CN112957927A - Porous ceramic oil-water separation membrane taking red mud waste residues as raw materials and preparation method thereof - Google Patents
Porous ceramic oil-water separation membrane taking red mud waste residues as raw materials and preparation method thereof Download PDFInfo
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- CN112957927A CN112957927A CN202110246120.XA CN202110246120A CN112957927A CN 112957927 A CN112957927 A CN 112957927A CN 202110246120 A CN202110246120 A CN 202110246120A CN 112957927 A CN112957927 A CN 112957927A
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- 238000000926 separation method Methods 0.000 title claims abstract description 103
- 239000012528 membrane Substances 0.000 title claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 239000002994 raw material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 52
- 241000758789 Juglans Species 0.000 claims abstract description 45
- 235000009496 Juglans regia Nutrition 0.000 claims abstract description 45
- 235000020234 walnut Nutrition 0.000 claims abstract description 45
- 239000010902 straw Substances 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000835 fiber Substances 0.000 claims abstract description 25
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 235000007164 Oryza sativa Nutrition 0.000 claims description 13
- 235000009566 rice Nutrition 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 241000209140 Triticum Species 0.000 claims description 5
- 235000021307 Triticum Nutrition 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 2
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 2
- 239000002245 particle Substances 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 8
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 239000011133 lead Substances 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 235000019476 oil-water mixture Nutrition 0.000 description 12
- 241000209094 Oryza Species 0.000 description 11
- 238000002386 leaching Methods 0.000 description 11
- 238000009616 inductively coupled plasma Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000004993 emission spectroscopy Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Abstract
A porous ceramic oil-water separation membrane using red mud waste residue as a raw material and a preparation method thereof are disclosed, wherein the separation membrane is prepared from walnut shell powder, straw fiber, zinc oxide powder, a forming agent solution and polluting red mud waste residue discharged during alumina extraction in the aluminum industry into porous ceramic, and meanwhile, the porous ceramic oil-water separation membrane is obtained by modification with fluorosilane. Based on the mass of the separation membrane, the mass percentage of the red mud waste residue is 55-65%, the mass percentage of the walnut shell powder is 15-20%, the mass percentage of the straw fiber is 5-10%, the mass percentage of the zinc oxide is 5-10%, the mass percentage of the forming agent solution is 10%, and the mass percentage of the fluorosilane is 1-3%. The porous ceramic is prepared from red mud waste residues, walnut shell powder, straw fibers, zinc oxide powder and a forming agent solution through the processes of crushing, proportioning, granulating, forming, calcining and the like, and meanwhile, the oil-water separation membrane with green and low cost is obtained by utilizing fluorosilane for modification. The separation membrane provided by the invention can realize resource utilization of red mud, walnut shells and straw fiber wastes, thoroughly solves heavy metal pollution in red mud waste residues, has a one-way water permeation function, has a heavy oil separation efficiency of over 99%, and has a wide market application prospect.
Description
Technical Field
The invention provides a porous ceramic oil-water separation membrane taking red mud waste residues as a raw material and a preparation method thereof, belonging to the field of waste product resource utilization and new environmental materials.
Background
China, as the first major alumina producing country in the world, discharges up to billions of tons of red mud every year. The open-air stacking of the red mud is taken as a main disposal mode of the current alumina production enterprises, the disposal cost of the red mud accounts for about 5 percent of the production value of alumina products, and the red mud is not effectively utilized. The red mud mainly contains chemical elements of calcium, silicon, aluminum, iron, sodium and titanium, a small amount of magnesium, potassium and sulfur, and trace heavy metal elements of manganese, zinc, copper, chromium and lead, and can form precipitates, suspended matters and soluble matters when leaking into underground water, surface water and other water bodies in the piling process, thereby causing heavy metal pollution, pH value rise of the water bodies and other adverse ecological influences. At present, the economic and environmental problems caused by the red mud with continuously increasing stacking quantity make the comprehensive utilization of the red mud become a difficult problem to be solved urgently in the development process of the aluminum industry. The patent CN201810204108.0 discloses that red mud is used as a mineral raw material and is applied to the fields of sand stratum grouting reinforcement and the like. Although the treatment mode can solve the problem of batch application of the red mud, the economic value is low, and the problem that the grouting material is polluted by heavy metal permeating when meeting water cannot be solved. Patent CN201310407079.5 discloses that red mud is used as raw material to prepare red mud-based polymer light separation membrane, and then photocatalytic decomposition of water is performed to prepare hydrogen. Although the complete utilization of the red mud raw material can be solved, the separation membrane needs to be separated again after each use, and the hydrogen production rate is low. Patent CN201510802366.5 discloses a red mud-based iron separation membrane prepared from red mud, and the separation membrane is applied to methane cracking to prepare hydrogen. Although the method can fully utilize the mineral composition with catalysis and catalysis assisting functions in the red mud, the red mud needs to be subjected to acid dissolution treatment during the preparation of the separation membrane, secondary pollution is caused, and the problem of large-scale application of the red mud cannot be solved. Therefore, the disposal of the red mud waste residue not only needs to improve the economic value of large-scale utilization, but also needs to consider the heavy metal pollution in the red mud waste residue and the secondary pollution problem in the preparation of the separation membrane.
