CN115722209B - Polyoxymethylene microfiber oil-water separation material and preparation method thereof - Google Patents
Polyoxymethylene microfiber oil-water separation material and preparation method thereof Download PDFInfo
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 170
- 229930040373 Paraformaldehyde Natural products 0.000 title claims abstract description 160
- -1 Polyoxymethylene Polymers 0.000 title claims abstract description 160
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229920001410 Microfiber Polymers 0.000 title claims abstract description 88
- 239000003658 microfiber Substances 0.000 title claims abstract description 88
- 238000000926 separation method Methods 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 64
- 238000010008 shearing Methods 0.000 claims abstract description 28
- 229920006240 drawn fiber Polymers 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000010298 pulverizing process Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 4
- 238000002074 melt spinning Methods 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 64
- 238000004804 winding Methods 0.000 claims description 36
- 238000009987 spinning Methods 0.000 claims description 25
- 238000012360 testing method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 2
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 claims 1
- 238000002474 experimental method Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 48
- 238000005520 cutting process Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 239000010779 crude oil Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 21
- 239000000155 melt Substances 0.000 description 17
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000008188 pellet Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
Classifications
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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- Artificial Filaments (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a polyoxymethylene microfiber oil-water separation material and a preparation method thereof, comprising the following steps: and obtaining a polyoxymethylene primary fiber through melt spinning of polyoxymethylene granules, and obtaining a polyoxymethylene drawn fiber through hot drawing, so that a fibrillated structure is formed inside the polyoxymethylene drawn fiber and is orderly arranged along the axial direction. Cutting the polyoxymethylene drawn fiber into short pieces, putting the short pieces together with water into a mechanical pulverizer, shearing, disassembling and pulverizing to obtain polyoxymethylene microfiber aqueous dispersion, carrying out suction filtration by using a suction filtration bottle, washing by using deionized water, and drying by using a drying oven to obtain the polyoxymethylene microfiber oil-water separation material. The process is simple and convenient, and no chemical reagent is used in the preparation process, so that the environment is not polluted; the polyoxymethylene has chemical stability, plasticity and self-supporting property, has good adsorption and separation effects on various oils and organic reagents, can meet various oil-water separation environments and conditions, and provides an effective solution for treating offshore crude oil leakage and purifying oily sewage.
Description
Technical field:
the invention belongs to the field of processing and preparing novel materials, relates to a preparation method of an oil-water separation material, and particularly relates to a polyoxymethylene microfiber oil-water separation material and a preparation method thereof.
Background
Recently, the treatment of crude oil leakage at sea and the purification of oily domestic sewage are more and more challenging, and the current treatment methods are roughly divided into the following steps: the materials with hydrophobic and oleophilic properties are used for recovering oil on the water surface, the dispersing agent is used for mixing the oil and the water to promote natural degradation of the oil and the water to be directly combusted to remove floating oil. A generally preferred method is to recover the oil slick on the water surface using a material with hydrophobic and oleophilic properties, which can properly handle the oil slick without secondary pollution. These hydrophobic oleophilic materials currently in use can be divided into hydrophobic powder materials, hydrophobic film materials and hydrophobic three-dimensional porous materials. Sun Litao the subject group utilizes a chemical reaction method to thermally reduce aqueous dispersion of graphite oxide to form graphene hydrogel, and then the hydrogel is subjected to freeze drying to obtain graphene aerogel, and the prepared aerogel has a porous structure and hydrophobic and oleophylic characteristics, so that the three-dimensional porous hydrophobic material has poor mechanical strength, a three-dimensional framework cannot deform or is easily crushed and destroyed, and the applicability is low in a complex environment where water-oil separation is actually carried out. The problem group Wu Dehai of Qinghua university prepares the three-dimensional porous spongy carbon nano tube fast-assembling material by a chemical vapor deposition method, and the carbon nano tube sponge has super-hydrophobic property, rich void structure and super-light density, so that the material has stronger oil absorption capacity and can absorb organic solvents or oil products, but the preparation method is complex and has high cost. Meanwhile, the common electrostatic spinning method in the prior art requires the addition of an organic solvent, damages human health and environmental pollution, has long preparation time, reduces production efficiency and is not beneficial to large-scale industrial production and application. The preparation method has the characteristics of complex preparation process, environmental pollution caused by using chemical reagents, and difficulty in large-scale production and application, and is not beneficial to guiding industrial production.
