CN114939353A - Hollow fiber membrane with spiral line structure, preparation method and membrane contact reactor - Google Patents
Hollow fiber membrane with spiral line structure, preparation method and membrane contact reactor Download PDFInfo
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- B01D—SEPARATION
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- B01D69/08—Hollow fibre membranes
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- 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
- B01D53/14—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 absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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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
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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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/366—Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
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- B01D71/36—Polytetrafluoroethene
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- B01J19/24—Stationary reactors without moving elements inside
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
The present disclosure provides a hollow fiber membrane having a helical structure, a method of preparing the same, and a membrane contact reactor, wherein the hollow fiber membrane having a helical structure includes: the fiber yarn comprises a hollow fiber base film and a fiber yarn spirally wound on the surface of the hollow fiber base film, wherein the wound fiber yarn is adhered to the surface of the hollow fiber base film to form a continuous whole.
Description
Technical Field
The disclosure belongs to the field of membrane preparation, and particularly relates to a hollow fiber membrane with a spiral line structure, a preparation method and a membrane contact reactor.
Background
The membrane contact technology is a membrane separation process which takes a hydrophobic membrane as a mass transfer interface and the concentration difference of two sides of the membrane as a mass transfer driving force, and has the great characteristic that the two-phase mass transfer is strengthened through a hollow fiber membrane, and the hollow fiber membrane has higher specific surface area and total volume mass transfer coefficient.
The traditional membrane contact reactor is prepared by randomly filling a large number of flat hollow fiber membranes into a membrane shell of the reactor, the membrane contact reactor has the problems of disordered membrane arrangement and uneven distribution, and a local dense stacking area or dead area is easily formed in the membrane contact reactor, so that the fluid flow state is poor, the problems of channeling, short circuit, dead area and the like are easily caused, the effective utilization area of the membrane contact reactor is greatly reduced, and the mass transfer capacity of the membrane contact reactor is reduced.
Although some researchers have improved the membrane contact reactor by weaving the flat hollow fiber membrane into a fabric or bundle shape to improve the contact efficiency of gas-liquid or liquid-liquid two phases, the weaving into a fabric or bundle shape has a certain limitation to the selection of the polymer material, and the hollow fiber membrane prepared by the method has a partial loss of the membrane area.
Disclosure of Invention
In view of the above technical problems, the present disclosure provides a hollow fiber membrane having a spiral line structure, a method for preparing the same, and a membrane contact reactor.
In order to solve the above technical problem, as one aspect of the present disclosure, there is provided a hollow fiber membrane having a spiral line structure, including: a hollow fiber-based membrane, and
and the fiber thread is spirally wound on the surface of the hollow fiber base membrane, wherein the wound fiber thread is adhered to the surface of the hollow fiber base membrane to form a continuous whole.
In one embodiment, the fiber wire has a diameter of 0.05-2 mm;
the lead of the fiber thread is 1-100 cm.
In one embodiment, the hollow fiber base membrane has a diameter of 0.5 to 10 mm.
In one embodiment, the material of the hollow fiber base membrane includes any one of:
polypropylene, polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, glass;
the material of the fiber line comprises any one of the following materials:
polypropylene, polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, polyester, polyvinyl chloride, polyamide.
As another aspect of the present disclosure, there is provided a method of preparing a hollow fiber membrane having a spiral structure, including the steps of:
winding fiber wires on the surface of the hollow fiber base membrane by using winding equipment;
sintering the hollow fiber base membrane wound with the fiber wires by using sintering equipment to obtain the hollow fiber membrane with the spiral line structure.
In another embodiment, the parameters of the winding device for winding the fiber thread on the surface of the hollow fiber base membrane include:
the speed of the fiber wire released by the winding equipment is 10-5000 rpm;
the advancing speed of the hollow fiber basal membrane is 0.1-50 m/min.
In another embodiment, the above winding apparatus for winding a spiral direction of a fiber strand on a surface of a hollow fiber base film comprises: left or right helix.
In another embodiment, the parameters of the sintering device for sintering the hollow fiber base film wound with the fiber yarn include:
the heating temperature of the sintering treatment includes: 100 ℃ and 400 ℃;
the time of the sintering treatment comprises the following steps: 5-100 s.
