CN112957927B - Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof - Google Patents
Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof Download PDFInfo
- Publication number
- CN112957927B CN112957927B CN202110246120.XA CN202110246120A CN112957927B CN 112957927 B CN112957927 B CN 112957927B CN 202110246120 A CN202110246120 A CN 202110246120A CN 112957927 B CN112957927 B CN 112957927B
- Authority
- CN
- China
- Prior art keywords
- red mud
- separation membrane
- oil
- porous ceramic
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002699 waste material Substances 0.000 title claims abstract description 55
- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 239000002994 raw material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 76
- 239000010902 straw Substances 0.000 claims abstract description 41
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 40
- 241000758789 Juglans Species 0.000 claims abstract description 33
- 235000009496 Juglans regia Nutrition 0.000 claims abstract description 33
- 235000020234 walnut Nutrition 0.000 claims abstract description 33
- 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 21
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000295 fuel oil Substances 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 14
- 235000007164 Oryza sativa Nutrition 0.000 claims description 13
- 235000009566 rice Nutrition 0.000 claims description 13
- 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
- 238000007493 shaping process Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 241000209140 Triticum Species 0.000 claims description 5
- 235000021307 Triticum Nutrition 0.000 claims description 5
- 230000003075 superhydrophobic effect Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 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
- 238000000465 moulding Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 7
- 239000011787 zinc oxide Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 235000019476 oil-water mixture Nutrition 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 241000209094 Oryza Species 0.000 description 11
- 238000000265 homogenisation Methods 0.000 description 11
- 238000002386 leaching Methods 0.000 description 11
- 238000007873 sieving Methods 0.000 description 11
- 238000009616 inductively coupled plasma 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
- 239000011133 lead Substances 0.000 description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000004993 emission spectroscopy Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002910 solid waste Substances 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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 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
- 239000003673 groundwater Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 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
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000013049 sediment 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
- 239000002689 soil Substances 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
- 239000002569 water oil cream Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A porous ceramic oil-water separation film using red mud waste residue as raw material and a preparation method thereof are provided, wherein the porous ceramic oil-water separation film is prepared from walnut shell powder, straw fiber, zinc oxide powder, forming agent solution and polluted red mud waste residue discharged during alumina extraction in aluminum production industry, and is modified by fluorosilane. Taking the mass of a separation membrane as a reference, the mass percentage of red mud waste residue is 55% -65%, the mass percentage of walnut shell powder is 15% -20%, the mass percentage of straw fiber is 5% -10%, the mass percentage of zinc oxide is 5% -10%, the mass percentage of forming agent solution is 10%, and the mass percentage of fluorosilane is 1% -3%. The red mud waste residue, walnut shell powder, straw fiber, zinc oxide powder and a forming agent solution are prepared into porous ceramics through the processes of crushing, proportioning, granulating, forming, calcining and the like, and the fluorosilane is used for modification to obtain the green low-cost oil-water separation membrane. The separation membrane provided by the invention not only can realize the recycling of three wastes of red mud, walnut shells and straw fibers, thoroughly solves the heavy metal pollution in red mud waste residues, but also has a unidirectional water permeation function, has the separation efficiency of heavy oil of more than 99%, and has a wide market application prospect.
Description
Technical Field
The invention provides a porous ceramic oil-water separation membrane using red mud waste residue as a raw material and a preparation method thereof, belonging to the field of resource utilization of waste products and new environmental materials.
