CN100464838C - Adsorbents for lead ion pyrolytic poly(m - phenylenediamine) desorption and circulating method - Google Patents
Adsorbents for lead ion pyrolytic poly(m - phenylenediamine) desorption and circulating method Download PDFInfo
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- CN100464838C CN100464838C CNB200710040183XA CN200710040183A CN100464838C CN 100464838 C CN100464838 C CN 100464838C CN B200710040183X A CNB200710040183X A CN B200710040183XA CN 200710040183 A CN200710040183 A CN 200710040183A CN 100464838 C CN100464838 C CN 100464838C
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Abstract
The invention discloses a desorption and cycle application method for lead ion absorbent polyvinyl m-phenylenediamine. The desorption method is that eluent nitric acid, muriatic acid and any kind of EDTA or the mixed solution of muriatic acid and nitric acid are added into the polyvinyl m-phenylenediamine absorbing lead ion and it is mixed or treated in ultrasonic for a certain time to achieve the desorption balance and filter. The market price of desorption agent selected in the invention is relative low to the concentrated muriatic acid, the concentrated nitric acid and EDTA. By using the desorption method in the invention, the maximum desorption rate can achieve 94%; the polyvinyl m-phenylenediamine has good absorption ability to lead ion after the absorption cycle is carried out; and reabsorption rates can achieve 52% and 60% respectively. In addition, after many desorption-absorptions are accomplished repeatedly, cumulated absorption capability can achieve more than 700mg/g.
Description
Technical field
The present invention relates to the regeneration situation of poly m-phenylene diamine as adsorbents for lead ion pyrolytic.
Background technology
In the waste water of industrial production such as metal smelt, chlor-alkali production, plating discharging, often contain the heavy metal ion that multiple harm humans is healthy and threaten ecological safety, lead ion is one of them, must remove from waste water, just can be discharged in the environment.In the method for conventional process lead waste water, but absorption method is a kind of effective method of commercial Application, is more and more paid close attention to by people.
Adsorbent is the basic material of absorption method, and in actual applications, the index of weighing a kind of performance of the adsorbent quality is many-sided often, and wherein, absorption property and regeneration ability thereof are most important two aspects.
The surface of adsorbent will cover by absorbate after certain hour is carried out in absorption, and adsorption capacity is sharply descended, and just needs this moment to make adsorbent obtain regeneration the absorbate desorption.Desorb and absorption are closely-related often aborning.For the higher material of the employed adsorbent of adsorption process, particularly some prices can be recycled, just need from adsorbent, separate the material that is adsorbed, thereby adsorbent is regenerated by desorb.In addition, in the time of recycling the metal that is adsorbed, also must desorb.The process of desorb is the removal process of heavy metal ion, also is the process of adsorbent reactivation.From the use cost angle, the regeneration of adsorbent or to be repeatedly used be the important means that reduces cost also is the important evidence that can be employed and promote.
When a kind of adsorbent reach absorption saturated after, with someway the material that is adsorbed being removed, and the process that the structure of adsorbent itself does not change is called the regeneration of adsorbent.For dissimilar adsorbents, the method of its regeneration is different, with the active carbon is example, its renovation process has (Chi Jinping such as thermal regeneration, chemical oxidation regeneration, solvent desorption regeneration and bio-regeneration, pacify beautiful. the new development of activated carbon fiber and the application [J] in water treatment. tec fiber and application, 2003,28 (6): 40-28.).The adsorbent regeneration method of document wide coverage mainly contains and utilizes chemical reagent desorption and regeneration (Vieira R S at present, Beppu M M.Dynamic and static adsorption and desorption of Hg (II) ions on chitosan membranes and spheres[J] .Water Research, 2006,40:1726-1734.), ultrasonic and the concussion regeneration (magnificent great waves .ACF is to the absorption of furfural waste-water and the research of ultrasonic desorption [D]. Shenyang: Northeastern University's safe practice and engineering, 2002,5-42.) and combination (the Hamdaoui O of above-mentioned two kinds of methods, Naffrechouxb E, Suptilb J, et al.Ultrasonic desorption of p-chlorophenol fromgranular activated carbon[J] .Chemical Engineering Journal, 2005,106:153-161.).Develop new effective, economic adsorbent regeneration method and be still present research topic.The adsorption capacity of ABSORBENTS ABSORPTION metal ion and its desorption ability have corresponding relation, generally speaking, the factor that helps adsorbing all has certain inhibition to the carrying out of desorption process, in the research process to desorption, adsorption conditions and the adsorption mechanism of understanding the ABSORBENTS ABSORPTION metal ion are the basics point of departure that the researcher attempts improving desorption effect.Remove in the application of heavy metal ion in absorption method, the adsorbent with high-adsorption-capacity is the emphasis of people's common concern always, if this kind adsorbent can demonstrate good desorption performance, this can reduce the totle drilling cost of adsorbent to a certain extent greatly.