As another aspect of the present disclosure, there is also provided a membrane contact reactor using the hollow fiber membrane having a spiral line structure described above.
In another embodiment thereof, the above membrane contact reactor is used for any one of membrane absorption, membrane degassing, and membrane distillation.
Based on the technical scheme, the hollow fiber membrane with the spiral line structure, the preparation method and the membrane contact reactor provided by the disclosure at least have the following beneficial effects:
(1) in the embodiment of the disclosure, the fiber thread is wound on the surface of the hollow fiber base membrane in the form of a spiral thread to form the hollow fiber membrane with a spiral thread structure, and the spiral thread structure on the outer surface of the hollow fiber base membrane can maintain a specific distance between the membranes of the hollow fiber membrane to maintain a fluid channel, thereby avoiding the mutual extrusion of the membranes and reducing the contact area between the membranes and gas or liquid.
(2) In the embodiment of the disclosure, the spiral line structure can be used as a micro turbulent component to play a role in strengthening radial mixing, reduce concentration polarization and temperature difference polarization effects inside the hollow fiber membrane contactor, and improve mass transfer driving force. In addition, the spiral line structure can also reduce the deposition of pollutants, relieve the membrane pollution and prolong the service life of the membrane.
(3) In the embodiments of the present disclosure, the pitch of the helical structure, i.e., the lead of the fiber thread, may be controlled by controlling the speed at which the winding device releases the fiber thread and the traveling speed of the hollow fiber membrane; by controlling the heating temperature and time, the spiral fiber lines are tightly attached to the surface of the hollow fiber membrane without falling off, and the stable hollow fiber membrane with fixed nodes of the spiral structure is obtained.
(4) In the embodiment of the disclosure, the membrane contact reactor comprises the hollow fiber membrane with a spiral line structure, the hollow fiber membrane with the spiral line structure is filled into the membrane contact reactor, and by utilizing the spiral structure of the hollow fiber membrane, even under higher filling density, the hollow fiber membrane can be uniformly distributed between the membranes and keep the distance to keep a fluid channel, thereby avoiding the problems of channeling, short circuit, dead zone and the like in the membrane contact reactor, further improving the effective contact area of the membrane and realizing higher mass transfer process.
(5) In the embodiment of the disclosure, the hollow fiber membrane with a spiral line structure is used to effectively improve the flow state of fluid in the membrane contact reactor, improve the utilization efficiency of the area of the hollow fiber membrane, strengthen the mass transfer process, and is suitable for the mass transfer process of gas-liquid or liquid-liquid membrane contact, such as membrane degassing, membrane absorption, membrane distillation and the like.
Drawings
FIG. 1A is an isometric view of a hollow fiber membrane having a spiral configuration in an embodiment of the present disclosure;
FIG. 1B is a top view of a hollow fiber membrane having a helical spiral configuration in an embodiment of the present disclosure;
FIG. 2 is a pictorial view of a polytetrafluoroethylene hollow fiber membrane having a helical configuration in accordance with an embodiment of the disclosure;
FIG. 3 is a schematic diagram of an apparatus for a spiral membrane contact reactor in an embodiment of the disclosure.
[ description of reference ]
3-1, a feed liquid outlet; 3-2 feed liquid inlets; 3-3 an absorption liquid outlet; 3-4 epoxy resin end-capping glue; 3-5 polytetrafluoroethylene hollow fiber membrane with helical structure; 3-6 polyvinyl chloride membrane shells; 3-7 absorption liquid inlet
Detailed Description
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure will be described in further detail below with reference to specific embodiments and the accompanying drawings.
