CN103435799A - Preparation method of high-polymer material capable of reducing gold and silver ions in wastewater - Google Patents
Preparation method of high-polymer material capable of reducing gold and silver ions in wastewater Download PDFInfo
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Abstract
The invention provides a preparation method of a high-polymer material capable of reducing gold and silver ions in wastewater. The preparation method comprises the following steps of: (1) pretreating activated carbon; (2) preparing an activated carbon aniline solution; (3) mixing 100-200 parts of 0.5-1.5mol/L HNO3 solution and 15-20 parts of ammonium persulfate so as to prepare an ammonium persulfate-nitric acid solution, dropping the prepared ammonium persulfate-nitric acid solution to the activated carbon aniline solution obtained in the step (2), reacting for 5-12 hours at 10-30 DEG C, filtering, washing filter cakes to be neutral, and drying to constant weight, thus obtaining the high-polymer material; or the high-polymer material is directly obtained through emulsion polymerization. The high-polymer material capable of reducing gold and silver ions in wastewater, which is prepared by the method, can be used for recovering gold, silver and other precious metal ions in water under the condition that no agents are added, and meanwhile can be used for reducing water pollution.
Description
Technical field
The present invention relates to a kind of preparation method of macromolecular material, especially relate to the Polymer materialspreparation method of gold and silver metal ion in a kind of energy reducing waste water.
Background technology
It is to be based upon environment is had on the basis of very big pollution that the present stage expanding economy has major part very, wherein comprises especially the pollution of heavy metal to water body, soil.The waste residue of the industry production such as machinofacture, mineral processing and smelting, plating, plastics, battery, chemical industry is the major industry source of discharge heavy metal.Heavy metal wastewater thereby directly discharges the ecotope around the meeting severe contamination, must could discharge or reuse through strict improvement.
The processing of heavy metal wastewater thereby, present stage main method have: chemical precipitation method (comprising neutralization precipitation method and sulphide precipitation); (comprising chemical reduction method, ferrite process and electrolytic process) processed in redox; Membrane separation process; Ion exchange method; Absorption method and biologic treating technique etc.At present, utilizing macromolecular material to process heavy metal wastewater thereby, is mainly to utilize ion exchange resin and resin to carry out enrichment to heavy metal, then landfill or burning, but will likely can cause secondary pollution like this.
Polyaniline is a kind of studied more conducting polymer composite, and people have a lot of reports to its electroconductibility.But polyaniline has reductibility preferably, utilize the reductibility of polyaniline to be processed heavy metal polluted waste water, can be directly by metal ion particularly precious metal be reduced into metal simple-substance.The reversible redox of polyaniline can be recycled material, so just makes polyaniline can regenerate and be repeated to utilize.Utilize polyaniline less to the research of the processing of heavy metal ions, its research is also just focused on to its reductibility, and ignore its solvability in solution, particularly ignored the stability of polyaniline under acidic conditions.
Summary of the invention
The technical problem to be solved in the present invention is, overcome the deficiencies in the prior art, provide a kind of preparation technology simple, production cost is low, products obtained therefrom is not soluble under acidic conditions, use simply, in reducing waste water, heavy metal ion is effective, regeneration rate is fast can reducing waste water in the Polymer materialspreparation method of gold and silver metal ion.
The technical scheme that the present invention solves its technical problem employing is that a kind of Polymer materialspreparation method of gold and silver metal ion in energy reducing waste water comprises the following steps:
(1) pre-treatment of gac: the block absorbent charcoal that 400-600 part is discarded is first used distilled water immersion, float the charcoal ash, then add NaOH solution 800-1200 part that concentration is 1-5wt%, boil and be incubated 25-40min, remove oily organism wherein, be washed till the aqueous solution with clear water and be neutral; Then add the HNO that concentration is 0.5-2mol/L
3solution or sulphuric acid soln, hydrochloric acid soln 800-1200 part are also boiled 20-40min, are washed with distilled water to neutrality, and 100-120 ℃ is dried to constant weight;
(2) get aniline 3-6 part, hydrazine hydrate 0-5 part, thiosemicarbazide 0-4 part, propylene oxide 0-5 part, pyrroles 0-3 part, Ortho Toluidine 0-4 part, add the salpeter solution that 60-120 part concentration is 0.5-1 mol/L, obtains the aniline salpeter solution; To be immersed in 2-4h in prepared aniline salpeter solution through the pretreated gac 15-30 of step (1) part, obtain the gac aniline solution, stand-by;
(3) get the HNO of 100-200 part 0.5-1.5 mol/L
3solution and 15-20 part ammonium persulphate, mix and be made into ammonium persulphate-salpeter solution; Prepared ammonium persulphate-salpeter solution is splashed in step (2) gained gac aniline solution, under 10-30 ℃, react 5-12h, filter, filter cake is washed to neutrality, under 78-82 ℃ (preferably 80 ℃), be dried to constant weight.
The reductibility macromolecular material that this programme makes can be called activated carbon loaded reductibility macromolecular material.
The present invention solves the another kind of technical scheme that its technical problem adopts, be letex polymerization, directly obtain the method for reductibility macromolecular material, comprise the following steps: get vinylbenzene 3-10 part, sodium lauryl sulphate 8-16 part, Pentyl alcohol 2-6 part, ammonium persulphate 2-6 part, water 60-100 part, mix, after mixture is heated to 50-70 ℃, return stirring 0.5-1h, make white emulsion shape liquid standby; Get vinylbenzene 2-8 part, aniline 2-8 part, thiosemicarbazide 0-2 part, ammonium persulphate 4-12 part, water 60-100 part, mix, by after mixture and prepared white emulsion shape liquid mixing, react at normal temperatures 3-10h, suction filtration, the repetitive scrubbing filter cake is neutral to filtrate pH, under 78-82 ℃ (preferably 80 ℃), is dried to constant weight.
The reductibility macromolecular material that this programme makes can be called letex polymerization reductibility macromolecular material.
The activated carbon loaded reductibility macromolecular material that the present invention makes, gold and silver metal ion in the energy reducing waste water, the reducible metal ions such as gold and silver more than 90% in 24h; The copoly type reducing material energy reductase 12 6.4mg of vinylbenzene-aniline
(metal ion)/ g
(reducing material), not needing to add any medicament in water body, the precious metal ions such as recyclable gold and silver, can reduce water pollution simultaneously; This material acid acceptance is good, with the nitric acid dousing material, can make material regeneration, reusable; The reductibility macromolecular material that utilizes the present invention to prepare, by the precious metal ions such as gold and silver be reduced into simple substance the time, technique is simple, operation of equipment is convenient, the process energy consumption is low, less investment.
The letex polymerization reductibility macromolecular material that the present invention makes, reductibility polyaniline material, reductibility polyaniline derivative material and reductibility polyaniline copolymer material are arranged, to heavy metal ion, particularly silver ions can selective reduction, reducing property is good, can reuse, industrial heavy metal wastewater thereby can be directly processed fast, and precious metal can be directly reclaimed.
The accompanying drawing explanation
Fig. 1 is the solubleness ultraviolet figure that high-molecular material A that embodiment 1 makes is affected by acid;
Fig. 2 is the solubleness ultraviolet figure that macromolecular material D that embodiment 4 makes is affected by acid;
Fig. 3 is that the macromolecular material F that embodiment 6 makes is subject to acid to affect solubleness ultraviolet figure;
Fig. 4 is that the macromolecular material H that embodiment 8 makes is subject to acid to affect solubleness ultraviolet figure;
Fig. 5 is that the macromolecular material I that embodiment 9 makes is subject to acid to affect solubleness ultraviolet figure.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
The present embodiment comprises the following steps:
(1) pre-treatment of gac: 400 parts of discarded block absorbent charcoals are first used to distilled water immersion, float the charcoal ash, then add 800 parts of the NaOH solution that concentration is 4.0wt%, after boiling, insulation 30min, remove oily organism wherein, is washed till the aqueous solution with clear water and is neutral; Then add the HNO that concentration is 0.9 mol/L
3800 parts of solution soak and boil, and continue 40min, are washed with distilled water to neutrality, and 100 ℃ are dried to constant weight;
(2) get 6 parts of aniline, add the salpeter solution that 88 parts of concentration are 1 mol/L, obtain the aniline salpeter solution; To be immersed in 3h in the aniline salpeter solution through 30 parts of the pretreated gacs of step (1), obtain the gac aniline solution, stand-by;
(3) get the HNO of 106 part of 1 mol/L
317.5 parts of solution, ammonium persulphate are made into ammonium persulphate-salpeter solution; Prepared ammonium persulphate-salpeter solution is splashed in step (2) gained gac aniline solution, react 8h at 25 ℃ of temperature, filter, filter cake is washed to neutrality, be dried to constant weight under 80 ℃, obtain having the high-molecular material A of reduction gold and silver metal ion.
