CN115090266A - Fluorine adsorbent, preparation method and adsorption method thereof - Google Patents
Fluorine adsorbent, preparation method and adsorption method thereof Download PDFInfo
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- CN115090266A CN115090266A CN202210702486.8A CN202210702486A CN115090266A CN 115090266 A CN115090266 A CN 115090266A CN 202210702486 A CN202210702486 A CN 202210702486A CN 115090266 A CN115090266 A CN 115090266A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000011737 fluorine Substances 0.000 title claims abstract description 102
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 102
- 239000003463 adsorbent Substances 0.000 title claims abstract description 62
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010936 titanium Substances 0.000 claims abstract description 58
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 58
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 23
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 53
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000000499 gel Substances 0.000 claims description 22
- 239000002133 porous carbon nanofiber Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000002121 nanofiber Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000003213 activating effect Effects 0.000 claims description 14
- 238000001523 electrospinning Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 229920001661 Chitosan Polymers 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 13
- 239000004917 carbon fiber Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 238000006115 defluorination reaction Methods 0.000 description 12
- 239000002134 carbon nanofiber Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a fluorine adsorbent, which consists of titanium-loaded porous nano carbon fibers and hydrophobic gel compounded on the surfaces of the porous nano carbon fibers. The application also provides a preparation method and specific application of the fluorine adsorbent. The fluorine adsorbent provided by the invention has the advantages of fluorine saturation adsorption capacity of 50mg/g, large adsorption capacity, high fluorine removal efficiency, wide pH application range and particular suitability for an acid system; meanwhile, the active adsorption sites on the surface interface of the fluorine adsorbent are uniformly distributed, and the fluorine adsorbent has strong affinity and adsorption capacity for fluorine.
Description
Technical Field
The invention relates to the technical field of green dressing and metallurgy of mineral resources, in particular to a fluorine adsorbent, and a preparation method and an adsorption method thereof.
Background
Fluorine is ubiquitous in mines and water bodies due to extremely strong electronegativity; meanwhile, the fluorine-containing industrial wastewater belongs to a secondary pollutant and has great harm to human bodies and the environment. The deep defluorination and comprehensive treatment of the fluorine-containing wastewater have important research significance for the field of green dressing and metallurgy.
During mineral mineralization, fluorine is generally introduced into the mineral lattice by replacing the hydroxyl groups at the interface; the fluorine-containing solution used in the beneficiation of aluminosilicate minerals often contains elements such as aluminum and valuable metals, and therefore, fluorine is mainly hydrogen fluoride in the leaching solutionAnd the complex fluorine acid exists in a form. The traditional chemical precipitation method can make aluminum take Al (OH) when the pH is adjusted 3 Form separation, adsorption of valuable elements and subsequent separation and recovery difficulty increase. The adsorption method has the characteristics of high selectivity and the like and is widely applied. However, the existing adsorbent mainly uses active aluminum as a carrier, and is not suitable for the environment for selecting and smelting high-aluminum and fluorine-containing solution. In addition, acidolysis is a common method for mineral resources. Therefore, the preparation of highly selective fluorine adsorbents for acid resistance is a key issue to be solved for deep defluorination.
Disclosure of Invention
The invention aims to provide a fluorine adsorbent which has strong adsorption capacity to fluorine and good cycle stability.
In view of the above, the present application provides a fluorine adsorbent, which is composed of titanium-supported porous filamentous nanocarbon and hydrophobic gel compounded on the surface of the porous filamentous nanocarbon.
Preferably, the titanium-loaded porous carbon nanofiber accounts for 0.1-10 wt% of the hydrophobic gel; the content of the porous carbon nanofibers in the titanium-loaded porous carbon nanofibers is 5-20 wt%.
The application also provides a preparation method of the fluorine adsorbent, which comprises the following steps:
mixing a titanium source and a carbon-containing polymer solution, and performing electrostatic spinning on the obtained electrospinning solution to obtain a titanium-loaded nanofiber membrane;
carbonizing and activating the titanium-loaded nanofiber film to obtain titanium-loaded porous carbon nanofibers;
and coating hydrophobic gel on the surface of the titanium-loaded porous carbon nanofiber to obtain the fluorine adsorbent.
Preferably, the polymer is selected from one or more of polyacrylonitrile, polyvinyl alcohol, polyvinylidene fluoride, chitosan, polyvinylpyrrolidone and polytetrafluoroethylene; the titanium source is selected from one or more of titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, titanium dioxide, ilmenite, vanadium titano-magnetite and rutile; in the electrospinning solution, when two polymers are selected, the content of one polymer is 5-15 wt% of the mass of the solvent, and the content of the other polymer is 0.5-15 wt% of the mass of the solvent; the content of the titanium source is 5-30 wt% of the polymer.
Preferably, the electrostatic spinning specifically comprises:
adding the obtained electrospinning solution into a spinning liquid storage device under the conditions that the temperature is 10-60 ℃ and the humidity is 20-60%, wherein the inner diameter of a spray head is 0.15-1.0 mm, the spinning distance is 10-25 cm, the spinning voltage is 10-30 kV, and the injection speed of the solution is 0.01-0.05 mL/min; spinning for 30-180 min to obtain the polymer nanofiber membrane with the fiber diameter of 100-500 nm, and drying in a vacuum drying oven at 25-80 ℃ for 6-24 h.
Preferably, the carbonization activating atmosphere is selected from one or more of nitrogen, helium and argon, the carbonization temperature is 400-1000 ℃, and the activating agent is selected from one or more of potassium hydroxide, sodium hydroxide and urea.
Preferably, the hydrophobic gel is selected from one or more of chitosan, cellulose, lignin and gelatin.
Preferably, the thickness of the hydrophobic gel is 0.01-0.1 cm.
The application also provides an adsorption method of the fluorine-containing solution, which comprises the following steps:
mixing a fluorine adsorbent and a fluorine-containing solution, and adsorbing;
the fluorine adsorbent is the fluorine adsorbent or the fluorine adsorbent prepared by the preparation method.
Preferably, the fluorine-containing solution is an acidic high-aluminum fluorine-containing solution; the adsorption time is 10 min-1 h.
The application provides a fluorine adsorbent, which consists of titanium-loaded porous nano carbon fibers and hydrophobic gel compounded on the surfaces of the porous nano carbon fibers; the porous carbon nanofibers in the fluorine adsorbent provided by the application are acid and alkali resistant, so that the fluorine adsorbent is wide in pH application range; meanwhile, the fluorine adsorbent has uniform distribution of interface active adsorption sites, strong affinity to fluorine and strong adsorption capacity; the fluorine adsorbent prepared by the invention has good cycle stability, easy adsorption-desorption cycle regeneration, small adsorbent dissolution loss in the adsorption process, simple filtration and separation, and greatly reduced operation cost.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
Aiming at the problems of low selectivity, difficult deep defluorination and the like in the existing acidic fluorine-containing wastewater treatment, the application provides an acid-resistant and selective defluorination fluorine adsorbent which is suitable for deep defluorination of a high-aluminum and fluorine-containing acid leaching solution system in leachate of an aluminosilicate mineral acidolysis process; the adsorbent provided by the application can realize selective removal of fluorine, and reduce loss of valuable elements in the defluorination process. Specifically, the embodiment of the invention discloses a fluorine adsorbent, which consists of titanium-loaded porous nano carbon fibers and hydrophobic gel compounded on the surfaces of the porous nano carbon fibers.
In the fluorine adsorbent provided by the application, the titanium-loaded porous carbon nanofiber accounts for 0.1-10 wt% of the hydrophobic gel; the content of the porous carbon nanofibers in the titanium-loaded porous carbon nanofibers is 5-20 wt%. In the present application, titanium in the titanium-supported porous filamentous nanocarbon is supported on the carbon fiber in the form of oxyhydroxide nanoparticles.
The application also provides a preparation method of the fluorine adsorbent, which comprises the following steps:
mixing a titanium source and a carbon-containing polymer solution, and performing electrostatic spinning on the obtained electrospinning solution to obtain a titanium-loaded nanofiber membrane;
carbonizing and activating the titanium-loaded nanofiber film to obtain titanium-loaded porous carbon nanofibers;
and coating hydrophobic gel on the surface of the titanium-loaded porous carbon nanofiber to obtain the fluorine adsorbent.
In the process of making the fluorine adsorbent, the present application first mixes a titanium source, in the present application, selected from one or more of titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, titanium dioxide, ilmenite, vanadium titano-magnetite, and rutile, with a carbon-containing polymer solution; the polymer is selected from one or more of polyacrylonitrile, polyvinyl alcohol, polyvinylidene fluoride, chitosan, polyvinylpyrrolidone and polytetrafluoroethylene; in particular embodiments, the titanium source is selected from titanium tetrachloride, tetrabutyl titanate, titanium dioxide, or titanium oxide, and the polymer is selected from the group consisting of a combination of polyacrylonitrile and polyvinylpyrrolidone, a combination of polyacrylonitrile and chitosan, and a combination of polyacrylonitrile and polyvinyl alcohol. In the electrospinning solution, when two polymers are selected, the content of one polymer is 5-15 wt% of the mass of the solvent, and the content of the other polymer is 0.5-15 wt% of the mass of the solvent; the content of the titanium source is 5-30 wt% of the mass of the polymer; more specifically, the content of the titanium source is 8-20 wt%, the content of one polymer is 5-10 wt%, and the content of the other polymer is 5-10 wt%. And mixing the two raw materials, fully stirring to obtain a uniformly mixed electro-deposition solution, and then carrying out electrostatic spinning to obtain the titanium-loaded nanofiber membrane. In the present application, the electrostatic spinning is specifically:
adding the obtained electrospinning solution into a spinning liquid storage device under the conditions that the temperature is 10-60 ℃ and the humidity is 20-60%, wherein the inner diameter of a spray head is 0.15-1.0 mm, the spinning distance is 10-25 cm, the spinning voltage is 10-30 kV, and the injection speed of the solution is 0.01-0.05 mL/min; spinning for 30-180 min to obtain the polymer nanofiber membrane with the fiber diameter of 100-500 nm, and drying in a vacuum drying oven at 25-80 ℃ for 6-24 h.
In the process, the carbon-containing polymer is a high-molecular conductive polymer which has better acid and alkali resistance, and can form uniform nano fibers under the action of an electric field to provide a carrier for titanium active sites. The polymer is melt-drawn under the action of an electric field to form a titanium-supported nanofiber film.
The titanium-supported nanofiber membrane is then carbonized and activated to obtain titanium-supported porous filamentous nanocarbons. In the process, the nano-fiber is carbonized to generate porous nano-carbon fiber, and meanwhile, different titanium sources generate titanium oxide to provide defluorination active sites. The carbonization activating atmosphere is selected from one or more of nitrogen, helium and argon, the carbonization temperature is 400-1000 ℃, and the activating agent is selected from one or more of potassium hydroxide, sodium hydroxide and urea. In a specific embodiment, the carbonization activating atmosphere is selected from nitrogen or argon, and the carbonization temperature is 500-900 ℃; the activating agent is selected from potassium hydroxide or urea.
According to the invention, the hydrophobic gel is coated on the surface of the titanium-loaded porous carbon nanofiber to obtain the fluorine adsorbent. After the hydrophobic gel is compounded on the surface of the titanium-loaded porous carbon nanofiber, the obtained adsorbent can stably exist in a solution and is not dispersed. The hydrophobic gel is selected from one or more of chitosan, cellulose, lignin and gelatin; more particularly, the hydrophobic gel is selected from chitosan or gelatin. The hydrophobic gel is coated in a manner of being uniformly coated on the surface of the porous carbon nanofiber in the form of a solution containing the hydrophobic gel. The mass fraction of the solution containing the hydrophobic gel is 1-2 wt%, wherein the solvent is a dilute acetic acid solution with the volume fraction of 1-5%; the thickness of the coating is 0.01-0.1 cm, and the hydrophobic gel can be obtained by drying at room temperature under the condition of controlling the humidity to be 35-70%.
The application also provides an adsorption method of the fluorine-containing solution, which comprises the following steps:
mixing a fluorine adsorbent with a fluorine-containing solution, and adsorbing;
the fluorine adsorbent is the fluorine adsorbent in the scheme.
The fluorine-containing solution provided by the application is a high-aluminum (>1g/L) solution with an acid pH value of 1-6 and a fluorine (>10mg/L) solution. The adsorption time is 10 min-1 h; the mixing temperature is 10-110 ℃, the mixing is carried out under the stirring condition, and the stirring speed is 80-250 r/min. And desorbing after the adsorption is finished, wherein in the desorption process, 0.1mol/L of sodium hydroxide is used for activation, and then 1mol/L of hydrochloric acid solution is used for desorption, the desorption time is 10-60 min, the stirring speed is 50-150 min, and the solution temperature is 10-50 ℃.
The fluorine adsorbent prepared by the invention has fluorine saturation adsorption capacity of 50mg/g, large adsorption capacity, high fluorine removal efficiency and wide pH application range, and is particularly suitable for an acid system; meanwhile, the active adsorption sites on the surface interface of the fluorine adsorbent are uniformly distributed, and the fluorine adsorbent has strong affinity and adsorption capacity for fluorine. Furthermore, the fluorine adsorbent prepared by the invention has good cycle stability, easy adsorption-desorption cycle regeneration, small adsorbent dissolution loss in the adsorption process, simple filtration and separation and greatly reduced operation cost.
For further understanding of the present invention, the following examples are given to illustrate the fluorine adsorbent, the preparation method and the application thereof, and the scope of the present invention is not limited by the following examples.
Example 1
Dissolving titanium tetrachloride (10 wt%) in a mixed solution of 10% polyacrylonitrile and 5% polyvinylpyrrolidone, fully stirring to obtain an electrospinning solution which is uniformly mixed, and preparing a titanium-loaded nanofiber film through electrostatic spinning; carbonizing the prepared film at 700 ℃ under nitrogen, and activating by adding potassium hydroxide to obtain titanium-loaded porous carbon nanofibers; uniformly coating a 2% chitosan solution on the surface of the titanium-loaded carbon fiber, and airing at the humidity of 40% to obtain the titanium-loaded carbon nanofiber composite fluorine adsorbent suitable for the acidic fluorine-containing wastewater.
0.50g of titanium-loaded carbon nanofiber fluorine adsorbent prepared in the example is added, the fluorine concentration is reduced to 8mg/L in a fluorine-containing solution with the pH value of 3 for 1h, the saturated adsorption capacity of the adsorbent to fluorine is 51.4mg/g, and the defluorination efficiency reaches 91%.
Except that the pH of the fluorine-containing solution is changed, the defluorination experiment in the specific embodiment of the invention has the following conditions: the fluorine ion concentration is 200mg/L, the fluorine-containing solution is 100mL, the stirring speed is 120r/min, and the adsorption is carried out for 1h at normal temperature.
Example 2
Dissolving 1g of tetrabutyl titanate in a mixed solution of 5% of polyacrylonitrile and 10% of polyvinylpyrrolidone, fully stirring to obtain an electrospinning solution which is uniformly mixed, and preparing titanium-loaded carbon nanofibers through electrostatic spinning; carbonizing the prepared film at 900 ℃ in nitrogen, and adding urea for activation treatment to obtain titanium-loaded porous carbon fibers; uniformly coating a 1% chitosan solution on the surface of the titanium-loaded carbon fiber film, and airing at the humidity of 70% to obtain the fluorine adsorbent of the titanium-loaded carbon nanofiber composite film suitable for the acidic fluorine-containing wastewater.
0.50g of titanium-loaded carbon nanofiber fluorine adsorbent prepared in the example is added, the fluorine concentration is reduced to 12mg/L in a fluorine-containing solution with the pH value of 1 for 1 hour, the saturated adsorption capacity of the adsorbent to fluorine is 45.4mg/g, and the defluorination efficiency reaches 89%.
Example 3
Uniformly dispersing 1g of titanium dioxide powder in a mixed solution of 8% polyacrylonitrile and 5% chitosan, fully stirring to obtain a uniformly mixed electrospinning solution, and preparing a titanium-loaded nanofiber film through electrostatic spinning; carbonizing the prepared film at 500 ℃ under argon, and activating by adding potassium hydroxide to obtain titanium-loaded porous carbon nanofibers; and (3) uniformly coating 5% of gelatin solution on the surface of the titanium-loaded carbon fiber, and airing at the humidity of 70% to obtain the fluorine adsorbent of the titanium-loaded carbon nanofiber composite film suitable for the acidic fluorine-containing wastewater.
0.50g of titanium-loaded carbon nanofiber fluorine adsorbent prepared in the example is added, the fluorine concentration is reduced to 22mg/L in a fluorine-containing solution with the pH value of 3 for 1h, the saturated adsorption capacity of the adsorbent to fluorine is 31.4mg/g, and the defluorination efficiency reaches 78%.
Example 4
Uniformly dispersing 1g of titanium oxide in a mixed solution of 8% polyacrylonitrile and 8% polyvinyl alcohol, fully stirring to obtain a uniformly mixed electrospinning solution, and preparing a titanium-loaded nanofiber membrane through electrostatic spinning; adding urea into the prepared film, carbonizing and activating the film at 700 ℃ under nitrogen to obtain titanium-loaded carbon nanofibers; uniformly coating 5% of chitosan solution on the surface of the titanium-loaded carbon fiber, and airing at the humidity of 70% to obtain the fluorine adsorbent of the titanium-loaded carbon nanofiber composite film suitable for the acidic fluorine-containing wastewater.
0.50g of titanium-loaded carbon nanofiber fluorine adsorbent prepared in the example is added, the fluorine concentration is reduced to 8mg/L in a fluorine-containing solution with the pH value of 6 for 1h, the saturated adsorption capacity of the adsorbent to fluorine is 41.5mg/g, and the defluorination efficiency reaches 82%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A fluorine adsorbent is composed of titanium-loaded porous carbon nanofibers and hydrophobic gel compounded on the surfaces of the porous carbon nanofibers.
2. The fluorine adsorbent of claim 1 wherein the titanium-supported porous filamentous nanocarbon is 0.1 to 10 wt% of the hydrophobic gel; the content of the porous carbon nanofibers in the titanium-loaded porous carbon nanofibers is 5-20 wt%.
3. The method for producing the fluorine adsorbent according to claim 1, comprising the steps of:
mixing a titanium source and a carbon-containing polymer solution, and performing electrostatic spinning on the obtained electrospinning solution to obtain a titanium-loaded nanofiber membrane;
carbonizing and activating the titanium-loaded nanofiber film to obtain titanium-loaded porous nanofiber;
and coating hydrophobic gel on the surface of the titanium-loaded porous carbon nanofiber to obtain the fluorine adsorbent.
4. The preparation method according to claim 3, wherein the polymer is selected from one or more of polyacrylonitrile, polyvinyl alcohol, polyvinylidene fluoride, chitosan, polyvinylpyrrolidone and polytetrafluoroethylene; the titanium source is selected from one or more of titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, titanium dioxide, ilmenite, vanadium titano-magnetite and rutile; in the electrospinning solution, when two polymers are selected, the content of one polymer is 5-15 wt% of the mass of the solvent, and the content of the other polymer is 0.5-15 wt% of the mass of the solvent; the content of the titanium source is 5-30 wt% of the polymer.
5. The preparation method according to claim 3, wherein the electrospinning is specifically:
adding the obtained electrospinning solution into a spinning liquid storage device under the conditions that the temperature is 10-60 ℃ and the humidity is 20-60%, wherein the inner diameter of a spray head is 0.15-1.0 mm, the spinning distance is 10-25 cm, the spinning voltage is 10-30 kV, and the injection speed of the solution is 0.01-0.05 mL/min; spinning for 30-180 min to obtain the polymer nanofiber membrane with the fiber diameter of 100-500 nm, and drying in a vacuum drying oven at 25-80 ℃ for 6-24 h.
6. The method according to claim 3, wherein the carbonization is performed in an activating atmosphere selected from one or more of nitrogen, helium and argon, the carbonization temperature is 400 to 1000 ℃, and the activating agent is selected from one or more of potassium hydroxide, sodium hydroxide and urea.
7. The method of claim 3, wherein the hydrophobic gel is selected from one or more of chitosan, cellulose, lignin and gelatin.
8. The method according to claim 3, wherein the thickness of the hydrophobic gel is 0.01 to 0.1 cm.
9. A method of adsorbing a fluorine-containing solution comprising:
mixing a fluorine adsorbent and a fluorine-containing solution, and adsorbing;
the fluorine adsorbent is the fluorine adsorbent according to any one of claims 1 to 2 or the fluorine adsorbent produced by the production method according to any one of claims 3 to 8.
10. The adsorption method according to claim 9, wherein the fluorine-containing solution is an acidic high-aluminum fluorine-containing solution; the adsorption time is 10 min-1 h.
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