CN112354266B - Filter material for treating oily wastewater and preparation method thereof - Google Patents
Filter material for treating oily wastewater and preparation method thereof Download PDFInfo
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- CN112354266B CN112354266B CN202010892911.5A CN202010892911A CN112354266B CN 112354266 B CN112354266 B CN 112354266B CN 202010892911 A CN202010892911 A CN 202010892911A CN 112354266 B CN112354266 B CN 112354266B
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000002351 wastewater Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 66
- 239000012528 membrane Substances 0.000 claims abstract description 59
- 238000001914 filtration Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002121 nanofiber Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000004065 wastewater treatment Methods 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 3
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 235000009120 camo Nutrition 0.000 claims description 3
- 235000005607 chanvre indien Nutrition 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000011487 hemp Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 36
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000009471 action Effects 0.000 abstract description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/0216—Bicomponent or multicomponent fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0414—Surface modifiers, e.g. comprising ion exchange groups
- B01D2239/0421—Rendering the filter material hydrophilic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0636—Two or more types of fibres present in the filter material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
Abstract
The invention provides a filtering material for treating oily wastewater and a preparation method thereof. According to the method, covering yarns or covering yarns obtained by compounding metal fibers and polymer fibers are used as base materials to prepare a metal organic composite yarn net, and then a layer of sanded layer with the thickness of 0.01-1 mm is prepared through sanding; and a layer of super-hydrophilic filtering membrane is prepared at the root of the sanded layer by taking the substrate as a base material. In the membrane preparation process, the short fiber of the root of the sanded layer and the polymer fiber on the surface of the root are crosslinked with the super-hydrophilic filtering membrane, so that the connection strength of the filtering membrane and the substrate is enhanced, and micro-nano pores are easily formed at the connection part of the root of the short fiber of the sanded layer and the filtering membrane, and the permeation of water molecules is facilitated. The invention utilizes the hydrophilicity of the milled velvet layer to guide the water in the oily wastewater to the root of the oily wastewater, and then realizes high-efficiency oil-water separation under the separation action of the super-hydrophilic filtering membrane.
Description
Technical Field
The invention relates to the technical field of membrane separation and wastewater treatment, in particular to a filtering material for treating oily wastewater and a preparation method thereof.
Background
With the development of modern science and technology and the improvement of industrial level, oil pollution gradually becomes common pollution, and the harm to environmental protection and ecological balance is great. At present, oily wastewater has wide sources, and the oily wastewater can be generated in industries such as petroleum exploitation, mechanical manufacturing, food processing, chemical pharmacy, electroplating metallurgy and the like. Therefore, the treatment of oily wastewater is one of the problems to be solved urgently in the field of environmental engineering nowadays.
At present, a great deal of research is carried out on the treatment of oily wastewater at home and abroad, and a plurality of methods for treating the oily wastewater are commonly known as a flocculation method, an air floatation method, an adsorption method, a biological method, a membrane separation method and the like. The membrane separation technology is a high-tech separation technology, and two-component or multi-component gas or liquid is separated, graded and enriched by using a selective permeable membrane as a separation medium under the promotion of external energy or chemical potential. The membrane separation technology has the advantages of relatively low operation cost, stable permeation quality, low energy consumption, small space requirement and the like. However, membrane separation methods also have some disadvantages, such as small membrane flux, susceptibility of the membrane to contamination, etc. In the process of treating the oily sewage by using the membrane separation technology, the water permeability flux of the membrane is inevitably reduced in long-time operation, so that the membrane is polluted.
Common substrate materials for membrane separations include metal meshes and polymeric substrates. The metal screen mesh is made of materials such as a copper mesh, a stainless steel mesh, a titanium mesh, a nickel mesh and the like, is the most widely applied material in oil-water separation research, and has the advantages of low price, excellent mechanical property, high temperature resistance, corrosion resistance, long service life and the like. However, the metal screen has the problems of large brittleness and small elasticity, brings certain difficulty for the forming processing of the membrane, does not have obvious super-hydrophilic-super-oleophobic characteristics, has poor oil-water selectivity, and needs to be modified when being used for oil-water separation. The polymer film has disadvantages in that it has poor mechanical properties and is easily deformed.
