CN113274986A - Magnetic solid phase extracting agent and preparation method, application and application method thereof - Google Patents
Magnetic solid phase extracting agent and preparation method, application and application method thereof Download PDFInfo
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- CN113274986A CN113274986A CN202110393682.7A CN202110393682A CN113274986A CN 113274986 A CN113274986 A CN 113274986A CN 202110393682 A CN202110393682 A CN 202110393682A CN 113274986 A CN113274986 A CN 113274986A
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- 239000007790 solid phase Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 86
- 239000011733 molybdenum Substances 0.000 claims abstract description 86
- -1 molybdenum ions Chemical class 0.000 claims abstract description 83
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 54
- 238000011084 recovery Methods 0.000 claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000002351 wastewater Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 239000012498 ultrapure water Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- ISQSUCKLLKRTBZ-UHFFFAOYSA-N (phosphonomethylamino)methylphosphonic acid Chemical compound OP(O)(=O)CNCP(O)(O)=O ISQSUCKLLKRTBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 30
- 238000003795 desorption Methods 0.000 description 26
- 238000001179 sorption measurement Methods 0.000 description 26
- 229910052681 coesite Inorganic materials 0.000 description 23
- 229910052906 cristobalite Inorganic materials 0.000 description 23
- 229910052682 stishovite Inorganic materials 0.000 description 23
- 229910052905 tridymite Inorganic materials 0.000 description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 239000002253 acid Substances 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 22
- 239000010949 copper Substances 0.000 description 22
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OWPHGLMKNSRHKC-UHFFFAOYSA-N [[hydroxy(methoxy)phosphoryl]oxyamino] methyl hydrogen phosphate Chemical compound N(OP(OC)(O)=O)OP(OC)(O)=O OWPHGLMKNSRHKC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2101/10—Inorganic compounds
Abstract
The invention provides a magnetic solid phase extracting agent, and a preparation method, application and an application method thereof. The magnetic solid phase extractant comprises magnetic nanoparticles, and the magnetic nanoparticles are provided with magnetic spheres and phosphate radicals. The magnetic ball includes a magnetic core and a shell surrounding the magnetic core. The magnetic solid phase extractant improves the selectivity of the magnetic nanoparticle material to molybdenum ions through phosphate radicals, thereby improving the recovery rate of the molybdenum ions, reducing the loss of the molybdenum ions and improving the recovery rate of the molybdenum ions.
Description
Technical Field
The invention relates to the field of nano composite materials, in particular to a magnetic solid phase extracting agent, and a preparation method, application and an application method thereof.
Background
Copper wires are often used for metal routing in tft devices, and a molybdenum layer is required to be plated in front of the copper wires to block copper diffusion and increase adhesion between metal and a silicon oxide layer. During the wet etching process, the concentration of molybdenum ions in the etching solution is continuously increased, and the molybdenum ions become wastewater when the end of the service life is reached, and meanwhile, the concentration of the molybdenum ions in the etching solution is also continuously increased.
At present, the recovery of copper ions in the etching solution is reported, but the recovery of molybdenum ions is not related. The molybdenum has less accumulation on the earth and the price is more or less expensive than that of copper, thereby having great recovery value. In addition, the excessive concentration of molybdenum ions in the wastewater can cause environmental pollution, so that the method has important significance for recovering and treating the molybdenum.
Disclosure of Invention
The invention aims to provide a magnetic solid-phase extracting agent, and a preparation method, application and an application method thereof, so as to solve the problem of difficult recovery of molybdenum ions in the prior art.
In order to achieve the purpose, the invention provides a magnetic solid-phase extractant which comprises magnetic nanoparticles, wherein the magnetic nanoparticles are provided with magnetic spheres and phosphate radicals. The magnetic ball includes a magnetic core and a shell surrounding the magnetic core. The chemical structural formula of the magnetic nanoparticles comprises the following structures:
wherein R is the magnetic sphere; the x, the y and the n are integers greater than or equal to 0 and less than 100.
Further, the magnetic core is ferroferric oxide nano particles, and the shell is silicon dioxide.
The invention also provides a preparation method of the magnetic solid phase extracting agent, which comprises the following steps:
synthesizing a first polymer having magnetic spheres by a first compound having iron ions, a second compound having ferrous ions, and a third compound having silane; modifying the surface of the magnetic ball in the first polymer by using a silane coupling agent to obtain a second polymer; adding a polymerization monomer with epoxy groups and a cross-linking agent into the second polymer, and reacting to form a third polymer containing epoxy polymer magnetic spheres; and adding a fourth compound with phosphate groups into the third polymer, and reacting to form the magnetic nanoparticles with the phosphate groups.
The magnetic nanoparticles have the following chemical structural formula:
r in the structural formula is the magnetic ball, and the magnetic ball comprises a magnetic core and a shell surrounding the magnetic core. X, y and n in the structural formula are integers which are more than or equal to 0 and less than 100.
Further, the step of synthesizing the first polymer having the magnetic spheres comprises:
dissolving 10-15g of the first compound and 1-10g of the second compound in 150-250mL of high-purity water to obtain a first mixed solution; under the protection of nitrogen, stirring and heating the first mixed solution to 80-90 ℃, adding ammonia monohydrate into the first mixed solution until the first mixed solution turns black, and reacting for 0.4-0.6 hour to obtain a first mixture, wherein the first compound contains a first polymer semi-finished product; washing the first mixture with high-purity water and ethanol respectively to obtain a first polymer semi-finished product; dispersing the first polymer semi-finished product in a mixed solution of ethanol and water to obtain a second mixed solution; adding the third compound and ammonia monohydrate into the second compound, and stirring and reacting for 11-13 hours to obtain a second mixture, wherein the second mixture contains the first polymer; and washing the first polymer by using high-purity water and ethanol respectively to obtain the first polymer.
The magnetic core of the magnetic ball is ferroferric oxide nano particles, and the shell of the magnetic ball is silicon dioxide.
Further, the step of modifying the surface of the magnetic spheres in the first polymer comprises:
dispersing 0.5-1.5g of first polymer in 75-125mL of ethanol and 30-70mL of water, adding ammonia monohydrate, and adjusting the pH value to 9-10 to obtain a third mixed solution; adding 1-3g of silane coupling agent into the third mixed solution, and fully reacting for 11-13 hours at the temperature of 35-45 ℃ to obtain a third mixture, wherein the third mixture contains the second polymer; and cooling the third mixture to room temperature, washing with high-purity water and ethanol respectively, and drying to obtain the second polymer.
Further, in the step of forming the third polymer, it comprises:
dispersing 400-600mg of second polymer in 40-60mL of dimethylformamide, adding 1-5g of polymerized monomer and 0.1-1g of cross-linking agent, and performing ultrasonic dispersion for 20-40 minutes to obtain a fourth mixed solution; under the argon atmosphere, stirring and heating the fourth mixed solution to 50-70 ℃, adding 90-150mg of azodiisobutyronitrile, then continuously heating to 70-90 ℃, and reacting for 2-5 hours to obtain a fourth mixture, wherein the fourth mixture contains the third polymer; and cooling the fourth mixture to room temperature, washing with ethanol, and drying to obtain the third polymer.
Further, in the step of forming the magnetic nanoparticles, it comprises:
dispersing 400-600mg of the third polymer in 40-60mL of ethanol, adding 1-5g of the fourth compound and 5-10mL of triethylamine, and heating for reacting for 2-5 hours to obtain a fifth mixture, wherein the fifth mixture has the magnetic nanoparticles; and washing the fifth mixture by using ethanol to obtain the magnetic nanoparticles.
Further, the first compound is ferric chloride, the second compound is ferrous chloride, the third compound is tetraethoxysilane, the fourth compound is imino-bis (methyl phosphoric acid), the polymerized monomer is glycidyl methacrylate, and the crosslinking agent is ethylene glycol dimethacrylate.
The magnetic solid phase extracting agent provided by the invention can be used for recovering molybdenum ions in wastewater.
The application method of the magnetic solid phase extracting agent provided by the invention comprises the following steps:
after the pH value of the wastewater is adjusted to 3-4, adding 5-20mg of a magnetic solid phase extracting agent, stirring or ultrasonically treating, and uniformly dispersing the magnetic solid phase extracting agent in the wastewater to enable molybdenum ions in the wastewater to be adsorbed on magnetic nano particles in the magnetic solid phase extracting agent; starting an electromagnetic device to perform magnetic separation operation, adsorbing the magnetic nanoparticles in the wastewater, and transferring the wastewater into a reaction container; adding 0.1-0.5mol of desorbent into the reaction container, and carrying out ultrasonic or oscillation treatment to elute the molybdenum ions adsorbed on the magnetic nanoparticles; adding ammonium chloride into the reaction vessel, carrying out an ammoniation reaction, and replacing molybdenum ions to prepare ammonium molybdate; and introducing hydrogen into the reaction vessel to carry out reduction reaction to prepare molybdenum metal.
The invention has the advantages that: the magnetic solid phase extracting agent has the advantages of large adsorption capacity, high selectivity, strong magnetism, no organic solvent consumption, faster adsorption-desorption kinetics and the like, and can effectively reduce the treatment time of wastewater so as to improve the recovery efficiency of the wastewater. Meanwhile, the magnetic solid phase extracting agent provided by the invention also has the advantages of high temperature resistance, strong acid resistance, strong alkali resistance and the like, has excellent stability, can be regenerated and reused, and can greatly save the recovery cost of molybdenum ions.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a process for preparing a magnetic solid-phase extractant in example 2 of the present invention;
FIG. 2 is a reaction scheme of step S11 in example 2 of the present invention;
FIG. 3 is a reaction scheme of step S12 in example 2 of the present invention;
FIG. 4 is a reaction scheme of step S13 in example 2 of the present invention;
FIG. 5 is a reaction scheme of step S14 in example 2 of the present invention;
FIG. 6 is a schematic flow chart showing a method for recovering molybdenum ions from wastewater according to example 3 of the present invention;
fig. 7 is a schematic diagram of a system for recovering molybdenum ions from wastewater in embodiment 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a magnetic solid phase extracting agent, and a preparation method and application thereof. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or an established order. Various embodiments of the invention may exist in a range of versions; it is to be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges such as, for example, from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range such as, for example, 1, 2, 3, 4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the indicated range.
Example 1
The embodiment of the invention provides a magnetic solid-phase extracting agent, which comprises Fe3O4@SiO2@ GMA-P magnetic nanoparticlesSaid Fe3O4@SiO2The chemical structural formula of the @ GMA-P magnetic nano particle is shown as a formula 1.
R in the formula 1 is a magnetic sphere, the magnetic sphere takes ferroferric oxide nano particles as magnetic cores, and silica is used as a shell to coat the magnetic cores. X, y and n in formula 1 are integers of 0 or more and less than 100.
As shown in formula 1, a large number of phosphate radicals and hydroxyl radicals are connected to the surface of the magnetic ball, and the phosphate radicals and the hydroxyl radicals can effectively enhance the selection of molybdenum ions and improve the adsorption rate of the molybdenum ions through coordination, electrostatic adsorption and the like.
Said Fe3O4@SiO2The @ GMA-P magnetic nanoparticles can adsorb molybdenum ions in wastewater based on the strong paramagnetism of magnetic spheres in the structure of the magnetic nanoparticles, and can enable the molybdenum ions to be quickly separated from the wastewater under the help of an external magnetic field, so that the extraction flow of the molybdenum ions is simplified, and the treatment time of the wastewater is greatly shortened. Said Fe3O4@SiO2The @ GMA-P magnetic nanoparticles also improve the selectivity of the magnetic nanoparticle material to molybdenum ions through phosphate radicals, so that the recovery rate of the molybdenum ions is improved, and the loss of the molybdenum ions is reduced.
Comprising said Fe3O4@SiO2The magnetic solid phase extractant of the @ GMA-P magnetic nanoparticles can be applied to extraction and recovery of molybdenum ions in wastewater, and the extraction and recovery of the molybdenum ions have the following steps:
and collecting the copper acid wastewater generated after the production into a container, wherein the copper acid wastewater contains molybdenum ions. Adjusting the pH value of the copper acid wastewater to 3-4, adding 10mg of a magnetic solid phase extraction agent, and uniformly dispersing the magnetic solid phase extraction agent in the wastewater through an ultrasonic device or a stirring device, so that the magnetic nanoparticles in the magnetic solid phase extraction agent fully adsorb molybdenum ions in the copper acid wastewater. And starting an electromagnetic device to perform magnetic separation operation, separating the magnetic nanoparticles adsorbing the molybdenum ions from the copper acid wastewater, and transferring the magnetic nanoparticles to a new reaction container. Adding a desorbent into the reaction container, and eluting the molybdenum ions adsorbed on the magnetic nano particles by an ultrasonic device or a vibration device. And adding ammonium chloride into the reaction vessel, carrying out ammoniation reaction, and replacing molybdenum ions to prepare ammonium molybdate. And introducing hydrogen into the reaction vessel, and performing reduction reaction on the ammonium molybdate and the hydrogen to prepare molybdenum metal, thereby completing the recovery of molybdenum ions in the wastewater.
When the magnetic solid phase extractant is applied to the recovery treatment of molybdenum ions in wastewater, the magnetic solid phase extractant is based on Fe in the magnetic solid phase extractant3O4@SiO2The @ GMA-P magnetic nanoparticles have good dispersibility and strong magnetism, can quickly realize the separation and enrichment of the aromatic heterocyclic compound, and improve the wastewater treatment efficiency. The material for adsorbing molybdenum ions can be recycled after acidolysis and adsorption, so that the treatment cost of wastewater is saved. Meanwhile, an organic solvent is not needed in the wastewater treatment process, so that the harm to the human health and the environment is reduced.
The use effect of the magnetic solid phase extractants provided in the examples of the present invention is demonstrated by the relevant data obtained in experiments 1 to 5 as follows:
experiment 1) adsorption effect experiment of magnetic solid phase material in molybdenum ion solution with different pH values:
5mL of molybdenum ion solutions with pH values of 1, 2, 3, 4, 5, 6 and 7 are prepared, and the concentration of molybdenum ions in 7 parts of the molybdenum ion solutions is 100 ppm. Respectively adding 5mg of magnetic solid phase extractant into 7 parts of molybdenum ion solution, uniformly dispersing the magnetic solid phase extractant by ultrasonic treatment or vibration, and standing for half an hour to ensure that Fe in the magnetic solid phase extractant3O4@SiO2The @ GMA-P magnetic nano particles fully adsorb the molybdenum ions in the molybdenum ion solution. Using an external magnetic field to make the Fe adsorbed with molybdenum ions3O4@SiO2And the @ GMA-P magnetic nano particles are separated from the residual liquid.
The stock solution and the residual solution of the molybdenum ion solution with different pH values are detected by ICP-OES (inductively coupled atomic emission spectrometry), the adsorption capacity of the magnetic solid phase extractant and the molybdenum ion removal efficiency can be calculated, and the obtained data are summarized and recorded to prepare the following table 1.
| pH value | Adsorption capacity (mg. g)-1) |
| 1 | 22.5±1.5 |
| 2 | 27.8±0.3 |
| 3 | 39.7±1.2 |
| 4 | 35.3±3.1 |
| 5 | 30.7±2.2 |
| 6 | 30.1±2.2 |
| 7 | 25.3±3.1 |
TABLE 1
As shown in table 1, the adsorption capacity increased with the increase in pH of the molybdenum ion solution, reached a maximum at pH 3, and continued increase in pH, the adsorption capacity hardly increased, and the maximum adsorption capacity (pH 3) should be 20 to 40mg g-1The removal efficiency is greater than 98%.
Experiment 2) desorption effect experiment of different desorption solutions:
fe extracted in experiment 13O4@SiO2The magnetic nano particles of @ GMA-P are divided into 4 parts, and Fe is added into 4 parts3O4@SiO21mL of magnetic nanoparticles with the concentration of 0.1 mol.L are respectively added into the @ GMA-P magnetic nanoparticles-1HPO of41mL of the solution was 0.2 mol. L-1HPO of41mL of the solution was 0.1 mol. L-1NaH (a)2PO4And 1mL of a solution having a concentration of 0.1 mol. L-1Na of (2)2HPO4The four desorption solutions were tested, and the measured data were summarized and recorded to obtain table 2.
| Desorption liquid | Desorption efficiency (%) |
| The concentration is 0.1 mol.L-1HPO of4 | 98.3±1.2 |
| The concentration is 0.2 mol.L-1HPO of4 | 99.6±0.5 |
| The concentration is 0.1 mol.L-1NaH (a)2PO4 | 98.2±2.0 |
| The concentration is 0.1 mol.L-1Na of (2)2HPO4 | 98.8±1.2 |
TABLE 2
As is clear from the data in Table 2, the concentration was 0.2 mol. L-1HPO of4The desorption rate of (A) can reach 98% or more, so that the desorption solution can be selectively used at a concentration of 0.2 mol.L-1HPO of4。
Experiment 3) adsorption effect experiment for different adsorption times:
6 parts of 20mg magnetic solid phase extractant was prepared, and each of the prepared magnetic solid phase extractants was added to 200mL of a molybdenum ion solution (each concentration of molybdenum ions was 10ppm) to conduct adsorption. The adsorption time of 6 parts of the molybdenum ion solution was 1 minute, 2 minutes, 3 minutes, 5 minutes, 10 minutes, and 15 minutes, and the desorption time was 20 minutes. After recovery, the stock solution and the desorption solution were measured, respectively, and the recovery rates were calculated and the data were collected and recorded to prepare table 3.
| Adsorption time (min) | Adsorption efficiency (%) |
| 1 | 93.0±0.4 |
| 2 | 97.7±0.3 |
| 3 | 99.5±1.1 |
| 5 | 99.4±1.3 |
| 10 | 98.8±1.4 |
| 15 | 99.2±0.8 |
TABLE 3
As is clear from the data in table 3, the adsorption time of about 3 minutes is sufficient to completely adsorb molybdenum ions in the molybdenum ion solution, and therefore the adsorption time in the molybdenum ion recovery process is preferably 3 minutes.
Experiment 4) desorption effect experiment for different desorption times:
6 parts of 20mg magnetic solid phase extractant are prepared and respectively added into 200mL of molybdenum ion solution (the concentration of molybdenum ions is 10ppm) for adsorption, and the adsorption time is 3 minutes. And adding desorption solution with the same volume and the same concentration for desorption after the adsorption is finished, wherein the desorption time of 6 parts of molybdenum ion solution is respectively 1 minute, 2 minutes, 3 minutes, 5 minutes, 10 minutes and 15 minutes. After recovery, the stock solution and the desorption solution were measured, respectively, and the recovery rate was calculated, and the data was summarized and recorded to prepare table 4.
| Desorption time (min) | Desorption efficiency (%) |
| 1 | 69.2±1.2 |
| 2 | 87.5±0.5 |
| 3 | 98.3±2.0 |
| 5 | 98.5±2.7 |
| 10 | 98.0±1.8 |
| 15 | 97.9±0.4 |
TABLE 4
As can be seen from the data in Table 4, the Fe content was completely reduced in about 5 minutes by the desorption time3O4@SiO2The molybdenum ions adsorbed on the @ GMA-P magnetic nanoparticles are desorbed, so the desorption time in the molybdenum ion recovery process is preferably 5 minutes.
Meanwhile, as can be seen from the data in tables 3 and 4, the magnetic solid-phase extraction agent provided in the embodiment of the present invention has fast adsorption-desorption kinetics, can reduce the wastewater treatment time, and can improve the wastewater treatment efficiency.
Experiment 5) stability and reusability experiments of the magnetic solid phase extractants provided in the examples of the present invention:
A. and (3) high temperature resistance test: baking the magnetic solid phase extracting agent at the high temperature of 100 ℃ for 24 hours;
B. acid resistance test: respectively soaking the magnetic solid phase extractant in 5mol of nitric acid, hydrochloric acid and sulfuric acid for 1 hour;
C. and (3) testing alkali resistance: and soaking the magnetic solid phase extractant in 5mol of sodium hydroxide for 1 hour.
Taking out the three tested magnetic solid phase extractants, respectively washing with clear water twice, and respectively using the magnetic solid phase extractants with the concentration of 0.2 mol.L-1HPO of4And (5) performing an adsorption and desorption experiment as a desorbent, detecting the concentration of the stock solution and the desorption solution, and calculating the recovery rate. The results show that the recovery rates of the three tested magnetic solid phase extractants are all more than 98 percent, which shows that the magnetic solid phase extractants have extremely strong high temperature resistance, acid and alkali resistance and extremely high stability.
In conclusion, the magnetic solid phase extracting agent is suitable for recovering molybdenum ions in copper acid wastewater with complex matrixes.
The magnetic solid phase extractant is continuously and repeatedly subjected to adsorption and desorption experiments, and the desorbent has the concentration of 0.2 mol.L-1HPO of4And detecting the concentrations of the stock solution and the desorption solution, and calculating the recovery rate. The result shows that the recovery rate of the magnetic solid phase extracting agent is still more than 95% after the magnetic solid phase extracting agent is repeatedly adsorbed and desorbed for 30 times, which indicates that the material has excellent stability, can be regenerated and reused, and saves the cost.
Adding 5g of magnetic solid phase extraction agent into 200mL of copper acid wastewater, adsorbing for 3 minutes under the action of ultrasonic wave or vibration, removing residual liquid, and adding the copper acid wastewater with the concentration of 0.2 mol.L-1HPO of4The desorption was carried out for 5 minutes. The stock solution and the desorption solution are introduced into ICP-OES for detection, and the result shows that the recovery rate is more than 95%. The magnetic solid phase extractant is suitable for recovering the molybdenum ions in the copper acid wastewater.
In conclusion, the magnetic solid phase extraction agent provided by the embodiment of the invention has the advantages of large adsorption capacity, high selectivity, strong magnetism, no organic solvent consumption, faster adsorption-desorption kinetics and the like, and can effectively reduce the treatment time of wastewater, thereby improving the recovery efficiency of the wastewater. Meanwhile, the magnetic solid phase extracting agent provided by the embodiment of the invention also has the advantages of high temperature resistance, strong acid resistance, strong alkali resistance and the like, has excellent stability, can be regenerated and reused, and can greatly save the recovery cost of molybdenum ions.
Example 2
The embodiment of the invention also provides a preparation method of the magnetic solid phase extracting agent, which is used for preparing the Fe-containing magnetic solid phase extracting agent in the embodiment 13O4@SiO2A magnetic solid phase extractant of the @ GMA-P magnetic nano particles. The flow of the preparation method of the magnetic solid phase extracting agent is shown in figure 1, and the preparation method comprises the following specific steps:
step S11) as shown in fig. 2, a first polymer having magnetic spheres was synthesized:
11.68g of a powder having iron ions (Fe)3+) And 4.3g of a mixture having ferrous ions (Fe)2+) The second compound (2) was dissolved in 200mL of high-purity water to obtain a first mixed solution. Under the protection of nitrogen, stirring and heatingThe temperature of the first mixed solution is up to 85 ℃, and 30 percent of ammonium monohydrate (NH) is added into the first mixed solution3·H2O) until the first mixed solution is black, reacting for 0.5 hour to obtain a first mixture, wherein the first mixture contains a first polymer semi-finished product-Fe3O4Nanoparticles. Washing the first compound with high-purity water and ethanol respectively to obtain the Fe3O4Nanoparticles, Fe which can be finally preserved in high-purity water3O4Nanoparticles.
Subjecting said Fe to3O4And dispersing the nano particles in a mixed solution of ethanol and water to obtain a second mixed solution. Wherein the ratio of ethanol to water in the mixed solution is 4: 1. Adding a third compound with silane and 30% ammonia monohydrate into the second mixed solution, and reacting for 12 hours under stirring to obtain a second mixture, wherein the second mixture contains a first polymer Fe3O4@SiO2Magnetic nanoparticles. Washing the second mixture with high-purity water and ethanol respectively to obtain the first polymer. The first polymer may be preserved with high purity water.
Wherein the first compound is ferric chloride, the second compound is ferrous chloride, and the third compound is Tetraethoxysilane (TEOS).
Step S12) as shown in fig. 3, the magnetic sphere surface in the first polymer is subjected to a modification treatment:
1g of the first polymer was dispersed in 100mL of ethanol and 50mL of purified water to obtain a third mixture. And adding 3mL of 30% ammonia monohydrate into the third mixed solution, and adjusting the pH value of the third mixed solution to 9-10. Adding 2g of silane coupling agent KH-570 into the third mixed solution, reacting for about 12 hours in an environment with the temperature of 40 ℃, and modifying the shell surface of the magnetic spheres in the first polymer to obtain a third mixture, wherein the third mixture contains a second polymer Fe3O4@SiO2@ KH-570 magnetic nanoparticles. After the third mixture is cooled to room temperature, respectively adopting high-purity water andwashing the second polymer with ethanol, and drying to obtain the second polymer.
Step S13) as shown in fig. 4, a third polymer containing epoxy-based polymer magnetic spheres is formed:
500mg of the second polymer was dispersed in 50mL of Dimethylformamide (DMF), and 2g of a polymerizable monomer having an epoxy group and 0.5g of a crosslinking agent were added, followed by ultrasonic dispersion for 30 minutes to obtain a fourth mixed solution. Transferring the fourth mixed solution into a 100mL three-neck flask, heating the mixed solution to 60 ℃ under the protection of argon, adding 120mg of Azobisisobutyronitrile (AIBN), continuously heating the mixed solution to 80 ℃, and reacting for 3 hours to obtain a fourth mixture, wherein the fourth mixture contains the third polymer Fe3O4@SiO2@ GMA magnetic nanoparticles. And after the fourth mixture is cooled to the room temperature, washing the fourth mixture by using ethanol, and drying to obtain the third polymer.
Wherein the polymerization monomer is Glycidyl Methacrylate (GMA), and the crosslinking agent is ethylene glycol dimethacrylate (EDGMA).
Step S14) as shown in fig. 5, magnetic nanoparticles containing magnetic spheres and phosphate groups are formed:
dispersing 500mg of the third polymer into 50mL of ethanol, adding 2g of the fourth compound with phosphate groups and 8mL of triethylamine, and heating for reacting for 3 hours to obtain a fifth mixture, wherein the fifth mixture contains the Fe3O4@SiO2@ GMA-P magnetic nanoparticles. Washing the fifth mixture with ethanol for multiple times to obtain the Fe3O4@SiO2@ GMA-P magnetic nanoparticles. Finally, the Fe obtained can be stored by using ethanol3O4@SiO2@ GMA-P magnetic nanoparticles.
Wherein the fourth compound is iminodi (methylphosphonic acid).
The magnetic solid phase extractant prepared by the method has the advantages of large adsorption capacity, high selectivity, strong magnetism and no consumption of organic solvent, and the magnetic solid phase extractant prepared by the method is used for treating copper acid wastewater, so that the extraction process flow is simplified, the molybdenum ion extraction process efficiency is improved, and the harm of the organic solvent to the environment and human body is reduced.
Example 3
In the embodiment of the present invention, there is provided a method for applying the magnetic solid phase extracting agent as described in example 1, wherein the magnetic solid phase extracting agent is used for recovering molybdenum ions in wastewater, and in this embodiment, the magnetic solid phase extracting agent as described in example 1 is preferably used for recovering molybdenum ions in copper acid wastewater in a factory.
The technological process of extracting molybdenum ions in copper acid wastewater of a plant by using the magnetic solid-phase extractant is shown in fig. 6, and the basic architecture of the recovery system of extracting molybdenum ions in copper acid wastewater of a plant by using the magnetic solid-phase extractant is shown in fig. 7. With reference to fig. 6 and 7, the method for recovering molybdenum ions includes the following steps:
step S21) molybdenum ions in the copper acid wastewater are adsorbed:
and closing a second valve, a third valve and a fourth valve in the molybdenum ion recovery system, and opening a first valve to enable the copper acid wastewater in the basement copper acid wastewater pool to flow into the magnetic solid phase extraction reaction tank. Wherein, the magnetic solid phase extraction reaction tank contains a large amount of magnetic solid phase extraction agent.
Closing the first valve, and opening a stirring device in the magnetic solid-phase extraction reaction tank to uniformly disperse the magnetic solid-phase extractant in the magnetic solid-phase extraction reaction tank in the copper acid wastewater, so that Fe in the magnetic solid-phase extractant3O4@SiO2The @ GMA-P magnetic nano particles can fully adsorb molybdenum ions in the copper acid wastewater.
Step S22) discharging a waste water residual liquid:
opening the electromagnetic device at the bottom of the magnetic solid phase extraction reaction tank to adsorb the Fe with molybdenum ions3O4@SiO2And the @ GMA-P magnetic nano particles are adsorbed to the bottom of the magnetic solid phase extraction reaction tank. And opening a second valve, and discharging the waste water residual liquid after the molybdenum ions are adsorbed away for treating other impurities. And after the waste liquid is completely discharged, closing the electromagnetic device.
Step S23) desorbing the molybdenum ions:
and closing the second valve, opening the third valve, and pumping the desorbent in the desorbent storage tank into the magnetic solid phase extraction reaction tank. Closing the third valve and opening the stirring device in the magnetic solid phase extraction reaction tank again to ensure that the Fe adsorbing the molybdenum ions3O4@SiO2The @ GMA-P magnetic nanoparticles are fully dispersed in the desorbent, so that the desorbent can fully exert the function thereof, and molybdenum ions are made to be Fe3O4@SiO2The @ GMA-P magnetic nanoparticles are detached and phosphomolybdic acid is formed.
Step S24) replacing the molybdenum ions by an ammoniation reaction:
opening the electromagnetic device at the bottom of the magnetic solid phase extraction reaction tank again to enable the Fe3O4@SiO2And the @ GMA-P magnetic nano particles are adsorbed to the bottom of the magnetic solid phase extraction reaction tank. And opening a fourth valve, and pumping the phosphomolybdic acid obtained after desorption into a desorbent storage tank. The fourth valve is closed, the fifth valve is opened, and the phosphomolybdic acid is pumped from the desorbent storage tank to the amination tank. And closing the fifth valve, and adding ammonium chloride into the ammoniation tank to ensure that the phosphomolybdic acid and the ammonium chloride carry out ammoniation reaction to obtain ammonium molybdate. And after the reaction is finished, standing for a moment to enable the ammonium molybdate to precipitate to the bottom of the ammoniation tank.
Step S25) molybdenum metal is produced by a reduction reaction:
and opening a sixth valve, introducing hydrogen, and carrying out reduction reaction on the hydrogen and the ammonium molybdate to obtain the molybdenum metal so as to complete the recovery of the molybdenum ions.
The method for recovering molybdenum ions in wastewater provided by the embodiment of the invention can quickly realize separation and enrichment of the aromatic heterocyclic compound and improve the wastewater treatment efficiency. The material for adsorbing molybdenum ions can be recycled after acidolysis and adsorption, so that the treatment cost of wastewater is saved. Meanwhile, an organic solvent is not needed in the wastewater treatment process, so that the harm to the human health and the environment is reduced.
Claims (10)
1. The magnetic solid phase extractant is characterized by comprising magnetic nanoparticles, wherein the magnetic nanoparticles are provided with magnetic spheres and phosphate radicals; the magnetic ball comprises a magnetic core and a shell surrounding the magnetic core;
the chemical structural formula of the magnetic nanoparticles comprises the following structures:
wherein R is the magnetic sphere; the x, the y and the n are integers greater than or equal to 0 and less than 100.
2. A magnetic solid phase extractant according to claim 1 wherein the magnetic core is a ferroferric oxide nanoparticle and the shell is silica.
3. The preparation method of the magnetic solid phase extractant is characterized by comprising the following steps of:
synthesizing a first polymer having magnetic spheres by a first compound having iron ions, a second compound having ferrous ions, and a third compound having silane;
modifying the surface of the magnetic ball in the first polymer by using a silane coupling agent to obtain a second polymer;
adding a polymerization monomer with epoxy groups and a cross-linking agent into the second polymer, and reacting to form a third polymer containing epoxy polymer magnetic spheres; and
adding a fourth compound with phosphate radicals into the third polymer, and reacting to form magnetic nanoparticles with phosphate radicals;
the magnetic nanoparticles have the following chemical structural formula:
the R is the magnetic ball; the magnetic ball comprises a magnetic core and a shell surrounding the magnetic core;
the x, the y and the n are integers greater than or equal to 0 and less than 100.
4. A process for the preparation of a magnetic solid phase extractant according to claim 3,
the step of synthesizing the first polymer having the magnetic spheres comprises:
dissolving 10-15g of the first compound and 1-10g of the second compound in 150-250mL of high-purity water to obtain a first mixed solution;
under the protection of nitrogen, stirring and heating the first mixed solution to 80-90 ℃, adding ammonia monohydrate into the first mixed solution until the first mixed solution turns black, and reacting for 0.4-0.6 hour to obtain a first mixture, wherein the first compound contains a first polymer semi-finished product;
washing the first mixture with high-purity water and ethanol respectively to obtain a first polymer semi-finished product;
dispersing the first polymer semi-finished product in a mixed solution of ethanol and water to obtain a second mixed solution, wherein the ratio of ethanol to water is 4: 1; adding the third compound and ammonia monohydrate into the second compound, and stirring and reacting for 11-13 hours to obtain a second mixture, wherein the second mixture contains the first polymer; and
washing the first polymer with high-purity water and ethanol respectively to obtain the first polymer;
the magnetic core of the magnetic ball is ferroferric oxide nano particles, and the shell of the magnetic ball is silicon dioxide.
5. A process for the preparation of a magnetic solid phase extractant according to claim 3,
the step of modifying the surface of the magnetic spheres in the first polymer comprises:
dispersing 0.5-1.5g of first polymer in 75-125mL of ethanol and 30-70mL of water, adding ammonia monohydrate, and adjusting the pH value to 9-10 to obtain a third mixed solution;
adding 1-3g of silane coupling agent into the third mixed solution, and fully reacting for 11-13 hours at the temperature of 35-45 ℃ to obtain a third mixture, wherein the third mixture contains the second polymer; and
and cooling the third mixture to room temperature, washing with high-purity water and ethanol respectively, and drying to obtain the second polymer.
6. A process for the preparation of a magnetic solid phase extractant according to claim 3,
in the step of forming the third polymer, comprising:
dispersing 400-600mg of second polymer in 40-60mL of dimethylformamide, adding 1-5g of polymerized monomer and 0.1-1g of cross-linking agent, and performing ultrasonic dispersion for 20-40 minutes to obtain a fourth mixed solution;
under the argon atmosphere, stirring and heating the fourth mixed solution to 50-70 ℃, adding 90-150mg of azodiisobutyronitrile, then continuously heating to 70-90 ℃, and reacting for 2-5 hours to obtain a fourth mixture, wherein the fourth mixture contains the third polymer; and
and cooling the fourth mixture to room temperature, washing with ethanol, and drying to obtain the third polymer.
7. A process for the preparation of a magnetic solid phase extractant according to claim 3,
in the step of forming the magnetic nanoparticles, comprising:
dispersing 400-600mg of the third polymer in 40-60mL of ethanol, adding 1-5g of the fourth compound and 5-10mL of triethylamine, and heating for reacting for 2-5 hours to obtain a fifth mixture, wherein the fifth mixture has the magnetic nanoparticles; and
and washing the fifth mixture by using ethanol to obtain the magnetic nanoparticles.
8. A process for the preparation of a magnetic solid phase extractant according to claim 3,
the first compound is ferric chloride;
the second compound is ferrous chloride;
the third compound is tetraethoxysilane;
the fourth compound is iminodi (methylphosphonic acid);
the polymerization monomer is glycidyl methacrylate;
the cross-linking agent is ethylene glycol dimethacrylate.
9. Use of a magnetic solid phase extractant according to claim 1 comprising: the method is used for recovering the molybdenum ions in the wastewater.
10. A method of using a magnetic solid phase extractant as recited in claim 1 wherein the recovery of molybdenum ions from wastewater comprises the steps of:
adjusting the pH value of the wastewater to 3-4, adding 5-20mg of a magnetic solid phase extractant, stirring or ultrasonically treating, and uniformly dispersing the magnetic solid phase extractant in the wastewater to enable molybdenum ions in the wastewater to be adsorbed on magnetic nanoparticles in the magnetic solid phase extractant;
starting an electromagnetic device to perform magnetic separation operation, adsorbing the magnetic nanoparticles in the wastewater, and transferring the wastewater into a reaction container;
adding 0.1-0.5mol of desorbent into the reaction container, and carrying out ultrasonic or oscillation treatment to elute the molybdenum ions adsorbed on the magnetic nanoparticles;
adding ammonium chloride into the reaction vessel, carrying out an ammoniation reaction, and replacing molybdenum ions to prepare ammonium molybdate; and
and introducing hydrogen into the reaction vessel to carry out reduction reaction to prepare molybdenum metal.
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| CN114272900A (en) * | 2021-11-26 | 2022-04-05 | 杭州景业智能科技股份有限公司 | Solid phase extracting agent and preparation method and application thereof |
| CN114272900B (en) * | 2021-11-26 | 2023-08-15 | 杭州景业智能科技股份有限公司 | Solid phase extractant, preparation method and application thereof |
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