CN114988519A - Oil-water separation membrane and preparation method and application thereof - Google Patents
Oil-water separation membrane and preparation method and application thereof Download PDFInfo
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- CN114988519A CN114988519A CN202210726178.9A CN202210726178A CN114988519A CN 114988519 A CN114988519 A CN 114988519A CN 202210726178 A CN202210726178 A CN 202210726178A CN 114988519 A CN114988519 A CN 114988519A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 238000000926 separation method Methods 0.000 title claims abstract description 117
- 239000012528 membrane Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 87
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012964 benzotriazole Substances 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims abstract description 12
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 239000006260 foam Substances 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 239000003921 oil Substances 0.000 claims description 31
- 235000019198 oils Nutrition 0.000 claims description 26
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 20
- 229960001545 hydrotalcite Drugs 0.000 claims description 20
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 235000012424 soybean oil Nutrition 0.000 claims description 11
- 239000003549 soybean oil Substances 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 9
- 239000010705 motor oil Substances 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019476 oil-water mixture Nutrition 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 241000894007 species Species 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 63
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000000243 solution Substances 0.000 description 43
- 239000000463 material Substances 0.000 description 34
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 27
- KADGIRHYYYQNRZ-UHFFFAOYSA-N [Fe].[Cu].[Mg] Chemical compound [Fe].[Cu].[Mg] KADGIRHYYYQNRZ-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- -1 hydroxide radicals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 102100024580 L-lactate dehydrogenase B chain Human genes 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 108010087599 lactate dehydrogenase 1 Proteins 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019089 Mg-Fe Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an oil-water separation membrane and a preparation method and application thereof. The oil separation membrane can synchronously remove benzotriazole during oil-water separation, and the preparation method comprises the following steps: dissolving divalent metal salt and trivalent metal salt in deionized water according to a preset ratio to obtain a composite salt solution, wherein the divalent metal salt is copper salt and magnesium salt, and the trivalent metal salt is iron salt; adding sodium stearate into the composite salt solution, and performing ultrasonic dispersion to obtain a mixed solution; and step three, placing the mixed solution, the precipitator and the pretreated foamed nickel in an airtight kettle to perform hydrothermal reaction according to preset conditions, cooling to room temperature, cleaning, and performing vacuum drying to obtain the oil-water separation membrane. The oil-water separation membrane provided by the invention has the advantages of simple preparation process, low cost, mild reaction conditions, high efficiency, good removal performance and good recoverability when being applied to organic wastewater separation.
Description
Technical Field
The invention belongs to the technical field of separation membranes, and particularly relates to an oil-water separation membrane as well as a preparation method and application thereof.
Background
Oily wastewater pollution discharged in industrial production and daily activities is harming ecological environment and human health. In most cases, the oily wastewater contains various insoluble oils and soluble organic pollutants because of its very complicated composition. The organic pollutant is synchronously degraded in the oil-water separation process to become one of hot spots for treating the oily wastewater.
At present, the membrane technology draws great attention in the field of oily wastewater treatment due to the advantages of simple and convenient operation, high efficiency, low energy consumption and the like. Among them, the foam film material is favored because of its advantages of excellent mechanical properties, abundant pores, etc. But the method has the problem of low efficiency caused by the defects of large fiber spacing, few active sites and the like in the efficient treatment of organic pollutants in complex water environment.
Therefore, in order to solve the problem that insoluble oil stains and soluble organic pollutants in oily wastewater are difficult to treat, it is necessary to develop a novel oil-water separation membrane capable of catalytically degrading organic pollutants in water while separating oil stains in water.
Disclosure of Invention
The invention aims to provide an oil-water separation membrane capable of synchronously removing benzotriazole during oil-water separation so as to solve the problems in the background art, the oil-water separation membrane is simple in preparation process, low in cost and mild in reaction conditions, and has the advantages of good organic matter removal performance, good oil-water separation efficiency, high efficiency and good recoverability when being applied to organic wastewater separation.