Therefore, it is urgently needed to provide a preparation method of a filtering material for treating oily wastewater, which modifies the material to endow the material with proper pore size and special wettability, and simultaneously enables the separation capacity, the anti-fouling capacity and the mechanical property of the membrane to reach higher industrial levels.
Disclosure of Invention
The invention aims to provide a filter material for treating oily wastewater and a preparation method thereof. The method takes core spun yarn or covered yarn obtained by compounding metal fiber and polymer fiber as a basic material to prepare a metal organic composite gauze, and then a layer of ground velvet layer is prepared; and a layer of super-hydrophilic filtering membrane is prepared at the root of the sanded layer by taking the substrate as a base material. The hydrophilicity of the milled fluff layer is utilized to guide water in the oil-containing wastewater to the root of the milled fluff layer, and then the high-efficiency oil-water separation is realized under the separation action of the super-hydrophilic filtering membrane.
In order to achieve the above object, the present invention provides a method for preparing a filter material for oily wastewater treatment, comprising the steps of:
s1, compounding metal fibers and polymer fibers with active groups on the surfaces to obtain core spun yarns or covered yarns serving as base materials, and manufacturing a metal organic composite gauze with the aperture of 50-500 mu m;
s2, sanding the metal organic composite gauze obtained in the step S1 to obtain a metal organic composite gauze with a sanded layer on the surface;
s3, adding quaternary ammonium salt chitosan, polyvinyl alcohol nanofiber and pentanediol into a mixed solvent of acetone and water to obtain a mixed solution;
s4, soaking the part below the milled down layer of the metal organic composite gauze with the milled down layer on the surface, obtained in the step S2, in the mixed solution obtained in the step S3, taking out the soaked and adsorbed part, drying and crosslinking the soaked and adsorbed part, and forming a super-hydrophilic filtering membrane on the root of the milled down layer to obtain the filtering material for treating the oily wastewater.
As a further improvement of the present invention, in step S1, the metal fiber is one of copper fiber, stainless steel fiber, gold fiber or nickel fiber; the polymer fiber is one of cotton fiber, hemp fiber, polyamide fiber or polyvinyl alcohol fiber.
As a further improvement of the invention, the diameter of the metal fiber is 1-10 μm, and the diameter of the polymer fiber is 0.2-1 μm.
In a further improvement of the present invention, in step S2, the thickness of the sanded layer is 0.01 to 1mm, and the diameter of the sanded staple fibers of the sanded layer is 0.1 to 0.5 μm.
As a further improvement of the invention, the thickness of the suede layer is 0.05-0.2 mm.
In a further improvement of the present invention, in step S3, the polyvinyl alcohol nanofibers have a diameter of 100 to 300nm and a length of 1 to 10 mm.
As a further improvement of the invention, in step S3, the mass percentage content ratio of the quaternary ammonium salt chitosan, the polyvinyl alcohol nanofiber and the pentanediol in the mixed solution is (1% -5%) (5% -20%) (0.5% -2%).
As a further improvement of the invention, in step S3, the volume ratio of the acetone to the water is 50% to 50% -80% to 20%.
As a further improvement of the present invention, in step S4, the pore size of the superhydrophilic filtration membrane is 2 to 50 nm; the thickness of the super-hydrophilic filter membrane is 1-100 mu m.
The invention also provides a filter material for treating oily wastewater, which is prepared by the method.
The invention has the beneficial effects that:
1. according to the invention, the metal fiber and the polymer fiber are compounded into the core-spun yarn or the cladding yarn, so that the metal organic composite gauze has the advantages of low price, excellent mechanical property, high temperature resistance, corrosion resistance, long service life and the like of the metal wire, and the advantages of uniform surface chemical structure, strong adjustability and easy hydrophilic modification of the polymer fiber, and the problems of large brittleness and small elasticity of the metal gauze are overcome, thereby providing powerful support for the preparation of subsequent filtering materials.
2. According to the invention, the metal organic composite gauze is subjected to sanding treatment, so that polymer fibers in the metal organic composite gauze generate sanded short fibers to form a sanded layer, on one hand, the sanded layer can increase the specific surface area of the substrate, on the other hand, the finer sanded short fibers can form a composite filtering structure with a subsequent super-hydrophilic filtering film, and the oil-water separation efficiency is improved.
