CN103191582A - Method for removing bivalent copper ions in aqueous solution - Google Patents
Method for removing bivalent copper ions in aqueous solution Download PDFInfo
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Abstract
The invention relates to a method for efficiently removing bivalent copper ions in aqueous solution. The method comprises the following steps of: (1) synthesizing cross-linked chitosan chelated resin through graft copolymerization of chitosan and epoxy chloropropane; (2) performing intercalation treatment on cross-linked chitosan and polyhydroxy aluminum cross-linked bentonite; (3) absorbing bivalent copper ions in aqueous solution by using the modified bentonite intercalated with the cross-linked chitosan; and (4) measuring the removal rate of bivalent copper ions. The modified bentonite obtained by the method provided by the invention is high in chitosan intercalation quantity, efficient and quick in absorbing and treating copper ions in aqueous solution, wide in pH application range, low in cost and the like, and can be widely applied to treatment of copper-containing industrial sewage.
Description
Technical field
A kind of method of removing bivalent cupric ion in the aqueous solution of the present invention, belong to field of environment engineering technology, be specifically related to a kind of shitosan and high characteristics of effectively removing metal ion in the aqueous solution of bentonite intercalation amount of fully utilizing, before composite modified, shitosan and bentonite are carried out crosslinkedization processing respectively, make the modified alta-mud composite of good stability, remove the technical scheme of the method for the copper ion in the aqueous solution.
Background technology
Fast development along with modernization industry, increasing water resource is subjected to the pollution of heavy metal ion, copper is heavy metal contaminants common in a kind of water body, it has multiple existence form, wherein bivalent cupric ion is the leading ion form to biological intoxicating, copper content seldom in the natural water, copper in the water mainly is that the pollution of industrial wastewater causes, mainly from plating, smelt five metals, chemical industry, departments such as mining, enrichment can take place in copper in the water body in vivo, and can not be by microorganism catabolism, in case enter human body, very easily affinity interaction takes place and cause the activity of enzyme to be suppressed with some tissue of human body, make cell membrane be subjected to major injury, human body is produced toxic action, can cause acute copper poisoning as drinking the beverage that is polluted by copper in a large number, the alimentary intoxication symptom occurs, in mouthful metallic taste is arranged, epigastric pain, n and V or diarrhoea; Gastrointestinal mucosa ulcer, haemolysis, hepatonecrosis, renal damage can appear in weight person, even low blood pressure, shock take place and death.Therefore set up the method for effectively removing copper pollution in the water body and just seem particularly necessary.
Shitosan has a large amount of free amine groups and hydroxyl because of it, can adsorb the heavy metal ion of the overwhelming majority under certain condition by the mode of physical absorption or chemical complexing.Bentonite is a kind of layer aluminosilicate clay mineral of being made up of nano-scale particle, belongs to nonmetallic minerals, has special imbibition and ion-exchange performance, and specific area is big, interlamellar spacing is controlled; Because its particular structure effect, bentonite has stronger adsorption capacity to environmental pollutants, and recyclable regenerative, repeated use; Simultaneously, bentonite also can reach application target by suitable modification, thereby have broad application prospects in waste water treatment at special component and the concentration of waste discharge.China is one of bentonitic main mine place of production, because aboundresources, Regional Distribution is wide, and is cheap, and development and exploiting economy be novel bentonite multifunctional ceiling enclosure material efficiently, has important significance for theories and actual application value undoubtedly.With shitosan and the compound intercalation of bentonite as the existing patent (ZL200710010951.7 of the adsorbent of heavy metal ion; ZL200910113818.3; ZL201010107961.4) and bibliographical information, but simple shitosan under solutions of weak acidity easily dissolving run off, limited its application, so must carry out modification to shitosan.Can overcome the loss of shitosan under acid condition by cross-linking modified mode, thereby enlarge the range of application of shitosan.The bentonite original soil of non-modified surface Si-O/Al-O radix order is limited in addition, bonding force is not strong, and the interlayer cation exchange capacity is subjected to the restriction of contained montmorillonite kind and content in the bentonite, its absorption property a little less than.
