CN116139697B - Mass transfer method for strengthening membrane contactor based on hydrophilic/hydrophobic double-layer membrane - Google Patents
Mass transfer method for strengthening membrane contactor based on hydrophilic/hydrophobic double-layer membrane Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
-
- 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
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of membrane contactors, in particular to a method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic double-layer membrane. The method comprises the steps of dispersing a high-activity catalyst for decomposing H 2O2 into polyvinylidene fluoride casting film liquid, preparing a hydrophilic/hydrophobic double-layer film by a certain technical means, constructing a film contactor system to enable the hydrophilic side of the double-layer film to be in direct contact with absorption liquid, and adding H 2O2 with a certain concentration into the absorption liquid. In the operation process of the membrane contactor, H 2O2 in the catalyst degradation absorption liquid in the hydrophilic side of the membrane generates O 2 nanometer micro-bubbles, in-situ bubbling improves the turbulence degree of a fluid boundary layer, obviously reduces the interface mass transfer resistance of the membrane contactor, and improves the mass transfer efficiency. The method for improving mass transfer does not need a complex device, has strong adaptability, is suitable for the technical field of membrane contactors, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of membrane contactors, in particular to a method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic double-layer membrane.
Background
Climate change is a global problem faced by humans, and as carbon dioxide is emitted from various countries, greenhouse gases are increased, which forms a threat to life systems. Under the background, greenhouse gases are reduced in a global agreement mode in countries of the world, and China brings forward carbon reaching peaks and carbon neutralization targets. Carbon capture technology is considered as a key means for carbon emission reduction, and at present, the carbon capture technology mainly comprises absorption separation, adsorption separation and membrane separation. The absorption method is a relatively mature carbon trapping technology at present and has wide application.
However, the biggest problem at present is that absorption liquid consumption is large, so that the power generation efficiency is reduced after the power plant installs the process, and a series of problems such as flooding exist in the absorption process. The membrane absorption system is a novel absorption system which combines the membrane with the common absorption, and has the characteristics of high mass transfer efficiency, small size of absorption equipment, easy operation and the like, but also has the defects of high mass transfer resistance and the like.
Disclosure of Invention
The invention aims to solve the technical problem of large mass transfer resistance in the process of absorbing CO 2 by a membrane absorption system, and provides a method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic double-layer membrane. The technical scheme adopted is as follows:
a method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic double-layer membrane utilizes a reaction of the hydrophilic/hydrophobic double-layer membrane at an interface of the membrane contactor, and in-situ bubbling reduces interface mass transfer resistance, and specifically comprises the following steps:
Step one, preparing a high-activity catalyst: preparing a high activity catalyst which can degrade H 2O2 to produce O 2;
Step two, preparing a casting film liquid: dissolving PVDF in an organic solvent, mechanically stirring at 60 ℃ for 24 hours, adding the high-activity catalyst and the additive prepared in the step 1 into the organic solvent, mechanically stirring at 60 ℃ for 12 hours, ultrasonically stirring for 3 hours, and vacuum defoaming for 24 hours to prepare hydrophilic side casting film liquid; dissolving PVDF in an organic solvent, mechanically stirring at 60 ℃ for 24 hours, and vacuum defoaming for 24 hours to prepare a hydrophobic side casting film solution;
Step three, preparing a hydrophilic/hydrophobic double-layer film: preparing the casting solution in the second step into a hydrophilic/hydrophobic double-layer membrane with a hydrophilic side loaded with a high-activity catalyst by a certain technical means;
Preparing absorption liquid and constructing a membrane contactor system: adding H 2O2 with a certain concentration into the absorption liquid, building a gas-liquid membrane contactor system, pumping the absorption liquid to the hydrophilic side of the hydrophilic/hydrophobic double-layer membrane, and pumping the gas to be absorbed to the hydrophobic side of the hydrophilic/hydrophobic double-layer membrane.
Preferably, in the first step, the prepared high-activity catalyst can degrade H 2O2 and generate O 2 nano micro-bubbles, including at least one of metal nano-particles, metal oxide and derivatives thereof, and catalase.