When the existing flat and straight hollow fiber membrane is used for manufacturing a membrane contact reactor, the problems of disordered arrangement and uneven distribution of the flat and straight hollow fiber membrane exist, so that liquid is difficult to enter due to dense stacking of the hollow fiber membrane in a local area of the membrane contact reactor, and a dead zone is formed; and because hollow fiber membranes are sparsely distributed to form empty areas, the fluid flow resistance is small, most of liquid passes through the membrane contact reactor from the empty areas, so that the problems of channeling and short circuit occur in the membrane contact reactor, the effective contact area efficiency of the membranes is lower than the theoretical level, and the membrane contact reactor has lower mass transfer efficiency. Based on the above, the present disclosure provides a hollow fiber membrane with a helical line structure, a preparation method thereof, and a membrane contact reactor, wherein the hollow fiber membrane with the helical line structure is obtained by winding a fiber line in a helical form on the outer surface of a hollow fiber base membrane and sintering the fiber line. The membrane contact reactor is manufactured by using the hollow fiber membrane with the spiral line structure, the uniform distribution between membranes of the hollow fiber membrane with the spiral line structure can be realized by using the spiral line structure on the outer surface of the hollow fiber base membrane, the mutual extrusion between the membranes is avoided, and the problems of channeling, short circuit, dead zones and the like which often occur in the membrane contact reactor are solved; the spiral line structure can also be used as a micro turbulence member to play a role in strengthening radial mixing so as to improve the effective contact area of the membrane, improve the flow state of a flow field and improve the mass transfer efficiency of the membrane. The hollow fiber membrane is a membrane with a fibrous appearance and a self-supporting function, and is usually processed into fiber filaments with a hollow inner cavity and has a selective permeability characteristic.
FIG. 1A is an isometric view of a hollow fiber membrane having a spiral configuration in an embodiment of the present disclosure; fig. 1B is a top view of a hollow fiber membrane having a helical spiral configuration in an embodiment of the present disclosure.
According to an embodiment of the present disclosure, as shown in fig. 1A-1B, a hollow fiber membrane having a spiral structure includes: the fiber yarn comprises a hollow fiber base film and a fiber yarn spirally wound on the surface of the hollow fiber base film, wherein the wound fiber yarn is adhered to the surface of the hollow fiber base film to form a continuous whole.
In the embodiment of the disclosure, the helical line structure on the outer surface of the hollow fiber base membrane is utilized to maintain a fixed distance between the hollow fiber membrane with the helical line structure and the membrane, so that the membranes are uniformly distributed, mutual extrusion is reduced, and the mass transfer efficiency of the membrane is improved; and the spiral line structure can be used as a turbulence member, so that the problems of concentration polarization and temperature difference polarization of the hollow fiber membrane with the spiral line structure are solved, the mass transfer process is strengthened, the deposition of pollutants on the surface of the membrane is reduced, and the service life of the membrane is prolonged.
According to an embodiment of the present disclosure, the fiber thread has a diameter of 0.05-2mm, wherein, optionally, 0.05, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.5, 1.6, 2.0mm, etc.
According to an embodiment of the present disclosure, the hollow fiber based membrane has a diameter of 0.5-10mm, wherein 0.5, 0.8, 1.0, 1.2, 1.6, 2.0, 2.4, 2.8, 3.0, 3.4, 3.8, 4.0, 4.4, 4.8, 5.0, 5.6, 6.0, 7.0, 7.6, 8.0, 8.6, 9.0, 9.6, 10mm, etc. may be selected.
In the disclosed embodiment, the diameter of the fiber strand is defined to be 0.05-2mm, and the diameter of the hollow fiber base membrane is defined to be 0.5-10mm, within which the diameter of the formed hollow fiber membrane having a spiral structure is prevented from being excessively large (the membrane is thick) to affect the mass transfer efficiency of the membrane. In addition, the hollow fiber membrane in the diameter range can meet the application of gas-liquid or liquid-liquid membrane contact mass transfer processes such as membrane degassing, membrane absorption, membrane distillation and the like.
According to an embodiment of the disclosure, the lead of the fiber thread is 1-100cm, wherein, optionally, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100cm, etc.
In the embodiments of the present disclosure, the lead is a linear distance that the fiber thread moves on the hollow fiber base film when the fiber thread is wound one turn on the outer surface of the hollow fiber base film, or it is understood that the helical line structure is a length of one repeating unit. By limiting the lead of the fiber thread to 1-100cm, the membrane can be maintained to have better dispersibility and higher contact area. If the length of the lead is further decreased, while the dispersibility of the hollow fiber membrane having a helical structure is further improved, at the same time, since the fiber threads occupy the surface positions of the hollow fiber base membrane, the effective contact area of the hollow fiber base membrane (or the hollow fiber membrane) with the liquid or gas is decreased; if the lead is further increased, the possibility of contact between the membranes of the hollow fiber membrane having a helical structure will be increased, that is, the effective contact area will be increased, but the dispersion effect of the hollow fiber membrane having a helical structure will also be deteriorated, and therefore the present disclosure limits the lead within this range, and can ensure both good dispersion of the membranes and good contact between the membranes.
