CN110368911A - A kind of preparation method of pyridine functional chitosan absorbent - Google Patents
A kind of preparation method of pyridine functional chitosan absorbent Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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
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- 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
- C02F2101/40—Organic compounds containing sulfur
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
Abstract
The invention discloses a kind of preparation methods of pyridine functional chitosan absorbent, comprising the following steps: S1: the sodium carbonate of the polyethyleneimine of 5-100 g/L mass concentration, the 2- chloromethyl pyridine hydrochloride of 2.5-100 g/L mass concentration and 10-100 g/L mass concentration being dissolved in the aqueous solution for the ethyl alcohol that volumetric concentration is 5-80%.Pyridine functional chitosan absorbent of the invention can be applied to the fields such as the removal synchronous with antibiotic of heavy metal in the livestock breeding wastewater under wide in range pH range, when solving synergistic sorption heavy metal and antibiotic, adsorbance is small and the rate of adsorption is slow, need amount of resin big in engineering, operating time is long, adsorbance is small under strongly acidic conditions or even technical problems, economic benefit and the obvious environment benefit such as does not adsorb.
Description
Technical field
The present invention relates to modified resin synthesis field more particularly to a kind of preparation sides of pyridine functional chitosan absorbent
Method.
Background technique
For that can promote growth of animal, improve feed efficiency and treatment control disease, veterinary antibiotic and a micro huge sum of money
Belong to element to be widely applied in intensive livestock and poultry breeding industry, antibiosis present in the livestock and poultry breeding industry waste water generated therewith
Element and micro heavy, which often mix, to be coexisted into soil, water body, constitutes huge potential danger to environmental and human health impacts
Evil.The processing method of common processing livestock breeding wastewater is biochemical method, but heavy metal therein and antibiotic are difficult to remove.State
Internal and external pin has membrane filter method, catalytic oxidation-reduction method, ion exchange to the minimizing technology of heavy metal and antibiotic combined pollutant
With absorption method, phytoremediation technology or group technology.Based on pollutant in physical and chemical adsorption principle removal water body have it is simple,
Quickly, the advantages such as green are the optimization techniques of breeding wastewater heavy metal and the removal of antibiotic combined pollutant.Wherein based on efficient
The absorption method of biomass adsorbent form because of the advantages that its operation is easy and efficient reliable, reproducible utilization and environment friendly
For selection process.
Biomass adsorbent has the conventional polymers material institutes such as biological degradability, raw material reproducibility and environment friendly
The green character not having, mainly by the method for physical-chemical, enriching heavy metal ion and organic matter in water body,
Reach the purpose for removing Heavy Metals in Waters ion and organic matter respectively.Such as application No. is CN201811142664.6, application is public
Cloth day is that the patent application document on December 14th, 2018 discloses a kind of preparation method of chelate sorbent, the system of the adsorbent
Preparation Method step are as follows: dissolve chitosan in acid solution, then mixed with organic solvent；Ethylenediamine tetra-acetic acid dianhydride is added
Grafted monomers (EDTAD), and graft polymerization reaction is carried out under 60~80 DEG C, inert gas shielding；It washs, dry after reaction
It is dry, obtain chitosan graft object.The chelate sorbent of the invention has good adsorptivity, the EDTAD being grafted on chitosan
Node is provided more particularly to firmly chelate calcium ion.The adsorbent after absorption can be recycled into metal ion by elution method, and
And sustainable use；There is preferable stability in the inside of tailing dam.Application No. is CN201810159080.3, Shen Qing Publications
It everyday discloses for the patent application document on July 31st, 2018 and is inhaled for the modified sodium alginate of tetracycline antibiotics absorption
Enclosure material and preparation method thereof, the preparation method step of the adsorbent material are as follows: Step 1: sodium alginate and solvent are pressed mass body
Product is swollen sodium alginate sufficiently, ultrasonic deaeration degassing obtains seaweed than being that the ratio of 1~3:97~99 is mixed evenly
Sour sodium colloidal sol；Step 2: it is to stir in 1~10wt% metal salt solution that sodium alginate colloidal sol, which is evenly added dropwise to mass concentration,
It mixes, cross-linking reaction 2~for 24 hours, it filters, it is dry, up to the modified sodium alginate adsorbent material for tetracycline antibiotics absorption.