Preferably, in the second step, the organic solvent used for preparing the homogeneous casting solution includes at least one of N-methylpyrrolidone (NMP), N-dimethylformamide, dimethylacetamide and dimethylsulfoxide.
Preferably, in the second step, the additive is at least one of polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone.
Preferably, in the second step, the PVDF content is 12-20%, the organic solvent content is 60-88%, the high activity catalyst addition amount is 0.1-2%, and the additive addition amount is 0-10%.
Preferably, in the third step, certain technical means include at least one of electrostatic spinning, wet spinning, hydrophilic modification of a hydrophobic film, plasma treatment, physical deposition and chemical deposition.
Preferably, in the fourth step, the organic amine CO 2 absorption liquid includes at least one of monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, diisopropanolamine, and diglycolamine.
Preferably, in the fourth step, the membrane contactor includes at least one of membrane distillation, membrane extraction, membrane absorption, membrane adsorption, membrane stripping and osmotic extraction.
Preferably, in the fourth step, the gas to be absorbed includes at least one of CO 2、H2S,NO2、SO2、NH3.
The method for strengthening mass transfer of the membrane contactor based on the hydrophilic/hydrophobic double-layer membrane is applied to the technical field of membrane contactors.
Compared with the prior art, the invention has the beneficial effects that:
1. The hydrophilic/hydrophobic double-layer membrane contactor prepared by the electrostatic spinning method generates a large number of O 2 nano micro-bubbles by degrading H 2O2 in CO 2 absorption liquid, the mass transfer resistance is obviously reduced by in-situ bubbling, and the absorption flux of CO 2 is improved by 118%.
2. The hydrophilic/hydrophobic double-layer membrane contactor prepared by the wet spinning method generates a large number of O 2 nano micro-bubbles by degrading H 2O2 in CO 2 absorption liquid, the mass transfer resistance is obviously reduced by in-situ bubbling, and the absorption flux of CO 2 is improved by 43%.
3. The hydrophilic/hydrophobic double-layer membrane contactor prepared by the hydrophobic membrane hydrophilic modification means generates a large number of O 2 nano micro-bubbles by degrading H 2O2 in CO 2 absorption liquid, the mass transfer resistance is obviously reduced by in-situ bubbling, and the absorption flux of CO 2 is improved by 61%.
Drawings
FIG. 1 is a schematic diagram of in situ bubbling to reduce interfacial mass transfer resistance;
FIG. 2 is a summary graph of CO 2 absorption flux data;
FIG. 3 is an SEM image of a hydrophilic/hydrophobic bilayer membrane contactor prepared by electrospinning in example 1, wherein FIG. 3 (a) is a hydrophilic side SEM image and FIG. 3 (b) is a hydrophobic side SEM image;
FIG. 4 is a vertical sectional view of a spinneret in the wet spinning process in example 2;
FIG. 5 is an SEM image of the surface of a membrane after hydrophilic modification of the hydrophobic membrane in example 3.
In fig. 4, 11-first spin pot channel; 12-a second spin pot channel, 13-a core liquid pot channel.
Detailed Description
The drawings are for illustrative purposes only; it is to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention.
The principles and features of the present invention are described below in connection with the following examples, which are provided to illustrate the invention and are not intended to limit the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. Different carbon dioxide isotope gases are all purchased standard products, and other technical methods which are not described adopt the prior art.
The present invention relates to the english abbreviations for some chemicals:
Polyvinylidene fluoride: PVDF;
N-methylpyrrolidone: NMP;
N, N-dimethylformamide: DMF;
dimethylacetamide: DMAc;
dimethyl sulfoxide: DMSO;
Polyethylene glycol: PEG;
polyvinylpyrrolidone: PVP;
Polyvinyl alcohol: PVA;
Monoethanolamine: an MEA;
Diethanolamine: DEA.
The present invention will be specifically described with reference to the drawings and examples.
