阅读说明：本技术 一种天然生物质材料油水分离膜及其制备方法和用途 (Natural biomass material oil-water separation membrane and preparation method and application thereof ) 是由 滕超 王杰 马晓燕 王睿琪 李展柏 杨龙 杜芳林 于 2021-07-19 设计创作，主要内容包括：本发明公开了一种天然生物质材料油水分离膜及其制备方法和用途。本发明的天然生物质材料油水分离膜材料来自于自然界,可自然降解,减少了对环境的污染；并且该膜的接触角大于150°,油滴不能润湿膜表面,但是水可以顺利通过；本发明的天然生物质材料油水分离膜在强酸、强碱、高盐以及高温的复杂环境下仍对油水混合溶液或者乳液具有高的分离效率,具有优异的化学稳定性,并且力学性质基本保持不变。另外,本发明的制备方法简单方便,生物质材料来源广泛,价格低廉,生产成本低,生长速度快,油水分离效果优异,能够适用于大规模生产。(The invention discloses a natural biomass material oil-water separation membrane and a preparation method and application thereof. The natural biomass material oil-water separation membrane material is from the nature, can be naturally degraded, and reduces the pollution to the environment; the contact angle of the membrane is more than 150 degrees, oil drops can not wet the surface of the membrane, but water can smoothly pass through the membrane; the natural biomass material oil-water separation membrane has high separation efficiency on oil-water mixed solution or emulsion in complex environments of strong acid, strong alkali, high salt and high temperature, has excellent chemical stability, and basically keeps mechanical properties unchanged. In addition, the preparation method is simple and convenient, the biomass material is wide in source, low in price, low in production cost, high in growth speed and excellent in oil-water separation effect, and can be suitable for large-scale production.)

1. A preparation method of a natural biomass material oil-water separation membrane is characterized by mainly comprising the following steps:

step 1: obtaining a biomass material from the nature, cutting the biomass material into 1-100cm long along the growth direction of the film by using laser, connecting the biomass material by using a siloxane oligomer cross-linking agent, cutting the polymerized material by using the laser, wherein the thickness of the polymerized material is 0.05-50000 mu m, and drying the polymerized material for 0.5-10 hours under the vacuum drying condition at 20-90 ℃ to obtain an oil-water separation membrane of the biomass material without holes;

step 2: fixing the biomass material oil-water separation membrane obtained in the step 1 on a platform of a punching system, performing different punching processes on the biomass material oil-water separation membrane through computer control equipment to obtain the biomass material oil-water separation membrane with the aperture of 0.001-500 mu m, and placing the biomass material oil-water separation membrane in an oil-water separation device to realize oil-water separation.

2. The method for preparing the oil-water separation membrane of the natural biomass material according to claim 1, wherein the biomass material in the step 1 is mainly prepared from the following raw materials: one or more of agaric, straw, kelp, seaweed, fish skin, wood, lotus leaf, sunflower stem, leaves or rice leaves.

3. The method for preparing the natural biomass material oil-water separation membrane according to claim 1, wherein the polysiloxane oligomer cross-linking agent in the step 1 mainly comprises: one or more of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane, or polyether polysiloxane.

4. The method for preparing the natural biomass material oil-water separation membrane according to claim 1, wherein in the step 2, the array mode of the holes mainly comprises the following steps: one or more of a square array, a rectangular array, a polygonal array, a circular array, or a linear array.

5. The method for preparing the natural biomass material oil-water separation membrane according to claim 1, wherein in the step 2, the number of punching is 1 to 500.

6. The method for preparing the natural biomass material oil-water separation membrane according to claim 1, wherein in the step 2, the perforation density is 500 holes/square centimeter.

7. The method for preparing the natural biomass material oil-water separation membrane according to claim 1, wherein in the step 2, the perforation power is 1-100%.

8. The method for preparing the natural biomass material oil-water separation membrane according to claim 1, wherein the laser cutting system and the punching system mainly comprise: numerical control automatic punching machine, hydraulic automatic punching machine, YAG laser punching machine, semiconductor laser cutting machine, laser welding machine, CO₂One or more of a laser marking machine, a micropore laser drilling machine, an ultramicropore through hole machining machine or a pinhole drilling machine.

9. The biomass material oil-water separation membrane obtained by the preparation method of the natural biomass material oil-water separation membrane according to claims 1-8, which is characterized by being degradable, high in toughness, resistant to polar conditions and high in oil-water separation efficiency.

10. The application of the natural biomass material oil-water separation membrane is characterized in that the natural biomass material oil-water separation membrane can be used for purifying water-containing oil materials, treating oil-containing sewage and treating marine oil-containing sewage.

Technical Field

The invention belongs to the technical field of separation membranes, and particularly relates to a natural biomass material oil-water separation membrane, and a preparation method and application thereof.

Background

Since the discharge of industrial oil and domestic waste oil and the frequent occurrence of oil spill at sea inevitably generate a large amount of oily waste water, if the waste water is directly discharged, the pollution to the marine ecology is serious, and the production and the life of human beings are greatly damaged. In addition, if the industry contains free water, the corrosion to mechanical equipment can be caused after the use, and a great potential safety hazard is generated.

