CN109174049A - The porous absorption lithium/rubidium ion material preparation method and application of trace - Google Patents

The porous absorption lithium/rubidium ion material preparation method and application of trace Download PDF

Info

Publication number
CN109174049A
CN109174049A CN201810886657.0A CN201810886657A CN109174049A CN 109174049 A CN109174049 A CN 109174049A CN 201810886657 A CN201810886657 A CN 201810886657A CN 109174049 A CN109174049 A CN 109174049A
Authority
CN
China
Prior art keywords
trace
rubidium ion
lithium
ion material
material preparation
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.)
Granted
Application number
CN201810886657.0A
Other languages
Chinese (zh)
Other versions
CN109174049B (en
Inventor
邱凤仙
王媛媛
蒲志龙
徐吉成
张涛
杨冬亚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University
Original Assignee
Jiangsu University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu University filed Critical Jiangsu University
Priority to CN201810886657.0A priority Critical patent/CN109174049B/en
Publication of CN109174049A publication Critical patent/CN109174049A/en
Application granted granted Critical
Publication of CN109174049B publication Critical patent/CN109174049B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J20/02—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention belongs to material preparation and separation technology fields, are related to the preparation of lithium/rubidium ion double suction enclosure material more particularly to a kind of preparation method and applications of trace porous adsorbing material.The present invention first carries out hydroxylating processing to carbon nanotube, and the hydroxyl on trimethoxy and carbon nanotube connected by silicon in 3- glycidyloxypropyl trimethoxy silane KH560 reacts, and introduces epoxy group；It is compound with phenolic hydroxyl group open loop of the trace to tert-butyl p tertButylcalixarene IC4A again, obtain trace porous adsorbing material.To the complexing effect coupled ion engram technology of tert-butyl p tertButylcalixarene, it is attached that efficient selective double suction can be carried out to lithium/rubidium ion.The invention also discloses the absorption that obtained material is applied to Lithium from Salt Lake Brine ion and rubidium ion.The method of the invention operation is relatively simple, and obtained trace porous adsorbing material stable structure, specific surface is larger, in conjunction with ionic imprinting technique, can increase the adsorption site of material, improve the absorption property of material.

Description

The porous absorption lithium/rubidium ion material preparation method and application of trace
Technical field
The invention belongs to material preparation and separation technology fields, are related to the preparation of lithium/rubidium ion double suction enclosure material, especially relate to And a kind of preparation method and applications of trace porous adsorbing material.
Background technique
The scientist lijima of Japanese NEC Corporation has found carbon nanotube (Carbon nanotubes, CNTs) since 1991 Since, carbon nanotube becomes focus concerned by people because of its unique property.Until nowadays, carbon nanotube be also various countries expert, The object that scholar, researcher pay close attention to.With going deep into for research, carbon nanotube functional material is gradually applied to work Among the every field of industry production.The structure that this rapid development is primarily due to carbon nanotube itself imparts very to it Brilliant mechanical property, electric property, thermal property and biggish draw ratio.
CNTs has hollow porous multi-layer structure, biggish specific surface area, high chemical inertness and strong-hydrophobicity, therefore quilt It is widely used in the processing of organic pollutant in water environment, metal ion and its complex etc..With the development of carbon nanotechnology, CNTs composite material receives more and more attention；Different from single nano material, CNTs composite material is by two kinds or two kinds The Material cladding of above Nano grade scale forms, can be integral by the integration of the material of multiple functions, so as to sufficiently benefit With the characteristic of multiple material multi-functional, therefore CNTs composite material has very big potentiality.It is previous studies have shown that CNTs surface modification organic polymer or metal, chelated metal oxide etc. can significantly improve the characteristic of CNTs.
Nevertheless, CNTs composite material still some problem is not well solved, for example CNTs is in matrix In dispersibility, interfacial adhesion situation and orientation etc..Due to the huge specific surface area of CNTs and surface energy, hold that it very Easy to reunite, this virtually will limit the dispersibility of CNTs in the base.The dispersion of CNTs in the base how is effectively improved, is made It can more efficiently transmit load, have become CNTs using institute's urgent problem.Therefore, the surface of CNTs is modified It is particularly important.
The physicochemical property that can change CNTs using functionalization makes it more suitable for chemistry and biologic applications.It is multiple to CNTs The research early start of condensation material is in compound, i.e., the metal, metal oxidation in CNTs surface modification of CNTs and metal_based material Object, chelated metal oxide or polymer etc., can not only improve the characteristic of CNTs, moreover it is possible to successfully prepare CNTs composite material.This A little composite materials can be integral by the integration of the material of multiple functions, so that CNTs composite material is shown multi-functional, greatly mentions The dispersibility of high CNTs makes it be preferably applied for the removal of pollutant in water environment, therefore CNTs composite material is with huge Potentiality.
Carbon nanotube is bonded by the present invention by silane coupling agent with calixarene chemistry, in combination with ionic imprinting technique system The standby trace porous adsorbing material (IC4ABC) with high specificity, stability a kind of out, and the material is had studied to Li (I), the performance of Rb (I) ionic adsorption separation etc., can effectively be applied to it in industrial production.
Summary of the invention
The purpose of the present invention is being directed to the disadvantages of carbon nano tube surface reactive group is few, easy to reunite, pass through chemical graft silicon Alkane coupling agent makes carbon nanotube have different functionalizing groups, to alleviate agglomeration, and then participates in the calixarenes of next step It is compound, realize carbon nanotube in the application of lithium/rubidium ion adsorbing separation field.The invention discloses a kind of porous adsorption materials of trace The preparation method of material, and prepared adsorbent material is applied to the extraction of Lithium from Salt Lake Brine/rubidium resource.
It is an object of the present invention to a kind of preparation method of trace porous adsorbing material be disclosed, first to carbon nanometer Pipe carries out hydroxylating processing, the trimethoxy connected by silicon in 3- glycidyloxypropyl trimethoxy silane (KH560) Base reacts with the hydroxyl in carbon nanotube, introduces epoxy group；Again with trace to the phenol of tert-butyl p tertButylcalixarene (IC4A) Hydroxyl open loop is compound, obtains trace porous adsorbing material (IC4ABC).
The porous absorption lithium/rubidium ion material preparation method of trace, includes the following steps:
A, it measures KH560 and hydroxyl carbon nano tube (MWCNTs) and triethylamine is added in dry toluene under container, magnetic agitation, Stirring and 110 DEG C~130 DEG C reflux 5~8 h, preferably 120 DEG C, 6h in drying nitrogen；
B, filter, successively use toluene, acetone, deionized water and acetone washing, 70 DEG C~90 DEG C 6~10 h of vacuum drying, preferably 80 DEG C, 8h；Obtain the carbon nanotube (KH560/MWCNTs) of KH560 grafting；
C, according to the solid-to-liquid ratio of 50mg:1mL, IC4A is placed in toluene, NaH is added under magnetic agitation, in N2Protect lower 70 DEG C ~90 DEG C of 20~40 min of oil bath, preferably 80 DEG C, 30min；
D, it stands and takes supernatant liquor, tetrabutylammonium bromide and KH560/MWCNTs is added, in dry N2Middle stirring simultaneously 80 DEG C micro- time Stream 20~30 h of reaction, preferably for 24 hours；
E, it filters, washs while hot, 100 DEG C~140 DEG C vacuum drying 8~12 h, preferably 120 DEG C, 10h obtain the porous suction of trace Enclosure material (IC4ABC).
Wherein, the proportion of each reactant are as follows:
The volume ratio of toluene and KH560 are 9mL~11mL:1mL, preferably 10mL:1mL；
The solid-to-liquid ratio of MWCNTs and KH560 is 3g~5g:8mL, preferably 4g:8mL；
The volume ratio of triethylamine and KH560 are 1mL:20mL~80mL, preferably 1mL:40mL；
The mass ratio of NaH and IC4A is 11mg~13mg:25mg, preferably 12mg:25mg；
The mass ratio of GBC and IC4A is 3mg~5mg:5mg, preferably 4mg:5mg.
Hydroxyl carbon nano tube (MWCNTs) of the present invention carries out at hydroxylating carbon nanotube using oxidation modification Reason, by distilled water, 98% H2SO4With 70% HNO3It is made into nitration mixture for the ratio of 3:2:1 with volume ratio, it is anti-to pour into polytetrafluoroethylene (PTFE) It answers in kettle, stands to room temperature；Addition carbon nanotube, 100~140 DEG C of 2~4 h of hydro-thermal reaction, preferably 120 DEG C, 3 h；It pours into big It dilutes and stands in amount deionized water, then remove supernatant liquor, repeatedly until the pH value of solution is about 2；Again through 0.45 μ The cellulose acetate film of m filters, and is repeatedly washed with ethyl alcohol to neutrality, 40~60 DEG C of vacuum drying, and preferably 50 DEG C；Obtain hydroxyl Base carbon nano tube (MWCNTs), wherein the solid-to-liquid ratio of nitration mixture and carbon nanotube is 5mg~7mg:6mL, preferably 5mg:5mL.
IC4A of the present invention, is produced using dispersion copolymerization method, comprising: take butyl titanate to be placed in conical flask, successively plus Enter dehydrated alcohol, deionized water, glacial acetic acid；Ultrasound 2~4h, preferably 3h；Be added appropriate hydrochloric acid, adjust pH be 2~3, stand to With.It will be to tert-butyl p tertButylcalixarene, LiClH2O and RbCl are dissolved in dehydrated alcohol, and the butyl titanate that set aside for use is added is molten Liquid pricks an aperture, 20~40 DEG C of 4~8h of ultrasound, preferably 30 DEG C, 6h after sealing bottleneck；Jelly is obtained, is washed with distilled water and removes Unreacted residue is removed, with 1 molL-1Hydrochloric acid elute Li+And Rb+Afterwards, 60~100 DEG C of vacuum drying, preferably 80 DEG C； Grinding is obtained containing Li+/Rb+The trace in hole is to tert-butyl p tertButylcalixarene (IC4A).
Wherein, the proportion of each reactant are as follows:
The solid-to-liquid ratio of butyl titanate and ethyl alcohol is 4g:10mL~12mL, preferably 4g:11mL；
The solid-to-liquid ratio of butyl titanate and deionized water is 4g:5mL~7mL, preferably 4g:6mL；
The solid-to-liquid ratio of butyl titanate and glacial acetic acid is 4g:4mL~6mL, preferably 4g:5mL；
Butyl titanate and be 7g~9g:1g, preferably 8g:1g to the mass ratio of tert-butyl p tertButylcalixarene；
To tert-butyl p tertButylcalixarene and LiClH2The mass ratio of O is 1g:1g~3g, preferably 1g:2g；
Mass ratio to tert-butyl p tertButylcalixarene and RbCl is 1g:2g~4g, preferably 1g:3g；
Solid-to-liquid ratio to tert-butyl p tertButylcalixarene and ethyl alcohol is 50mg:4mL~6mL, preferably 50mg:5mL.
Another object of the present invention, the trace porous adsorbing material being prepared according to disclosed method can incite somebody to action Its absorption for being applied to Lithium from Salt Lake Brine ion and rubidium ion.
The present invention carries out adsorption test to simulate salt lake bittern.
(1) mixed solution of a certain concentration lithium, rubidium, sodium, potassium, calcium, magnesium and cesium ion is prepared.
(2) in 10mL colorimetric cylinder, above-mentioned solution is added, adds a certain amount of trace porous adsorbing material as suction Attached dose, oscillation, Static Adsorption measures until adsorption equilibrium, the solution after absorption is centrifugated, supernatant is taken at room temperature Each ion concentration of surplus solution.
Then trace porous adsorbing material is in time t to lithium/rubidium ion adsorption capacity Q tIt can be calculated with following equation.
Qt=(C0-Ct)V/W
In formula: the initial solubility of lithium/rubidium ion is C0(mg/L), the lithium after absorption/rubidium ion concentration is Ct (mg/L)；W is trace The quality (g) of porous adsorbing material；V is Li (I)/Rb (I) solion volume (L).
Sulfuric acid used in the present invention, nitric acid, hydrochloric acid, toluene, acetone, ethyl alcohol, lithium chloride (LiClH2O), rubidium chloride (RbCl), 3- glycidyloxypropyl trimethoxy silane (KH560), Sinopharm Chemical Reagent Co., Ltd.；NaH, Tetrabutylammonium bromide, to tert-butyl p tertButylcalixarene, Shanghai Aladdin biochemical technology limited liability company.
Beneficial effect
The trace porous adsorbing material specific surface that the present invention is synthesized using carbon nanotube as matrix is larger, in conjunction with ion blotting skill Art can largely increase the adsorption site of material, to improve the absorption property of material.To tert-butyl-calix [4] virtue It is attached can to carry out efficient selective double suction to lithium/rubidium ion for the complexing effect coupled ion engram technology of hydrocarbon；Utilize the present invention Disclosed method, using the trace porous adsorbing material that carbon nanotube is synthesized as matrix, stable structure is easy to operate, and has Good absorption property.
Detailed description of the invention
The synthesis schematic diagram of Fig. 1 trace porous adsorbing material (IC4ABC).
The scanning electron microscope (SEM) photograph of Fig. 2 MWCNTs (a) and IC4ABC (b).
The FT-IR spectrum of Fig. 3 MWCNTs (a), KH560/MWCNTs (b), IC4ABC (c).
The XRD spectra of Fig. 4 MWCNTs and IC4ABC.
The XPS map (a) of Fig. 5 MWCNTs and IC4ABC；O1s map (b)；C1s Gauss is deconvoluted spectrum (c, d)； The Si2p map (e) of IC4ABC.
Fig. 6 pH is to trace porous adsorbing material (IC4ABC) and non-trace porous adsorbing material (C4ABC) adsorption effect It influences.
Fig. 7 trace porous adsorbing material (IC4ABC) and non-trace porous adsorbing material (C4ABC) are to lithium/rubidium ion Selectivity analysis.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair It is bright, but the invention is not limited to following embodiments.
Embodiment 1
(1) it takes 4 mL KH560 and the dry toluene of 44 mL in 100 mL three neck round bottom flask, 2.5 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.2 mL triethylamine, stirring and 130 DEG C of reflux 8h in drying nitrogen；Toluene, third are successively used in filtering Ketone, deionized water and acetone washing, 90 DEG C of 10 h of vacuum drying；Obtain the carbon nanotube (KH560/MWCNTs) of KH560 grafting.
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added under magnetic agitation 1.3 g NaH, N2Protect 40 min of lower 90 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 2.5 g are added KH560/MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 30 h of back flow reaction；It filters while hot, washing to filtrate achromaticity and clarification is Only.140 DEG C of obtained solid 12 h of vacuum drying, obtain trace porous adsorbing material (IC4ABC).
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 15.77mgg greatly-1And 13.91mgg-1。
Embodiment 2
(1) it takes 4 mL KH560 and the dry toluene of 38 mL in 100 mL three neck round bottom flask, 1.6 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.16 mL triethylamine, stirring and 120 DEG C of reflux 6h in drying nitrogen；Filtering, successively with toluene, Acetone, deionized water and acetone washing, 90 DEG C of 8 h of vacuum drying；Obtain the carbon nanotube (KH560/ of KH560 grafting MWCNTs).
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added under magnetic agitation 1.2 g NaH, N2Protect 40 min of lower 80 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 1.7 g are added KH560/MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 22 h of back flow reaction；It filters while hot, washing to filtrate achromaticity and clarification is Only.140 DEG C of obtained solid 10 h of vacuum drying, obtain trace porous adsorbing material (IC4ABC).
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 16.01mgg greatly-1And 12.97mgg-1。
Embodiment 3
(1) it takes 4 mL KH560 and the dry toluene of 41 mL in 100 mL three neck round bottom flask, 2.2 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.12 mL triethylamine, stirring and 130 DEG C of reflux 5h in drying nitrogen；Filtering, successively with toluene, Acetone, deionized water and acetone washing, 80 DEG C of 10 h of vacuum drying；Obtain the carbon nanotube (KH560/ of KH560 grafting MWCNTs).
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added 1.1 under magnetic agitation G NaH, N2Protect 20 min of lower 90 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 2.1 g KH560/ are added MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 26 h of back flow reaction；It filters, is washed until filtrate achromaticity and clarification while hot.Institute 130 DEG C of vacuum drying 8h of solid are obtained, trace porous adsorbing material (IC4ABC) is obtained.
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 15.49mgg greatly-1And 14.08mgg-1。
Embodiment 4
(1) it takes 4 mL KH560 and the dry toluene of 40 mL in 100 mL three neck round bottom flask, 2.0 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.1 mL triethylamine, stirring and 120 DEG C of reflux 6h in drying nitrogen；Toluene, third are successively used in filtering Ketone, deionized water and acetone washing, 80 DEG C of 8 h of vacuum drying；Obtain the carbon nanotube (KH560/MWCNTs) of KH560 grafting.
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added 1.2 under magnetic agitation G NaH, N2Protect 30 min of lower 80 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 2.0 g KH560/ are added MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 24 h of back flow reaction；It filters, is washed until filtrate achromaticity and clarification while hot.Institute 120 DEG C of solid 10 h of vacuum drying are obtained, trace porous adsorbing material (IC4ABC) is obtained.
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 16.15mgg greatly-1And 14.36mgg-1。
Embodiment 5
(1) it takes 4 mL KH560 and the dry toluene of 39 mL in 100 mL three neck round bottom flask, 2.4 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.18 mL triethylamine, stirring and 120 DEG C of reflux 7h in drying nitrogen；Filtering, successively with toluene, Acetone, deionized water and acetone washing, 90 DEG C of 6 h of vacuum drying；Obtain the carbon nanotube (KH560/ of KH560 grafting MWCNTs).
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added 1.3 under magnetic agitation G NaH, N2Protect 20 min of lower 80 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 2.3 g KH560/ are added MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 28 h of back flow reaction；It filters, is washed until filtrate achromaticity and clarification while hot.Institute 120 DEG C of solid 12 h of vacuum drying are obtained, trace porous adsorbing material (IC4ABC) is obtained.
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 13.64mgg greatly-1And 13.17mgg-1。
Embodiment 6
(1) it takes 4 mL KH560 and the dry toluene of 36 mL in 100 mL three neck round bottom flask, 1.5 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.05 mL triethylamine, stirring and 110 DEG C of reflux 5h in drying nitrogen；Filtering, successively with toluene, Acetone, deionized water and acetone washing, 70 DEG C of 6 h of vacuum drying；Obtain the carbon nanotube (KH560/ of KH560 grafting MWCNTs).
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added 1.1 under magnetic agitation G NaH, N2Protect 20 min of lower 70 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 1.5 g KH560/ are added MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 20 h of back flow reaction；It filters, is washed until filtrate achromaticity and clarification while hot.Institute 100 DEG C of solid 8 h of vacuum drying are obtained, trace porous adsorbing material (IC4ABC) is obtained.
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 12.83mgg greatly-1And 12.06mgg-1。
Embodiment 7
(1) it takes 4 mL KH560 and the dry toluene of 42 mL in 100 mL three neck round bottom flask, 2.1 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.15 mL triethylamine, stirring and 110 DEG C of reflux 8h in drying nitrogen；Filtering, successively with toluene, Acetone, deionized water and acetone washing, 80 DEG C of 6 h of vacuum drying；Obtain the carbon nanotube (KH560/ of KH560 grafting MWCNTs).
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added 1.3 under magnetic agitation G NaH, N2Protect 40 min of lower 70 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 2.2 g KH560/ are added MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 24 h of back flow reaction；It filters, is washed until filtrate achromaticity and clarification while hot.Institute 110 DEG C of solid 12 h of vacuum drying are obtained, trace porous adsorbing material (IC4ABC) is obtained.
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 14.87mgg greatly-1And 13.51mgg-1。
Embodiment 8
(1) it takes 4 mL KH560 and the dry toluene of 37 mL in 100 mL three neck round bottom flask, 1.8 g is added under magnetic stirring Carboxylic carbon nano-tube and 0.07 mL triethylamine, stirring and 130 DEG C of reflux 7h in drying nitrogen；Filtering, successively with toluene, Acetone, deionized water and acetone washing, 70 DEG C of 10 h of vacuum drying；Obtain the carbon nanotube (KH560/ of KH560 grafting MWCNTs).
(2) it takes 2.5 g IC4A in 100 mL three neck round bottom flask, 50 mL toluene is added, are added 1.3 under magnetic agitation G NaH, N2Protect 40 min of lower 70 DEG C of oil baths；Standing takes supernatant liquor, and tetrabutylammonium bromide and 1.9 g KH560/ are added MWCNTs, in dry N2Middle stirring and 80 DEG C of micro- 20 h of back flow reaction；It filters, is washed until filtrate achromaticity and clarification while hot.Institute 120 DEG C of solid 8 h of vacuum drying are obtained, trace porous adsorbing material (IC4ABC) is obtained.
Simulate salt lake bittern adsorption experiment
Prepared lithium chloride/rubidium chloride mixed solution is added in 10mL colorimetric cylinder, it is porous to add a certain amount of trace Adsorbent material (IC4ABC) is used as adsorbent, and oscillation, Static Adsorption, measures to lithium/rubidium ion adsorption capacity most at room temperature It respectively may be about 13.83mgg greatly-1And 13.11mgg-1。
The result shows that trace porous adsorbing material produced by the present invention, has good structural stability, and operate letter List is easily isolated, not can cause environmental pollution.Using trace porous adsorbing material as adsorbent, lithium chloride/rubidium chloride mixing is molten Liquid is absorption object, has preferable adsorption capacity and selectivity.The sorbent structure stablize, to Lithium from Salt Lake Brine/rubidium from The adsorption rate of son is high, selectivity is good, has certain practical value.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields, Similarly it is included within the scope of the present invention.

Claims (9)

1. the porous absorption lithium/rubidium ion material preparation method of trace, which comprises the steps of:
It measures KH560 and hydroxyl carbon nano tube (MWCNTs) and triethylamine is added in dry toluene under container, magnetic agitation, dry Stirring and 110 DEG C~130 DEG C 5~8 h of reflux in dry nitrogen；
Filtering, successively uses toluene, acetone, deionized water and acetone washing, and 70 DEG C~90 DEG C 6~10 h of vacuum drying are obtained The carbon nanotube KH560/MWCNTs of KH560 grafting；
According to the solid-to-liquid ratio of 50mg:1mL, IC4A is placed in toluene, NaH is added under magnetic agitation, in N2Protect lower 70 DEG C~90 DEG C 20~40 min of oil bath；
Standing takes supernatant liquor, and tetrabutylammonium bromide and KH560/MWCNTs is added, in dry N2Simultaneously 80 DEG C of micro- reflux are anti-for middle stirring Answer 20~30 h；
Filter while hot, wash, 100 DEG C~140 DEG C 8~12 h of vacuum drying to get.
2. the porous absorption lithium/rubidium ion material preparation method of trace according to claim 1, which is characterized in that participate in anti- The proportion for each reactant answered are as follows:
The volume ratio of toluene and KH560 are 9mL~11mL:1mL, preferably 10mL:1mL；
The solid-to-liquid ratio of MWCNTs and KH560 is 3g~5g:8mL, preferably 4g:8mL；
The volume ratio of triethylamine and KH560 are 1mL:20mL~80mL, preferably 1mL:40mL；
The mass ratio of NaH and IC4A is 11mg~13mg:25mg, preferably 12mg:25mg；
The mass ratio of GBC and IC4A is 3mg~5mg:5mg, preferably 4mg:5mg.
3. the porous absorption lithium/rubidium ion material preparation method of trace according to claim 1, it is characterised in that: step A Stirring and 120 DEG C of 6 h of reflux in drying nitrogen.
4. the porous absorption lithium/rubidium ion material preparation method of trace according to claim 1, it is characterised in that: step B institute Filtering is stated, toluene, acetone, deionized water and acetone washing, 80 DEG C of vacuum drying 8h are successively used.
5. the porous absorption lithium/rubidium ion material preparation method of trace according to claim 1, it is characterised in that: step C institute It is set forth in N2Protect 30 min of lower 80 DEG C of oil baths.
6. the porous absorption lithium/rubidium ion material preparation method of trace according to claim 1, it is characterised in that: step D institute It states in dry N2It is middle stirring and 80 DEG C of micro- back flow reactions for 24 hours.
7. the porous absorption lithium/rubidium ion material preparation method of trace according to claim 1, it is characterised in that: step E institute It states and filters while hot, wash, 120 DEG C of 10 h of vacuum drying.
8. the porous absorption lithium/rubidium ion material of trace made from -7 any the methods according to claim 1.
9. a kind of by the porous absorption lithium/rubidium ion material application of trace described in claim 8, it is characterised in that: applied In the absorption of Lithium from Salt Lake Brine ion and rubidium ion.
CN201810886657.0A 2018-08-06 2018-08-06 Preparation method and application of imprinted porous lithium/rubidium ion adsorption material Active CN109174049B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810886657.0A CN109174049B (en) 2018-08-06 2018-08-06 Preparation method and application of imprinted porous lithium/rubidium ion adsorption material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810886657.0A CN109174049B (en) 2018-08-06 2018-08-06 Preparation method and application of imprinted porous lithium/rubidium ion adsorption material

Publications (2)

Publication Number Publication Date
CN109174049A true CN109174049A (en) 2019-01-11
CN109174049B CN109174049B (en) 2021-07-20

Family

ID=64920314

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810886657.0A Active CN109174049B (en) 2018-08-06 2018-08-06 Preparation method and application of imprinted porous lithium/rubidium ion adsorption material

Country Status (1)

Country Link
CN (1) CN109174049B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111229174A (en) * 2020-01-13 2020-06-05 江苏大学 Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane
CN113244895A (en) * 2021-04-08 2021-08-13 浙江工业大学 Preparation method of lithium ion imprinted cross-linked chitosan porous microspheres
CN116496509A (en) * 2023-06-21 2023-07-28 北京建工环境修复股份有限公司 Magnetic calixarene polymer and preparation method and application thereof
CN117015436A (en) * 2023-06-16 2023-11-07 广东邦普循环科技有限公司 Preparation method and application of lithium ion sieve particles

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050215762A1 (en) * 2004-03-26 2005-09-29 Council Of Scientific And Industrial Research Synthesis of ion imprinted polymer particles
CN102626611A (en) * 2012-04-11 2012-08-08 哈尔滨工程大学 Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance
CN106902745A (en) * 2017-03-08 2017-06-30 江苏大学 A kind of preparation method and applications of lithium/rubidium ion synchronization adsorbent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050215762A1 (en) * 2004-03-26 2005-09-29 Council Of Scientific And Industrial Research Synthesis of ion imprinted polymer particles
CN102626611A (en) * 2012-04-11 2012-08-08 哈尔滨工程大学 Method for preparing metal ion imprinting adsorbent with underwater selective recognition performance
CN106902745A (en) * 2017-03-08 2017-06-30 江苏大学 A kind of preparation method and applications of lithium/rubidium ion synchronization adsorbent

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XUBIAO LUO ET AL.: "Recovery of Lithium from Wastewater Using Development of Li Ion-Imprinted Polymers", 《ACS SUSTAINABLE CHEM. ENG.》 *
黄东方 等: "铷离子印迹聚合物的制备及其吸附性能研究", 《分析仪器》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111229174A (en) * 2020-01-13 2020-06-05 江苏大学 Preparation method and application of Li-IIMs (lithium-ion organic Compounds) ion imprinting membrane
CN113244895A (en) * 2021-04-08 2021-08-13 浙江工业大学 Preparation method of lithium ion imprinted cross-linked chitosan porous microspheres
CN113244895B (en) * 2021-04-08 2022-05-17 浙江工业大学 Preparation method of lithium ion imprinted cross-linked chitosan porous microspheres
CN117015436A (en) * 2023-06-16 2023-11-07 广东邦普循环科技有限公司 Preparation method and application of lithium ion sieve particles
CN116496509A (en) * 2023-06-21 2023-07-28 北京建工环境修复股份有限公司 Magnetic calixarene polymer and preparation method and application thereof
CN116496509B (en) * 2023-06-21 2023-12-08 北京建工环境修复股份有限公司 Magnetic calixarene polymer and preparation method and application thereof

Also Published As

Publication number Publication date
CN109174049B (en) 2021-07-20

Similar Documents

Publication Publication Date Title
CN109174049A (en) The porous absorption lithium/rubidium ion material preparation method and application of trace
CN112679731B (en) Covalent organic framework material containing sulfonic acid group and preparation and application thereof
CN105170095A (en) In-based organic framework-graphene oxide composite material as well as preparation method and application thereof
CN106076271B (en) A kind of nano-magnetic polylysine/（Graphene oxide-carbon nanotube）The preparation method and application of biological adsorption material
CN102716722A (en) Preparation method of graphene-based novel nano magnetic biological adsorbent
CN113368812B (en) Co3O4Halloysite composite material, preparation method and application
CN106732470A (en) A kind of preparation of 2 mercaptopyrimidine modified magnetic CNT porous adsorbent
CN108940237A (en) A kind of preparation method and application of magnetic adsorptive material
CN101279206A (en) MFI molecular sieve film and applications thereof in aspects of CO2 recovery and process
CN109569720A (en) It is a kind of using carboxylated carbon-based material as the preparation method of the monatomic catalyst of the metal of carrier
CN109289531A (en) A kind of preparation method of the dimethyl silicone polymer for organic solvent nanofiltration/meso-porous nano silicon composite membrane
CN109621910A (en) Nano zero valence iron-metal organic frame core-shell material preparation method and applications
CN110560001A (en) Preparation method and application of Fe-MOFs nano material containing ionic liquid
CN107999019B (en) Amphiphilic magnetic nanosphere and preparation method and adsorption application thereof
Su et al. KOH-activated geopolymer microspheres recycle Co (II) with higher adsorption capacity than NaOH-activated ones
CN115490879A (en) EDTA (ethylene diamine tetraacetic acid) -modified UIO-66 (Zr) metal organic framework material as well as preparation method and application thereof
CN108636387A (en) A kind of iron ion absorption sponge and its preparation method and application
Wang et al. Silver-modified porous polystyrene sulfonate derived from Pickering high internal phase emulsions for capturing lithium-ion
CN107827108A (en) A kind of pole micro-pore carbon material and preparation method thereof
CN108440767A (en) It is a kind of that nanometer Au is combined to the new method for preparing Au@MOF composite materials with porous MOF
Chen et al. Effective adsorption of heavy metal ions in water by sulfhydryl modified nano titanium dioxide
CN103977835B (en) Sulfonated graphite thiazolinyl Ru (bpy)32+nanometer heterogeneous catalysis and preparation method thereof
CN106540663B (en) A kind of preparation method of the crown ether modified carbon nano tube tube material for adsorption uranium
CN108201883A (en) It is a kind of for magnetic Nano material of hexavalent chromium and preparation method thereof in water body of degrading
CN110314637B (en) Modified goethite and preparation method and application thereof

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
GR01 Patent grant
GR01 Patent grant