Example 1
The method for strengthening mass transfer of the membrane contactor based on the hydrophilic/hydrophobic double-layer membrane provided by the invention is adopted to prepare the hydrophilic/hydrophobic double-layer membrane contactor by an electrostatic spinning means, and specifically comprises the following steps:
step 1, preparing MnO 2 high activity catalyst
50ML of distilled water and 14mL of nitric acid (2M/L) are added into a round-bottom flask and marked as solution A, 2mM glycine and 20mM KMnO 4 are weighed and dissolved in 25mL of distilled water, the solution B is uniformly stirred and marked as solution B, the solution B is slowly dripped into the solution A, the solution B is reacted in a water bath at 70 ℃ for 1h to prepare brown suspension, the suspension is centrifuged at 8000rpm, the obtained powder is frozen in liquid nitrogen, and the obtained powder is freeze-dried for 24h to prepare the MnO 2 high activity catalyst.
Step 2, preparing casting film liquid
Dissolving 7g of PVDF in 39.5g of DMF, mechanically stirring at 60 ℃ for 12h to form a homogeneous casting solution, vacuum defoaming for 24h, adding 0.5g of MnO 2 high activity catalyst and 3g of PEG prepared in the step 1 into the casting solution, mechanically stirring at 60 ℃ for 12h, and performing ultrasonic treatment for 3h to form a homogeneous casting solution, namely casting solution 1, wherein the casting solution 1 is a hydrophilic side casting solution; 10g of PVDF was dissolved in 40g of DMF and mechanically stirred at 60℃for 12 hours to form a homogeneous casting solution, which was then defoamed in vacuo for 24 hours and designated as casting solution 2, and casting solution 2 was a hydrophobic side casting solution.
Step 3, preparing and preparing a hydrophilic/hydrophobic double-layer membrane contactor
The casting solution 1 is injected into an injector, a 25-gauge needle is arranged on the injector, the casting solution is injected into a booster of the electrostatic spinning equipment by the injector, the advancing speed of the booster is adjusted to be 0.08mm/min, the distance between the needle and a receiver is adjusted to be 8cm, a layer of tinfoil paper is covered on the receiver of the electrostatic spinning equipment, and the rotating speed of the receiver is set to be 80r/min. Connecting the positive high voltage of a high-voltage power supply with a syringe needle, adjusting the voltage to 14.0kV, adjusting the negative voltage of the high-voltage power supply to-1.3 kV, starting a syringe, and spinning for 6 hours by using electrostatic spinning equipment under the conditions that the temperature is 30 ℃ and the relative humidity is 50%; and spinning the membrane casting solution 2 for 6 hours according to the same parameters, taking off the PVDF nanofiber membrane from a rotating wheel receiver of the electrostatic spinning equipment after spinning, and drying at 60 ℃ for 24 hours to obtain the hydrophilic/hydrophobic double-layer membrane contactor. The SEM image of the hydrophilic/hydrophobic bilayer is shown in fig. 3, wherein fig. 3 (a) is a SEM image of the hydrophilic side and fig. 3 (b) is a SEM image of the hydrophobic side. As can be seen from fig. 3 (a), the MnO 2 high-activity catalyst is uniformly dispersed inside and on the surface of the hydrophilic side membrane substrate, and when the absorption liquid contacts with the MnO 2 high-activity catalyst in the hydrophilic side membrane, H 2O2 in the absorption liquid is degraded to generate a large number of O 2 nano micro bubbles, and the solid-liquid interface is disturbed by in-situ bubbling, so that the mass transfer resistance is effectively reduced, and the mass transfer efficiency is improved. As can be seen from fig. 3 (b), the hydrophobic side is mainly PVDF polymer fiber.
Step 4, preparing absorption liquid and constructing a membrane contactor system
A 30% mass concentration Monoethanolamine (MEA) CO 2 absorption liquid was prepared, a 0.5% mass concentration H 2O2 solution was added, a membrane absorption system was set up, the CO 2 absorption liquid was pumped to the hydrophilic side of the hydrophilic/hydrophobic double membrane contactor at a feed rate of 50mL/min, and simulated flue gas (N 2/CO2 =85/15) was pressurized to the hydrophobic side of the hydrophilic/hydrophobic double membrane contactor at a relative pressure of 20kpa, and CO 2 absorption performance test was performed, and the CO 2 absorption flux was measured to be 1.88×10 -3(mol·m-2·s-1), as summarized in fig. 2.
