CN110747642A - Preparation and application of high-flux emulsion separation material - Google Patents

Preparation and application of high-flux emulsion separation material Download PDF

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CN110747642A
CN110747642A CN201911078015.9A CN201911078015A CN110747642A CN 110747642 A CN110747642 A CN 110747642A CN 201911078015 A CN201911078015 A CN 201911078015A CN 110747642 A CN110747642 A CN 110747642A
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emulsion
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黄鑫
肖涵中
石碧
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Sichuan University
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Abstract

The invention discloses a preparation and application of a high-flux emulsion separation material, which comprises the steps of firstly coordinating metal ions with specific concentration with collagen fibers under the action of high-speed stirring, then growing a metal organic framework compound screening layer on the surfaces of the collagen fibers by controlling the molar concentration ratio and the reaction time of the metal ions and organic ligands, and then carrying out surface hydrophobic treatment on the obtained collagen fibers modified by the metal organic framework compound by using a low-surface-energy substance, thereby preparing the high-flux emulsion separation material. The emulsion separation material can separate a plurality of microemulsions and nanoemulsions with stable surfactants in high flux due to the capillary action of the collagen fibers.

Description

Preparation and application of high-flux emulsion separation material
Technical Field
The invention relates to preparation and application of a high-flux emulsion separation material, and belongs to the technical field of materials.
Background
A large amount of emulsion wastewater is generated in the production process of the industries of petrifaction, light industry, steel and the likeBecomes a tremendous environmental pressure (Putattunda S, Bhattacharya S, Sen D, Bhattacharjee C. A review on the application of differential processing for engineered oil water [ J]. International Journal of Environmental Science and Technology, 2019, 16:2525-2536. Si Y F, Guo Z G. Superwetting materials of oil-water emulsionseparation[J]Chemistry Letters, 2015, 44: 874-. In recent years, porous sieving materials have been widely used in the field of emulsion separation (Yang C, Han N, Han C Y, Wang M L, Zhang W X, Wang W J, Zhang Z X, Li W, Zhang X. Design of a Janus F-TiO)2@PPS porous membrane withasymmetric wettability for switchable oil/water separation[J]. ACS AppliedMaterials&Interfaces, 2019, 11: 22408-22418. Gao X F, Xu L P, Xue Z X, FengL, Peng J T, Wen Y Q, Wang S T, Zhang X J. Dual-scaled porous nitrocellulosemembranes with underwater superoleophobicity for highly efficient oil/waterseparation[J]Advanced Materials, 2014, 26: 1771-. However, there is a "seesaw effect" between the separation flux and the separation efficiency of the conventional porous sieving material, which causes a bottleneck problem of low separation flux when the sieving material separates the microemulsion and nanoemulsion with small particle size and high stability stabilized by the surfactant. As is known from the Hagen-Poiseuille theory, the separation flux is inversely proportional to the thickness of the screening layer of the screening material (Baker R W. Membrane technology and applications [ M ]]. John Wiley&Sons, Ltd, 2004: 8. Cheng X Q,Wang Z X, Jiang X, Li T X, Lau C H, Guo Z H, Ma J, Shao L. Towardssustainable ultrafast molecular-separation membranes: from conventionalpolymers to emerging materials[J]Progress in Materials Science, 2018, 92: 258-. However, the currently developed emulsion separation materials with ultra-thin sieving layers have the bottleneck problems of non-uniform sieving pore size distribution and low porosity utilization efficiency, i.e. too large sieving pores cannot perform the emulsion separation function, and too small sieving pores inevitably cause too low separation flux.
Metal organic framework compounds (MOFs) are microporous crystalline materials formed by the coordinated growth of metal ions and organic ligands with a symmetric structure. MOF has a uniform and regular pore structure (Yang Q H, XuQ, Jiang H L, Metal-organic frames media: synthetic for enhanced catalysis [ J ]. Chemical Society Reviews, 2017, 46: 4774-. However, mass transfer in the pore channels of the MOF is mainly internal diffusion, and the kinetic defect of slow mass transfer rate exists, which is not favorable for obtaining high separation flux during emulsion separation. Therefore, the thickness of MOFs as sieving material must be controlled. Based on this, a feasible approach is to build an ultra-thin MOF sieving layer on the surface of the substrate, which can provide sieving, while the substrate provides the necessary mechanical strength.
