CN114515448A - Preparation and application of collagen fiber-based super-amphiphilic porous separation material - Google Patents
Preparation and application of collagen fiber-based super-amphiphilic porous separation material Download PDFInfo
- Publication number
- CN114515448A CN114515448A CN202210201268.6A CN202210201268A CN114515448A CN 114515448 A CN114515448 A CN 114515448A CN 202210201268 A CN202210201268 A CN 202210201268A CN 114515448 A CN114515448 A CN 114515448A
- Authority
- CN
- China
- Prior art keywords
- water
- separation
- super
- collagen fiber
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Colloid Chemistry (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention belongs to the technical field of materials, and discloses preparation and application of a collagen fiber-based super-amphiphilic porous separation material. The invention takes collagen fiber as raw material, and prepares the super-amphiphilic porous separation material with super-porosity and super-infiltration characteristics (super-oleophylic/super-hydrophilic under oil, super-hydrophilic/super-oleophobic under water) by self-assembly of the collagen fiber. The super-amphiphilic porous separation material prepared by the invention can realize high-efficiency separation of two types of emulsions of water-in-oil and oil-in-water, and has the characteristics of large separation flux, stable separation flux, good anti-fouling performance and good reusability.
Description
Technical Field
The invention relates to the technical field of materials, in particular to preparation and application of a collagen fiber-based super-amphiphilic porous separation material.
Background
Petroleum and water are indispensable key resources in human life and production. However, in practical applications, oil and water often contaminate each other. The use performance of oil materials can be affected by a small amount of water or even a trace amount of water, and on the contrary, the water environment can be polluted by a small amount of oil in the water. From the viewpoint of environmental protection and sustainable development, the development of efficient oil-water separation materials is of great importance for alleviating the problem of fuel and water pollution (Zarghami S, Mohammadi T, Sadrzadeh M, et al. Superhydraulic and underserver super waterborne membranes-a review of synthesis methods [ J ]. Progress in Polymer Science, 2019, 98: 101166. Ejet D, Wang C F, Kuo S W, et al. Preparation of super hydrophilic and super waterborne Chemical-based materials for extreme high water-in-oil emulsion [ J ]. Engineering Journal, 2020, 402: 126289.). In recent years, super-wetting separation Materials have been widely used in the field of Oil-water separation (Chu Z, Feng Y, Seeger S. Oil/water separation with selective super-wetting/super-wetting surface Materials [ J ]. Angewandte chemical International Edition, 2015, 54(8): 2328. Zheng W, Huang J, Li S, et al. Advanced Materials with specific wet-wetting interaction [ J ]. ACS Applied Materials & Interfaces 2020, 13(1): 67-87.). Generally, superhydrophilic materials are based primarily on selective entrapment of the oil dispersed phase leaving the water continuous phase free to pass for efficient separation of oil-in-water emulsions, while superhydrophobic materials are based on selective entrapment of the water dispersed phase leaving the oil continuous phase free to pass for separation of water-in-oil emulsions. However, the entrapped dispersed phase is easy to block in the pore channels of the materials to cause material pollution, and the surface infiltration performance required for realizing selective permeability of the materials can be changed, so that the super-infiltration material based on the selective entrapment separation strategy generally has the problems of gradually reducing the separation efficiency and the separation flux in the separation process, and even the entrapped dispersed phase is gathered and obstructed between the super-infiltration material and the separated emulsion, so that the subsequent emulsion is difficult to contact with the super-infiltration separation material and can not be continuously separated, and finally, the continuous treatment capacity of the emulsion wastewater is limited. Therefore, there is a need to develop a separation material having a stable flux to achieve a continuous stable separation of an emulsion.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to solve the problems in the background art, a first object of the present invention is to provide a method for preparing a collagen fiber-based super-amphiphilic porous separation material, which avoids the problem of damaging the amphipathy, has a simple synthesis line, and can synthesize a separation material having high porosity, super-oleophilic/oil-super-hydrophilic, super-hydrophilic/water-super-oleophobic properties.
The second purpose of the invention is to provide the application of the collagen fiber-based super-amphiphilic porous separation material in the emulsion separation, and the separation material can realize high-efficiency continuous separation of different kinds of emulsions.
In order to achieve the above purpose, the first technical scheme adopted by the invention is as follows:
a collagen fiber-based super-amphiphilic porous separation material is prepared by adding collagen fibers into a sodium carboxymethylcellulose solution, stirring for reaction, and freeze-drying.
Preferably, the mass ratio of the sodium carboxymethyl cellulose to the collagen fibers in the sodium carboxymethyl cellulose solution is 1:6-1: 20.
The invention also discloses a collagen fiber-based super-amphiphilic porous separation material obtained by the preparation method.
The second technical scheme adopted by the invention is as follows:
the application of collagen fiber-based super-amphiphilic porous separation material in emulsion separation.
Preferably, the method for separating the emulsion comprises the following steps:
loading the collagen fiber-based super-amphiphilic porous separation material into a column, separating a water-in-oil emulsion and an oil-in-water emulsion by adopting a column separation method, controlling the liquid inlet speed of the emulsion by using a constant flow pump, and collecting filtrate by using an automatic partial collector.
Compared with the prior art, the invention has the following beneficial effects:
1. the collagen fiber-based super-amphiphilic porous separation material prepared by the invention has ultrahigh porosity, and developed pore structures of the material can be respectively used as a water dispersion phase in a water-in-oil emulsion and an oil dispersion phase in an oil-in-water emulsion stored in a water storage pool and an oil storage pool, so that the blockage and pollution of materials for emulsion dispersion are effectively avoided, and the super-stable separation flux is ensured to be obtained in the continuous emulsion separation process.
2. The collagen fiber-based super-amphiphilic porous separation material prepared by the invention is a stacked layered porous structure formed by self-assembly of collagen fibers, and can rapidly pass through a water continuous phase of an oil-in-water emulsion and an oil continuous phase in a water-in-oil emulsion, so that high flux is obtained.
3. Different from the traditional super-wetting emulsion separation material, the super-amphiphilic porous separation material simultaneously has super-oleophilic/oil-down super-hydrophilic property and super-hydrophilic/underwater super-oleophobic property, and can realize high-efficiency double separation of water-in-oil emulsion and oil-in-water emulsion.
4. The preparation method provided by the invention is different from the traditional homogeneous solution foaming, but directly foams in a heterogeneous system by taking the collagen fiber as a solid raw material, and provides a convenient process route for preparing the collagen fiber-based separation material.
Drawings
FIG. 1 is a plot of porosity and pore size distribution of a collagen fiber-based super amphiphilic porous separation material prepared in example 1;
FIG. 2 is a scanning electron microscope image of the collagen fiber-based super-amphiphilic porous separation material prepared in example 1 (the inset in the a-diagram is an object diagram of the collagen fiber-based super-amphiphilic porous separation material prepared in example 1);
FIG. 3 is a water contact angle diagram of a water drop in an air medium during the surface infiltration process of the collagen fiber-based super-amphiphilic porous separation material prepared in example 1;
FIG. 4 is a graph of oil contact angle of oil drop (dodecane) in an air medium during the surface infiltration process of the collagen fiber-based super-amphiphilic porous separation material prepared in example 1;
FIG. 5 is a water contact angle diagram of a process of wetting water drops in an oil medium (dodecane) on the surface of the collagen fiber-based super amphiphilic porous separation material prepared in example 1;
FIG. 6 is a graph of oil contact angle of oil drop (carbon tetrachloride) in an aqueous medium during the surface infiltration process of the collagen fiber-based super-amphiphilic porous separation material prepared in example 1;
FIG. 7 is a graph showing the particle size distribution of the water-in-oil emulsion NE1 before and after separation of the collagen fiber-based super amphiphilic porous separation material prepared in example 1;
FIG. 8 is a digital photograph of the water-in-oil emulsion NE1 before and after separation of the prepared collagen fiber-based super amphiphilic porous separation material in example 1;
FIG. 9 is a graph showing the particle size distribution of a collagen fiber-based super amphiphilic porous separation material prepared from oil-in-water emulsion NE13 in example 1;
FIG. 10 is a digital photograph of the oil-in-water emulsion NE13 in example 1 before and after separation by the prepared collagen fiber-based super amphiphilic porous separation material;
FIG. 11 is a graph showing the relationship between separation efficiency and separation flux and time in 3 anti-fouling performance tests of the collagen fiber-based super-amphiphilic porous separation material prepared from the water-in-oil emulsion NE1 in example 1;
FIG. 12 is a graph of the separation efficiency and the separation flux versus time of a collagen fiber-based super amphiphilic porous separation material prepared from the oil-in-water emulsion NE13 in example 1 during 10 anti-fouling performance experiments;
FIG. 13 is a graph showing the separation efficiency and water content in relation to the separation volume in the continuous separation process of the collagen fiber-based super amphiphilic porous separation material prepared from the water-in-oil emulsion NE1 in example 1;
FIG. 14 is a graph of the separation efficiency and oil content versus separation volume in a continuous separation process of a collagen fiber-based super amphiphilic porous separation material prepared from oil in water emulsion NE13 in example 1;
FIG. 15 is a digital photograph of the collagen fiber-based aerogel-1 prepared in comparative example 1 before and after being exposed to water;
FIG. 16 is a digital photograph of the collagen fiber-based aerogel-2 prepared in comparative example 2 before and after being exposed to water;
fig. 17 is a digital photograph of the sodium carboxymethylcellulose aerogel prepared in comparative example 3 before and after being exposed to water;
FIG. 18 is a digital photograph showing the separation column clogged when the waste collagen fibers prepared in comparative example 4 were separated into a water-in-oil emulsion NE 1;
fig. 19 is a digital photograph of the waste collagen fibers prepared in comparative example 4 when the separation column was clogged when separating oil-in-water emulsion NE 13.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Collagen fibers are an amphiphilic material with good affinity for both water and oil. In addition, collagen fibers are rich in polar groups (e.g., -OH, -NH)2and-COOH) to form a needed supermolecular structure through the action of multipoint hydrogen bonds, thereby further improving the hydrophilicity and lipophilicity of the collagen fiber and preparing the super-amphiphilic novel separation material. When the collagen fiber is used for constructing the supermolecular structure, the change of the wetting property of the surface of the collagen fiber needs to be avoided, otherwise, the amphipathy of the collagen fiber is destroyed, and the super amphipathy cannot be obtained. In addition, when self-assembly is performed by using collagen fibers, the formed supramolecular structure configuration of the collagen fibers needs to be effectively regulated and controlled, so that high porosity and excellent liquid transmission channels can be obtained.