When the hydrophobic powder material is applied to the oil-water separation process, the oil absorption capacity of the material is higher because the material has rich void structures and can provide a space for storing oil products. The polyoxymethylene is one of the wide general plastics, is cheap and easy to obtain, has stable chemical property, has hydrophobic and oleophylic properties, can be more effectively subjected to oil-water separation after being processed into microfiber powder materials, is easy to process and form, has low preparation cost and can be repeatedly utilized, and has remarkable advantages, important value and profound significance in actual large-scale continuous production and industrial application.
Disclosure of Invention
The invention aims to prepare the microfiber oil-water separation material which has the advantages of simple process flow, simple operation, no need of adding chemical reagents, no pollution, environmental friendliness, low cost, remarkable oil adsorption and oil-water separation effects, chemical stability, recycling property and plasticity and capability of large-scale continuous production.
In order to achieve the above purpose, the invention provides a preparation scheme of a polyoxymethylene microfiber oil-water separation material:
(1) Adding the polyformaldehyde granules into a screw extruder of spinning equipment for spinning, obtaining polyformaldehyde nascent fibers without stretching ratio through melt spinning, stretching the polyformaldehyde nascent fibers in an air stretching machine, and obtaining polyformaldehyde stretched fibers after winding by a winding machine;
(2) Chopping the polyoxymethylene drawn fiber obtained in the step (1) by using a cutter to obtain polyoxymethylene chopped fiber, putting the polyoxymethylene chopped fiber into a mechanical pulverizer, adding water, and carrying out mechanical shearing pulverization and disassembly to obtain polyoxymethylene micro-fiber aqueous dispersion;
(3) And (3) carrying out suction filtration on the polyoxymethylene microfiber aqueous dispersion liquid obtained in the step (2), washing with deionized water, and then putting into a drying oven for drying to finally obtain the polyoxymethylene microfiber oil-water separation material.
Preferably, in the spinning process of the step (1), the temperature of 6 zones of a single screw of a spinning machine is 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃, the rotation speed of the single screw of the extruder is 90rpm, the rotation speed of a metering pump is 60rpm, the winding speed of a winding machine is 300rpm, and the frequency of a reciprocating shaft is 200Hz.
Preferably, the heat drawing process of the step (1) is carried out at a temperature of 100 ℃,110 ℃,120 ℃ and a drawing ratio of 5 to 10 times. Further preferably, the stretching ratio is 6 to 9 times, and most preferably, the stretching ratio is 7 times.
Preferably, in the step (2), when the polyoxymethylene chopped fibers are mechanically sheared and pulverized and disassembled, 2 liters of water is added to the mechanical pulverizer every time the shearing and pulverizing and the disassembling are performed, and the shearing rate is 10 5 s -1 The time is 5-120 minutes. Further preferably 30 to 60 minutes, and most preferably 50 minutes.
Compared with the prior art, the invention has the following positive and beneficial effects:
(1) The present invention utilizes the fact that during the hot drawing process, the fibrillated microfibrillated structure is generated inside the fiber and oriented along the axial direction of the fiber, and the anisotropic nascent fiber of the drawn fiber is not present, which can be confirmed by XRD spectrum (figure 3). The polyoxymethylene microfiber oil-water separation material (figure 2) is obtained by mechanically shearing, crushing and disassembling the polyoxymethylene drawn fiber, destroying weak binding force among microfiber radial directions, retaining strong binding force (chemical bond) inside microfiber, and mutually overlapping, penetrating and supporting the polyoxymethylene microfiber in a suction filtration mode. The method for preparing the microfibers by mechanical shearing, crushing and disassembling solves the problem that the existing preparation method is difficult to continuously produce the porous oil-water separation material in large scale at low cost, and greatly reduces the production cost.
(2) In the method for preparing the polyoxymethylene microfiber oil-water separation material, the used raw materials are cheap and easy to obtain, and the polyoxymethylene microfiber oil-water separation material has excellent hydrophobicity, lipophilicity and chemical stability; the preparation process has no chemical reagent, only deionized water is used, no pollution is caused to the environment, and the processing process is safe and environment-friendly.
