CN111408249A - Method and device for desulfurization and decarburization of flue gas by multi-section membrane absorption - Google Patents
Method and device for desulfurization and decarburization of flue gas by multi-section membrane absorption Download PDFInfo
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 116
- 239000003546 flue gas Substances 0.000 title claims abstract description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 62
- 230000023556 desulfurization Effects 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000005261 decarburization Methods 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 67
- 239000002250 absorbent Substances 0.000 claims abstract description 57
- 230000002745 absorbent Effects 0.000 claims abstract description 56
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- 239000000919 ceramic Substances 0.000 claims abstract description 34
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- -1 amine compound Chemical class 0.000 claims description 31
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- 238000003860 storage Methods 0.000 claims description 8
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- 239000011148 porous material Substances 0.000 claims description 5
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- 239000004642 Polyimide Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a flue gas combined desulfurization and decarburization device adopting a multi-section membrane absorption method, which comprises at least two sections of membrane absorption devices; the process comprises the following steps: the pretreated flue gas is selectively desulfurized by a hydrophilic ceramic membrane contactor in a desulfurization section, and then enters a hydrophobic ceramic membrane contactor in a decarburization section for quick decarburization. The principle is as follows: under the drive of concentration gradient, the SO is firstly treated by utilizing the property difference of hydrophilic and hydrophobic ceramic membranes and the reaction characteristic of the absorbent2Selective absorption for CO reconversion2The rapid absorption is carried out, the extremely high desulfurization selectivity is presented, and the aim of combined desulfurization and decarburization of the flue gas is finally realized. The process avoids direct contact of gas phase and liquid phase, has high load capacity on high temperature and high pressure flue gas and alkaline absorbent, has the advantages of flexible operation, compact structure and high integration, and is suitable for use in industrial productionThe method is used for upgrading and reconstructing desulfurization and decarburization processes of small and medium-sized coal-fired thermal power plants and other flue gas generating equipment.
Description
Technical Field
The invention belongs to the crossing field of an atmospheric pollution control technology and a membrane separation technology, and particularly relates to an industrial waste gas treatment device for realizing combined desulfurization and decarburization of flue gas by using a multi-section ceramic membrane contactor and using an organic alcohol amine solution as an absorbent.
Background
By the end of 2016, the amount of thermal power installed in China reaches 10.5 hundred million kilowatts, thermal power mainly generated by coal and natural gas still accounts for more than 70% of the total installed amount, a large amount of harmful flue gas is generated in the combustion process of fossil fuels, and the flue gas discharged into the atmosphere contains various acidic gases such as sulfur dioxide, hydrogen sulfide, carbon dioxide and the like, so that great harm is caused to human health and the environment, and meanwhile, the method is a great challenge to the realization of the 2030 energy-saving and emission-reduction plan provided by the government of China.
The traditional desulfurization and carbon capture processes are generally carried out in a packed column or a spray tower, taking a limestone-gypsum method as an example, the conventional method generally has the problems of high investment cost, large occupied area, complex equipment, difficult operation and the like, and although technical means such as a spray drying method, an electron beam radiation method and even low-temperature liquefaction separation and the like are developed in succession, the process also generally has high investment, large energy consumption or is immature, and industrial application is difficult to realize in a short time. The membrane absorption is coupled with the characteristics of the traditional absorption and membrane separation technology, and has the outstanding advantages of flexible operation, compact structure, high integration degree and the like, so that the membrane absorption is concerned by a plurality of scientific researchers, and has been successfully applied to the flue gas treatment of the world multi-electric factory in recent years.
Patent document CN107349759A discloses a "desulfurization and decarbonization treatment device is combined with marine exhaust", which mainly includes a double-loop absorption tower, which is divided into a demisting section, a decarbonization section and a desulfurization section from top to bottom, alkaline absorption liquid is first desulfurized, then decarbonized and then demisted through a spray device, and finally pregnant solution is recovered by membrane electrolysis technology. The device still belongs to the improvement to traditional spray column in essence, and not only the treatment effeciency is low unstable, and the gas-liquid direct contact can be difficult to avoid the production flooding, the entrainment scheduling problem. In addition, although the process claims that the desulfurization tower and the decarbonization tower do not need to be separately constructed, the inevitable result is that the double-loop absorption tower needs to occupy more space to achieve the same effect, and the device is not the optimal choice from the viewpoint of space saving and investment.