Adsorbent material obtained by the invention is cheap and easy to get, and adsorbent preparation process is simple, high to tetracycline antibiotics removal efficiency, inhales
Attached dose of use is rear biodegradable, renewable, is not in secondary pollution, has a good application prospect.Document Zhao, G.,
Huang, X., Tang, Z. et al. Polymer-Based Nanocomposites for Heavy Metal Ions
Removal from Aqueous Solution: A Review[J]. Polym. Chem., 2018, 9(26): 3562-
3582.The method that the above patent or document disclose the biomass adsorbent of preparation can only adsorb single heavy metal or antibiotic,
Removing heavy metals and antibiotic cannot be synchronized, solve the problems, such as selectivity and synergistic sorption heavy metal and antibiotic, this to locate
Heavy metal or antibiotic in reason combined pollutant water body are restricted.
It is low to heavy metal adsorption capacity in peracid hypersaline environment for existing biomass adsorbent, cannot synchronize removal weight
Metal and antibiotic, solve the problems, such as selectivity and synergistic sorption heavy metal and antibiotic, and the present invention provides a kind of pyridine functional
Change the preparation method of chitosan absorbent.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of systems of pyridine functional chitosan absorbent
Preparation Method.
A kind of preparation method of pyridine functional chitosan absorbent proposed by the present invention, comprising the following steps:
S1: by the polyethyleneimine of 5-100 g/L mass concentration, the 2- chloromethylpyridine hydrochloric acid of 2.5-100 g/L mass concentration
Salt and the sodium carbonate of 10-100 g/L mass concentration are dissolved in the aqueous solution for the ethyl alcohol that volumetric concentration is 5-80%, the water of ethyl alcohol
The solution temperature of solution is set as 20-90 DEG C, and the dissolution time of the aqueous solution of ethyl alcohol is set as 2-10 h, while utilizing 85
Magnetic force is stirred until stir evenly in DEG C oil bath, then using cooling device progress cooling down operation, cooling device first with
The rate of 3-5 DEG C/min is cooled down, and until being cooled to 30 DEG C, cooling device is carried out again with the rate of 0.3-0.5 DEG C/min cold
But, it until being cooled to room temperature, recycles centrifugation apparatus and filter screen successively to carry out centrifugally operated, filtration treatment, finally passes through
After the revolving of 1-60min, oily phase is obtained；
S2: the Chitosan powder of 2-50 g/L mass concentration is dissolved in the acetic acid solution that volumetric concentration is 1-8%, acetic acid is molten
The solution temperature of liquid is set as 20-80 DEG C, and the dissolution time of acetic acid solution is set as 20-90 min, while being set using stirring
Standby to be stirred until stir evenly, then filter plant is from top to bottom successively using multiple sieves progress multistage filtering, and from
The mesh of multiple sieves under gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 1-60 h with the reaction time of chitosan mother liquor, are carried out during reaction using mixing plant
It stirs evenly, and the epoxychloropropane for being 0.4-15% with volumetric concentration is just crosslinked, the crosslinking temperature that epoxychloropropane is just crosslinked is set
It is set to 20-80 DEG C, and crosslinking time is set as 1-20 h, obtains mixing mother liquor；
S4: mixing mother liquor obtained in S3 is added in coagulating bath, and coagulating bath is dissolved with sodium sulphate, sodium hydroxide, trimerization phosphorus
One or more of mixed solution in sour sodium and sodium pyrophosphate, and the mass concentration of the sodium sulphate and sodium hydroxide in coagulating bath point
Not Wei 10-200 g/L and 10-200 g/L, through precipitating solidification obtain complex microsphere；
The complex microsphere of 2-40 g/L in step S4: being carried out the extracting of 2-10 h by S5 through Soxhlet extractor, removes resin hole
Remaining pore-foaming agent in road after dehydration, takes out complex microsphere and is added to the hydrogen that pH is 10-14 successively with ethyl alcohol, distillation water washing
In the aqueous solution of sodium oxide molybdena, post-crosslinking, the friendship of epoxychloropropane crosslinking are carried out with the epoxychloropropane that volumetric concentration is 0.01-1%
Joining temperature setting is 20-80 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 1-10 h, and crosslinked microsphere, crosslinking is made
Microballoon, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine functional chitosan absorbent.
