temperature of the absorbent is 75 ℃. The measured sulfur dioxide concentration of the purified gas is 52 mg/Nm3Left and right.
Example 6
Gas composition: oxygen 7.26% (nitrogen), sulfur dioxide content 10000 mg/Nm3And the balance of nitrogen. Gas flow rate 97 m3H, space velocity 600 h-1And the heat preservation temperature of the absorbent is 85 ℃. The measured sulfur dioxide concentration of the purified gas was 32 mg/Nm3Left and right.
Example 7
Gas composition: oxygen 7.26% (nitrogen), sulfur dioxide content 20000 mg/Nm3And the balance of nitrogen. Gas flow rate 97 m3H, space velocity 600 h-1And the heat preservation temperature of the absorbent is 80 ℃. The concentration of sulfur dioxide in the purified gas is measured to be more than 1000 mg/Nm3。
Example 8
The regeneration water was introduced into the absorption column in example 1, and after a certain period of regeneration, the regeneration water was again introduced into the absorption column containing 10000 mg/Nm3The volume fraction of oxygen is 7.26%, and the gas flow is 97 m3H, the measured sulfur dioxide concentration of the purified gas is 36 mg/Nm3Left and right.

Claims (10)

1. An absorption recovery system for sulfur dioxide flue gas is characterized in that the absorption recovery system comprises a water supplementing system, an absorption system, a regeneration system and a sulfuric acid recovery system; the water supplementing system is provided with a first flue gas inlet and a first flue gas flowmeter; the water replenishing system is also provided with an oxygen inlet and an oxygen inlet flowmeter; the water supplementing system is also provided with a smoke buffer tank, a second smoke inlet, a water supplementing tank and electric heating; the flue gas enters the buffer tank through the first flue gas inlet and enters the water supplementing tank through the second flue gas inlet, and the water supplementing tank is electrically heated to ensure that the flue gas takes away enough water vapor for subsequent absorption catalysis; the absorption system comprises an absorption tower, an absorbent, an upper flange of the absorption tower, a lower flange of the absorption tower, a purifier outlet and lower evacuation of the absorption tower; the gas inlet in the absorption system is arranged at the bottom of the absorption tower, and the purified gas outlet is arranged at the top of the absorption tower; the regeneration system comprises a regeneration water tank, regeneration water, a regeneration water pump and a regeneration water flowmeter; the sulfuric acid recovery system comprises a sulfuric acid pipeline, a sulfuric acid tank, sulfuric acid and a sulfuric acid tank emptying device.
2. The absorption and recovery system for sulfur dioxide flue gas as recited in claim 1, wherein the water replenishing tank of the water replenishing system is provided with a water inlet of the water replenishing tank; the water supplementing tank is provided with a thermocouple and a transformer; the second flue gas inlet is arranged at the upper part of the liquid level of the water replenishing tank, and the flue gas outlet of the water replenishing tank is arranged at the top of the water replenishing tank.
3. The absorption recovery system for sulfur dioxide flue gas as recited in claim 1, wherein the absorption system further comprises absorption tower circulating water, an absorption tower circulating water flow meter, an absorption tower circulating water pump and an absorption tower circulating water thermostatic water tank or electric heating.
4. A process using the system for absorption recovery of sulphur dioxide flue gas as claimed in any of claims 1 to 3, comprising the steps of: the flow of the flue gas containing sulfur dioxide and oxygen is controlled by the first flue gas flowmeter and the oxygen inlet flowmeter, the flue gas and the oxygen enter a buffer tank to be mixed, then the flue gas and the oxygen enter a water supplementing tank through a second flue gas inlet, and wet flue gas with the temperature of above 40 ℃ is obtained after water supplementing and heating; the wet flue gas is contacted with an absorbent in an absorption tower, and clean tail gas is obtained through catalytic absorption; the absorption tower is regenerated through a regeneration system, normal-temperature water is sprayed into the absorption tower for regeneration, and regenerated liquid is recycled through the sulfuric acid pipeline; the regenerated absorbent is reused for catalyzing and absorbing sulfur dioxide.
5. The process as claimed in claim 4, wherein in step (1), the maximum sulfur dioxide content of the sulfur dioxide-containing flue gas with a maximum concentration of sulfur dioxide is 10000 mg/Nm3；(ii) a The temperature of the heated wet flue gas is 40-85 ℃; the pressure of the buffer tank is 101-110 kPa.
6. The process according to claim 5, wherein in the step (1), the temperature of the heated wet flue gas is 40 ℃; the pressure in the buffer tank was 105 kPa.
7. The process as claimed in claim 4, wherein in the step (2), the raw material gas enters an absorption tower after being heated and humidified, and is absorbed within the range of 40-95 ℃; the absorbent is activated carbon modified by one or more metal oxides, wherein the oxide is one or more of Cu, Cr, Fe, Ni, Co and Ce; the absorbent is cylindrical or spherical, and the packing density is 0.45-0.85 g/cm3。
8. The process according to claim 7, wherein in the step (2), the raw material gas enters an absorption tower after being heated and humidified, and is absorbed within the range of 80 ℃; the absorbent is columnar, and has a packing density of 0.75 g/cm3。
9. The process according to claim 4, wherein in the step (3), the regeneration water is desalted water and the temperature is 10-30 ℃.
10. The process of claim 4, wherein in step (4), the regenerated absorbent is used directly for catalytic absorption of sulfur dioxide.
CN202010270814.2A 2020-04-08 2020-04-08 Absorption recovery system and process for sulfur dioxide flue gas Pending CN113491945A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003047829A (en) * 2001-08-08 2003-02-18 Chiyoda Corp Method for removing gaseous sulfur dioxide
CN1505592A (en) * 2000-12-11 2004-06-16 美国过滤公司 Activated carbon for odor control and method for making same
CN102614775A (en) * 2011-01-26 2012-08-01 四川大学 Method for removing and recovering low concentration sulfur dioxide in industrial exhaust gas
CN105327612A (en) * 2015-09-25 2016-02-17 四川大学 Flue gas low-temperature combined desulfurization and denitration technology method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1505592A (en) * 2000-12-11 2004-06-16 美国过滤公司 Activated carbon for odor control and method for making same
JP2003047829A (en) * 2001-08-08 2003-02-18 Chiyoda Corp Method for removing gaseous sulfur dioxide
CN102614775A (en) * 2011-01-26 2012-08-01 四川大学 Method for removing and recovering low concentration sulfur dioxide in industrial exhaust gas
CN105327612A (en) * 2015-09-25 2016-02-17 四川大学 Flue gas low-temperature combined desulfurization and denitration technology method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张蕾: "《烟气脱硫脱硝技术及催化剂的研究进展》", 31 July 2016, 中国矿业大学出版社 *

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