The poly m-phenylene diamine that synthesizes with chemical oxidization method has good lead ion adsorption function, and at room temperature saturated adsorption capacity can reach 242.7mgg
-1(Huang M R, Peng Q Y, Li X G.Rapid and effective adsorption of lead ions onfine poly (phenylenediamine) microparticles[J] .Chemistry-A European Journal, 2006,12:4341-4350.), it is the adsorbents for lead ion pyrolytic of excellent performance, yet, recycling of adsorbent also is one of examination index of its combination property in actual use, if can to this adsorbent the strippant of best desorption effect be arranged by exploration discovery, will play very big impetus for adsorbent of poly m-phenylene diamine research and development at home.
Summary of the invention
Purpose of the present invention is exactly a kind of good parsing to be provided and to recycle method for the poly m-phenylene diamine adsorbents for lead ion pyrolytic.
The concrete technical scheme that the present invention adopts is as follows:
The desorption method of adsorbents for lead ion pyrolytic poly (m-phenylenediamine), this method is the mixed liquor that adds any or nitric acid and hydrochloric acid among elutriant nitric acid, hydrochloric acid and the EDTA (ethylenediamine tetra-acetic acid) in being adsorbed with the poly m-phenylene diamine of lead ion, stirring or ultrasonic certain hour make it to reach the desorb balance, filter.
The method that recycles of adsorbents for lead ion pyrolytic poly (m-phenylenediamine), this method be will be adsorbed with lead ion poly m-phenylene diamine according to above-mentioned desorption method desorb, then the adsorbent of collecting is come into operation again, desorb again, so repeatedly the circulation get final product.
Solution after the desorb is filtered, collect filtrate, the content of lead ion in the solution of analytic solution absorption back; With adsorbent fully filter do after, repeat the step of the attached experiment of first round absorption-desorption.Make desorption efficiency to the initial concentration of elutriant and the graph of a relation of desorption time according to the desorption efficiency data of gained, determine pairing elutriant optium concentration of maximum desorption efficiency and best desorption time.By comprehensively relatively obtaining the best desorption mode behind the poly m-phenylene diamine adsorpting lead ion.
Test shows that the desorption and regeneration ability of adsorbent is subjected to the influence of elutriant kind, elutriant concentration, desorption time, and among the present invention, used elutriant concentration range is 0.0001～1molL
-1, preferably 0.01～0.5molL
-1, desorption time is 2-60 minute.
Take all factors into consideration cost of material, desorption performance and adsorbent and utilize ability again, when being applied to the large-scale industry water treatment, concentration is 0.1～0.5molL
-1Hydrochloric acid can make adsorbent of poly m-phenylene diamine have potential actual application value as elutriant.When being applied to a spot of becoming more meticulous during work study, concentration is 0.01～0.03molL
-1The EDTA elutriant then for optimal selection.
Utilize desorb of the present invention and recycle method, the poly m-phenylene diamine adsorbents for lead ion pyrolytic recycle 1～10 time still effective, recycle after more times, adsorption effect can weaken gradually.
