CN100503031C - Poly (m-phenylenediamine) adsorbing column for pump ion dynamic adsorption and using method thereof - Google Patents
Poly (m-phenylenediamine) adsorbing column for pump ion dynamic adsorption and using method thereof Download PDFInfo
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Abstract
The present invention relates to the mercury ion dynamic removal technical field. The present invention provides a poly (m-phenylenediamine) absorption column used for a dynamic absorption of mercury ion; a filling of the column is poly (m-phenylenediamine) absorption blocks, which are embedded by polyvinyl alcohol; the top of the absorption column is filled flat and compacted by an inert fibre. The price of the poly (m-phenylenediamine) is cheap; the cost of an absorption agent which is synthesized by the poly (m-phenylenediamine) is low; in addition, PVA is also an embedding agent with low cost, therefore the absorption column which is filled by the poly (m-phenylenediamine) embedding blocks has the advantages of cheap price and easy availability. The absorption column, which contains the embedding block of poly (m-phenylenediamine) absorption agent is used for the dynamic absorption treatment towards mercury ion solution, and the performance of which is better than the performance of the reported mercury ion absorption agent under the similar dynamic operation condition, and the absorption column has very good regeneration and cycle use performance. Synthetically considering the raw material cost, the manufacture cost and the absorption performance, the poly (m-phenylenediamine) absorption column of the present invention has great potential practically application value.
Description
Technical field
The present invention relates to mercury ion dynamic removal technical field.
Background technology
Because grave danger that mercury causes ecological safety and human health, the waste water of industry such as metal smelt, chlor-alkali production, metal processing, plating generation must just can be discharged in the environment after the removal of mercury.Otherwise environment water will be subjected to mercury pollution, can be transformed into to propagate the methyl mercury that gathers with biological food chain, and human security is caused huge potential threat.Seeking efficiently, the environment water purification method more and more receives researcher's concern.In recent years, owing to advantages such as absorption method processing mercury solution concentration range are wide, and the cost energy consumption is low, and is efficient quick, exploitation can be handled the continous way operation of mercury-containing waste water on a large scale and more and more be paid attention to by people.Compare static adsorptive method, but dynamic adsorption method have on-line continuous operation, treating capacity big, be convenient to adsorbent reactivation and advantage such as separate, become the main mode of operation that adsorbent is applied to water treatment.Can therefore, investigate the practical application of marching toward of a kind of new and effective adsorbent, the quality of dynamic adsorption be one of main reference index.
The height key of absorption method usefulness is the performance of adsorbent.It at first is static absorption property.Synthetic class mercury ion adsorbent has specific adsorbing CN-, RS-, SH-, NH because of having to mercury ion
2-, groups such as-CO-, and demonstrate the advantage that is better than natural adsorbent.The once disclosed a kind of mercury ion adsorbent of the applicant gathers 1, and 8-naphthylenediamine (CN1803276) is a kind of mercury ion adsorbent of new and effective vast capacity, and static saturated adsorption capacity is up to 2863mg/g, and building-up process is simple and convenient.(application number: 200710037535.6), maximum static saturated adsorption capacity can reach 1499mg/g to the another kind of efficient mercury ion adsorbent poly m-phenylene diamine of the applicant's invention, and not only building-up process is simple and convenient, and monomer is cheap.Yet static efficiently absorption property only is it is applied to the necessary index of water treatment, but is not abundant index.After having excellent static absorption property, also must have good dynamic adsorption.And this depends on adsorption rate largely.The good news is that the above-mentioned poly m-phenylene diamine of the applicant invention just has the very fast rate of adsorption, 30 ℃ of 50mg poly m-phenylene diamine inputs, initial concentration are that static absorption can reach adsorption equilibrium in about 15 minutes in the 25mL mercuric nitrate solution of 399.2mg/L.And the monomer of synthetic this adsorbent does not rely on import, is based on national chemical products, is convenient to further apply.