Patent document CN206955973U discloses a "biogas desulfurization and decarbonization device", which mainly comprises a tank body, a barren liquor tank and a rich liquor collecting tank, wherein the tank body is internally provided with a cylindrical guide cylinder and a polyimide hollow fiber membrane wire component, and the desulfurization is carried out by a wet method, and then the membrane separation and decarbonization are adopted. The device is only applicable to natural gas system purification to be not applicable to high temperature high pressure flue gas treatment, the commonality problem of wet flue gas desulfurization can't be avoided moreover: the gas phase and the liquid phase are directly contacted, and the adjusting range is narrow. In addition, polyimide as an organic membrane material has the defects of small gas flux and easy aging, and the hollow fiber membrane module has certain difficulty in terms of replacement and long-term maintenance.
The traditional membrane absorption process mostly adopts hydrophobic membrane materials to absorb SO2And CO2When the coexisting system of (2) carries out preferential desulfurization, some problems in the application process can exist, mainly comprising:
1. due to the co-presence of SOxAnd CO2So that the product is not easy to be recycled after the absorption liquid is subjected to absorption treatment; when NaOH solution is used as the absorption liquid, Na is contained in the absorption liquid after treatment2CO3、Na2SO3、Na2SO4And inorganic salts have high separation difficulty and low product reutilization rate.
2. When alcohol amine solution is adopted for absorption, SO in the solutionxCan lead to SOxCan react with alcohol amine to generate stable salt, thus reducing the recycling rate of the alcohol amine and bringing the cost of the whole process to rise.
3.SOxAnd CO2In the process of co-removal, the primary utilization rate of alkali liquor is not high, and SOxInfluence on absorption liquid such as alcohol amine solution on CO2Absorption of (2).
Disclosure of Invention
The invention aims to solve the problem that the prior art simultaneously contains SO2And CO2The problems of poor selective absorption effect, low product utilization rate, low reutilization property of absorption liquid and the like in the process of desulfurizing and decarbonizing the gas provide a new method for removing SO2And CO2The method of desulfurizing and decarbonizing a gas according to (1). The method is particularly a flue gas combined desulfurization and decarburization process by a multi-section membrane absorption method, wherein at least two sections of ceramic membrane contactors are utilized to form a multi-section membrane absorption device, organic alcohol amine is used as an absorbent, and the flue gas combined desulfurization and decarburization are realized in the same process.
In a first aspect of the present invention, there is provided:
a method for desulfurization and decarburization of flue gas by multi-section membrane absorption comprises the following steps:
In one embodiment, SO is first treated with a hydrophilic porous membranexAnd CO2System for selective removal of SOxAnd then using hydrophobic porous membrane to CO2And the carbon resources are collected and recycled.
In one embodiment, SOxOne or a mixture of two selected from them.
In one embodiment, the first absorption liquid uses an inorganic base as an absorbent, more preferably, the inorganic base is selected from NaOH or KOH; the mass concentration of the inorganic base may range from 1 to 30 wt%.
In one embodiment, the second absorption liquid adopts an amine compound as an absorbent, and more preferably, the amine compound is one or more organic alcohol amines selected from primary alcohol amine including methyldiethanolamine, secondary alcohol amine, tertiary alcohol amine, steric hindrance amine, cyclic organic amine and the like; the mass concentration of the amine compound may be in the range of 5 to 40 wt%.
In one embodiment, SOxTotal content of 100-2000 ppm, CO2The total content is 1-30% (volume fraction).
In one embodiment, the hydrophilic porous membrane has a pore size ranging from 0.05 to 3 μm and a water drop contact angle ranging from 10 to 50 °.
In one embodiment, the hydrophobic porous membrane has a pore size in the range of 0.05 to 3 μm and a water drop contact angle in the range of 90 to 170 °.
In one embodiment, the absorption raffinate from step 1 after absorption can be crystallized to recover high value by-product Na2SO3Or K2SO3
In one embodiment, the absorbing liquid after absorption in step 2 is heated to heat CO2Desorbing from the absorption liquid to make the absorption liquid regenerated and recycled.
