CN102745765B - Method for treating waste water containing phenol by coordination polymer - Google Patents
Method for treating waste water containing phenol by coordination polymer Download PDFInfo
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- CN102745765B CN102745765B CN201210267963.9A CN201210267963A CN102745765B CN 102745765 B CN102745765 B CN 102745765B CN 201210267963 A CN201210267963 A CN 201210267963A CN 102745765 B CN102745765 B CN 102745765B
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- phenol
- waste water
- hadab
- coordination polymer
- ligand polymer
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Abstract
The invention aims to provide a waste water treatment method which has the advantages of strong pertinence to phenol, high adsorption efficiency and raw material recycling, i.e. a method for treating waste water containing the phenol by a coordination polymer. The method comprises the following steps: (1) synthesis: obtaining the coordination polymer [Cd(Hadab)(H2O)]; (2) adsorption: putting the coordination polymer [Cd(Hadab)(H2O)] into the waste water containing the phenol according to a weight volume ratio of (1-100):1,000, sufficiently stirring, and adsorbing for 10-40 minutes; (3) filtering: filtering the waste water treated in the step (2) to filter out a coordination polymer I adsorbing the phenol; and (4) regeneration: soaking the coordination polymer adsorbing the phenol for 2-16 hours with alcohol, washing twice with alcohol, and then drying for recycling.
Description
Technical field
The present invention relates to Handling Waste Water by Absorbing Way field, particularly a kind of method of ligand polymer as sorbent material that adopted.
Background technology
Phenol is the basic raw material of chemical industry, is also in water body, to common are organic pollutants.And the phenolic wastewater very typical and ubiquitous industrial organic waste water that is one, phenol solution is more easily absorbed by the skin than pure phenol, lower concentration adsorption treatment is to be relatively effectively also a kind of processing mode being most widely used at present, and a kind of desirable sorbing material should be that preparation is simple, regeneration is easy to material.But existing sorbing material such as, the cost of activated carbon class sorbent material is higher, although the sorbing material of natural crystal and clay component is cheaply easy to get, has the difficult problem of regeneration.
Ligand polymer is that a class has reticulated structure, duct homogeneous, aperture is adjustable and has the organic materials of huge specific surface area, as Chinese University of Science and Technology's Ph D dissertation, " synthetic, the structure of aromatic polycarboxylic acids ligand polymer and functional study " discloses a kind of ligand polymer, i.e. [Cd (Hadab) (H2O)].This class material be mainly used at present hydrogen, carbonic acid gas, the absorption of the micro-molecular gas such as methane.But be never used as the sorbing material in water body, and, experiment showed, not to be all ligand polymer aldehydes matter in adsorbed water body well.
Summary of the invention
The object of this invention is to provide that a kind of Pyrogentisinic Acid is with strong points, adsorption efficiency is high, and the method for wastewater treatment that raw material can recycling use.
Be such for realizing the technical scheme that the object of the invention adopts, a kind of method of ligand polymer Phenol-Containing Wastewater Treatment, is characterized in that, comprises the following steps:
1) synthetic: to obtain ligand polymer [Cd (Hadab) (H
2o)];
2) absorption: by [Cd (Hadab) (H
2o)] by weight 1-100: 1000 drop into the waste water containing phenol, and shake well, adsorbs 10～40 minutes;
3) filter: will be through step 2) waste water filtering of processing, leach the ligand polymer I that has adsorbed phenol;
4) regeneration: use alcohol immersion after 2～16 hours described ligand polymer of having adsorbed phenol, then use washing with alcohol twice, recycle after drying.
Ligand polymer of the present invention is a kind of sorbing material of porous, and it is synthetic conventionally through following a and b two steps:
A, aromatic polycarboxylic acids part N-(3-carboxyl phenyl) iminodiethanoic acid (H
3synthesizing adab):
100 milliliters of potassium hydroxide (33.6 g, 0.6 mol) aqueous solution is slowly added drop-wise to 100 milliliters of Mono Chloro Acetic Acid (28.4 g, 0.3 mol) the aqueous solution in (keep system temperature lower than 10 ℃), in this basic solution, add gavaculine (13.7 g, 0.1 mol) and at 86 ℃, reflux 30 hours, be then acidified to and produce white precipitate (pH is about 2.5) by reaction system cool to room temperature and with hydrochloric acid (6 mol/L).Filter, distilled water wash, and after water recrystallization, can obtain white plates solid (productive rate: 57%, based on gavaculine).Nuclear magnetic data: 1H NMR (300 MHz, D
2o, 25 ° of C): 7.29 (t, J=7.7 Hz, 1 H), 7.14 (d, J=7.4 Hz, 1 H), 7.00 (s, 1 H), 6.65 (d, J=7.7 Hz, 1 H), 3.94 (s, 4 H) ppm.IR spectrum (KBr compressing tablet, cm – 1): 3436 (m), 2924 (m), 2553 (w), 1723 (s), 1680 (s), 1604 (m), 1580 (m), 1494 (w), 1466 (m), 1423 (w), 1367 (m), 1305 (m), 1181 (m), 757 (s), 672 (m), 606 (m).
The self-assembly of b, ligand polymer:
In the polytetrafluoroethylliner liner of water heating kettle, (25mL hydrothermal reaction kettle) adds middle Cd (ClO successively
4)
26H
2o (0.10-1.00 mmol),
n-(3-carboxyl phenyl) iminodiethanoic acid (0.10-1.00 mmol), water (0.4-8 mL) and DMF (0.1-8 mL), after shake well, seal, add water heating kettle stainless steel casing, it is to heat after 4-16 hour and obtain clear crystal in the baking oven of 80-140 ℃ that sealing is placed in temperature, with after washing with alcohol, in baking oven 60 ℃ dry (productive rate: 80%, based on H
3adab).Ultimate analysis, calculated value (is pressed C
11h
11cdNO
7calculate) (%): C, 34.62; H, 2.91; N, 3.67.Experimental value: C, 34.99; H, 2.81; N, 3.74.Infrared spectra (KBr, cm – 1): 3495 (w), 2954 (m), 2919 (m), 2665 (w), 1702 (s), 1585 (s), 1448 (s), 1418 (s), 1341 (m), 1313 (m), 1296 (m), 1264 (m), 1198 (m), 1136 (m), 993 (m), 971 (m), 932 (m), 880 (m), 809 (m), 774 (m), 756 (m), 721 (m), 690 (s), 665 (m), 641 (m), 569 (m), 471 (m).
Technique effect of the present invention is mathematical, ligand polymer [Cd (Hadab) (H
2o)] Pyrogentisinic Acid's waste water adsorption effect is obvious, and recovery method is simple and the rate of recovery is very high, ligand polymer [Cd (the Hadab) (H reclaiming
2o) ,] after manipulation of regeneration, its adsorption effect is substantially constant.
Embodiment
Below in conjunction with embodiment, the invention will be further described, only limits to following embodiment but should not be construed the above-mentioned subject area of the present invention.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacements and change, all should be included in the scope of the present invention.
Adopt synthetic [Cd (the Hadab) (H of the method disclosed in the present
2o)] (hereinafter to be referred as ligand polymer I)
In embodiment, also select cheap oxalic acid as organic ligand, obtained two kinds of ligand polymer, but processed in experiment and find its poor effect at follow-up phenolic waste water.Its synthetic method is as follows:
Selection oxalic acid is organic ligand, according to literature method (Fu Xucheng, " research of oxalic acid, propanedioic acid and metallic ion coordination polymkeric substance ", Central China Normal University's Master's thesis, 2006) self-assembly, obtains oxalic acid-manganese coordination polymer light yellow crystal (hereinafter referred to as ligand polymer II), after washing with alcohol, in baking oven 60 ℃ dry (productive rate: 73%, based on oxalic acid).Again according to literature method (Yu Lianxiang etc., " Hydrothermal Synthesis Magnetic Properties of Three-Dimensional Supramolecular Complex ligand polymer [Cd (C
2o
4) (H
2o)
2] H
2o and crystalline structure ", artificial lens journal, 2007,36 (1): 146-151) obtain oxalic acid-cadmium coordination polymer colourless transparent crystal (hereinafter referred to as ligand polymer III).
embodiment 1:by [Cd (Hadab) (H
2o)] volume ratio 1-100 by weight: 1000 drop into the waste water containing phenol, and (for the ease of operation, weightmeasurement ratio is g/mL or kg/L, i.e. [Cd (Hadab) (H
2o)] by weight, waste water by volume).In the present embodiment, 0.1 g ligand polymer I is dropped into and filled in 50mL phenolic wastewater, described waste water is the phenol solution of 50mg/L concentration, in constant temperature oscillation case, after temperature control jolting, get supernatant centrifugal, measure its residual concentration with ultraviolet-visible pectrophotometer, after 15 minutes, reach adsorption equilibrium, phenol clearance reaches 99.9%.Ligand polymer alcohol immersion 2-16 hour after absorption, washs 2 times again with ethanol after suction filtration, and dry, the rate of recovery is more than 95%.
embodiment 2:0.1 g ligand polymer I is dropped into and filled in 50mL phenolic wastewater, described waste water is the phenol solution of 100mg/L concentration, in constant temperature oscillation case, after temperature control jolting, get supernatant centrifugal, measure its residual concentration with ultraviolet-visible pectrophotometer, after 20 minutes, reach adsorption equilibrium, phenol clearance reaches 99.9%.Ligand polymer alcohol immersion 2-16 hour after absorption, washs 2 times again with ethanol after suction filtration, and dry, the rate of recovery is more than 95%.
embodiment 3:0.1 g ligand polymer I is dropped into and filled in 50mL phenolic wastewater, described waste water is the phenol solution of 150mg/L concentration, in constant temperature oscillation case, after temperature control jolting, get supernatant centrifugal, measure its residual concentration with ultraviolet-visible pectrophotometer, after 30 minutes, reach adsorption equilibrium, phenol clearance reaches 99.9%.Ligand polymer alcohol immersion 2-16 hour after absorption, washs 2 times again with ethanol after suction filtration, and dry, the rate of recovery is more than 95%.
embodiment 4: 0.1 g ligand polymer I is dropped into and filled in 50mL phenolic wastewater, described waste water is: the phenol solution of 200mg/L concentration, in constant temperature oscillation case, after temperature control jolting, get supernatant centrifugal, measure its residual concentration with ultraviolet-visible pectrophotometer, after 40 minutes, reach adsorption equilibrium, phenol clearance reaches 99.9%.Ligand polymer alcohol immersion 2-16 hour after absorption, washs 2 times again with ethanol after suction filtration, and dry, the rate of recovery is more than 95%.
embodiment 5: the ligand polymer I that 0.1 g is recycled drops into and fills in 50mL phenolic wastewater, described waste water is: the phenol solution of 200mg/L concentration, in constant temperature oscillation case, after temperature control jolting, get supernatant centrifugal, measure its residual concentration with ultraviolet-visible pectrophotometer, after 40 minutes, reach adsorption equilibrium, phenol clearance reaches 99.9%.Ligand polymer I alcohol immersion 2-16 hour after absorption, washs 2 times again with ethanol after suction filtration, and dry, the rate of recovery is more than 95%.
embodiment 6: 0.1 g ligand polymer II is dropped into and filled in 50mL phenolic wastewater, described waste water is: the phenol solution of 100mg/L concentration, in constant temperature oscillation case, after temperature control jolting, get supernatant centrifugal, measure its residual concentration with ultraviolet-visible pectrophotometer, after 20 minutes, reach adsorption equilibrium, phenol clearance reaches 5%, the non-constant of adsorption effect.
embodiment 7: 0.1 g ligand polymer III is dropped into and filled in 50mL phenolic wastewater, described waste water is: the phenol solution of 100mg/L concentration, in constant temperature oscillation case, after temperature control jolting, get supernatant centrifugal, measure its residual concentration with ultraviolet-visible pectrophotometer, after 20 minutes, reach adsorption equilibrium, phenol clearance reaches 20%, and adsorption effect is not good.
Claims (1)
1. a method for ligand polymer Phenol-Containing Wastewater Treatment, is characterized in that, comprises the following steps:
1) synthetic: to obtain ligand polymer [Cd (Hadab) (H
2o)]; Described [Cd (Hadab) (H
2o) be] in 25mL hydrothermal reaction kettle, to add successively Cd (ClO
4)
26H
2o 0.10-1.00 mmol,
n-(3-carboxyl phenyl) iminodiethanoic acid 0.10-1.00 mmol, water 0.4-8 mL, and DMF 0.1-8 mL, it is to heat after 4-16 hour and obtain white crystal in the baking oven of 80-140 ℃ that sealing is placed in temperature; Described [Cd (Hadab) (H
2o)] aperture is 0.8-4nm;
2) absorption: by [Cd (Hadab) (H
2o)] volume ratio 1-100 by weight: 1000 drop into the waste water containing phenol, and shake well, adsorbs 10～40 minutes;
3) filter: will be through step 2) waste water filtering of processing, leach [Cd (the Hadab) (H that has adsorbed phenol
2o)];
4) regeneration: by described [Cd (the Hadab) (H that has adsorbed phenol
2o)] use alcohol immersion after 2～16 hours, then use washing with alcohol twice, after drying, recycle.
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