Reported adsorption column is listed in table 1 to the mercury ion dynamic absorption property.As can be known, at present mercury ion dynamic absorption research is focused mostly at the synthetic class adsorbent or the modified natural adsorbent of static good adsorption performance, loadings is many between 0.2g～20g, and the initial ion concentration of mercury of processing is many about 1000mg/L.Although the scale of each adsorption column, operating parameter difference, make dynamic adsorption be difficult to directly compare, but, we still as can be seen, the dynamic adsorption of typical case's adsorbent shitosan can not show a candle to its static absorption property, no matter is to make membranaceous or after graininess loads into post, when loadings is the 2g or the 17g left and right sides, time of break-through all is no more than 50min, and corresponding mercury ion solution-treated amount all is no more than 130mL.(Vieira R S，Beppu M M.Dynamic and static adsorption and desorption of Hg(II)ions on chitosanmembranes and spheres[J].Water Research，2006，40：1726-1734)。The grafting thiourea resin ITU that loadings is less, because of the ion concentration of mercury of handling is low to moderate 50mg/L, time of break-through and corresponding treating capacity respectively can be up to 12.5h and 1500mL, but more loaded down with trivial details (the Zuo G of this adsorbent preparation process, Muhammed M.Selective binding of mercuryto thiourea-based coordinating resins[J] .Reactive and functional polymers, 1995,27:187-198).When the less SOL-AD-IV adsorption column of loadings is used for concentration of treatment up to the 1500mg/L mercury solution, time of break-through reaches 3h, showed the better dynamic absorption property, unfortunately its recycling performance is poor, cause high (the Nam KH of use cost, Tavlarides L L.Mercury removal from acidic waste solutions using a thiol functionalorgano-ceramic adsorbent[J] .Solvent extract ion and ion exchange, 2003,21 (6): 899-913).Time of break-through only is 10min when being used for mercury ion and dynamically adsorbing as for the solidified tannin film; can't satisfy industrial requirement of actual application (Ma Hewei according to present research scale; Liao Xuepin; Wang Ru; Deng. the preparation of materials with hide glue fibril solidified tannin film and to the absorption [J] of plumbous in the aqueous solution and mercury. the chemical industry journal; 2005,56 (10): 1907-1911).To be ion exchange resin Dowex XZS-1 near the commercial Application scale, its loadings is up to 20g, the inlet velocity of handling 80mg/L mercury ion solution is up to 300mL/min, although its time of break-through is 5.5min only, but its corresponding volume of handling has shown very high treatment effeciency up to 99L.Yet, this efficiently treatment effeciency need under the operating condition of negative pressure of vacuum, could obtain (Monteagudo J M, Ortiz M J.Removal of inorganic mercury from mine waste waterby ion exchange[J] .Journal of chemical technology and biotechnology, 2000,75:767-772).Obviously this is a kind of power consumption operation.
Table 1 adsorption column is to the mercury ion dynamic adsorption
| Adsorbent/quality (g) | Ion concentration of mercury (mg/L) | Adsorption column size H (mm) * D (mm) | Flow velocity (mL/min) | Time of break-through/processing volume | Saturation time (h)/processing volume (L) |
| Chitosan film/about 17 | 1225 | 200×13.5 | 2.7 | 0.8h/ |
20/3.24 |
| Shitosan ball/about 2 | 225 | 55×7.6 | 1.8 | 0.7h/75.6 |
40/4.32 |
| Grafting thiourea resin ITU/1.5 | 50 | 100×6 | 2 | 12.5h/1.5L | 87.5/10.5 |
| SOL-AD-IV/ 0.2 | 1500 | 100×7 | 1 | 3.0h/180mL | 5.9/0.355 |
| Solidified tannin film/0.3 | 141.2 | - | 12 | 10min/120mt | 0.42/0.3 |
| Ion exchange resin Dowex XZS-1/ 20 | 80 | 500×30 | 300 | 5.5min/99L | 0.17/180 |
Can find to be used at present the adsorbent of dynamic process mercury ion or cause mercury-containing waste water up to standardly not handle by above summary, or because the preparation of adsorbent process is loaded down with trivial details, cost is higher, all is difficult to satisfy industrial instructions for use because of too fast the penetrating of adsorption column.As seen find a kind of synthetic simple and easyly, with low cost, the adsorbent that mercury ion is had the high-efficiency dynamic absorption property is very important.
Summary of the invention
One of purpose of the present invention just provides and a kind ofly is easy to load into post, be easy to dynamic operation and mercury ion is had the poly m-phenylene diamine embedded block adsorption column of high-efficiency dynamic absorption property.
Another object of the present invention provides the method for utilizing above-mentioned adsorption column that mercury ion is dynamically adsorbed.
For reaching above-mentioned purpose, the concrete technical scheme that the present invention takes is as follows:
As the poly m-phenylene diamine adsorption column of mercury ion dynamic absorption, fill poly m-phenylene diamine Attraction block in its post with polyvinyl alcohol embedding, the adsorption column upper and lower side is leveled up compacting with inert fiber.
Above-mentioned Attraction block, wherein poly m-phenylene diamine and polyvinyl alcohol weight ratio are 0.8～2:1, preferred weight ratio is 1.4～1.8:1.
The technology of preparing of poly m-phenylene diamine sees that application number is 200710037535.6 patent, adopts chemical oxidative polymerization to obtain.
The poly m-phenylene diamine Attraction block of polyvinyl alcohol embedding is meant poly m-phenylene diamine joined in the poly-vinyl alcohol solution and mixes, the dry then embedded block that obtains.
The method that the poly m-phenylene diamine adsorption column dynamically adsorbs mercury ion, its step is as follows:
A, in adsorption column, add water, make the abundant wetting swelling of adsorbent embedded block, regulate the required rate of outflow simultaneously, after treating that current to the greatest extent in the post, the solution that will contain mercury ion injects adsorption column, makes its liquid level surpass the adsorbent piece, and it is constant to keep this liquid level by adjusting import water velocity;
B, treat that adsorption column reaches capacity after, with elutriant drip washing adsorption column, do not contain mercury ion, thereby realize desorption and regeneration adsorption column until leacheate;
C, the solution that will contain mercury ion once more inject adsorption column, recycle so repeatedly.
The said elutriant of step b has the mixed liquor of any or nitric acid and hydrochloric acid among nitric acid, hydrochloric acid and the EDTA (ethylenediamine tetra-acetic acid).The elutriant concentration range is 0.0001～1molL
-1, preferably 0.01～0.5molL
-1Concentration is 0.1～0.5molL
-1Hydrochloric acid industrial actual application value arranged as elutriant most.
The dynamic adsorption of adsorbent is subjected to the influence of flow velocity, regeneration times, among the present invention, circulate the attached number of times of dynamic absorption-desorption 5 times all fine with interior effect, what handled mercurous solion can be in mercuric nitrate solution, the mercuric chloride solutions etc. is a kind of.
Beneficial effect of the present invention: m-phenylene diamine (MPD) low price, it is the raw material of industry of dyestuff, medicine and coatings industry, price is 2～30,000 yuan/ton, with low cost by its synthetic adsorbent, add that PVA also is an embedding medium with low cost, therefore, the adsorption column of poly m-phenylene diamine embedded block filling has advantage cheap and easy to get.The embedded block adsorption column that contains the 1.00g adsorbent of poly m-phenylene diamine, the time of break-through of the mercury ion solution that to be used for dynamic adsorption treatment initial concentration be 399.2mg/L reaches 19.8h, and the corresponding mercury ion solution amount of handling is 1.19L; Saturation time reaches 58h, and handling the mercury ion solution amount accordingly is 3.48L.Be higher than the performance of reported mercury ion adsorbent under similar dynamic operation condition.And this adsorption column has good regeneration cycle serviceability, behind the diluted nitric acid aqueous solution desorption and regeneration, takes turns dynamic adsorption appearance deterioration to a certain degree the 5th, but still can keep higher mercury ion solution-treated amount.Take all factors into consideration cost of material, cost of manufacture and absorption property, adsorbent of poly m-phenylene diamine has very big potential actual application value.
Description of drawings
Fig. 1 for concentration under the room temperature be the mercury ion solution of 399.2mg/L with the flow velocity of the 1mL/min adsorption column of flowing through, flow out ion concentration of mercury and time relation figure in the liquid
Fig. 2 for concentration under the room temperature be the mercury ion solution of 399.2mg/L with the flow velocity of the 1mL/min adsorption column of flowing through, flow out in the liquid, the relation of ion concentration of mercury and effluent volume is seen figure
The time of break-through that can be calculated this adsorption column by Fig. 1 and Fig. 2 is 19.8h, and the volume of handling mercury solution accordingly is 1.19L, and saturation time is 58h, and the volume of handling mercury solution accordingly is 3.48L.