In a second aspect of the present invention, there is provided:
a multi-section membrane absorption flue gas desulfurization and decarbonization device comprises:
a hydrophilic porous membrane and a hydrophobic porous membrane;
a first liquid pump for flowing a first absorbent through the absorbent side of the hydrophilic porous membrane;
a second liquid pump for flowing a second absorbent through the absorbent side of the hydrophobic porous membrane;
a gas supply means for supplying a gas to be treated to a gas side of the hydrophilic porous membrane;
the gas side outlet of the hydrophilic porous membrane communicates with the gas side inlet of the hydrophobic porous membrane.
In one embodiment, the absorption device further comprises a first absorption liquid storage tank for storing the first absorption liquid; and a second absorption liquid storage tank for storing the second absorption liquid.
In one embodiment, the apparatus further comprises a first waste absorbent liquid storage tank for storing the first absorbent liquid after the absorption treatment discharged from the absorbent liquid side of the hydrophilic porous membrane; and a second spent absorbent storage tank for storing the second absorbent after the absorption treatment discharged from the absorbent side of the hydrophobic porous membrane.
In one embodiment, a gas pretreatment device for pretreating a gas supplied to the hydrophilic porous membrane is further included.
In one embodiment, the gas pretreatment device is a filtration device for removing particulate matter from a gas.
In one embodiment, the hydrophilic porous membrane is a tubular ceramic membrane, the inside of the tube being the absorption liquid side and the outside of the tube being the gas side; the aperture range is 0.05-3 mu m, and the water drop contact angle range is 10-50 degrees.
In one embodiment, the hydrophobic porous membrane is a tubular ceramic membrane, the inside of the tube being the absorption liquid side and the outside of the tube being the gas side; the aperture range is 0.05-3 mu m, and the water drop contact angle range is 90-170 degrees.
Advantageous effects
By constructing a combined absorption process of first absorbing with a hydrophilic membrane and then absorbing with a hydrophobic membrane, SO2 can be selectively removed first with little absorption of CO2Then the hydrophobic membrane is used for absorbing all CO2Realizes the complete separation of sulfur and carbon and has extremely high selectivity. Compared with the traditional column type gas absorption equipment or other desulfurization and decarburization processes, the invention has the beneficial effects that:
1. the invention adopts a multi-section membrane absorption device, gas and liquid phases independently flow in the shell pass and the tube pass of the membrane contactor, do not interfere with each other, can be flexibly operated, has compact structure and high integration, and is suitable for the upgrading and the reconstruction of desulfurization and decarburization processes of medium and small coal-fired thermal power plants and other flue gas generating equipment;
2. the multi-section membrane absorption device is made of ceramic membranes, has high gas permeation flux, natural dust pollution resistance and self-cleaning capacity, and has better load capacity on high-temperature and high-pressure flue gas and alkaline absorbent;
3. the multi-section membrane absorption process can realize selective desulfurization and quick decarburization in the desulfurization section and the decarburization section, realize combined desulfurization and decarburization of flue gas, maximize the utilization of absorbents in the desulfurization section and the decarburization section, and desorb the obtained SO from rich solution2And CO2The product purity is high, resource utilization can be realized, the rich liquor collected by the rich liquor tank at the decarburization section contains less heat-stable salt, and the energy consumption required by desorption is lower.
4. According to the invention, almost all SO can be removed firstly by adopting the hydrophilic membrane in the multi-section membrane absorption device2And the trace sulfur to CO in the process of hydrophobic membrane is reduced2The influence of absorption and high desulfurization and decarburization rate.
5. The invention calculates the concentration distribution in different membrane contactors by establishing a mass transfer model, theoretically proves the feasibility of desulfurization and decarburization by a multi-section membrane absorption method, and can carry out experimental prediction and process design through the model.
Drawings
FIG. 1 is a schematic structural diagram of a multi-stage membrane absorption flue gas combined desulfurization and decarbonization device.
FIG. 2 is a schematic diagram of the structure and operation mode of the hydrophilic and hydrophobic ceramic membrane contactor (6-7) according to the present invention.
FIG. 3 shows SO in hydrophilic and hydrophobic membranes2And CO2And (4) removing efficiency.
FIG. 4 shows SO in hydrophilic and hydrophobic membranes2And CO2Absorbing the flux.
FIG. 5 shows SO in hydrophilic and hydrophobic membranes2/CO2A selectivity factor.
FIG. 6 is a schematic diagram of the structure of a membrane module.
