CN115779859A - Magnetic adsorbent, preparation method thereof and treatment method of oily sewage - Google Patents
Magnetic adsorbent, preparation method thereof and treatment method of oily sewage Download PDFInfo
- Publication number
- CN115779859A CN115779859A CN202211522663.0A CN202211522663A CN115779859A CN 115779859 A CN115779859 A CN 115779859A CN 202211522663 A CN202211522663 A CN 202211522663A CN 115779859 A CN115779859 A CN 115779859A
- Authority
- CN
- China
- Prior art keywords
- solution
- magnetic adsorbent
- mixed system
- magnetic
- antioxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 95
- 239000010865 sewage Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 44
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 37
- 239000000696 magnetic material Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000004519 grease Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000701 coagulant Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 5
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 claims description 5
- JFLIEFSWGNOPJJ-JTQLQIEISA-N N(2)-phenylacetyl-L-glutamine Chemical compound NC(=O)CC[C@@H](C(O)=O)NC(=O)CC1=CC=CC=C1 JFLIEFSWGNOPJJ-JTQLQIEISA-N 0.000 claims description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004147 Sorbitan trioleate Substances 0.000 claims description 5
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 5
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 5
- 239000000176 sodium gluconate Substances 0.000 claims description 5
- 229940005574 sodium gluconate Drugs 0.000 claims description 5
- 235000012207 sodium gluconate Nutrition 0.000 claims description 5
- 239000001433 sodium tartrate Substances 0.000 claims description 5
- 229960002167 sodium tartrate Drugs 0.000 claims description 5
- 235000011004 sodium tartrates Nutrition 0.000 claims description 5
- 235000019337 sorbitan trioleate Nutrition 0.000 claims description 5
- 229960000391 sorbitan trioleate Drugs 0.000 claims description 5
- 239000001589 sorbitan tristearate Substances 0.000 claims description 5
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 5
- 229960004129 sorbitan tristearate Drugs 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 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 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229960002969 oleic acid Drugs 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 28
- 125000000524 functional group Chemical group 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 239000007864 aqueous solution Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000005415 magnetization Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000006247 magnetic powder Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CETKIJQGQREPFE-UHFFFAOYSA-N 2,6-ditert-butyl-4-methylphenol;ethanol Chemical compound CCO.CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CETKIJQGQREPFE-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000026058 directional locomotion Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of wastewater treatment, in particular to a magnetic adsorbent, a preparation method thereof and a treatment method of oily sewage. The preparation method of the magnetic adsorbent comprises the following steps: (a) Providing a first solution of a ferrous salt, a ferric salt and water; mixing the first solution with a precipitator under the stirring condition to obtain a first mixed system containing a nano magnetic material, and then mixing the first mixed system with a metal antioxidant for reaction to obtain a second mixed system; and mixing the second mixed system with a lipophilic surfactant for reaction, adding a grease antioxidant for reaction to obtain a third mixed system, washing and performing solid-liquid separation, collecting solid matters and drying. The invention takes the nano magnetic material as the core of the adsorbent, and ensures that the magnetic adsorbent keeps the magnetic performance not to be reduced by surface anti-oxidation and anti-agglomeration coating and then carrying out oleophylic functional group coating, so that the magnetic iron oxide magnetic material has the performance of adsorbing oil particles.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a magnetic adsorbent, a preparation method thereof and a treatment method of oily sewage.
Background
The magnetic adsorbent is a functional material which has magnetism and can adsorb various fine particles. The magnetic adsorbent is in a nanometer level, and has the characteristics of surface effect, small-size effect, macroscopic quantum tunneling effect, volume effect, superparamagnetism, high magnetic susceptibility and the like. The research and application of the magnetic adsorbent are expanded from the original chemical material field to a plurality of fields of water treatment, medicine, biochemistry, microelectronics, automatic control, optics and the like, a multi-discipline cross cooperation and common development situation is formed, and new properties and new performances of the magnetic adsorbent are continuously developed.
The discharge amount of oily sewage generated in the production of enterprises and the life of people is getting larger and larger, and how to efficiently treat the oily sewage becomes a problem to be faced by various urban sewage treatment plants.
At present, the treatment mode of oily sewage mainly comprises the following steps: 1) The physical mode is as follows: the method mainly comprises a gravity separation method, a centrifugal separation method, a coarse granulation method, a filtration method and a membrane separation filtration method, and has the advantages of mature technology, low cost, high efficiency, stable operation and the like, and has the defects of large occupied area, long treatment time, high initial investment, high maintenance cost and the like; 2) The physical and chemical modes are as follows: the method mainly comprises an air floatation method, an adsorption method, an electrochemical method and an ultrasonic method, and has the advantages of mature process, simple operation and good effect. The disadvantages are large occupied area, more consumed medicine and scum after separation; 3) The chemical mode is as follows: mainly comprises a chemical demulsification method and a chemical oxidation method, and has the advantages of high removal rate, simple equipment, easy operation and the like. It has the disadvantages of large dosage, easy secondary pollution, slow separation speed, large occupied area and the like; 4) A biochemical method: its advantages are high treating effect, no secondary pollution, low cost, and high temp.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic adsorbent, which takes a nano magnetic material as an adsorbent core, and ensures that the magnetic adsorbent keeps the magnetic property and has the property of adsorbing oil particles at the same time by surface anti-oxidation treatment and oleophylic functional group coating treatment.
The invention also aims to provide the magnetic adsorbent prepared by the preparation method of the magnetic adsorbent.
Another object of the present invention is to provide a method for treating oily sewage.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the preparation method of the magnetic adsorbent comprises the following steps:
(a) Providing a first solution of a ferrous salt, a ferric salt and water; mixing the first solution with a precipitator under the stirring condition to obtain a first mixed system containing a nano magnetic material;
(b) Mixing the first mixed system with a metal antioxidant and reacting to obtain a second mixed system; mixing the second mixed system with a lipophilic surfactant for reaction, adding a grease antioxidant for reaction to obtain a third mixed system;
(c) And washing and solid-liquid separation are carried out on the third mixed system, and solids are collected and dried.
