CN112982020A - Preparation method of high-strength and high-efficiency oil-water separation filter paper - Google Patents
Preparation method of high-strength and high-efficiency oil-water separation filter paper Download PDFInfo
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- CN112982020A CN112982020A CN202110301821.9A CN202110301821A CN112982020A CN 112982020 A CN112982020 A CN 112982020A CN 202110301821 A CN202110301821 A CN 202110301821A CN 112982020 A CN112982020 A CN 112982020A
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- filter paper
- water
- oil
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- cellulose
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000926 separation method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000001913 cellulose Substances 0.000 claims abstract description 26
- 229920002678 cellulose Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 16
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OIGFJWQIBLRMLZ-UHFFFAOYSA-K [OH-].S(=O)(=O)([O-])[O-].[Cu+3] Chemical compound [OH-].S(=O)(=O)([O-])[O-].[Cu+3] OIGFJWQIBLRMLZ-UHFFFAOYSA-K 0.000 abstract description 7
- 229920002873 Polyethylenimine Polymers 0.000 abstract description 3
- 239000000839 emulsion Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002569 water oil cream Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 Metal hydroxide salts Chemical class 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
Abstract
The invention relates to lamellar nickel-doped hydroxyl copper sulfate modified high-strength oil-water separation filter paper. Taking cellulose filter paper as a matrix, performing crosslinking reaction by using amino in polyethyleneimine and carboxyl on the surface of the cellulose filter paper, and constructing a crosslinking grid on the surface of the filter paper to enhance the dry/wet strength of the cellulose filter paper; and then growing nickel-doped hydroxyl copper sulfate nanosheets on the surface of the cellulose filter paper for surface modification, and finally obtaining the high-efficiency oil-water separation filter paper with super-hydrophilic/underwater super-oleophobic performance. The oil-water separation filter paper prepared by the invention has excellent mechanical strength and good recycling property, and can realize high-efficiency separation and recovery of various oil-water emulsions.
Description
Technical Field
The invention relates to an oil-water separation membrane material, in particular to high-efficiency oil-water separation cellulose filter paper with a rough structure of surface nickel-doped hydroxyl copper sulfate and a preparation method thereof, and belongs to the technical field of new materials.
Background
With the continuous development of green economy, the water resource pollution generated in the oil exploitation process becomes a limitation on sustainable development and becomes a primary problem to be solved urgently, and the development of a novel green new material for efficiently treating oily sewage is an effective means for solving the problem. A large number of materials with special wettability emerge in the process of continuous research and exploration in the field of oil-water separation, wherein the membrane material is widely researched due to the comprehensive advantages of high cost performance, high separation efficiency, low energy consumption, simple and convenient preparation and the like. Cellulose is a degradable environment-friendly material widely existing in the nature, wherein the filter paper has great application potential in the field of oil-water separation as a cellulose material with light weight, low cost, high porosity and wide application. Metal hydroxide salts have been widely used in various fields due to their high specific surface area, controllable microstructure, high chemical stability and high mechanical strength. By controlling the doping of different metal elements, the metal hydroxide material can be designed into a plurality of specific structures for improving the physical and chemical properties of the matrix. Based on the preparation method, the cellulose filter paper with the lamellar nanosheet structure on the surface is prepared, and on the premise of high mechanical strength, the wettability of the material is improved by increasing the surface roughness, so that the high-efficiency oil-water emulsion separation is realized.
Currently, there are two main ways to obtain membrane separation materials with ideal super-wettability: enhancing the surface energy of the membrane, and modifying by using a material with higher surface energy; and secondly, constructing a film material with a microstructure with high surface roughness. Jun et al prepared a hydrogel-coated cellulose paper by crosslinking glutaraldehyde as a crosslinking agent with hydrophilic polyvinyl alcohol through a simple aldol condensation reaction, and effectively separated an oil-water two-phase mixed solution. (Advanced Functional Materials,2015,25(33): 5368-5375.); kaiki et al successfully prepared hydrophilic cellulose/polyacrylonitrile composite fiber membranes using electrospinning and successfully separated water-in-oil mixtures (Separation and Purification Technology,2019,210: 913-.
According to the invention, nickel-doped hydroxyl copper sulfate is selected as a filter paper surface modification material, and the nano-sheet composite filter paper with a rough surface structure is prepared by depositing nickel-doped hydroxyl copper sulfate nano-sheets on the surface of the modified cellulose filter paper. By utilizing the surface roughness and the super-hydrophilic/underwater super-oleophobic performance of the hydroxyl copper sulfate, the wetted membrane surface obtains a water locking layer, and the contact of oil to the membrane is isolated. Thus, low oil adhesion and oil stain resistance thereof are achieved. The preparation method is simple and easy to implement, and the filter paper has good separation performance and has great reference value and application prospect in the field of oil-water emulsion separation.
Disclosure of Invention
The invention aims to provide environment-friendly degradable high-efficiency super-hydrophilic/underwater super-oleophobic cellulose filter paper with high mechanical strength and a preparation method thereof, and solves the problems of low mechanical strength, low oil-water separation efficiency and the like of the existing intrinsic filter paper.
In order to achieve the purpose, the specification provides super-hydrophilic/underwater super-oleophobic filter paper with a lamellar nanosheet structure, which is characterized in that the surface of the cellulose filter paper is modified with a lamellar nickel-doped copper hydroxysulfate, and the size of the nanosheet is about ten microns;
the following briefly explains the implementation of the present invention. Firstly, forming a stable cross-linked network on cellulose filter paper in a polyethyleneimine solution, and then soaking the cellulose filter paper in a glutaraldehyde solution for cross-linking to obtain high-mechanical-strength modified cellulose filter paper; depositing nickel-doped hydroxyl copper sulfate nanosheets on the surface of the cross-linked filter paper after heating in a water bath, and finally obtaining the high-efficiency oil-water emulsion separation composite filter paper with high mechanical strength and super-hydrophilic-super-lipophilic performance.
The invention relates to a preparation method of oil-water separation filter paper, which is realized according to the following specific steps:
(1) preparing a polyethyleneimine-methanol mixed solution, wherein a solvent is water, and heating to 35 ℃;
(2) selecting experimental qualitative filter paper with a clean surface, and putting the filter paper into a polyethyleneimine-methanol solution heated to 35 ℃ in a water bath to obtain a stable cross-linked network;
(3) preparing a glutaraldehyde solution with a certain concentration, adding the cellulose filter paper crosslinked in the first step into the glutaraldehyde solution by using water as a solvent, and crosslinking for a certain time at room temperature;
(4) preparing a reaction solution from copper sulfate pentahydrate, nickel sulfate hexahydrate and urea, wherein a solvent is water, putting the cross-linked filter paper obtained in the step (3) into the prepared reaction solution, and carrying out water bath reaction for 3 hours at 85 ℃;
(5) and (5) taking out the filter paper obtained in the step (4), simply washing the filter paper with deionized water, and carrying out vacuum drying at 40 ℃ to finally obtain the high-strength super-hydrophilic/underwater super-oleophobic filter paper.
The modified cellulose filter paper can be applied to oil-water separation, has good separation effect on different oil-water emulsion mixtures, has mechanical strength far superior to that of common filter paper, and has great application prospect in the treatment of milky oily sewage.
Description of the drawings:
FIG. 1 is a scanning electron microscope photograph of a cellulose composite filter paper according to the present invention. Wherein, the left figure is an SEM image of the surface of the composite filter paper under low magnification, and the right figure is an SEM image of the microstructure of the surface of the composite filter paper under high magnification.
FIG. 2 shows the underwater oil contact angle of the oil-water separation filter paper.
FIG. 3 is a schematic diagram of the process of separating crude oil/water and n-hexane/water emulsion by oil-water separation filter paper.
FIG. 4 shows a schematic representation of the underwater oil repellency achieved with n-hexane (Sudan Red stain) after the composite filter paper is immersed in the oil-water mixture.
FIG. 5 shows a process diagram of the super oleophobicity of crude oil after composite filter paper is placed on the surface of the oil-water mixture.
FIG. 6 shows a macroscopic view of the normal filter paper and the modified filter paper after separation under the same pressure.
The specific implementation mode is as follows:
the invention is described in detail below with reference to the drawings and examples.
(1) Dissolving 1 g of polyethyleneimine in 50 ml of deionized water, stirring for 20 minutes, adding 100 ml of methanol, stirring for 20 minutes, and heating in a water bath to 35 ℃;
(2) taking experimental qualitative filter paper with a clean surface, and putting the experimental qualitative filter paper into the solution obtained in the step (1) to react for 1 hour at 35 ℃;
(3) adding 10 ml of 50 wt% glutaraldehyde into 240 ml of deionized water, magnetically stirring for 20 minutes to obtain 2 wt% glutaraldehyde solution, immersing the cellulose filter paper reacted in the step (2) into the glutaraldehyde solution, standing and soaking for 1 hour;
(4) adding 2.25 g of copper sulfate pentahydrate, 1.04 g of nickel nitrate hexahydrate and 3.67 g of urea into 150 ml of deionized water, fully stirring until the solution is clear and has no crystal precipitate, adding the fully crosslinked cellulose filter paper obtained in the step (3) into the mixed solution, and reacting for 3 hours under the condition of water bath at 85 ℃; (5) and after the reaction is finished, the filter paper taken out is simply washed by deionized water, and is dried in vacuum at 40 ℃ for 24 hours, so that the super-hydrophilic/underwater super-oleophobic filter paper with high mechanical strength is finally obtained.
Claims (2)
1. A preparation method of high-efficiency oil-water separation filter paper with a multi-stage structure comprises the following specific steps:
(1) preparing a polyethyleneimine-methanol mixed solution, wherein a solvent is water, and heating to 35 ℃;
(2) selecting experimental cellulose filter paper with a clean surface, and putting the experimental cellulose filter paper into a polyethyleneimine-methanol solution which is heated to 35 ℃ in a water bath for preliminary reaction to obtain the cellulose filter paper with cross-linked grids;
(3) preparing a glutaraldehyde solution with a certain concentration, taking water as a solvent, adding the cellulose filter paper obtained in the step (2) into the glutaraldehyde solution, and further crosslinking for a certain time at room temperature;
(4) preparing a reaction solution from copper sulfate pentahydrate, nickel sulfate hexahydrate and urea, wherein a solvent is water, putting the cross-linked filter paper obtained in the step (3) into the prepared reaction solution, and carrying out water bath reaction for 3 hours at 85 ℃;
(5) and (5) taking out the filter paper obtained in the step (4), simply washing the filter paper with deionized water, and carrying out vacuum drying at 40 ℃ to finally obtain the high-strength super-hydrophilic/underwater super-oleophobic filter paper.
2. The super-hydrophilic/underwater super-oleophobic filter paper with the rough surface structure prepared based on the method of claim 1 is characterized in that a layer deposited on the surface of the cellulose filter paper is flaky nickel-doped copper hydroxysulfate, wherein the size of the nanosheet is about ten microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110301821.9A CN112982020B (en) | 2021-03-22 | 2021-03-22 | Preparation method of high-strength and high-efficiency oil-water separation filter paper |
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| CN202110301821.9A CN112982020B (en) | 2021-03-22 | 2021-03-22 | Preparation method of high-strength and high-efficiency oil-water separation filter paper |
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| CN112982020A true CN112982020A (en) | 2021-06-18 |
| CN112982020B CN112982020B (en) | 2022-04-15 |
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| CN202110301821.9A Expired - Fee Related CN112982020B (en) | 2021-03-22 | 2021-03-22 | Preparation method of high-strength and high-efficiency oil-water separation filter paper |
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| CN110975651A (en) * | 2019-12-25 | 2020-04-10 | 中国石油大学(华东) | Multifunctional efficient sewage treatment membrane and preparation method thereof |
| CN111420693A (en) * | 2020-03-30 | 2020-07-17 | 湘潭大学 | Preparation method of N-doped Cu modified nickel-based activated carbon catalyst and application of N-doped Cu modified nickel-based activated carbon catalyst in nitrocyclohexane hydrogenation reaction |
-
2021
- 2021-03-22 CN CN202110301821.9A patent/CN112982020B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2487030A1 (en) * | 2002-06-11 | 2003-12-18 | Basf Aktiengesellschaft | (meth)acrylic esters of polyalkoxylated glycerine |
| CN106758520A (en) * | 2016-12-07 | 2017-05-31 | 昆明理工大学 | The preparation method of glutaraldehyde cross-linking polyethyleneimine paper substrate film |
| CN106807380A (en) * | 2017-01-13 | 2017-06-09 | 安徽师范大学 | A kind of copper-based ternary composite metal oxide hollow nano-material, preparation method and application |
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