The present embodiment comprises the following steps:
(1) pre-treatment of gac: 500 parts of discarded block absorbent charcoals are first used to distilled water immersion, float the charcoal ash, then add 1000 parts of the NaOH solution that concentration is 4.0 wt%, after boiling, insulation 30min, remove oily organism wherein, is washed till the aqueous solution with clear water and is neutral; Then add the HNO that concentration is 0.9 mol/L
31000 parts of solution soak and boil, and continue 40min, are washed with distilled water to neutrality, and 100 ℃ are dried to constant weight;
(2) get 6 parts of aniline, join in the salpeter solution that 88 parts of concentration are 0.8 mol/L, obtain the aniline salpeter solution; To be immersed in the aniline salpeter solution through 30 parts of the pretreated gacs of step (1) that to obtain the gac aniline solution after 3h stand-by;
(3) get the HNO of 110 part of 1 mol/L
3solution, 18 parts of ammonium persulphates are made into ammonium persulphate-salpeter solution; Ammonium persulphate-salpeter solution is splashed in step (2) gained gac aniline solution, react 10h at 25 ℃ of temperature, filter, filter cake is washed to neutrality, be dried to constant weight under 80 ℃, obtain loading on gac the macromolecular material B with reduction gold and silver metal ion.
The present embodiment comprises the following steps:
(1) pre-treatment of gac: 500 parts of discarded block absorbent charcoals are first used to distilled water immersion, float the charcoal ash, then add 1100 parts of the NaOH solution that concentration is 3.5 wt%, after boiling, insulation 40min, remove oily organism wherein, is washed till the aqueous solution with clear water and is neutral; The sulphuric acid soln 1200ml that is then 2mol/L by concentration soaks and boils, and continues 30min, is washed with distilled water to neutrality, and 120 ℃ are dried to constant weight;
(2) get 6 parts of aniline, 1.6 parts of thiosemicarbazide, add the salpeter solution that 84 parts of concentration are 1.5 mol/L, obtains the aniline salpeter solution; To be immersed in the aniline salpeter solution through 30 parts of the pretreated gacs of step (1) that to obtain the gac aniline solution after 3h stand-by;
(3) get the HNO of 110 part of 1 mol/L
3solution, 18 parts of wiring solution-formings of ammonium persulphate; Ammonium persulphate-salpeter solution is splashed in the gac aniline solution, at 30 ℃ of temperature, react 6h, filter, filter cake is washed to neutrality, be dried to constant weight under 80 ℃, obtain loading on gac the macromolecular material C with reduction gold and silver metal ion.
The present embodiment comprises the following steps:
(1) pre-treatment of gac: 500 parts of discarded block absorbent charcoals are first used to distilled water immersion, float the charcoal ash, then add 900 parts of the NaOH solution that concentration is 5wt%, after boiling, insulation 35min, remove oily organism wherein, is washed till the aqueous solution with clear water and is neutral; Follow 1200 parts of the hydrochloric acid solns that is 1mol/L by concentration and soak and boil, continue 30min, be washed with distilled water to neutrality, 110 ℃ are dried to constant weight;
(2) get 6 parts of aniline, 2.8 parts of propylene oxide, add the salpeter solution that 120 parts of concentration are 1 mol/L, obtains the aniline salpeter solution; To be immersed in 2h in the aniline salpeter solution through 30 parts of the pretreated gacs of step (1), obtain the gac aniline solution, stand-by;
(3) get the HNO of 150 part of 1 mol/L
3solution, 15 parts of ammonium persulphate wiring solution-formings; Ammonium persulphate-salpeter solution is splashed in step (2) gained gac aniline solution, react 5h at 30 ℃ of temperature, filter, filter cake is washed to neutrality, be dried to constant weight under 80 ℃, obtain loading on gac the macromolecular material D with reduction gold and silver metal ion.
The present embodiment comprises the following steps:
(1) pre-treatment of gac: 600 parts of discarded block absorbent charcoals are first used to distilled water immersion, float the charcoal ash, then add the NaOH solution 1200ml that concentration is 5wt%, after boiling, insulation 40min, remove oily organism wherein, is washed till the aqueous solution with clear water and is neutral; The HNO that is then 1.5mol/L by concentration
3solution 1200ml soaks and boils, and continues 40min, is washed with distilled water to neutrality, and 120 ℃ are dried to constant weight;
(2) get 6 parts of aniline, 5 parts of hydrazine hydrates, 2 parts of thiosemicarbazide, 0.5 part of pyrroles, add the salpeter solution that 120 parts of concentration are 1 mol/L, obtains the aniline salpeter solution; To be immersed in the aniline salpeter solution through 30 parts of the pretreated gacs of step (1) that to obtain the gac aniline solution after 4h stand-by;
(3) get the HNO of 150 part of 1 mol/L
3solution, 20 parts of wiring solution-formings of ammonium persulphate; Ammonium persulphate-salpeter solution is splashed in step (2) gained gac aniline solution, react 10h at 30 ℃ of temperature, filter, filter cake is washed to neutrality, be dried to constant weight under 80 ℃, obtain loading on gac the macromolecular material E with reduction gold and silver metal ion.
Embodiment 6
The present embodiment comprises the following steps:
(1) pre-treatment of gac: 600 parts of discarded block absorbent charcoals are first used to distilled water immersion, float the charcoal ash, then add the NaOH solution 1200ml that concentration is 5wt%, after boiling, insulation 40min, remove oily organism wherein, is washed till the aqueous solution with clear water and is neutral; The HNO that is then 1.5mol/L by concentration
3solution 1200ml soaks and boils, and continues 40min, is washed with distilled water to neutrality, and 120 ℃ are dried to constant weight;
(2) get 3 parts of aniline, 0.5 part of thiosemicarbazide, 0.5 part of propylene oxide, 3.5 parts of Ortho Toluidines, add the salpeter solution that 100 parts of concentration are 0.9mol/L, obtains the aniline salpeter solution; To be immersed in the aniline salpeter solution through 30 parts of the pretreated gacs of step (1) that to obtain the gac aniline solution after 4h stand-by;
(3) get the HNO of 150 part of 1 mol/L
3solution, 17.5 parts of wiring solution-formings of ammonium persulphate; Ammonium persulphate-salpeter solution is splashed in gac aniline salpeter solution, at 28 ℃ of temperature, react 8h, filter, filter cake is washed to neutrality, be dried to constant weight under 80 ℃, obtain having the macromolecular material F of reduction gold and silver metal ion.
Embodiment 7
The present embodiment comprises the following steps:
(1) pre-treatment of gac: 400 parts of discarded block absorbent charcoals are first used to distilled water immersion, float the charcoal ash, then add 800 parts of the NaOH solution that concentration is 5wt%, after boiling, insulation 25min, remove oily organism wherein, is washed till the aqueous solution with clear water and is neutral; The HNO that is then 2mol/L by concentration
3solution 1200ml soaks and boils, and continues 40min, is washed with distilled water to neutrality, and 120 ℃ are dried to constant weight;
(2) get 3 parts of aniline, 2.5 parts of pyrroles, 0.5 part of Ortho Toluidine, add the salpeter solution that 120 parts of concentration are 1 mol/L, obtains the aniline salpeter solution; To be immersed in the aniline salpeter solution through 30 parts of the pretreated gacs of step (1) that to obtain the gac aniline solution after 2h stand-by;
(3) get the HNO of 150 part of 1 mol/L
3solution, 19 parts of wiring solution-formings of ammonium persulphate; Ammonium persulphate-salpeter solution is splashed in the gac aniline solution, at 19 ℃ of temperature, react 10h, filter, filter cake is washed to neutrality, be dried to constant weight under 80 ℃, obtain loading on gac the macromolecular material G with reduction gold and silver metal ion.
Embodiment 8
The present embodiment comprises the following steps:
Get 4 parts of vinylbenzene, 10 parts of sodium lauryl sulphate, 3.3 parts of Pentyl alcohols, 2.5 parts of ammonium persulphates, 85 parts, water, mix, mixture is heated to 60 ℃ after return stirring 1h, make white emulsion shape liquid standby; Get 2 parts of vinylbenzene, 5.5 parts of aniline, 10 parts of ammonium persulphates, 80 parts, water, mix, by after mixture and prepared white emulsion shape liquid mixing, react at normal temperatures 7h, suction filtration then, when the repetitive scrubbing filter cake is neutrality to filtrate pH, be dried to constant weight under 80 ℃, obtain having the macromolecular material H of reduction gold and silver metal ion.
Embodiment 9
The present embodiment comprises the following steps:
Get 5 parts of vinylbenzene, 10 parts of sodium lauryl sulphate, 3.5 parts of Pentyl alcohols, 3 parts of ammonium persulphates, 70 parts, water, mix, be heated to 70 ℃ after return stirring 1h, make white emulsion shape liquid standby; Get 2 parts of vinylbenzene, 5.5 parts of aniline, 1 part of thiosemicarbazide, 10 parts of ammonium persulphates, 80 parts, water, mix, by after mixture and prepared white emulsion shape liquid mixing, react at normal temperatures 8h, suction filtration, when the repetitive scrubbing filter cake is neutrality to filtrate pH, be dried to constant weight under 80 ℃, obtain having the macromolecular material I of reduction gold and silver metal ion.
Implementation result:
Reductibility high-molecular material A, B, C, D, E, F, G, H, I are taken respectively to 0.2g, then the Erlenmeyer flask that adds 9 250ml, next add the nitrate aqueous solution that the 200ml concentration of silver ions is 10mg/L in each container, under normal temperature, shake, get the water sample of different time sections, investigate the reducing power of these materials to silver ions, it the results are shown in following table 1:
From table 1, the reduction effect of A, D, H, tetra-kinds of materials of I is better, and reduction ratio all reaches more than 90%, and wherein the reduction rate of H, I is very fast, and the reduction ratio of I material reaches more than 99%.As can be seen here; in the situation that do not add any medicament; only use reductibility macromolecular material of the present invention just can make solution in 24 hours in silver ion reduction more than 99% become simple substance silver; effectively changed the recovery method of silver ions; reduce the pollution of water body medicament simultaneously, effectively protected environment.
For obtaining the water-soluble and stability of material under different acidity, take respectively materials A, D, F, H, I 0.05g, be added into respectively in the salpeter solution of the different pH values of 50ml (solution acidity is adjusted to respectively 0,1,2,3,4,5 with nitric acid), shake 24h under normal temperature, get filtrate and carry out ultraviolet detection, research acid is on the water miscible impact of each material.Fig. 1 is the solubleness ultraviolet figure that materials A is affected by acid; Fig. 2 is the solubleness ultraviolet figure that material D is affected by acid; Fig. 3 is that material F is subject to acid to affect solubleness ultraviolet figure; Fig. 4 is that material H is subject to acid to affect solubleness ultraviolet figure; Fig. 5 is that material I is subject to acid to affect solubleness ultraviolet figure.
From figure 1 – Fig. 5, can find out, absorption peak mainly concentrates between 200-300nm, is to be caused by the ∏ of phenyl ring → ∏ * transition, according to Law of Lambert-Beer, sample is directly proportional to the concentration of sample to the absorbancy of light, and absorbancy is higher, and illustrative material is more unstable under acidic conditions.It can also be seen that, it is larger that material D, F are affected by acid, can cause a small amount of loss of material; It is less that but materials A, H, I are affected by acid, and reduction effect is more satisfactory; And trend and other class materials by the acid impact of material I are different, the solvability of other materials is that the increase with acidity increases gradually, and material I is to be within 1,2 o'clock, to show acid is had to stability preferably at pH, this just can provide different reductibility materials for the different acidity water sample.
The stability of material is related to the use cost of this Technology and work-ing life and the service efficiency of reductibility macromolecular material, and the reasonable problem that has solved reduction efficiency and work-ing life of reductibility macromolecular material of the present invention, can not only reclaim the precious metal ion in waste water, and can also be for the smelting technology of noble metal, changing traditional noble metal and smelt and recovery process, is very promising material.
In specification sheets of the present invention, unless otherwise specified outside, described umber is weight part.
Claims (4)
1. the Polymer materialspreparation method of gold and silver metal ion in an energy reducing waste water, is characterized in that, comprises the following steps:
(1) pre-treatment of gac: the block absorbent charcoal that 400-600 part is discarded is first used distilled water immersion, float the charcoal ash, then add NaOH solution 800-1200 part that concentration is 1-5wt%, boil and be incubated 25-40min, remove oily organism wherein, be washed till the aqueous solution with clear water and be neutral; Then add the HNO that concentration is 0.5-2mol/L
3solution or sulphuric acid soln, hydrochloric acid soln 800-1200 part are also boiled 20-40min, are washed with distilled water to neutrality, and 100-120 ℃ is dried to constant weight;
(2) get aniline 3-6 part, hydrazine hydrate 0-5 part, thiosemicarbazide 0-4 part, propylene oxide 0-5 part, pyrroles 0-3 part, Ortho Toluidine 0-4 part, add the salpeter solution that 60-120 part concentration is 0.5-1 mol/L, obtains the aniline salpeter solution; To be immersed in 2-4h in prepared aniline salpeter solution through the pretreated gac 15-30 of step (1) part, obtain the gac aniline solution, stand-by;
(3) get the HNO of 100-200 part 0.5-1.5 mol/L
3solution and 15-20 part ammonium persulphate, mix and be made into ammonium persulphate-salpeter solution; Prepared ammonium persulphate-salpeter solution is splashed in step (2) gained gac aniline solution, under 10-30 ℃, react 5-12h, filter, filter cake is washed to neutrality, be dried to constant weight under 78-82 ℃, obtain;
Described umber is weight part.
2. the Polymer materialspreparation method of gold and silver metal ion in energy reducing waste water as claimed in claim 1, is characterized in that, in step (3), the filtration cakes torrefaction temperature is 80 ℃.
3. the Polymer materialspreparation method of gold and silver metal ion in an energy reducing waste water, it is characterized in that, comprise the following steps: get vinylbenzene 3-10 part, sodium lauryl sulphate 8-16 part, Pentyl alcohol 2-6 part, ammonium persulphate 2-6 part, water 60-100 part, mix, after mixture is heated to 50-70 ℃, return stirring 0.5-1h, make white emulsion shape liquid standby; Get vinylbenzene 2-8 part, aniline 2-8 part, thiosemicarbazide 0-2 part, ammonium persulphate 4-12 part, water 60-100 part, mix, by after mixture and prepared white emulsion shape liquid mixing, react at normal temperatures 3-10h, suction filtration, the repetitive scrubbing filter cake is neutral to filtrate pH, is dried to constant weight under 78-82 ℃;
Described umber is weight part.
4. the Polymer materialspreparation method of gold and silver metal ion in energy reducing waste water as claimed in claim 3, is characterized in that, the filtration cakes torrefaction temperature is 80 ℃.
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| CN104388675A (en) * | 2014-11-24 | 2015-03-04 | 哈尔滨工业大学 | Recyclable polymer membrane used for recovering precious metals rapidly as well preparation method, use method and regeneration method thereof |
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| CN101612554A (en) * | 2009-08-13 | 2009-12-30 | 沈阳建筑大学 | The preparation method of conducting polymer modified active carbon |
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| CN101612554A (en) * | 2009-08-13 | 2009-12-30 | 沈阳建筑大学 | The preparation method of conducting polymer modified active carbon |
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| 姚慧玲等: "聚苯胺/聚（苯乙烯-苯乙烯磺酸钠）纳米核-壳结构聚合物的微乳液法合成及性能表征", <<山东大学学报（理学版）>>, vol. 43, no. 3, 31 March 2008 (2008-03-31), pages 26 - 29 * |
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| CN104388675A (en) * | 2014-11-24 | 2015-03-04 | 哈尔滨工业大学 | Recyclable polymer membrane used for recovering precious metals rapidly as well preparation method, use method and regeneration method thereof |
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