Summary of the invention
A kind of purpose of removing the method for copper ion in the aqueous solution of the present invention is: for solving above-mentioned problems of the prior art, metal ion in the high effectively removal of a kind of comprehensive utilization shitosan and the bentonite intercalation amount aqueous solution is disclosed, before composite modified, shitosan and bentonite are carried out crosslinkedization processing respectively, make the modified alta-mud composite of good stability, remove the technical scheme of the method for the copper ion in the aqueous solution
A kind of method of removing copper ion in the aqueous solution of the present invention, it is characterized in that it being metal ion in the high effectively removal of a kind of comprehensive utilization shitosan and the bentonite intercalation amount aqueous solution, before composite modified, shitosan and bentonite are carried out crosslinkedization processing respectively, make the modified alta-mud composite of good stability, remove the method for the copper ion in the aqueous solution, concrete steps are as follows:
(1) AlCl of preparation 0.4mol/L
3Solution under 55 ~ 65 ℃ temperature, is added drop-wise to AlCl with the 0.4mol/L sodium hydroxide solution with the speed of 1mL/min
3In the solution, until n (OH
-): n (Al
3+)=2.4 then in 55 ~ 65 ℃ of ageing 47 ~ 49h, make poly-hydroxyl-aluminum pillared agent; Get the 1g sodium-ionized bentonite, to gather the hydroxyl-aluminum pillared agent in Al/ soil for the ratio of 10mmol/g is added in the bentonite, stir 3.5 ~ 4.5h under 55 ~ 65 ℃ the temperature, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake 40 ~ 70 ℃ dry down, grind, namely get poly-hydroxy Al cross-linked bentonite, standby.
(2) shitosan being dissolved in mass fraction is in 4 ~ 6% the acetic acid solution, and ratio is in 4 ~ 6% the acetic acid solution for the 1g shitosan is dissolved into 30 ~ 35ml mass fraction; The mixed liquor that makes is placed the there-necked flask that agitator and thermometer are housed, add atoleine, ratio adds 30 ~ 35ml atoleine for the 1g shitosan, be warmed up to 45 ~ 55 ℃ after stirring 8 ~ 30min under the startup agitator normal temperature, drip 3 ~ 4 span 80, emulsification 8 ~ 15min is warmed up to 55 ~ 65 ℃ then, drips formalin reaction 0.5 ~ 2h, the amount of dropping formalin is 4:1 with the amount of substance ratio of chitosan structure unit, and transferring system pH is 9 ~ 11; In this system, add epoxychloropropane, the amount of dropping epoxychloropropane is 3:1 with the amount of substance ratio of chitosan structure unit, be warmed up to 65 ~ 75 ℃ afterwards, slowly dripping mass fraction with constant pressure funnel is 4 ~ 6% sodium hydrate aqueous solution, make system pH remain at 9 ~ 11, reaction 1.5 ~ 3h filters, washing; Place apparatus,Soxhlet's to remove residual organic matter with the benzinum extracting this system, at 65 ~ 75 ℃ resin is handled 8 ~ 12h with the 1mo1/L hydrochloric acid solution at last, washing, sodium carbonate is washed, and is washed to neutrality, and vacuum drying is to constant weight, make epoxychloropropane cross-linked chitosan chelating resin, standby;
(3) the poly-hydroxy Al cross-linked bentonite that (1) is obtained adds water and is mixed with 50% suspension, stir, make poly-hydroxy Al cross-linked bentonite fully disperse, according to cross-linked chitosan and the poly-hydroxy Al cross-linked bentonite ratio that is 1:4 ~ 1:20, the crosslinked chitosan resin that (2) are obtained joins in the above poly-hydroxy Al cross-linked bentonite slurries, under 50 ~ 70 ℃ of constant temperature, stir 3 ~ 5h, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake is dry down at 40 ~ 70 ℃, grind, namely obtain to adsorb cross-linked chitosan/poly-hydroxy Al cross-linked bentonite of removing bivalent cupric ion in the water;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 20 ~ 400mg/L according to the ratio of 5 ~ 50g/L, transfers system pH to be 4.5 ~ 7,25 ℃ of vibration absorption 0.3 ~ 6h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, to the standard copper reagent solution 5ml that wherein adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculate clearance according to initial concentration and the balance densimeter of copper ion: R=(C
0-C
e)/C
0* 100%
R is clearance (%), C
0Be initial copper ion concentration mg/L, C
eAdsorption equilibrium concentration mg/L for copper ion.