According to an embodiment of the present disclosure, the material of the hollow fiber base membrane includes any one of: polypropylene, polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, glass.
According to an embodiment of the present disclosure, the material of the fiber thread includes any one of: polypropylene, polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, polyester, polyvinyl chloride, polyamide.
There is also provided, in accordance with an embodiment of the present disclosure, a method of preparing a hollow fiber membrane having a helical structure, including the steps of: winding fiber wires on the surface of the hollow fiber base membrane by using winding equipment; and sintering the hollow fiber base membrane wound with the fiber yarns by using sintering equipment to obtain the hollow fiber membrane with the spiral line structure.
In the embodiments of the present disclosure, by controlling the release speed of the fiber threads and the traveling speed of the hollow fiber base film, the fiber threads having a helical structure of different leads can be obtained; by controlling the heating temperature and time in the sintering treatment process, the fiber wires wound on the outer surface of the hollow fiber base membrane can be in close contact with the hollow fiber base membrane to form a continuous and stable hollow fiber membrane with a spiral line structure.
According to an embodiment of the present disclosure, the speed at which the winding device releases the fiber thread is 10-5000rpm, wherein 10, 100, 150, 200, 250, 300, 400, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000rpm, etc. may be selected.
In the embodiment of the present disclosure, when the traveling speed of the hollow fiber base film is constant, the speed of releasing the fiber threads determines the lead of the spiral thread structure, and the faster the speed of releasing the fiber threads, the denser the fiber threads wound on the outer surface of the hollow fiber base film, the smaller the lead.
According to an embodiment of the present disclosure, the traveling speed of the hollow fiber base membrane is 0.1 to 50m/min, wherein 0.1, 1, 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 45, 50m/min is optional.
In the embodiment of the present disclosure, the larger the traveling speed of the hollow fiber membranes, the larger the production amount of the hollow fiber membranes having the spiral structure, but the higher the traveling speed of the hollow fiber base membrane is, the higher the requirement of the equipment, the economical principle is to limit the traveling speed of the hollow fiber base membrane to 0.1 to 50 m/min.
According to an embodiment of the present disclosure, a winding apparatus winding a spiral direction of a fiber wire on a surface of a hollow fiber base film includes: left or right helix.
According to the embodiment of the disclosure, the parameters of the sintering device for sintering the hollow fiber base film wound with the fiber wire include: the heating temperature of the sintering treatment includes: 100 ℃ and 400 ℃; the time of the sintering treatment comprises the following steps: 5-100 s. Wherein, the heating temperature of the sintering treatment can be selected to be 100, 120, 140, 180, 200, 240, 250, 280, 300, 340, 380 and 400 ℃; the time of the sintering treatment can be selected from 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100s and the like.
In the embodiment of the present disclosure, the purpose of the sintering process is to adhere the fiber threads to the hollow fiber base membrane, so as to form a stable hollow fiber membrane with a helical structure and fixed helical structure nodes. The heating temperature is set near the melting point of the fiber wire material, so that the material is partially melted, the fiber wire can be well attached to the outer surface of the hollow fiber base film, and if the sintering heating temperature is too high, the fiber wire material is melted or decomposed; if the sintering heating temperature is too low, the adhesion between the fiber strands and the hollow fiber base film may be poor, and the fiber strands may easily fall off from the surface of the hollow fiber base film. The sintering heating time is also a key parameter for controlling the adhesion of the fiber thread, and the proper heating time is selected according to the selected fiber thread material, so that the fiber thread part is melted and the appearance of the fiber thread is basically not changed greatly.
According to an embodiment of the present disclosure, there is provided a membrane contact reactor including a hollow fiber membrane having a spiral line structure.
According to an embodiment of the present disclosure, the membrane contact reactor is used for any one of membrane absorption, membrane degassing, and membrane distillation.