(3) The polyoxymethylene microfiber oil-water separation material prepared by the invention has micron-level holes formed by interpenetration, overlapping and supporting among a large number of microfibers, and has higher contact angle of water in air and oil, oil adsorption capacity and oil-water separation efficiency for various oils and organic solvents.
(4) As shown in fig. 9, the polyoxymethylene microfiber material prepared by the invention is in a powder shape, has plasticity, can be molded into various shapes, and can be molded into a polyoxymethylene microfiber oil-water separation cup with self-supporting property, so as to meet the oil-water separation environment under various conditions, and provide a feasible solution for treating offshore crude oil leakage and purifying oily domestic sewage.
(5) In the process of preparing the polyoxymethylene microfiber material, the chemical structure of polyoxymethylene is not destroyed, and the chemical stability of the polyoxymethylene is not lost in the preparation process, so that the polyoxymethylene microfiber material can resist separation of various oils and organic solvents. While chemical stability has an important contribution to the recycling of the material. Therefore, as shown in fig. 5-8, in the oil-water separation application, the polyoxymethylene microfiber has long service life, and can maintain the ultrahigh contact angle of water in air and oil, the oil adsorption capacity and the oil-water separation effect after being repeatedly recycled for 10 times. Meanwhile, after the material is used, the material can be subjected to treatments such as crushing, dispersing, washing and filtering again to prepare the recovered polyoxymethylene microfiber material, the material is reused for oil-water separation, and the material still has high contact angle of water in air and oil, high oil adsorption capacity and high oil-water separation efficiency in 10 times of recycling, so that the cost and time of oil-water separation are greatly reduced, recovery and reuse are realized, and high social and economic benefits are realized.
Drawings
FIG. 1 is a macroscopic photograph of polyoxymethylene microfibers prepared in example 4.
Fig. 2 (a) (b) is a cross-sectional SEM morphology of the polyoxymethylene primary fibers in the comparative example and the drawn fibers in example 4, and fig. 2 (c) (d) is a SEM morphology of polyoxymethylene powder prepared from the polyoxymethylene primary fibers and polyoxymethylene microfibers prepared from the polyoxymethylene drawn fibers.
Fig. 3 is one-dimensional and two-dimensional XRD patterns of the polyoxymethylene primary fibers in the comparative example and the polyoxymethylene drawn fibers in example 4.
FIG. 4 shows the air-water contact angles of polyoxymethylene microfiber films obtained in examples 1 to 6, wherein the mechanical shearing pulverization time was 5 minutes, 10 minutes, 30 minutes, 50 minutes, 90 minutes, and 120 minutes, respectively.
Fig. 5 (a) is the water contact angle of air, oil (chloroform and cyclohexane) for 10 cycles of the polyoxymethylene microfibers in example 4, and fig. 5 (b) is the water contact angle of air, oil (chloroform and cyclohexane) for 10 cycles of the recovered polyoxymethylene microfibers in example 4.
Fig. 6 (a) is the adsorption amount of the polyoxymethylene microfibers in example 4 to various oils and organic solvents, and fig. 6 (b) is the adsorption amount of the recovered polyoxymethylene microfibers in example 4 to various oils and organic solvents.
FIG. 7 shows the adsorption amount of oil (chloroform and cyclohexane) for 10 times of recycling of polyoxymethylene microfibers in example 4.
Fig. 8 (a) shows the oil-water separation and continuous separation efficiency after 10 cycles of the polyoxymethylene microfibers in example 4, and fig. 8 (b) shows the oil-water separation and continuous separation efficiency after 10 cycles of the recovered polyoxymethylene microfibers in example 4.
Fig. 9 (a) is a photograph of the polyoxymethylene microfibers of example 4 molded into various shapes, and fig. 9 (b) is a self-made, self-supporting polyoxymethylene microfiber oil-water separation cup, which can be used for continuous oil-water separation.