A kind of advantage of removing the method for bivalent cupric ion in the aqueous solution of the present invention is:
1. the present invention is different from the general shitosan bentonite composite material, shitosan just is adsorbed in bentonitic surfaces externally and internally, after the present invention has been beforehand with crosslinkedization processing with poly-hydroxy Al to bentonite, make cross-linked chitosan can enter into bentonitic interlayer, measure calculating through X-ray diffraction, the interlamellar spacing of former sodium-ionized bentonite is 1.255nm, interlamellar spacing all increased to more than the 1.9nm after the cross-linked chitosan of different proportion and poly-hydroxy Al cross-linked bentonite were composite modified, and the 1.883nm that all is higher than poly-hydroxy Al cross-linked bentonite, when wherein the ratio of cross-linked chitosan and poly-hydroxy Al cross-linked bentonite is 1:8, interlamellar spacing reaches 1.945nm, illustrate composite modified after, the cross-linked chitosan intercalation has advanced the interlayer of poly-hydroxy Al cross-linked bentonite, increased adsorption capacity, its performance is higher than simple shitosan bentonite composite material.
2. intercalation amount height of the present invention, ratio at cross-linked chitosan and poly-hydroxy Al cross-linked bentonite is respectively 1:4,1:8,1:10,1:15, during 1:20, the intercalation amount of cross-linked chitosan is respectively 36%, 26% in the sample, 27%, 27.5%, 25%, be higher than 18% intercalation amount of general shitosan bentonite composite material.
3. the present invention has done crosslinkedization processing to shitosan, overcome the shortcoming of shitosan copper removal weak effect under acid condition, again in conjunction with the pillared bentonitic absorption of exchange simultaneously, as shown in Figure 3, pH was low to moderate 6 o'clock, at consumption 10g/L, 25 ℃ of temperature, under the 100mg/L copper ion solution condition, still can reach more than 85% the copper ion clearance, be higher than under the simple shitosan equal conditions about 60% clearance.
4. the present invention keeps high clearance under high concentration copper ion aqueous conditions, as shown in Figure 2, in 20 ~ 400mg/L copper ion concentration scope, increase along with copper ion concentration, clearance is on a declining curve, and clearance still can reach more than 90% when copper ion concentration reaches 400mg/L, therefore this adsorbent has and extensively is suitable for concentration range, the copper ion concentration of employed about 5mg/L during far above general simple shitosan absorbing copper ion.
5. the present invention compares with the derivative adsorbent of shitosans such as CMC and has characteristics with low cost.
6. the present invention combines shitosan and bentonite advantage aspect the copper ion in adsorption aqueous solution, and solved under the acid condition shitosan softening problem that runs off easily with epoxychloropropane and chitosan graft copolymerization, increased shitosan stability, poly-hydroxy Al cross-linked bentonite has increased shitosan intercalation amount betwixt in the effect of performance cation exchange in addition, make absorption property improve greatly, copper ion in the double cross connection shitosan bentonite adsorption treatment aqueous solution that this method is prepared has stable, efficiently, fast, use the wide characteristics of pH scope, can be widely used in the processing of cupric industrial wastewater.
Description of drawings
Fig. 1 is the copper ion adsorption curve under the different modified adsorbent consumption conditions.
Fig. 2 is the copper ion adsorption curve of variable concentrations copper nitrate solution.
Fig. 3 is different pH copper ion adsorption curves.
Fig. 4 is the copper ion adsorption curve of different time.
The specific embodiment:
Embodiment 1 ~ 5 is cross-linked chitosan/crosslinked chitosan resin and poly-hydroxy Al cross-linked bentonite intercalation scale bar piece optimization when poly-hydroxy Al cross-linked bentonite is used for the adsorbed water bivalent cupric ion.