The mechanism of the invention is as follows:
The mass transfer resistance of the membrane contactor system comprises in-membrane diffusion Resistance (RM), liquid boundary layer diffusion Resistance (RL) and gas boundary layer diffusion Resistance (RG), the diffusion resistance is mainly concentrated in two boundary layers, and the eddy current diffusion mass transfer efficiency is higher than that of molecular diffusion under the normal condition, so that the mass transfer resistance can be obviously reduced by improving the turbulence degree of the fluid boundary layer, and the mass transfer efficiency is improved. Based on the analysis, a method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic bilayer membrane is provided, as shown in fig. 1, mass transfer resistance is mainly concentrated at a gas-liquid interface, the hydrophilic/hydrophobic bilayer membrane is prepared in example 1 through an electrostatic spinning technology, when a CO 2 absorption liquid containing H 2O2 contacts with a high-activity catalyst on a membrane hydrophilic side MnO 2, H 2O2 is degraded, O 2 nano micro bubbles are generated, the gas-liquid interface is disturbed through in-situ bubbling, and a diffusion mode is changed from molecular diffusion to vortex diffusion, so that the mass transfer resistance is effectively reduced, and the mass transfer efficiency is improved.
Example 2
The method for strengthening mass transfer of the membrane contactor based on the hydrophilic/hydrophobic double-layer membrane provided by the invention is adopted to prepare the hydrophilic/hydrophobic double-layer membrane contactor by a wet spinning method, and specifically comprises the following steps:
step 1, preparing MnO 2 high activity catalyst
50ML of distilled water and 14mL of nitric acid (2M/L) are added into a round bottom flask and marked as a solution C, 2mM glycine and 20mM KMnO 4 are weighed and dissolved in 25mL of distilled water, the mixture is stirred uniformly and marked as a solution D, the solution D is slowly dripped into the solution C, the solution D is reacted in a water bath at 70 ℃ for 1h to prepare a brown suspension, the suspension is centrifuged at 8000rpm, the obtained powder is frozen in liquid nitrogen, and the obtained powder is freeze-dried for 24h to prepare the MnO 2 high activity catalyst.
Step2, preparing a homogeneous casting solution
Dissolving 6g of PVDF in 39.5g of NMP organic solvent to prepare casting solution, mechanically stirring at 60 ℃ for 24 hours, adding 0.5g of MnO 2 high activity catalyst prepared in the step 1 and 4g of PVA into the casting solution, mechanically stirring at 60 ℃ for 12 hours to form homogeneous casting solution, carrying out ultrasonic treatment for 3 hours, and carrying out vacuum deaeration for 24 hours, wherein the casting solution is designated as casting solution 3, and the casting solution 3 is hydrophilic side casting solution; 10g of PVDF was dissolved in 40g of NMP organic solvent to prepare a casting solution, and the casting solution was mechanically stirred at 60℃for 24 hours, and was designated as casting solution 4, and casting solution 4 was a hydrophobic side casting solution.
Step3, preparing a hydrophilic/hydrophobic double-layer membrane contactor
Adding 20mL of water into 30mL of NMP solution, stirring uniformly to prepare core liquid, pumping the core liquid into a core liquid tank channel 13 of a spinning head at a feeding speed of 2mL/min by adopting a wet spinning technology in the prior art as shown in figure 4, and maintaining the temperature of the core liquid tank at 30 ℃; placing the casting solution 3 prepared in the step 2 into a spinning tank, and pumping the casting solution 3 to a first spinning tank channel 11 of a spinning head at a feeding speed of 3mL/min, wherein the temperature of the spinning tank is maintained at 45 ℃; and (3) placing the casting solution 4 prepared in the step (2) in another spinning tank, pumping the casting solution 4 into a second spinning tank channel 12 of a spinning head at a feeding speed of 3mL/min, maintaining the temperature of the spinning tank at 45 ℃, introducing the extruded hollow fiber membrane into a coagulation bath at 25 ℃ for phase conversion, soaking the prepared hollow fiber membrane in deionized water for 3 days, soaking the hollow fiber membrane in 30% glycerol solution at 25 ℃ for 12 hours, taking out membrane filaments, naturally airing the membrane filaments in a constant temperature and humidity laboratory, and assembling the hollow fiber membrane contactor.
Step 4, preparing absorption liquid and constructing a membrane contactor system
Preparing an MEA CO 2 absorption liquid with the mass concentration of 30%, adding an H 2O2 solution with the mass concentration of 0.5%, and constructing a membrane absorption system. The CO 2 absorption liquid was pumped to the hydrophilic side of the hydrophilic/hydrophobic double membrane contactor at a feed rate of 50mL/min, and the simulated flue gas (N 2/CO2 =85/15) was sent under pressure to the hydrophobic side of the hydrophilic/hydrophobic double membrane contactor at a relative pressure of 20kpa, and the CO 2 absorption performance test was performed, and the CO 2 absorption flux was measured to be 7.99×10 -4(mol·m-2·s-1), and the summary diagram is shown in fig. 2.
Example 3
The method for strengthening mass transfer of the membrane contactor based on the hydrophilic/hydrophobic double-layer membrane provided by the invention is adopted, and the hydrophilic/hydrophobic double-layer membrane contactor is prepared by a hydrophobic membrane hydrophilic modification means, and specifically comprises the following steps:
step 1, preparing a beta-FeO-OH high-activity catalyst
70MM ferric chloride powder is added into 100mL of deionized water, 50mL of hydrochloric acid solution with pH=2 is added, stirring is carried out until ferric chloride is completely dissolved, the mixture is placed in a water bath kettle at 60 ℃ for hydrothermal reaction for 24 hours to prepare a tan suspension, the suspension is centrifuged at 8000rpm, the obtained powder is frozen in liquid nitrogen, and freeze drying is carried out for 24 hours to prepare the beta-FeO-OH high activity catalyst.
Step2, preparing a homogeneous casting solution
10G of PVDF was dissolved in 40g of DMF and mechanically stirred at 60℃for 12 hours to form a homogeneous casting solution, which was then defoamed in vacuo for 24 hours and designated as casting solution 5, and casting solution 5 was a hydrophobic side casting solution.
Step 3, preparing and preparing a hydrophilic/hydrophobic double-layer membrane contactor
Pouring the casting solution 5 on a non-woven fabric, setting the height of a scraper of a film scraping machine to be 200 mu m for scraping films, immersing the films prepared by the scraping in a deionized water coagulation bath for phase conversion, and immersing the films after phase conversion in deionized water for 24 hours to obtain the PVDF hydrophobic film. Fixing a hydrophobic membrane in a polytetrafluoroethylene plate frame, pre-wetting with ethanol, pouring 2g/L tannic acid on the surface of the PVDF hydrophobic membrane, pouring out the solution after 5min, pouring 2g/L FeCl 3·6H2 O solution on the surface of the PVDF hydrophobic membrane, pouring out the solution after 5min of modification, and soaking the modified membrane in deionized water for 24h to obtain the PVDF membrane with single-sided hydrophilic modification. Adding 70mM ferric chloride powder into 100mL of deionized water, adding 50mL of hydrochloric acid solution with pH=2, stirring until ferric chloride is completely dissolved, placing in a water bath kettle with the temperature of 60 ℃ for standby, immersing a single-sided hydrophilic modified PVDF membrane into the solution, carrying out hydrothermal reaction for 24h, and immersing the modified membrane in the deionized water for 24h to obtain the hydrophilic/hydrophobic double-layer membrane contactor. As shown in the SEM image of the membrane surface after hydrophilic modification of the hydrophobic membrane as shown in figure 5, spindle-shaped beta-FeO-OH high-activity catalyst grows on the membrane surface, the size range is 100-200nm, when the absorption liquid contacts the beta-FeO-OH high-activity catalyst in the hydrophilic side membrane, H 2O2 in the absorption liquid is degraded to generate a large number of O 2 nanometer microbubbles, and solid-liquid interface disturbance is performed through in-situ bubbling, so that mass transfer resistance is effectively reduced, and mass transfer efficiency is improved.