At present, oil-water separation devices with complex preparation process and high energy consumption, such as separation technologies of centrifugation, filtration, gravity and the like, are widely applied in the field of oil-water separation. On this basis, separation techniques based on specific wettability have been developed as an emerging, environmentally friendly and simple to prepare technique. The technology has the advantages of low energy consumption, easy operation, simple flow and the like, arouses wide attention and interest of scientific researchers, and becomes a hotspot of research on oil-water separation membranes in recent years.

The Chinese patent with publication number CN108744600A discloses a preparation method of an oil-water separation membrane with special wettability, the material has the properties of super oleophylicity under air and oil and super hydrophobicity under oil, the contact angle is up to 157 degrees, in a polar environment, the oil-water separation effect is basically unchanged, but the material is not degradable, and secondary pollution is generated after application.

The Chinese patent with publication number CN112090295A discloses a degradable oil-water separation membrane material and a preparation method thereof, wherein a nanofiber tube and a nanofluid are doped into a solution prepared from polylactic acid, and a spinning mode is adopted to prepare a degradable fiber membrane for oil-water separation, and the process is repeated for many times.

The Chinese patent with publication number CN102728104A discloses a corrosion-resistant oil-water separation net film, a preparation method and application thereof, the net film is a fiber woven net coated with conductive polymer hydrogel, and has super-hydrophilicity and super-oleophobicity under water, but the defects of poor mechanical property, complex preparation process, low adhesion and the like exist, and the industrial application of oil-water separation is seriously influenced.

In fact, in the oil-water separation process, a complex external environment, such as a strong acid, a strong base or a salt solution, is usually exposed, and therefore, an oil-water separation membrane with excellent mechanical properties, natural degradation and resistance to polar conditions is urgently needed.

Disclosure of Invention

Based on the above, the main purpose of the present invention is to provide a natural biomass material oil-water separation membrane, and a preparation method and a use thereof, wherein the natural biomass material oil-water separation membrane of the present invention not only can realize efficient oil-water separation, but also has excellent mechanical properties, natural degradability and performance under polar resistant conditions.

In order to achieve the purpose, the technical scheme of the invention is as follows:

firstly, the invention discloses a preparation method of a natural biomass material oil-water separation membrane, which comprises the following steps:

step 1: obtaining a biomass material from the nature, cutting the biomass material into 1-100cm long along the growth direction of a film, connecting the biomass material by using a polysiloxane oligomer cross-linking agent, cutting the polymerized material by using laser, wherein the thickness of the polymerized material is 0.05-50000 mu m, and drying the polymerized material for 0.5-10 hours under the vacuum drying condition at 20-90 ℃ to obtain an oil-water separation membrane of the biomass material without holes;

step 2: fixing the biomass material oil-water separation membrane obtained in the step 1 on a platform of a punching system, performing different punching processes on the biomass material oil-water separation membrane through computer control equipment to obtain the biomass material oil-water separation membrane with the aperture of 0.001-500 mu m, and placing the biomass material oil-water separation membrane into an oil-water separation device to realize oil-water separation.

Further, the biomass material in step 1 is mainly derived from: one or more of agaric, straw, kelp, seaweed, fish skin, wood, lotus leaf, sunflower stem, leaves or rice leaves.

Further, the polysiloxane oligomer cross-linking agent described in step 1 mainly comprises: one or more of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane, or polyether polysiloxane.

Further, the array mode of the holes in step 2 mainly comprises: one or more of a square array, a rectangular array, a polygonal array, a circular array, or a linear array.

Further, the punching times in the step 2 are 1-500; the perforating power is 1-100%, and the hole density is 500 holes/square centimeter.

Further, the laser cutting system and the punching system in step 1 and step 2 of the preparation method mainly comprise: numerical control automatic punching machine, hydraulic automatic punching machine, YAG laser punching machine, semiconductor laser cutting machine, laser welding machine, CO₂One or more of a laser marking machine, a micropore laser drilling machine, an ultramicropore through hole machining machine or a pinhole drilling machine.

Furthermore, the invention also discloses the application of the natural biomass material oil-water separation membrane, and the oil-water separation membrane can be used for purifying water-containing oil, treating oil-containing sewage and treating marine oil-containing sewage.

The principle of the invention is as follows:

the natural biomass material oil-water separation membrane prepared by the invention can realize barrier-free oil-water separation, and mainly benefits from the special wetting characteristic that the surface of the separation membrane presents hydrophilicity and lipophobicity: when water contacts the membrane surface, water can pass through the membrane due to the super-hydrophilic characteristic of the membrane; when the oil contacts the membrane surface, the oil is successfully trapped due to the superoleophobic characteristic, and separation of the mixture is finally achieved. In addition, the oil-water separation membrane of the natural biomass material has a special three-dimensional cross-linking structure, the structure can better disperse the tensile stress of the membrane, and the mechanical property of the membrane is not affected even if a large number of micron holes are punched.