Meanwhile, as a big agricultural country, China can generate more than 7 hundred million tons of straws every year, so that the straws become wastes which are not used much but need to be treated, and the crop straws belong to a valuable biomass energy resource in an agricultural ecological system. Therefore, the improvement of the comprehensive development and utilization of the straws of the crops such as rice, wheat and the like and the utilization rate thereof have important significance for promoting the income increase of farmers, environmental protection, resource saving and sustainable development of agricultural economy. In addition, the walnut shell powder is used as a water quality purification filtering material and is widely applied to industrial sewage treatment in oil fields, chemical industry, leather making and the like and urban water supply and drainage engineering at present. However, the walnut shell powder is used as a filter material for a limited number of times, and a large amount of solid waste can still be generated after the filtration performance of the walnut shell powder is reduced. Therefore, the method has important research significance for improving the resource utilization value of the walnut shell powder and thoroughly solving the solid waste pollution.
The increasingly tense natural resources of the earth and the increasingly hostile environment sound the police bell. The water environment system, which is an important component of the earth, is now being destroyed by frequent oil leakage and randomly discharged production and living sewage. In order to effectively treat the generated pollution and reasonably treat the oil-water waste liquid, a great deal of work is done by people, and people tend to adopt an oil-water separation membrane filtration mode to treat the environmental problems along with the continuous development of membrane technology. The special-wettability membrane material has the advantages of high separation efficiency and high membrane flux in the separation process in the field of oil-water separation. With the membrane technology, people apply the membrane material with special wettability to oil-water separation, and the efficiency of the oil-water separation is further improved. In addition, people have expanded the application range of the oil-water separation membrane with special wettability to the demulsification and separation of different kinds of oil-water emulsions. At present, most of oil-water separation membrane materials can only be used for unidirectional oil-blocking water filtration or water-blocking oil filtration, and part of membranes capable of realizing bidirectional separation are complex to operate and high in preparation cost, so that a novel simple high-efficiency barrier-free oil-water separation membrane preparation technology is particularly important.
In view of the technical problems of large amount of red mud waste residues, straws and walnut shell powder, lack of advanced safe disposal and high value-added resource utilization in China, the invention innovatively provides an oil-water separation membrane prepared from walnut shell powder, straw fibers, zinc oxide powder, forming agent solution, red mud waste residues and fluorosilane, fundamentally solves the disposal problem of large amount of red mud waste residues, straws and walnut shell powder, and realizes high value-added resource utilization. The main basis is as follows: most of the oxide surfaces in the red mud waste residues contain hydroxyl groups, the red mud waste residues have super-strong hydrophilicity, and the performance of the separation membrane is improved by adding a proper amount of zinc oxide powder and utilizing the synergistic effect of active components in the red mud waste residues and zinc oxide. After the red mud waste residue is prepared into the porous ceramic, heavy metal ions can be fixed in the ceramic separation membrane, the problem of heavy metal secondary pollution can not be caused in the using process, meanwhile, straw fibers and walnut shell powder are added to improve the pore structure in the porous ceramic, the porosity of the ceramic is improved, the separation efficiency is improved, and heavy oil can be prevented from passing through by modifying the surface of the porous ceramic through fluorosilane. The successful application of the invention can not only thoroughly solve the problem of safe disposal of the red mud waste residue, the straw and the walnut shell powder, but also solve the problem of separation of heavy oil and water as a separation membrane, thereby bringing great economic, environmental and social benefits.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a porous ceramic oil-water separation membrane taking red mud waste residues as raw materials.