However, growing ultra-thin MOF sieve layers on the substrate surface is extremely difficult, mainly because when the MOF sieve layers are grown on the substrate surface, MOFs tend to preferentially grow by self-coordination in solution rather than along the substrate surface. Furthermore, the MOF sieve layer on the substrate surface cannot achieve emulsion separation if it cannot form a continuous coating. However, it is very challenging to form a continuous dense MOF layer on the substrate surface. Therefore, the development of a novel substrate material for organic combination with a metal organic framework compound, which significantly improves the defects of the transport kinetics of the MOF sieving layer, is one of the effective ways to realize high-throughput emulsion separation.
Disclosure of Invention
The invention provides a preparation method and application of a high-flux emulsion separation material, aiming at the problem of the existing emulsion separation material in the separation flux aspect.
The invention provides a preparation method of a high-flux emulsion separation material, which comprises the following steps:
(1) stirring the metal ion solution and the collagen fiber at a high speed under the condition of a specific dosage and proportion for coordination, adjusting the pH of a system in the coordination process, and carrying out coordination reaction for 1.0 h to obtain the collagen fiber with the surface loaded with metal ions;
(2) adding the collagen fibers with the surface loaded with metal ions into an organic ligand solution with a specific concentration, stirring at a high speed for 5.0min at normal temperature, standing for reaction for 24 h, and drying at 45 ℃. Crushing and grinding the dried material by using a 0.5 mm screen to obtain a metal organic framework compound modified collagen fiber (CF @ MOF);
(3) and carrying out surface treatment on the CF @ MOF by using a low-surface-energy substance, and drying at 45 ℃ to obtain the high-flux emulsion separation material.
Further, the metal ion solution in the step (1) is any one of a zinc ion solution and a copper ion solution.
Further, the dosage ratio of the metal ions and the collagen fibers in the metal ion solution is controlled as follows: 0.30 to 0.60mmol (metal ion)/g (collagen fiber).
Further, the organic ligand in the step (2) is selected from 2-methylimidazole with the concentration of 11.98-59.93 mmol/L or trimesic acid with the concentration of 19.03-33.5 mmol/L.
Further, the low surface energy material in the step (3) is 5.0wt% Polydimethylsiloxane (PDMS) solution.
Further, the solvent of the Polydimethylsiloxane (PDMS) solution is dodecane.
Further, the method for carrying out surface treatment on the CF @ MOF by the low-surface-energy substance comprises the following steps: and (2) soaking the CF @ MOF in a 5.0wt% PDMS solution, taking out after 5.0min, and drying at 45 ℃ to obtain the CF @ MOF/PDMS.
The invention also provides an application of the high-flux material in emulsion separation, which specifically comprises the following steps:
wet packing high flux material CF @ MOF/PDMS into a column, separating water-in-oil nano emulsion and microemulsion which are stable in compounded surfactant 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 advantages:
1. the method provided by the invention is characterized in that metal ions are coordinated with active groups of the collagen fibers at specific concentrations; on the basis, metal ions loaded on the surface of the collagen fiber in a proper amount and organic ligands with specific concentration in the solution are used for carrying out coordination growth, and a reaction system needs to be kept still for a long time during growth so as to ensure that an MOF (metal organic framework) screening layer is formed on the surface of the collagen fiber.
2. The method provided by the invention has the advantages that the collagen fibers have obvious capillary effect, so that the demulsified oil phase can be rapidly transmitted along the fiber direction, the defect of MOF transmission dynamics is effectively overcome, and the emulsion separation flux is improved and can reach 1122-3261L m-2h-1。
3. According to the method provided by the invention, the MOF is loaded on the surface of the collagen fiber in an in-situ growth mode, so that a complex post-screening layer transfer step is avoided, an ultrathin MOF screening layer can be constructed on the surface of the collagen fiber, and the high-flux separation of the emulsion is realized based on the cooperation between the collagen fiber substrate and the ultrathin MOF screening layer.
