CN115090266B - Fluorine adsorbent, preparation method and adsorption method thereof - Google Patents
Fluorine adsorbent, preparation method and adsorption method thereof Download PDFInfo
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- CN115090266B CN115090266B CN202210702486.8A CN202210702486A CN115090266B CN 115090266 B CN115090266 B CN 115090266B CN 202210702486 A CN202210702486 A CN 202210702486A CN 115090266 B CN115090266 B CN 115090266B
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011737 fluorine Substances 0.000 title claims abstract description 96
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 96
- 239000003463 adsorbent Substances 0.000 title claims abstract description 58
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000010936 titanium Substances 0.000 claims abstract description 66
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 66
- 239000002133 porous carbon nanofiber Substances 0.000 claims abstract description 27
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 55
- 229920000642 polymer Polymers 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 23
- 239000000499 gel Substances 0.000 claims description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000004917 carbon fiber Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002121 nanofiber Substances 0.000 claims description 16
- 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
- 230000004913 activation Effects 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
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 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
- 230000002378 acidificating effect Effects 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
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 239000000835 fiber Substances 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
- 239000012528 membrane Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 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
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000001035 drying Methods 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
- 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
- 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
- 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
- 239000002105 nanoparticle Substances 0.000 claims description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 abstract description 5
- 238000006115 defluorination reaction Methods 0.000 description 10
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000003795 desorption Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation 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
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000021110 pickles Nutrition 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
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The application provides a fluorine adsorbent, which consists of porous carbon nanofibers loaded by titanium and hydrophobic gel compounded on the surfaces of the porous carbon nanofibers. The application also provides a preparation method and specific application of the fluorine adsorbent. The fluorine adsorbent provided by the application has the advantages of saturated adsorption capacity of 50mg/g for fluorine, large adsorption capacity, high fluorine removal efficiency and wide applicable pH range, and is especially suitable for an acid system; meanwhile, the surface active adsorption sites of the fluorine adsorbent are uniformly distributed, and the fluorine adsorbent has strong affinity to fluorine and strong adsorption capacity.
Description
Technical Field
The application relates to the technical field of mineral resource green dressing and smelting, in particular to a fluorine adsorbent, a preparation method and an adsorption method thereof.
Background
Fluorine is ubiquitous in mines and water due to its extremely strong electronegativity; meanwhile, the fluorine-containing industrial wastewater belongs to secondary pollutants 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 green dressing and smelting field.
During mineral mineralization, fluorine typically enters the mineral lattice through hydroxyl groups that replace the interfaces; fluorine-containing solution in the process of dressing and smelting aluminosilicate minerals often contains elements such as aluminum, valuable metals and the like, so that fluorine mainly exists in the leaching solution in the forms of hydrogen fluoride and fluoric acid. Conventional chemical precipitation methods result in Al (OH) in the presence of pH adjustment 3 The form is separated out, valuable elements are adsorbed, and the subsequent separation and recovery difficulty is increased. 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 of high aluminum concentration and fluorine-containing solution concentration. In addition, acidolysis is a common method for mineral resources. Thus, the preparation of acid-resistant, highly selective fluorine adsorbents is a critical issue to be addressed by deep defluorination.
Disclosure of Invention
The technical problem solved by the application is to provide the fluorine adsorbent which has stronger adsorption capacity to fluorine and good cycle stability.
In view of the above, the present application provides a fluorine adsorbent composed of porous carbon nanofibers supported by titanium and hydrophobic gel composited on the surface of the porous carbon nanofibers.
Preferably, the titanium-loaded porous nano carbon fiber is 0.1-10wt% of the hydrophobic gel; the content of the porous carbon nanofiber in the titanium-loaded porous carbon nanofiber is 5-20wt%.
The application also provides a preparation method of the fluorine adsorbent, which comprises the following steps:
mixing a titanium source with a carbon-containing polymer solution, and carrying out electrostatic spinning on the obtained electrospun solution to obtain a titanium-loaded nanofiber film;
carbonizing and activating the titanium-loaded nanofiber film to obtain titanium-loaded porous carbon nanofiber;
and coating hydrophobic gel on the surface of the titanium-loaded porous nano carbon fiber 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 titanomagnetite 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 5-30wt% of the mass of the polymer.
Preferably, the electrospinning specifically comprises:
adding the obtained electrospinning solution into a spinning liquid reservoir under the conditions of the temperature of 10-60 ℃ and the humidity of 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 push injection speed of the solution is 0.01-0.05 mL/min; spinning for 30-180 min to obtain polymer nanometer fiber film with fiber diameter of 100-500 nm, and drying in vacuum drier at 25-80 deg.c for 6-24 hr.
Preferably, the carbonization and activation atmosphere is selected from one or more of nitrogen, helium and argon, the carbonization temperature is 400-1000 ℃, and the activation activator 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 with a fluorine-containing solution for adsorption;
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 porous carbon nanofibers loaded by titanium and hydrophobic gel compounded on the surfaces of the porous carbon nanofibers; the porous carbon nanofiber in the fluorine adsorbent is acid and alkali resistant, so that the pH of the fluorine adsorbent is wide in application range; meanwhile, the fluorine adsorbent has uniformly distributed interfacial active adsorption sites, has strong affinity to fluorine and strong adsorption capacity; the fluorine adsorbent prepared by the method has good circulation stability, easy adsorption-desorption circulation regeneration and small dissolution loss of the adsorbent in the adsorption process, and can be simply filtered and separated, thereby greatly reducing the operation cost.
Detailed Description
For a further understanding of the present application, preferred embodiments of the application are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the application, and are not limiting of the claims of the application.
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 pickle liquor system in an acidolysis process leaching solution of an aluminosilicate mineral; the adsorbent provided by the application can realize the selective removal of fluorine and reduce the loss of valuable elements in the defluorination process. Specifically, the embodiment of the application discloses a fluorine adsorbent which consists of porous carbon nanofibers loaded by titanium and hydrophobic gel compounded on the surfaces of the porous carbon nanofibers.
In the fluorine adsorbent provided by the application, the porous nano carbon fiber loaded by titanium accounts for 0.1-10wt% of the hydrophobic gel; the content of the porous carbon nanofiber in the titanium-loaded porous carbon nanofiber is 5-20wt%. In the present application, titanium in the titanium-supported porous carbon nanofiber 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 with a carbon-containing polymer solution, and carrying out electrostatic spinning on the obtained electrospun solution to obtain a titanium-loaded nanofiber film;
carbonizing and activating the titanium-loaded nanofiber film to obtain titanium-loaded porous carbon nanofiber;
and coating hydrophobic gel on the surface of the titanium-loaded porous nano carbon fiber to obtain the fluorine adsorbent.
In the process of preparing the fluorine adsorbent, firstly mixing a titanium source and a carbon-containing polymer solution, wherein the titanium source is one or more selected from titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, titanium dioxide, ilmenite, vanadium titanomagnetite and rutile; the polymer is one or more selected from polyacrylonitrile, polyvinyl alcohol, polyvinylidene fluoride, chitosan, polyvinylpyrrolidone and polytetrafluoroethylene; in specific 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 5-30wt% of the mass of the polymer; more specifically, the titanium source is contained in an amount of 8 to 20wt%, the one polymer is contained in an amount of 5 to 10wt%, and the other polymer is contained in an amount of 5 to 10wt%. The two raw materials are fully stirred after being mixed to obtain a uniformly mixed electric access solution, and then electrostatic spinning is carried out to obtain the titanium-loaded nanofiber membrane. In the application, the electrostatic spinning specifically comprises the following steps:
adding the obtained electrospinning solution into a spinning liquid reservoir under the conditions of the temperature of 10-60 ℃ and the humidity of 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 push injection speed of the solution is 0.01-0.05 mL/min; spinning for 30-180 min to obtain polymer nanometer fiber film with fiber diameter of 100-500 nm, and drying in vacuum drier at 25-80 deg.c for 6-24 hr.
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 melted and drawn under the action of an electric field to form the nanofiber membrane loaded with titanium.
The application then carries out carbonization and activation on the titanium-loaded nanofiber membrane to obtain the titanium-loaded porous carbon nanofiber. In the process, the nanofiber is carbonized to generate porous carbon nanofiber, and meanwhile, different titanium sources generate titanium oxide to provide defluorinated active sites. The carbonization and activation atmosphere is selected from one or more of nitrogen, helium and argon, the carbonization temperature is 400-1000 ℃, and the activation agent is selected from one or more of potassium hydroxide, sodium hydroxide and urea. In a specific embodiment, the carbonization and activation atmosphere is selected from nitrogen or argon, and the carbonization temperature is 500-900 ℃; the activator is selected from potassium hydroxide or urea.
According to the application, finally, hydrophobic gel is coated on the surface of the porous nano carbon fiber loaded by titanium, so as to obtain the fluorine adsorbent. After the hydrophobic gel is compounded on the surface of the porous carbon nanofiber loaded with titanium, the obtained adsorbent can exist stably in a solution and is not dispersed. The hydrophobic gel is selected from one or more of chitosan, cellulose, lignin and gelatin; more specifically, the hydrophobic gel is selected from chitosan or gelatin. The hydrophobic gel is coated on the surface of the porous nano carbon fiber in a 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 cm to 0.1cm, and the hydrophobic gel can be obtained by controlling the humidity to be 35 percent to 70 percent and airing at room temperature.
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 for adsorption;
the fluorine adsorbent is the fluorine adsorbent according to the scheme.
The fluorine-containing solution provided by the application is high-alumina (> 1 g/L) and fluorine (> 10 mg/L) solution with an acidic pH of 1-6. The adsorption time is 10 min-1 h; the temperature of the mixing is 10-110 ℃, the mixing is carried out under the stirring condition, and the stirring speed is 80-250 r/min. And (3) carrying out desorption after the adsorption is finished, wherein 0.1mol/L sodium hydroxide is adopted for activation during the desorption, then 1mol/L 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 application has the advantages of saturated fluorine adsorption capacity up to 50mg/g, large adsorption capacity, high fluorine removal efficiency and wide applicable pH range, and is particularly suitable for an acidic system; meanwhile, the surface active adsorption sites of the fluorine adsorbent are uniformly distributed, and the fluorine adsorbent has strong affinity to fluorine and strong adsorption capacity. Furthermore, the fluorine adsorbent prepared by the method has good circulation stability, is easy to adsorb-analyze and recycle and regenerate, has small dissolution loss in the adsorption process, can be simply filtered and separated, and greatly reduces the operation cost.
In order to further understand the present application, the following examples are provided to illustrate the fluorine adsorbent, the preparation method thereof and the application thereof in detail, and the scope of the present application is not limited by the following examples.
Example 1
Titanium tetrachloride (10 wt%) is dissolved in a mixed solution of 10% polyacrylonitrile and 5% polyvinylpyrrolidone, and the mixture is fully stirred to obtain an electrospun solution which is uniformly mixed, and the electrospun solution is used for preparing a titanium-loaded nanofiber film; carbonizing the prepared film at 700 ℃ under nitrogen, and adding potassium hydroxide for activation to obtain titanium-loaded porous carbon nanofiber; uniformly coating 2% chitosan solution on the surface of the titanium-loaded carbon fiber, and airing at the humidity of 40% to obtain the titanium-loaded nano carbon fiber composite fluorine adsorbent applicable to 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 quantity of the adsorbent to fluorine is 51.4mg/g, and the defluorination efficiency reaches 91%.
In the specific embodiment of the application, except that the pH of the fluorine-containing solution is changed, the rest conditions are as follows: the concentration of fluoride ion is 200mg/L, the stirring speed of the fluorine-containing solution is 100mL, the stirring speed is 120r/min, and the fluorine-containing solution is adsorbed for 1h at normal temperature.
Example 2
1g of tetrabutyl titanate is dissolved in a mixed solution of 5 percent polyacrylonitrile and 10 percent polyvinylpyrrolidone, and the mixture is fully stirred to obtain an evenly mixed electrospinning solution, and the titanium-loaded carbon nanofiber is prepared by electrospinning; carbonizing the prepared film at 900 ℃ under nitrogen, and adding urea for activation treatment to obtain titanium-loaded porous carbon fibers; uniformly coating 1% chitosan solution on the surface of the titanium-loaded carbon fiber film, and airing at 70% humidity to obtain the fluorine adsorbent applicable to the titanium-loaded carbon nanofiber composite film of the acid 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 1h, the saturated adsorption quantity 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, and fully stirring to obtain a uniformly mixed electrospinning solution, and carrying out electrospinning to prepare a titanium-loaded nanofiber film; carbonizing the prepared film under argon at 500 ℃, and adding potassium hydroxide for activation to obtain titanium-loaded porous carbon nanofiber; uniformly coating 5% gelatin solution on the surface of the titanium-loaded carbon fiber, and airing at 70% humidity to obtain the fluorine adsorbent applicable to the titanium-loaded carbon nanofiber composite film of the acid 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 quantity 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, and fully stirring to obtain a uniformly mixed electrospinning solution, and carrying out electrospinning to prepare a titanium-loaded nanofiber film; adding urea into the prepared film, carbonizing and activating the film at 700 ℃ under nitrogen to obtain titanium-loaded nano carbon fibers; uniformly coating a chitosan solution with the concentration of 5% on the surface of the carbon fiber loaded by titanium, and airing the carbon fiber under the humidity of 70% to obtain the fluorine adsorbent applicable to the carbon nanofiber composite film loaded by titanium of the acid 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 of 6 for 1h, the saturated adsorption quantity of the adsorbent to fluorine is 41.5mg/g, and the defluorination efficiency reaches 82%.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. 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 application. Thus, the present application 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 (6)
1. A method for preparing a fluorine adsorbent, comprising the steps of:
mixing a titanium source with a carbon-containing polymer solution, and carrying out electrostatic spinning on the obtained electrospun solution to obtain a titanium-loaded nanofiber film;
carbonizing and activating the titanium-loaded nanofiber film to obtain titanium-loaded porous carbon nanofiber;
coating hydrophobic gel on the surface of the titanium-loaded porous nano carbon fiber to obtain a fluorine adsorbent;
the fluorine adsorbent consists of porous carbon nanofibers loaded with titanium and hydrophobic gel compounded on the surfaces of the porous carbon nanofibers, wherein titanium in the porous carbon nanofibers loaded with titanium is loaded on the carbon fibers by hydroxyl oxide nanoparticles;
the titanium-loaded porous nano carbon fiber is 0.1-10wt% of the hydrophobic gel; the content of the porous carbon nanofiber in the titanium-loaded porous carbon nanofiber is 5-20wt%;
the carbonization and activation atmosphere is selected from one or more of nitrogen, helium and argon, the carbonization temperature is 400-1000 ℃, and the activation activator is selected from one or more of potassium hydroxide, sodium hydroxide and urea;
the hydrophobic gel is selected from one or more of chitosan, cellulose, lignin and gelatin.
2. The preparation method according to claim 1, wherein the polymer is one or more selected from the group consisting 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 titanomagnetite 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 5-30wt% of the mass of the polymer.
3. The preparation method according to claim 1, wherein the electrospinning specifically comprises:
adding the obtained electrospinning solution into a spinning liquid reservoir at the temperature of 10-60 ℃ and the humidity of 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 push injection speed of the solution is 0.01-0.05 mL/min; spinning for 30-180 min to obtain a polymer nanofiber membrane with the fiber diameter of 100-500 nm, and drying the polymer nanofiber membrane in a vacuum drying oven at 25-80 ℃ for 6-24 h.
4. The preparation method according to claim 1, wherein the thickness of the hydrophobic gel is 0.01-0.1 cm.
5. A method of adsorbing a fluorine-containing solution comprising:
mixing a fluorine adsorbent with a fluorine-containing solution for adsorption;
the fluorine adsorbent is prepared by the preparation method according to any one of claims 1 to 4.
6. The adsorption method of claim 5, 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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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191700A (en) * | 2013-04-15 | 2013-07-10 | 北京中地泓科环境科技有限公司 | Chitosan/natural zeolite material for removing fluorine in water |
| KR101336286B1 (en) * | 2012-11-13 | 2013-12-03 | 재단법인대구경북과학기술원 | Manufacturing method for carbon nano fiber complex and carbon nano fiber complex |
| CN106824156A (en) * | 2017-02-09 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of titanium dioxide based active carbon fiber composite catalyst and its production and use |
| CN109112728A (en) * | 2018-08-03 | 2019-01-01 | 东华大学 | The preparation method of the flexible compound porous micro/nano fibrous membrane material of titanium dioxide/carbon |
| CN112796093A (en) * | 2019-11-13 | 2021-05-14 | 万华化学集团股份有限公司 | Method for preparing super-hydrophobic activated carbon fiber and prepared super-hydrophobic activated carbon fiber |
| CN113540478A (en) * | 2021-07-12 | 2021-10-22 | 南京工业大学 | Porous carbon-based nanofiber film material loaded by metal single atom and metal derivative thereof, and preparation method and application thereof |
-
2022
- 2022-06-21 CN CN202210702486.8A patent/CN115090266B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101336286B1 (en) * | 2012-11-13 | 2013-12-03 | 재단법인대구경북과학기술원 | Manufacturing method for carbon nano fiber complex and carbon nano fiber complex |
| CN103191700A (en) * | 2013-04-15 | 2013-07-10 | 北京中地泓科环境科技有限公司 | Chitosan/natural zeolite material for removing fluorine in water |
| CN106824156A (en) * | 2017-02-09 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of titanium dioxide based active carbon fiber composite catalyst and its production and use |
| CN109112728A (en) * | 2018-08-03 | 2019-01-01 | 东华大学 | The preparation method of the flexible compound porous micro/nano fibrous membrane material of titanium dioxide/carbon |
| CN112796093A (en) * | 2019-11-13 | 2021-05-14 | 万华化学集团股份有限公司 | Method for preparing super-hydrophobic activated carbon fiber and prepared super-hydrophobic activated carbon fiber |
| CN113540478A (en) * | 2021-07-12 | 2021-10-22 | 南京工业大学 | Porous carbon-based nanofiber film material loaded by metal single atom and metal derivative thereof, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吸附法处理含氟废水的研究进展;周钰明,余春香;离子交换与吸附(05);369-376 * |
| 静电纺丝法制备交联多孔纳米碳纤维膜及其电化学电容性能;卢建建;应宗荣;刘信东;赵双生;;物理化学学报(11);第2099-2108页 * |
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