CN103113506A - Ester-adsorbed ternary macroporous adsorption resin - Google Patents
Ester-adsorbed ternary macroporous adsorption resin Download PDFInfo
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- CN103113506A CN103113506A CN2012105458816A CN201210545881A CN103113506A CN 103113506 A CN103113506 A CN 103113506A CN 2012105458816 A CN2012105458816 A CN 2012105458816A CN 201210545881 A CN201210545881 A CN 201210545881A CN 103113506 A CN103113506 A CN 103113506A
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Abstract
The invention provides macroporous adsorption resin with MA-MMA-DVB (methyl acrylate-methyl methacrylate-divinyl benzene) terpolymer as a framework which is designed and synthesized based on a physical adsorption principle, wherein a monomer comprises an ester group so that the macroporous adsorption resin is mainly used for adsorbing phenol in waste water. The macroporous adsorption resin disclosed by the invention has a good effect on the phenol in an aqueous solution, wherein the adsorption isotherm is fitted by an Freudlich isothermal adsorption equation, the correlation coefficient R is larger than 0.98 and the result is credible.
Description
Technical field
The present invention relates to a kind of ternary macroporous adsorbent resin.
Background technology
Macroporous adsorbent resin is a kind of organic high molecular polymer sorbent material that is insoluble to acid, alkali and various organic solvents, and the technology that the application macroporous adsorbent resin separates is one of separation technology after ion exchange resin that grows up late 1960s.Polymeric adsorbent be with a class being adsorbed as characteristics, organism is had the porousness high molecular polymer of concentrated and centrifugation.At present, the separating mechanism of polymeric adsorbent mainly contains two kinds: a kind of is to utilize some substances by resin absorption, and all the other materials can not be reached the separation purpose by resin absorption; Another kind is avidity size different of utilizing each adsorbate and interlaminar resin, by strong adsorbate, the replacement effect of weak adsorbate is reached the purpose of separation.General adsorption separation process is to improve the separating effect of resin than strong interaction by changing absorption and elution requirement, introducing hydrogen bond and ionization etc.
Macroporous adsorbent resin has good absorption property, is mainly used in the fields such as industry decolouring, environment protection.In recent years, macroporous adsorbent resin has been widely used in the extraction of activeconstituents in natural phant, as the extraction separation of the macromolecular cpds such as glycoside, flavones, alkaloid.Fractionation by adsorption to biological chemistry goods such as iridoid glycoside, peoniflorin, Radix Clematidis total glycosides, Herba Epimedii, flavones, Ginkgo total flavones, corydalis alkaloid, Nuciferine, multiple natural pigment, traditional Chinese compound medicine extraction and microbiotic, VITAMIN has good effect.
Macroporous adsorbent resin is also mainly for the treatment of dyestuff, agricultural chemicals and the factory effluents such as medicine and intermediate and coking.Can be used for absorption and reclaim phenols, amine, organic acid, nitro thing, halohydrocarbon etc., as reluctant naphthalidine, 1-naphthols, beta naphthal, 2,3-acid, 1,2, the naphthalenes intermediate waste water such as 4-acid and oxysome, Schollkopf acid, amido-J-acid, meta-cresol, paranitrophenol sodium salt, oil of mirbane, nitro-chlorobenzene, aniline, mutual-amido two polyaniline, O-Phenylene Diamine, toluylic acid and fluorine (chlorine) are for the wastewater treatment of the organic intermediates such as toluene.Not only effectively administer poisonous organic chemical waste water, strictly controlled the toxic organic pollutant discharging, also realized enrichment, recovery and the comprehensive utilization of waste water Raw and intermediate.
Macroporous adsorbent resin is showing the effect that it is unique aspect extraction natural drug effective constituent day by day, it has wide application future, not only provide more effective, reliable means of purification for Chinese medicine preparation quality control and modernization of cmm, the more important thing is the shortcomings such as the outward appearance that can improve traditional Chinese medicine compound preparation " thick, large, black " and dose be excessive, the innovation of Chinese medicine preparation is played positive pushing effect.Macroporous adsorbent resin is the parting material that adsorptivity and molecular sieve principle combine.The lip-deep atom of the polymeric adsorbent field of force is unsaturated, the surface energy is arranged, thereby can adsorb some molecule to fall low surface energy.Its adsorptivity is Van der Waals force or the result that produces hydrogen bond, and molecular sieve is by itself cellular structure decision.Macroporous adsorbent resin can adsorb the various types of compounds with different chemical character effectively, its absorption property depends primarily on the surface properties of sorbent material, and namely the wetting ability on surface or hydrophobicity have determined that it is to the characterization of adsorption of different organic compound.In general, non-polar resin adsorbs apolar substance in polar solvent (adding water), polar resin easily adsorbs polar material in non-polar solvent, the Semi-polarity resin both can adsorb apolar substance in polar solvent, can adsorb polar material again in non-polar solvent.