Beneficial effect of the present invention: poly m-phenylene diamine to lead ion at room temperature saturated adsorption capacity can reach 242.7mgg
-1, the very fast rate of adsorption is arranged, the short time promptly reaches adsorption equilibrium.The market price of the selected strippant of the present invention is cheap relatively, and the market price of concentrated hydrochloric acid, red fuming nitric acid (RFNA) and EDTA is followed successively by 643 yuan/ton, 2500 yuan/ton, 22000 yuan/ton.Under 30 ℃ of water bath with thermostatic control conditions, utilize concentration to be 0.02molL
-1The EDTA elutriant poly m-phenylene diamine powder that has adsorbed lead ion is stirred the maximum desorption efficiency of desorption can reach 94%.And utilize concentration to be 0.5molL respectively
-1Nitric acid elutriant and concentration be 0.3molL
-1The hydrochloric acid elutriant poly m-phenylene diamine powder that has adsorbed lead ion stirred the best desorption efficiency that desorption obtains be respectively 50% and 43%, experienced poly m-phenylene diamine after the adsorption-desorption circulation and still had preferably lead ion adsorption capacity again, adsorption rate reaches 52% and 60% respectively again.In addition, repeat after desorb-absorption repeatedly, the accumulation adsorption capacity reaches 700mg/g.
The specific embodiment
Following embodiment is used for illustrative explanation and provides, thereby they can not be interpreted as it is limitation of the present invention.
The poly m-phenylene diamine that utilizes among the present invention adopts chemical oxidization method synthetic, and concrete operations are as follows:
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 (quality 18.256g) of 0.08mol 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.Weigh and calculate productive rate.
The present invention at the method for poly m-phenylene diamine adsorpting lead ion, adopt static adsorptive method (or claiming batch method).
Plumbum ion concentration before and after the absorption is higher than 50mgL at plumbum ion concentration
-1The time can adopt EDTA complexometry direct titrimetric method to measure, plumbum ion concentration is lower than 50mgL after absorption
-1Shi Caiyong inductively coupled plasma method is measured.
Calculate adsorbent to Pb according to formula (1) and formula (2)
2+Adsorption capacity and adsorption rate.
Q: to Pb
2+Adsorbance (mgg
-1); C
0: Pb
2+Initial concentration (mgL
-1);
V: used Pb during absorption
2+The volume of solution (mL); M: the weight of adsorbent (mg);
Q: to Pb
2+Adsorption rate (%); C: Pb in the solution of absorption back
2+Concentration (mgL
-1).
The desorption method of the poly m-phenylene diamine behind the adsorpting lead ion of the present invention adopts the steady-state solution absorption method.
Adopt formula (3) to calculate desorption efficiency.
Q ': desorption rate (%); C
D: Pb in the elutriant after the desorb
2+Concentration (mgL
-1);
V
D: the volume of stripping liquid (mL); C
0: Pb
2+Initial concentration (mgL
-1);
C ': Pb in the solution of absorption back
2+Concentration (mgL
-1);
V: used Pb during absorption
2+The volume of solution (mL).
Make desorption efficiency to the initial concentration of elutriant and the graph of a relation of desorption time according to the desorption efficiency data of gained, determine pairing elutriant optium concentration of maximum desorption efficiency and best desorption time.By comprehensively relatively obtaining the best desorption mode behind the poly m-phenylene diamine adsorpting lead ion.
Regeneration method in the adsorbents for lead ion pyrolytic poly (m-phenylenediamine) practical application of the present invention, the processing method that promptly adopts above-mentioned static state absorption to combine with static desorb.Repeat the attached step of absorption-desorption, so move in circles and carry out, utilize adsorption rate and desorption efficiency after formula (2) and (3) are calculated circulation each time respectively.
Take turns absorption of using in the circulation according to each and conciliate adsorption effect, this kind adsorbent utilizes ability more as can be known.