Detailed Description
The present invention is specifically described below by way of examples, and the technical solution of the present invention is not limited to the specific embodiments listed below. It should be noted that the present embodiment is only for further illustration and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by the engineers in the field from the above disclosure are also considered to fall within the scope of the present invention.
Example 1:
(1) preparation of CF @ MOF (HKUST-1)/PDMS: dissolving 1.0 g of blue vitriol in 100mL of deionized water, adding 10 g of hide powder, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze to obtain the Cu-loaded carrier2+The collagen fibers of (4); will carry Cu2+Transferring the collagen fiber into 500 mL deionized water containing 2.0 g of trimesic acid, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering the reacted sample with 200-mesh gauze, and mixing deionized water and deionized waterRespectively washing with absolute ethyl alcohol, and drying at 45 ℃ to obtain CF @ MOF (HKUST-1); selecting a 0.5 mm screen to carry out crushing and grinding treatment on CF @ MOF (HKUST-1), then placing the obtained product into a 5.0wt% PDMS dodecane solution to be soaked for 5.0min, and drying the obtained product at 45 ℃ to obtain CF @ MOF (HKUST-1)/PDMS;
(2) preparing a water-in-oil emulsion stabilized by an ionic/nonionic compound surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), stirring the dodecane solution of Span80 at the rotating speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80 at the rotating speed of 1000rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion with stable Span 80/SDBS; dissolving Span80 (0.05 g) in dodecane (95 mL), dissolving SDBS (0.01 g) in deionized water (5.0 mL), placing a Span80 dodecane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the Span80 dodecane solution, increasing the rotation speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/SDBS stable microemulsion; dissolving Span80 (0.05 g) in n-octane (100 mL), dissolving CTAB (0.01 g) in deionized water (1.0 mL), stirring the Span80 n-octane solution at the rotation speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Span80 n-octane solution at the rotation speed of 1000rpm, increasing the rotation speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/CTAB stable n-octane water-in-water nanoemulsion; dissolving Span80 (0.05 g) in n-octane (95 mL), dissolving CTAB (0.01 g) in deionized water (5.0 mL), placing the Span80 n-octane solution at the rotating speed of 1000rpm, stirring, maintaining the rotating speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Span80 n-octane solution, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/CTAB stable water-in-n-octane microemulsion;
(3) the emulsion separation was carried out on the CF @ MOF (HKUST-1)/PDMS prepared in this example: wet packing 2.0 g of the prepared CF @ MOF (HKUST-1)/PDMS into a column, separating the water-in-oil emulsion stabilized by the compound surfactant in the step (2) by a column separation method, controlling the liquid inlet speed of the emulsion by using a constant flow pump, and using an automatic partThe subcollector collects the filtrate. The experimental result shows that the separation efficiency of the emulsion prepared in the CF @ MOF (HKUST-1)/PDMS pair (2) is higher than 99.99%, and the flux of the water-in-dodecane nano emulsion can reach 3261L m when the water-in-dodecane nano emulsion stabilized by Span80/SDBS is separated-2h-1While the highest flux for the separation of the same emulsion by pure HKUST-1 as a control sample was only 978L m-2h-1。
Example 2:
(1) preparation of CF @ MOF (HKUST-1)/PDMS: dissolving 1.25 g of blue vitriol in 100mL of deionized water, adding 10 g of hide powder, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze to obtain the Cu-loaded carrier2+The collagen fibers of (4); will carry Cu2+Transferring the collagen fiber into 500 mL of deionized water containing 3.0 g of trimesic acid, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering the reacted sample with 200-mesh gauze, washing with deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃ to obtain CF @ MOF (HKUST-1); selecting a 0.5 mm screen to carry out crushing and grinding treatment on CF @ MOF (HKUST-1), then placing the obtained product into a 5.0wt% PDMS dodecane solution to be soaked for 5.0min, and drying the obtained product at 45 ℃ to obtain CF @ MOF (HKUST-1)/PDMS;