A large amount of holes and very large specific surface area are arranged in macroporous adsorbent resin, can be used for adsorbing Phenol for Waste Water class material, resin can be regenerated and Reusability, and can reclaim aldehydes matter.An important indicator of macroporous resin performance is selectivity, so the synthetic resin that phenols is had specific selective adsorption performance is a major issue during phenolic wastewater is processed.The polymeric adsorbent major part that is used at present wastewater treatment is styrene resin, and less to the research of acrylates adsorption resin.Therefore, the research of the polymeric adsorbent of esters of acrylic acid has very important significance for the development of polymeric adsorbent.
Summary of the invention
The present invention is according to the synthetic macroporous adsorbent resin take methyl acrylate-methyl methacrylate-Vinylstyrene (MA-MMA-DVB) terpolymer as skeleton of physical adsorption principle design, because contain ester group in monomer, so this resin is mainly used in phenol in wastewater is adsorbed.
The present invention mainly comprises following content:
1) preparation of water: weighing polyvinyl alcohol, sodium-chlor is dissolved in deionized water, is stirred well to dissolving fully, gets water.
2) preparation of oil phase: take respectively divinylbenzene, methyl acrylate, methyl methacrylate, pore-creating agent, then mix, then drip the Diisopropyl azodicarboxylate of 0.3～0.5g, stir, get oil phase.
3) synthetic: that water is added in reactor, open and stir, stop after slowly being heated to 40 ℃ stirring, add oil phase, regulating stirring velocity is 35～50 rev/mins, after being warming up to 63～66 ℃ with the speed of 0.5 ℃/min, in the situation that keep stirring velocity constant, then constant temperature 4～7h slowly is warming up to 85 ℃ at the same rate, constant temperature 4h, stopped reaction.
4) washing is dry: after above-mentioned product is cooled to room temperature, use respectively hot water, cold water and washing with alcohol, vacuum-drying, get white dried, then resin is gone out pore-creating agent with Petroleum ether extraction in apparatus,Soxhlet's, change the resin after extracting into water with the alcohol immersion postposition, then suction filtration, dry, get the ternary macroporous adsorbent resin.
Further, in the preparation process of water, polyvinyl alcohol, sodium-chlor, deionized water takes in mass ratio.
Further, in the preparation process of oil phase, the mass ratio of divinylbenzene, methyl acrylate, methyl methacrylate is 3～5: 3～4: 2～3.5.
Further, pore-creating agent is heptane and toluene or heptane and liquid wax.
Further, (DVE: MA: MMA)=5: 3: 2, pore-creating agent was that liquid wax and toluene and mass ratio are that the gained resin property was best constantly in 1: 2 at m.
Beneficial effect of the present invention can show by Pyrogentisinic Acid's Static Adsorption:
Accurately take the resin of certainweight in tool plug Erlenmeyer flask, add in the phenol solution of a series of different concns of 0.1200g, be placed in the constant temperature oscillator isothermal vibration more than 8 hours, make absorption reach balance.Measure the concentration C of phenol in raffinate with ultraviolet-visible pectrophotometer
e, calculate its equilibrium adsorption capacity according to following formula:
q
e＝(C
0-C
e)V/m.
In formula, q
eBe adsorptive capacity (mg/g),
C
0, C
eBe respectively the concentration (mg/L) of Phenol in Aqueous Solution before and after adsorbing,
V is the volume (L) of adsorption liquid,
M is resin quality (g).
Table 1 resin Static Adsorption situation 1.
Table 2 resin Static Adsorption situation 2.
Table 3 resin Static Adsorption situation 3.
Match gained Freudlich isothermal adsorpting equation is:
Table 4 Freudlich isothermal adsorption fit equation
As can be seen from Table 4, three kinds of resins are to the Freudlich isothermal adsorpting equation match of the adsorption isothermal line of phenol in aqueous solution, coefficient R is all greater than 0.98, illustrate that it is believable that the Freudlich isothermal adsorpting equation carries out match to it. simultaneously, constant n is all greater than 1, and the absorption that resin Pyrogentisinic Acid of the present invention is described is preferential absorption.The resin 1. absorption affinity to phenol in aqueous solution is the strongest.
Figure of description
Fig. 1: resin 1., resin 2., resin 3. under 298k, q
eChange curve with phenol concentration;
Fig. 2: Freudlich isothermal adsorption matched curve.
Claims (6)
1. the ternary macroporous adsorbent resin of ester group absorption, it is characterized in that: the preparation process of described resin comprises the following steps:
1) preparation of water: weighing polyvinyl alcohol, sodium-chlor is dissolved in deionized water, is stirred well to dissolving fully, gets water.
2) preparation of oil phase: take respectively divinylbenzene, methyl acrylate, methyl methacrylate, pore-creating agent, then mix, then drip the Diisopropyl azodicarboxylate of 0.3～0.5g, stir, get oil phase.