Has the advantages that:

1. the oil-water separation membrane with special wettability prepared by the invention has the characteristics of water and oil repellency, so that the separation of various oil-water mixtures can be realized, the separation efficiency can reach more than 99 percent, and the oil-water separation membrane has good oil circulation;

2. the oil-water separation membrane prepared by the invention has excellent mechanical properties, the mechanical value of the membrane is 1-2 orders of magnitude higher than that of other hydrogel applied to oil-water separation, and the mechanical value of the membrane is basically unchanged relative to the original natural biomass material after the membrane is perforated;

3. the oil-water separation membrane prepared by the invention still keeps excellent separation effect and mechanical property in the complex environment of strong acid, strong alkali, high salt and high temperature;

4. the preparation method of the oil-water separation membrane is simple and convenient, and the oil-water separation membrane has the advantages of green raw materials, natural degradation, environmental protection, wide sources and great reduction of the production cost;

5. the invention can obtain a novel, high-efficiency, low-price, environment-friendly, degradable, high-toughness and polarity-resistant natural biomass material oil-water separation membrane.

Drawings

FIG. 1 is an SEM image of an oil-water separation membrane of a natural biomass material in step 1 of the example of the present invention;

FIG. 2 shows the contact angle and the rolling angle of the oil-water separation membrane of the natural biomass material obtained in step 2 of the embodiment of the invention in dichloromethane and water;

FIG. 3 shows the mechanical properties of the oil-water separation membrane of the natural biomass material obtained in step 2 of the embodiment of the present invention in different environments;

FIG. 4 shows the results of testing the oil-water separation efficiency of the oil-water separation membrane of the natural biomass material obtained in step 2 of the embodiment of the present invention;

FIG. 5 shows the natural biomass material obtained by the embodiment of the present invention before and after the oil-water separation membrane is perforated.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to specific examples, and the methods in the following examples are conventional in the art unless otherwise specified.

Examples preparation methods:

step 1: obtaining a biomass material kelp from the nature, cutting the kelp into 10cm long along the growth direction of the film, connecting the biomass material by using a polymer and a cross-linking agent, cutting the polymerized material by using laser, wherein the thickness of the cut kelp is 0.5cm, and drying the kelp for 6 hours under the condition of vacuum drying at the temperature of 80 ℃ to obtain an oil-water separation film of the biomass material without holes;

step 2: fixing the biomass material oil-water separation membrane obtained in the step 1 on a platform of a punching system, punching the biomass material oil-water separation membrane into circular array holes by a computer-controlled YAG laser punching machine, wherein the punching frequency is 450, the punching power is 75%, and the punching density is 500 holes/square centimeter, so as to obtain the biomass material oil-water separation membrane with the aperture of 200 mu m, and placing the biomass material oil-water separation membrane into an oil-water separation device to realize oil-water separation.

Aiming at the biomass material oil-water separation membrane obtained in the embodiment, the microstructure, wettability, mechanical property, separation efficiency and flux of the membrane are researched, and the results are as follows:

in order to further observe the surface morphology of the natural biomass oil-water separation membrane, the microstructure of the obtained natural oil-water separation membrane was characterized by Scanning Electron Microscopy (SEM) (as shown in fig. 1). Through the graph 1, it can be found that the micro-nano mastoid structure on the surface of the oil-water separation membrane of the biomass material in the embodiment endows the kelp membrane with super oleophobic property, and the micro-nano hierarchical structure is beneficial to effective separation of oil/water incompatible mixtures.

In order to fully study the wettability of the membrane, the natural biomass material oil-water separation membrane in the example is used to separate dichloromethane and water (as shown in fig. 2), the contact angle of dichloromethane on the membrane surface in the example is as high as 150 ° or more, and the contact angle of water is close to 0 °, so that the natural oil-water separation membrane surface has super-oleophobic and super-hydrophilic characteristics. The wetting property is such that the film allows the continuous aqueous phase to pass through, while the oil phase is blocked.

The mechanical property of the oil-water separation membrane is a key factor influencing the mechanical reliability of the material in the use process. FIG. 3a shows a typical stress-strain curve of oil-water separation membrane of natural biomass material, with tensile strength as high as 2.5MPa and elongation at break as high as 182%. Fig. 3b shows a typical stress-strain curve of the oil-water separation membrane of the natural biomass material after perforation, and the mechanical properties of the membrane are similar to those of the natural biomass material.

As shown in fig. 4a, the natural biomass material oil-water separation membrane in the example is used for separating incompatible mixtures of n-hexane/water, n-dodecane/water, gasoline/water, diesel oil/water, peanut oil/water and engine oil/water, the separation efficiency is as high as more than 99.9%, the separation flux is as high as 2000L/square meter/hour, and the separation efficiency and the separation flux are negligible due to the viscosity of oil. As shown in fig. 4b, the natural biomass material oil-water separation membrane in the example is recycled, and the oil-water separation efficiency and the separation flux are slightly reduced without any treatment, but the separation efficiency is still as high as 99.8%.

The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.