CN108970593A - A kind of phenolic aldehyde trace resin particle preparation method - Google Patents
A kind of phenolic aldehyde trace resin particle preparation method Download PDFInfo
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- CN108970593A CN108970593A CN201810848849.2A CN201810848849A CN108970593A CN 108970593 A CN108970593 A CN 108970593A CN 201810848849 A CN201810848849 A CN 201810848849A CN 108970593 A CN108970593 A CN 108970593A
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- resin particle
- phenolic aldehyde
- phenolic
- appropriate
- trace
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- 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
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
Abstract
The application provides a kind of phenolic aldehyde trace resin particle, and raw material is according to mass percent meter, comprising: catalyst n aOH:8%~12%；Phenol: 45~55%；Formaldehyde 30%~40%；Crosslinking agent 3%~7%；Appropriate pore-foaming agent；Appropriate template molecule.There is high selection adsorption effect to copper ion using the resin particle that the application method is prepared, under conditions of higher concentration other ions have coexisted, 90% or more can achieve to the adsorption rate of copper ion, and it is equal less than 15% to the adsorption rate of other heavy metal ion.
Description
Technical field
The present invention relates to chemical material technical fields more particularly to a kind of phenolic aldehyde trace resin particle and preparation method thereof.
Background technique
A large amount of heavy metal ion-containing waste water, especially copper ions waste water, toxicity are discharged in various industrial processes
Big and be easy to be enriched with by organism, processing difficulty is larger, can not copper ion in selective recovery waste water.In order to effectively remove
And the copper ion in waste water is recycled, need to explore a kind of selective absorbent.Phenolic resin microspheres due to being easy to get with raw material,
The simple advantage of synthetic method, be it is a kind of apply earliest and wider high molecular material, its weak dissociation with regard to phenolic hydroxyl group in resin
Property, the ability of ion exchange, and phenolic resin microspheres large specific surface area are made it have, property is stablized, and is widely used at water
The fields such as reason, medical industry and food industry, but since selectivity of the phenolic hydroxyl group as function base for heavy metal ion is inhaled
Attached effect is poor.In recent years, in order to expand the application range of phenolic resin, increase resin adsorption amount, enhance it to metal ion
Selection characterization of adsorption, developed phenol aldehyde type ion exchange/chelating resin, by select suitably have reactivity site
Phenol parent nucleus, will to metal ion have good adsorption properties chelation group be introduced into resin.Function is utilized in this method
Can group to the chelation of metal ion, but since the chelating that general utility functions group does not have specificity to metal ion is made
With, therefore its selectivity is than relatively limited, in addition to the alkali metal ion suction-operated weaker to coordination ability is poor, to transition metal
Or heavy metal has suction-operated, to bring difficulty to heavy metal recovery.With the development of ion imprinted polymer, for spy
The birth that ion has highly selective material is determined, so that certain heavy metal ion are available in medicine, food, industrial wastewater
Separation, recycling and analysis detection.
Summary of the invention
It is an object of the invention to solve the problems of the above-mentioned prior art, provide it is a kind of based on ionic imprinting technique with
Phenolic resin preparation technology combine the property of can choose absorption copper ion phenolic aldehyde trace resin and its preparation method.
A kind of phenolic aldehyde trace resin particle, raw material is according to mass percent meter, comprising:
Catalyst n aOH:8%~12%；Phenol: 45~55%；Formaldehyde 30%~40%；Crosslinking agent 3%~7%；In right amount
Pore-foaming agent；Appropriate template molecule.
Further, phenolic aldehyde trace resin particle as described above, the pore-foaming agent are ethyl acetate, polyethylene glycol or poly-
Vinyl alcohol.
Further, phenolic aldehyde trace resin particle as described above, the crosslinking agent are epoxychloropropane.
A kind of preparation method of phenolic aldehyde trace resin particle, includes the following steps:
(a) phenol and NaOH are mixed, formaldehyde are then added dropwise, after solution is completely mixed, in stirring
Under be heated to 90 DEG C, constant temperature stirs 30min, then oil bath constant temperature 18h, generates phenolic aldehyde prepolymer；
(b) copper-bath is added into step (a) system is template molecule, and appropriate epoxychloropropane is added, and appropriate
Pore-foaming agent is heated to 100~110 DEG C, and constant temperature is for 24 hours, forms phenolic resin particle, is cooled to room temperature；
(c) the phenolic resin particle in step (b) is eluted using eluant, eluent, until being examined in eluent without copper ion
Out, then drying obtains resin particle finished product.
The present invention is based on the phenolic resin particle that the means of molecular engram have prepared alternative absorption copper ion, tools
There are good function of molecular engram, including following advantage:
The selective absorption phenolic resin particle prepared by the method for the invention is good to the adsorption effect of copper ion, synthesizes road
Line is short, and synthesis process control is simple, and resin high temperature resistant itself, and toxicity is lower, is a kind of good selective absorption recycling
The material of copper ion.
Detailed description of the invention
Fig. 1 is that the atomic force microscope of middle resin in the prior art detects figure；
Fig. 2 is that the atomic force microscope of resin in the application detects figure；
Fig. 3 is selection adsorption efficiency figure of the phenolic resin particle to various concentration Cu2+；
Fig. 4 is elution rate of recovery figure of the hydrochloric acid to copper ion；
Fig. 5 is that phenolic resin particle passes through 20 adsorption efficiency variation diagrams (copper ion concentration 2mg/L) recycled.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear
Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.The basic principle of ionic imprinting technique of the present invention is as follows: when template from
When sub (copper ion) and polymer monomer contact, by polymerization crosslinking process by the effect between template ion and polymer monomer
It memorizes, once polymer is formed, after template ion is removed, will occur and template molecule space steric configuration in polymer
The hole to match, such hole will have Selective recognition characteristic to template ion and the like.
In order to reach above-mentioned target, the present invention uses following technical solution: one kind based on selective absorption copper from
The phenolic aldehyde trace resin particle of son, is made the raw material and its mass percentage composition of the resin particle: catalyst n aOH:8%~
12%；Phenol: 45~55%；Formaldehyde 30%~40%；Crosslinking agent 3%~7%；Appropriate pore-foaming agent；Appropriate template molecule；It is above-mentioned
The sum of mass percent of raw material is 100%.
The preparation method of above-mentioned resin particle, using phenolic resin as matrix, synthesis has very highly selective suction to copper ion
Attached resin, includes the following steps:
(a) phenol of formula ratio is added to and fills 150mL deionized water, the appropriate PVA of 60mL dehydrated alcohol (10%),
20min is stirred at 50 DEG C, 40% NaOH solution is added as catalyst and stirs 40min, is then burnt with syringe to three mouthfuls
37% formula ratio formaldehyde is added dropwise in bottle, it is after solution is completely mixed, agitator speed is constant for 350rpm, heating liter
For temperature to 90 DEG C, constant temperature stirs 30min, and three-necked flask is then placed into constant temperature 18h in 35 DEG C of oil baths, generates phenolic aldehyde prepolymer
(b) copper-bath that 20mL concentration is 0.5mg/L is added into step (a) system is template molecule, is added suitable
Amount epoxychloropropane is crosslinking agent, and appropriate polyethylene glycol is added as pore-foaming agent, is heated to 100~110 DEG C, and constant temperature
For 24 hours, phenolic resin particle is formed, is cooled to room temperature
(c) the phenolic resin particle in step (b) is eluted using eluant, eluent, until being examined in eluent without copper ion
Out, then drying obtains resin particle finished product.
It is 0.2~2mm by the phenolic resin diameter of particle being prepared.
The eluant, eluent used in step (c) is the hydrochloric acid of 0.05mol/L.
Pore-foaming agent of the present invention can be ethyl acetate, polyethylene glycol or polyvinyl alcohol, by specific experimental study,
Wherein the effect of polyethylene glycol is best, and the material adsorption effect of synthesis is best, and specific surface area is maximum, specific comparison such as table 1.
1 three kinds of pore-foaming agent synthetic surfaces characteristics of table
After pore-foaming agent is added in the present invention, the specific surface area of resin material increases, and structure is more loose, and real density reduces, and inhales
Attachment position and adsorption capacity increase in the order of magnitude, and maximum adsorption capacity can achieve 10mg/g, while the absorption service life of resin
It increase accordingly, it can be by Reusability and adsorption effect is without being remarkably decreased.
Application No. is 201010531624.8, a kind of entitled preparation side of nickel ion high-selectivity adsorption resin
Method gives a kind of high-selectivity adsorption resin, similar with the raw material of the application and preparation method thereof, but in the prior art
Disclosed resin is different from the application, specifically: selecting property absorption its structure of resin that the prior art provides is finer and close, accordingly
Adsorption capacity is smaller, as shown in Figure 1, and the application passes through addition pore-foaming agent, the corresponding hole of resin surface generation, so that resin
Structure it is more loose, the adsorption capacity of resin is increase accordingly, shown in specific surface texture Fig. 2.After pore-foaming agent is added, the application
The specific surface area of resin is by 0.058m2/ g rises to 1.3m2/ g, adsorption capacity rise to 10mg/g by 0.45mg/g.
Fig. 3 is selection adsorption efficiency figure of the phenolic resin particle to various concentration Cu2+；It is found by Fig. 3, present invention tree
Rouge particle has high selection adsorption effect to copper ion, under conditions of higher concentration other ions have coexisted, to copper ion
Adsorption rate can achieve 90% or more, and equal less than 15% to the adsorption rate of other heavy metal ion.
Fig. 4 is elution rate of recovery figure of the hydrochloric acid to copper ion；It is found by Fig. 4, is carried out using the hydrochloric acid of 0.05mol/L
Elution, the elution rate of recovery highest of copper ion can achieve 80% or more, conducive to the further recycling of copper ion；
Fig. 5 is that phenolic resin particle is logical by 20 adsorption efficiency variation diagrams (copper ion concentration 2mg ,/L) recycled
Fig. 5 discovery is crossed, by carrying out adsorption experiment repeatedly to the resin particle, it was demonstrated that the resin property is stablized, by 20 times or more
Circulating repetition utilizes, and can still keep 85% or more selection adsorption efficiency.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (4)
1. a kind of phenolic aldehyde trace resin particle, which is characterized in that its raw material is according to mass percent meter, comprising:
Catalyst n aOH:8%~12%；Phenol: 45~55%；Formaldehyde 30%~40%；Crosslinking agent 3%~7%；Appropriate pore
Agent；Appropriate template molecule.
2. phenolic aldehyde trace resin particle according to claim 1, which is characterized in that the pore-foaming agent is ethyl acetate, gathers
Ethylene glycol or polyvinyl alcohol.
3. phenolic aldehyde trace resin particle according to claim 1, which is characterized in that the crosslinking agent is epoxychloropropane.
4. a kind of preparation method of phenolic aldehyde trace resin particle, which comprises the steps of:
(a) phenol and NaOH are mixed, formaldehyde is then added dropwise, after solution is completely mixed, added under stirring
Heat is warming up to 90 DEG C, and constant temperature stirs 30min, then oil bath constant temperature 18h, generates phenolic aldehyde prepolymer；
(b) copper-bath is added into step (a) system is template molecule, appropriate epoxychloropropane is added, with appropriate pore
Agent is heated to 100~110 DEG C, and constant temperature is for 24 hours, forms phenolic resin particle, is cooled to room temperature；
(c) the phenolic resin particle in step (b) is eluted using eluant, eluent, until being detected in eluent without copper ion, so
Drying obtains resin particle finished product afterwards.
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| CN201810848849.2A CN108970593A (en) | 2018-07-28 | 2018-07-28 | A kind of phenolic aldehyde trace resin particle preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063387A (en) * | 2020-09-21 | 2020-12-11 | 武汉大学 | Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063387A (en) * | 2020-09-21 | 2020-12-11 | 武汉大学 | Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof |
| CN112063387B (en) * | 2020-09-21 | 2021-06-18 | 武汉大学 | Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof |
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Application publication date: 20181211 |