1-flue gas pretreatment device; 2-flue gas flow control device; 3-a first flue gas analyzer; 4-a second flue gas analyzer; 5-a third flue gas analyzer; 6-a hydrophilic ceramic membrane contactor; 7-hydrophobic ceramic membrane contactor; 8-a first valve; 9-a second valve; 10-a third valve; 11-a fourth valve; 12-a fifth valve; 13-a sixth valve; 14-a first liquid pump; 15-a second liquid pump; 16-a first lean liquor tank; 17-a second lean liquor tank; 18-a first rotameter; 19 a second rotameter; 20-a first rich liquor tank; 21 a second rich liquid tank; 22-a first pressure gauge; 23-second pressure gauge.
Detailed Description
The technical scheme of the invention is mainly used for simultaneously containing SO2And CO2The gas of (2) is subjected to desulfurization and decarbonization treatment to realize selective SO treatment2And CO2Respectively removing, and improving the utilization rate of the product and the utilization rate of the absorption liquid.
The gas of the invention can be derived from the tail gas generated in the combustion process of fossil fuel (such as ship fuel oil units) or from the gas generated in the fermentation process (such as biogas fermentation), wherein SO2And CO2The content of (A) is not particularly limited, and in some embodiments, may be SOxTotal content of 100-2000 ppm, CO2The total content is 1-30% (volume fraction), and the temperature is 20-180 ℃ after the pretreatment of temperature reduction and dust removal.
In the treatment method, the gas can be pretreated firstly, and is mainly used for removing some particulate matters in the gas, so that the subsequent normal operation of the porous membrane can be effectively protected. The pretreatment may be performed by a dust removal treatment such as filtration or electrostatic adsorption.
Selective absorption for hydrophilic porous membranes:
in the treatment method of the present invention, it is first necessary to carry out membrane absorption of a gas by using a hydrophilic porous membrane, and in the process, an inorganic alkaline solution such as NaOH or KOH is mainly used as an absorbing solutionxHas high selective absorption to CO2Low absorption, SO2/CO2The selective separation factor can reach 124 (fig. 5); after absorption treatment, SOxCan penetrate hydrophilic membrane layer to generate Na2SO3After subsequent concentration and purification, the inorganic salt can be used asIn order to recover the salts for reuse, CO exists in the absorption process compared with the absorption process adopting a hydrophobic membrane2The absorption by the inorganic alkali solution causes that the absorption solution also contains Na2CO3Make it difficult to react with Na2SO3The recovery of the product is less useful. The hydrophilic membrane can greatly improve the one-time utilization rate of the alkaline absorbent and reduce the absorption cost.
In this step, a conventional porous membrane may be used as the membrane absorption device, wherein the porous membrane should have good hydrophilicity, which is understood to mean that the contact angle of water drops is in the range of 10 to 50 °, and the porous membrane may be a tubular porous ceramic membrane, so that the absorption liquid passes through the tube side, the gas passes through the shell side, the flue gas and the absorbent respectively flow in a two-phase parallel countercurrent manner on the shell side and the tube side of the membrane contactor, and the absorption of the gas occurs on the surface of the membrane. The aperture of the ceramic membrane is 0.05-3 μm.
Selective absorption for hydrophobic porous membranes:
in the step, alcohol amine absorption liquid is mainly adopted, for example, the absorbent is formed by combining one or more organic alcohol amines of primary alcohol amine including methyl diethanol amine, secondary alcohol amine, tertiary alcohol amine, steric hindrance amine, cyclic organic amine and the like, and the mass fraction of the absorbent is 5-40%. The present inventors have surprisingly found that the use of hydrophobic porous membranes provides a higher CO uptake in the membrane absorption process described above2Selective absorption of for SOxHas a low selective absorption for CO2And SOxThe selective separation factor of (a) can reach 3; after absorption treatment, CO2Can permeate hydrophobic film layer and be absorbed by alcohol amine absorption liquid, and CO can be absorbed by subsequent temperature rise process2Desorbing to regenerate alcohol amine solution for reuse. Due to selective separation of SO by hydrophilic porous membranesxAfter that, SO in the decarbonizing sectionxAlready in small quantities and due to the hydrophobic nature of the decarbonization sectionPorous membranes for SOxHas low selective absorption and avoids SOxThe alcohol amine reacts with alcohol amine substances to generate heat stability salt, so that the reuse rate of an alcohol amine solution can be effectively improved after subsequent treatment.