Embodiment is 5 ~ 20 for cross-linked chitosan/condition optimizing of pH value of solution when poly-hydroxy Al cross-linked bentonite is used for the adsorbed water bivalent cupric ion, as Fig. 3.
Embodiment 21 ~ 27 is cross-linked chitosan/condition optimizing of adsorption time when poly-hydroxy Al cross-linked bentonite is used for the adsorbed water bivalent cupric ion, as Fig. 4.
Embodiment 1
(1) AlCl of preparation 0.4mol/L
3Solution under 55 ℃ temperature, is added drop-wise to AlCl with the 0.4mol/L sodium hydroxide solution with the speed of 1mL/min
3In the solution, until n (OH
-): n (Al
3+)=2.4 then in 55 ℃ of ageing 47h, make poly-hydroxyl-aluminum pillared agent; Get the 1g sodium-ionized bentonite, to gather the hydroxyl-aluminum pillared agent in Al/ soil for the ratio of 10mmol/g is added in the bentonite, stir 3.5h under 55 ℃ the temperature, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake 40 ℃ dry down, grind, namely get poly-hydroxy Al cross-linked bentonite, standby;
(2) shitosan being dissolved in mass fraction is in 4% the acetic acid solution, and ratio is in 4% the acetic acid solution for the 1g shitosan is dissolved into 30 ml mass fractions; The mixed liquor that makes is placed the there-necked flask that agitator and thermometer are housed, add atoleine, ratio adds the 30ml atoleine for the 1g shitosan, start under the agitator normal temperature and be warmed up to 45 ℃ behind the stirring 8min, drip 3 span 80, emulsification 8min is warmed up to 55 ℃ then, drips formalin reaction 0.5h, the amount of dropping formalin is 4:1 with the amount of substance ratio of chitosan structure unit, and transferring system pH is 9; In this system, add epoxychloropropane, the amount of dropping epoxychloropropane is 3:1 with the amount of substance ratio of chitosan structure unit, be warmed up to 65 ℃ afterwards, slowly dripping mass fraction with constant pressure funnel is 4% sodium hydrate aqueous solution, make system pH remain at 9, reaction 1.5h filters, washing; Place apparatus,Soxhlet's to remove residual organic matter with the benzinum extracting this system, at 65 ℃ resin is handled 8h with the 1mo1/L hydrochloric acid solution at last, washing, sodium carbonate is washed, and is washed to neutrality, and vacuum drying is to constant weight, make epoxychloropropane cross-linked chitosan chelating resin, standby;
(3) the poly-hydroxy Al cross-linked bentonite that (1) is obtained is mixed with 50% suspension, stir, make poly-hydroxy Al cross-linked bentonite fully disperse, according to cross-linked chitosan and the poly-hydroxy Al cross-linked bentonite ratio that is 1:4, the crosslinked chitosan resin that (2) are obtained joins in the above poly-hydroxy Al cross-linked bentonite slurries, under 50 ℃ of constant temperature, stir 3h, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake is dry down at 40 ℃, grind, namely obtain to adsorb cross-linked chitosan/poly-hydroxy Al cross-linked bentonite of removing bivalent cupric ion in the water;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 87%.