The invention is based on a heterogeneous system foaming method, takes collagen fibers as raw materials, develops the super-amphiphilic porous separation material which has high porosity, super-oleophylic/oil-down super-hydrophilic and super-hydrophilic/underwater super-oleophobic properties, and effectively solves the problem that the continuous treatment flux of emulsion wastewater is gradually reduced due to easy pollution of the traditional super-wetting separation material in the separation process, thereby realizing efficient and continuous separation of different types of emulsions. The invention not only solves the problem of flux reduction caused by easy pollution of the existing emulsion separation material.
The first embodiment provided by the invention is as follows: a preparation method of collagen fiber-based super-amphiphilic porous separation material comprises the steps of adding collagen fibers into a sodium carboxymethylcellulose solution, stirring for reaction, and then carrying out freeze drying to prepare the collagen fiber-based super-amphiphilic porous separation material, wherein the mass ratio of the sodium carboxymethylcellulose to the collagen fibers in the sodium carboxymethylcellulose solution is 1:6-1: 20.
The method is different from the traditional homogeneous solution foaming, but directly utilizes the solid collagen fiber to foam in a heterogeneous system, effectively maintains the amphipathy of the collagen fiber after the foaming treatment, avoids the technical problem of destroying the amphipathy due to the foaming treatment, and provides a simple and convenient synthetic route for the preparation of the collagen fiber-based super-amphiphilic separation material.
The second embodiment provided by the invention is as follows: the application of collagen fiber-based super-amphiphilic porous separation material in emulsion separation.
The collagen fiber-based super-amphiphilic porous separation material has ultrahigh porosity, and developed pore structures of the material can be used as a water dispersion phase in a water-in-oil emulsion and an oil dispersion phase in an oil-in-water emulsion stored in a water storage pool and an oil storage pool respectively, so that the material can effectively avoid blockage and pollution of emulsion dispersion relative materials when the material is applied to emulsion separation, and the super-stable separation flux can be obtained in the continuous emulsion separation process.
In some preferred embodiments, the method of emulsion separation is: the collagen fiber-based super-amphiphilic porous separation material is packed in a column, a water-in-oil emulsion and an oil-in-water emulsion are separated by adopting a column separation method, the liquid inlet speed of the emulsion is controlled by using a constant flow pump, and filtrate is collected by an automatic part collector.
In order to better understand the technical scheme provided by the present invention, the following specific examples respectively illustrate the preparation method, application and performance test of the collagen fiber-based super-amphiphilic porous separation material provided by the above embodiments of the present invention.
Example 1
(1) Preparing a collagen fiber-based super-amphiphilic porous separation material: 0.5 g of sodium carboxymethylcellulose was added to 150 mL of deionized water, and 5.0 g of waste collagen fibers was added. The system is stirred for 3.0 h at the temperature of 40 ℃ and the rotating speed of 500 rpm, and then the collagen fiber-based super-amphiphilic porous separation material is prepared by freeze drying.
The porosity of the collagen fiber-based super-amphiphilic porous separation material prepared in the embodiment is 99.64% through testing (figure 1). As shown in figure 2, the prepared collagen fiber-based super-amphiphilic porous separation material has a stacked layered porous structure, and retains the multi-level full-fiber structure of the original collagen fibers. As shown in FIG. 3, the complete infiltration time of water drops on the surface of the collagen fiber-based super-amphiphilic porous separation material prepared in the embodiment is 0.02 s in the air medium, which indicates that the prepared separation material has super-hydrophilicity. As shown in fig. 4, in the air medium, the complete infiltration time of oil droplets on the surface of the collagen fiber-based super-amphiphilic porous separation material prepared in this example is 0.01 s, which indicates that the prepared separation material has super lipophilicity. In the oil phase (dodecane) medium, the contact angle of the water drop on the surface of the collagen fiber-based super-amphiphilic porous separation material prepared in the embodiment is gradually reduced, and the water drop is completely permeated after 0.12 s (fig. 5), which shows that the collagen fiber-based super-amphiphilic porous separation material has the super-hydrophilicity under oil. In an aqueous medium, oil droplets (carbon tetrachloride) are almost spherical on the surface of the collagen fiber-based super-amphiphilic porous separation material prepared in the embodiment, and the underwater oil contact angle is 164.3 degrees, as shown in fig. 6, which shows that the collagen fiber-based super-amphiphilic porous separation material has underwater super-oleophobic property.
(2) Preparation of nonionic surfactant-stabilized water-in-oil emulsion: adding 2.0 g of Span80 into 1000 mL of dodecane, dropwise adding 8.0 mL of deionized water into the solution at the rotating speed of 3000 rpm, and continuously stirring for 1.0 h to prepare water-in-dodecane emulsion with stable nonionic surfactant, wherein the emulsion is marked as NE 1; adding 2.0 g of Span80 into 1000 mL of kerosene, dropwise adding 8.0 mL of deionized water into the solution at the rotating speed of 3000 rpm, and continuously stirring for 1.0 h to prepare a kerosene-in-water emulsion with stable nonionic surfactant, which is recorded as NE 2; adding 2.0 g of Span80 into 1000 mL of n-octane, dropwise adding 8.0 mL of deionized water into the solution at the rotating speed of 3000 rpm, and continuously stirring for 1.0 h to prepare a non-ionic surfactant stable n-octane water-in-water emulsion, which is recorded as NE 3; 2.0 g of Span80 was added to 1000 mL of petroleum ether, 8.0 mL of deionized water was added dropwise to the solution at 3000 rpm, and stirring was continued for 1.0 h to produce a nonionic surfactant stabilized water-in-petroleum ether emulsion, denoted NE 4.
(3) Preparing an anionic/nonionic compound surfactant-stabilized water-in-oil emulsion: adding 1.5 g of Span80 into 1000 mL of dodecane, adding 0.1 g of SDBS into 10 mL of deionized water, stirring the solution of Span80 dodecane at the rotating speed of 2000 rpm, dropwise adding the aqueous solution of SDBS into the solution of Span80 dodecane while keeping the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to obtain a stable aqueous dodecane-in-water emulsion of SDBS/Span 80, wherein the stable aqueous dodecane-in-water emulsion is marked as NE 5; adding 1.5 g of Span80 into 1000 mL of kerosene, adding 0.1 g of SDBS into 10 mL of deionized water, stirring the Span80 kerosene solution at the rotating speed of 2000 rpm, dropwise adding an SDBS aqueous solution into the Span80 kerosene solution while keeping the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to obtain an SDBS/Span 80 stable kerosene water-in-water emulsion, which is recorded as NE 6; adding 1.5 g of Span80 into 1000 mL of n-octane, adding 0.1 g of SDBS into 10 mL of deionized water, stirring the Span80 n-octane solution at the rotating speed of 2000 rpm, dropwise adding an SDBS aqueous solution into the Span80 n-octane solution at the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to obtain an SDBS/Span 80 stable water-in-n-octane emulsion, wherein the N-octane water-in-octane emulsion is marked as NE 7; adding 1.5 g of Span80 into 1000 mL of petroleum ether, adding 0.1 g of SDBS into 10 mL of deionized water, stirring the Span80 petroleum ether solution at the rotating speed of 2000 rpm, dropwise adding the SDBS aqueous solution into the Span80 petroleum ether solution at the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to obtain the SDBS/Span 80 stable petroleum ether water-in-water emulsion, wherein the NE8 is recorded.
(4) Preparing a cationic/nonionic compound surfactant stable water-in-oil emulsion: adding 1.5 g of Span 80 into 1000 mL of dodecane, adding 0.1 g of CTAB into 10 mL of deionized water, stirring the Span 80 dodecane solution at 2000 rpm, dropwise adding a CTAB aqueous solution into the Span 80 dodecane solution while maintaining the rotation speed of 2000 rpm, increasing the rotation speed to 3000 rpm, and stirring for 1.0 h to obtain a CTAB/Span 80 stable dodecane water-in-dodecane emulsion, which is marked as NE 9; adding 1.5 g of Span 80 into 1000 mL of kerosene, adding 0.1 g of CTAB into 10 mL of deionized water, stirring the Span 80 kerosene solution at the rotating speed of 2000 rpm, dropwise adding a CTAB aqueous solution into the Span 80 kerosene solution at the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, stirring for 1.0 h to prepare a stable kerosene water-in-water emulsion of CTAB/Span 80, and marking as NE 10; adding 1.5 g of Span 80 into 1000 mL of n-octane, adding 0.1 g of CTAB into 10 mL of deionized water, stirring the Span 80 n-octane solution at the rotating speed of 2000 rpm, dropwise adding a CTAB aqueous solution into the Span 80 n-octane solution at the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, stirring for 1.0 h to prepare a CTAB/Span 80 stable water-in-n-octane emulsion, which is marked as NE 11; adding 1.5 g of Span 80 into 1000 mL of petroleum ether, adding 0.1 g of CTAB into 10 mL of deionized water, stirring the Span 80 petroleum ether solution at the rotating speed of 2000 rpm, dropwise adding a CTAB aqueous solution into the Span 80 petroleum ether solution at the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to obtain a CTAB/Span 80 stable petroleum ether-in-water nano emulsion, which is recorded as NE 12.