According to the invention, the red mud waste residue, the walnut shell powder, the straw fiber, the zinc oxide powder, the forming agent solution and the fluorosilane are prepared into the oil-water separation membrane, and the walnut shell powder and the straw fiber are added to mainly improve the pore structure inside the porous ceramic and improve the porosity of the ceramic, so that the separation efficiency of the porous ceramic separation membrane is improved; on the other hand, most of the oxides in the red mud waste residue have hydrophilicity, and proper amount of zinc oxide powder is added, so that the performance of the separation membrane is improved by utilizing the synergistic effect of the active components in the red mud waste residue and the zinc oxide. The method is characterized in that red mud waste residues are used as main raw materials, walnut shell powder, straw fibers, zinc oxide powder and a forming agent solution are added, and meanwhile, fluorosilane is used for modification to obtain the porous ceramic oil-water separation membrane, so that the treatment and high-added-value resource utilization of the red mud waste residues, the straws and the walnut shell powder are thoroughly and effectively solved, and the problem of separation of heavy oil and water is solved.
According to one aspect of the invention, a porous ceramic oil-water separation membrane using red mud waste residues as raw materials is provided, wherein porous ceramic is prepared from walnut shell powder, straw fibers, zinc oxide powder, a forming agent solution and the red mud waste residues, and meanwhile, fluorosilane is used for modification to obtain the porous ceramic oil-water separation membrane; based on the mass of the separation membrane, the mass percentage of the red mud waste residue is 55-65%, the mass percentage of the walnut shell powder is 15-20%, the mass percentage of the straw fiber is 5-10%, the mass percentage of the zinc oxide is 5-10%, the mass percentage of the forming agent solution is 10%, and the mass percentage of the fluorosilane is 1-3%.
Preferably, the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 7%; the red mud waste residue is polluted red mud discharged when aluminum oxide is extracted in the aluminum production industry, the granularity is 0.106-0.150mm, and the fluorosilane is one of heptadecafluorodecyltriethoxysilane or tridecafluorooctyltriethoxysilane.
Preferably, the granularity of the walnut shell powder is 0.250-0.425 mm; the granularity of the zinc oxide powder is 0.106-0.150 mm; the straw fiber is rice or wheat straw and has a length of less than 5 mm.
The red mud waste residue is suitable for the red mud waste residues produced by all manufacturers.
According to another aspect of the present invention, the present invention provides a method for preparing the above separation membrane, which comprises the following steps:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing straws of rice or wheat by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing raw material powder sieved in the step (1) in sequence, uniformly stirring, then weighing forming agent solution and a proper amount of deionized water, mixing, grinding and granulating, wherein the mass ratio of the forming agent solution to the deionized water is 1: 1;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and then placing the ceramic blank into a muffle furnace for calcining to obtain porous ceramic;
(4) surface modification
And (3) adding fluorosilane into an open glass container, soaking the single surface of the porous ceramic obtained in the step (3) in the glass container for 5-10 min at room temperature, and taking out to obtain the oil-water separation membrane with the one-way water permeation function.
Preferably: the red mud waste residue in the step (1) is polluted red mud discharged when aluminum oxide is extracted in the aluminum industry, and the granularity is 0.106-0.150 mm;
preferably: the forming agent solution in the step (2) is a polyvinyl alcohol solution with the mass fraction of 7%;
preferably: the calcining temperature in the step (3) is 900-1000 ℃, and the heat preservation time is 4-6 h.
Preferably: the area ratio of the volume of the fluorosilane to the single surface of the porous ceramic in the step (4) is (25-75 muL): l cm2。
The separation conditions and results of the present invention: and (3) loading 1 small sample of the separation membrane into a performance evaluation device, and introducing an oil-water mixture for evaluation of separation efficiency. The oil-water mixture is: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and pressure for 5min, and the separation efficiency reaches more than 99%.
The invention has the beneficial effects that:
the leaching rates of lead, zinc and chromium elements of the oil-water separation membrane prepared by the invention are far lower than the limit value requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the contents of each element in GB25466-2010 lead and zinc industrial pollutant discharge standard, and the secondary pollution and high value-added resource utilization of red mud waste residue are thoroughly and effectively solved. Meanwhile, the separation efficiency is improved by utilizing the synergistic effect of the active components in the red mud and the zinc oxide. One side of the oil-water separation membrane with the one-way water permeation function is in a super-hydrophobic state, namely the modification surface is a super-hydrophobic surface, and the other side of the oil-water separation membrane is in a super-hydrophilic state, so that the oil-water separation membrane has the one-way permeation performance of water, and based on the one-way permeation performance, the barrier-free separation of a mixture of heavy oil and water can be realized. The oil-water separation membrane has high separation efficiency, wide application range and wide market application prospect.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
(1) Raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing the rice straws by a crusher to obtain straw fibers with the length of less than 5 mm.