Step 4, preparing absorption liquid and constructing a membrane contactor system
A 30% mass concentration Monoethanolamine (MEA) CO 2 absorption liquid was prepared, a 0.5% mass concentration H 2O2 solution was added, a membrane absorption system was set up, the CO 2 absorption liquid was pumped to the hydrophilic side of the hydrophilic/hydrophobic double membrane contactor at a feed rate of 50mL/min, and simulated flue gas (N 2/CO2 =85/15) was pressurized to the hydrophobic side of the hydrophilic/hydrophobic double membrane contactor at a relative pressure of 20kpa, and CO 2 absorption performance test was performed, and the CO 2 absorption flux was measured to be 9.90×10 -4(mol·m-2·s-1), as summarized in fig. 2.
Comparative example 1
Step1, step1 is the same as in example 1.
Step2, the same as step2 of example 1.
Step 3, the same as step 3 of example 1.
Step 4, preparing absorption liquid and constructing a membrane contactor system
An MEA CO 2 absorption liquid with the mass concentration of 30% is prepared, a membrane absorption system is built, the CO 2 absorption liquid is pumped to the hydrophilic side of the hydrophilic/hydrophobic double-layer membrane contactor at the feeding speed of 50mL/min, simulated flue gas (N 2/CO2 =85/15) is pumped to the hydrophobic side of the hydrophilic/hydrophobic double-layer membrane contactor under the pressure of 20kpa, the CO 2 absorption performance test is carried out, the CO 2 absorption flux is measured to be 8.63 multiplied by 10 -4(mol·m-2·s-1), and the summary diagram is shown in figure 2.
Comparative example 2
Step1, as in example 2, step 1.
Step2, step2 is the same as in example 2.
Step 3, the same as step 3 of example 2.
Step 4, preparing absorption liquid and constructing a membrane contactor system
An MEA CO 2 absorption liquid with the mass concentration of 30% is prepared, a membrane absorption system is built, the CO 2 absorption liquid is pumped to the hydrophilic side of the hydrophilic/hydrophobic double-layer membrane contactor at the feeding speed of 50mL/min, simulated flue gas (N 2/CO2 =85/15) is pressed to the hydrophobic side of the hydrophilic/hydrophobic double-layer membrane contactor under the relative pressure of 20kpa, the CO 2 absorption performance test is carried out, the CO 2 absorption flux is measured to be 5.59x10 -4(mol·m-2·s-1), and the summary graph is shown in figure 2.
Comparative example 3
Step1, step1 is the same as in example 3.
Step2, step2 is the same as in example 3.
Step 3, step 3 is the same as example 3.
Step 4, preparing absorption liquid and constructing a membrane contactor system
An MEA CO 2 absorption liquid with the mass concentration of 30% is prepared, a membrane absorption system is built, the CO 2 absorption liquid is pumped to the hydrophilic side of the hydrophilic/hydrophobic double-layer membrane contactor at the feeding speed of 50mL/min, simulated flue gas (N 2/CO2 =85/15) is pumped to the hydrophobic side of the hydrophilic/hydrophobic double-layer membrane contactor under the pressure of 20kpa, the CO 2 absorption performance test is carried out, the CO 2 absorption flux is measured to be 6.15x -4(mol·m-2·s-1), and the summary diagram is shown in figure 2.
As shown in fig. 2, comparing the absorption fluxes of CO 2 measured in examples 1-3 and comparative examples 1-3 together, it is known that the hydrophilic/hydrophobic double-layer membrane contactor prepared by the electrostatic spinning method generates a large amount of O 2 nano microbubbles by degrading H 2O2 in the CO 2 absorption liquid, the in-situ bubbling significantly reduces mass transfer resistance, and the absorption flux of CO 2 is improved by 118%; the hydrophilic/hydrophobic double-layer membrane contactor prepared by the wet spinning method has the advantage that the absorption flux of CO 2 is improved by 43%; the hydrophilic/hydrophobic double-layer membrane contactor prepared by the hydrophilic modification means of the hydrophobic membrane has the advantage that the absorption flux of CO 2 is improved by 61%. The idea of reducing interface mass transfer resistance by in-situ bubbling is applied to three different membrane preparation technologies, the absorption flux of CO 2 is improved, and the method for strengthening the membrane contactor mass transfer by using the hydrophilic/hydrophobic double-layer membrane is proved to have universal adaptability.