Comparative example
The method comprises the steps of setting the temperature of 6 heating areas of a screw of a spinning machine to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheating for 1 hour, pouring polyoxymethylene granules into a storage bin for melting, starting winding when the melt flows out of a spinneret plate of a spinning component, wherein the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, and obtaining polyoxymethylene primary fibers without stretching multiplying powerDimension. Then, the polyoxymethylene primary fibers were chopped to 2cm with a cutter to obtain chopped fibers, which were put into a mechanical pulverizer, and 2 liters of water was added to perform mechanical shearing pulverization and disassembly. The pulverizing time was 50 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyformaldehyde powder aqueous dispersion, washing 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain polyformaldehyde powder.
The polyoxymethylene powder obtained in this example had a porosity of 56.4% and exhibited a lamellar structure without microfibril morphology. The polyoxymethylene powder material of this example was filtered to form a film, and the test gave an air water contact angle value of 70 °, and the water contact angle of oil (chloroform and cyclohexane) could not be measured since the polyoxymethylene powder was too loose, the adsorption amount to (chloroform) was 8.9 times, and the oil (chloroform and cyclohexane) water separation efficiency was 88.3%.
Example 1
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 700rpm, i.e., the draw ratio was 7 times.
And then cutting the obtained polyoxymethylene drawn fiber to 2cm by a cutter to obtain a chopped fiber, putting the chopped fiber into a mechanical pulverizer, adding 2 liters of water, and carrying out mechanical shearing pulverization and disassembly. The pulverizing time was 5 minutes and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 70.2%, a diameter of about 30 to 35 μm and a length of about 110 to 130. Mu.m. The polyoxymethylene microfiber material of this example was filtered to form a film, and the test gave an air water contact angle value of 93 °, a water contact angle of 155 ° in oil (chloroform and cyclohexane), an adsorption amount to (chloroform) of 16.6 times, and an oil (chloroform and cyclohexane) water separation efficiency of 89.8%.
Example 2
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 700rpm, i.e., the draw ratio was 7 times.
And then cutting the obtained polyoxymethylene drawn fiber to 2cm by a cutter to obtain a chopped fiber, putting the chopped fiber into a mechanical pulverizer, adding 2 liters of water, and carrying out mechanical shearing pulverization and disassembly. The pulverizing time was 10 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 76.4%, a diameter of about 20 to 25 μm and a length of about 110 to 120. Mu.m. The polyoxymethylene microfiber material of this example was filtered to form a film, and the test gave an air water contact angle value of 109 °, a water contact angle of 156 ° in oil (chloroform and cyclohexane), an adsorption amount to (chloroform) of 17.8 times, and an oil (chloroform and cyclohexane) water separation efficiency of 95.6%.
Example 3
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 700rpm, i.e., the draw ratio was 7 times.
And then cutting the obtained polyoxymethylene drawn fiber to 2cm by a cutter to obtain a chopped fiber, putting the chopped fiber into a mechanical pulverizer, adding 2 liters of water, and carrying out mechanical shearing pulverization and disassembly. The pulverizing time was 30 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 82.9%, a diameter of about 10 to 20 μm and a length of about 100 to 110. Mu.m. The polyoxymethylene microfiber material of this example was filtered to form a film, and the test gave an air water contact angle value of 125 °, a water contact angle of 158 ° in oil (chloroform and cyclohexane), an adsorption amount to (chloroform) of 18.6 times, and an oil (chloroform and cyclohexane) water separation efficiency of 96.4%.
Example 4
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 700rpm, i.e., the draw ratio was 7 times.
And then cutting the obtained polyoxymethylene drawn fiber to 2cm by a cutter to obtain a chopped fiber, putting the chopped fiber into a mechanical pulverizer, adding 2 liters of water, and carrying out mechanical shearing pulverization and disassembly. The pulverizing time was 50 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 89.1%, a diameter of about 10 to 20 μm and a length of about 80 to 100. Mu.m. The polyoxymethylene microfiber material prepared in this example was filtered to form a film, and the air contact angle with water and the oil contact angle with water (chloroform and cyclohexane) were 131 ° and 160 °, and the air contact angle with water after 10 times of recycling was maintained at about 130 ° and 160 °, which is substantially the same as the initial test result (fig. 5). As shown in fig. 6 and 7, the adsorption amount of the polyoxymethylene microfibers to various oils and organic solvents was 19.5 times as high as that to chloroform, and the adsorption amount of the oils (chloroform and cyclohexane) after 10 times of recycling was not greatly changed. As shown in fig. 8, the polyoxymethylene microfiber material had an oil (chloroform) water separation and continuous oil-water separation efficiency of 99% or more after 10 times of recycling. As shown in FIG. 9, the polyoxymethylene microfiber material can achieve plasticity by using various dies, and can be self-made into a self-supporting continuous oil-water separation cup, so that efficient oil-water separation can be achieved.