Background
China is the first large alumina producer in the world, with annual emissions of red mud up to hundreds of millions of tons. The open-air stacking of the red mud is used as a main disposal mode of the current alumina production enterprises, the disposal cost of the open-air stacking of the red mud is about 5% of the alumina product yield, and meanwhile, the red mud is not effectively utilized. The main chemical elements of the red mud are calcium, silicon, aluminum, iron, sodium, titanium and a small amount of magnesium, potassium and sulfur, and also have trace amounts of heavy metal elements of manganese, zinc, copper, chromium and lead, and sediment, suspended matters and solubles can be formed when the heavy metal elements leak into water bodies such as groundwater and surface water in the stacking process, so that the heavy metal pollution is caused, and the pH value of the water bodies is increased. At present, the economic and environmental problems caused by the continuously increased stockpiling amount of the red mud make the comprehensive utilization of the red mud a problem to be solved in the development process of the aluminum industry. Patent CN201810204108.0 discloses that red mud is used as a mineral raw material, and is applied to the fields of grouting reinforcement of sandy soil stratum and the like. The disposal mode can solve the problem of batch application of the red mud, but has lower economic value, and can not solve the problem that the grouting material permeates out of heavy metal pollution when meeting water. Patent CN201310407079.5 discloses that red mud is used as a raw material to prepare a red mud-based polymer light separation membrane for preparing hydrogen by photocatalytic decomposition of water. Although the full 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. The patent CN201510802366.5 discloses that red mud is used as a raw material to prepare a red mud-based iron separation membrane, and the red mud-based iron separation membrane is applied to methane pyrolysis hydrogen production. Although the method can fully utilize the mineral composition with the catalysis and the catalysis assisting functions in the red mud, the method not only needs to carry out acid dissolution treatment on the red mud when preparing the separation membrane, but also causes secondary pollution, so that 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 problems of heavy metal pollution in the red mud waste residue and secondary pollution in the preparation of the separation membrane.
Meanwhile, as a large agricultural country, 7 hundred million tons of straw can be produced each year, and the straw becomes waste which is not very useful but must be treated, and the crop straw belongs to a very precious biomass energy resource in an agricultural ecological system. Therefore, the improvement of the comprehensive development and utilization of crop straws such as rice, wheat and the like and the utilization rate thereof has important significance for promoting the income increase of farmers, environmental protection, resource conservation and sustainable development of agricultural economy. In addition, walnut shell powder is used as a water quality purifying and filtering material, and is widely applied to industrial sewage treatment in oil fields, chemical industry, leather making and other industrial sewage treatment and urban water supply and drainage engineering at present. However, the walnut shell powder is used as a filtering material for a limited number of times, and a large amount of solid waste is still generated after the filtering performance of the walnut shell powder is reduced. Therefore, the improvement of the resource utilization value of walnut shell powder and the thorough solution of the pollution of solid wastes thereof become an important research-significance subject.
The increasingly intense nature of the earth's resources and the increasingly harsh environment give people a knock. The water environment system is taken as an important component of the earth, and is now being destroyed by frequent petroleum leakage and randomly discharged production and domestic sewage. In order to effectively treat pollution and reasonably dispose of oil-water waste liquid, a great deal of work is done, and with the continuous development of membrane technology, people tend to treat the environmental problems by adopting an oil-water separation membrane filtration mode. The membrane material with special wettability has the advantages of high separation efficiency and high membrane flux in the separation process in the field of oil-water separation. Along with the membrane technology, people apply the membrane material with special wettability to oil-water separation, and further improve the efficiency of oil-water separation. And, people have expanded the application scope of special wettability oil water separating membrane to the demulsification separation of different kinds of oil water emulsion. At present, most oil-water separation membrane materials can only cut oil and drain or cut water and drain in one direction, and the membranes which can realize bidirectional separation in part are complex in operation and high in preparation cost, so that a novel simple and efficient barrier-free oil-water separation membrane preparation technology is particularly important.