(1) AlCl of preparation 0.4mol/L
3Solution under 65 ℃ temperature, is added drop-wise to AlCl with the 0.4mol/L sodium hydroxide solution with the speed of 1mL/min
3In the solution, until n (OH
-): n (Al
3+)=2.4 then in 65 ℃ of ageing 49h, make poly-hydroxyl-aluminum pillared agent; Get the 1g sodium-ionized bentonite, to gather the hydroxyl-aluminum pillared agent in Al/ soil for the ratio of 10mmol/g is added in the bentonite, stir 4.5h under 65 ℃ the temperature, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake 70 ℃ dry down, grind, namely get poly-hydroxy Al cross-linked bentonite, standby;
(2) shitosan being dissolved in mass fraction is in 6% the acetic acid solution, and ratio is in 6% the acetic acid solution for the 1g shitosan is dissolved into the 35ml mass fraction; The mixed liquor that makes is placed the there-necked flask that agitator and thermometer are housed, add atoleine, ratio adds the 35ml atoleine for the 1g shitosan, start under the agitator normal temperature and be warmed up to 55 ℃ behind the stirring 30min, drip 4 span 80, emulsification 15min is warmed up to 65 ℃ then, drips formalin reaction 2h, the amount of dropping formalin is 4:1 with the amount of substance ratio of chitosan structure unit, and transferring system pH is 11; In this system, add epoxychloropropane, the amount of dropping epoxychloropropane is 3:1 with the amount of substance ratio of chitosan structure unit, be warmed up to 75 ℃ afterwards, slowly dripping mass fraction with constant pressure funnel is 6% sodium hydrate aqueous solution, make system pH remain at 11, reaction 3h filters, washing; Place apparatus,Soxhlet's to remove residual organic matter with the benzinum extracting this system, at 75 ℃ resin is handled 12h with the 1mo1/L hydrochloric acid solution at last, washing, sodium carbonate is washed, and is washed to neutrality, and vacuum drying is to constant weight, make epoxychloropropane cross-linked chitosan chelating resin, standby;
(3) the poly-hydroxy Al cross-linked bentonite that (1) is obtained is mixed with 50% suspension, stir, make poly-hydroxy Al cross-linked bentonite fully disperse, according to cross-linked chitosan and the poly-hydroxy Al cross-linked bentonite ratio that is 1:8, the crosslinked chitosan resin that (2) are obtained joins in the above poly-hydroxy Al cross-linked bentonite slurries, under 70 ℃ of constant temperature, stir 5h, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake is dry down at 70 ℃, grind, namely obtain to adsorb cross-linked chitosan/poly-hydroxy Al cross-linked bentonite of removing bivalent cupric ion in the water;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 95%.
(1) AlCl of preparation 0.4mol/L
3Solution under 60 ℃ temperature, is added drop-wise to AlCl with the 0.4mol/L sodium hydroxide solution with the speed of 1mL/min
3In the solution, until n (OH
-): n (Al
3+)=2.4 then in 60 ℃ of ageing 48h, make poly-hydroxyl-aluminum pillared agent; Get the 1g sodium-ionized bentonite, to gather the hydroxyl-aluminum pillared agent in Al/ soil for the ratio of 10mmol/g is added in the bentonite, stir 4h under 60 ℃ the temperature, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake 60 ℃ dry down, grind, namely get poly-hydroxy Al cross-linked bentonite, standby;
(2) shitosan being dissolved in mass fraction is in 5% the acetic acid solution, and ratio is in 5% the acetic acid solution for the 1g shitosan is dissolved into the 33ml mass fraction; The mixed liquor that makes is placed the there-necked flask that agitator and thermometer are housed, add atoleine, ratio adds the 33ml atoleine for the 1g shitosan, start under the agitator normal temperature and be warmed up to 50 ℃ behind the stirring 10min, drip 4 span 80, emulsification 10min is warmed up to 60 ℃ then, drips formalin reaction 1h, the amount of dropping formalin is 4:1 with the amount of substance ratio of chitosan structure unit, and transferring system pH is 10; In this system, add epoxychloropropane, the amount of dropping epoxychloropropane is 3:1 with the amount of substance ratio of chitosan structure unit, be warmed up to 70 ℃ afterwards, slowly dripping mass fraction with constant pressure funnel is 5% sodium hydrate aqueous solution, make system pH remain at 10, reaction 2h filters, washing; Place apparatus,Soxhlet's to remove residual organic matter with the benzinum extracting this system, at 70 ℃ resin is handled 9h with the 1mo1/L hydrochloric acid solution at last, washing, sodium carbonate is washed, and is washed to neutrality, and vacuum drying is to constant weight, make epoxychloropropane cross-linked chitosan chelating resin, standby;
(3) the poly-hydroxy Al cross-linked bentonite that (1) is obtained is mixed with 50% suspension, stir, make poly-hydroxy Al cross-linked bentonite fully disperse, according to cross-linked chitosan and the poly-hydroxy Al cross-linked bentonite ratio that is 1:10, the crosslinked chitosan resin that (2) are obtained joins in the above poly-hydroxy Al cross-linked bentonite slurries, under 60 ℃ of constant temperature, stir 4h, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake is dry down at 50 ℃, grind, namely obtain to adsorb cross-linked chitosan/poly-hydroxy Al cross-linked bentonite of removing bivalent cupric ion in the water;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 97%.
(1) (2) are with embodiment 3;
(3) the poly-hydroxy Al cross-linked bentonite that (1) is obtained is mixed with 50% suspension, stir, make poly-hydroxy Al cross-linked bentonite fully disperse, according to cross-linked chitosan and the poly-hydroxy Al cross-linked bentonite ratio that is 1:15, the crosslinked chitosan resin that (2) are obtained joins in the above poly-hydroxy Al cross-linked bentonite slurries, under 60 ℃ of constant temperature, stir 4h, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake is dry down at 50 ℃, grind, namely obtain to adsorb cross-linked chitosan/poly-hydroxy Al cross-linked bentonite of removing bivalent cupric ion in the water;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 82%.
(1) (2) are with embodiment 3;
(3) the poly-hydroxy Al cross-linked bentonite that (1) is obtained is mixed with 50% suspension, stir, make poly-hydroxy Al cross-linked bentonite fully disperse, according to cross-linked chitosan and the poly-hydroxy Al cross-linked bentonite ratio that is 1:20, the crosslinked chitosan resin that (2) are obtained joins in the above poly-hydroxy Al cross-linked bentonite slurries, under 60 ℃ of constant temperature, stir 4h, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake is dry down at 50 ℃, grind, namely obtain to adsorb cross-linked chitosan/poly-hydroxy Al cross-linked bentonite of removing bivalent cupric ion in the water;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 76%.
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 2.5g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 66.5%.
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 5g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 83.7%.
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 25g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 98.4%.
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 50g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 94.8%.
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 20mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 99.4%.
Embodiment 11
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 50mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 98.6%.
Embodiment 12
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 80mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 97.8%.
Embodiment 13
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 200mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 94.4%.
Embodiment 14
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 400mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 90.2%.
Embodiment 15
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 4.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 22.8%.
Embodiment 16
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 29.2%.
Embodiment 17
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 5.5,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 46%.
Embodiment 18
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.0,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 83.6%.
Embodiment 19
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.3,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 92.6%.
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 7.0,25 ℃ of vibration absorption 4h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 98.6%.
Embodiment 21
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 0.3h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 68.1%.
Embodiment 22
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 0.5h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 70.6%.
Embodiment 23
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 0.7h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 80.3%.
Embodiment 24
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 1h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 87.4%.
Embodiment 25
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 2h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 93.9%.
Embodiment 26
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 3h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 95.8%.
Embodiment 27
(1) (2) (3) are with embodiment 3;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 100mg/L according to the ratio of 10g/L, transfers system pH to be 6.5,25 ℃ of vibration absorption 6h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, the standard copper reagent solution 5ml that adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculating clearance according to the initial concentration of copper ion and balance densimeter is 97.1%.
Claims (1)
1. method of removing copper ion in the aqueous solution, it is characterized in that it being metal ion in the high effectively removal of a kind of comprehensive utilization shitosan and the bentonite intercalation amount aqueous solution, before composite modified, shitosan and bentonite are carried out crosslinkedization processing respectively, make the modified alta-mud composite of good stability, remove the method for the copper ion in the aqueous solution, concrete steps are as follows:
(1) AlCl of preparation 0.4mol/L
3Solution under 55 ~ 65 ℃ temperature, is added drop-wise to AlCl with the 0.4mol/L sodium hydroxide solution with the speed of 1mL/min
3In the solution, until n (OH
-): n (Al
3+)=2.4 then in 55 ~ 65 ℃ of ageing 47 ~ 49h, make poly-hydroxyl-aluminum pillared agent; Get the 1g sodium-ionized bentonite, to gather the hydroxyl-aluminum pillared agent in Al/ soil for the ratio of 10mmol/g is added in the bentonite, stir 3.5 ~ 4.5h under 55 ~ 65 ℃ the temperature, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake 40 ~ 70 ℃ dry down, grind, namely get poly-hydroxy Al cross-linked bentonite, standby;
(2) shitosan being dissolved in mass fraction is in 4 ~ 6% the acetic acid solution, and ratio is in 4 ~ 6% the acetic acid solution for the 1g shitosan is dissolved into 30 ~ 35ml mass fraction; The mixed liquor that makes is placed the there-necked flask that agitator and thermometer are housed, add atoleine, ratio adds 30 ~ 35ml atoleine for the 1g shitosan, be warmed up to 45 ~ 55 ℃ after stirring 8 ~ 30min under the startup agitator normal temperature, drip 3 ~ 4 span 80, emulsification 8 ~ 15min is warmed up to 55 ~ 65 ℃ then, drips formalin reaction 0.5 ~ 2h, the amount of dropping formalin is 4:1 with the amount of substance ratio of chitosan structure unit, and transferring system pH is 9 ~ 11; In this system, add epoxychloropropane, the amount of dropping epoxychloropropane is 3:1 with the amount of substance ratio of chitosan structure unit, be warmed up to 65 ~ 75 ℃ afterwards, slowly dripping mass fraction with constant pressure funnel is 4 ~ 6% sodium hydrate aqueous solution, make system pH remain at 9 ~ 11, reaction 1.5 ~ 3h filters, washing; Place apparatus,Soxhlet's to remove residual organic matter with the benzinum extracting this system, at 65 ~ 75 ℃ resin is handled 8 ~ 12h with the 1mo1/L hydrochloric acid solution at last, washing, sodium carbonate is washed, and is washed to neutrality, and vacuum drying is to constant weight, make epoxychloropropane cross-linked chitosan chelating resin, standby;
(3) the poly-hydroxy Al cross-linked bentonite that (1) is obtained adds water and is mixed with 50% suspension, stir, make poly-hydroxy Al cross-linked bentonite fully disperse, according to cross-linked chitosan and the poly-hydroxy Al cross-linked bentonite ratio that is 1:4 ~ 1:20, the crosslinked chitosan resin that (2) are obtained joins in the above poly-hydroxy Al cross-linked bentonite slurries, under 50 ~ 70 ℃ of constant temperature, stir 3 ~ 5h, be cooled to room temperature, decompress filter, be washed with distilled water to neutrality, suction filtration again, the gained filter cake is dry down at 40 ~ 70 ℃, grind, namely obtain to adsorb cross-linked chitosan/poly-hydroxy Al cross-linked bentonite of removing bivalent cupric ion in the water;
(4) cross-linked chitosan that (3) are obtained/poly-hydroxy Al cross-linked bentonite joins in the copper nitrate solution that concentration is 20 ~ 400mg/L according to the ratio of 5 ~ 50g/L, transfers system pH to be 4.5 ~ 7,25 ℃ of vibration absorption 0.3 ~ 6h, and is centrifugal, gets supernatant, to be measured;
(5) get the liquid 1ml dilution to be measured that (4) obtain, constant volume in the 100ml volumetric flask is got dilution 50ml, to the standard copper reagent solution 5ml that wherein adds 100mg/L, transferring pH with the pure ammoniacal liquor of analysis is 9, in the absorbance of ultraviolet specrophotometer mensuration 450nm, brings the calibration curve equation into
, calculate the copper ion equilibrium concentration, calculate clearance according to initial concentration and the balance densimeter of copper ion: R=(C
0-C
e)/C
0* 100%
R is clearance (%), C
0Be initial copper ion concentration mg/L, C
eAdsorption equilibrium concentration mg/L for copper ion.
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| CN108315774A (en) * | 2018-02-06 | 2018-07-24 | 广州超邦化工有限公司 | The processing method of nickel and copper impurity in a kind of trivalent chromium chrome plating liquid |
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| CN112563492A (en) * | 2020-12-11 | 2021-03-26 | 广东凯金新能源科技股份有限公司 | Surface micro-oxidation porous carbon-based negative electrode material and preparation method thereof |
| CN112563492B (en) * | 2020-12-11 | 2021-09-24 | 广东凯金新能源科技股份有限公司 | Surface micro-oxidation porous carbon-based negative electrode material and preparation method thereof |
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