The adsorption column 1mol/L HNO that Fig. 3 reaches capacity for absorption among the embodiment 1
3Flow velocity with 1mL/min carries out drip washing, the elution curve figure that obtains
As seen from Figure 3, the peak width of elution curve is narrower, shows desorb feature fast at the desorb initial stage, and 2h can get off most mercury ion drip washing.Although conditions of streaking appears in the desorb later stage, about 12h, can reach complete desorb.
The specific embodiment
The preparation of poly m-phenylene diamine:
0.08mol (8.652g) monomer m-phenylene diamine (MPD) is dissolved in the 200mL distilled water, ultrasonic 3～5 minutes, impel it fully to dissolve, then monomer solution is placed 30 ℃ of water-baths, balance half an hour.The oxidant ammonium persulfate of 0.08mol (18.256g) is dissolved in the 100mL distilled water, also it is maintained 30 ℃.This ammonium persulfate solution is added in the above-mentioned monomer solution.Reacted 24 hours, suction filtration, and with distilled water wash products in funnel, until using BaCl
2Solution check sulfate radical-free ion.Drain after cleaning, product was descended dry 3 days at 50 ℃, obtain poly m-phenylene diamine, productive rate 80.6%.
The preparation of Attraction block
The 4g polyvinyl alcohol is dissolved in the 46mL90 ℃ of left and right sides hot water, after waiting to dissolve it is cooled to about 40 ℃, be mixed with the poly-vinyl alcohol solution that weight concentration is 8wt%.Measure this poly-vinyl alcohol solution of 10mL to the 200mL beaker, add 0.8g poly m-phenylene diamine powder, stirring also with glass bar, ultrasonic processing impelled the two to mix about 20 minutes.This mixture is poured in the culture dish of clean drying, made it sprawl thick flat board into about 5mm.After 40 ℃ of dryings, then film is divided into square block standby of 10mm.Through breakage rate test, be 10.2% with the adsorbent of poly m-phenylene diamine breakage rate of polyvinyl alcohol embedding.
Poly m-phenylene diamine powder consumption is 1.2g, and the preparation method is identical with embodiment 1, through breakage rate test, is 12.3% with the adsorbent of poly m-phenylene diamine breakage rate of polyvinyl alcohol embedding.
The preparation of adsorption column
Fill 1.667g poly m-phenylene diamine embedded block in adsorption column, wherein containing poly m-phenylene diamine is 1.000g.The adsorption column upper and lower side is leveled up compacting with inert fiber, and the adsorbent embedded block of filling in the middle of guaranteeing is fixed.The adsorption column internal diameter is 1cm, and effectively the filling part height is 10cm.
Adopt dynamic adsorption method absorption mercury ion, step is as follows:
The deionized water that at first in adsorption column, adds about 30 ℃, make the abundant wetting swelling of adsorbent embedded block, regulating cock reaches the required rate of outflow simultaneously, as 1mL/min or 5mL/min, behind about 7～8h, stop to add water, treat in the post that current to the greatest extent after, with initial concentration is that the mercuric nitrate solution of 399.2mg/L injects adsorption column, and its liquid level is surpassed on the adsorbent about aspect scale 15cm.This liquid level is dynamically being kept constant by regulating the import water velocity in the adsorption process substantially.When the exit aqueous solution flows out with the flow velocity of setting, pick up counting after flowing out with first mercury solution, access a liquid that flows out with the clean dry every 8min of penicillin bottle, up to the adsorption column bed is saturated when no longer adsorbing mercury ion.Adopt the Fo Erhadefa titration to flow out the concentration C (mg/L) of remaining mercury ion in the liquid, and be calculated as follows:
In the formula: C
NaSCNConcentration (mg/L) for the NaSCN standard liquid; V
NaSCN: the volume (mL) of the NaSCN solution that is consumed during for titration.
Volume (mL) for the outflow mercury ion solution drawn.
Be abscissa with delivery time, effluent volume respectively, flowing out the liquid ion concentration of mercury is that ordinate is made the adsorption penetration curve.And by stipulating on the engineering, get that flowing out liquid intermediate ion concentration reaches at 5% o'clock that flows to liquid intermediate ion concentration, the identification adsorption column reaches and penetrates; Get outflow liquid intermediate ion concentration and reach at 95% o'clock that flows to liquid intermediate ion concentration, assert that adsorption column reaches capacity.Can obtain time of break-through and corresponding accessible mercury solution volume and the saturation time and the corresponding accessible mercury solution volume of adsorption column like this from the adsorption curve.