In order to achieve the above object, the present invention provides a method for preparing an oil-water separation membrane capable of synchronously removing benzotriazole during oil-water separation, the method comprising the steps of:
dissolving divalent metal salt and trivalent metal salt in deionized water according to a preset ratio to obtain a composite salt solution, wherein the divalent metal salt is copper salt and magnesium salt, and the trivalent metal salt is iron salt;
step two, adding sodium stearate into the composite salt solution, and performing ultrasonic dispersion to obtain a mixed solution;
placing the mixed solution, the precipitator and the pretreated foamed nickel in an airtight kettle to perform hydrothermal reaction according to preset conditions, cooling to room temperature, cleaning and drying in vacuum to obtain the oil-water separation membrane; wherein the preset conditions are as follows: the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 18-24 h.
In a specific embodiment, in step three, the pretreatment method of the foamed nickel is as follows: soaking the foamed nickel in dilute nitric acid for 1.5-4 h, and washing with acetone, ethanol and water for multiple times.
In a specific embodiment, in step three, the vacuum drying conditions are as follows: the drying temperature is 60-70 ℃, and the drying time is 8-16 h.
In a specific embodiment, in step three, the precipitating agent is urea, and the ratio of the amount of the substance of urea to the sum of the amounts of the substances of metal ions in the complex salt solution is: (0.06-0.1) 1, wherein the ratio of the sum of the amounts of the metal ion species in the complex salt solution to the area of the nickel foam is: 1 mol: (0.1 to 2.5) m 2 。
In one embodiment, in step two, the ratio of the amount of sodium stearate species to the sum of the amount of metal ion species in the complex salt solution is: (0.001-0.01): 1.
in a specific embodiment, in the second step, the temperature of the ultrasonic dispersion is 60 to 80 ℃.
In a specific embodiment, in the first step, the molar ratio of the copper salt, the magnesium salt and the iron salt is: (2-4): (1-3): 1, the molarity of the iron salt is as follows: 0.5 to 1 mol/L.
The invention also provides an oil-water separation membrane, which comprises foamed nickel, hydrotalcite crystals growing on the foamed nickel and sodium stearate attached to the hydrotalcite crystals, and is prepared by the preparation method.
The invention also provides an application of the oil-water separation membrane prepared by the preparation method in separation of oil-water mixture containing benzotriazole.
In a specific embodiment, the oily substance in the oil-water mixture comprises at least one of engine oil, soybean oil and petroleum ether, and the volume ratio of oil to water is (1.5-9): 1.
the beneficial effects of the invention at least comprise:
according to the preparation method of the oil-water separation membrane, a large amount of free nickel ions are formed on the surface of the foamed nickel under the conditions of high temperature and high pressure, and further nucleation and crystallization are carried out on the nickel ions, metal ions in a mixed solution and hydroxide radicals provided by urea, so that compact hydrotalcite crystals are successfully generated on the nickel foam membrane material, and meanwhile, sodium stearate forms hydrogen bonds with hydrotalcite materials on the nickel foam membrane under the action of high temperature and high pressure in the preparation process, so that the sodium stearate is attached to the membrane material, the prepared oil-water separation membrane can synchronously degrade benzotriazole during water-oil separation, the treatment efficiency of oily organic wastewater is greatly improved, and the oil-water separation membrane has the advantages of good organic matter removal performance, good oil-water separation efficiency and good recoverability.
The oil-water separation membrane prepared by the method can be used for treating oily wastewater by a simple device without providing any external energy source, and meanwhile, the membrane material can be recycled, so that the treatment cost is greatly saved.
The preparation method of the oil-water separation membrane provided by the invention has the advantages of simple process, mild reaction conditions, low energy consumption and low cost, and is beneficial to industrial development.