3. The part below the sanded layer is immersed in the mixed solution of the filtering membrane, and a layer of super-hydrophilic filtering membrane is formed only on the surface of the metal organic composite gauze below the root of the sanded layer. Because the polymer fiber and the mixed solution both contain crosslinkable active groups, the polymer fiber can also be chemically crosslinked with groups in the filter membrane, so that the strength of the membrane is enhanced. When the separation treatment of the oily wastewater is carried out, water molecules are preferentially adsorbed by the milled short fibers because the milled short fibers of the milled layer have hydrophilicity; because the super-hydrophilic filtering membrane at the root has better hydrophilicity, water molecules are quickly guided into the root and flow to the other side of the filtering membrane through the pores of the super-hydrophilic filtering membrane, and oil in the wastewater is intercepted, so that the high-efficiency oil-water separation is realized.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a filtering material for treating oily wastewater, which comprises the following steps:
s1, compounding metal fibers and polymer fibers with active groups on the surfaces to obtain core spun yarns or covered yarns serving as base materials, and manufacturing a metal organic composite gauze with the aperture of 50-500 mu m;
wherein the metal fiber is one of copper fiber, stainless steel fiber, gold fiber or nickel fiber; the polymer fiber is one of cotton fiber, hemp fiber, polyamide fiber or polyvinyl alcohol fiber. The polymer fibers selected by the invention are all fibers containing active groups such as hydroxyl, carboxyl or amino and the like, and have good hydrophilicity.
The diameter of the metal fiber is 1-10 mu m, and the diameter of the polymer fiber is 0.2-1 mu m.
According to the invention, the metal fiber and the polymer fiber are compounded into the core-spun yarn or the cladding yarn, so that the metal-organic composite gauze has the advantages of low price, excellent mechanical property, high temperature resistance, corrosion resistance, long service life and the like of the metal wire, and the advantages of uniform surface chemical structure, strong adjustability and easy hydrophilic modification of the polymer fiber, and the problems of large brittleness and small elasticity of the metal gauze are overcome, and a powerful support is provided for the subsequent preparation of the filter material.
S2, sanding the metal organic composite gauze obtained in the step S1 to obtain a metal organic composite gauze with a sanded layer on the surface;
in a further improvement of the present invention, in step S2, the thickness of the sanded layer is 0.01 to 1mm, and the diameter of the sanded staple fibers of the sanded layer is 0.1 to 0.5 μm.
As a further improvement of the invention, the thickness of the suede layer is 0.05-0.2 mm.
According to the invention, the metal organic composite gauze is subjected to sanding treatment, so that polymer fibers in the metal organic composite gauze generate sanded short fibers to form a sanded layer, on one hand, the sanded layer can increase the specific surface area of the substrate, on the other hand, the finer sanded short fibers can form a composite filtering structure with a subsequent super-hydrophilic filtering film, and the oil-water separation efficiency is improved. Therefore, the diameter and the thickness of the sanded short fibers have important influence on the method, and when the diameter is too large, the formation of a super-hydrophilic filtering membrane is not facilitated; the thickness is too large, so that the filtration resistance is increased, and the filtration flux is reduced; if the thickness is too small, the water absorption and introduction effect is weak.
S3, adding quaternary ammonium salt chitosan, polyvinyl alcohol nanofiber and pentanediol into a mixed solvent of acetone and water to obtain a mixed solution;
wherein the polyvinyl alcohol nanofiber has a diameter of 100-300 nm and a length of 1-10 mm.
The mass percentage content ratio of the quaternary ammonium salt chitosan, the polyvinyl alcohol nano fiber and the pentanediol in the mixed solution is (1% -5%) (5% -20%) (0.5% -2%).
The volume ratio of the acetone to the water is 50 percent to 80 percent to 20 percent.
The invention selects the polyvinyl alcohol nano fiber as the raw material for preparing the filtering membrane, can improve the mechanical strength of the filtering membrane, has smaller fiber diameter and can increase the specific surface area of the filtering membrane. Because the polyvinyl alcohol nano-fiber is soluble in water, the invention selects acetone and water as a mixed solvent, improves the dispersibility of the polyvinyl alcohol nano-fiber and reduces the solubility of the polyvinyl alcohol nano-fiber.
S4, soaking the part below the milled down layer of the metal organic composite gauze with the milled down layer on the surface, obtained in the step S2, in the mixed solution obtained in the step S3, taking out the soaked and adsorbed part, drying and crosslinking the soaked and adsorbed part, and forming a super-hydrophilic filtering membrane on the root of the milled down layer to obtain the filtering material for treating the oily wastewater.
As a further improvement of the invention, in step S4, the pore diameter of the super-hydrophilic filter membrane is 2-50 nm.
As a further improvement of the present invention, in step S4, the thickness of the super-hydrophilic filter membrane is 1 to 100 μm.
In the present invention, a super-hydrophilic filter membrane is formed only on the surface of the metal-organic composite gauze below the root of the sanded layer by immersing the part below the sanded layer in the mixed solution obtained in step S3. Because the polymer fiber and the mixed solution both contain crosslinkable active groups, the polymer fiber can also be chemically crosslinked with the groups in the filter membrane, so that the strength of the membrane is enhanced. When the separation treatment of the oily wastewater is carried out, because the milled short fibers of the milled layer have hydrophilicity, water molecules are preferentially adsorbed by the milled short fibers; because the super-hydrophilic filtering membrane at the root has better hydrophilicity, water molecules are quickly guided into the root and flow to the other side of the filtering membrane through the pores of the super-hydrophilic filtering membrane, and oil in the wastewater is intercepted, so that the high-efficiency oil-water separation is realized.
The invention also provides a filter material for treating oily wastewater, which is prepared by the method.
Example 1
A preparation method of a filter material for oily wastewater treatment comprises the following steps:
s1, compounding copper fibers with the diameter of 5 microns and polyvinyl alcohol fibers with the diameter of 0.5 microns to obtain core-spun yarns serving as base materials, and manufacturing a metal-organic composite gauze with the aperture of 200 microns;
s2, sanding the metal organic composite gauze obtained in the step S1 to obtain a metal organic composite gauze with a surface containing a sanded layer with the thickness of 0.1mm and the diameter of sanded short fibers of 0.4 mu m;
s3, adding quaternary ammonium salt chitosan, polyvinyl alcohol nano fibers with the diameter of 200nm and the length of 5mm and pentanediol into a mixed solvent of acetone and water, wherein the volume ratio of the acetone to the water is 65% to 35%, and the mass percentage content ratio of the quaternary ammonium salt chitosan, the polyvinyl alcohol nano fibers and the pentanediol is 2.5% to 12% to 1%, so as to obtain a mixed solution;
s4, soaking the part, below the milled down layer, of the metal organic composite gauze with the milled down layer on the surface, obtained in the step S2, in the mixed solution obtained in the step S3 for 30min, taking out the soaked part, drying and crosslinking the soaked part, and forming a super-hydrophilic filtering membrane with the aperture of 2-50 nm and the thickness of 50 microns at the root of the milled down layer to obtain the filtering material for treating the oily wastewater.
Tests prove that the oil-water separation efficiency of the filter material prepared by the embodiment is as high as 99.8%, and the flux of filtered water is as high as 4600L (m)2·h)-1(ii) a After 10 times of circulating separation, the oil-water separation efficiency is still as high as 99.1%.
Examples 2 to 7
Examples 2 to 7 are different from example 1 in that the thickness of the sanded layer and the diameter of the sanded staple fibers in step S2 are shown in table 1, and the other steps are substantially the same as example 1, and are not repeated.
TABLE 1 preparation conditions and Performance test results for examples 2-7
As can be seen from table 1, when the thickness of the sanded layer is too low, both the oil-water separation efficiency and the filtered water flux decrease; when the thickness of the matte layer is too large, the oil-water separation efficiency is slightly reduced, but the reduction of the filtration water flux is significant. The thickness of the suede layer is too large, and the water flow resistance is increased. As the diameter of the sanded staple fibers increases, both the oil-water separation efficiency and the filtered water flux gradually decrease, so appropriately decreasing the diameter of the sanded staple fibers contributes to improving the separation efficiency.
Examples 8 to 15
Examples 8 to 15 differ from example 1 in that the preparation conditions in step S3 are shown in table 2, and the rest are substantially the same as example 1, and thus detailed description thereof is omitted.
TABLE 2 preparation conditions and Performance test results for examples 8-15
As can be seen from table 2, both the diameter and the length of the polyvinyl alcohol nanofibers have some influence on the filtration performance, especially when the fiber length is too long, both the separation efficiency and the water flux are reduced, which may be due to too long fibers, which is not favorable for the filter membrane to form a uniform porous structure.
Comparative example 1
A method for preparing a filter material for oily wastewater treatment, which is different from example 1 in that the step S2 is not included, i.e., the metal-organic composite gauze is not subjected to sanding treatment. The rest is substantially the same as embodiment 1, and will not be described again.
Comparative example 2
A method for preparing a filter material for oily wastewater treatment, which is different from example 1 in that the step S1 comprises: making copper fiber with diameter of 5 μm into copper mesh with aperture of 200 μm; and then directly performing the treatments of steps S3 and S4, namely preparing a layer of super-hydrophilic filtering membrane on the surface of the copper mesh. The rest is substantially the same as embodiment 1, and will not be described again.
Comparative example 3
A method for preparing a filter material for oily wastewater treatment, which is different from example 1 in that the step S1 comprises: polyvinyl alcohol fibers having a diameter of 0.5 μm were made into a polyvinyl alcohol fiber web having a pore diameter of 200. mu.m. The rest is substantially the same as that of embodiment 1, and will not be described herein.
TABLE 3 test results for comparative examples 1-3
| Comparative example | Oil-water separation efficiency (%) | Filtered water flux L (m)2·h)-1 |
| Comparative example 1 | 96.8 | 4030 |
| Comparative example 2 | 95.5 | 3890 |
| Comparative example 3 | 97.5 | 4210 |
As can be seen from table 3, when the metal-organic composite gauze was not subjected to the roughening treatment, the separation efficiency and the filtration water flux were significantly reduced, indicating that the formation of the hydrophilic roughened layer indeed contributes to the introduction of water molecules to the surface of the filtration membrane, thereby improving the separation efficiency. When the metal mesh or the polymer fiber mesh is selected as a substrate material, the oil-water separation efficiency and the filtered water flux are also obviously reduced, and the reduction of the metal mesh substrate is more obvious. On the one hand because the metal mesh cannot be sanded and on the other hand because the polymer web is more hydrophilic, but the mechanical strength of the polymer web alone is inferior to that of the metal-organic composite gauze.
In summary, the filter material for treating oily wastewater and the preparation method thereof provided by the invention have the advantages that the core spun yarn or the clad yarn obtained by compounding the metal fiber and the polymer fiber is used as a base material to prepare a metal organic composite yarn net, and then a layer of sanded layer with the thickness of 0.01-1 mm is prepared through sanding; and a layer of super-hydrophilic filtering membrane is prepared at the root of the sanded layer by taking the substrate as a base material. In the membrane making process, the short fiber at the root of the sanded layer and the polymer fiber on the surface of the root are crosslinked with the super-hydrophilic filtering membrane, so that the connection strength of the filtering membrane and the substrate is enhanced, and the micro-nano pores are easily formed at the connection part of the root of the sanded short fiber and the filtering membrane, and the permeation of water molecules is facilitated. When the separation treatment of the oily wastewater is carried out, because the sanded short fibers of the sanded layer have hydrophilicity, water molecules are preferentially adsorbed by the sanded short fibers; because the super-hydrophilic filtering membrane at the root has better hydrophilicity, water molecules are quickly guided into the root and flow to the other side of the filtering membrane through the pores of the super-hydrophilic filtering membrane, and oil in the wastewater is intercepted, so that the high-efficiency oil-water separation is realized.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a filter material for oily wastewater treatment is characterized by comprising the following steps:
s1, compounding metal fibers and polymer fibers with active groups on the surfaces to obtain core spun yarns or covered yarns serving as base materials, and manufacturing a metal organic composite gauze with the aperture of 50-500 mu m;
s2, sanding the metal organic composite gauze obtained in the step S1 to obtain a metal organic composite gauze with a sanded layer on the surface;
s3, adding quaternary ammonium salt chitosan, polyvinyl alcohol nanofiber and pentanediol into a mixed solvent of acetone and water to obtain a mixed solution;
s4, soaking the part, below the milled down layer, of the metal organic composite gauze with the milled down layer on the surface, obtained in the step S2, in the mixed solution obtained in the step S3, taking out the soaked and adsorbed part, drying and crosslinking the soaked and adsorbed part, and forming a super-hydrophilic filtering membrane on the root of the milled down layer to obtain the filtering material for treating the oily wastewater.
2. The method for preparing a filter material for oily wastewater treatment as claimed in claim 1, wherein in step S1, said metal fiber is one of copper fiber, stainless steel fiber, gold fiber or nickel fiber; the polymer fiber is one of cotton fiber, hemp fiber, polyamide fiber or polyvinyl alcohol fiber.
3. The method for preparing a filter material for oily wastewater treatment according to claim 2, wherein the diameter of the metal fiber is 1 to 10 μm, and the diameter of the polymer fiber is 0.2 to 1 μm.
4. The method for preparing a filter material for oily wastewater treatment as claimed in claim 1, wherein in step S2, the thickness of said sanded layer is 0.01 to 1mm, and the diameter of the sanded staple fibers of said sanded layer is 0.1 to 0.5 μm.
5. The method for preparing a filter material for oily wastewater treatment according to claim 4, wherein the thickness of the sanded layer is 0.05-0.2 mm.
6. The method for preparing a filter material for oily wastewater treatment according to claim 1, wherein in step S3, the polyvinyl alcohol nanofibers have a diameter of 100 to 300nm and a length of 1 to 10 mm.
7. The method of claim 1, wherein in step S3, the weight percentage of the quaternary ammonium salt chitosan, the polyvinyl alcohol nanofiber and the pentanediol in the mixed solution is (1% -5%) (5-20%) (0.5% -2%).
8. The method for preparing a filter material used in the treatment of oil-containing wastewater as set forth in claim 1, wherein the volume ratio of acetone to water is 50%: 80%: 20% in step S3.
9. The method for preparing a filter material for oily wastewater treatment according to claim 1, wherein in step S4, the super-hydrophilic filtration membrane has a pore size of 2 to 50nm and a thickness of 1 to 100 μm.
10. A filter material for the treatment of oily wastewater, characterized in that it is obtained by the process according to any one of claims 1 to 9.
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| CN103157299A (en) * | 2013-03-26 | 2013-06-19 | 清华大学 | Oil-water separation mesh film with acid-base salt stabilizing function and with underwater super-oleophobic property and preparation method thereof |
| CN105214509A (en) * | 2015-10-14 | 2016-01-06 | 湖北聚孚膜科技有限公司 | A kind of high-intensity hollow fiber filter film and preparation method thereof |
| JP2017104817A (en) * | 2015-12-11 | 2017-06-15 | 株式会社アイ・イー・ジェー | Method for removing water in oil, and material therefor |
| CN108671764A (en) * | 2018-06-13 | 2018-10-19 | 洛阳纳诺环保科技有限公司 | A kind of method that one-step method prepares super hydrophilic/underwater superoleophobic water-oil separationg film |
| CN208250529U (en) * | 2018-03-22 | 2018-12-18 | 海宁昱品环保材料有限公司 | A kind of anti-electrostatic filter cloth |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014119183A1 (en) * | 2014-12-19 | 2016-06-23 | Karlsruher Institut für Technologie | Process for the separation of liquids and their use |
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|---|---|---|---|---|
| CN103157299A (en) * | 2013-03-26 | 2013-06-19 | 清华大学 | Oil-water separation mesh film with acid-base salt stabilizing function and with underwater super-oleophobic property and preparation method thereof |
| CN105214509A (en) * | 2015-10-14 | 2016-01-06 | 湖北聚孚膜科技有限公司 | A kind of high-intensity hollow fiber filter film and preparation method thereof |
| JP2017104817A (en) * | 2015-12-11 | 2017-06-15 | 株式会社アイ・イー・ジェー | Method for removing water in oil, and material therefor |
| CN208250529U (en) * | 2018-03-22 | 2018-12-18 | 海宁昱品环保材料有限公司 | A kind of anti-electrostatic filter cloth |
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Denomination of invention: Filter materials and preparation methods for oily wastewater treatment Granted publication date: 20210730 Pledgee: China People's Property Insurance Co.,Ltd. Qingdao Branch Pledgor: QINGDAO HAINA ENERGY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT CO.,LTD. Registration number: Y2024370010008 |