After treating that adsorption column reaches capacity, use 1mol/L HNO
3Flow velocity drip washing adsorption column with 1mL/min does not contain mercury ion until leacheate, thereby realizes the desorption and regeneration to adsorption column.In the desorption process, access 5mL drip washing at regular intervals and flow out liquid, use wherein ion concentration of mercury of Fo Erhadefa titration equally.Leacheate volume with time, outflow is an abscissa respectively, and contained ion concentration of mercury is that ordinate is made desorption curve in the leacheate of outflow.
Adsorption column is neutral with deionized water drip washing to flowing out liquid after the desorb, carries out next round absorption again, and then investigates the ability that adsorption column can reuse.
The dynamic adsorption of adsorbent is subjected to the influence of flow velocity, regeneration times, and among the present invention, flow rates is 1～5mL/min, and the attached number of times of dynamic absorption-desorption that circulates is 5 times.Mercurous solion can be in mercuric nitrate solution, the mercuric chloride solution etc. a kind of.
The more detailed dynamic adsorption that has illustrated that poly m-phenylene diamine is superior to mercury ion of following experimental example.
Experimental example 1
The solution that under the room temperature with ion concentration of mercury is 399.2mg/L flows out ion concentration of mercury and time relation such as Fig. 1 in the liquid with the flow velocity of the 1mL/min adsorption column of flowing through.The relation of ion concentration of mercury and effluent volume is seen Fig. 2 in the outflow liquid.
The time of break-through that can be calculated this adsorption column by Fig. 1 and Fig. 2 is 19.8h, and the volume of handling mercury solution accordingly is 1.19L, and saturation time is 58h, and the volume of handling mercury solution accordingly is 3.48L.
Embodiment 2
The adsorption column 1mol/L HNO that reaches capacity will be adsorbed in the experimental example 1
3Flow velocity with 1mL/min carries out drip washing, and elution curve is seen Fig. 3.Treat that drip washing is extremely neutral through deionized water drip washing again after complete.
As seen from Figure 3, the peak width of elution curve is narrower, shows desorb feature fast at the desorb initial stage.2h can get off most mercury ion drip washing.Although conditions of streaking appears in the desorb later stage, about 12h, can reach complete desorb.
Experimental example 3
The adsorption column of experimental example 2 regeneration is carried out the 2nd take turns absorption, the adsorption operations condition can obtain 2 and take turns breakthrough curve with experimental example 1.Can obtaining this adsorption column the 2nd thus, to take turns the time of break-through of absorption be 15.5h, and the amount of handling mercury ion accordingly is 0.93L, and saturation time is 54.5h, and the amount of handling mercury ion accordingly is 3.27L.Adsorption column with this after saturated by the mode of experimental example 2 carry out second take turns the drip washing desorb after, be used for third round absorption.The adsorption operations condition can obtain 3 and take turns breakthrough curve with experimental example 1.Can obtaining this adsorption column the 3rd thus, to take turns the time of break-through of absorption be 11.6h, and the amount of handling mercury ion accordingly is 0.696L, and saturation time is 51.9h, and the amount of handling mercury ion accordingly is 3.11L.
Experimental example 4
Adsorption column through above-mentioned 3 take turns adsorption and desorption circulation after, carries out the 4th again and take turns and the 5th take turns the attached operation of circulation adsorption and desorption, but the 4th flow velocity of taking turns mercury ion solution when taking turns adsorption operations with the 5th all is adjusted to 5mL/min, all the other conditions are constant.Can obtain breakthrough curve and desorption curve equally.Can obtaining this adsorption column the 4th thus, to take turns the time of break-through of absorption be 2.07h, and the amount of handling mercury ion accordingly is 0.621L, and saturation time is 7.5h, and the amount of handling mercury ion accordingly is 2.25L.The 5th time of break-through of taking turns absorption is 1.29h, and the amount of handling mercury ion accordingly is 0.387L, and saturation time is 5.7h, and the amount of handling mercury ion accordingly is 1.71L.