(2) preparing a water-in-oil emulsion stabilized by an ionic/nonionic compound surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), stirring the dodecane solution of Span80 at the rotating speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80 at the rotating speed of 1000rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion with stable Span 80/SDBS; dissolving Span80 (0.05 g) in dodecane (95 mL), dissolving SDBS (0.01 g) in deionized water (5.0 mL), placing a Span80 dodecane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the Span80 dodecane solution, increasing the rotation speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/SDBS stable microemulsion; dissolving Span80 (0.05 g) in n-octane (100 mL), dissolving CTAB (0.01 g) in deionized water (1.0 mL), stirring the Span80 n-octane solution at the rotation speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Span80 n-octane solution at the rotation speed of 1000rpm, increasing the rotation speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/CTAB stable n-octane water-in-water nanoemulsion; dissolving Span80 (0.05 g) in n-octane (95 mL), dissolving CTAB (0.01 g) in deionized water (5.0 mL), placing the Span80 n-octane solution at the rotating speed of 1000rpm, stirring, maintaining the rotating speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Span80 n-octane solution, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/CTAB stable water-in-n-octane microemulsion;
(3) the emulsion separation was carried out on the CF @ MOF (HKUST-1)/PDMS prepared in this example: 2.0 g of the prepared CF @ MOF (HKUST-1)/PDMS is subjected to wet column packing, the water-in-oil emulsion stabilized by the compound surfactant in the step (2) is separated by adopting a column separation method, the liquid inlet speed of the emulsion is controlled by using a constant flow pump, and the filtrate is collected by using an automatic partial collector. The experimental result shows that the separation efficiency of the emulsion prepared in the CF @ MOF (HKUST-1)/PDMS pair (2) is higher than 99.99%, and the flux of the stable water-in-dodecane nano emulsion of Span80/SDBS can reach 2293L m-2h-1。
Example 3:
(1) preparation of CF @ MOF (HKUST-1)/PDMS: dissolving 1.5 g of blue vitriol in 100mL of deionized water, adding 10 g of hide powder, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze to obtain the Cu-loaded carrier2+The collagen fibers of (4); will carry Cu2+Transferring the collagen fiber into 500 mL of deionized water containing 3.52 g of trimesic acid, fully mixing, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering the reacted sample by using 200-mesh gauze, washing by using the deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃ to obtain CF @ MOF (HKUST-1); selecting a 0.5 mm screen to carry out crushing and grinding treatment on CF @ MOF (HKUST-1), then placing the obtained product into a 5.0wt% PDMS dodecane solution to be soaked for 5.0min, and drying the obtained product at 45 ℃ to obtain CF @ MOF (HKUST-1)/PDMS;
(2) preparing a water-in-oil emulsion stabilized by an ionic/nonionic compound surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), stirring the dodecane solution of Span80 at the rotating speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80 at the rotating speed of 1000rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion with stable Span 80/SDBS; dissolving Span80 (0.05 g) in dodecane (95 mL), dissolving SDBS (0.01 g) in deionized water (5.0 mL), placing a Span80 dodecane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the Span80 dodecane solution, increasing the rotation speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/SDBS stable microemulsion; dissolving Span80 (0.05 g) in n-octane (100 mL), dissolving CTAB (0.01 g) in deionized water (1.0 mL), stirring the Span80 n-octane solution at the rotation speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Span80 n-octane solution at the rotation speed of 1000rpm, increasing the rotation speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/CTAB stable n-octane water-in-water nanoemulsion; dissolving Span80 (0.05 g) in n-octane (95 mL), dissolving CTAB (0.01 g) in deionized water (5.0 mL), placing the Span80 n-octane solution at the rotating speed of 1000rpm, stirring, maintaining the rotating speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Span80 n-octane solution, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to prepare a Span80/CTAB stable water-in-n-octane microemulsion;