The used polyoxymethylene microfibers are put into 1 liter of water and are dispersed again by a high-speed dispersing machine at 10000rpm, the recycled polyoxymethylene microfiber material is obtained by re-suction filtration, the contact angle of water in air and oil which are circularly used for 10 times is tested, the oil adsorption quantity and the oil-water separation efficiency are respectively shown in figures 5, 6 and 8.
Example 5
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 700rpm, i.e., the draw ratio was 7 times.
And then cutting the obtained polyoxymethylene drawn fiber to 2cm by a cutter to obtain a chopped fiber, putting the chopped fiber into a mechanical pulverizer, adding 2 liters of water, and carrying out mechanical shearing pulverization and disassembly. The pulverizing time was 90 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 83.7%, a diameter of about 10 to 15 μm and a length of about 70 to 80. Mu.m. The polyoxymethylene microfiber material of this example was filtered by suction to form a film, and the test gave an air water contact angle value of 121 °, a water contact angle of 159 ° in oil (chloroform and cyclohexane), an adsorption amount to (chloroform) of 19.3 times, and an oil (chloroform and cyclohexane) water separation efficiency of 99.2%.
Example 6
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 700rpm, i.e., the draw ratio was 7 times.
The resulting polyoxymethylene drawn fibers are thenCutting with a cutter to 2cm to obtain chopped fiber, placing into a mechanical pulverizer, adding 2L of water, and mechanically shearing, pulverizing and disassembling. The pulverizing time was 120 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 81.8%, a diameter of about 5 to 10 μm and a length of about 50 to 60. Mu.m. The polyoxymethylene microfiber material of this example was filtered to form a film, and the test gave an air water contact angle value of 121 °, a water contact angle of 158 ° in oil (chloroform and cyclohexane), an adsorption amount to (chloroform) of 19.0 times, and an oil (chloroform and cyclohexane) water separation efficiency of 99.2%.
Example 7
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 500rpm, i.e., the draw ratio was 5 times.
And then cutting the obtained polyoxymethylene drawn fiber to 2cm by a cutter to obtain a chopped fiber, putting the chopped fiber into a mechanical pulverizer, adding 2 liters of water, and carrying out mechanical shearing pulverization and disassembly. The pulverizing time was 50 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 85.5%, a diameter of about 15 to 25 μm and a length of about 80 to 90. Mu.m. The polyoxymethylene microfiber material of this example was filtered to form a film, and the test gave an air water contact angle value of 120 °, a water contact angle of 156 ° in oil (chloroform and cyclohexane), an adsorption amount to (chloroform) of 19.0 times, and an oil (chloroform and cyclohexane) water separation efficiency of 90.4%.
Example 8
The temperature of 6 heating areas of the screw of the spinning machine is respectively set to 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃ and preheated for 1 hour, and then polyoxymethylene pellets are poured into a storage bin to be melted, the single screw speed of the extruder is 90rpm, and the speed of a metering pump is 60rpm. When the melt flows out of the spinneret plate of the spinning component, the melt starts to be wound, the winding speed of a winding machine is 300rpm, the frequency of a reciprocating shaft is 200Hz, the polyoxymethylene primary fibers are obtained, and then the polyoxymethylene primary fibers are subjected to air thermal drafting, wherein the temperatures of 3 areas are respectively 100 ℃,110 ℃ and 120 ℃. The unwinding speed of the polyoxymethylene primary fiber was 100rpm, and the winding speed of the polyoxymethylene drawn fiber after heat drawing was 900rpm, i.e., the draw ratio was 9 times.