The method for strengthening mass transfer of the membrane contactor based on the hydrophilic/hydrophobic double-layer membrane can be applied to the technical field of membrane contactors, and the method comprises the steps of dispersing a high-activity catalyst for decomposing H 2O2 into polyvinylidene fluoride casting solution, preparing the hydrophilic/hydrophobic double-layer membrane by technical means such as electrostatic spinning, wet spinning, hydrophilic modification of the hydrophobic membrane, plasma treatment, physical deposition, chemical deposition and the like, constructing a membrane contactor system to enable the hydrophilic side of the double-layer membrane to be in direct contact with absorption solution, and adding a certain concentration of H 2O2 into the absorption solution. In the operation process of the membrane contactor, H 2O2 in the catalyst catalytic absorption liquid in the hydrophilic side of the membrane generates O 2 nanometer micro-bubbles, in-situ bubbling improves the turbulence degree of a fluid boundary layer, obviously reduces the interface mass transfer resistance of the membrane contactor, and improves the mass transfer efficiency.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.
Claims (7)
1. A method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic double-layer membrane is characterized by utilizing a reaction of the hydrophilic/hydrophobic double-layer membrane at an interface of the membrane contactor, and reducing interface mass transfer resistance by in-situ bubbling, and specifically comprises the following steps:
Step one, preparing a high-activity catalyst: preparing a high activity catalyst which can degrade H 2O2 to produce O 2, wherein the high activity catalyst is MnO 2 or beta-FeO-OH;
Step two, preparing a casting film liquid: dissolving PVDF in an organic solvent, mechanically stirring at 60 ℃ for 24 hours, adding the high-activity catalyst and the additive prepared in the step 1 into the organic solvent, mechanically stirring at 60 ℃ for 12 hours, ultrasonically stirring for 3 hours, and vacuum defoaming for 24 hours to prepare hydrophilic side casting film liquid; dissolving PVDF in an organic solvent, mechanically stirring at 60 ℃ for 24 hours, and vacuum defoaming for 24 hours to prepare a hydrophobic side casting film solution;
the additive is at least one of polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone;
Step three, preparing a hydrophilic/hydrophobic double-layer film: preparing the casting solution in the second step into a hydrophilic/hydrophobic double-layer membrane with a hydrophilic side loaded with a high-activity catalyst by a certain technical means;
The certain technical means comprise any one of electrostatic spinning, wet spinning and plasma treatment;
preparing absorption liquid and constructing a membrane contactor system: adding H 2O2 with a certain concentration into the absorption liquid, building a gas-liquid membrane contactor system, pumping the absorption liquid to the hydrophilic side of the hydrophilic/hydrophobic double-layer membrane, and pumping the gas to be absorbed to the hydrophobic side of the hydrophilic/hydrophobic double-layer membrane;
The absorption liquid comprises at least one of monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, diisopropanolamine and diglycolamine.
2. The method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic bilayer membrane according to claim 1, wherein in the first step, the prepared high activity catalyst degrades H 2O2 and generates O 2 nano micro bubbles.
3. The method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic bilayer membrane according to claim 1, wherein in the second step, the organic solvent used for preparing the membrane casting solution comprises any one of N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide and dimethylsulfoxide.
4. The mass transfer method of the membrane contactor reinforced by the hydrophilic/hydrophobic bilayer membrane according to claim 1, wherein in the second step, the PVDF content is 12-20%, the organic solvent content is 60-88%, the high activity catalyst addition amount is 0.1-2%, and the additive addition amount is 0-10%.
5. The method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic bilayer membrane according to claim 1, wherein in the fourth step, the membrane contactor system is applied to any one of the fields of membrane distillation, membrane extraction, membrane absorption, membrane adsorption, membrane stripping and osmotic extraction.
6. The method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic bilayer membrane according to claim 1 wherein in said step four, the gas to be absorbed comprises at least one of CO 2、H2S、SO2 and NH 3.
7. A method for strengthening mass transfer of a membrane contactor based on a hydrophilic/hydrophobic double-layer membrane is applied to the technical field of membrane contactors.
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| CN105854627A (en) * | 2016-05-04 | 2016-08-17 | 上海交通大学 | Multifunctional nano-composite sewage purification film and preparation method and application thereof |
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