In this step, a conventional porous membrane can be used as the membrane absorption device, wherein the porous membrane should have good hydrophobicity, which is understood to mean that the contact angle of water drops is in the range of 90-170 °, and the porous membrane can be a tubular porous ceramic membrane, so that the absorption liquid passes through the tube side, the gas passes through the shell side, the flue gas and the absorbent respectively flow in a two-phase parallel countercurrent mode on the shell side and the tube side of the membrane contactor, and the absorption of the gas occurs on the surface of the membrane. The aperture of the ceramic membrane is 0.05-3 μm.
Based on the above method, the structure of the device adopted by the invention is shown in FIG. 1.
Comprises a hydrophilic ceramic membrane contactor with at least a desulfurization section and a hydrophobic ceramic membrane contactor with a decarburization section, which are two sections of membrane absorption devices; the device also comprises a flue gas pretreatment device (1), a flue gas flow control device (2), a flue gas component analysis device (3-5) and a rich liquor tank (20-21); the flue gas pretreatment device (1) is positioned on a front end pipe section of the flue gas flow control device (2), and the rear end of the flue gas flow control device (2) is connected with a gas phase inlet of a shell pass of the hydrophilic ceramic membrane contactor (6); a liquid phase inlet of a tube pass of the hydrophilic ceramic membrane contactor (6) is connected with a first barren liquor tank (16), and a liquid phase outlet is connected to a first rich liquor tank (20) through a first liquid pump (14); a liquid phase inlet of a tube pass of the hydrophobic ceramic membrane contactor (7) is connected with a second liquid pump (15), a liquid phase outlet is connected with a second rich liquid tank (21), and a second lean liquid tank (17) is positioned on a front end pipe section of the second liquid pump (15); the flue gas component analysis devices (3-5) are respectively arranged on the front end pipe section, the middle end pipe section and the rear end pipe section of the desulfurization section and the decarburization section, valves (8-13), rotor flow meters (18-19) and pressure gauges (22-23) are distributed on the pipe sections, and the flue gas flow control devices (2), the first liquid pumps (14) and the second liquid pumps (15) are adjusted and controlled in real time according to data obtained through monitoring. The specific process steps are as follows: firstly, cooling and then removing dust of flue gas by a flue gas pretreatment device; step two, the flue gas obtained in the step one is sent into a shell pass of a hydrophilic ceramic membrane contactor of a desulfurization section after the flow of the flue gas is regulated by a flue gas flow control device, an absorbent of the desulfurization section is sent into a tube pass by adopting a pumping way, two phases react in the membrane contactor in a parallel countercurrent way, the absorbent after the reaction enters a pregnant solution tank of the desulfurization section, and the flue gas continues to enter a decarbonization section; step three, sending the flue gas obtained in the step two into a shell side of a hydrophobic ceramic membrane contactor of a decarburization section, sending an absorbent of the decarburization section into a tube side by adopting a pumping mode, reacting the two phases in the membrane contactor in a parallel countercurrent mode, sending the absorbent after the reaction into a rich solution tank of the decarburization section, and carrying out component analysis on tail gas of the decarburization section; and step four, collecting rich liquid of the absorbent in the desulfurization section and the decarburization section, and discharging the tail gas in the decarburization section into the atmosphere after the tail gas reaches the standard.
Example 1
The combined desulfurization and decarburization device for flue gas and the process thereof shown in figure 1 are adopted to treat tail gas of a Claus process, and the tail gas flow is 10 m3H, the temperature of the flue gas is 20 ℃, SO2Volume fraction of 100ppm, CO2The volume fraction was 1% (volume fraction). After being dedusted by a flue gas pretreatment device, the flue gas enters a hydrophilic ceramic membrane contactor (the membrane aperture is 0.05 mu m, the contact angle is 10 degrees) through a flue gas flow control device; the absorbent of the desulfurization section is 5wt% of methyldiethanolamine, and the flow of the absorbent is 10 m3H, treating tail gas SO by a desulfurization section2The content is reduced to 5ppm, CO2About 1% (volume fraction), and the desulfurization zone is aligned with SO2The removal rate of the catalyst can reach more than 99 percent, and the catalyst can remove CO2The removal rate of (A) is less than 1%; then enters a hydrophobic ceramic membrane contactor (the membrane aperture is 0.05 mu m, the contact angle is 90 degrees), the absorbent of the decarburization section consists of 10 percent of methyldiethanolamine, and the flow of the absorbent is still 10 m3H, treatment of CO by a decarbonization section2The content is reduced to about 0.1% (volume fraction), and the decarbonization section is used for CO2The recovery rate can reach 90 percent; and respectively collecting the absorbents after the reactions of the desulfurization section and the decarburization section into a rich solution tank, and discharging tail gas after the tail gas reaches the standard through detection.
Example 2
The flue gas combined desulfurization and decarburization device and the process thereof shown in figure 1 are adopted to treat certain gasThe flow of the Claus process tail gas is 200 m3The temperature of the flue gas is 100 ℃ and SO2Volume fraction 1000ppm, CO2The volume fraction was 10% (volume fraction). After being dedusted by a flue gas pretreatment device, the flue gas enters a hydrophilic ceramic membrane contactor (the membrane aperture is 1 mu m, the contact angle is 50 degrees) through a flue gas flow control device; the absorbent of the desulfurization section is 15wt% of sodium hydroxide solution, and the flow of the absorbent is 100m3H, treating tail gas SO by a desulfurization section2The content is reduced to 8ppm, CO2About 9.9% (volume fraction), desulfurization zone to SO2The removal rate of the catalyst can reach more than 99 percent, and the catalyst can remove CO2The removal rate of (A) is 1%; then enters a hydrophobic ceramic membrane contactor (the membrane aperture is 3 mu m, the contact angle is 170 degrees), an absorbent in the decarburization section is formed by mixing 15 percent of methyldiethanolamine and 40 percent of monoethanolamine, and the flow of the absorbent is still 100m3H, treatment of CO by a decarbonization section2The content is reduced to about 0.5% (volume fraction), and the decarbonization section is used for CO2The recovery rate can reach 94%; and respectively collecting the absorbents after the reactions of the desulfurization section and the decarburization section into a rich solution tank, and discharging tail gas after the tail gas reaches the standard through detection.
Comparative example 1
The combined desulfurization and decarburization device for flue gas and the process thereof shown in figure 1 are adopted to treat tail gas of a Claus process, and the tail gas flow is 200 m3The temperature of the flue gas is 100 ℃ and SO2Volume fraction 1000ppm, CO2The volume fraction was 10%. After being dedusted by a flue gas pretreatment device, the flue gas enters a hydrophobic ceramic membrane contactor (the membrane aperture is 1 mu m, the contact angle is 170 degrees) through a flue gas flow control device; the absorbent of the desulfurization section is 15wt% of sodium hydroxide solution, and the flow of the absorbent is 100m3H, treating tail gas SO by a desulfurization section2The content is reduced to 8ppm, CO2About 3% (volume fraction), and the desulfurization zone is aligned with SO2The removal rate of the catalyst can reach more than 99 percent, but CO2The removal rate of (A) is 70%; then enters a hydrophilic ceramic membrane contactor (the membrane aperture is 3 mu m, the contact angle is 150 degrees), an absorbent in the decarburization section is formed by mixing 15 percent of methyldiethanolamine and 40 percent of monoethanolamine, and the flow of the absorbent is still 100m3H, treatment of CO by a decarbonization section2The content is reduced to about 0 percent, and the decarbonization section is opposite to CO2The recovery rate can reach 100%; the absorbent after the reaction of the desulfurization section and the decarburization section is respectively collected into a rich solution tank, and CO cannot be realized through the hydrophobic ceramic membrane contactor and the hydrophilic ceramic membrane contactor2With SO2The complete separation of the components can not meet the requirements of respective desulfurization and decarburization.
As can be seen from the experiments of example 1 and comparative example 1, the hydrophilic porous membrane exhibited SO in the membrane absorption process applied to the NaOH solution2High selectivity for removing SO when directly using hydrophobic membrane2And CO2The selective removal effect is poor; therefore, the alcohol amine solution applied to the subsequent hydrophobic porous membrane absorbs CO2Can effectively achieve the selective removal of SOxAnd CO2The effect of (3) can improve the utilization rate of the absorption liquid.