(3) the emulsion separation was carried out on the CF @ MOF (HKUST-1)/PDMS prepared in this example: 2.0 g of the prepared CF @ MOF (HKUST-1)/PDMS is subjected to wet column packing, the water-in-oil emulsion stabilized by the compound surfactant in the step (2) is separated by adopting a column separation method, the liquid inlet speed of the emulsion is controlled by using a constant flow pump, and the filtrate is collected by using an automatic partial collector. The experimental result shows that the separation efficiency of the emulsion prepared from the CF @ MOF (HKUST-1)/PDMS pair (2) is higher than 99.99%, and the flux of the stable water-in-dodecane nano emulsion of Span80/SDBS can reach 2043L m-2h-1。
Example 4:
(1) preparation of CF @ MOF (ZIF-8)/PDMS: 0.892 g of zinc nitrate hexahydrate is dissolved inDissolving in 100mL of deionized water, adding 10 g of hide powder, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze to obtain the Zn-loaded carrier2+The collagen fibers of (4); will be loaded with Zn2+Transferring the collagen fiber into 500 mL of deionized water containing 0.492 g of 2-methylimidazole, fully mixing, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering a reacted sample by using 200-mesh gauze, washing by using deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃ to obtain CF @ MOF (ZIF-8); selecting a 0.5 mm screen to crush and grind CF @ MOF (ZIF-8), then placing the crushed and ground CF @ MOF (ZIF-8) into 5.0wt% of PDMS dodecane solution to be soaked for 5.0min, and drying the soaked solution at 45 ℃ to obtain CF @ MOF (ZIF-8)/PDMS;
(2) preparation of a water-in-oil emulsion stabilized by a built surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), placing the dodecane solution of Span80 at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion stable by Span 80/SDBS; dissolving Tween80 (0.05 g) in n-heptane (100 mL), dissolving SDS (0.01 g) in deionized water (1.0 mL), placing the Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding the SDS aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/SDS-stabilized n-heptane water-in-water nano-emulsion; dissolving Tween80 (0.05 g) in n-heptane (90 mL), dissolving SDS (0.01 g) in deionized water (10 mL), placing a Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDS aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/SDS-stabilized n-heptane water-in-water microemulsion; dissolving Tween80 (0.05 g) in n-heptane (100 mL), dissolving CTAB (0.01 g) in deionized water (1.0 mL), placing the Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding the CTAB aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/CTAB stable n-heptane water-in-water nanoemulsion; dissolving Tween80 (0.05 g) in n-heptane (90 mL), dissolving CTAB (0.01 g) in deionized water (10 mL), placing the Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding the CTAB aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/CTAB stable n-heptane water-in-water microemulsion;
(3) the CF @ MOF (ZIF-8)/PDMS prepared in this example was subjected to emulsion separation: and (3) carrying out wet column packing on 2.0 g of the prepared CF @ MOF (ZIF-8)/PDMS, separating the water-in-oil emulsion stabilized by the compound surfactant in the step (2) 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. Experimental results show that the separation efficiency of the prepared emulsion in the CF @ MOF (ZIF-8)/PDMS pair (2) is higher than 99.98%, and the flux of the stable dodecane water-in-water nano emulsion of Span80/SDBS can reach 2038L m-2h-1While the highest flux for the separation of the same emulsion by pure ZIF-8 as a control was only 866L m-2h-1。
Example 5:
(1) preparation of CF @ MOF (ZIF-8)/PDMS: dissolving 1.284 g of zinc nitrate hexahydrate in 100mL of deionized water, adding 10 g of hide powder, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze to obtain the loaded Zn2+The collagen fibers of (4); will be loaded with Zn2+Transferring the collagen fiber into 500 mL of deionized water containing 1.058 g of 2-methylimidazole, fully mixing, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering a reacted sample by using 200-mesh gauze, washing by using deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃ to obtain CF @ MOF (ZIF-8); selecting a 0.5 mm screen to crush and grind CF @ MOF (ZIF-8), then placing the crushed and ground CF @ MOF (ZIF-8) into 5.0wt% of PDMS solution to be soaked for 5.0min, and drying the solution at 45 ℃ to obtain CF @ MOF (ZIF-8)/PDMS;
(2) preparation of a water-in-oil emulsion stabilized by a built surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), placing the dodecane solution of Span80 at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion stable by Span 80/SDBS; dissolving Span80 (0.05 g) in dodecane (90 mL), dissolving SDBS (0.01 g) in deionized water (10 mL), placing the Span80 dodecane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the Span80 dodecane solution, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare the Span80/SDBS stable water-in-dodecane microemulsion; dissolving Tween80 (0.05 g) in dodecane (100 mL), dissolving CTAB (0.01 g) in deionized water (1.0 mL), placing the Tween80 dodecane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Tween80 dodecane solution, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare a Tween 80/CTAB stable dodecane-in-water nanoemulsion; dissolving Tween80 (0.05 g) in dodecane (90 mL), dissolving CTAB (0.01 g) in deionized water (10 mL), placing the Tween80 dodecane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding a CTAB aqueous solution into the Tween80 dodecane solution, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare the Tween 80/CTAB stable dodecane water-in-water microemulsion;
(3) the CF @ MOF (ZIF-8)/PDMS prepared in this example was subjected to emulsion separation: and (3) carrying out wet column packing on 2.0 g of the prepared CF @ MOF (ZIF-8)/PDMS, separating the water-in-oil emulsion stabilized by the compound surfactant in the step (2) 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. Experimental results show that the separation efficiency of the prepared emulsion in the CF @ MOF (ZIF-8)/PDMS pair (2) is higher than 99.99%, and the flux can reach 1582L m% when the stable water-in-dodecane nano emulsion of Span80/SDBS is separated-2h-1。
Example 6:
(1) preparation of CF @ MOF (ZIF-8)/PDMS: dissolving 1.785 g zinc nitrate hexahydrate in 100mL deionized water, adding 10 g of hide powder, stirring at 2000 rpm for 1.0 h, and filtering with 200 mesh gauzeNamely to obtain Zn-loaded2+The collagen fibers of (4); will be loaded with Zn2+Transferring the collagen fiber into 500 mL of deionized water containing 2.46 g of 2-methylimidazole, fully mixing, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering a reacted sample by using 200-mesh gauze, washing by using deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃ to obtain CF @ MOF (ZIF-8); selecting a 0.5 mm screen to crush and grind CF @ MOF (ZIF-8), then placing the crushed and ground CF @ MOF (ZIF-8) into 5.0wt% of PDMS dodecane solution to be soaked for 5.0min, and drying the soaked solution at 45 ℃ to obtain CF @ MOF (ZIF-8)/PDMS;
(2) preparation of a water-in-oil emulsion stabilized by a built surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), placing the dodecane solution of Span80 at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion stable by Span 80/SDBS; dissolving Tween80 (0.05 g) in n-heptane (100 mL), dissolving SDS (0.01 g) in deionized water (1.0 mL), placing the Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding the SDS aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/SDS-stabilized n-heptane water-in-water nano-emulsion; dissolving Tween80 (0.05 g) in n-heptane (90 mL), dissolving SDS (0.01 g) in deionized water (10 mL), placing a Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDS aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/SDS-stabilized n-heptane water-in-water microemulsion; dissolving Tween80 (0.05 g) in n-heptane (100 mL), dissolving CTAB (0.01 g) in deionized water (1.0 mL), placing the Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding the CTAB aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/CTAB stable n-heptane water-in-water nanoemulsion; dissolving Tween80 (0.05 g) in n-heptane (90 mL), dissolving CTAB (0.01 g) in deionized water (10 mL), placing the Tween80 n-heptane solution at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding the CTAB aqueous solution into the Tween80 n-heptane solution, increasing the rotation speed to 2000 rpm, stirring for 1.0 h, and preparing the Tween 80/CTAB stable n-heptane water-in-water microemulsion;