And then cutting the obtained polyoxymethylene drawn fiber to 2cm by a cutter to obtain a chopped fiber, putting the chopped fiber into a mechanical pulverizer, adding 2 liters of water, and carrying out mechanical shearing pulverization and disassembly. The pulverizing time was 50 minutes, and the shear rate was 10 5 s -1 . After shearing, crushing and disassembling are finished, carrying out suction filtration on the obtained polyoxymethylene microfiber aqueous dispersion, washing for 3 times by deionized water, and then drying in a drying oven at 70 ℃ for 10 hours to obtain the polyoxymethylene microfiber oil-water separation material.
The polyoxymethylene microfibers obtained in this example had a porosity of 84.6%, a diameter of about 10 to 20 μm and a length of about 85 to 100. Mu.m. The polyoxymethylene microfiber material of this example was filtered by suction to form a film, and the test gave an air water contact angle value of 123 °, a water contact angle of 157 ° in oil (chloroform and cyclohexane), an adsorption amount to (chloroform) of 18.6 times, and an oil (chloroform and cyclohexane) water separation efficiency of 96.1%.
Table 1 comparative examples and various parameters and experimental results of each example
Claims (6)
1. The preparation method of the polyoxymethylene microfiber oil-water separation material is characterized by comprising the following steps:
(1) Adding the polyformaldehyde granules into a screw extruder of spinning equipment for spinning, obtaining polyformaldehyde nascent fibers without stretching ratio through melt spinning, stretching the polyformaldehyde nascent fibers in an air hot stretching machine, and obtaining polyformaldehyde stretched fibers after winding by a winding machine;
(2) Chopping the polyoxymethylene drawn fiber obtained in the step (1) by using a cutter to obtain polyoxymethylene chopped fiber, putting the polyoxymethylene chopped fiber into a mechanical pulverizer, adding water, and carrying out mechanical shearing pulverization and disassembly to obtain polyoxymethylene micro-fiber aqueous dispersion;
(3) Carrying out suction filtration on the polyoxymethylene microfiber aqueous dispersion liquid obtained in the step (2), washing with deionized water, then putting into a baking oven for baking, finally obtaining a polyoxymethylene microfiber oil-water separation material, and carrying out experiments and tests;
wherein, in the air thermal drafting process in the step (1), the temperature of 3 zones is 100 ℃, the temperature of 110 ℃ and the temperature of 120 ℃, the unwinding speed of the polyoxymethylene primary fiber is 100rpm, the winding speed of the drawn fiber is 500-1000 rpm, and the drawing multiplying power is 5-10 times.
2. The preparation method of the polyoxymethylene microfiber oil-water separation material according to claim 1, wherein the microfiber has a diameter of 5-35 μm and a length of 50-130 μm, the polyoxymethylene microfiber oil-water separation material prepared by suction filtration has an air-water contact angle of 90-130 degrees, a porosity of 70-90%, a water contact angle of 155-160 degrees, a chloroform adsorption amount of 16-20 times, and a chloroform-water mixture separation efficiency of 90-99.5%.
3. The method for preparing the polyoxymethylene microfiber oil-water separation material according to claim 1, wherein the screw of the spinning machine in the step (1) is a single screw extruder, the screw speed of the extruder is 90rpm, the temperatures in the 1-6 regions are 150 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃, the rotational speed of a metering pump is 60rpm, the winding speed of a winding machine is 300rpm, and the reciprocating shaft frequency is 200Hz.
4. The method for preparing a polyoxymethylene microfiber oil-water separation material as set forth in claim 1, wherein the length of the chopped fibers prepared in step (2) is 2cm, the ratio of the mass of polyoxymethylene fibers added in the mechanical shearing and crushing and disassembling processes to the deionized water added is 10g of fibers corresponding to 2 liters of deionized water, and the shearing rate is 10 5 s -1 The time is 5-120 minutes.
5. The method for preparing a polyoxymethylene microfiber oil-water separation material according to claim 1, wherein the deionized water washing in step (3) is performed 3 times, the oven drying temperature is 70 ℃, and the drying time is 10 hours.
6. A polyoxymethylene microfiber oil-water separation material is characterized in that: the polyoxymethylene microfiber oil-water separation material is prepared by the preparation method of any one of claims 1 to 5.
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