Take turns the attached performance of adsorption and desorption with above-mentioned 5 and list in table 2:
Many wheels dynamic adsorption of table 2 poly m-phenylene diamine embedded block adsorption column
| No | Flow velocity (mL/min) | Time of break-through (h) | Penetration volume (L) | Saturation time (h) | Saturated volume (L) |
| 1 | 1 | 19.8 | 1.19 | 58.0 | 3.48 |
| 2 | 1 | 15.5 | 0.93 | 54.5 | 3.27 |
| 3 | 1 | 11.6 | 0.696 | 51.9 | 3.11 |
| 4 | 5 | 2.07 | 0.621 | 7.5 | 2.25 |
| 5 | 5 | 1.29 | 0.387 | 5.7 | 1.71 |
From above experimental example as seen, simple, with low cost by the adsorbent of poly m-phenylene diamine block materials making of PVA embedding, be applicable to the dress post fully and implement dynamic operation.The adsorption column that is loaded by 1.66g adsorbent of poly m-phenylene diamine embedded block handle intermediate concentration contain mercury solution the time, time of break-through can reach nearly 20h during first run adsorption operations, handles capacity accordingly and can reach about 1.2L; Saturation time can reach nearly 60h, and handling capacity accordingly can reach about 3.5L.Take turns after adsorption and desorption recycles through 5, still can keep the good adsorption performance.This adsorption column has shown mercury ion dynamic adsorption efficiently, is a kind of good adsorption column that industrial mercury-containing waste water is handled that can be applicable to of economy.
Claims (6)
1, be used as the using method of the poly m-phenylene diamine adsorption column of mercury ion dynamic absorption, it is characterized in that, fill the poly m-phenylene diamine Attraction block with polyvinyl alcohol embedding in its post, the adsorption column upper and lower side is leveled up compacting with inert fiber, and its step is as follows:
A, in adsorption column, add water, make the abundant wetting swelling of Attraction block, regulate the required rate of outflow simultaneously, after treating that current to the greatest extent in the post, the solution that will contain mercury ion injects adsorption column, makes its liquid level surpass Attraction block, and it is constant to keep this liquid level by adjusting import water velocity;
B, treat that adsorption column reaches capacity after, with elutriant drip washing adsorption column, do not contain mercury ion, thereby realize desorption and regeneration adsorption column until leacheate;
C, the solution that will contain mercury ion once more inject adsorption column, recycle so repeatedly.
2, the using method that is used as the poly m-phenylene diamine adsorption column of mercury ion dynamic absorption as claimed in claim 1, it is characterized in that: poly m-phenylene diamine and polyvinyl alcohol weight ratio are 0.8～2:1 in the said Attraction block.
3, the using method that is used as the poly m-phenylene diamine adsorption column of mercury ion dynamic absorption as claimed in claim 2, it is characterized in that: poly m-phenylene diamine and polyvinyl alcohol weight ratio are 1.4～1.8:1 in the said Attraction block.
4, the using method of the described poly m-phenylene diamine adsorption column as mercury ion dynamic absorption of claim 1 is characterized in that: the said elutriant of step b is the mixed liquor of any or nitric acid and hydrochloric acid among nitric acid, hydrochloric acid and the EDTA.
5, the described using method that is used as the poly m-phenylene diamine adsorption column of mercury ion dynamic absorption of claim 4, it is characterized in that: the said elutriant concentration range of step b is 0.0001～1molL
-1
6, the described using method that is used as the poly m-phenylene diamine adsorption column of mercury ion dynamic absorption of claim 1, it is characterized in that: the attached number of times of dynamic absorption-desorption that circulates is 1～5 time.
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Non-Patent Citations (4)
| Title |
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| Rapid and Effective Adsorption of Lead Ions on FinePoly(phenylenediamine) Microparticles. Mer-Rong Huang, et al.Chem. Eur. J.,No.12. 2006 |
| Rapid and Effective Adsorption of Lead Ions on FinePoly(phenylenediamine) Microparticles. Mer-Rong Huang, et al.Chem. Eur.J.,No.12. 2006 * |
| 聚间苯二胺作为Pb2+吸附剂的包埋. 谢素芬等.济南大学学报（自然科学版），第21卷第1期. 2007 |
| 聚间苯二胺作为Pb2+吸附剂的包埋. 谢素芬等.济南大学学报(自然科学版)，第21卷第1期. 2007 * |
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