Example 3
In the embodiment, the influence of different gas flow conditions on the hydrophilic membrane and the hydrophobic membrane in the absorption process is examined, the pore diameter of the hydrophilic ceramic membrane contactor membrane is 0.05 mu m, and the contact angle is 10 degrees; the hydrophobic ceramic membrane contactor has a membrane aperture of 0.05 μm, a contact angle of 140 deg.C, a gas temperature of 20 deg.C, and an absorbent flow of 10 m3SO in the intake air using 0.4 mol/L NaOH solution as absorbent in hydrophilic and hydrophobic membranes, respectively2Concentration 1000ppm (molar concentration), CO2The effect of gas flow on the selectivity factor was investigated at a concentration of 10% (molarity). It was found that SO is present in hydrophilic membranes compared to hydrophobic membranes2Has higher removal efficiency and absorption flux, CO2Lower removal efficiency and absorption flux (as shown in fig. 3 and 4), SO hydrophilic membrane contactors are more favorable to SO overall2It can be seen from FIG. 5 that the selectivity factor of 124 was reached at a gas flow rate of 1200 Nm L/min.
Claims (10)
1. A method for desulfurization and decarburization of flue gas by multi-section membrane absorption is characterized by comprising the following steps:
step 1, adopting a first absorption liquid to absorb SOxAnd CO2The gas is subjected to membrane absorption by adopting a hydrophilic porous membrane to remove SOx；
Step 2, adopting a second absorption liquid to carry out membrane absorption on the gas treated in the step 1 by adopting a hydrophobic porous membrane to remove CO2。
2. The method for desulfurization and decarbonization of flue gas by multi-stage membrane absorption according to claim 1, wherein in one embodiment, SOxSelected from SO2Or SO3One or a mixture of both; in one embodiment, the first absorption liquid uses an inorganic base as an absorbent, more preferably, the inorganic base is selected from NaOH or KOH; the mass concentration of the inorganic base may range from 1 to 30 wt%.
3. The method for desulfurization and decarbonization of flue gas by multi-stage membrane absorption according to claim 1, wherein in one embodiment, an amine compound is used as an absorbent in the second absorption liquid, and more preferably, the amine compound is selected from one or more organic alcohol amines selected from primary alcohol amine including methyldiethanolamine, secondary alcohol amine, tertiary alcohol amine, steric hindrance amine, cyclic organic amine and the like; the mass concentration of the amine compound can be 5-40 wt%; in one embodiment, SOxTotal content of 100-2000 ppm, CO2The total content is 1-30% (volume fraction).
4. The method for desulfurization and decarburization of flue gas by multi-stage membrane absorption according to claim 1, wherein in one embodiment, the pore diameter of the hydrophilic porous membrane is in the range of 0.05 to 3 μm, and the contact angle of water drops is in the range of 10 to 50 °; in one embodiment, the hydrophobic porous membrane has a pore size in the range of 0.05 to 3 μm and a water drop contact angle in the range of 90 to 170 °.
5. The method for desulfurization and decarbonization of flue gas by multi-stage membrane absorption according to claim 1, wherein in one embodiment, the absorption raffinate after absorption in step 1 can be crystallized to recover high-value Na byproduct2SO3Or K2SO3(ii) a In one embodiment, the absorbing liquid after absorption in step 2 is heated to heat CO2Desorbing from the absorption liquid to make the absorption liquid regenerated and recycled.
6. The utility model provides a multistage membrane absorption flue gas desulfurization decarbonization device which characterized in that includes:
a hydrophilic porous membrane and a hydrophobic porous membrane;
a first liquid pump for flowing a first absorbent through the absorbent side of the hydrophilic porous membrane;
a second liquid pump for flowing a second absorbent through the absorbent side of the hydrophobic porous membrane;
a gas supply means for supplying a gas to be treated to a gas side of the hydrophilic porous membrane;
the gas side outlet of the hydrophilic porous membrane communicates with the gas side inlet of the hydrophobic porous membrane.
7. The multi-sectional membrane absorption flue gas desulfurization and decarbonization device of claim 6, further comprising a first absorption liquid storage tank for storing the first absorption liquid; and a second absorption liquid storage tank for storing a second absorption liquid; in one embodiment, the apparatus further comprises a first waste absorbent liquid storage tank for storing the first absorbent liquid after the absorption treatment discharged from the absorbent liquid side of the hydrophilic porous membrane; and a second spent absorbent storage tank for storing the second absorbent after the absorption treatment discharged from the absorbent side of the hydrophobic porous membrane.
8. The multi-stage membrane absorption flue gas desulfurization and decarbonization device according to claim 6, further comprising a gas pretreatment device for pretreating a gas supplied into the hydrophilic porous membrane in one embodiment; in one embodiment, the gas pretreatment device is a filtration device for removing particulate matter from a gas.
9. The multi-sectional membrane absorption flue gas desulfurization and decarbonization device of claim 6, wherein in one embodiment, the hydrophilic porous membrane is a tubular ceramic membrane, the inside of the tube is the absorption liquid side, and the outside of the tube is the gas side; the aperture range is 0.05-3 mu m, and the water drop contact angle range is 10-50 degrees.
10. The multi-sectional membrane absorption flue gas desulfurization and decarbonization device of claim 6, wherein in one embodiment, the hydrophobic porous membrane is a tubular ceramic membrane, the inside of the tube is the absorption liquid side, and the outside of the tube is the gas side; the aperture range is 0.05-3 mu m, and the water drop contact angle range is 90-170 degrees.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114159936A (en) * | 2021-12-03 | 2022-03-11 | 江苏集萃功能材料研究所有限公司 | Carbon dioxide capture utilization and energy comprehensive utilization process and application thereof |
| CN114563310A (en) * | 2021-05-08 | 2022-05-31 | 南京工业大学 | CO (carbon monoxide)2/N2Method for predicting diffusion process of binary mixture through multilayer ceramic membrane |
| CN114684988A (en) * | 2022-03-04 | 2022-07-01 | 信丰华锐钨钼新材料有限公司 | High-efficiency resource utilization method for high-concentration ammonia nitrogen wastewater containing carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228772A (en) * | 2011-07-11 | 2011-11-02 | 中国石油化工集团公司 | Process method for capturing carbon dioxide in flue gas through membrane absorption of amino solution |
| CN103120886A (en) * | 2013-01-25 | 2013-05-29 | 重庆大学 | Method for efficiently removing CO2 from flue gas with utilization of hollow fiber hydrophobic membrane |
| GB2506689A (en) * | 2012-10-08 | 2014-04-09 | Odour Services Internat Ltd | Air pollution control apparatus and method of use |
| CN103203174B (en) * | 2013-03-27 | 2016-01-13 | 华北电力大学（保定） | SO in a kind of trapping coal-fired plant flue gas 2and CO 2and the method for production chemical product |
-
2019
- 2019-08-26 CN CN201910791840.7A patent/CN111408249B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228772A (en) * | 2011-07-11 | 2011-11-02 | 中国石油化工集团公司 | Process method for capturing carbon dioxide in flue gas through membrane absorption of amino solution |
| GB2506689A (en) * | 2012-10-08 | 2014-04-09 | Odour Services Internat Ltd | Air pollution control apparatus and method of use |
| CN103120886A (en) * | 2013-01-25 | 2013-05-29 | 重庆大学 | Method for efficiently removing CO2 from flue gas with utilization of hollow fiber hydrophobic membrane |
| CN103203174B (en) * | 2013-03-27 | 2016-01-13 | 华北电力大学（保定） | SO in a kind of trapping coal-fired plant flue gas 2and CO 2and the method for production chemical product |
Non-Patent Citations (2)
| Title |
|---|
| XINGYIN GAO等: "Feasibility analysis of SO2 absorption using a hydrophilic ceramic membrane contactor", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
| 黄勇等: "陶瓷膜接触器在润湿模式下吸收SO2的传质强化", 《环境科学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114563310A (en) * | 2021-05-08 | 2022-05-31 | 南京工业大学 | CO (carbon monoxide)2/N2Method for predicting diffusion process of binary mixture through multilayer ceramic membrane |
| CN114159936A (en) * | 2021-12-03 | 2022-03-11 | 江苏集萃功能材料研究所有限公司 | Carbon dioxide capture utilization and energy comprehensive utilization process and application thereof |
| CN114684988A (en) * | 2022-03-04 | 2022-07-01 | 信丰华锐钨钼新材料有限公司 | High-efficiency resource utilization method for high-concentration ammonia nitrogen wastewater containing carbonate |
| CN114684988B (en) * | 2022-03-04 | 2024-01-02 | 信丰华锐钨钼新材料有限公司 | Efficient recycling method for high-concentration ammonia nitrogen wastewater containing carbonate |
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