In view of the problems of large amounts of red mud waste residues, straws and walnut shell powder in China and the lack of advanced safe disposal and high added value recycling, the invention creatively provides an oil-water separation membrane prepared from the walnut shell powder, straw fibers, zinc oxide powder, a forming agent solution, the red mud waste residues and fluorosilane, thereby fundamentally solving the disposal problem of large amounts of red mud waste residues, straws and the walnut shell powder and realizing the high added value recycling. The main basis is: the surface of most oxides in the red mud waste residue contains hydroxyl groups, has super-strong hydrophilicity, and is added with a proper amount of zinc oxide powder, so that the performance of the separation membrane is improved by utilizing the synergistic effect of active components in the red mud waste residue and zinc oxide. And after the red mud waste residue is prepared into porous ceramic, heavy metal ions can be fixed in the ceramic separation membrane, the problem of secondary pollution of heavy metal can not be caused in the use process, and simultaneously, straw fibers and walnut shell powder are added to improve the pore channel structure in the porous ceramic, so that the ceramic porosity is improved, the separation efficiency is improved, and the 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 thoroughly solve the problem of safe disposal of red mud waste residue, straw and walnut shell powder, and can also solve the problem of separation of heavy oil and water by being used 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 using red mud waste residue as a raw material.
According to the invention, red mud waste residue, walnut shell powder, straw fiber, zinc oxide powder, a forming agent solution and fluorosilane are prepared into the oil-water separation membrane, and the addition of the walnut shell powder and the straw fiber mainly improves the pore channel structure in the porous ceramic, and improves the ceramic porosity, so that the separation efficiency of the porous ceramic separation membrane is improved; on the other hand, most oxides in the red mud waste residue have hydrophilicity, and a proper amount of zinc oxide powder is added, so that the performance of the separation membrane is improved by utilizing the synergistic effect of active components in the red mud waste residue and zinc oxide. The porous ceramic oil-water separation membrane is prepared by taking red mud waste residue as a main raw material, adding walnut shell powder, straw fiber, zinc oxide powder and a forming agent solution, and modifying by utilizing fluorosilane.
According to one aspect of the invention, a porous ceramic oil-water separation membrane is provided, which takes red mud waste residue as a raw material, is prepared from walnut shell powder, straw fiber, zinc oxide powder, a forming agent solution and red mud waste residue, and is modified by fluorosilane to obtain the porous ceramic oil-water separation membrane; taking the mass of a separation membrane as a reference, the mass percentage of red mud waste residue is 55% -65%, the mass percentage of walnut shell powder is 15% -20%, the mass percentage of straw fiber is 5% -10%, the mass percentage of zinc oxide is 5% -10%, the mass percentage of forming agent solution is 10%, and the mass percentage of fluorosilane is 1% -3%.
Preferably, the forming agent solution is 7% polyvinyl alcohol solution by mass percent; the red mud waste residue is pollution red mud discharged during alumina extraction in aluminum production industry, the granularity is 0.106-0.150mm, and the fluorosilane is one of heptadecafluorodecyl triethoxysilane or tridecafluorooctyl triethoxysilane.
Preferably, the granularity of the walnut shell powder is 0.250-0.425mm; the granularity of the zinc oxide powder is 0.106-0.150mm; the straw fiber is rice or wheat straw, and the length is below 5 mm.
The red mud waste residue is applicable to 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 separation membrane, which specifically comprises the steps of:
(1) Crushing of raw materials
Respectively crushing the red mud waste residue and zinc oxide powder by a ball mill, and then sieving the crushed red mud waste residue and zinc oxide powder by a 100-140-target standard sieve (0.106-0.150 mm) for homogenization for standby; crushing walnut shell powder by a crusher, and sieving by a 40-60 target standard sieve (0.250-0.425 mm) for homogenization for standby; crushing rice or wheat straw by a crusher to obtain straw fiber with the length of less than 5mm;
(2) Proportioning and granulating
Sequentially weighing the raw material powder sieved in the step (1), uniformly stirring, then weighing the 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, a step of;
(3) Shaping and calcining
Extruding the granulated pug to form a ceramic blank, and then placing the ceramic blank in a muffle furnace for calcination to obtain porous ceramic;
(4) Surface modification
Adding fluorosilane into an open glass container, dipping one side of the porous ceramic obtained in the step (3) into the glass container, dipping for 5-10 min at room temperature, and taking out to obtain the oil-water separation membrane with the unidirectional water permeation function.