In one embodiment, the ferric salt comprises FeCl 3 ·6H 2 O。
In one embodiment, the ferrous salt comprises (HN) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O。
In one embodiment, the metal antioxidant comprises at least one of polyacrylic acid, polymethacrylic acid, sodium gluconate, and sodium tartrate.
In one embodiment, the lipophilic surfactant comprises at least one of oleic acid, sorbitan trioleate, sorbitan tristearate and ethylene glycol distearate.
In one embodiment, the oil antioxidant comprises at least one of N-phenylacetyl-L-glutamine, dilauryl thiodipropionate, 2, 6-di-tert-butyl-4-methylphenol, and tert-butyl-4-hydroxyanisole.
In one embodiment, the precipitation agent comprises an aqueous ammonia solution.
In one embodiment, in step (a), the ferrous salt, the ferric salt and the water are used in a ratio of (50 to 70) g: (65-95) g: (120-180) mL.
In one embodiment, in step (a), the ferrous salt, the ferric salt and the precipitating agent are used in a ratio of (50 to 70) g: (65-95) g: (100-150) mL.
In one embodiment, the weight ratio of the ferrous salt, the ferric salt, the metal antioxidant, the lipophilic surfactant and the grease antioxidant is (50-70): (65-95): (0.5-2): (8-25): (0.7-1.5).
In one embodiment, in step (a), nitrogen is sparged into the first solution.
In one embodiment, in step (a), the first solution is mixed with a precipitating agent, specifically comprising: adding the first solution to the precipitant.
In one embodiment, in step (a), the rotation speed of the stirring is 250 to 350r/min.
In one embodiment, in step (b), the first mixed system is mixed with a metal antioxidant and reacted, specifically comprising: and (3) heating the temperature of the first mixed system to 80-90 ℃, stirring for 3-6 min, adding the metal antioxidant, and stirring for 3-6 min.
In one embodiment, in step (b), the second mixing system is mixed with a lipophilic surfactant and reacted, specifically comprising: and adding the lipophilic surfactant into the second mixed system for 5-6 times within three minutes.
In one embodiment, the second mixed system is mixed with the lipophilic surfactant and reacted for a reaction time of 25 to 35min.
In one embodiment, in step (b), the protective gas is continuously introduced during each reaction.
In one embodiment, in step (b), the adding of the grease antioxidant and the reaction are carried out, and specifically the method comprises the following steps: adding the alcoholic solution of the grease antioxidant for 3 to 4 times, and reacting for 4 to 6min.
In one embodiment, the number of washes is 5 to 7.
In one embodiment, the temperature of the drying is 35 to 45 ℃, and the time of the drying is 10 to 13 hours.
The magnetic adsorbent is prepared by the preparation method of the magnetic adsorbent.
In one embodiment, the magnetic adsorbent has a particle size in the range of 10 to 40nm.
The treatment method of the oily sewage comprises the following steps:
heating oily sewage, adding a magnetic adsorbent under the stirring condition, and then adding a coagulant aid solution and a flocculant solution to obtain a mixed system A; adding the mixed system A into a separation device for oil removal, wherein an electromagnet is arranged at the bottom of the separation device;
the magnetic adsorbent is the magnetic adsorbent.
In one embodiment, the heating temperature is 75 to 85 ℃.
In one embodiment, the amount ratio of the oily wastewater, the magnetic adsorbent, the coagulant aid solution and the flocculant solution is (900 to 1100) mL: (12-16) g: (45-55) mL: (45-55) mL; in the coagulant aid solution, the concentration of the coagulant aid is 0.2-0.4%, and in the flocculant solution, the concentration of the flocculant is 9-11%.
In one embodiment, the magnetic adsorbent is added to the oily water 10 to 12 times within two minutes.
In one embodiment, the rotation speed of the stirring is 300-400 r/min, and the stirring time is 25-35 min.
In one embodiment, the coagulant aid solution comprises a polyacrylamide solution; the flocculant solution comprises a polymeric ferric sulfate solution.
In one embodiment, the current of the separation device is set to 9 to 12A.
In one embodiment, the time for degreasing is 14 to 18min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the nano magnetic iron oxide magnetic material as the core of the adsorbent, and the magnetic adsorbent is prepared by carrying out surface anti-oxidation and anti-agglomeration coating, then carrying out secondary coating of oleophylic functional groups, and carrying out double-coating treatment to ensure that the magnetic property of the nano magnetic iron oxide magnetic material is not reduced, and simultaneously ensure that the magnetic iron oxide magnetic material has the property of adsorbing oil particles.
(2) The magnetic adsorbent prepared by the invention has good oil absorption capacity and high separation speed; the lattice structure of the material can reach a nearly perfect inverse spinel structure, and the saturation magnetization can be improved to the maximum extent.
(3) The method for treating the oily sewage can quickly combine with oil particles in water through the oleophylic functional groups on the surface of the magnetic adsorbent, and form directional movement under the assistance of a magnetic field and a certain amount of coagulant aids and flocculating agents, thereby finishing the function of cleaning the oil particles in the water.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an X-ray diffraction pattern of the magnetic adsorbent of example 1;
FIG. 2 is a graph showing a particle size distribution of the magnetic adsorbent in example 1;
FIG. 3 is a graph of oil removal rate for example 5;
FIG. 4 is an X-ray diffraction pattern of the magnetic adsorbent in example 2;
FIG. 5 is a graph showing a particle size distribution of the magnetic adsorbent in example 2;
FIG. 6 is a graph of oil removal rate for example 6;
FIG. 7 is an X-ray diffraction pattern of the magnetic adsorbent in example 3;
FIG. 8 is a graph showing a particle size distribution of the magnetic adsorbent in example 3;
FIG. 9 is a graph of oil removal rate of example 7;
FIG. 10 is an X-ray diffraction pattern of the magnetic adsorbent of example 4;
FIG. 11 is a graph showing a particle size distribution of the magnetic adsorbent in example 4;
FIG. 12 is a graph of oil removal rate of example 8;
FIG. 13 is a photograph of the magnetic adsorbent in example 1;
fig. 14 is a graph of oil removal rate in comparative example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
According to one aspect of the invention, the invention relates to a method for preparing a magnetic adsorbent, comprising the steps of:
(a) Providing a first solution of a ferrous salt, a ferric salt and water; mixing the first solution with a precipitator under the stirring condition to obtain a first mixed system containing a nano magnetic material;
(b) Mixing the first mixed system with a metal antioxidant and reacting to obtain a second mixed system; mixing the second mixed system with a lipophilic surfactant for reaction, adding a grease antioxidant for reaction to obtain a third mixed system;
(c) And washing and solid-liquid separation are carried out on the third mixed system, and solids are collected and dried.
The invention adopts inorganic metal salt flux to prepare the nano magnetic iron oxide magnetic material under the action of a precipitator, modifies the crystal shape and structure of the nano magnetic material, improves the saturation magnetization intensity of the nano magnetic material, adds an antioxidant to protect the structure of the nano magnetic material from being damaged, adds a lipophilic surfactant to modify and transform the surface of the nano magnetic material again, implants a lipophilic functional group into the surface of the nano magnetic material, and ensures that the nano magnetic material has lipophilic property.
Iron salts include FeCl 3 ·6H 2 O。
In one embodiment, the ferrous salt comprises (HN) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O。
In one embodiment, the metal antioxidant comprises one or a combination of polyacrylic acid, polymethacrylic acid, sodium gluconate and sodium tartrate.
In one embodiment, the lipophilic surfactant comprises a combination of one or more of oleic acid, sorbitan trioleate, sorbitan tristearate and ethylene glycol distearate.
In one embodiment, the grease antioxidant comprises one or more of N-phenylacetyl-L-glutamine, dilauryl thiodipropionate, 2, 6-di-tert-butyl-4-methylphenol, and tert-butyl-4-hydroxyanisole.
In one embodiment, the precipitation agent comprises an aqueous ammonia solution.
In one embodiment, in step (a), the ferrous salt, ferric salt and water are used in a ratio of (50 to 70) g: (65-95) g: (120-180) mL. For example 50.
In one embodiment, in step (a), the ferrous salt, the ferric salt and the precipitant are used in a ratio of (50 to 70) g: (65-95) g: (100-150) mL. For example 50.
In one embodiment, the weight ratio of the ferrous salt, the ferric salt, the metal antioxidant, the lipophilic surfactant and the grease antioxidant is (50-70): (65-95): (0.5-2): (8-25): (0.7-1.5).
In one embodiment, in step (a), nitrogen is sparged into the first solution.
In one embodiment, in step (a), the first solution is mixed with a precipitating agent, specifically comprising: adding the first solution to the precipitant.
In one embodiment, in step (a), the rotation speed of the stirring is 250 to 350r/min. The stirring speed includes but is not limited to 250r/min, 260r/min, 270r/min, 280r/min, 290r/min, 300r/min, 330r/min or 350r/min. By adopting proper stirring speed, the uniform and stable nano magnetic material can be obtained.
In one embodiment, in step (b), the first mixed system is mixed with a metal antioxidant and reacted, specifically comprising: and (3) raising the temperature of the first mixed system to 80-90 ℃, stirring for 3-6 min, adding the metal antioxidant, and stirring for 3-6 min. The invention is favorable for the reaction by adopting proper temperature, and the antioxidant is added at one time, so that the antioxidant can be better coated on the surface of the nano magnetic material, the lattice structure of the magnetic iron oxide magnetic material can be protected to be kept complete for a long time, the magnetic iron oxide magnetic material is not easily oxidized by the oxidant in the environment, and the saturation magnetization of the magnetic adsorbent can be kept not to be reduced for a long time. In one embodiment, the temperature of the first mixed system is raised to 80 ℃, 82 ℃, 85 ℃ or 88 ℃.
In one embodiment, in step (b), the second mixed system is mixed with a lipophilic surfactant and reacted, specifically comprising: adding the lipophilic surfactant to the second mixed system in 5-6 times within three minutes. Through adding the lipophilic surfactant for multiple times, the implantation of the lipophilic functional group on the surface of the nano magnetic material is better realized. Under the action of the oleophylic functional group, the magnetic adsorbent can form a stable chemical bond with the oil particles, so that the molecular force between the magnetic adsorbent and the oil particles is firmer and is not easy to separate. Thus, oil particles in water can be captured by the magnetic adsorbent and can be rapidly separated under the action of a magnetic field.
In one embodiment, the second mixed system is mixed with the lipophilic surfactant and reacted for a reaction time of 25 to 35min. For example 26min, 30min, 33min or 35min.
In one embodiment, the protective gas is continuously introduced during each reaction in step (b). And continuously introducing nitrogen for atmosphere protection in the reaction process.
In one embodiment, in step (b), the adding of the grease antioxidant and the reaction are carried out, and the method specifically comprises the following steps: adding the alcoholic solution of the grease antioxidant for 3 to 4 times, and reacting for 4 to 6min. For example 4.5min, 5min, 5.5min or 6min.
In one embodiment, the number of washes is 5 to 7. For example 5, 6 or 7 times.
In one embodiment, the drying temperature is 35 to 45 ℃, and the drying time is 10 to 13 hours.
In one embodiment, the raw materials of the precipitant, the oleic acid and the like are analytically pure.
According to another aspect of the invention, the invention also relates to the magnetic adsorbent prepared by the preparation method of the magnetic adsorbent.
The size of the core magnetic iron oxide magnetic material of the magnetic adsorbent can reach 10-40nm, the crystal lattice structure can reach an approximately perfect inverse spinel structure, and the saturation magnetization of the magnetic adsorbent can be improved to the maximum extent. The magnetic iron oxide magnetic material is coated and protected by the antioxidant, so that the lattice structure of the magnetic iron oxide magnetic material can be kept complete for a long time, the magnetic iron oxide magnetic material is not easily oxidized by the oxidant in the environment, and the saturation magnetization of the magnetic adsorbent can be kept not to be reduced for a long time. The magnetic iron oxide magnetic material is subjected to secondary coating modification by the oleophylic surfactant, and the outer surface of the magnetic iron oxide magnetic material is implanted with an oleophylic functional group to form a core-shell structure. The core is magnetic iron oxide magnetic material with lipophilic functional group as the outer shell. Under the action of the oleophylic functional group, the magnetic adsorbent can form a stable chemical bond with the oil particles, so that the molecular force between the magnetic adsorbent and the oil particles is firmer and is not easy to separate.
In one embodiment, the method for treating trivalent oily sewage comprises the following steps:
heating the oily sewage, adding a magnetic adsorbent under the stirring condition, and then adding a coagulant aid and a flocculating agent to obtain a mixed system A; adding the mixed system A into a separation device for oil removal, wherein an electromagnet is arranged at the bottom of the separation device; the magnetic adsorbent is the magnetic adsorbent.
According to the method for treating the oily sewage, oil particles in the water can be captured by the magnetic adsorbent, and are quickly separated under the action of a magnetic field through the auxiliary action of a certain amount of coagulant aid and flocculant; the oil in the sewage can be efficiently removed, and the removal rate is more than 91%; meanwhile, the scheme is simple to operate, long in storage period and easy for industrial production.
In one embodiment, the heating temperature is 75 to 85 ℃. For example, 76 ℃, 80 ℃, 83 ℃ and the like.
In one embodiment, the amount ratio of the oily wastewater, the magnetic adsorbent, the coagulant aid and the flocculant is (900-1100) mL: (12-16) g: (45-55) mL: (45-55) mL; in the coagulant aid solution, the concentration of the coagulant aid is 0.2-0.4 percent, such as 0.25 percent, 0.3 percent, 0.35 percent and the like; in the flocculant solution, the concentration of the flocculant is 9% to 11%, for example, 9.5%, 10%, 10.5%, etc.
In one embodiment, the wastewater contains oil in an amount greater than 100mg/L, such as 100 to 130mg/L, for example 106.7mg/L, 110mg/L, 115mg/L, 125mg/L, and the like.
In one embodiment, the magnetic adsorbent is added to the oily water 10 to 12 times within two minutes. For example 10 times, 11 times or 12 times. The magnetic adsorbent is added in batches for multiple times, so that the adsorption of the oil in the sewage is facilitated.
In one embodiment, the rotation speed of the stirring is 300-400 r/min, and the stirring time is 25-35 min. In one embodiment, the rotational speed of the agitation includes, but is not limited to, 300r/min, 310r/min, 330r/min, 350r/min, 370r/min, 390r/min, or 400r/min. The stirring time includes, but is not limited to, 25min, 26min, 27min, 28min, 30min, 32min, 34min, and the like. By adopting proper stirring speed and time, the magnetic adsorbent can better adsorb the oil in the sewage.
In one embodiment, the separation device has a ratio of length, width and height of (45-55): (25-35): (8-15). In one embodiment, the ratio of the length, width and height of the separation device includes, but is not limited to, 45.
In one embodiment, the coagulant aid comprises polyacrylamide; the flocculant comprises polymeric ferric sulfate.
In one embodiment, the current of the separation device is set to 9 to 12A. Such as 10A, 11A, etc.
In one embodiment, the time for degreasing is 14 to 18min. In one embodiment, the time for degreasing includes, but is not limited to, 15min, 16min, or 17min.
The following is further illustrated with reference to specific examples.
Example 1
The preparation method of the magnetic adsorbent comprises the following steps:
the formula is as follows: 60.0g (HN) 4 ) 2 Fe(SO 4 ) 2 ·eH 2 O；80.0g FeCl 3 ·6H 2 O;120mL of ammonia water; 1.2mL of polyacrylic acid; 12mL of oleic acid; 1.0g of tert-butyl-4-hydroxyanisole;
(1) 60.0g (HN) are weighed out separately 4 ) 2 Fe(SO 4 ) 2 ·eH 2 O and 80.0g FeCl 3 ·6H 2 O, dissolved in 150mL of deionized water in 250mL beakers, and purged with nitrogen. Then 120mL of ammonia are weighed out and poured into a 500mL three-necked flask, and (HN) 4 ) 2 Fe(SO 4 ) 2 ·eH 2 O solution and FeCl 3 ·6H 2 And mixing the O solution in a 500mL beaker, immediately and quickly adding the O solution into a three-necked bottle at one time under the condition of about 300 revolutions/min, heating to 80 ℃, stirring for 5min, adding 1.2mL of polyacrylic acid at one time, and stirring for 5min. Adding 12mL of oleic acid into the mixture for 5 times within three minutes, keeping the reaction at a constant temperature for 30 minutes (nitrogen is continuously introduced in the reaction process for atmosphere protection), dissolving 1.0g of tert-butyl-4-hydroxyanisole into 20mL of ethanol, adding the ethanol solution of tert-butyl-4-hydroxyanisole into the mixture for 3 times within one minute, and reacting for 5 minutes to obtain black suspension. And after the reaction is finished, washing the black powder with deionized water for 5 times, finally filtering the black powder by using a reduced pressure filtering device, and drying the black powder for 12 hours at 40 ℃ by using a vacuum oven to obtain magnetic powder with the final particle size range of 10-35nm to obtain the magnetic adsorbent.
The X-ray diffraction pattern of the magnetic adsorbent in the present example is shown in FIG. 1;
the particle size distribution of the magnetic adsorbent in this example is shown in fig. 2.
A picture of the magnetic adsorbent is shown in fig. 13.
Example 2
The preparation method of the magnetic adsorbent comprises the following steps:
the formula is as follows: 70.0g (HN) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O；93.0g FeCl 3 ·6H 2 O;140mL of ammonia water; 1.5mL of polymethacrylic acid; 23mL of sorbitan trioleate; 1.3g of 2, 6-di-tert-butyl-4-methylphenol;
(1) Weighing 70.0g (HN) respectively 4 ) 2 Fe(SO 4 ) 2 ·eH 2 O and 93.0g FeCl 3 ·6H 2 O, dissolved in 150mL of deionized water in 250mL beakers, and purged with nitrogen. Then, 140mL of ammonia water was weighed and poured into a 500mL three-necked flask, and the mixture was poured into a flask (HN) 4 ) 2 Fe(SO 4 ) 2 ·eH 2 O solution and FeCl 3 ·6H 2 And mixing the O solution in a 500mL beaker, immediately and quickly adding the O solution into a three-necked bottle at one time under the condition of about 300 revolutions/min, heating to 80 ℃, stirring for 5min, adding 1.5mL of polymethacrylic acid (metal antioxidant) at one time, and stirring for 5min. Adding 23mL of sorbitan trioleate into the mixture 5 times within three minutes, continuously reacting for 30 minutes at constant temperature (nitrogen is continuously introduced into the reaction process for atmosphere protection), dissolving 1.3g of 2, 6-di-tert-butyl-4-methylphenol into 30mL of ethanol, adding the 2, 6-di-tert-butyl-4-methylphenol ethanol solution into the mixture 3 times within one minute, and reacting for 5 minutes to obtain black suspension. And washing the mixture for 5 times by using deionized water after the reaction is finished, finally filtering the mixture by using a reduced pressure filtering device, and drying the obtained black powder for 12 hours at 40 ℃ by using a vacuum oven to obtain magnetic powder with the final particle size range of 10-37 nm to obtain the magnetic adsorbent.
The X-ray diffraction pattern of the magnetic adsorbent in this example is shown in fig. 4;
the particle size distribution of the magnetic adsorbent in this example is shown in fig. 5.
Example 3
The preparation method of the magnetic adsorbent comprises the following steps:
the formula is as follows: 50.0g (HN) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O；67.0g FeCl 3 ·6H 2 O;105mL of ammonia water; 0.8g of sodium gluconate; 9g of sorbitan tristearate; 0.8g of dilauryl thiodipropionate.
(1) Weighing 50.0g (HN) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O and 67.0gFeCl 3 ·6H 2 O, dissolved in 150mL of deionized water in 250mL beakers, and purged with nitrogen. Then, 105mL of ammonia (precipitant) was added to a 500mL three-necked flask 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O solution and FeCl 3 ·6H 2 And mixing the O solution in a 500mL beaker, immediately and quickly adding the O solution into a three-necked bottle at one time under the condition of about 300 revolutions/min, heating to 80 ℃, stirring for 5min, adding 0.8g of sodium gluconate (metal antioxidant) at one time, and stirring for 5min. 9g of sorbitan tristearate (surfactant) is added into the mixture for 4 times within three minutes, the mixture is continuously reacted for 30 minutes at a constant temperature (nitrogen is continuously introduced into the mixture for atmosphere protection in the reaction process), 0.8g of dilauryl thiodipropionate is added into the mixture for 3 times within one minute, and the black suspension is obtained after the reaction is carried out for 5 minutes. And after the reaction is finished, washing the black powder with deionized water for 5 times, finally filtering the black powder by using a reduced pressure filtering device, and drying the black powder for 12 hours at 40 ℃ by using a vacuum oven to obtain the magnetic powder with the final particle size range of 10-40nm, thereby obtaining the magnetic adsorbent.
The X-ray diffraction pattern of the magnetic adsorbent in this example is shown in fig. 7;
the particle size distribution of the magnetic adsorbent in this example is shown in fig. 8.
Example 4
The preparation method of the magnetic adsorbent comprises the following steps:
the formula is as follows: 55.0g (HN) 4 ) 2 Fe(SO 4 ) 2 ·eH 2 O；75.0g FeCl 3 ·6H 2 O;115mL of ammonia water; 0.7g sodium tartrate; 10g of ethylene glycol distearate; 1.1g of N-phenylacetyl-L-glutamine;
(1) Separately, 55.0g (HN) 4 ) 2 Fe(SO 4 ) 2 ·eH 2 O and 75.0gFeCl 3 ·6H 2 O, dissolved in 150mL of deionized water in 250mL beakers, and purged with nitrogen. Then, 115mL of ammonia water was weighed and poured into a 500mL three-necked flask, and the mixture was poured into a flask (HN) 4 )
2 Fe(SO 4 ) 2 ·eH 2 O solution and FeCl 3 ·6H 2 And mixing the O solution in a 500mL beaker, immediately and quickly adding the O solution into a three-necked bottle at one time under the condition of about 300 revolutions/min, heating to 80 ℃, stirring for 5min, adding 0.7g of sodium tartrate at one time, and stirring for 5min. Adding 10g of ethylene glycol distearate into the mixture for 4 times within three minutes, reacting for 30 minutes at constant temperature (nitrogen is continuously introduced into the reaction process for atmosphere protection), adding 1.1g of N-phenylacetyl-L-glutamine into the mixture for 3 times within one minute, and reacting for 5 minutes to obtain a black suspension. And after the reaction is finished, washing the black powder with deionized water for 5 times, finally filtering the black powder by using a reduced pressure filtering device, and drying the black powder for 12 hours at 40 ℃ by using a vacuum oven to obtain the magnetic powder with the final particle size range of 10-40nm, thereby obtaining the magnetic adsorbent.
The X-ray diffraction pattern of the magnetic adsorbent in the present example is shown in fig. 10;
the particle size distribution of the magnetic adsorbent in this example is shown in fig. 11.
Example 5
The treatment method of the oily sewage comprises the following steps:
1000mL of simulated sewage containing 106.7mg/L of oil was placed in a 2L beaker, heated to 80 ℃ and 15g of the magnetic adsorbent prepared in example 1 was pulverized and added to the oily sewage 11 times in two minutes at 350 rpm, and stirred for 30 minutes. Cooling to room temperature, slowly adding 50mL each of 0.3% polyacrylamide aqueous solution and 10% polyferric sulfate aqueous solution into the oily sewage within two minutes under the condition of stirring, stirring for 10 minutes, then adding into a separation tank with the length of 50cm, the width of 30cm and the height of 10cm, wherein the bottom of the separation tank is provided with an electromagnet, a magnetic field can be fully distributed in the separation tank, the current is set to be 10A, and after 15 minutes of precipitation, separating the sewage. The oil content of the treated oily sewage is 7.469mg/L and the removal rate is 93.00 percent by using an infrared oil tester.
The oil removal rate map of the present example is shown in fig. 3.
Example 6
The treatment method of the oily sewage comprises the following steps:
1000mL of simulated sewage containing 106.7mg/L of oil was placed in a 2L beaker, heated to 80 ℃ and 15g of the magnetic adsorbent prepared in example 2 was pulverized and added to the simulated sewage at 350 rpm for 11 times in two minutes, and stirred for 30 minutes. Cooling to room temperature, taking 50mL of each of 0.3% polyacrylamide aqueous solution and 10% polyferric sulfate aqueous solution, slowly adding the aqueous solution and the 10% polyferric sulfate aqueous solution into the oily sewage within two minutes under the condition of stirring, stirring for 10 minutes, then adding the aqueous solution and the 10% polyferric sulfate aqueous solution into a separation tank with the length of 50cm, the width of 30cm and the height of 10cm, wherein the bottom of the separation tank is provided with an electromagnet, a magnetic field can be fully distributed in the separation tank, the current is set to be 10A, and after 15 minutes of precipitation, the sewage is separated. The oil content of the treated oily sewage is 7.853mg/L and the removal rate is 92.64 percent by using an infrared oil tester.
The oil removal rate chart of this example is shown in fig. 6.
Example 7
The treatment method of the oily sewage comprises the following steps:
1000mL of simulated sewage containing 106.7mg/L of oil was placed in a 2L beaker, heated to 80 ℃ and 15g of the magnetic adsorbent prepared in example 3 was pulverized and added to the oily sewage 11 times in two minutes at about 350 rpm, and stirred for 30 minutes. Cooling to room temperature, taking 50mL of each of 0.3% polyacrylamide aqueous solution and 10% polyferric sulfate aqueous solution, slowly adding the aqueous solution and the 10% polyferric sulfate aqueous solution into the oily sewage within two minutes under the condition of stirring, stirring for 10 minutes, then adding the aqueous solution and the oily sewage into a separation tank with the length of 50cm, the width of 30cm and the height of 10cm, arranging electromagnets at the bottom of the separation tank, distributing magnetic fields in the separation tank, setting the current to be 10A, and precipitating for 15 minutes to separate the sewage. The oil content of the treated oily sewage is detected to be 8.359mg/L by an infrared oil tester, and the removal rate is 92.17 percent.
The oil removal rate chart of this example is shown in fig. 9.
Example 8
The treatment method of the oily sewage comprises the following steps:
1000mL of simulated sewage containing 106.7mg/L of oil was placed in a 2L beaker, heated to 80 ℃ and 15g of the magnetic adsorbent prepared in example 1 was ground into powder, added to the oil-containing sewage in 11 portions in two minutes at 350 rpm, and stirred for 30 minutes. Cooling to room temperature.
And (2) slowly adding 50mL of each of 0.3% polyacrylamide aqueous solution and 10% polyferric sulfate aqueous solution into the oily sewage within two minutes under the condition of stirring, stirring for 10 minutes, then adding into a separation tank with the length of 50cm, the width of 30cm and the height of 10cm, wherein the bottom of the separation tank is provided with an electromagnet, a magnetic field can be fully distributed in the separation tank, the current is set to be 10A, and after 15 minutes of precipitation, separating the sewage. The oil content of the treated oily sewage is 9.286mg/L and the removal rate is 91.30 percent by using an infrared oil tester. The oil removal rate map of this example is shown in fig. 12.
Comparative example 1
The treatment method of the oily sewage comprises the following steps:
1000mL of simulated sewage containing 106.7mg/L oil was placed in a 2L beaker. And (2) slowly adding 50mL of each of 0.3% polyacrylamide aqueous solution and 10% polyferric sulfate aqueous solution into the oily sewage within two minutes under the condition of stirring, stirring for 10 minutes, then adding into a separation tank with the length of 50cm, the width of 30cm and the height of 10cm, arranging electromagnets at the bottom of the separation tank, fully distributing a magnetic field in the separation tank, setting the current to be 10A, and separating the sewage after 15 minutes of precipitation. The oil removing rate of the present comparative example is shown in fig. 14.
Therefore, the magnetic adsorption material prepared by the specific method has the characteristics of high oil absorption capacity, high separation speed, low environmental pollution and the like. Oil particles in water can be captured by the magnetic adsorbent, and are rapidly separated under the action of a magnetic field through the auxiliary action of a certain amount of coagulant aid and flocculant; the removal rate is more than 91%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the magnetic adsorbent is characterized by comprising the following steps:
(a) Providing a first solution of a ferrous salt, a ferric salt and water; mixing the first solution with a precipitator under the stirring condition to obtain a first mixed system containing a nano magnetic material;
(b) Mixing the first mixed system with a metal antioxidant and reacting to obtain a second mixed system; mixing the second mixed system with a lipophilic surfactant for reaction, adding a grease antioxidant for reaction, and obtaining a third mixed system;
(c) And washing and solid-liquid separation are carried out on the third mixed system, and solids are collected and dried.
2. The method for producing a magnetic adsorbent according to claim 1, characterized by comprising at least one of the following features (1) to (6):
(1) The ferric salt comprises FeCl 3 ·6H 2 O；
(2) The ferrous salt comprises (HN) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O；
(3) The metal antioxidant comprises at least one of polyacrylic acid, polymethacrylic acid, sodium gluconate and sodium tartrate;
(4) The lipophilic surfactant comprises at least one of oleic acid, sorbitan trioleate, sorbitan tristearate and ethylene glycol distearate;
(5) The grease antioxidant comprises at least one of N-phenylacetyl-L-glutamine, dilauryl thiodipropionate, 2, 6-di-tert-butyl-4-methylphenol and tert-butyl-4-hydroxyanisole;
(6) The precipitant comprises an aqueous ammonia solution.
3. The method for producing a magnetic adsorbent according to claim 1 or 2, characterized by comprising at least one of the following features (1) to (3):
(1) In the step (a), the dosage ratio of the ferrous salt to the ferric salt to the water is (50-70) g: (65-95) g: (120-180) mL;
(2) In the step (a), the dosage ratio of the ferrous salt to the ferric salt to the precipitating agent is (50-70) g: (65-95) g: (100-150) mL;
(3) The weight ratio of the ferrous salt to the ferric salt to the metal antioxidant to the lipophilic surfactant to the grease antioxidant is (50-70): (65-95): (0.5-2): (8-25): (0.7-1.5).
4. The method for producing a magnetic adsorbent according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) In step (a), introducing nitrogen into the first solution;
(2) In step (a), mixing the first solution with a precipitant, specifically comprising: adding the first solution to the precipitant;
(3) In the step (a), the rotating speed of the stirring is 250-350 r/min.
5. The method for producing a magnetic adsorbent according to claim 1, characterized by comprising at least one of the following features (1) to (5):
(1) In the step (b), the first mixed system and the metal antioxidant are mixed and react, and the method specifically comprises the following steps: heating the temperature of the first mixed system to 80-90 ℃, stirring for 3-6 min, adding the metal antioxidant, and stirring for 3-6 min;
(2) In the step (b), the second mixed system is mixed with the lipophilic surfactant and reacts, and the method specifically comprises the following steps: adding the lipophilic surfactant into the second mixed system for 5-6 times within three minutes;
(3) The second mixed system is mixed with the lipophilic surfactant and reacts for 25-35 min;
(4) In the step (b), continuously introducing protective gas in the process of each reaction;
(5) In the step (b), adding a grease antioxidant and reacting, wherein the reaction specifically comprises: adding the alcoholic solution of the grease antioxidant for 3-4 times, and reacting for 4-6 min.
6. The method for producing a magnetic adsorbent according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The washing times are 5-7 times;
(2) The drying temperature is 35-45 ℃, and the drying time is 10-13 h.
7. The magnetic adsorbent produced by the method for producing a magnetic adsorbent according to any one of claims 1 to 6.
8. The magnetic adsorbent of claim 7, wherein the magnetic adsorbent has a particle size in a range of 10 to 40nm.
9. The method for treating the oily sewage is characterized by comprising the following steps of:
heating oily sewage, adding a magnetic adsorbent under the stirring condition, and then adding a coagulant aid solution and a flocculant solution to obtain a mixed system A; adding the mixed system A into a separation device for oil removal, wherein an electromagnet is arranged at the bottom of the separation device;
the magnetic adsorbent is the magnetic adsorbent according to claim 7 or 8.
10. The method for treating oily sewage according to claim 9, characterized by comprising at least one of the following features (1) to (7):
(1) The heating temperature is 75-85 ℃;
(2) The dosage ratio of the oily sewage, the magnetic adsorbent, the coagulant aid solution and the flocculant solution is (900-1100) mL: (12-16) g: (45-55) mL: (45-55) mL; in the coagulant aid solution, the concentration of the coagulant aid is 0.2-0.4%, and in the flocculant solution, the concentration of the flocculant is 9-11%;
(3) Adding the magnetic adsorbent into the oily sewage 10-12 times within two minutes;
(4) The stirring speed is 300-400 r/min, and the stirring time is 25-35 min;
(5) The coagulant aid solution comprises a polyacrylamide solution; the flocculant solution comprises a polymeric ferric sulfate solution;
(6) The current of the separation device is set to be 9-12A;
(7) The oil removing time is 14-18 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211522663.0A CN115779859A (en) | 2022-11-30 | 2022-11-30 | Magnetic adsorbent, preparation method thereof and treatment method of oily sewage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211522663.0A CN115779859A (en) | 2022-11-30 | 2022-11-30 | Magnetic adsorbent, preparation method thereof and treatment method of oily sewage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115779859A true CN115779859A (en) | 2023-03-14 |
Family
ID=85443918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211522663.0A Pending CN115779859A (en) | 2022-11-30 | 2022-11-30 | Magnetic adsorbent, preparation method thereof and treatment method of oily sewage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115779859A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664841A (en) * | 1981-02-27 | 1987-05-12 | Ricoh Co., Ltd. | Fine particle substance-containing non-aqueous dispersions |
| US5236783A (en) * | 1990-02-21 | 1993-08-17 | Toda Kogyo Corp. | Superparamagnetic fine particles of iron oxide and magnetic recording media containing said particles |
| JPH11294598A (en) * | 1998-04-09 | 1999-10-29 | Nittetsu Mining Co Ltd | Magnetic fluid seal |
| US20130084385A1 (en) * | 2010-06-13 | 2013-04-04 | Mingjie Zhou | Method for producing core-shell magnetic alloy nanoparticle |
| CN103050211A (en) * | 2012-12-31 | 2013-04-17 | 江苏理工学院 | Organic magnetic composite material and preparing method thereof |
| CN103977764A (en) * | 2014-05-27 | 2014-08-13 | 哈尔滨工业大学 | Method for preparing magnetic oil absorbing microsphere with emulsion method |
| CN105017666A (en) * | 2014-04-30 | 2015-11-04 | 上海楚堰实业有限公司 | Magnetic material and preparation method thereof |
| CN105061885A (en) * | 2015-07-13 | 2015-11-18 | 安徽成方新材料科技有限公司 | Oil-absorbing composite with magnetic adsorption function and preparation method thereof |
| CN108421533A (en) * | 2018-03-22 | 2018-08-21 | 清华大学 | A kind of magnetic nanoparticle of surface modification, preparation method, application and regeneration method |
| CN109772264A (en) * | 2019-02-20 | 2019-05-21 | 谭祖陆 | A kind of preparation method of flue gas desulfurization activated coke |
| CN110828094A (en) * | 2019-11-13 | 2020-02-21 | 黑龙江省科学院高技术研究院 | Preparation method of magnetic fluid for high-magnetic-sedimentation-resistance sealing under strong magnetic field condition |
| CN112142155A (en) * | 2020-09-22 | 2020-12-29 | 成都新柯力化工科技有限公司 | Magnetic porous foam material for wastewater purification and preparation method thereof |
-
2022
- 2022-11-30 CN CN202211522663.0A patent/CN115779859A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664841A (en) * | 1981-02-27 | 1987-05-12 | Ricoh Co., Ltd. | Fine particle substance-containing non-aqueous dispersions |
| US5236783A (en) * | 1990-02-21 | 1993-08-17 | Toda Kogyo Corp. | Superparamagnetic fine particles of iron oxide and magnetic recording media containing said particles |
| JPH11294598A (en) * | 1998-04-09 | 1999-10-29 | Nittetsu Mining Co Ltd | Magnetic fluid seal |
| US20130084385A1 (en) * | 2010-06-13 | 2013-04-04 | Mingjie Zhou | Method for producing core-shell magnetic alloy nanoparticle |
| CN103050211A (en) * | 2012-12-31 | 2013-04-17 | 江苏理工学院 | Organic magnetic composite material and preparing method thereof |
| CN105017666A (en) * | 2014-04-30 | 2015-11-04 | 上海楚堰实业有限公司 | Magnetic material and preparation method thereof |
| CN103977764A (en) * | 2014-05-27 | 2014-08-13 | 哈尔滨工业大学 | Method for preparing magnetic oil absorbing microsphere with emulsion method |
| CN105061885A (en) * | 2015-07-13 | 2015-11-18 | 安徽成方新材料科技有限公司 | Oil-absorbing composite with magnetic adsorption function and preparation method thereof |
| CN108421533A (en) * | 2018-03-22 | 2018-08-21 | 清华大学 | A kind of magnetic nanoparticle of surface modification, preparation method, application and regeneration method |
| CN109772264A (en) * | 2019-02-20 | 2019-05-21 | 谭祖陆 | A kind of preparation method of flue gas desulfurization activated coke |
| CN110828094A (en) * | 2019-11-13 | 2020-02-21 | 黑龙江省科学院高技术研究院 | Preparation method of magnetic fluid for high-magnetic-sedimentation-resistance sealing under strong magnetic field condition |
| CN112142155A (en) * | 2020-09-22 | 2020-12-29 | 成都新柯力化工科技有限公司 | Magnetic porous foam material for wastewater purification and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 于英仪等: ""使用抗氧化剂提高氮化铁磁性液体的抗氧化稳定性"", 《粉末冶金工业》, vol. 13, no. 3, pages 3 * |
| 姜翠玉;祝威;宋浩;刘慧英;耿毅;吴鲁宁;张小波;: "包覆Fe_3O_4纳米粒子的制备及其在油田污水处理中的应用初探", 《油田化学》, no. 03, pages 328 * |
| 迟佳龙: ""基于纳米Fe3O4磁粉的油酸吸附剂制备及处理油田回注水效能"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 02, pages 590 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Duan et al. | Effective removal of Pb (II) using magnetic Co0. 6Fe2. 4O4 micro-particles as the adsorbent: Synthesis and study on the kinetic and thermodynamic behaviors for its adsorption | |
| Zhou et al. | Heavy metal removal from wastewater in fluidized bed reactor | |
| US7651973B2 (en) | Contact and adsorbent granules | |
| Tao et al. | Simultaneous removal of acid green 25 and mercury ions from aqueous solutions using glutamine modified chitosan magnetic composite microspheres | |
| WO2005102942A1 (en) | Reducing water purification material, method for producing reducing water purification material, method for treating wastewater, and wastewater treatment apparatus | |
| CN111790422A (en) | Graphitized radical nitrogen complexed Fe (III) -Fe0Catalyst and synthesis method and application thereof | |
| CN108786893B (en) | Copper-doped carbon nitrogen polymer multiphase Fenton catalyst and synthesis and application thereof | |
| CN112169748B (en) | Adsorbent and preparation method and application thereof | |
| CN111359580A (en) | Preparation method and application of carbon-iron composite material with porous structure | |
| CN101503217B (en) | Preparation and use method of dephosphorization carboxyl functionalized nano Fe2O3 adsorbing agent for wastewater | |
| CN106512971A (en) | Attapulgite-loaded zero-valent iron repair material and preparation method thereof | |
| CN113713774B (en) | Efficient and reproducible nano demanganizing agent and preparation method and application thereof | |
| JP5352853B1 (en) | Method of treating radioactive Cs contaminated water | |
| CZ304650B6 (en) | Adsorbents for removing arsenic and selenium from water | |
| CN110876917B (en) | Superparamagnetic response nano phosphorus adsorbent and preparation method thereof | |
| CN114425305B (en) | Mercury adsorption material, preparation method thereof and application thereof in flue gas or solution mercury removal | |
| CN110064357B (en) | Preparation method of efficient antimony removal adsorbent and application of efficient antimony removal adsorbent in printing and dyeing wastewater treatment | |
| Liu et al. | Three-dimensional porous aerogel-bead absorbent with high dispersibility of lanthanum active sites to boost phosphorus scavenging | |
| CN113694876B (en) | Preparation and application of nano magnetic layered double hydroxide adsorbent | |
| CN110862137A (en) | Preparation of sulfuration modified nano zero-valent iron and application of sulfuration modified nano zero-valent iron in treatment of antibiotic resistance gene | |
| CN108144592B (en) | Superparamagnetic composite nanoparticle, preparation method thereof and method for efficiently and selectively recovering phosphate | |
| CN115779847B (en) | In-situ adsorption material and preparation method and application thereof | |
| CN110614079A (en) | Preparation method and application of net-shaped magnetic graphene oxide | |
| CN112607785A (en) | MnFe2O4/C nano composite microsphere and preparation method thereof | |
| CN115779859A (en) | Magnetic adsorbent, preparation method thereof and treatment method of oily sewage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |