CN111408249B - 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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- 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
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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
- B01D53/46—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 multi-section membrane absorption method flue gas combined desulfurization and decarburization device, 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 absorbent 2 Selective absorption for CO regeneration 2 The 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 and liquid phases, has higher load capacity on high-temperature and high-pressure flue gas and alkaline absorbent, has the outstanding advantages of flexible operation, compact structure and high integration, and is suitable for upgrading and reconstructing desulfurization and decarburization processes of medium and small 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 SO 2 And CO 2 When the preferential desulfurization is carried out in the coexisting system, some problems in the application process can exist, mainly comprising:
1. due to the co-presence of SO x And CO 2 So 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 treatment 2 CO 3 、Na 2 SO 3 、Na 2 SO 4 And inorganic salts have high separation difficulty and low product reutilization rate.
2. When alcohol amine solution is adopted for absorption, SO in the solution x Can lead to SO x Can 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.SO x And CO 2 In the process of co-removal, the primary utilization rate of alkali liquor is not high, and SO x Influence on absorption liquid such as alcohol amine solution on CO 2 Absorption of (2).
Disclosure of Invention
The invention aims to solve the problem that the prior art simultaneously contains SO 2 And CO 2 The 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 SO 2 And CO 2 The method of desulfurizing and decarbonizing a gas according to (1). The method is a flue gas combined desulfurization and decarburization process by a multi-section membrane absorption method, and at least two sections of ceramic membrane contactors are utilized to form a multi-section membrane absorption device so as to realize the desulfurization and decarburization of flue gasOrganic alcohol amine is used as an absorbent, and the combined desulfurization and decarburization of the flue gas can be 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 membrane x And CO 2 System for selective removal of SO x And then using hydrophobic porous membrane to CO 2 And the carbon resources are collected and recycled.
In one embodiment, SO x One 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, SO x Total content of 100-2000 ppm, CO 2 The 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 Na 2 SO 3 Or K 2 SO 3
In one embodiment, the absorbing solution after absorption in step 2 is heated to convert CO into CO 2 Desorbing 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
Selective removal of SO2 without substantial absorption of CO by constructing a combined absorption process of first absorbing with a hydrophilic membrane and then absorbing with a hydrophobic membrane 2 Then the hydrophobic membrane is used to absorb all CO 2 Realizes 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 solution 2 And CO 2 The 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 device 2 And the trace sulfur to CO in the process of hydrophobic membrane is reduced 2 The 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 decarburization 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 films 2 And CO 2 And (4) removing efficiency.
FIG. 4 shows SO in hydrophilic and hydrophobic films 2 And CO 2 Absorbing the flux.
FIG. 5 shows SO in hydrophilic and hydrophobic films 2 /CO 2 A selectivity factor.
FIG. 6 is a schematic view of the membrane module configuration.
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 SO 2 And CO 2 The gas of (2) is subjected to desulfurization and decarbonization treatment to realize selective SO treatment 2 And CO 2 Respectively 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 SO 2 And CO 2 The content of (A) is not particularly limited, and in some embodiments, may be SO x Total content of 100-2000 ppm, CO 2 The 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 solution x Has high selective absorption to CO 2 Low absorption, SO 2 /CO 2 The selective separation factor can reach 124 (fig. 5); after absorption treatment, SO x Can penetrate hydrophilic membrane layer to generate Na 2 SO 3 After subsequent concentration and purification, the inorganic salt can be reused as a recovered salt, and compared with the method adopting a hydrophobic membrane for absorption, CO exists 2 The absorption by the inorganic alkali solution causes that the absorption solution also contains Na 2 CO 3 Make it difficult to react with Na 2 SO 3 The 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 membrane:
in the step, alcohol amine absorption liquid is mainly adopted, for example, the absorbent can be 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 above 2 Selective absorption of for SO x Has a low selective absorption for CO 2 And SO x The selective separation factor of (a) can reach 3; after absorption treatment, CO 2 Can permeate the hydrophobic film layer to be absorbed by the absorption liquid of alcamines, and can absorb CO through the subsequent temperature rise process 2 Desorbing to regenerate alcohol amine solution for reuse. Due to selective separation of SO by hydrophilic porous membranes x After that, SO in the decarbonizing section x Already in small quantities and due to the hydrophobic porous membrane of the decarbonization section being permeable to SO x Has low selective absorption and avoids SO x The 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 m 3 H, the temperature of the flue gas is 20 ℃, SO 2 Volume fraction of 100ppm, CO 2 The 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 m 3 H, treating tail gas SO by a desulfurization section 2 The content is reduced to 5ppm, CO 2 About 1% (volume fraction), and the desulfurization zone is aligned with SO 2 The removal rate of the catalyst can reach more than 99 percent, and the catalyst can remove CO 2 The 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 m 3 H, treatment of CO by a decarbonization section 2 The content is reduced to about 0.1% (volume fraction), and the decarbonization section is used for CO 2 The 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 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 m 3 The temperature of the flue gas is 100 ℃ and SO 2 Volume fraction 1000ppm, CO 2 The 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 100m 3 H, treating tail gas SO by a desulfurization section 2 The content is reduced to 8ppm, CO 2 About 9.9% (volume fraction), desulfurization zone to SO 2 The removal rate of the catalyst can reach more than 99 percent, and the catalyst has high CO removal rate 2 The 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 100m 3 H, at the decarbonized stagePhysical CO 2 The content is reduced to about 0.5% (volume fraction), and the decarbonization section is used for CO 2 The recovery rate of the method 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 is detected to reach the standard.
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 m 3 H, the flue gas temperature is 100 ℃, SO 2 Volume fraction 1000ppm, CO 2 The 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 100m 3 H, treating the tail gas SO by a desulfurization section 2 The content is reduced to 8ppm, CO 2 About 3% (volume fraction), and the desulfurization zone is aligned with SO 2 The removal rate of the catalyst can reach more than 99 percent, but CO 2 The removal rate of (2) 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 100m 3 H, treatment of CO by a decarbonization section 2 The content is reduced to about 0 percent, and the decarbonization section is opposite to CO 2 The 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 contactor 2 With SO 2 The complete separation of the components cannot 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 solution 2 High selectivity for removing SO when directly using hydrophobic membrane 2 And CO 2 The selective removal effect is poor; therefore, the alcohol amine solution applied to the subsequent hydrophobic porous membrane absorbs CO 2 Can effectively achieve the selective removal of SO x And CO 2 The 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 m 3 H is the ratio of the total weight of the catalyst to the total weight of the catalyst. Respectively using 0.4mol/L NaOH solution as absorbent in hydrophilic membrane and hydrophobic membrane, and SO in inlet air 2 Concentration 1000ppm (molar concentration), CO 2 The 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 membranes 2 Has higher removal efficiency and absorption flux, CO 2 Lower removal efficiency and absorption flux (as shown in fig. 3 and 4), SO hydrophilic membrane contactors are more favorable to SO overall 2 It can be seen from FIG. 5 that the selectivity factor reached 124 at a gas flow rate of 1200 NmL/min.
Claims (1)
1. For the hydrophilic porous membrane containing SO x And CO 2 Is characterized by containing SO x And CO 2 In the gas of (2) x The total content is 100-2000 ppm, CO 2 The total content is 1-30% by volume fraction;
the pore diameter range of the hydrophilic porous membrane is 0.05-3 mu m, and the contact angle of a water drop ranges from 10 degrees to 50 degrees;
the application comprises the following steps:
step 1, adopting a first absorption liquid to absorb SO x And CO 2 The gas is subjected to membrane absorption by adopting a hydrophilic porous membrane to remove SO x (ii) a 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 CO 2 ；
Inorganic base is adopted as an absorbent in the first absorption liquid, and the inorganic base is selected from NaOH or KOH; the mass concentration range of the inorganic base is 1-30 wt%;
amine compounds are adopted as an absorbent in the second absorption liquid, and the amine compounds are selected from methyldiethanolamine; the mass concentration range of the amine compound is 5-40 wt%;
hydrophilic porous membrane for SO during membrane absorption x Has high selective absorption to CO 2 Low absorption, SO 2 /CO 2 The selective separation factor is 124.
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