The technical solution of the present disclosure is further illustrated by the following specific examples in combination with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only, and the scope of the present disclosure is not limited thereto. The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
Examples
The embodiment provides a preparation method of a hollow fiber membrane with a spiral line structure, the hollow fiber base membrane takes polytetrafluoroethylene as a material, the fiber line also takes polytetrafluoroethylene as a material, and the specific preparation flow is as follows:
firstly, a polytetrafluoroethylene hollow fiber base membrane is prepared by adopting a cold pressing extrusion-stretching sintering process, and the method comprises the following specific steps:
18 parts by mass of aviation kerosene was added to 100 parts by mass of polytetrafluoroethylene resin, and the mixture was thoroughly mixed at 25 ℃ with a mixer to obtain a wet and uniform polytetrafluoroethylene film-forming resin. The polytetrafluoroethylene resin is placed in a briquetting machine, and a hollow tubular compact primary blank is prepared under the pressure of 2 MPa. And then, putting the primary blank into an extruder to prepare a hollow fiber primary membrane, and then putting the hollow fiber primary membrane into stretching and sintering equipment for membrane preparation to obtain a polytetrafluoroethylene hollow fiber base membrane, wherein the outer diameter of the obtained polytetrafluoroethylene hollow fiber base membrane is 1.6mm, the inner diameter of the obtained polytetrafluoroethylene hollow fiber base membrane is 0.8mm, the porosity of the obtained polytetrafluoroethylene hollow fiber base membrane is 53.9 percent, and the average pore diameter of the obtained polytetrafluoroethylene hollow fiber base membrane is 0.21 mu m. The specific parameters related to the film making process in the stretching and sintering equipment are as follows: 3m/min stretching rate, 60 ℃ stretching temperature, 2.4 times stretching ratio, 355 ℃ sintering temperature and 2min sintering time.
Then, winding the fiber wire on the outer surface of the polytetrafluoroethylene hollow fiber base membrane, and sintering to obtain the hollow fiber membrane with the spiral line structure, wherein the specific steps are as follows:
taking the polytetrafluoroethylene hollow fiber base film and the polytetrafluoroethylene fiber wire (the diameter is 0.4mm), winding the fiber wire on the surface of the polytetrafluoroethylene hollow fiber base film by adopting a fiber wire winding device, setting the speed of releasing the fiber wire by the winding device to be 150 r/min, and limiting the advancing speed of the polytetrafluoroethylene hollow fiber base film to be 3m/min, thereby obtaining the uniform fiber wire spirally wound on the polytetrafluoroethylene hollow fiber base film with the lead of 20 mm. And then, an infrared heating furnace is adopted, the heating temperature is set to 340 ℃, the heating time is set to 10s, so that the wound polytetrafluoroethylene fiber wires are closely adhered to the polytetrafluoroethylene hollow fiber base film, and the hollow fiber film with the spiral line structure and stable structure and uniform distribution is obtained.
Fig. 2 is a physical representation of a polytetrafluoroethylene hollow fiber membrane with a helical structure in an embodiment of the disclosure.
The polytetrafluoroethylene hollow fiber membrane having a spiral structure prepared in the example was characterized by having a pore diameter of 0.2 μm and a porosity of 52.4%. This shows that the winding and sintering fixing of the fiber yarns have little influence on the hollow fiber base membrane, and the performance of the hollow fiber base membrane can be well maintained.
Comparative example
The method for manufacturing the flat polytetrafluoroethylene hollow fiber base film of the comparative example was the same as that of the example except that the fiber threads were not wound on the outer surface of the hollow fiber base film.
The following films prepared using examples and comparative examples will be used to verify the effectiveness of the presently disclosed technical solution.
The polytetrafluoroethylene hollow fiber membranes having a spiral line structure in the examples and the flat polytetrafluoroethylene hollow fiber membranes in the comparative examples were used to fabricate membrane contact reactors, respectively, and the efficiency of the membrane contact reactors was evaluated by a membrane deamination experiment and a membrane distillation experiment of the membrane contact reactors.
The membrane contact reactor in the examples was prepared as follows:
spiral membrane contact reactor: 48 polytetrafluoroethylene hollow fiber membranes with spiral line structures are selected and encapsulated in a transparent polyvinyl chloride membrane shell by epoxy resin to obtain the spiral line membrane contact reactor.
FIG. 3 is a schematic diagram of an apparatus for a spiral wire membrane contact reactor in an embodiment of the present disclosure.