The invention has the benefit that
(1) present invention prepares the lower cost for material of resin, and the function base modified has a stable space structure, pyridyl group and
Multiple nitrogen-atoms on amido can play coordination chelation to heavy metal and antibiotic simultaneously；
(2) chelating resin provided by the invention increasing because of nitrogenous function base adsorption site significantly improves to heavy metal and resists
Raw element adsorption capacity, solves and removes removing heavy metals or antibiotic in livestock breeding wastewater, and adsorbance is small and the rate of adsorption is slow
Problem；
(3) chelating resin provided by the invention by change heavy metal ion and antibiotic adsorb pH value range, salt resistance characteristic with
And adsorption site with space structure, it can be achieved that heavy metal and the selective removal of antibiotic and synchronous recycling, in wide in range pH model
It has broad application prospects in terms of the selectivity and Collaborative Control of livestock breeding wastewater combined pollutant under enclosing.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment 1
A kind of preparation method for pyridine functional chitosan absorbent that the present embodiment proposes, comprising the following steps:
S1: by polyethyleneimine that 0.1g mass concentration is 5-100 g/L, the 2- chlorine that 0.05g mass concentration is 2.5-100 g/L
The sodium carbonate that methyl pyridinium chloride and 0.2g mass concentration are 10-100 g/L is dissolved in 1 ml ethyl alcohol and 5 ml distilled water
In aqueous solution, solution temperature is set as 85 DEG C, and dissolution time is set as 2 h, while being carried out using magnetic force in 85 DEG C of oil baths
Stirring is until stir evenly, then using cooling device progress cooling down operation, cooling device first with the rate of 3-5 DEG C/min into
Row cooling, until being cooled to 30 DEG C, cooling device is cooled down again with the rate of 0.3-0.5 DEG C/min, until being cooled to room
Temperature recycles centrifugation apparatus and filter screen successively to carry out centrifugally operated, filtration treatment, finally revolves by 50 DEG C of Rotary Evaporators
Dry 15 min, obtain oily phase；
S2: the Chitosan powder that 0.06g mass concentration is 2-50 g/L is dissolved in 0.3 ml glacial acetic acid and 29.4 ml distilled water
Aqueous solution in, solution temperature is set as room temperature, and dissolution time is set as 20 min, while being stirred using mixing plant
It mixes until stirring evenly, then filter plant successively carries out multistage filtering using multiple sieves from top to bottom, and from top to bottom
The mesh of multiple sieves gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 1 h with the reaction time of chitosan mother liquor, are stirred during reaction using mixing plant
Uniformly, and with 0.144ml volumetric concentration the epoxychloropropane for being 0.4-15% is just crosslinked, the crosslinking temperature that epoxychloropropane is just crosslinked
Degree is set as 20 DEG C, and crosslinking time is set as 1 h, obtains mixing mother liquor；
S4: gained mixing mother liquor in S3 is pumped into the coagulating bath that 1000ml contains 3 g anhydrous sodium sulfates and 3 g sodium hydroxides solid
It is melted into ball, stands 30min, obtains complex microsphere through precipitating solidification；
Complex microsphere in step S4: being carried out the extracting of 2h by S5 through Soxhlet extractor, removes remaining pore in resin duct
Agent after dehydration, takes out 0.2g complex microsphere and is added to the hydrogen that 100ml pH value is 10 successively with ethyl alcohol, distillation water washing each 3 times
In the aqueous solution of sodium oxide molybdena, post-crosslinking, epoxychloropropane are carried out with the epoxychloropropane that 0.01 ml volumetric concentration is 0.01-1%
The crosslinking temperature of crosslinking is set as 20 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 1 h, and crosslinked microsphere is made, and hands over
Connection microballoon, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine functional chitosan absorbent A.
Embodiment 2
A kind of preparation method for pyridine functional chitosan absorbent that the present embodiment proposes, comprising the following steps:
S1: by polyethyleneimine that 0.2g mass concentration is 5-100 g/L, the 2- chlorine that 0.05g mass concentration is 2.5-100 g/L
The sodium carbonate that methyl pyridinium chloride and 0.2g mass concentration are 10-100 g/L is dissolved in 1 ml ethyl alcohol and 5 ml distilled water
In aqueous solution, solution temperature is set as 85 DEG C, and dissolution time is set as 2 h, while being carried out using magnetic force in 85 DEG C of oil baths
Stirring is until stir evenly, then using cooling device progress cooling down operation, cooling device first with the rate of 3-5 DEG C/min into
Row cooling, until being cooled to 30 DEG C, cooling device is cooled down again with the rate of 0.3-0.5 DEG C/min, until being cooled to room
Temperature recycles centrifugation apparatus and filter screen successively to carry out centrifugally operated, filtration treatment, finally revolves by 50 DEG C of Rotary Evaporators
Dry 15 min, obtain oily phase；
S2: the Chitosan powder that 0.06g mass concentration is 2-50 g/L is dissolved in 0.3 ml glacial acetic acid and 29.4 ml distilled water
Aqueous solution in, solution temperature is set as room temperature, and dissolution time is set as 20 min, while being stirred using mixing plant
It mixes until stirring evenly, then filter plant successively carries out multistage filtering using multiple sieves from top to bottom, and from top to bottom
The mesh of multiple sieves gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 1 h with the reaction time of chitosan mother liquor, are stirred during reaction using mixing plant
Uniformly, and with 0.144ml volumetric concentration the epoxychloropropane for being 0.4-15% is just crosslinked, the crosslinking temperature that epoxychloropropane is just crosslinked
Degree is set as 20 DEG C, and crosslinking time is set as 1 h, obtains mixing mother liquor；
S4: gained mixing mother liquor in S3 is pumped into the coagulating bath that 1000ml contains 3 g anhydrous sodium sulfates and 3 g sodium hydroxides solid
It is melted into ball, stands 30min, obtains complex microsphere through precipitating solidification；
Complex microsphere in step S4: being carried out the extracting of 2h by S5 through Soxhlet extractor, removes remaining pore in resin duct
Agent after dehydration, takes out 0.2g complex microsphere and is added to the hydrogen that 100ml pH value is 10 successively with ethyl alcohol, distillation water washing each 3 times
In the aqueous solution of sodium oxide molybdena, post-crosslinking, epoxychloropropane are carried out with the epoxychloropropane that 0.01 ml volumetric concentration is 0.01-1%
The crosslinking temperature of crosslinking is set as 20 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 1 h, and crosslinked microsphere is made, and hands over
Connection microballoon, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine functional chitosan absorbent B.
Embodiment 3
A kind of preparation method for pyridine functional chitosan absorbent that the present embodiment proposes, comprising the following steps:
S1: by polyethyleneimine that 0.7g mass concentration is 5-100 g/L, the 2- chlorine that 0.25g mass concentration is 2.5-100 g/L
The sodium carbonate that methyl pyridinium chloride and 0.3231g mass concentration are 10-100 g/L is dissolved in 15 ml ethyl alcohol and 5 ml distillation
In the aqueous solution of water, solution temperature is set as 85 DEG C, and dissolution time is set as 2 h, while utilizing magnetic force in 85 DEG C of oil baths
It is stirred until stirring evenly, then using cooling device progress cooling down operation, cooling device is first with the speed of 3-5 DEG C/min
Rate is cooled down, and until being cooled to 30 DEG C, cooling device is cooled down again with the rate of 0.3-0.5 DEG C/min, until being cooled to
To room temperature, centrifugation apparatus and filter screen is recycled successively to carry out centrifugally operated, filtration treatment, finally passes through 50 DEG C of rotary evaporation
Instrument is spin-dried for 15 min, obtains oily phase；
S2: the Chitosan powder that 0.5g mass concentration is 2-50 g/L is dissolved in 0.6 ml glacial acetic acid and 29.4 ml distilled water
Aqueous solution in, solution temperature is set as room temperature, and dissolution time is set as 30 min, while being stirred using mixing plant
It mixes until stirring evenly, then filter plant successively carries out multistage filtering using multiple sieves from top to bottom, and from top to bottom
The mesh of multiple sieves gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 2 h with the reaction time of chitosan mother liquor, are stirred during reaction using mixing plant
Uniformly, and with 0.23ml volumetric concentration the epoxychloropropane for being 0.4-15% is just crosslinked, the crosslinking temperature that epoxychloropropane is just crosslinked
60 DEG C are set as, and crosslinking time is set as 2h, obtain mixing mother liquor；
S4: gained mixing mother liquor in S3 is pumped into 1000ml and is contained in the coagulating bath of 13 g anhydrous sodium sulfates and 16 g sodium hydroxides
Solidify balling-up, stand 30min, obtains complex microsphere through precipitating solidification；
Complex microsphere in step S4: being carried out the extracting of 4h by S5 through Soxhlet extractor, removes remaining pore in resin duct
Agent after dehydration, takes out 2g complex microsphere and is added to the hydrogen-oxygen that 100ml pH value is 13 successively with ethyl alcohol, distillation water washing each 3 times
In the aqueous solution for changing sodium, post-crosslinking, epoxychloropropane crosslinking are carried out with the epoxychloropropane that 0.3 ml volumetric concentration is 0.01-1%
Crosslinking temperature be set as 60 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 2 h, and crosslinked microsphere is made, and is crosslinked micro-
Ball, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine functional chitosan absorbent C.