Drawings
FIG. 1 is an SEM image of an oil-water separation membrane and foamed nickel provided by the invention;
FIG. 2 is a FT-IR chart of the Cu-Mg-Fe hydrotalcite prepared in example 1 and the oil-water separation membrane prepared in example 3;
FIG. 3 is a contact angle diagram of the nickel-based copper-magnesium-iron hydrotalcite prepared in example 2 and the oil-water separation membrane prepared in example 3;
FIG. 4 shows that the volume ratio of petroleum ether to water separated by the oil-water separation membrane provided by the invention is 9: 1 ultraviolet absorption visible spectrum of the oil-containing wastewater containing benzotriazole;
FIG. 5 is a diagram showing the effect of oil-water separation of benzotriazole-containing oily wastewater by the oil-water separation membrane provided by the present invention;
FIG. 6 is a cycle performance diagram showing the oil-water separation effect of the oil-water separation membrane for separating oil-containing wastewater containing benzotriazole according to the present invention;
FIG. 7 is a benzotriazole-removing cycle performance diagram of oil-water separation membrane provided by the invention for separating oily wastewater containing benzotriazole;
fig. 8 is an XRD pattern of the hydrotalcite-like compounds prepared in example 1, example 2 and comparative example 1.
Detailed Description
The invention is described in detail below with reference to the figures and examples, but can be implemented in many different ways, which are limited and covered by the claims.
The copper salt in the invention comprises at least one of copper nitrate, copper sulfate and copper chloride, the magnesium salt comprises at least one of magnesium nitrate, magnesium sulfate and magnesium chloride, and the iron salt comprises at least one of ferric nitrate, ferric sulfate and ferric chloride.
Example 1
Preparing copper-magnesium-iron hydrotalcite: 48.32g of copper salt (Cu (NO) were weighed out separately 3 ) 2 ·3H 2 O), 25.64g magnesium salt (Mg (NO) 3 ) 2 ·6H 2 O), 26.93g iron salt (Fe (NO) 3 ) 3 ·9H 2 O) is dissolved in 500mL of deionized water to obtain a copper-magnesium-iron salt composite solution, wherein Cu is 2+ ：Mg 2+ ：Fe 3+ The molar ratio is 6: 3: 2; 24 grams of sodium hydroxide was weighed and added to deionized water to a constant volume to obtain 500mL of sodium hydroxide solution (sodium hydroxide molar solubility of 1.2 mol/L). Slowly dropwise adding the prepared copper-magnesium-iron salt composite solution and sodium hydroxide solution by a peristaltic pump, mixing into a container filled with deionized water, violently stirring at 70 ℃ of water bath temperature, introducing nitrogen, and preventing CO in air 2 And (3) the pH value of the solution is maintained at 9.8-10.2, and the titration end point is that the copper-magnesium-iron salt composite solution and/or the sodium hydroxide solution are added dropwise. And aging the dropwise added solution for 18h under the condition of 70 ℃ water bath, performing suction filtration after aging, repeatedly washing the solution for a plurality of times by using alcohol and deionized water after suction filtration, drying the solution in an oven at 80 ℃ for 12h, and grinding the dried solid to obtain a sample of the copper-magnesium-iron hydrotalcite, which is recorded as CuMgFe LDH.
Example 2
Preparation of nickel-based copper-magnesium-iron hydrotalcite
1) 48.32g of copper salt (Cu (NO) were weighed out separately 3 ) 2 ·3H 2 O), 25.64g magnesium salt (Mg (NO) 3 ) 2 ·6H 2 O), 26.93g iron salt (Fe (NO) 3 ) 3 ·9H 2 O) is dissolved in 500mL of deionized water to obtain a copper-magnesium-iron salt composite solution, wherein Cu is 2+ ：Mg 2+ ：Fe 3+ The molar ratio is 6: 3: 2; 24 grams of sodium hydroxide was weighed and added to deionized water to a constant volume to obtain 500mL of sodium hydroxide solution (sodium hydroxide molar solubility of 1.2 mol/L). Slowly dropwise adding the prepared copper-magnesium-iron salt composite solution and sodium hydroxide solution by a peristaltic pump, mixing into a container filled with deionized water, violently stirring at 70 ℃ of water bath temperature, introducing nitrogen, and preventing CO in air 2 And (3) the pH value of the solution is maintained at 9.8-10.2, and the titration end point is that the copper-magnesium-iron salt composite solution and/or the sodium hydroxide solution are added dropwise. And aging the dropwise added solution for 18h under the condition of 70 ℃ water bath, performing suction filtration after aging, repeatedly washing the solution for a plurality of times by using alcohol and deionized water after suction filtration, drying the solution in an oven at 80 ℃ for 12h, and grinding the dried solid to obtain the sample copper-magnesium-iron hydrotalcite.
2) Weighing a proper amount of copper-magnesium-iron hydrotalcite, soaking the copper-magnesium-iron hydrotalcite in a nickel nitrate solution with the concentration of 1-3 mol/L for 24 hours, evaporating the copper-magnesium-iron hydrotalcite in a rotary evaporator to dryness, wherein the heating temperature in the evaporation process is 60-100 ℃, the pressure in the evaporation process is 0-0.1 MPa, and naturally cooling the copper-magnesium-iron hydrotalcite to room temperature after evaporation to dryness to obtain the nickel-based copper-magnesium-iron hydrotalcite, which is recorded as Ni/CuMgFe LDH.
Example 3
Preparing an oil-water separation membrane:
1) 48.32g of copper salt (Cu (NO) were weighed out separately 3 ) 2 ·3H 2 O), 25.64g magnesium salt (Mg (NO) 3 ) 2 ·6H 2 O), 26.93g iron salt (Fe (NO) 3 ) 3 ·9H 2 O) is dissolved in 100mL of deionized water to obtain a copper-magnesium-iron salt composite solution, wherein Cu is 2+ ：Mg 2+ ：Fe 3+ The molar ratio is 6: 3: 2; the molar concentration of copper is 2mol/L, the molar concentration of magnesium is 1mol/L, and the molar concentration of iron is 0.667 mol/L;
2) adding 8mmol of sodium Stearate (SA) into the dissolved composite solution, diluting to 120mL with deionized water, and performing ultrasonic treatment at 60 ℃ to uniformly disperse the solution to obtain a mixed solution;
3) soaking foamed nickel (Ni foam) in dilute nitric acid for 2h, and washing with acetone, ethanol and water for multiple times to obtain pretreated foamed nickel with the size of 30cm × 30 cm;
4) and (2) placing the mixed solution and the pretreated foamed nickel into an airtight polytetrafluoroethylene lining autoclave (200mL), adding 25mmol of urea, placing the reaction kettle into a blast drying oven, heating for 24 hours at 120 ℃, washing the foamed nickel for multiple times by deionized water and ethanol after cooling, and drying for 10 hours in vacuum at 60 ℃ to obtain an oil-water separation membrane which is marked as a CuMgFe LDH/Ni foam + SA membrane.
Referring to fig. 1 to 3, fig. 1 is an SEM image of the oil-water separation membrane and the nickel foam prepared in example 3, fig. 2 is an FT-IR diagram of the copper-magnesium-iron hydrotalcite prepared in example 1 and the oil-water separation membrane prepared in example 3, and fig. 3 is a contact angle diagram of the Ni/CuMgFe LDH prepared in example 2 and the oil-water separation membrane prepared in example 3. As can be seen from fig. 1, lamellar crystals were generated on the originally smooth Ni foam material, confirming successful attachment of LDH to the nickel foam, providing more attachment sites for contaminants. As can be seen from FIG. 2, the C-O IR peak was increased, indicating that sodium Stearate (SA) containing C-O bonds was successfully attached to the surface of CuMgFe LDH/Ni foam membrane material. From FIG. 3, it can be seen that the contact angle of the CuMgFe LDH/Ni foam + SA film material is increased to 109.78 degrees, sodium stearate SA is successfully loaded on the surface of the CuMgFe LDH/Ni foam film material in the synthesis process, and good surface interface hydrophobic property is provided for the CuMgFe LDH/Ni foam + SA film material.
Oil-water separation experiment
Example 4
An experiment for separating and synchronously removing oily wastewater containing benzotriazole is carried out on a Ni foam (nickel foam) material, and in the experiment, the wastewater containing petroleum ether and benzotriazole, the wastewater containing soybean oil and benzotriazole and the wastewater containing engine oil and benzotriazole are respectively used for simulating complex oily wastewater of soluble organic matters. The experimental process is fixed Ni foam membrane material on separator for using self-made separator, pours oily waste water into the device again, can not realize oil-water separation.
Example 5
The CuMgFe LDH/Ni foam + SA membrane material obtained in example 3 is subjected to an experiment for separating and synchronously removing oil-containing wastewater containing benzotriazole, wherein the volume ratio of petroleum ether to water is 9: the benzotriazole-containing wastewater of 1 simulates complex oily wastewater of soluble organic matters. The experimental process comprises the steps of fixing CuMgFe LDH/Ni foam + SA membrane materials on a self-made separation device, pouring oily wastewater into the separation device, sucking filtrate by using needle tubes at 0s, 5 s, 10 s, 20s, 25 s, 60 s and 120s respectively, transferring the filtrate into a cuvette by using a polyether sulfone (PES) filter head with the aperture of 0.22 mu m, and testing the absorbance of benzotriazole in the filtrate at different times by using ultraviolet absorption spectrum to test the synchronous removal effect of the separation. The specific results of example 5 are shown in FIG. 4.
FIG. 4 shows that the volume ratio of petroleum ether to water separated by the oil-water separation membrane provided by the invention is 9: 1, because the absorbance is linearly related to the solution concentration of benzotriazole, fig. 4 can reveal that the CuMgFe LDH/Ni foam + SA film material can synchronously remove benzotriazole when applied to the separation of oily wastewater, has the advantages of rapid degradation and strong removal capability, and is a material which has great potential to be applied to the actual water-soluble pollutant degradation of oily wastewater.
Example 6
The CuMgFe LDH/Ni foam + SA membrane material obtained in example 3 is subjected to an experiment for separating and synchronously removing oil-containing wastewater containing benzotriazole, wherein the volume ratio of petroleum ether to water is 9: 1, the benzotriazole-containing wastewater simulates complex oily wastewater of soluble organic matters, and the total volume of the oily wastewater is 50 ml. The experimental process is that CuMgFe LDH/Ni foam + SA membrane material is fixed on a separation device by using a self-made separation device, then oily wastewater is poured into the separation device, under the action of gravity, the oily wastewater is subjected to water-oil separation and is filtered for 10 minutes, the oil-water separation efficiency is tested, and the oil-water separation efficiency is calculated according to the following formula: C-Vt/V0, where C is the separation efficiency, and Vt and V0 represent the filtered oil phase solution volume and the initial oil phase solution volume, respectively, for the corresponding time, and the test results are detailed in fig. 5.
Examples 7 to 9
The experimental methods of examples 7 to 9 are the same as those of example 6, except that the volume ratio of petroleum ether to water in the oil-containing wastewater is different, and the volume ratio of petroleum ether to water in example 6 is 9: 1, the volume ratio of petroleum ether to water in example 7 is 8: 2, the volume ratio of petroleum ether to water in example 8 is 7: 3, the volume ratio of the petroleum ether to the water in example 9 is 6: 4. the oil-water separation efficiency obtained in the tests of examples 6 to 8 is shown in detail in FIG. 5.
Example 10
The CuMgFe LDH/Ni foam + SA membrane material obtained in example 3 is subjected to an experiment for separating and synchronously removing oil-containing wastewater containing benzotriazole, wherein the volume ratio of soybean oil to water is 9: the benzotriazole-containing wastewater of 1 simulates complex oily wastewater of soluble organic matters, and the total volume of the oily wastewater is 50 ml. The experimental process is that CuMgFe LDH/Ni foam + SA membrane material is fixed on a separation device by using a self-made separation device, then oily wastewater is poured into the separation device, under the action of gravity, the oily wastewater is subjected to water-oil separation and is filtered for 10 minutes, the oil-water separation efficiency is tested, and the oil-water separation efficiency is calculated according to the following formula: c — Vt/V0, where C is separation efficiency, and Vt and V0 represent the filtered oil phase solution volume and initial oil phase solution volume, respectively, for the corresponding time, and the test results are detailed in fig. 5.
Examples 11 to 13
The experimental methods of examples 11 to 13 are the same as those of example 10, except that the volume ratio of soybean oil to water in the oily wastewater is different, and the volume ratio of soybean oil to water in example 10 is 9: 1, the volume ratio of soybean oil to water in example 11 was 8: 2, the volume ratio of soybean oil to water in example 12 was 7: 3, the volume ratio of soybean oil to water in example 13 was 6: 4. the oil-water separation efficiency obtained in the tests of examples 11 to 13 is shown in FIG. 5.
Example 14
An experiment for separating and synchronously removing oily wastewater containing benzotriazole is carried out on the CuMgFe LDH/Ni foam + SA film material obtained in the example 3, and the volume ratio of engine oil to water is 9: 1, the benzotriazole-containing wastewater simulates complex oily wastewater of soluble organic matters, and the total volume of the oily wastewater is 50 ml. The experimental process is that CuMgFe LDH/Ni foam + SA membrane material is fixed on a separation device by using a self-made separation device, then oily wastewater is poured into the separation device, under the action of gravity, the oily wastewater is subjected to water-oil separation and is filtered for 10 minutes, the oil-water separation efficiency is tested, and the oil-water separation efficiency is calculated according to the following formula: C-Vt/V0, where C is the separation efficiency, and Vt and V0 represent the filtered oil phase solution volume and the initial oil phase solution volume, respectively, for the corresponding time, and the test results are detailed in fig. 5.
Examples 15 to 17
The experimental methods of examples 15 to 17 are the same as those of example 14, except that the volume ratio of soybean oil to water in the oil-containing wastewater is different, and the volume ratio of the engine oil to water in example 14 is 9: 1, the volume ratio of the engine oil to the water in example 15 was 8: 2, the volume ratio of the engine oil to the water in example 16 was 7: 3, the volume ratio of the engine oil to the water in example 17 was 6: 4. the oil-water separation efficiency obtained in the tests of examples 15 to 17 is shown in FIG. 5.
FIG. 5 is a graph showing the results of the oil-water separation efficiency of the oil-containing wastewater containing benzotriazole by the oil-water separation membrane of the present invention. As can be seen from FIG. 5, the oil-water separation membrane provided by the invention has the best oil-water separation effect on the petroleum ether-containing wastewater, namely engine oil and soybean oil.
Example 18
The CuMgFe LDH/Ni foam + SA membrane material obtained in example 3 is subjected to an experiment for separating and synchronously removing oil-containing wastewater containing benzotriazole, wherein the volume ratio of petroleum ether to water is 9: the benzotriazole-containing wastewater of 1 simulates complex oily wastewater of soluble organic matters, and the total volume of the oily wastewater is 50 ml. The experimental process is characterized in that a self-made separation device is used for fixing CuMgFe LDH/Ni foam + SA membrane materials on the separation device, then oily wastewater is poured into the separation device, under the action of gravity, the oily wastewater is subjected to water-oil separation, the filtration is carried out for 10 minutes, and the oil-water separation efficiency is tested. After separation, the CuMgFe LDH/Ni foam + SA membrane material is taken out of the separation device, washed by DI water and dried at 60 ℃, the dried CuMgFe LDH/Ni foam + SA membrane material is fixed on the separation device after drying, then oily wastewater is poured into the separation device, filtered for 10 minutes, and the oil-water separation efficiency is tested. The experiment was repeated four times to test the oil-water separation efficiency, and the detailed results are shown in fig. 6.
Examples 19 to 20
Examples 19 to 20 are the same as example 18 except that the oil contained in the oily wastewater is different, and example 18 uses the following components in a volume ratio of 9: 1, example 19 used a petroleum ether and water in a volume ratio of 9: 1, example 20 used a soy oil and water in a volume ratio of 9: 1 oil and water, the oil-water separation efficiency results are shown in figure 6.
FIG. 6 is a cycle performance diagram of the oil-water separation effect of the oil-water separation membrane for separating oily wastewater according to the present invention; from FIG. 6, it can be seen that the wettability of the CuMgFe LDH/Ni foam + SA membrane material is not obviously changed, and the oil-water separation efficiency is maintained to be more than 92% within 4 cycles, which indicates that the recoverability of the CuMgFe LDH/Ni foam + SA membrane material is good.
Example 21
The CuMgFe LDH/Ni foam + SA membrane material prepared in example 3 is subjected to an experiment for separating and synchronously removing oil-containing wastewater containing benzotriazole, wherein the volume ratio of the CuMgFe LDH/Ni foam + SA membrane material to the CuMgFe LDH/Ni foam + SA membrane material is 9: 1 petroleum ether and water benzotriazole-containing wastewater mimics complex oily wastewater of soluble organics. The experimental process comprises the steps of fixing CuMgFe LDH/Ni foam + SA membrane materials on a self-made separation device, pouring oily wastewater into the separation device, filtering for 10min, sucking filtrate by using a needle tube, transferring the filtrate into a cuvette by using a polyether sulfone (PES) filter head with the aperture of 0.22 mu m, and testing the absorbance of benzotriazole in the filtrate at different times by using ultraviolet absorption spectrum to test the synchronous separation and removal effect. After separation, the CuMgFe LDH/Ni foam + SA membrane material is taken out of the separation device, washed by DI water and dried at 60 ℃, the dried CuMgFe LDH/Ni foam + SA membrane material is fixed on the separation device after drying, then oily wastewater is poured into the separation device, after filtering for 10min, filtrate is sucked by a needle tube, a polyether sulfone (PES) filter head with the aperture of 0.22 mu m is used for transferring the filtrate into a cuvette, and the absorbance of benzotriazole in the filtrate at different times is tested by ultraviolet absorption spectroscopy so as to test the synchronous removal effect of the separation. The experiment was repeated four times, and the cycle performance and removal efficiency (calculated by absorbance) were tested, and the specific results of example 21 are shown in FIG. 7. The concentration of benzotriazole was evaluated by measuring the absorbance at a wavelength of 259nm using an ultraviolet spectrophotometer, and the relationship between the absorbance and the solution concentration was: the solution concentration was 0.00381x +0.04953 with a correlation coefficient of 0.9998.
Fig. 7 is a graph showing the cycle performance of removing benzotriazole from oil-containing wastewater containing benzotriazole by using the membrane for oil-water separation of the present invention, and it can be seen from fig. 7 that the removal rate of benzotriazole slightly decreases with the increase of the cycle number, but the decrease is very small, and the removal rate is still 60% after 4 cycles.
It should be noted that when the oil-water separation membrane of the present invention is used to separate oil-containing wastewater containing benzotriazole, the oil-water separation efficiency can be maximized within 10 minutes, and benzotriazole can be maximized within 120 seconds.
Comparative example 1
(embodiment of high-concentration coprecipitation method) preparation of copper-magnesium-iron hydrotalcite: 193.28g of copper salt, 102.56g of magnesium salt and 106.92g of iron salt are respectively weighed and dissolved in 500mL of deionized water to obtain a copper-magnesium-iron salt composite solution, wherein Cu is 2+ ：Mg 2+ ：Fe 3+ The molar ratio is 6: 3: 2; 96 g of sodium hydroxide is weighed and added into deionized water to be constant volume, so as to obtain 500mL of sodium hydroxide solution (the molar solubility of the sodium hydroxide is 4.8 mol/L). Slowly dropwise adding the prepared copper-magnesium-iron salt composite solution and sodium hydroxide solution by a peristaltic pump, mixing into a container filled with deionized water, violently stirring at 70 ℃ of water bath temperature, introducing nitrogen, and preventing CO in air 2 And (3) the pH value of the solution is maintained at 9.8-10.2, and the titration end point is that the copper-magnesium-iron salt composite solution and/or the sodium hydroxide solution are added dropwise. And aging the dropwise added solution for 18H under the condition of 70 ℃ water bath, performing suction filtration after aging, repeatedly washing the solution for a plurality of times by using alcohol and deionized water after suction filtration, drying the solution in a drying oven at 80 ℃ for 12H, and grinding the dried solid to obtain a sample of the copper-magnesium-iron hydrotalcite, which is recorded as CuMgFe LDH-H.
FIG. 8 is an XRD diagram of hydrotalcite-like compounds prepared in example 1, example 2 and comparative example 1, and it can be seen from FIG. 8 that CuMgFe LDH and Ni/CuMgFe LDH both can present typical characteristic peaks of good LDH materials, while CuMgFe LDH-H has low crystallinity due to too high salt ion concentration during the preparation process.
The foregoing is a further detailed description of the present invention in connection with specific preferred embodiments thereof, and it is not intended to limit the invention to the specific embodiments thereof. For those skilled in the art to which the invention pertains, several simple deductions and substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of an oil-water separation membrane capable of synchronously removing benzotriazole during oil-water separation is characterized by comprising the following steps:
dissolving divalent metal salt and trivalent metal salt in deionized water according to a preset ratio to obtain a composite salt solution, wherein the divalent metal salt is copper salt and magnesium salt, and the trivalent metal salt is iron salt;
step two, adding sodium stearate into the composite salt solution, and performing ultrasonic dispersion to obtain a mixed solution;
placing the mixed solution, the precipitator and the pretreated foamed nickel in an airtight kettle to perform hydrothermal reaction according to preset conditions, cooling to room temperature, cleaning, and performing vacuum drying to obtain the oil-water separation membrane; wherein the preset conditions are as follows: the hydrothermal reaction temperature is 100-150 ℃, and the hydrothermal reaction time is 18-24 h.
2. The oil-water separation membrane of claim 1, wherein in step three, the pretreatment method of the foamed nickel is as follows: soaking the foamed nickel in dilute nitric acid for 1.5-4 h, and washing with acetone, ethanol and water for multiple times.
3. The oil-water separation membrane according to claim 1, wherein the vacuum drying conditions in step three are as follows: the drying temperature is 60-70 ℃, and the drying time is 8-16 h.
4. The membrane of claim 1, wherein in step three, the precipitant is urea, and the ratio of the amount of urea to the sum of the amounts of metal ions in the complex salt solution is: (0.06-0.1) 1, wherein the ratio of the sum of the amounts of the metal ion species in the complex salt solution to the area of the nickel foam is: 1 mol: (0.1 to 2.5) m 2 。
5. The oil-water separation membrane according to claim 1, wherein in step two, the ratio of the amount of the sodium stearate substance to the sum of the amounts of the metal ion substances in the complex salt solution is: (0.001-0.01): 1.
6. the oil-water separation membrane according to claim 1, wherein the temperature of the ultrasonic dispersion in the second step is 60 to 80 ℃.
7. The oil-water separation membrane according to claim 1, wherein in the first step, the molar ratio of the copper salt to the magnesium salt to the iron salt is: (2-4): (1-3): 1, the molarity of the iron salt is as follows: 0.5 to 1 mol/L.
8. An oil-water separation membrane comprising foamed nickel, hydrotalcite crystals grown on the foamed nickel, and sodium stearate attached to the hydrotalcite crystals, wherein the oil-water separation membrane is produced by the production method according to any one of claims 1 to 7.
9. An application of the oil-water separation membrane prepared by the preparation method of any one of claims 1 to 7 in separation of oil-water mixture containing benzotriazole.
10. The application of claim 9, wherein the oily substance in the oil-water mixture comprises at least one of engine oil, soybean oil and petroleum ether, and the volume ratio of oil to water is (1.5-9): 1.
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