Embodiment 1
Pipetting initial concentration with pipette is 500mgL
-1Lead ion solution 25mL place the dry conical flask of 50mL band plug, add 50mg adsorbent poly m-phenylene diamine powder, stirring and adsorbing 24h in 30 ℃ water bath with thermostatic control.To adsorb back solution and filter, collect filtrate, the adsorbent on the filter paper will fully be dried in the air to no longer including filtrate oozing out, must be adsorbed with the poly m-phenylene diamine of lead ion with dry beaker with funnel.
Embodiment 2
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.5molL
-1The nitric acid elutriant, 30 ℃ of stirred in water bath desorption 2 minutes, after filter paper filtered, with the content of lead ion in the filtrate after the absorption of EDTA compleximetry analytic solution, the result showed that desorption efficiency is 41.2% under this kind situation.
Repeat embodiment 2, change desorption time and be respectively 5 minutes, 10 minutes, 20 minutes, 40 minutes, 60 minutes, the gained desorption efficiency is respectively 45.4%, 46.6%, 49.9%, 50.1%, 49.9%.As seen can reach the desorb balance in 20 minutes.
Embodiment 3
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.2molL
-1The nitric acid elutriant, 30 ℃ of stirred in water bath desorbs 2 minutes, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 29.5% under this kind situation.
Under the similarity condition, change desorption time and be respectively 5 minutes, 10 minutes, 20 minutes, 40 minutes, 60 minutes, the gained desorption efficiency is respectively 33.5%, 37.6%, 38.0%, 38.8%, 39.4%.As seen can reach the desorb balance in 10 minutes.
Embodiment 4
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.04molL
-1The nitric acid elutriant, 30 ℃ of stirred in water bath desorption 2 minutes, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 22.76% under this kind situation.
Under the similarity condition, change desorption time and be respectively 5 minutes, 10 minutes, 20 minutes, 40 minutes, 60 minutes, the gained desorption efficiency is respectively 24.7%, 24.9%, 25.1%, 25.3%, 25.2%.As seen can reach the desorb balance in 5 minutes.
Embodiment 5
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.004molL
-1Nitric acid as elutriant, 30 ℃ of stirred in water bath desorption 60 minutes, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 17.2% under this kind situation.
Under the similarity condition, change stripping liquid concentration and be respectively 0.01molL
-1, 0.04molL
-1, 0.1molL
-1, 0.2molL
-1, 0.3molL
-1, 0.5molL
-1, 1molL
-1The gained desorption efficiency is respectively 25.1%, 26.0%, 33.7%, 39.4%, 46.0%, 49.9%, 49.9%.The optium concentration of the nitric acid elutriant under this condition is 0.5molL as can be known
-1
Embodiment 6
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.5molL
-1The nitric acid elutriant, desorption is 30 minutes under 30 ℃ of ultrasonic concussion conditions, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate solution, the result showed that desorption efficiency is 47.0% under this kind situation.
When other condition was all identical, the desorption efficiency that obtains when 30 ℃ of stirred in water bath mode desorbs was 49.9%.
Embodiment 7
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.5molL
-1The nitric acid elutriant, 30 ℃ of stirred in water bath desorption 2 minutes, after filter paper filters, content with lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, with the adsorbent on the filter paper fully filter do after, all transfer in the dry tool plug conical flask, repeat the step of the attached experiment of first round absorption-desorption.
So move in circles and carry out totally 6 times.The result shows, one to six takes turns in the circulation adsorption rate and the accumulation adsorption capacity is respectively: the first round 85.1% and 212.6mg/g, second takes turns 50.5% and 238.9mg/g, third round 51.4% and 356.8mg/g, four-wheel 51.7% and 476.4mg/g, the 5th takes turns the 53.8% and 598.6mg/g, the 6th takes turns 53.4% and 720.4mg/g.
Can learn that thus the polymer powder that has experienced continuous absorption-desorption additive process still has good lead ion adsorption capacity after 6 circulations.Use 0.5molL
-1During the desorb of nitric acid elutriant, the adsorption rate of adsorbent can maintain about 52% in the repetitive cycling utilization.
Embodiment 8
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.05molL
-1The hydrochloric acid elutriant, 30 ℃ of stirred in water bath desorption 3 minutes, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 23.4% under this kind situation.
Under the similarity condition, change desorption time and be respectively 5 minutes, 11 minutes, 20 minutes, 30 minutes, the gained desorption efficiency is respectively 23.1%, 24.8%, 25.4%, 25.0%.As seen can reach the desorb balance in 5 minutes.
Embodiment 9
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.1molL
-1The hydrochloric acid elutriant, 30 ℃ of stirred in water bath desorption 3 minutes, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 28.06% under this kind situation.
Under the similarity condition, change desorption time and be respectively 5 minutes, 11 minutes, 20 minutes, 30 minutes, the gained desorption efficiency is respectively 28.8%, 29.0%, 30.0%, 30.5%.As seen can reach the desorb balance in 5 minutes.
Embodiment 10
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.2molL
-1The hydrochloric acid elutriant, 30 ℃ of stirred in water bath desorption 3 minutes, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 34.35% under this kind situation.
Under the similarity condition, change desorption time and be respectively 5 minutes, 11 minutes, 20 minutes, 30 minutes, the gained desorption efficiency is respectively 41.3%, 42.8%, 43.2%, 43.2%.As seen can reach the desorb balance in 5 minutes.
Embodiment 11
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.005molL
-1Hydrochloric acid as elutriant, 30 ℃ of stirred in water bath desorption 60 minutes, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 16.9% under this kind situation.
Under the similarity condition, change stripping liquid concentration and be respectively 0.05molL
-1, 0.1molL
-1, 0.2molL
-1, 0.3molL
-1, 0.5molL
-1, 1molL
-1The gained desorption efficiency is respectively 25.4%, 29.7%, 42.1%, 42.1%, 43.2%, 44.8%.The optium concentration of the hydrochloric acid elutriant under this condition is 0.5molL as can be known
-1
Embodiment 12
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.3molL
-1The hydrochloric acid elutriant, desorption is 30 minutes under the condition of 30 ℃ of ultrasonic concussions, after filter paper filtered, with the content of lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, the result showed that desorption efficiency is 42.7% under this kind situation.When other condition was all identical, the desorption efficiency that obtains when 30 ℃ of stirred in water bath mode desorbs was 43.2%.
Embodiment 13
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.3molL
-1The hydrochloric acid elutriant, 30 ℃ of stirred in water bath desorption 30 minutes, after filter paper filters, content with lead ion in the EDTA compleximetry analytic solution absorption rear filtrate, with the adsorbent on the filter paper fully filter do after, all transfer in the dry tool plug conical flask, repeat attached totally 5 times of first round absorption-desorption.The result shows, one to five takes turns in the circulation adsorption rate and the accumulation adsorption capacity is respectively: the first round 83.1% and 207.6mg/g, and second takes turns 57.4% and 263.7mg/g, third round 59.2% and 397.2mg/g, four-wheel 61.0% and 533.5mg/g, the 5th takes turns 60.9% and 672.9mg/g.
Can learn that thus the polymer powder that has experienced continuous absorption-desorption additive process still has good lead ion adsorption capacity after 5 circulations.Use 0.3molL
-1During the desorb of hydrochloric acid elutriant, the adsorption rate of adsorbent can maintain about 60% in the repetitive cycling utilization.
Embodiment 14
Leaded poly m-phenylene diamine powder among the embodiment 1 is all transferred in the dry tool plug conical flask, and adding 25mL concentration is 0.002molL
-1EDTA as elutriant, 30 ℃ of stirred in water bath desorption 30 minutes, after filter paper filters, measure the content of lead ion in the desorption rear filtrate with ICP, the result shows that desorption efficiency is 71.2% under this kind situation.
Under the similarity condition, change stripping liquid concentration and be respectively 0.003molL
-1, 0.004molL
-1, 0.02molL
-1The gained desorption efficiency is respectively 77.3%, 82.5%, 94.2%.As seen, the EDTA desorption ability obviously is better than inorganic acid.
By above embodiment as seen, method of operating is simple and easy to do when utilizing strippant that the adsorbent of poly m-phenylene diamine that has adsorbed lead ion is carried out desorb, and the desorption required balance time is very short, because nitric acid and hydrochloric acid cost are much lower with respect to m-phenylene diamine (MPD) monomer cost, and through the circulation of adsorbent after the desorb strong and value of keeing relative stability of adsorption capacity again, so be applicable to large-scale industrial production.In addition, the cost of EDTA is suitable with m-phenylene diamine (MPD) monomer cost, but it carries out the desorption efficiency higher (more than 94%) that the back acquisition is handled in desorb to adsorbent, so the EDTA stripping liquid can adopt when become more meticulous on a small quantity research or precious metal ion reclaim.
Claims (4)
1, the desorption method of adsorbents for lead ion pyrolytic poly (m-phenylenediamine), this method is the mixed liquor that adds any or hydrochloric acid and nitric acid in elutriant nitric acid and the hydrochloric acid in being adsorbed with the poly m-phenylene diamine of lead ion, stirring or ultrasonic certain hour make it to reach the desorb balance, filter, used elutriant concentration range is 0.01～0.5molL
-1, desorption time is 2-60 minute.
2, the desorption method of adsorbents for lead ion pyrolytic poly (m-phenylenediamine) as claimed in claim 1 is characterized in that: when being applied to Treatment of Industrial Water, it is 0.1～0.5molL that elutriant adopts concentration
-1Hydrochloric acid.
3, the method that recycles of adsorbents for lead ion pyrolytic poly (m-phenylenediamine), this method is to be adsorbed with the desorption method desorb of the poly m-phenylene diamine of lead ion according to claim 1 or 2, then the adsorbent of collecting is come into operation again, desorb again, circulation gets final product so repeatedly.
4, the method that recycles of adsorbents for lead ion pyrolytic poly (m-phenylenediamine) as claimed in claim 3 is characterized in that: the poly m-phenylene diamine adsorbents for lead ion pyrolytic recycles 1～10 time.
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| CN113413887B (en) * | 2021-07-04 | 2022-09-23 | 南昌大学 | Compound lead ion adsorbent m-phenylenediamine polymerized pectin microspheres and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485345A (en) * | 2002-09-23 | 2004-03-31 | 李青燕 | Novel heavy metal ion collecting agent with environment protection function |
| CN1657431A (en) * | 2005-01-28 | 2005-08-24 | 湖南大学 | Method of adsorbing lead-contained in industial wste water using mushroom culture medium waste material |
| CN1840235A (en) * | 2005-03-30 | 2006-10-04 | 同济大学 | Use of Pb ion absorbent of polyphenylene diamine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485345A (en) * | 2002-09-23 | 2004-03-31 | 李青燕 | Novel heavy metal ion collecting agent with environment protection function |
| CN1657431A (en) * | 2005-01-28 | 2005-08-24 | 湖南大学 | Method of adsorbing lead-contained in industial wste water using mushroom culture medium waste material |
| CN1840235A (en) * | 2005-03-30 | 2006-10-04 | 同济大学 | Use of Pb ion absorbent of polyphenylene diamine |
Non-Patent Citations (2)
| Title |
|---|
| Rapid and effective adsorption of Lead ions on finepoly(phenylenediamine) microparticles. Mei-Rong Huang et al.Chem. Eur. J.,Vol.112 . 2006 |
| Rapid and effective adsorption of Lead ions on finepoly(phenylenediamine) microparticles. Mei-Rong Huang et al.Chem. Eur. J.,Vol.112 . 2006 * |
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