Embodiment 4
A kind of preparation method for pyridine functional chitosan absorbent that the present embodiment proposes, comprising the following steps:
S1: by polyethyleneimine that 0.7g mass concentration is 5-100 g/L, the 2- chlorine that 0.25g mass concentration is 2.5-100 g/L
The sodium carbonate that methyl pyridinium chloride and 0.3231g mass concentration are 10-100 g/L is dissolved in 15 ml ethyl alcohol and 5 ml distillation
In the aqueous solution of water, solution temperature is set as 85 DEG C, and dissolution time is set as 2 h, while utilizing magnetic force in 85 DEG C of oil baths
It is stirred until stirring evenly, then using cooling device progress cooling down operation, cooling device is first with the speed of 3-5 DEG C/min
Rate is cooled down, and until being cooled to 30 DEG C, cooling device is cooled down again with the rate of 0.3-0.5 DEG C/min, until being cooled to
To room temperature, centrifugation apparatus and filter screen is recycled successively to carry out centrifugally operated, filtration treatment, finally passes through 50 DEG C of rotary evaporation
Instrument is spin-dried for 15 min, obtains oily phase；
S2: the Chitosan powder that 0.9g mass concentration is 2-50 g/L is dissolved in 0.6 ml glacial acetic acid and 29.4 ml distilled water
Aqueous solution in, solution temperature is set as room temperature, and dissolution time is set as 30 min, while being stirred using mixing plant
It mixes until stirring evenly, then filter plant successively carries out multistage filtering using multiple sieves from top to bottom, and from top to bottom
The mesh of multiple sieves gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 2 h with the reaction time of chitosan mother liquor, are stirred during reaction using mixing plant
Uniformly, and with 0.23ml volumetric concentration the epoxychloropropane for being 0.4-15% is just crosslinked, the crosslinking temperature that epoxychloropropane is just crosslinked
60 DEG C are set as, and crosslinking time is set as 2h, obtain mixing mother liquor；
S4: gained mixing mother liquor in S3 is pumped into 1000ml and is contained in the coagulating bath of 13 g anhydrous sodium sulfates and 16 g sodium hydroxides
Solidify balling-up, stand 30min, obtains complex microsphere through precipitating solidification；
Complex microsphere in step S4: being carried out the extracting of 4h by S5 through Soxhlet extractor, removes remaining pore in resin duct
Agent after dehydration, takes out 2g complex microsphere and is added to the hydrogen-oxygen that 100ml pH value is 13 successively with ethyl alcohol, distillation water washing each 3 times
In the aqueous solution for changing sodium, post-crosslinking, epoxychloropropane crosslinking are carried out with the epoxychloropropane that 0.3 ml volumetric concentration is 0.01-1%
Crosslinking temperature be set as 60 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 2 h, and crosslinked microsphere is made, and is crosslinked micro-
Ball, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine functional chitosan absorbent D.
Embodiment 5
A kind of preparation method for pyridine functional chitosan absorbent that the present embodiment proposes, comprising the following steps:
S1: by polyethyleneimine that 0.7g mass concentration is 5-100 g/L, the 2- chlorine that 0.5g mass concentration is 2.5-100 g/L
The sodium carbonate that methyl pyridinium chloride and 0.3231g mass concentration are 10-100 g/L is dissolved in 15 ml ethyl alcohol and 5 ml distillation
In the aqueous solution of water, solution temperature is set as 85 DEG C, and dissolution time is set as 2 h, while utilizing magnetic force in 85 DEG C of oil baths
It is stirred until stirring evenly, then using cooling device progress cooling down operation, cooling device is first with the speed of 3-5 DEG C/min
Rate is cooled down, and until being cooled to 30 DEG C, cooling device is cooled down again with the rate of 0.3-0.5 DEG C/min, until being cooled to
To room temperature, centrifugation apparatus and filter screen is recycled successively to carry out centrifugally operated, filtration treatment, finally passes through 50 DEG C of rotary evaporation
Instrument is spin-dried for 15 min, obtains oily phase；
S2: the Chitosan powder that 0.9g mass concentration is 2-50 g/L is dissolved in 0.6 ml glacial acetic acid and 29.4 ml distilled water
Aqueous solution in, solution temperature is set as room temperature, and dissolution time is set as 30 min, while being stirred using mixing plant
It mixes until stirring evenly, then filter plant successively carries out multistage filtering using multiple sieves from top to bottom, and from top to bottom
The mesh of multiple sieves gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 2 h with the reaction time of chitosan mother liquor, are stirred during reaction using mixing plant
Uniformly, and with 0.23ml volumetric concentration the epoxychloropropane for being 0.4-15% is just crosslinked, the crosslinking temperature that epoxychloropropane is just crosslinked
60 DEG C are set as, and crosslinking time is set as 2h, obtain mixing mother liquor；
S4: gained mixing mother liquor in S3 is pumped into 1000ml and is contained in the coagulating bath of 13 g anhydrous sodium sulfates and 16 g sodium hydroxides
Solidify balling-up, stand 30min, obtains complex microsphere through precipitating solidification；
Complex microsphere in step S4: being carried out the extracting of 4h by S5 through Soxhlet extractor, removes remaining pore in resin duct
Agent after dehydration, takes out 2g complex microsphere and is added to the hydrogen-oxygen that 100ml pH value is 13 successively with ethyl alcohol, distillation water washing each 3 times
In the aqueous solution for changing sodium, post-crosslinking, epoxychloropropane crosslinking are carried out with the epoxychloropropane that 0.3 ml volumetric concentration is 0.01-1%
Crosslinking temperature be set as 60 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 2 h, and crosslinked microsphere is made, and is crosslinked micro-
Ball, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine functional chitosan absorbent E.
Embodiment 6
A kind of preparation method for pyridine functional chitosan absorbent that the present embodiment proposes, comprising the following steps:
S1: by polyethyleneimine that 2g mass concentration is 5-100 g/L, the 2- chloromethyl that 2g mass concentration is 2.5-100 g/L
Pyridine hydrochloride and 2g mass concentration are that the sodium carbonate of 10-100 g/L is dissolved in the aqueous solution of 15 ml ethyl alcohol and 5 ml distilled water
In, solution temperature is set as 85 DEG C, and dissolution time is set as 2 h, while being stirred directly using magnetic force in 85 DEG C of oil baths
To stirring evenly, cooling down operation then is carried out using cooling device, cooling device carries out first with the rate of 3-5 DEG C/min cold
But, until being cooled to 30 DEG C, cooling device is cooled down again with the rate of 0.3-0.5 DEG C/min, until being cooled to room temperature, then
Centrifugally operated, filtration treatment are successively carried out using centrifugation apparatus and filter screen, is finally spin-dried for 15 by 50 DEG C of Rotary Evaporators
Min obtains oily phase；
S2: the Chitosan powder that 1.5g mass concentration is 2-50 g/L is dissolved in 2.4 ml glacial acetic acid and 29.4 ml distilled water
Aqueous solution in, solution temperature is set as room temperature, and dissolution time is set as 90 min, while being stirred using mixing plant
It mixes until stirring evenly, then filter plant successively carries out multistage filtering using multiple sieves from top to bottom, and from top to bottom
The mesh of multiple sieves gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 8h with the reaction time of chitosan mother liquor, are stirred during reaction using mixing plant
Uniformly, and with 2ml volumetric concentration the epoxychloropropane for being 0.4-15% is just crosslinked, and the crosslinking temperature that epoxychloropropane is just crosslinked is set
70 DEG C are set to, and crosslinking time is set as 8h, obtain mixing mother liquor；
S4: gained mixing mother liquor in S3 is pumped into 1000ml and is contained in the coagulating bath of 50 g anhydrous sodium sulfates and 50 g sodium hydroxides
Solidify balling-up, stand 30min, obtains complex microsphere through precipitating solidification；
Complex microsphere in step S4: being carried out the extracting of 10h by S5 through Soxhlet extractor, removes remaining pore in resin duct
Agent after dehydration, takes out 4g complex microsphere and is added to the hydrogen-oxygen that 100ml pH value is 14 successively with ethyl alcohol, distillation water washing each 3 times
In the aqueous solution for changing sodium, post-crosslinking, epoxychloropropane crosslinking are carried out with the epoxychloropropane that 0.5ml volumetric concentration is 0.01-1%
Crosslinking temperature be set as 70 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 7 h, and crosslinked microsphere is made, and is crosslinked micro-
Ball, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine functional chitosan absorbent F.
Embodiment 7
A kind of preparation method for pyridine functional chitosan absorbent that the present embodiment proposes, comprising the following steps:
S1: by polyethyleneimine that 2g mass concentration is 5-100 g/L, the 2- chloromethyl that 2g mass concentration is 2.5-100 g/L
Pyridine hydrochloride and 2g mass concentration are that the sodium carbonate of 10-100 g/L is dissolved in the aqueous solution of 15 ml ethyl alcohol and 5 ml distilled water
In, solution temperature is set as 85 DEG C, and dissolution time is set as 2 h, while being stirred directly using magnetic force in 85 DEG C of oil baths
To stirring evenly, cooling down operation then is carried out using cooling device, cooling device carries out first with the rate of 3-5 DEG C/min cold
But, until being cooled to 30 DEG C, cooling device is cooled down again with the rate of 0.3-0.5 DEG C/min, until being cooled to room temperature, then
Centrifugally operated, filtration treatment are successively carried out using centrifugation apparatus and filter screen, is finally spin-dried for 15 by 50 DEG C of Rotary Evaporators
Min obtains oily phase；
S2: the Chitosan powder that 1.5g mass concentration is 2-50 g/L is dissolved in 2.4 ml glacial acetic acid and 29.4 ml distilled water
Aqueous solution in, solution temperature is set as room temperature, and dissolution time is set as 90 min, while being stirred using mixing plant
It mixes until stirring evenly, then filter plant successively carries out multistage filtering using multiple sieves from top to bottom, and from top to bottom
The mesh of multiple sieves gradually reduces, and finally obtains chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually set as 10h with the reaction time of chitosan mother liquor, are stirred during reaction using mixing plant
Uniformly, and with 4ml volumetric concentration the epoxychloropropane for being 0.4-15% is just crosslinked, and the crosslinking temperature that epoxychloropropane is just crosslinked is set
80 DEG C are set to, and crosslinking time is set as 10h, obtain mixing mother liquor；
S4: gained mixing mother liquor in S3 is pumped into 1000ml and is contained in the coagulating bath of 50 g anhydrous sodium sulfates and 50 g sodium hydroxides
Solidify balling-up, stand 30min, obtains complex microsphere through precipitating solidification；
Complex microsphere in step S4: being carried out the extracting of 10h by S5 through Soxhlet extractor, removes remaining pore in resin duct
Agent after dehydration, takes out 4g complex microsphere and is added to the hydrogen-oxygen that 100ml pH value is 14 successively with ethyl alcohol, distillation water washing each 3 times
In the aqueous solution for changing sodium, post-crosslinking is carried out with the epoxychloropropane that 1ml volumetric concentration is 0.01-1%, epoxychloropropane crosslinking
Crosslinking temperature is set as 80 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 10 h, and crosslinked microsphere, crosslinked microsphere is made
It recycles and is washed to neutrality with distillation, dehydrated preservation is spare to obtain pyridine functional chitosan absorbent G.
Adsorbent to study pyridine functional chitosan inhales the absorption property of heavy metal and antibiotic as follows
Attached experiment, specific adsorption conditions are as follows: 0.5g adsorbent is respectively placed in 50ml copper nitrate, cadmium nitrate, zinc nitrate, tetracycline, ring
Single Bicomponent Adsorption is carried out in third husky star and sulfamethoxazole, wherein the concentration of heavy metal is 1mmol/l, the concentration of antibiotic
It is 0.5mmol/l, the initial pH for adjusting solution is 5, and adsorption temp is 25 DEG C, and concussion rate is 130r/min, adsorption time
For for 24 hours.Gained compound adsorbent A-G the results are shown in Table 1 to the adsorption capacity of single heavy metal, antibiotic solution and elemental analysis,
Table 2.
Adsorption capacity of the compound adsorbent to single heavy metal, antibiotic solution in 1 embodiment A-G of table:
1-7 in conjunction with the embodiments provides the pyridine functional chitosan absorbent of the method synthesis of preparation, method letter using the present invention
It is single, low in cost, environmentally protective, can have extensively in the fields such as heavy metal removal synchronous with antibiotic in livestock breeding wastewater
General application value.
The serial pyridine functional chitosan absorbent the key technical indexes prepared in 2 embodiment A-G of table
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, and it is any
Those familiar with the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its invents
Design is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of pyridine functional chitosan absorbent, which comprises the following steps:
S1: polyethyleneimine, 2- chloromethyl pyridine hydrochloride and sodium carbonate are dissolved in the aqueous solution of ethyl alcohol, while utilizing 85
Magnetic force is stirred until stir evenly in DEG C oil bath, is then cooled to room temperature using cooling device, is recycled centrifugation and filtering
Processing, finally after the revolving of 1-60min, obtains oily phase；
S2: Chitosan powder is dissolved in acetic acid solution, while being stirred using mixing plant until stirring evenly, then
Multistage filtering is carried out using filter plant, forms chitosan mother liquor；
S3: the oil prepared in step S1 is mutually added dropwise in the chitosan mother liquor prepared in S2, time for adding is set as 5-
60 min, oil are mutually reacted with chitosan mother liquor, are stirred uniformly during reaction using mixing plant, and use ring
Oxygen chloropropane is just crosslinked, and obtains mixing mother liquor；
S4: mixing mother liquor obtained in S3 is added in coagulating bath, obtains complex microsphere through precipitating solidification；
S5: the complex microsphere in step S4 is stripped through Soxhlet extractor, removes remaining pore-foaming agent in resin duct, according to
Secondary ethyl alcohol, distillation water washing, after dehydration, take out complex microsphere and are added in the aqueous solution of sodium hydroxide, use epoxychloropropane
Post-crosslinking is carried out, crosslinked microsphere is made, crosslinked microsphere, which is recycled, is washed to neutrality with distillation, and dehydrated preservation is spare to obtain pyridine function
Chitosan absorbent can be changed.
2. a kind of preparation method of pyridine functional chitosan absorbent according to claim 1, which is characterized in that described
In S1, the mass concentration of polyethyleneimine is 5-100 g/L, and the mass concentration of 2- chloromethyl pyridine hydrochloride is 2.5-100 g/
L, the mass concentration of sodium carbonate are 10-100 g/L, and the volumetric concentration of the aqueous solution of ethyl alcohol is 5-80%, the aqueous solution of ethyl alcohol it is molten
Solving temperature setting is 20-90 DEG C, and the dissolution time of the aqueous solution of ethyl alcohol is set as 2-10 h.
3. a kind of preparation method of pyridine functional chitosan absorbent according to claim 1, which is characterized in that described
In S2, the mass concentration of Chitosan powder is 2-50 g/L, and the volumetric concentration of acetic acid solution is 1-8%, the dissolution of acetic acid solution
Temperature setting is 20-80 DEG C, and the dissolution time of acetic acid solution is set as 20-90 min.
4. a kind of preparation method of pyridine functional chitosan absorbent according to claim 1, which is characterized in that described
In S3, oil is mutually set as 1-60 h with the reaction time of chitosan mother liquor, and the volumetric concentration of epoxychloropropane is 0.4-15%,
The crosslinking temperature that epoxychloropropane is just crosslinked is set as 20-80 DEG C, and crosslinking time is set as 1-20 h.
5. a kind of preparation method of pyridine functional chitosan absorbent according to claim 1, which is characterized in that described
In S4, coagulating bath is molten dissolved with mixing one or more of in sodium sulphate, sodium hydroxide, sodium tripolyphosphate and sodium pyrophosphate
Liquid.
6. a kind of preparation method of pyridine functional chitosan absorbent according to claim 5, which is characterized in that described
The mass concentration of sodium sulphate and sodium hydroxide is respectively 10-200 g/L and 10-200 g/L.
7. a kind of preparation method of pyridine functional chitosan absorbent according to claim 1, which is characterized in that described
In S5, the dosage of complex microsphere is 2-40 g/L, and the extraction times of Soxhlet extractor are set as 2-10 h, the water of sodium hydroxide
The pH of solution is 10-14, and the volumetric concentration of epoxychloropropane is 0.01-1%, and the crosslinking temperature of epoxychloropropane crosslinking is set as
20-80 DEG C, and the crosslinking time of epoxychloropropane crosslinking is set as 1-10 h.
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