(3) the CF @ MOF (ZIF-8)/PDMS prepared in this example was subjected to emulsion separation: and (3) carrying out wet column packing on 2.0 g of the prepared CF @ MOF (ZIF-8)/PDMS, separating the water-in-oil emulsion stabilized by the compound surfactant in the step (2) 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. Experimental results show that the separation efficiency of the prepared CF @ MOF (ZIF-8)/PDMS (polydimethylsiloxane) to the emulsion in the (2) is higher than 99.99%, and when the stable water-in-dodecane nano emulsion of Span80/SDBS is separated, the flux can reach 1122L m-2h-1。
Comparative example 1:
(1) preparation of CF/PDMS: adding 10 g of hide powder into 100mL of deionized water, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze; transferring the filtered sample into 500 mL of deionized water, fully mixing, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering the reacted sample with 200-mesh gauze, washing with deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃; selecting a 0.5 mm screen to crush and grind the CF, then placing the CF into 5.0wt% PDMS dodecane solution to be soaked for 5.0min, and drying the CF/PDMS at 45 ℃ to obtain CF/PDMS;
(2) preparation of a water-in-oil emulsion stabilized by a built surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), placing the dodecane solution of Span80 at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion stable by Span 80/SDBS;
(3) emulsion separation was performed on the CF/PDMS prepared in this comparative example: wet packing 2.0 g of the CF/PDMS prepared above into a column, separating the Span80/SDBS stable sodium dodecane water nanoemulsion prepared in (2) by a column separation method, controlling the emulsion feed rate by using a constant flow pump, and collecting the filtrate by using an automatic fraction collector. The experimental results show that: CF/PDMS failed to separate the Span80/SDBS stabilized aqueous sodium dodecane emulsion described above.
Comparative example 2:
(1) preparation of control CF @ MOF (HKUST-1)/PDMS: dissolving 0.25 g of blue vitriol in 100mL of deionized water, adding 10 g of hide powder, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze to obtain the Cu-loaded carrier2+The collagen fibers of (4); will carry Cu2+Transferring the collagen fiber into 500 mL of deionized water containing 1.05 g of trimesic acid, fully mixing, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering the reacted sample by using 200-mesh gauze, washing by using the deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃ to obtain CF @ MOF (HKUST-1); selecting a 0.5 mm screen to crush and grind the prepared CF @ MOF (HKUST-1), then putting the crushed and ground CF @ MOF (HKUST-1) into a 5.0wt% PDMS dodecane solution to be soaked for 5.0min, and drying the solution at 45 ℃ to obtain a control CF @ MOF (HKUST-1)/PDMS;
(2) preparation of a water-in-oil emulsion stabilized by a built surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), stirring the dodecane solution of Span80 at the rotating speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80 at the rotating speed of 1000rpm, increasing the rotating speed to 3000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion with stable Span 80/SDBS;
(3) emulsion separation was performed on the control CF @ MOF (HKUST-1)/PDMS prepared in this comparative example: 2.0 g of the control CF @ MOF (HKUST-1)/PDMS prepared above was subjected to wet column packing, the Span80/SDBS stabilized aqueous sodium dodecane emulsion prepared in (2) was separated by column separation, the feed rate of the emulsion was controlled by a constant flow pump, and the filtrate was collected by an automatic fraction collector. The experimental results show that: the control CF @ MOF (HKUST-1)/PDMS failed to isolate the Span80/SDBS stable aqueous sodium dodecane emulsion described above.