3) synthetic: that water is added in reactor, open and stir, stop after slowly being heated to 40 ℃ stirring, add oil phase, regulating stirring velocity is 35～50 rev/mins, after being warming up to 63～66 ℃ with the speed of 0.5 ℃/min, in the situation that keep stirring velocity constant, then constant temperature 4～7h slowly is warming up to 85 ℃ at the same rate, constant temperature 4h, stopped reaction.
4) washing is dry: after above-mentioned product is cooled to room temperature, use respectively hot water, cold water and washing with alcohol, vacuum-drying, get white dried, then resin is gone out pore-creating agent with Petroleum ether extraction in apparatus,Soxhlet's, change the resin after extracting into water with the alcohol immersion postposition, then suction filtration, get the ternary macroporous adsorbent resin after drying.
2. greatly also polymeric adsorbent of the ternary of a kind of ester group absorption as described in claim 1 is characterized in that: in the preparation process of described water, polyvinyl alcohol, sodium-chlor, deionized water in mass ratio 0.27～2.2: 1～13: 85～98.7 take.
3. greatly also polymeric adsorbent of the ternary of a kind of ester group absorption as described in claim 1, it is characterized in that: in the preparation process of described oil phase, the mass ratio of divinylbenzene, methyl acrylate, methyl methacrylate is 3～5: 3～4: 2～3.5.
4. greatly also polymeric adsorbent of the ternary of a kind of ester group absorption as described in claim 1, it is characterized in that: the mass ratio of described water and oil phase is: 4～6: 1.
5. greatly also polymeric adsorbent of the ternary of a kind of ester group absorption as described in claim 1, it is characterized in that: described pore-creating agent is heptane and toluene or heptane and liquid wax.
6. greatly also polymeric adsorbent of the ternary of a kind of ester group absorption as described in claim 1, it is characterized in that: (DVE: MA: MMA)=5: 3: 2, pore-creating agent was that liquid wax and toluene and mass ratio are that 1: 2 o'clock gained resin Pyrogentisinic Acid's absorption property is best at m.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530307A (en) * | 2014-12-19 | 2015-04-22 | 西南石油大学 | Preparation of hydrophilic acrylic adsorption resin and application of acrylic adsorption resin in phenolic wastewater treatment |
| CN104549180A (en) * | 2015-01-19 | 2015-04-29 | 李�杰 | Method for preparing purification resin for removing arsenic and fluorine in underground water |
| CN109705254A (en) * | 2018-12-28 | 2019-05-03 | 北京宝辰联合科技股份有限公司 | A kind of aqueous polymer emulsion porous adsorbent and preparation method thereof |
| CN110627941A (en) * | 2019-10-11 | 2019-12-31 | 河北利江生物科技有限公司 | Resin with high ester group content and ultrahigh crosslinking structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1724292A2 (en) * | 2005-05-18 | 2006-11-22 | Rohm And Haas Company | Process for producing macroporous acrylic resins |
| CN102408511A (en) * | 2011-10-12 | 2012-04-11 | 武汉德骼拜尔外科植入物有限公司 | Synthesis method for linear PMMA-MA (Polymethyl Methacrylate-Methyl Acrylate) bead powder |
| CN102671718A (en) * | 2012-06-11 | 2012-09-19 | 淄博东大弘方化工有限公司 | Supermacroporous strong base anion exchange resin with quaternary amine group and preparation process thereof |
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2012
- 2012-12-17 CN CN2012105458816A patent/CN103113506A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1724292A2 (en) * | 2005-05-18 | 2006-11-22 | Rohm And Haas Company | Process for producing macroporous acrylic resins |
| CN102408511A (en) * | 2011-10-12 | 2012-04-11 | 武汉德骼拜尔外科植入物有限公司 | Synthesis method for linear PMMA-MA (Polymethyl Methacrylate-Methyl Acrylate) bead powder |
| CN102671718A (en) * | 2012-06-11 | 2012-09-19 | 淄博东大弘方化工有限公司 | Supermacroporous strong base anion exchange resin with quaternary amine group and preparation process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高俊刚 等: "MMA-DVB 大孔树脂对二氯苯酚等的吸附性能", 《河北大学学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530307A (en) * | 2014-12-19 | 2015-04-22 | 西南石油大学 | Preparation of hydrophilic acrylic adsorption resin and application of acrylic adsorption resin in phenolic wastewater treatment |
| CN104549180A (en) * | 2015-01-19 | 2015-04-29 | 李�杰 | Method for preparing purification resin for removing arsenic and fluorine in underground water |
| CN109705254A (en) * | 2018-12-28 | 2019-05-03 | 北京宝辰联合科技股份有限公司 | A kind of aqueous polymer emulsion porous adsorbent and preparation method thereof |
| CN109705254B (en) * | 2018-12-28 | 2024-01-30 | 北京宝辰联合科技股份有限公司 | Porous adsorbent for aqueous polymer emulsion and preparation method thereof |
| CN110627941A (en) * | 2019-10-11 | 2019-12-31 | 河北利江生物科技有限公司 | Resin with high ester group content and ultrahigh crosslinking structure and preparation method thereof |
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Application publication date: 20130522 |