As shown in FIG. 3, the membrane contact reactor includes a feed liquid outlet 3-1; a feed liquid inlet 3-2; an absorption liquid outlet 3-3; 3-7 of an absorption liquid inlet; 3-5 parts of a polytetrafluoroethylene hollow fiber membrane with a spiral line structure; 3-4 parts of epoxy resin end-capping glue and 3-6 parts of polyvinyl chloride film shell are adopted.
The feed liquid outlet 3-1 and the feed liquid inlet 3-2 of the membrane contact reaction are positioned at the same side or two sides of the polyvinyl chloride membrane shell 3-6, the absorption liquid outlet 3-3 is positioned at the top of the polyvinyl chloride membrane shell 3-6, the absorption liquid inlet 3-7 is positioned at the bottom of the polyvinyl chloride membrane shell 3-6, the absorption liquid outlet 3-3 and the absorption liquid inlet 3-7 are symmetrically arranged, the polytetrafluoroethylene hollow fiber membrane 3-5 with a spiral line structure is positioned inside the polyvinyl chloride membrane shell 3-6, and the epoxy resin end-capping glue 3-4 is used for end capping.
The membrane contact reactor in the comparative example was prepared as follows:
flat membrane contact reactor: 48 straight polytetrafluoroethylene hollow fiber membranes are selected and encapsulated in a transparent polyvinyl chloride membrane shell by epoxy resin to obtain a straight membrane contact reactor, and the arrangement mode of the straight polytetrafluoroethylene hollow fiber membranes in the comparative example is the same as that in the example.
The effective length of the membrane in the membrane contact reactor of the above comparative example and example was 23cm, and the membrane area was 0.055m 2 . The membrane contact reactors in the comparative example and the example are selected to carry out deamination experiment comparison, and the specific method of the deamination experiment is as follows:
500ml of alkaline raw material liquid containing ammonia nitrogen (pH is 11.5, ammonia nitrogen concentration is 1000mg/L) and 500ml of acidic absorption liquid (3.5 wt% sulfuric acid) are prepared respectively; introducing alkali liquor into the shell side of the membrane contact reactor through a peristaltic pump, introducing acid liquor into the tube side of the membrane contact reactor, and circularly flowing at the flow rate of 100 mL/min; sampling every 20min to test the ammonia nitrogen concentration in the alkali liquor, and the results are shown in the following table:
TABLE 1 comparison of the Membrane deamination effectiveness of different Membrane contact reactors
As can be seen from Table 1, the deamination efficiency using the spiral membrane contact reactor reached 99.1% at 120min, whereas the deamination efficiency using the flat membrane contact reactor was only 80.2%, which was much higher than the deamination efficiency of the membrane contact reactor in the comparative example by a factor of 2.38. The main reasons are as follows: the spiral line membrane contact reactor is composed of hollow fiber membranes with spiral line structures, the spiral line structures of the membranes can maintain the space between the membranes, fluid channels between the membranes are reserved, and the effective contact area of liquid and the membranes is increased. In addition, in the process of membrane contact of the straight membrane contact reactor, due to transmembrane transfer of substances, the phenomenon that the substance concentration is greatly lower than that of a main body of the feed liquid occurs near the membrane surface on the feed liquid side, so that the concentration difference of two sides of the membrane is lower, the mass transfer power and the mass transfer efficiency are lower, and the problem of concentration polarization exists. In the disclosure, the helical line structure can be used as a micro turbulent component to play a role in strengthening radial mixing, reduce the concentration polarization effect on two sides of the hollow fiber membrane with the helical line structure, and improve the mass transfer power and the mass transfer efficiency. In addition, the spiral line structure can reduce the deposition of pollutants, relieve the problem of membrane pollution and prolong the service life of the membrane.
In order to further verify the advantages of the hollow fiber membrane with the spiral line structure, the two membrane contact reactors are explored in the membrane distillation process.
The specific method of the membrane distillation experiment is as follows: the evaluation of the membrane distillation was carried out by direct contact using a spiral membrane contact reactor and a flat membrane contact reactor. The feed liquid is deionized water, the temperature of the feed liquid entering the membrane contact reactor is 60 ℃, the feed liquid circularly flows in the membrane shell pass, and the flow rate is set to be 50-500 mL/min; the permeate side was also deionized water, entering the membrane contact reactor at 15 ℃ and circulating in the membrane pass at a flow rate of 380 mL/min. The membrane distilled water flux of the two membrane contact reactors at different feed side circulation rates was measured and the specific test results are shown in table 2.
TABLE 2 comparison of the membrane distillation effects of different membrane contact reactions
As can be seen from Table 2, compared with the flat membrane contact reactor, the membrane distillation water production rate of the spiral membrane contact reactor is obviously improved, and the distilled water flux is improved by 57-117%. In the process of membrane contact of the flat membrane contact reactor, due to transmembrane transmission of generated energy, the phenomenon that the temperature near the membrane surface of the feed liquid side is greatly lower than that of a feed liquid main body occurs, so that the temperature difference between two sides of the membrane is lower, the mass transfer power and the mass transfer efficiency are lower, and the temperature difference polarization effect exists. In this disclosure, utilize helix structure except can effectively increasing the area of contact of liquid with the membrane, can also strengthen the radial mixture in the membrane contact reactor, reduce the temperature difference polarization phenomenon of membrane both sides, improve the mass transfer power between the gas-liquid two-phase for membrane flux promotes by a wide margin.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (10)
1. A hollow fiber membrane having a helical configuration, comprising:
a hollow fiber-based membrane, and
and the fiber threads are spirally wound on the surface of the hollow fiber base membrane, wherein the wound fiber threads are adhered to the surface of the hollow fiber base membrane to form a continuous whole.
2. The hollow fiber membrane having a spiral structure according to claim 1,
the diameter of the fiber wire is 0.05-2 mm;
the lead of the fiber thread is 1-100 cm.
3. The hollow fiber membrane having a spiral structure according to claim 1,
the diameter of the hollow fiber basal membrane is 0.5-10 mm.
4. The hollow fiber membrane having a spiral structure according to claim 1,
the material of the hollow fiber base membrane comprises any one of the following materials:
polypropylene, polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, glass;
the material of the fiber line comprises any one of the following materials:
polypropylene, polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, polyester, polyvinyl chloride, polyamide.
5. A method for producing a hollow fiber membrane having a spiral structure according to any one of claims 1 to 4, comprising the steps of:
winding fiber wires on the surface of the hollow fiber base membrane by using winding equipment;
and sintering the hollow fiber base membrane wound with the fiber yarns by using sintering equipment to obtain the hollow fiber membrane with the spiral line structure.
6. The method of claim 5, wherein the winding device winding the fiber yarn on the surface of the hollow fiber base film comprises:
the speed of the fiber wire released by the winding equipment is 10-5000 rpm;
the advancing speed of the hollow fiber basal membrane is 0.1-50 m/min.
7. The method of claim 5, wherein the winding device winding the spiral direction of the fiber thread on the surface of the hollow fiber base film comprises: left or right helix.
8. The method of claim 5, wherein the parameters of the sintering device for sintering the hollow fiber base film wound with the fiber yarn include:
the heating temperature of the sintering treatment includes: 100 ℃ and 400 ℃;
the time of the sintering treatment comprises the following steps: 5-100 s.
9. A membrane contact reactor comprising a hollow fiber membrane having a spiral line structure according to any one of claims 1 to 4.
10. The membrane contact reactor according to claim 9, wherein the membrane contact reactor is used for any one of membrane absorption, membrane degassing, and membrane distillation.
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| CN202638297U (en) * | 2012-05-15 | 2013-01-02 | 北京碧水源膜科技有限公司 | Composite reinforced hollow fiber membrane |
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| CN104226116A (en) * | 2014-07-01 | 2014-12-24 | 杭州求是膜技术有限公司 | Novel membrane contactor and manufacturing technology thereof |
| CN107952369A (en) * | 2016-10-14 | 2018-04-24 | 中国科学院大连化学物理研究所 | A kind of hollow fiber membrane contactors and its application |
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| CN202638297U (en) * | 2012-05-15 | 2013-01-02 | 北京碧水源膜科技有限公司 | Composite reinforced hollow fiber membrane |
| CN103143266A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院生态环境研究中心 | Preparation method of hollow fiber membrane with spiral reinforcing ribs and spinning nozzle |
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