Comparative example 3:
(1) preparation of control CF @ MOF (ZIF-8)/PDMS: dissolving 0.357 g zinc nitrate hexahydrate in 100mL deionized water, adding 10 g peel powder, stirring at 2000 rpm for 1.0 h, and filtering with 200-mesh gauze to obtain the Zn-loaded carrier2+The collagen fibers of (4); will be loaded with Zn2+Transferring the collagen fiber into 500 mL of deionized water containing 0.197 g of 2-methylimidazole, fully mixing, stirring at 1000rpm for 5.0min, standing for reaction for 24 h, filtering the reacted sample by using 200-mesh gauze, washing by using deionized water and absolute ethyl alcohol respectively, and drying at 45 ℃ to obtain CF @ MOF (ZIF-8); selecting a 0.5 mm screen to crush and grind the prepared CF @ MOF (ZIF-8), then placing the crushed material into 5.0wt% of PDMS dodecane solution to be soaked for 5.0min, and drying the soaked material at 45 ℃ to obtain a control sample CF @ MOF (ZIF-8)/PDMS;
(2) preparation of a water-in-oil emulsion stabilized by a built surfactant: dissolving Span80 (0.05 g) in dodecane (100 mL), dissolving SDBS (0.01 g) in deionized water (1.0 mL), placing the dodecane solution of Span80 at the rotation speed of 1000rpm, stirring, keeping the rotation speed of 1000rpm, dropwise adding an SDBS aqueous solution into the dodecane solution of Span80, increasing the rotation speed to 2000 rpm, and stirring for 1.0 h to prepare a water-in-dodecane nano emulsion stable by Span 80/SDBS;
(3) emulsion separation was performed on the control CF @ MOF (ZIF-8)/PDMS prepared in this comparative example: 2.0 g of the control CF @ MOF (ZIF-8)/PDMS prepared above was wet-packed into a column, and the Span80/SDBS stabilized aqueous sodium dodecane emulsion prepared in (2) was separated by column separation, and the emulsion feed rate was controlled by a constant flow pump, and the filtrate was collected by an automatic fraction collector. The experimental results show that: the control CF @ MOF (ZIF-8)/PDMS failed to isolate the Span80/SDBS stable aqueous sodium dodecane emulsion described above.

Claims (9)

1. A preparation method of a high-flux emulsion separation material is characterized by comprising the following steps:
(1) stirring the metal ion solution and the collagen fiber at a high speed for coordination, not adjusting the pH value of a system in the coordination process, and carrying out coordination reaction for 1.0 h to obtain the collagen fiber with the surface loaded with metal ions;
(2) adding the collagen fiber with the surface loaded with metal ions into an organic ligand solution, stirring at a high speed for 5.0min at normal temperature, standing for 24 h for reaction, drying at 45 ℃, and crushing and grinding the dried material by using a 0.5 mm screen to obtain the metal organic framework compound modified collagen fiber (CF @ MOF);
(3) and carrying out surface treatment on the CF @ MOF by using a low-surface-energy substance, and drying at 45 ℃ to obtain the high-flux emulsion separation material.
2. The method according to claim 1, wherein the metal ion solution in step (1) is any one of a zinc ion solution and a copper ion solution.
3. The method according to claim 1, wherein the ratio of the metal ions to the collagen fibers in the metal ion solution is controlled to be: 0.30 to 0.60mmol (metal ion)/g (collagen fiber).
4. The method according to claim 1, wherein the organic ligand in step (2) is selected from 2-methylimidazole with a concentration of 11.98-59.93 mmol/L or trimesic acid with a concentration of 19.03-33.5 mmol/L.
5. The method according to claim 1, wherein the low surface energy material in the step (3) is 5.0wt% Polydimethylsiloxane (PDMS) solution.
6. The method according to claim 5, wherein the solvent of the Polydimethylsiloxane (PDMS) solution is dodecane.
7. The method of claim 1, wherein the low surface energy substance is a surface treatment of CF @ MOF by: and (2) soaking the CF @ MOF in a 5.0wt% PDMS solution, taking out after 5.0min, and drying at a low temperature of 45 ℃ to obtain the CF @ MOF/PDMS.
8. Use of a high throughput material prepared according to the method of any one of claims 1 to 7 in emulsion separation.
9. Use according to claim 8, characterized in that: the method for using the high-flux material for emulsion separation comprises the following steps: wet packing high flux material CF @ MOF/PDMS into a column, separating water-in-oil nano emulsion and microemulsion which are stable in compounded surfactant 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.
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