(2) Proportioning and granulating
Weighing 55g of red mud waste residue powder, 15g of walnut shell powder, 10g of rice straw fiber and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating.
(3) Shaping and calcining
And extruding and molding the granulated pug to obtain 20 cylindrical ceramic blanks (the diameter is 20mm), placing the cylindrical ceramic blanks in a muffle furnace, and calcining for 4 hours at 900 ℃ in an air atmosphere to obtain the porous ceramic.
(4) Surface modification
And (3) adding 78.5 mu L of fluorosilane into an open glass container, soaking the single surface of the cylindrical porous ceramic obtained in the step (3) in the glass container for 5min at room temperature, and taking out the cylindrical porous ceramic to obtain the oil-water separation membrane with the one-way water permeation function.
(5) Testing of separation Membrane Performance
And (3) loading 1 small sample of the separation membrane into a performance evaluation device, and introducing an oil-water mixture for evaluation of separation efficiency. The oil-water mixture is: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and pressure for 4min, and the separation efficiency reaches 99.7%.
(6) Heavy metal element leaching test of separation membrane
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit value requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard.
Example 2:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing the rice straws by a crusher to obtain straw fibers with the length of less than 5 mm.
(2) Proportioning and granulating
Weighing 65g of red mud waste residue powder, 15g of walnut shell powder, 5g of rice straw fiber and 5g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating.
(3) Shaping and calcining
And extruding and molding the granulated pug to obtain 20 cylindrical ceramic blanks (the diameter is 20mm), placing the cylindrical ceramic blanks in a muffle furnace, and calcining for 6 hours at 1000 ℃ in an air atmosphere to obtain the porous ceramic.
(4) Surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, soaking the single surface of the cylindrical porous ceramic obtained in the step (3) in the glass container, soaking at room temperature for 10min, and taking out to obtain the oil-water separation membrane with the one-way water permeation function.
(5) Testing of separation Membrane Performance
And (3) loading 1 small sample of the separation membrane into a performance evaluation device, and introducing an oil-water mixture for evaluation of separation efficiency. The oil-water mixture is: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and pressure for 5min, and the separation efficiency reaches more than 99.9%.
(6) Heavy metal element leaching test of separation membrane
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit value requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard.
Example 3:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing the rice straws by a crusher to obtain straw fibers with the length of less than 5 mm.
(2) Proportioning and granulating
Weighing 55g of red mud waste residue powder, 20g of walnut shell powder, 5g of rice straw fiber and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating.
(3) Shaping and calcining
And extruding and molding the granulated pug to obtain 20 cylindrical ceramic blanks (the diameter is 20mm), placing the cylindrical ceramic blanks in a muffle furnace, and calcining for 6 hours at 900 ℃ in an air atmosphere to obtain the porous ceramic.
(4) Surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, soaking the single surface of the cylindrical porous ceramic obtained in the step (3) in the glass container, soaking at room temperature for 10min, and taking out to obtain the oil-water separation membrane with the one-way water permeation function.
(5) Testing of separation Membrane Performance
And (3) loading 1 small sample of the separation membrane into a performance evaluation device, and introducing an oil-water mixture for evaluation of separation efficiency. The oil-water mixture is: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and pressure for 5min, and the separation efficiency reaches more than 99.9%.
(6) Heavy metal element leaching test of separation membrane
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit value requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard.
Comparative example 1
(1) Raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and then homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use.
(2) Proportioning and granulating
Weighing 80g of red mud waste residue powder and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating.
(3) Shaping and calcining
And extruding and molding the granulated pug to obtain 20 cylindrical ceramic blanks (the diameter is 20mm), placing the cylindrical ceramic blanks in a muffle furnace, and calcining for 6 hours at 900 ℃ in an air atmosphere to obtain the porous ceramic.
(4) Surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, soaking the single surface of the cylindrical porous ceramic obtained in the step (3) in the glass container, soaking at room temperature for 10min, and taking out to obtain the oil-water separation membrane with the one-way water permeation function.
(5) Testing of separation Membrane Performance
And (3) loading 1 small sample of the separation membrane into a performance evaluation device, and introducing an oil-water mixture for evaluation of separation efficiency. The oil-water mixture is: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and pressure for 4 hours, and the separation efficiency reaches over 86 percent.
(6) Heavy metal element leaching test of separation membrane
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
(7) The contrast effect is as follows: compared with the examples 1-3, when the walnut shell powder and the straw powder are not added during the preparation of the separation membrane, the separation rate is greatly reduced, and the efficiency is also obviously reduced.
Comparative example 2
(1) Raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing rice straws by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing 55g of red mud waste residue powder, 15g of walnut shell powder, 10g of rice straw fiber and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain 20 cylindrical ceramic blanks (the diameter is 20mm), placing the cylindrical ceramic blanks in a muffle furnace, and calcining for 4 hours at 500 ℃ in air atmosphere to obtain porous ceramic;
(4) surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, soaking the single surface of the cylindrical porous ceramic obtained in the step (3) in the glass container, soaking at room temperature for 10min, and taking out to obtain the oil-water separation membrane with the one-way water permeation function.
(5) Testing of separation Membrane Performance
And (3) loading 1 small sample of the separation membrane into a performance evaluation device, and introducing an oil-water mixture for evaluation of separation efficiency. The oil-water mixture is: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and pressure for 5min, and the separation efficiency reaches more than 99.9%.
(6) Heavy metal element leaching test of separation membrane
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) exceed the limit value requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element in GB25466-2010 lead and zinc industrial pollutant emission standard.
(7) The contrast effect is as follows: compared with examples 1 to 3, the calcination temperature is lowered during the preparation of the separation membrane, and although the adsorption effect is not lowered, heavy metal elements cannot be fixed inside the separation membrane, and are easy to precipitate to cause secondary environmental pollution.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A porous ceramic oil-water separation membrane taking red mud waste residues as raw materials is characterized in that: the separation membrane is prepared into porous ceramic by using walnut shell powder, straw fiber, zinc oxide powder, forming agent solution and red mud waste residue, and meanwhile, the porous ceramic oil-water separation membrane is obtained by modifying with fluorosilane;
wherein: red mud: walnut shell powder: straw fiber: zinc oxide powder: forming agent solution: the mass ratio of the fluorosilane is 55-65: 15-20: 5-10: 5-10: 10: 1-3;
the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 7%; the red mud waste residue is polluted red mud discharged when aluminum oxide is extracted in the aluminum production industry, the particle size is 0.106-0.150mm, and the fluorosilane is one of heptadecafluorodecyltriethoxysilane or tridecafluorooctyltriethoxysilane.
2. The separation membrane of claim 1, wherein: the granularity of the walnut shell powder is 0.250-0.425 mm; the granularity of the zinc oxide powder is 0.106-0.150 mm; the straw fiber is rice or wheat straw and has a length of less than 5 mm.
3. The method for producing a separation membrane according to any of claims 1 to 2, which is produced by:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and then homogenizing the crushed materials by a standard sieve of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing by a standard sieve of 40-60 meshes for later use; crushing straws of rice or wheat by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing raw material powder sieved in the step (1) in sequence, uniformly stirring, then weighing forming agent solution and a proper amount of deionized water, mixing, grinding and granulating, wherein the mass ratio of the forming agent solution to the deionized water is 1: 1;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and then placing the ceramic blank into a muffle furnace for calcining to obtain porous ceramic;
(4) surface modification
And (3) adding fluorosilane into an open glass container, soaking the single surface of the porous ceramic obtained in the step (3) in the glass container for 5-10 min at room temperature, and taking out to obtain the oil-water separation membrane with the one-way water permeation function.
4. The production method according to claim 3, characterized in that: the granularity of the walnut shell powder in the step (1) is 0.250-0.425 mm; the granularity of the zinc oxide powder is 0.106-0.150 mm.
5. The production method according to claim 3, characterized in that: the red mud waste residue in the step (1) is polluted red mud discharged when aluminum oxide is extracted in the aluminum industry, and the granularity is 0.106-0.150 mm.
6. The production method according to claim 3, characterized in that: in the step (2), the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 7%.
7. The production method according to claim 3, characterized in that: and (4) calcining at 900-1000 ℃ for 4-6 h.
8. The production method according to claim 3, characterized in that: the area ratio of the volume of the fluorosilane to the single surface of the porous ceramic in the step (4) is (25-75 muL): l cm2。
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