(5) Preparation of oil-in-water emulsion: placing 1000 mL of deionized water at a rotating speed of 2000 rpm, stirring, dropwise adding 8.0 mL of dodecane into the deionized water while maintaining the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 hour to obtain dodecane-in-water emulsion, wherein the dodecane-in-water emulsion is marked as NE 13; placing 1000 mL of deionized water at a rotating speed of 2000 rpm, stirring, dropwise adding 8.0 mL of kerosene into the deionized water while maintaining the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, stirring for 1.0 h, and obtaining a kerosene-in-water emulsion, which is marked as NE 14; placing 1000 mL of deionized water at a rotating speed of 2000 rpm, stirring, dropwise adding 8.0 mL of n-octane into the deionized water while maintaining the rotating speed of 2000 rpm, increasing the rotating speed to 3000 rpm, stirring for 1.0 hour to obtain an n-octane-in-water emulsion, which is marked as NE 15; placing 1000 mL of deionized water at 2000 rpm, stirring, dropwise adding 8.0 mL of petroleum ether into the deionized water while maintaining the rotation speed of 2000 rpm, increasing the rotation speed to 3000 rpm, and stirring for 1.0 hour to obtain a petroleum ether-in-water emulsion, wherein the petroleum ether-in-water emulsion is marked as NE 16.
(6) The prepared emulsion is separated by adopting the collagen fiber-based super-amphiphilic porous separation material prepared in the embodiment:
1.6 g of the collagen fiber-based super amphiphilic porous separating material prepared as described above was packed in a column, the height of the bed was kept at 10 cm, 12 kinds of water-in-oil emulsions (NE 1, NE2, NE3, NE4, NE6, NE7, NE8, NE9, NE10, NE11, NE 12) prepared in (2), (3), (4) and (5) were separated from 4 kinds of oil-in-water emulsions (NE 13, NE14, NE15, NE 16) by a column separation method, the feeding speed of the emulsions was controlled by a constant current pump, and the filtrate was collected and analyzed by measurement.
The experimental result shows that the collagen fiber-based super-amphiphilic porous separation material pair (2), (3) prepared by the embodiment,(4) The 12 water-in-oil emulsions (NE 1, NE2, NE3, NE4, NE6, NE7, NE8, NE9, NE10, NE11, NE 12) and the 4 oil-in-water emulsions (NE 13, NE14, NE15, NE 16) prepared in (5) showed excellent separation performance, and the 16 emulsions became clear and transparent after separation. Taking emulsions NE1 and NE13 as examples, the particle size diagrams and digital photographs before and after the separation of emulsion NE1 are shown in FIGS. 7 and 8, and the particle size diagrams and digital photographs before and after the separation of NE13 are shown in FIGS. 9 and 10. The separation efficiencies of the super-amphiphilic porous separation material prepared in the embodiment on water-in-oil emulsions (NE 1, NE2, NE3 and NE 4) which are stable to four nonionic surfactants are 99.9935%, 99.9924%, 99.9923% and 99.9940%, respectively, and the separation fluxes are 6160L m% respectively-2 h-1, 7220 L m-2h-1, 7510 L m-2 h-1And 6150L m-2 h-1. The water-in-oil emulsions stabilized against four anionic/nonionic surfactants (NE 5, NE6, NE7, NE 8) have separation efficiencies of 99.9930%, 99.9920%, 99.9922% and 99.9933%, respectively, and separation fluxes of 5150L m-2 h-1, 5240 L m-2 h-1, 5560 L m-2 h-1And 5530L m-2 h-1. The separation efficiency of the water-in-oil emulsion (NE 9, NE10, NE11, NE 12) stabilized against four cationic/nonionic surfactants was 99.9924%, 99.9921%, 99.9921% and 99.9934%, respectively, and the separation flux was 5240L m -2 h-1, 5230 L m-2 h-1, 5860 L m-2 h-1And 5240L m-2 h-1. The separation efficiencies for the four oil-in-water emulsions (NE 13, NE14, NE15, NE 16) were 99.9992%, 99.9991%, 99.9991% and 99.9991%, respectively, and the separation fluxes were 4810L m%, respectively-2h-1, 4940 L m-2 h-1, 4850 L m-2 h-1And 4900L m-2 h-1. Namely, the collagen fiber-based super-amphiphilic porous separation material prepared by the embodiment has high separation efficiency and high separation flux for the separation of water-in-oil emulsion and oil-in-water emulsion.
The separation efficiency and separation flux versus time curves of the collagen fiber-based super amphiphilic porous separation material prepared in the example during three-cycle separation (2) of the water-in-oil emulsion NE1 and ten-cycle separation (5) of the water-in-oil emulsion NE13 are shown in fig. 11 and 12, and the collagen fiber-based super amphiphilic porous separation material has excellent separation stability and antifouling property for separation of oil-in-water and water-in-oil emulsions. The separation efficiency and the relationship between water content and throughput of the collagen fiber-based super-amphiphilic porous separation material obtained in this example in the continuous treatment of water-in-oil emulsion NE1 in (2) are shown in FIG. 13, and the separation efficiency and the relationship between oil content and throughput of the water-in-oil emulsion NE13 in (5) are shown in FIG. 14, which indicates that the super-amphiphilic porous separation material can be used for large-scale treatment of both water-in-oil and oil-in-water emulsions.
Example 2
(1) Preparing a collagen fiber-based super-amphiphilic porous separation material: 0.5 g of sodium carboxymethylcellulose was added to 150 mL of deionized water, followed by 3.0 g of waste collagen fibers. The system is stirred for 3.0 hours at the rotating speed of 500 rpm at the temperature of 40 ℃, and then the collagen fiber-based super-amphiphilic porous separation material is prepared by freeze drying.
(2) The collagen fiber-based super amphiphilic porous separation material prepared in the embodiment is used for separating the NE1 and NE13 emulsions in the embodiment 1:
loading 1.5 g of the super-amphiphilic porous separation material prepared in the step (1) into a column, keeping the height of a bed layer at 10 cm, separating a water-in-oil emulsion (NE 1) from an oil-in-water emulsion (NE 13) by adopting a column separation method, controlling the liquid inlet speed of the emulsions by using a constant flow pump, and collecting filtrate for determination and analysis.
The experimental results show that the collagen fiber-based super-amphiphilic porous separation material prepared in the embodiment shows excellent separation performance on water-in-oil emulsion (NE 1) and oil-in-water emulsion (NE 13). When NE1 is separated, the separation flux can reach 6120L m-2 h-1The separation efficiency can reach 99.9912%. When NE13 is separated, the separation flux can reach 4800L m-2 h-1The separation efficiency can reach 99.9986%.
Example 3
(1) Preparing a collagen fiber-based super-amphiphilic porous separation material: 0.5 g of sodium carboxymethylcellulose was added to 150 mL of deionized water, followed by 7.0 g of waste collagen fibers. The system is stirred for 3.0 hours at the rotating speed of 500 rpm at the temperature of 40 ℃, and then the collagen fiber-based super-amphiphilic porous separation material is prepared by freeze drying.
(2) The collagen fiber-based super amphiphilic porous separation material prepared in the embodiment is used for separating the NE1 and NE13 emulsions in the embodiment 1:
loading 2.8 g of the collagen fiber-based super-amphiphilic porous separation material into a column, keeping the height of a bed layer at 10 cm, separating a water-in-oil emulsion (NE 1) and an oil-in-water emulsion (NE 13) by using a column separation method, controlling the liquid inlet speed of the emulsions by using a constant flow pump, and collecting the filtrate for determination and analysis.
The experimental results show that the collagen fiber-based super-amphiphilic porous separation material prepared in the embodiment shows excellent separation performance on water-in-oil emulsion (NE 1) and oil-in-water emulsion (NE 13) emulsions. When NE1 is separated, the separation flux is 1800L m-2h-1The separation efficiency was 99.9917%. When NE13 is separated, the separation flux is 930L m-2 h-1The separation efficiency was 99.9992%.
Example 4
(1) Preparing a collagen fiber-based super-amphiphilic porous separation material: 0.5 g of sodium carboxymethylcellulose was added to 150 mL of deionized water, and 10 g of waste collagen fibers were added. The system is stirred for 3.0 h at the temperature of 40 ℃ and the rotating speed of 500 rpm, and then the collagen fiber-based super-amphiphilic porous separation material is prepared by freeze drying.
(2) The collagen fiber-based super amphiphilic porous separation material prepared in the embodiment is used for separating the NE1 and NE13 emulsions in the embodiment 1:
loading 5.0 g of the collagen fiber-based super-amphiphilic porous separation material into a column, keeping the height of the bed layer at 10 cm, separating the water-in-oil emulsion (NE 1) and the oil-in-water emulsion (NE 13) by using a column separation method, controlling the liquid inlet speed of the emulsion by using a constant current pump, and collecting filtrate for determination and analysis.
The experimental results show that the super-amphiphilic porous separation prepared in the exampleThe material shows excellent separation properties for water-in-oil emulsion (NE 1) and oil-in-water emulsion (NE 13) emulsions. When NE1 is separated, the separation flux is 960L m-2 h-1The separation efficiency was 99.9940%. When NE13 is separated, the separation flux is 420L m-2 h-1The separation efficiency was 99.9993%.
Comparative example 1
Preparation of collagen fiber-based aerogel-1: and adding 5.0 g of waste collagen fibers into 150 mL of deionized water, stirring the system at 40 ℃ for 3.0 h at the rotating speed of 500 rpm, and freeze-drying to obtain the collagen fiber-based aerogel-1.
Experiments show that the collagen fiber-based aerogel-1 prepared using only collagen fibers collapsed upon contact with water and could not be used for emulsion separation (see fig. 15).
Comparative example 2
Preparation of collagen fiber-based aerogel-2: 0.5 g of sodium carboxymethylcellulose was added to 150 mL of deionized water, followed by 1.0 g of waste collagen fibers. The system is stirred for 3.0 h at the temperature of 40 ℃ and the rotating speed of 500 rpm, and then the collagen fiber based aerogel-2 is prepared by freeze drying.
Experiments show that the amount of the collagen fiber used in the comparative example is too low, so that the prepared collagen fiber-based aerogel-2 collapses after being exposed to water and cannot be used for emulsion separation (see fig. 16).
Comparative example 3
Preparing sodium carboxymethyl cellulose aerogel: 5.0 g of sodium carboxymethylcellulose is added into 150 mL of deionized water, and the system is stirred for 3.0 h at 40 ℃ and the rotating speed of 500 rpm and then is frozen and dried to prepare the collagen fiber based aerogel-2.
Experiments have shown that sodium carboxymethyl cellulose aerogel prepared using sodium carboxymethyl cellulose alone collapsed upon contact with water and could not be used for emulsion separation (see fig. 17).
Comparative example 4
The emulsions NE1 and NE13 of example 1 were separated directly from waste collagen fibers.
3.5 g of waste collagen fibers were packed in a column, the height of the bed was kept at 10 cm, the water-in-oil (NE 1) emulsion and the oil-in-water (NE 13) emulsion prepared in (1) and (2) were separated by column separation, the feed rate of the emulsion was controlled by a constant flow pump, and the filtrate was collected and analyzed.
The experimental results show that the separation efficiency of the waste collagen fiber of the comparative example on the water-in-oil emulsion (NE 1) is 99.9907%, and the separation flux is 1320L m-2 h-1. The separation efficiency for oil-in-water emulsion (NE 13) was 99.9991%, and the separation flux was 1360L m-2 h-1. However, in the waste collagen fiber separation emulsions NE1 and NE13 of this example, as the separation proceeds, the emulsions clog the column to interrupt the separation (see FIGS. 18 and 19).
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A preparation method of collagen fiber-based super-amphiphilic porous separation material is characterized in that collagen fiber is added into sodium carboxymethylcellulose solution, stirred for reaction and then freeze-dried to prepare the collagen fiber-based super-amphiphilic porous separation material.
2. The method for preparing a collagen fiber-based super amphiphilic porous separating material according to claim 1, wherein the mass ratio of the sodium carboxymethyl cellulose to the collagen fibers in the sodium carboxymethyl cellulose solution is 1:6-1: 20.
3. A collagen fiber-based super amphiphilic porous separation material obtained by the preparation method according to claim 1 or 2.
4. Use of a collagen fibre-based super amphiphilic porous separating material according to claim 3 in emulsion separation.
5. The use according to claim 4, wherein the emulsion separation is carried out by:
loading the collagen fiber-based super-amphiphilic porous separation material into a column, separating a water-in-oil emulsion and an oil-in-water emulsion by adopting a column separation method, controlling the liquid inlet speed of the emulsion by using a constant flow pump, and collecting filtrate by using an automatic partial collector.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210201268.6A CN114515448B (en) | 2022-03-03 | 2022-03-03 | Preparation and application of collagen fiber-based super-amphiphilic porous separation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210201268.6A CN114515448B (en) | 2022-03-03 | 2022-03-03 | Preparation and application of collagen fiber-based super-amphiphilic porous separation material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114515448A true CN114515448A (en) | 2022-05-20 |
| CN114515448B CN114515448B (en) | 2023-03-21 |
Family
ID=81599007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210201268.6A Active CN114515448B (en) | 2022-03-03 | 2022-03-03 | Preparation and application of collagen fiber-based super-amphiphilic porous separation material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114515448B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115671797A (en) * | 2022-12-12 | 2023-02-03 | 四川大学 | Efficient anti-fouling emulsion separation material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06142504A (en) * | 1992-11-06 | 1994-05-24 | Showa Shell Sekiyu Kk | Oil and water separating material |
| CN105412987A (en) * | 2015-12-14 | 2016-03-23 | 天津医科大学口腔医院 | Fibrous internal and external mineralized collagen scaffold and preparation method thereof |
| WO2018026328A1 (en) * | 2016-08-04 | 2018-02-08 | Nanyang Technological University | Multifunctional superhydrophilic and underwater superoleophobic activated glass derived from waste glass |
| CN108301068A (en) * | 2017-12-29 | 2018-07-20 | 浙江大学 | There is nuclear shell structure nano fiber and method by prepared by gel emulsion oil-in-water electrostatic spinning |
| JP2019070205A (en) * | 2017-10-06 | 2019-05-09 | 株式会社ベルポリエステルプロダクツ | Polyester-based porous film and oil-water separation device |
| CN109985529A (en) * | 2018-11-29 | 2019-07-09 | 福建工程学院 | A kind of preparation method and application method of amphipathic water-oil separating filter membrane |
| CN112095337A (en) * | 2020-09-17 | 2020-12-18 | 四川大学 | Preparation and application of emulsion separation functional fiber with underwater super-oleophobic property and underwater hydrophilic property |
| CN113026356A (en) * | 2021-03-24 | 2021-06-25 | 四川大学 | Preparation method and application of double-separation functional fiber |
| CN113522255A (en) * | 2021-07-14 | 2021-10-22 | 兰州大学 | Application and preparation method of water-condensation bead material |
-
2022
- 2022-03-03 CN CN202210201268.6A patent/CN114515448B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06142504A (en) * | 1992-11-06 | 1994-05-24 | Showa Shell Sekiyu Kk | Oil and water separating material |
| CN105412987A (en) * | 2015-12-14 | 2016-03-23 | 天津医科大学口腔医院 | Fibrous internal and external mineralized collagen scaffold and preparation method thereof |
| WO2018026328A1 (en) * | 2016-08-04 | 2018-02-08 | Nanyang Technological University | Multifunctional superhydrophilic and underwater superoleophobic activated glass derived from waste glass |
| JP2019070205A (en) * | 2017-10-06 | 2019-05-09 | 株式会社ベルポリエステルプロダクツ | Polyester-based porous film and oil-water separation device |
| CN108301068A (en) * | 2017-12-29 | 2018-07-20 | 浙江大学 | There is nuclear shell structure nano fiber and method by prepared by gel emulsion oil-in-water electrostatic spinning |
| CN109985529A (en) * | 2018-11-29 | 2019-07-09 | 福建工程学院 | A kind of preparation method and application method of amphipathic water-oil separating filter membrane |
| CN112095337A (en) * | 2020-09-17 | 2020-12-18 | 四川大学 | Preparation and application of emulsion separation functional fiber with underwater super-oleophobic property and underwater hydrophilic property |
| CN113026356A (en) * | 2021-03-24 | 2021-06-25 | 四川大学 | Preparation method and application of double-separation functional fiber |
| CN113522255A (en) * | 2021-07-14 | 2021-10-22 | 兰州大学 | Application and preparation method of water-condensation bead material |
Non-Patent Citations (2)
| Title |
|---|
| 伍冬平: "生物医用天然高分子纤维材料", 《国外丝绸》 * |
| 刘一山，石碧: "胶原纤维-植物纤维复合屏蔽材纸的制备及其微波屏蔽性能研究", 《中国造纸》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115671797A (en) * | 2022-12-12 | 2023-02-03 | 四川大学 | Efficient anti-fouling emulsion separation material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114515448B (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104801208B (en) | Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof | |
| CN107790102B (en) | Three-dimensional folded spherical MOFs @ rGO oil absorption material and preparation method thereof | |
| CN106163805B (en) | Inorganic microporous amberplex suitable for redox flow batteries | |
| CN114515448B (en) | Preparation and application of collagen fiber-based super-amphiphilic porous separation material | |
| CN102015958A (en) | Graphene compositons and drilling fluids derived therefrom | |
| CN109663549A (en) | A kind of preparation method of graphene microcapsules | |
| CN110551486A (en) | Preparation method of aerogel-containing phase-change film | |
| CN103170257A (en) | Compound forward osmosis membrane and preparation method thereof | |
| CN114618331B (en) | Covalent organic framework doped polyamide reverse osmosis membrane and preparation method thereof | |
| CN104437132A (en) | Composite separation membrane and separation membrane element using the same | |
| CN106185908A (en) | A kind of graphene aerogel microsphere and preparation method thereof | |
| CN110523301A (en) | A kind of membrane distillation membrane material and preparation method thereof | |
| Jihao et al. | Advanced materials for separation of oil/water emulsion | |
| CN108479396A (en) | Based on nano zinc oxide modified positive osmosis composite membrane and preparation method | |
| Liu et al. | Strategies for the construction of special wettability metal organic framework membranes: A review | |
| CN114904404A (en) | Mixed matrix forward osmosis membrane based on MOF-808(Zr) and preparation method thereof | |
| Ni et al. | Flux vs. permeability: How to effectively evaluate mass transfer performance of membranes in oil-water separation | |
| CN110270235A (en) | The composite nanometer filtering film that a kind of pair of monovalence, divalent salts efficiently separate | |
| CN106345316B (en) | A kind of miillpore filter of acid-resisting corrosion | |
| CN115463562B (en) | Preparation method for rapidly synthesizing metal-organic framework MOF (metal-organic framework) membrane material without defects | |
| CN113026356B (en) | Preparation method and application of double-separation functional fiber | |
| CN109173730A (en) | A kind of method that MOFs@f-GO hybridized film is prepared in situ in Freeze Drying Technique | |
| CN109364756A (en) | Based on MIL-53 (Fe)/γ-Al2O3Flat mixed-matrix forward osmosis membrane and preparation method | |
| CN113101816B (en) | Preparation method and application of self-antibacterial silver nanoparticle and cellulose nanocrystal composite filter membrane | |
| CN109370666A (en) | A kind of separation method for bio oil high-efficiency dehydration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |