CN110252263A - A kind of peanut shell base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application - Google Patents
A kind of peanut shell base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application Download PDFInfo
- Publication number
- CN110252263A CN110252263A CN201910586361.1A CN201910586361A CN110252263A CN 110252263 A CN110252263 A CN 110252263A CN 201910586361 A CN201910586361 A CN 201910586361A CN 110252263 A CN110252263 A CN 110252263A
- Authority
- CN
- China
- Prior art keywords
- peanut shell
- porous carbon
- stage porous
- shell base
- imprinted material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
-
- 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
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation methods of peanut shell base magnetism multi-stage porous carbon surface imprinted material, the preparation of preparation, peanut shell base magnetism multi-stage porous carbon including peanut shell activated feedstock and the preparation of peanut shell base magnetism multi-stage porous carbon surface imprinted material, for the present invention using cheap, abundance agricultural wastes peanut shell as raw material, preparing can be from the imprinted material effectively identified in complex system with phenols endocrine disruptors in separation and concentration environment.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly to a kind of peanut shell base magnetism multi-stage porous carbon table
Face imprinted material and its preparation method and application.
Background technique
Environment incretion interferent (Environmental Endocrine Disruptors, EEDs), refers to that the mankind exist
Production, life in can be discharged into environment the synthesis that human body and animal hormone in vivo can be influenced as hormone or antihormones,
The substance of the links such as secretion, effect and metabolism generally has bioaccumulation, environmental persistence, high toxicity, moves over long distances
The important features such as shifting ability.Existing EEDs mainly has more than 70, multi-chlorophenol (such as pentachlorophenol, tetrachlorophenol, trichlorine therein
Phenol and chlorophenesic acid etc.) and bis-phenol (such as bisphenol-A, bisphenol AF, bisphenol-ap and tetrabromobisphenol A) etc. it is special with its similar structure
Quasi-waverider vehicle of seeking peace gradually is divided into a new class of analysis and research object, referred to as phenols endocrine disruptors
(Phenolic Endocrine Disruptors, PEDs).
Currently, having much for the processing method of PEDs class organic pollutant, traditional water treatment technology is unable to satisfy at all
The demand of advanced treating.What absorption method had is particularly advantageous in that easy to operate, high-efficient, low energy consumption, investment cost is low, does not produce
Raw secondary pollution, the pollutant that toxicity will not be brought bigger or more difficult to degrade, but common adsorbent is in the prevalence of selection
The disadvantages of property is poor, thermal stability is poor, adsorption capacity is small, and equilibration time is long.Therefore, highly selective, big adsorption capacity, excellent is developed
The new adsorbent of regenerability, establishing targeting separation/enrichment system is research field very active at present.
Molecularly imprinted polymer (MIPs) be by molecular imprinting technology synthesis to target molecule have specific recognition with
The polymer of selective absorption, the biggest advantage is to have high selectivity recognition capability and specificity to target molecule by MIPs
Affinity has good mechanical strength, crushing resistance and stability.
The active group rich in such as various agricultural wastes such as stalk, shell, have good biocompatibility and
Reproducibility, resourceful, cheap and easy to get, less toxic and be readily biodegradable, and organic polymer good compatibility, if being subject to effectively
It utilizes, the cost for preparing functional form material can be substantially reduced.Especially agricultural wastes-peanut shell, fibre rich in
Tie up the organic substances such as element and lignin, active group rich in, specific surface area with higher and hole in peanut shell powder
Gap rate.
Therefore, how to prepare a kind of pair of phenols endocrine disruptors using agricultural wastes has specific recognition capability
Porous carbon-based imprinted material is of great significance.
Summary of the invention
In view of this, the present invention is with cheap, the peanut shell being readily biodegradable provides a kind of flower as raw material
Raw shell base magnetism multi-stage porous carbon surface imprinted material has specific recognition capability to phenols endocrine disruptors.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, comprising the following steps:
(1) preparation of peanut shell activated feedstock
Peanut shell powder is added in phosphoric acid solution, vacuum is dry after a period of time is stirred to react under condition of water bath heating
It is dry to obtain peanut shell activated feedstock；
(2) preparation of peanut shell base magnetism multi-stage porous carbon
The peanut shell activated feedstock is uniformly mixed and is ground with potassium hydroxide, the ethanol solution of iron chloride is added
It is stirred, will be transferred in tube furnace after said mixture vacuum drying, high temperature cabonization magnetizes under inert gas protection, passes through
Peanut shell base magnetism multi-stage porous carbon is obtained after cooling, washing, drying；
(3) preparation of peanut shell base magnetism multi-stage porous carbon surface imprinted material
4- chlorophenol is dissolved in the reaction flask equipped with toluene, 4-vinylpridine, dimethacrylate second is then added
Diol ester ultrasonic mixing is uniform, sealing and standing 12-24h, continuously add (the 2- methyl-propyl miaow) dihydrochloride of 2,2- azo two and
Peanut shell base magnetism multi-stage porous carbon is passed through nitrogen-sealed reaction flask after being sufficiently mixed, carry out magnetic agitation and obtain pulverulent solids,
By washing, drying, extraction, peanut shell base magnetism multi-stage porous carbon surface imprinted material is obtained.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (1)
Described in peanut shell powder be to be cleaned using discarded peanut shell as raw material with tap water, it is drying, broken, be sized to 150-200 μm
It is made.
The beneficial effect of above-mentioned technical proposal is: peanut shell powder both can guarantee and be prepared in this particle size range
Surface imprinted material has good mechanical stability, and ensure that the higher porosity of surface imprinted material and specific surface
Product.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (1)
The mass ratio of middle peanut shell powder and phosphoric acid solution is 1:1-3, and wherein the mass percentage concentration of phosphoric acid solution is 10-20%.
The beneficial effect of above-mentioned technical proposal is: phosphoric acid has activation as activator, to peanut shell, with peanut shell
The restriction of powder quality ratio can make surface imprinted material reach optimal activation effect.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (1)
Described in water bath heating temperature be 70-80 DEG C, time 2-5h.
The beneficial effect of above-mentioned technical proposal is: the activation effect of peanut shell powder can be improved in heating water bath, and leads to
It crosses experimental studies have found that above-mentioned temperature and time can achieve optimal activation effect.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (1)
Described in vacuum drying temperature be 80-100 DEG C, time 12-24h.
The beneficial effect of above-mentioned technical proposal is: the peanut shell activated feedstock of available drying, in order to subsequent hydrogen-oxygen
Change the activation of potassium.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (2)
The mass ratio of middle peanut shell activated feedstock and potassium hydroxide is 1-3:1.
The beneficial effect of above-mentioned technical proposal is: potassium hydroxide plays a role as activator, peanut shell activated feedstock with
The restriction of hydroxide collection ratio peomotes in subsequent activation process activator potassium hydroxide in peanut shell multi-stage porous carbon
Interior diffusion improves activation efficiency, increases the specific surface area and pore volume of carbon material.
Since the initial activation stage, radially activation was main activated form, what is mainly generated is micropore, when temperature reaches 800
DEG C or so when, activation enters lateral activation stage, and what is mainly generated at this time is biggish hole, if further increasing potassium hydroxide
Amount and activation time and temperature, the pore canal system of multi-stage porous carbon will collapse by serious destruction.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (2)
The mass ratio of the ethanol solution of middle peanut shell activated feedstock, the quality sum of potassium hydroxide and iron chloride is 5:15-20, wherein chlorine
The concentration for changing the ethanol solution of iron is 0.05-0.3g/mL.
The beneficial effect of above-mentioned technical proposal is: the ethanol solution of iron chloride is added to peanut shell base multi-stage porous carbon
Magnetization, the restriction of aforementioned proportion can guarantee prepared peanut shell base magnetism multi-stage porous carbon have enough intensity of magnetization and
Magnetic responsiveness.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (2)
Described in carbonization magnetization be to be warming up to 600-800 DEG C with the rate of 8-10 DEG C/min, carbonization magnetizing time is 3-5h.
The beneficial effect of above-mentioned technical proposal is: passing through the heating rate in carbonization magnetic history, temperature, the control of time
System realizes the control to char-forming material pass structure, synthesizes the activated carbon with high-specific surface area and pore volume, and make it have
Good stability and regenerability.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (2)
Described in drying temperature be 80-100 DEG C, the flow velocity of the inert gas is 120-150mL/min.
The beneficial effect of above-mentioned technical proposal is: 80-100 DEG C of drying temperature ensure that the speed and quality of drying；It is lazy
Property gas plays the role of protection, if air velocity is not achieved limit value and can weaken the protective effect of inert gas.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (2)
Described in washing solution be volume ratio be 1:1 ethanol distillation water mixed solution.
The beneficial effect of above-mentioned technical proposal is: can achieve the thorough mesh of cleaning by the processing of above-mentioned washing solution
's.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (3)
Middle 4- chlorophenol, toluene, 4-vinylpridine, ethylene glycol dimethacrylate, 2,2- azo two (2- methyl-propyl miaow) disalt
Hydrochlorate and peanut shell base magnetism multi-stage porous carbon amount ratio are 1:(150-200): (150-200): (2.0-3.0): (40-50): (3-
5)(g/mL/μL/mL/mg/g)
The beneficial effect of above-mentioned technical proposal is: 4- chlorophenol is as template molecule, its print for being added to make to prepare
Mark material has the imprinted cavity to 4- chlorophenol Selective recognition；4-vinylpridine is synthesis macromolecule as function monomer
The important monomer of polymer；Ethylene glycol dimethacrylate is crosslinking agent, 2,2- azo two (2- methyl-propyl miaow) two hydrochloric acid
Salt is water soluble starter, and in the aqueous solution polymerization for polymerization macromolecule synthesis, efficiency of initiation is high, the average molecular matter of product
It measures relatively high, good water solubility and Remained mass is few.4-vinylpridine function monomer and ethylene glycol dimethacrylate are handed over
Join agent in the presence of initiator (2,2- azo two (2- methyl-propyl miaow) dihydrochloride), carries out polymerisation in solution, the height of synthesis
Molecularly Imprinted Polymer has good mechanical strength and antioxygenic property.
The additive amount of each substance will affect the mechanical strength of polymerization speed and high molecular polymer, be by serial real
Test one group of data that optimization obtains.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (3)
Described in magnetic agitation temperature be 60-70 DEG C, time 12-24h.
The beneficial effect of above-mentioned technical proposal is: can guarantee that the material mixing being added is more abundant, make the polymerization of preparation
Object has better mechanical performance, chemical stability and thermal stability.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (3)
Described in drying be to dry in 50-60 DEG C of vacuum oven to constant weight.
The beneficial effect of above-mentioned technical proposal is: drying both can guarantee prepared molecule in 50-60 DEG C of vacuum oven
Imprinted material is dried to constant weight, and does not influence the subsequent absorption property of material.
Preferably, in a kind of above-mentioned preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, step (3)
Described in extract be with volume ratio be 9:1 methanol and acetic acid mixed solution Soxhlet extraction for 24 hours, until eluent in can't detect
4- chlorophenol.
The beneficial effect of above-mentioned technical proposal is: with methanol and acetic acid volume ratio be 9:1 mixed liquor Soxhlet extraction for 24 hours,
It is more thorough can to guarantee that template molecule extracts.
The present invention also provides a kind of peanut shell base magnetism multi-stage porous carbon being prepared according to the above method is surface imprinted
Material.
And a kind of application for the peanut shell base magnetism multi-stage porous carbon surface imprinted material being prepared according to the above method,
The imprinted material is used for the separation and enrichment of phenols endocrine disruptors.
It can be seen via above technical scheme that compared with prior art, the present disclosure provides a kind of peanut shell base magnetic
Property multi-stage porous carbon surface imprinted material, it is simultaneous with organic polymer with resourceful, cheap and easy to get, less toxic and be readily biodegradable
The good peanut shell of capacitive has obtained the peanut shell of a kind of highly selective, big adsorption capacity and excellent regenerability as raw material
Base magnetism multi-stage porous carbon surface imprinted material, to phenols endocrine disruptors in water with high selectivity recognition capability and specifically
Property affinity.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 attached drawing is that the SEM of peanut shell of embodiment of the present invention base magnetism multi-stage porous carbon surface imprinted material schemes；
Fig. 2 attached drawing is the thermogravimetric analysis figure of peanut shell of embodiment of the present invention base magnetism multi-stage porous carbon surface imprinted material；
Fig. 3 attached drawing is that peanut shell of embodiment of the present invention base magnetism multi-stage porous carbon and peanut shell base magnetism multi-stage porous carbon surface print
The magnetic property analysis chart of mark material；
Fig. 4 attached drawing is that peanut shell of embodiment of the present invention base magnetism multi-stage porous carbon surface imprinted material and non-imprinted material are adsorbed
The adsorption isotherm map of 4- chlorophenol；
Fig. 5 attached drawing is that peanut shell of embodiment of the present invention base magnetism multi-stage porous carbon surface imprinted material and non-imprinted material are adsorbed
The adsorption dynamics adsorption kinetics figure of 4- chlorophenol；
Fig. 6 attached drawing is peanut shell of embodiment of the present invention base magnetism multi-stage porous carbon surface imprinted material and non-trace adsorbent material
To the selective absorption figure of a variety of chlorophenols compounds；
Fig. 7 attached drawing is the regeneration of peanut shell base magnetism multi-stage porous carbon surface imprinted material after the embodiment of the present invention repeatedly recycles
Performance；
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The embodiment of the invention discloses a kind of preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, steps
It is as follows:
(1) preparation of peanut shell base magnetism multi-stage porous carbon
It by discarded peanut shell, is cleaned with tap water, drying is crushed, and is sized to 150-200um, peanut shell powder is made
Above-mentioned peanut shell powder is added in the phosphoric acid solution that mass concentration is 10%-20% and stirs by end, peanut shell powder and phosphoric acid
The mass ratio of solution (activator) is 1:1-3, under the conditions of -80 DEG C of temperature 70 C, heating water bath 2.0-5.0h；It is 80 in temperature
Under the conditions of DEG C -100 DEG C, it is dried in vacuo 12-24h, obtains peanut shell activated feedstock；Potassium hydroxide and peanut shell activated feedstock are pressed
It is uniformly mixed according to the mass ratio of 1:1-3, is put into mortar and is ground；It is then 0.05-0.3g/ml by said mixture and concentration
The ethanol solution of iron chloride is mixed according to the ratio that mass ratio is 5:15-20, and mechanical stirring is uniformly mixed, in 80-100 DEG C of baking oven
Middle vacuum drying.Above-mentioned material is transferred in tube furnace, under inert nitrogen gas protection, gas flow rate 120-150mL/
Min is heated up 600-800 DEG C with 8-10 DEG C/min heating rate, and carbonization magnetizing time is 3.0-5.0h, after natural cooling, will be managed
Product in formula furnace takes out, the ethyl alcohol/distilled water washed product for being 1:1 with volume ratio, drying, and it is magnetic multistage to obtain peanut shell base
Hole carbon.
(2) preparation of peanut shell base magnetism multi-stage porous carbon surface imprinted material (MMIPs)
By 4- chlorophenol, toluene, 4-vinylpridine, ethylene glycol dimethacrylate, (the 2- methyl-propyl of 2,2- azo two
Miaow) dihydrochloride and peanut shell base magnetism multi-stage porous carbon be according to 1:(150-200): (150-200): (2.0-3.0): (40-50):
The ratio of (3-5) (g/mL/ μ L/mL/mg/g), 4- chlorophenol (4-CP) is dissolved in the round-bottomed flask of the 100mL equipped with toluene,
4-vinylpridine and ethylene glycol dimethacrylate are then added thereto, ultrasonic mixing is uniform, sealing, static 12-
24h.Then, (the 2- methyl-propyl miaow) dihydrochloride (APPH) of 2,2- azo two is added in Xiang Shangshu solution and peanut shell base is magnetic
Multi-stage porous carbon after being sufficiently mixed, is passed through nitrogen 20-30min, seals reaction flask, be placed in magnetic force in 60-70 DEG C of constent temperature heater
12.0-24.0h is stirred, pulverulent solids is obtained, is repeatedly washed with dehydrated alcohol, is then done in 50-60 DEG C of vacuum oven
It is dry to constant weight.Then by the solid after drying with volume ratio be 9:1 methanol and acetic acid mixed solution Soxhlet extraction for 24 hours, until
It can't detect 4- chlorophenol (4-CP) in eluent.
The preparation method of peanut shell base magnetism multi-stage porous carbon surface non-imprinted material is same as above, and 4- chlorophenol is only not added in the process
(4-CP)。
Referring to attached drawing 1-3, for the peanut shell base magnetism multi-stage porous carbon surface imprinted material that the present embodiment is prepared
(MMIPs) detection carried out, as a result as follows:
It can be seen that peanut shell base magnetism multi-stage porous carbon surface prepared by the present embodiment from the scanning electron microscope map of Fig. 1
Imprinted material (MMIPs) favorable dispersibility is in uniform spherical structure, and having a size of between 100-250nm, peanut shell base is magnetic more
The surface roughness of grade hole carbon surface imprinted material (MMIPs), is coated with one layer of trace polymerization layer, illustrates to obtain by polymerization
Obtain uniform polymeric layer.
It is non-to peanut shell base magnetism multi-stage porous carbon surface imprinted material (MMIPs) and peanut shell base magnetism multi-stage porous carbon surface
Imprinted material (MNIPs) carries out nitrogen adsorption-desorption analysis, as a result referring to table 1:
Nitrogen adsorption-desorption analysis of table 1 MMIPs and MNIPs compares
From table 1 it follows that compared with peanut shell base magnetism multi-stage porous carbon surface non-imprinted material (MNIPs), peanut
Shell base magnetism multi-stage porous carbon surface imprinted material (MMIPs) possesses bigger Kong Rong, specific surface area and average cell size.
It is respectively peanut shell base magnetism multi-stage porous carbon (a), peanut shell base magnetism multi-stage porous carbon surface imprinted material in Fig. 2
(MMIPs) thermogravimetric analysis figure of (b) and peanut shell base magnetism multi-stage porous carbon surface non-imprinted material (MNIPs) (c).Initial
In 300 DEG C, peanut shell base magnetism multi-stage porous carbon, MMIPs and MNIPs thermal stability are relatively good, and corresponding weight-loss ratio is respectively
3.850%, 7.320% and 13.56%, mainly due to the weightlessness of free water, when temperature rises to 700 DEG C, MMIPs and
There is biggish weightlessness in MNIPs, and weight-loss ratio is respectively 75.20% and 81.80%, this is attributed to point of surface imprinted polymer layer
Solution, the remaining substance of MMIPs and MNIPs is mainly the Fe of thermal resistance at 800 DEG C3O4Magnetic nano-particle and a small amount of carbon or stone
Ink.
Fig. 3 a is that peanut shell base magnetism multi-stage porous carbon and peanut shell base magnetism multi-stage porous carbon surface imprinted material (MMIPs) exist
Hysteresis loop when room temperature.Comparing two hysteresis loops in figure, it can be seen that the variation tendency of two curves is similar with shape,
It and is all to show that peanut shell base magnetism multi-stage porous carbon and MMIPs all have superparamagnetism, at room temperature peanut about origin symmetry
The saturation magnetization of shell base magnetism multi-stage porous carbon and MMIPs are respectively 8.788emug-1And 3.686emug-1。
Studies have shown that MMIPs possesses enough magnetic response abilities, Magnetic Isolation effect is obvious.Fig. 3 b is pH value pair
The influence of MMIPs magnetic stability is leaked out from MMIPs in the range of pH value is 4.0-8.0 almost without iron ion,
With the reduction of pH value, the leakage rate of iron ion is increased slightly, and in pH=4.0, the magnetic flux leakage of MMIPs reaches maximum, often
There are about the leakages of 7.688 μ g iron ions in 50mgMMIPs.
The peanut shell base magnetism multi-stage porous carbon that the present embodiment is prepared below with reference to specific embodiment is surface imprinted
The application of material is described further:
Absorption property evaluation is completed using Static Adsorption test in the present embodiment specific embodiment.
25ml 4- chlorophenol (4-CP) solution is added in centrifuge tube, it is magnetic more that 10mg peanut shell base is added thereto respectively
Grade hole carbon surface imprinted material (MMIPs) and non-imprinted material (MNIPs), it is static in room-temperature water bath, respectively investigation adsorption time,
Influence of the initial concentration solution to 4- chlorophenol (4-CP) adsorption capacity.After absorption reaches balance, MMIPs and MNIPs Nd-Fe-B
Permanent magnet separates, and the concentration of 4- chlorophenol (4-CP) is measured with UV-vis method in balance solution, unadsorbed 4- chlorophenol in solution
(4-CP) concentration is measured with ultraviolet-uisible spectrophotometer (being at 282nm in wavelength).UV detector maximum absorption wavelength point
Not in 272nm, 288nm and 292nm) at measure phenol, 2,4,6- trichlorophenol, 2,4,6,-T (6-TCP) and 5-TCP content.
Q=[(C0-Ce)V]/W
C0(μm ol/L) and CeConcentration when (μm ol/L) is respectively the initial concentration and balance of 4-CP, V (mL) and W (mg)
The respectively dosage of liquor capacity and adsorbent material.
Test example 1: taking 25ml initial concentration is respectively the 4-CP of 10,20,30,50,60,80,100,150,200 μm of ol/L
Solution is added in centrifuge tube, is separately added into 10mg peanut shell base magnetism multi-stage porous carbon surface imprinted material and non-imprinted material,
Test solution is placed in room temperature water bath and is stood for 24 hours, unadsorbed 4-CP concentration is measured with ultraviolet-uisible spectrophotometer,
Calculate adsorption capacity.
As shown in figure 4, adsorption capacity increases therewith with the raising of concentration, surface imprinted material saturated adsorption capacity is
54.80umol/g, the saturated adsorption capacity of non-imprinted material are 36.22umol/g, peanut shell base magnetism multi-stage porous carbon surface print
Mark material is much larger than non-imprinted material to 4-CP adsorption capacity to the adsorption capacity of 4-CP, illustrates peanut shell base magnetism multi-stage porous carbon
There are a large amount of trace holes to match as active site and 4-CP molecule for surface imprinted material, shows good trace effect
Fruit.
Test example 2: taking 25ml initial concentration is that the 4-CP solution of 200 μm of ol/L is added in centrifuge tube, and 10mg flower is added
Test solution is placed in room temperature water bath and stands respectively by raw shell base magnetism multi-stage porous carbon surface imprinted material and non-imprinted material
5,10,30,45,60,90,120 and 150min after reaching time of repose, collects supernatant, and unadsorbed 4-CP concentration is purple
Outer visible spectrophotometer measurement, calculates adsorption capacity.
As can be known from Fig. 5, the incipient stage, adsorption capacity increased sharply with the increase of adsorption time, and absorption reaches after 60min
To balance, in entire adsorption time, the adsorption capacity of peanut shell base magnetism multi-stage porous carbon surface imprinted material is all larger than non-print
Adsorption capacity of the mark material to 4-CP.
Test example 3: selection phenol, 2,4,6- trichlorophenol, 2,4,6,-Ts (6-TCP) and 5-TCP are the phenolic compound of competitive Adsorption,
Above-mentioned three kinds of phenolic compounds that solution concentration is 150 μm of ol/L are prepared respectively, take the configured solution of 20ml that centrifuge tube is added
In, it is then separately added into 10mg peanut shell base magnetism multi-stage porous carbon surface imprinted material and non-imprinted material, in 25 DEG C of thermostatted waters
12h is stood in bath.MMIPs and MNIPs is separated with Nd-Fe-B permanent magnet, collects supernatant, and unadsorbed various competitions are inhaled
Attached phenolic compound concentration is measured with ultraviolet-uisible spectrophotometer, calculates adsorption capacity.
From fig. 6 it can be seen that trace adsorbent material has significant specific selection identification and separation and concentration energy to 4-CP
Power, adsorption capacity are apparently higher than other phenolic compounds.
Test example 4: the regenerability of adsorbent material
After peanut shell base magnetism multi-stage porous carbon surface imprinted material absorption 4-CP reaches balance, supernatant is removed, print is collected
Mark material is used as eluant, eluent with the mixed solution (9:1, V/V) of methanol and acetic acid, takes under 10.0mL eluant, eluent ultrasound condition
60min elutes imprinted material.Five attached circulations of adsorption/desorption according to the method described above.
From figure 7 it can be seen that the imprinted material after five regeneration is in single 4-CP solution and the similar phenol generalization of structure
In the mixed solution of adduct molecule 17.22% and 18.21% are reduced to the adsorption capacity of 4-CP respectively, shows the present embodiment institute
The peanut shell base magnetism multi-stage porous carbon surface imprinted material material of preparation has excellent regenerability.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For device disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
1. a kind of preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material, which comprises the following steps:
(1) preparation of peanut shell activated feedstock
Peanut shell powder is added in phosphoric acid solution, is dried in vacuo after a period of time is stirred to react under condition of water bath heating
To peanut shell activated feedstock；
(2) preparation of peanut shell base magnetism multi-stage porous carbon
The peanut shell activated feedstock is uniformly mixed and is ground with potassium hydroxide, the ethanol solution stirring of iron chloride is added
Mixing, will be fitted into tube furnace after said mixture vacuum drying, and high temperature cabonization magnetizes under inert gas protection, through being subcooled
But, wash, obtain peanut shell base magnetism multi-stage porous carbon after drying；
(3) preparation of peanut shell base magnetism multi-stage porous carbon surface imprinted material
4- chlorophenol is dissolved in the reaction flask equipped with toluene, 4-vinylpridine, ethylene glycol dimethacrylate is then added
Ester ultrasonic mixing is uniform, sealing and standing 12-24h, continuously adds (the 2- methyl-propyl miaow) dihydrochloride of 2,2- azo two and peanut
Shell base magnetism multi-stage porous carbon, is passed through nitrogen-sealed reaction flask after being sufficiently mixed, obtain to reaction flask progress magnetic agitation powdered
Solid obtains peanut shell base magnetism multi-stage porous carbon surface imprinted material by washing, drying, extraction.
2. the preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material according to claim 1, feature exist
In the mass ratio of peanut shell powder and phosphoric acid solution is 1:1-3 in step (1), and wherein the mass percentage concentration of phosphoric acid solution is
10%-20%.
3. the preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material according to claim 1, feature exist
In the mass ratio of peanut shell activated feedstock and potassium hydroxide is 1-3:1 in step (2).
4. the preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material according to claim 1 or 3, feature
It is, the mass ratio of the ethanol solution of peanut shell activated feedstock, the quality sum of potassium hydroxide and iron chloride is 5 in step (2):
15-20, wherein the concentration of the ethanol solution of iron chloride is 0.05-0.3g/mL.
5. the preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material according to claim 1, feature exist
In carbonization magnetization described in step (2) is to be warming up to 600-700 DEG C with the rate of 8-10 DEG C/min, and carbonization magnetizing time is 3-
5h。
6. the preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material according to claim 1, feature exist
In 4- chlorophenol, toluene, 4-vinylpridine, ethylene glycol dimethacrylate, (the 2- methyl-prop of 2,2- azo two in step (3)
Base miaow) dihydrochloride and peanut shell base magnetism multi-stage porous carbon amount ratio be 1g:(150-200) mL:(150-200) μ L:(2.0-
3.0) mL:(40-50) mg:(3-5) g.
7. the preparation method of peanut shell base magnetism multi-stage porous carbon surface imprinted material according to claim 1, feature exist
In, extraction described in step (3) be with volume ratio be 9:1 methanol and acetic acid mixed solution Soxhlet extraction for 24 hours, until eluent
In can't detect 4- chlorophenol.
8. the peanut shell base magnetism multi-stage porous carbon that any one of -7 the methods are prepared a kind of according to claim 1 is surface imprinted
Material.
9. the peanut shell base magnetism multi-stage porous carbon that any one of -7 the methods are prepared a kind of according to claim 1 is surface imprinted
The application of material, which is characterized in that the surface imprinted material is used for the separation and enrichment of phenols endocrine disruptors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910586361.1A CN110252263A (en) | 2019-07-01 | 2019-07-01 | A kind of peanut shell base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910586361.1A CN110252263A (en) | 2019-07-01 | 2019-07-01 | A kind of peanut shell base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110252263A true CN110252263A (en) | 2019-09-20 |
Family
ID=67923690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910586361.1A Pending CN110252263A (en) | 2019-07-01 | 2019-07-01 | A kind of peanut shell base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110252263A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406108A (en) * | 2013-07-10 | 2013-11-27 | 江苏大学 | Preparation method of carbon-based magnetic temperature-sensitive surface imprinted adsorbent |
| CN104130441A (en) * | 2014-07-18 | 2014-11-05 | 浙江大学宁波理工学院 | Magnetic field-induced preparation method of molecularly-imprinted magnetic enrichment material of trace quantity of chlorophenol pollutant molecules in seawater |
| CN104341562A (en) * | 2014-10-28 | 2015-02-11 | 武夷学院 | Magnetic molecularly-imprinted polymer for identifying and enriching varieties of trace antibiotics and preparation method and application thereof |
| CN104741097A (en) * | 2015-03-16 | 2015-07-01 | 河南城建学院 | Preparation method of chloramphenicol molecular imprinted adsorbing material on surface of magnetic carbon microsphere |
| CN104892867A (en) * | 2015-03-16 | 2015-09-09 | 河南城建学院 | Preparation method for illite magnetic composite surface imprinting temperature-sensitive adsorbent |
| US20150344607A1 (en) * | 2012-12-21 | 2015-12-03 | Universite De Toulon | Imprinted polymer and method for preparing the same |
| CN105170112A (en) * | 2015-07-27 | 2015-12-23 | 河南城建学院 | Preparation method for magnetic carbon microsphere surface cephalexin molecular imprinted adsorbent material |
| CN107115843A (en) * | 2017-05-23 | 2017-09-01 | 江苏大学 | A kind of preparation method and applications for coming from peanut shell modified activated carbon |
-
2019
- 2019-07-01 CN CN201910586361.1A patent/CN110252263A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150344607A1 (en) * | 2012-12-21 | 2015-12-03 | Universite De Toulon | Imprinted polymer and method for preparing the same |
| CN103406108A (en) * | 2013-07-10 | 2013-11-27 | 江苏大学 | Preparation method of carbon-based magnetic temperature-sensitive surface imprinted adsorbent |
| CN104130441A (en) * | 2014-07-18 | 2014-11-05 | 浙江大学宁波理工学院 | Magnetic field-induced preparation method of molecularly-imprinted magnetic enrichment material of trace quantity of chlorophenol pollutant molecules in seawater |
| CN104341562A (en) * | 2014-10-28 | 2015-02-11 | 武夷学院 | Magnetic molecularly-imprinted polymer for identifying and enriching varieties of trace antibiotics and preparation method and application thereof |
| CN104741097A (en) * | 2015-03-16 | 2015-07-01 | 河南城建学院 | Preparation method of chloramphenicol molecular imprinted adsorbing material on surface of magnetic carbon microsphere |
| CN104892867A (en) * | 2015-03-16 | 2015-09-09 | 河南城建学院 | Preparation method for illite magnetic composite surface imprinting temperature-sensitive adsorbent |
| CN105170112A (en) * | 2015-07-27 | 2015-12-23 | 河南城建学院 | Preparation method for magnetic carbon microsphere surface cephalexin molecular imprinted adsorbent material |
| CN107115843A (en) * | 2017-05-23 | 2017-09-01 | 江苏大学 | A kind of preparation method and applications for coming from peanut shell modified activated carbon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Fabricating magnetic hydrophilic molecularly imprinted resin with enhanced adsorption and recognition performance for targeted detecting chlorophenols in environmental water | |
| CN102527349B (en) | Magnetic composite material surface imprinting thermosensitive adsorbent, and preparation method and application thereof | |
| CN102350319B (en) | Preparation method of fly ash superbead magnetic composite material surface imprinting adsorbent | |
| CN102977288B (en) | Molecularly imprinted magnetic microsphere, preparation method and application thereof | |
| CN105131178B (en) | Preparation method of molecularly imprinted composite material for enriching and separating glycoprotein | |
| CN102580696A (en) | Preparation method of temperature sensitive adsorbent of halloysite magnetic composite material surface blotting | |
| CN106076271B (en) | A kind of nano-magnetic polylysine/（Graphene oxide-carbon nanotube）The preparation method and application of biological adsorption material | |
| CN109174023A (en) | A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application | |
| CN105218765B (en) | A kind of Preparation method and use of photoresponse intelligence trace mesoporous material | |
| CN104128161B (en) | A kind of amino modified activated coke heavy metal absorbent and preparation method thereof | |
| Liao et al. | Rational design of hyper‐crosslinked polymers for biomedical applications | |
| CN103657600A (en) | Modified water treatment absorbent and preparation method and application thereof | |
| CN109317120A (en) | A kind of super crosslinked polymeric materials and preparation method thereof | |
| CN109232782A (en) | A kind of preparation method for the molecularly imprinted polymer targeting adsorbing separation taxol | |
| CN106046256B (en) | The preparation method of geniposide molecular engram polymer magnetic microballoon | |
| Wang et al. | Preparation of magnetic molecularly imprinted polymer beads and their recognition for baicalein | |
| CN103613722B (en) | Preparation has the method for the magnetic halloysite molecularly imprinted polymer of specific adsorption to 2,4 dichlorophenoxyacetic acid | |
| CN105289514B (en) | A kind of preparation and application of the magnetic oxygenated graphene adsorbent of 1-hydroxy ethylidene-1,1-diphosphonic acid modification | |
| CN102380353B (en) | Method for preparing magnetic magnesium oxide surface molecular imprinting solid phase extractant | |
| CN107262054A (en) | A kind of preparation method and applications of magnetic lignin base adsorbent | |
| CN104693363A (en) | Artesunate surface molecular imprint porous magnetic cellulose microsphere as well as preparation method and application thereof | |
| CN112851848A (en) | Preparation method of temperature-sensitive magnetic molecularly imprinted polymer for selectively separating and enriching aristolochic acid I | |
| CN110252263A (en) | A kind of peanut shell base magnetism multi-stage porous carbon surface imprinted material and its preparation method and application | |
| CN106977746A (en) | Ultrabranching polyamide or derivatives thereof mesoporous molecular sieve composite material, its preparation method and application | |
| CN108408869A (en) | The recycling processing method and its recycling product of a kind of organic wastewater and application |
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 |