Preferably: the red mud waste residue in the step (1) is pollution red mud discharged during alumina extraction in the aluminum production industry, and the granularity is 0.106-0.150mm;
preferably: the forming agent solution in the step (2) is 7% polyvinyl alcohol solution by mass fraction;
preferably: the calcination 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 and the single surface of the porous ceramic in the step (4) is (25 mu L-75 mu L): l cm 2 。
The separation conditions and results of the present invention: and (3) loading 1 separation membrane sample into a performance evaluation device, and introducing an oil-water mixture to evaluate the separation efficiency. The oil-water mixture is as follows: 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 film 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 content of each element in GB25466-2010 emission standard of lead-zinc industrial pollutants, and the secondary pollution of red mud waste residues and the high added value recycling are thoroughly and effectively solved. Meanwhile, the synergistic effect of active components in the red mud and zinc oxide is utilized, so that the separation efficiency is improved. The oil-water separation membrane with the unidirectional water permeation function has the advantages that one side of the oil-water separation membrane is in a super-hydrophobic state, namely, the modified 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 unidirectional water permeation performance, and barrier-free separation of a mixture of heavy oil and water can be realized based on the unidirectional water permeation performance. The oil-water separation membrane has high separation efficiency and wide application range, and has wide market application prospect.
Detailed Description
The invention is further illustrated below with reference to examples, but the scope of the invention is not limited thereto:
example 1
(1) Crushing of raw materials
Respectively crushing the red mud waste residue and zinc oxide powder by a ball mill, and then sieving the crushed red mud waste residue and zinc oxide powder by a 100-140-target standard sieve (0.106-0.150 mm) for homogenization for standby; crushing walnut shell powder by a crusher, and sieving by a 40-60 target standard sieve (0.250-0.425 mm) for homogenization for standby; crushing rice straw by a crusher to obtain straw fiber with the length of less than 5 mm.
(2) Proportioning and granulating
55g of red mud waste residue powder, 15g of walnut shell powder, 10g of rice straw fiber and 10g of zinc oxide powder are weighed, 10g of polyvinyl alcohol solution and 10g of deionized water are weighed, mixed, ground and granulated.
(3) Shaping and calcining
Extruding the granulated pug to obtain 20 cylindrical ceramic blanks (with the diameter of 20 mm), and placing the cylindrical ceramic blanks in a muffle furnace for calcining for 4 hours at 900 ℃ in air atmosphere to obtain the porous ceramic.
(4) Surface modification
Adding 78.5 mu L of fluorosilane into an open glass container, dipping one side of the cylindrical porous ceramic obtained in the step (3) into the glass container, dipping for 5min at room temperature, and taking out to obtain the oil-water separation membrane with the unidirectional water permeation function.
(5) Separation membrane Performance test
And (3) loading 1 separation membrane sample into a performance evaluation device, and introducing an oil-water mixture to evaluate the separation efficiency. The oil-water mixture is as follows: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and normal pressure for 4min, and the separation efficiency reaches 99.7%.
(6) Separation membrane heavy metal element leaching test
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting an 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 emission standards of lead and zinc industrial pollutants.
Example 2:
(1) Crushing of raw materials
Respectively crushing the red mud waste residue and zinc oxide powder by a ball mill, and then sieving the crushed red mud waste residue and zinc oxide powder by a 100-140-target standard sieve (0.106-0.150 mm) for homogenization for standby; crushing walnut shell powder by a crusher, and sieving by a 40-60 target standard sieve (0.250-0.425 mm) for homogenization for standby; crushing rice straw by a crusher to obtain straw fiber with the length of less than 5 mm.
(2) Proportioning and granulating
65g of red mud waste residue powder, 15g of walnut shell powder, 5g of rice straw fiber and 5g of zinc oxide powder are weighed, 10g of polyvinyl alcohol solution and 10g of deionized water are weighed, mixed, ground and granulated.
(3) Shaping and calcining
Extruding the granulated pug to obtain 20 cylindrical ceramic blanks (with the diameter of 20 mm), and placing the cylindrical ceramic blanks in a muffle furnace for calcining for 6 hours at the temperature of 1000 ℃ in the air atmosphere to obtain the porous ceramic.
(4) Surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, dipping one side of the cylindrical porous ceramic obtained in the step (3) into the glass container, dipping for 10min at room temperature, and taking out to obtain the oil-water separation membrane with the unidirectional water permeation function.
(5) Separation membrane Performance test
And (3) loading 1 separation membrane sample into a performance evaluation device, and introducing an oil-water mixture to evaluate the separation efficiency. The oil-water mixture is as follows: 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) Separation membrane heavy metal element leaching test
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting an 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 emission standards of lead and zinc industrial pollutants.
Example 3:
(1) Crushing of raw materials
Respectively crushing the red mud waste residue and zinc oxide powder by a ball mill, and then sieving the crushed red mud waste residue and zinc oxide powder by a 100-140-target standard sieve (0.106-0.150 mm) for homogenization for standby; crushing walnut shell powder by a crusher, and sieving by a 40-60 target standard sieve (0.250-0.425 mm) for homogenization for standby; crushing rice straw by a crusher to obtain straw fiber with the length of less than 5 mm.
(2) Proportioning and granulating
55g of red mud waste residue powder, 20g of walnut shell powder, 5g of rice straw fiber and 10g of zinc oxide powder are weighed, 10g of polyvinyl alcohol solution and 10g of deionized water are weighed, mixed, ground and granulated.
(3) Shaping and calcining
Extruding the granulated pug to obtain 20 cylindrical ceramic blanks (with the diameter of 20 mm), and placing the cylindrical ceramic blanks in a muffle furnace for calcining for 6 hours at 900 ℃ in air atmosphere to obtain the porous ceramic.
(4) Surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, dipping one side of the cylindrical porous ceramic obtained in the step (3) into the glass container, dipping for 10min at room temperature, and taking out to obtain the oil-water separation membrane with the unidirectional water permeation function.
(5) Separation membrane Performance test
And (3) loading 1 separation membrane sample into a performance evaluation device, and introducing an oil-water mixture to evaluate the separation efficiency. The oil-water mixture is as follows: 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) Separation membrane heavy metal element leaching test
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting an 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 emission standards of lead and zinc industrial pollutants.
Comparative example 1
(1) Crushing of raw materials
Respectively crushing the red mud waste residue and zinc oxide powder by a ball mill, and then sieving the crushed red mud waste residue and zinc oxide powder by a 100-140-target standard sieve (0.106-0.150 mm) for homogenization for standby.
(2) Proportioning and granulating
80g of red mud waste residue powder and 10g of zinc oxide powder are weighed, 10g of polyvinyl alcohol solution and 10g of deionized water are weighed, mixed, ground and granulated.
(3) Shaping and calcining
Extruding the granulated pug to obtain 20 cylindrical ceramic blanks (with the diameter of 20 mm), and placing the cylindrical ceramic blanks in a muffle furnace for calcining for 6 hours at 900 ℃ in air atmosphere to obtain the porous ceramic.
(4) Surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, dipping one side of the cylindrical porous ceramic obtained in the step (3) into the glass container, dipping for 10min at room temperature, and taking out to obtain the oil-water separation membrane with the unidirectional water permeation function.
(5) Separation membrane Performance test
And (3) loading 1 separation membrane sample into a performance evaluation device, and introducing an oil-water mixture to evaluate the separation efficiency. The oil-water mixture is as follows: 10mL of dichloroethane and 40mL of water. The separation membrane can separate the two at normal temperature and normal pressure for 4 hours, and the separation efficiency reaches more than 86 percent.
(6) Separation membrane heavy metal element leaching test
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 emission standards of lead and zinc industrial pollutants
(7) Contrast effect: compared with examples 1-3, when the walnut shell powder and the straw powder are not added in the preparation of the separation membrane, the separation rate is greatly reduced, and the efficiency is also obviously reduced.
Comparative example 2
(1) Crushing of raw materials
Respectively crushing the red mud waste residue and zinc oxide powder by a ball mill, and then sieving the crushed red mud waste residue and zinc oxide powder by a 100-140-target standard sieve (0.106-0.150 mm) for homogenization for standby; crushing walnut shell powder by a crusher, and sieving by a 40-60 target standard sieve (0.250-0.425 mm) for homogenization for standby; crushing rice straw by a crusher to obtain straw fiber with the length of less than 5mm;
(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 the granulated pug to obtain 20 cylindrical ceramic blanks (with the diameter of 20 mm), and then placing the cylindrical ceramic blanks in a muffle furnace, and calcining for 4 hours at the temperature of 500 ℃ in the air atmosphere to obtain porous ceramic;
(4) Surface modification
Adding 235.6 mu L of fluorosilane into an open glass container, dipping one side of the cylindrical porous ceramic obtained in the step (3) into the glass container, dipping for 10min at room temperature, and taking out to obtain the oil-water separation membrane with the unidirectional water permeation function.
(5) Separation membrane Performance test
And (3) loading 1 separation membrane sample into a performance evaluation device, and introducing an oil-water mixture to evaluate the separation efficiency. The oil-water mixture is as follows: 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) Separation membrane heavy metal element leaching test
The leaching rates of lead, zinc and chromium elements of the sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are beyond the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 emission standards for lead and zinc industrial pollutants.
(7) Contrast effect: compared with examples 1-3, the calcination temperature is reduced during preparation of the separation membrane, and the adsorption effect is not reduced, but heavy metal elements cannot be fixed in the separation membrane, so that secondary environmental pollution is easily caused by precipitation.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A preparation method of a porous ceramic oil-water separation membrane using red mud waste residue as a raw material is characterized by comprising the following steps:
the preparation method comprises the following steps:
step (1): crushing of raw materials
Respectively crushing the red mud waste residue and zinc oxide powder by a ball mill, and homogenizing by a standard sieve with 100-140 meshes for standby; crushing walnut shell powder by a crusher, and homogenizing by a 40-60 mesh standard sieve for standby; crushing rice or wheat straw by a crusher to obtain straw fiber with the length of less than 5mm;
step (2): proportioning and granulating
Sequentially weighing the raw material powder sieved in the step (1), uniformly stirring, then weighing the 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, a step of;
step (3): shaping and calcining
Extruding the granulated pug to form a ceramic blank, and then placing the ceramic blank in a muffle furnace for calcination to obtain porous ceramic;
step (4): surface modification
Adding fluorosilane into an open glass container, dipping one side of the porous ceramic obtained in the step (3) into the glass container, dipping for 5-10 min at room temperature, and taking out to obtain an oil-water separation membrane with a unidirectional water permeation function;
the separation membrane is prepared from walnut shell powder, straw fiber, zinc oxide powder, a forming agent solution and red mud waste residue into porous ceramic, and the porous ceramic oil-water separation membrane is obtained by modifying with fluorosilane;
wherein: red mud: walnut shell powder: straw fiber: zinc oxide powder: molding agent solution: the mass ratio of the fluorosilanes 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 pollution red mud discharged during alumina extraction in aluminum production industry, the granularity is 0.106-0.150mm, and the fluorosilane is one of heptadecafluorodecyl triethoxysilane or tridecafluorooctyl triethoxysilane;
the porous ceramic oil-water separation membrane has the one-way water permeation function, wherein one side of the oil-water separation membrane is in a super-hydrophobic state, namely the modified surface is a super-hydrophobic surface, and one side of the oil-water separation membrane is in a super-hydrophilic state, so that the porous ceramic oil-water separation membrane has the one-way water permeation performance, and barrier-free separation of a mixture of heavy oil and water can be realized based on the one-way water permeation performance.
2. The method of manufacturing according to claim 1, characterized in that: the granularity of the walnut shell powder is 0.250-0.425mm, the granularity of the zinc oxide powder is 0.106-0.150mm, the straw fiber is rice or wheat straw, and the length is less than 5 mm.
3. The method of manufacturing according to claim 1, characterized in that: the forming agent solution in the step (2) is a polyvinyl alcohol solution with the mass fraction of 7%.
4. The method of manufacturing according to claim 1, characterized in that: and (3) calcining at 900-1000 ℃ for 4-6 hours.
5. The method of manufacturing according to claim 1, 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 mu L-75 mu L): 1 cm 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110246120.XA CN112957927B (en) | 2021-03-05 | 2021-03-05 | Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110246120.XA CN112957927B (en) | 2021-03-05 | 2021-03-05 | Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112957927A CN112957927A (en) | 2021-06-15 |
| CN112957927B true CN112957927B (en) | 2024-04-05 |
Family
ID=76276594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110246120.XA Active CN112957927B (en) | 2021-03-05 | 2021-03-05 | Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112957927B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113750823B (en) * | 2021-07-19 | 2022-11-25 | 青岛科技大学 | Natural biomass material oil-water separation membrane and preparation method and application thereof |
| CN114213103A (en) * | 2022-01-07 | 2022-03-22 | 烟台大学 | Granite-based gold mine tailing doped ceramic filtering membrane and preparation process and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014008432A (en) * | 2012-06-28 | 2014-01-20 | Ngk Spark Plug Co Ltd | Ceramic porous membrane, and ceramic filter and manufacturing method thereof |
| CN106955601A (en) * | 2017-04-07 | 2017-07-18 | 哈尔滨工业大学 | A kind of preparation method of the water-oil separationg film with unidirectional water penetration function |
| CN107352980A (en) * | 2017-07-11 | 2017-11-17 | 芜湖市宝艺游乐科技设备有限公司 | A kind of aluminum oxide ceramic membrane with super hydrophobic surface and preparation method thereof |
| CN109603849A (en) * | 2018-12-26 | 2019-04-12 | 南京工业大学 | Porous ceramic membrane catalyst taking waste rare earth-based denitration catalyst as raw material and preparation method and application thereof |
| JP2019081141A (en) * | 2017-10-30 | 2019-05-30 | 株式会社ノリタケカンパニーリミテド | Ceramic porous support body for separation membrane |
| CN111116224A (en) * | 2019-12-31 | 2020-05-08 | 南京环福新材料科技有限公司 | Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof |
| CN111659410A (en) * | 2020-06-24 | 2020-09-15 | 南京溙科新材料科技有限公司 | Porous ceramic membrane dedusting, denitration and dioxin removal catalyst taking blast furnace slag as raw material and preparation method thereof |
| CN111747774A (en) * | 2020-07-10 | 2020-10-09 | 武汉理工大学 | Red mud ceramic membrane support and preparation method and application thereof |
| CN111871361A (en) * | 2020-07-21 | 2020-11-03 | 湖南农业大学 | Environment repairing material and preparation method and application thereof |
| CN112316913A (en) * | 2020-06-17 | 2021-02-05 | 金奇杰 | Water treatment adsorbent using red mud waste residues as raw materials and preparation method thereof |
-
2021
- 2021-03-05 CN CN202110246120.XA patent/CN112957927B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014008432A (en) * | 2012-06-28 | 2014-01-20 | Ngk Spark Plug Co Ltd | Ceramic porous membrane, and ceramic filter and manufacturing method thereof |
| CN106955601A (en) * | 2017-04-07 | 2017-07-18 | 哈尔滨工业大学 | A kind of preparation method of the water-oil separationg film with unidirectional water penetration function |
| CN107352980A (en) * | 2017-07-11 | 2017-11-17 | 芜湖市宝艺游乐科技设备有限公司 | A kind of aluminum oxide ceramic membrane with super hydrophobic surface and preparation method thereof |
| JP2019081141A (en) * | 2017-10-30 | 2019-05-30 | 株式会社ノリタケカンパニーリミテド | Ceramic porous support body for separation membrane |
| CN109603849A (en) * | 2018-12-26 | 2019-04-12 | 南京工业大学 | Porous ceramic membrane catalyst taking waste rare earth-based denitration catalyst as raw material and preparation method and application thereof |
| CN111116224A (en) * | 2019-12-31 | 2020-05-08 | 南京环福新材料科技有限公司 | Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof |
| CN112316913A (en) * | 2020-06-17 | 2021-02-05 | 金奇杰 | Water treatment adsorbent using red mud waste residues as raw materials and preparation method thereof |
| CN111659410A (en) * | 2020-06-24 | 2020-09-15 | 南京溙科新材料科技有限公司 | Porous ceramic membrane dedusting, denitration and dioxin removal catalyst taking blast furnace slag as raw material and preparation method thereof |
| CN111747774A (en) * | 2020-07-10 | 2020-10-09 | 武汉理工大学 | Red mud ceramic membrane support and preparation method and application thereof |
| CN111871361A (en) * | 2020-07-21 | 2020-11-03 | 湖南农业大学 | Environment repairing material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112957927A (en) | 2021-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112316913A (en) | Water treatment adsorbent using red mud waste residues as raw materials and preparation method thereof | |
| CN102249730B (en) | Method for preparing ceramsite by using chemical sludge incineration ash | |
| CN103553492B (en) | It is a kind of that with polyaluminium waste slag of aluminum and red mud, to be major ingredient non-burning brick and preparation method thereof | |
| CN112957927B (en) | Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof | |
| CN103449796A (en) | Sludge autoclaved brick and preparation method thereof | |
| CN102070352A (en) | Method for recycling dewatered sludge, channel sediment and fly ash | |
| CN106810204B (en) | Fenton iron mud cathode and anode integrated ceramsite and method for preparing ceramsite by utilizing Fenton iron mud | |
| CN106904924A (en) | The system and method for 3D printing material is built using municipal waste and Industrial Solid Waste | |
| CN103553702A (en) | Resource utilization method of residual sludge from petrochemical organic wastewater biological treatment | |
| CN106866066B (en) | Baking-free brick manufactured by treating municipal sludge through special soil stabilizer resource | |
| CN101962590A (en) | Regenerative coal produced by multiple kinds of oily sludge in oil refinery and preparation method thereof | |
| CN114394800B (en) | Method for resource utilization of sludge biochar | |
| WO2017152817A1 (en) | Electroplating wastewater treatment process | |
| CN110922108B (en) | Method for solidifying municipal solid waste incineration fly ash based on rice hull ash-red mud composite cementing material | |
| CN104355674A (en) | Method for sintering porous ceramic material by city sludge | |
| CN111116224B (en) | Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof | |
| CN102659372A (en) | Light building material manufactured through waste incineration ash and manufacturing method | |
| CN113562999A (en) | Light ceramsite prepared from incineration fly ash of waste power plant and preparation method thereof | |
| CN116283142A (en) | Commercial mixing station carbon fixation ready-mixed concrete and preparation method thereof | |
| CN113461356B (en) | Method for preparing active admixture by sludge and muck | |
| CN107573005B (en) | Preparation method of ceramsite filter material | |
| CN108588882A (en) | A kind of industrial residue based composite fibre and preparation method thereof | |
| CN101670264A (en) | Desulfurized ash slag waste water dephosphorization materials prepared by baking-free method and preparation method | |
| CN108793964B (en) | Ancient building ceramic prepared from municipal sludge and preparation method thereof | |
| CN112456888A (en) | Electrolytic manganese slag recycling method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |