CN103418335A - Compound nano adsorbent used for removing trivalent chromium ions in waste water, and removal method - Google Patents
Compound nano adsorbent used for removing trivalent chromium ions in waste water, and removal method Download PDFInfo
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- CN103418335A CN103418335A CN2013103405683A CN201310340568A CN103418335A CN 103418335 A CN103418335 A CN 103418335A CN 2013103405683 A CN2013103405683 A CN 2013103405683A CN 201310340568 A CN201310340568 A CN 201310340568A CN 103418335 A CN103418335 A CN 103418335A
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Abstract
The invention relates to a method for removing trivalent chromium ions in waste water and belongs to the technical field of waste water treatment. A compound nano absorbent is added into waste water containing trivalent chromium ions with an initial concentration of 5 to 50 mg/L to enable the content of the compound nano absorbent in the waste water to be 0.5 to 4 g/L, the pH value is regulated to 4 to 6, and a reaction is performed for 5 to 60 min at ordinary temperature under the ultrasonic and pneumatic condition, wherein the compound nano absorbent is prepared from nano ferroferric oxide and nano elemental particles, the nano elemental particles are composed of one or two of nano nickel particles, nano cobalt particles and nano iron particles, and the mass ratio of the nano ferroferric oxide to the nano elemental particles is (7:3)-(3:7). A dispersing agent can be added in the adsorption process to promote the nano absorbent to disperse during adsorption. The method has the advantages that the removal rate of waste water containing the trivalent chromium ions with the initial concentration of 5 to 20 mg/L can reach 100%, and the removal rate of waste water containing the trivalent chromium ions with the initial concentration of 50 mg/L can reach 96.6%.
Description
Technical field
The invention belongs to technical field of sewage, particularly a kind of nano adsorber and removal method for removing trivalent chromic ion.
Background technology
Along with global economy develop rapidly and population constantly increase, human society increases rapidly the demand of water.In recent decades, the mankind increase year by year to the consumption of fresh water, produce thus a large amount of waste water; can't recycle; cause serious water environment pollution, affect the utilization of structure, function and the water resource of aquatic ecosystem, make many countries and regions in the world water resources crisis occur.Increasing to activities in production such as the exploitation of heavy metal, smelting, processing along with the mankind wherein, no matter what discharge in various industrial processes is all greatly to increase in quantity or kind containing heavy metal ion, cause many heavy metals to enter the ecosystem, caused serious environmental pollution and the wasting of resources.Its intractability and harmfulness belong to the waste water that difficult for biological degradation has again very large toxicity.As everyone knows, the heavy metal ion in water body can be along biological chain by biological adsorption and enrichment, at people's cylinder accumulation and cause poisoning.Therefore, the improvement of heavy metal wastewater thereby is the key subjects of world's field of Environment Protection always, is also the object of environmental scientific research workers primary study.
At present, traditional heavy metal wastewater thereby improvement method, exist that cost is high, the unsettled shortcoming of effect.Except application cleaner production and recycling economy technology from source to heavy metal use and discharge contained, also need research and development new type natural adsorbent, heavy metal chelating agent and the biotechnology improvement to heavy metal pollution more, bring into play the advantage that their costs are low, efficiency is high, and strengthen the integrated application of multiple improvement technology, find and administer the new effective way of heavy metal pollution.
Summary of the invention
Technical problem to be solved by this invention is: in prior art, traditional heavy metal wastewater thereby improvement method, exist that cost is high, the unsettled shortcoming of effect.
For solving this technical problem, the technical solution used in the present invention is:
The invention provides a kind of trivalent chromic ion compound adsorbent, compound adsorbent be by, nano ferriferrous oxide and nano simple substance particle, ratio cooperation for 7:3~3:7 forms in mass ratio, wherein, the nano simple substance particle is selected from one or both compositions in nano nickel, nanometer cobalt, nano iron particles, the diameter 20-25nm of nano particle.
The present invention also provides a kind of above-mentioned compound adsorbent that utilizes, the method of trivalent chromic ion in absorption waste water, concrete operations are: the pH that regulates the waste water that the trivalent chromic ion initial concentration is 5-50mg/L is 4-6, under pneumatic ultrasound condition, amount by composite nano adsorbent with 0.5-4g/L, put in this waste water, react 5-60min under 20-25 ℃, finally from solution, isolate composite nano adsorbent.
In said method, in pneumatic ultrasound condition, supersonic frequency is made as 20-50kHz, and ultrasonic power is 20-1000W.
Because the nano adsorber particle diameter is little, surface-active is high, in solution, very easily reunites, and can make the clearance of trivalent chromic ion reduce, and therefore, in adsorption process, adopts pneumatic Vltrasonic device, is dispersed in solution with impelling the composite nano adsorbent uniform particles;
In order to play better the effect of scattered adsorption agent, in adsorption process, can also in reaction system, add dispersant, dispersant is selected from one or both mixing organic matters in ethanol, polyethylene glycol, glycerine, cyclohexanol, glucose, the mass ratio of dispersant and composite nano adsorbent is 0.1-1
Above-mentioned dispersant can be introduced nano ferriferrous oxide by oh group, and other absorbent particles surfaces, reduces interfacial tension, dispersant adsorption in particle surface, absorption firmly, the effective radius of particle is increased, thereby strengthen repulsion between particle, thereby can effectively prevent interparticle reunion.And these dispersants have high-temperature stability and the chemical stability of good dissolubility, excellence, easily biological-degradable, Environmental compatibility is good.
The invention has the beneficial effects as follows:
1, the nano adsorber raw materials that the present invention uses is simple, easily obtain, cost is low, and dosage is little, and clearance is high, after single treatment, can reach the highest permission concentration of emission of sewage drainage standard first kind pollutant, and be difficult for causing secondary pollution;
2, remove the easy control of process conditions of trivalent chromic ion in waste water in the present invention, but intermittent operation while removing in waste water trivalent chromic ion, but also continous way operation, can reach very high clearance at normal temperature, overcome the higher temperature conditions needed in some conventional method;
What 3, the present invention adopted is pneumatic ultrasonic, and effectively dispersing nanometer tri-iron tetroxide and other absorbent particles, prevent from reuniting;
4, processing method of the present invention can reclaim nano adsorber, can not cause secondary pollution, and the trivalent chromic ion be adsorbed can recycling.
The accompanying drawing explanation
Fig. 1: in solution, when the concentration of nano ferriferrous oxide and nano nickel is 1g/L, pneumatic ultrasonic dispersion rear suspension liquid concentration is relation over time.Can find out, pneumatic ultrasonic after, the suspension quite stable. after standing 48h, the nano adsorber granule density only reduces by 8%, and decrease speed is very slow.This explanation is pneumatic ultrasonic in water, and the reunion that can break the nano adsorber particle disperses with being effective.
The specific embodiment
Embodiment 1
The industrial wastewater that is 20mg/L to trivalent chromic ion concentration is processed:
Add NaOH and sulfuric acid, regulating the industrial wastewater pH that trivalent chromic ion concentration is 20mg/L is 5.Under pneumatic ultrasound condition, (frequency is 20kHz, ultrasonic power is 800W), in this industrial wastewater, press nano ferriferrous oxide concentration 1g/L, nano nickel concentration 1g/L, the compound adsorbent that adds nano ferriferrous oxide and nano nickel, under 20-25 ℃, pneumatic ultrasonic 60min, use magnet adsorption, isolates composite nano adsorbent from waste water.
Record in the industrial wastewater after processing, trivalent chromic ion concentration is 0mg/L, adsorbance △=20mg/L.
Comparative Examples 1
To trivalent chromic ion concentration, to be 20mg/L industrial wastewater is processed equally:
Add NaOH and sulfuric acid, regulating the industrial wastewater pH that trivalent chromic ion concentration is 20mg/L is 5.Under pneumatic ultrasound condition, (frequency is 20kHz, ultrasonic power is 800W), in this industrial wastewater, press nano ferriferrous oxide concentration 1g/L, add nano ferriferrous oxide, as the single adsorption agent, pneumatic ultrasonic 60min under 20-25 ℃, use magnet adsorption, isolate nano adsorber from waste water.
In industrial wastewater after treatment, trivalent chromic ion concentration is 11.4mg/L, adsorbance △=8.6mg/L.
Comparative Examples 2
To trivalent chromic ion concentration, to be 20mg/L industrial wastewater is processed equally:
Add NaOH and sulfuric acid, regulating the industrial wastewater pH that trivalent chromic ion concentration is 20mg/L is 5.Under pneumatic ultrasound condition (frequency is 20kHz, and ultrasonic power is 800W), in this industrial wastewater, press nano nickel concentration 1g/L, add nano nickel, as the single adsorption agent, under 20-25 ℃, pneumatic ultrasonic 60min, use magnet adsorption, isolates nano adsorber from waste water.
In industrial wastewater after treatment, trivalent chromic ion concentration is 13.7mg/L, adsorbance △=6.3mg/L.
Comparative Examples 3
The industrial wastewater that is 20mg/L to trivalent chromic ion concentration is processed:
Step 1:
Add NaOH and sulfuric acid, regulating the industrial wastewater pH that trivalent chromic ion concentration is 20mg/L is 5.Under pneumatic ultrasound condition, (frequency is 20kHz, ultrasonic power is 800W), in this industrial wastewater, press nano ferriferrous oxide concentration 1g/L, add nano ferriferrous oxide, as the single adsorption agent, pneumatic ultrasonic 60min under 20-25 ℃, use magnet adsorption, isolate nano adsorber from waste water;
Step 2:
Under pneumatic ultrasound condition (frequency is 20kHz, and ultrasonic power is 800W), in the industrial wastewater after processing to step 1, press nano nickel concentration 1g/L, add nano nickel, as the single adsorption agent, under 20-25 ℃, pneumatic ultrasonic 60min, use magnet adsorption, isolates nano adsorber from waste water.
After testing, in the industrial wastewater after processing, trivalent chromic ion concentration is 4.7mg/L, adsorbance △=15.3mg/L.
The adsorbance △ of comparing embodiment 1, Comparative Examples 1, Comparative Examples 2, Comparative Examples 3 can learn, nano ferriferrous oxide and nano nickel are combined, and as adsorbent, uses, the summation of the adsorbance that adsorption effect is greater than these two kinds of nano particles while using respectively.
Embodiment 2
The industrial wastewater that is 50mg/L to trivalent chromic ion concentration is processed:
In the industrial wastewater that is 50mg/L to trivalent chromic ion concentration, adding NaOH and salt acid for adjusting pH is 6.Under pneumatic ultrasound condition, (frequency is 40kHz, ultrasonic power is 800W), press nano ferriferrous oxide concentration 2g/L, nanometer cobalt concentration 2g/L, to the compound adsorbent that adds nano ferriferrous oxide and nanometer cobalt in above-mentioned waste water, add glycerine as dispersant (concentration by 2g/L adds), under 20-25 ℃, pneumatic ultrasonic 60min, use magnet adsorption, isolates composite nano adsorbent from waste water.
Record in the industrial wastewater after processing, trivalent chromic ion concentration is 1.7mg/L, adsorbance △=48.3mg/L.
Comparative Examples 4:
To trivalent chromic ion concentration, to be 50mg/L industrial wastewater is processed equally:
In adsorption process, only adding nano ferriferrous oxide concentration is 2g/L, and as single adsorbent, all the other operate with consistent in embodiment 2,
Record in the industrial wastewater after processing, trivalent chromic ion concentration is 29.4mg/L, adsorbance △=20.6mg/L.
Comparative Examples 5:
To trivalent chromic ion concentration, to be 50mg/L industrial wastewater is processed equally:
In adsorption process, only adding nanometer cobalt concentration is 2g/L, and as single adsorbent, all the other operate with consistent in embodiment 2,
Record in the industrial wastewater after processing, trivalent chromic ion concentration is 33.6mg/L, adsorbance △=16.4mg/L.
Comparative Examples 6:
The industrial wastewater that is 50mg/L to trivalent chromic ion concentration is processed:
Step 1:
In the industrial wastewater that is 50mg/L to trivalent chromic ion concentration, adding NaOH and salt acid for adjusting pH is 6.Under pneumatic ultrasound condition, (frequency is 40kHz, ultrasonic power is 800W), press nano ferriferrous oxide concentration 2g/L, add the agent of nano ferriferrous oxide single adsorption in above-mentioned waste water, add glycerine as dispersant (concentration by 2g/L adds), under 20-25 ℃, pneumatic ultrasonic 60min, use magnet adsorption, isolates nano adsorber from waste water;
Step 2:
Under pneumatic ultrasound condition (frequency is 40kHz, and ultrasonic power is 800W), in the industrial wastewater after processing to step 1, press nanometer cobalt concentration 1g/L, add nanometer cobalt, as the single adsorption agent, under 20-25 ℃, pneumatic ultrasonic 60min, use magnet adsorption, isolates nano adsorber from waste water.
After testing, in the industrial wastewater after processing, trivalent chromic ion concentration is 10.7mg/L, adsorbance △=39.3mg/L.
Embodiment 3:
The industrial wastewater that is 5mg/L to trivalent chromic ion concentration is processed:
In the industrial wastewater that is 5mg/L to trivalent chromic ion concentration, adding NaOH and sulphur acid for adjusting pH is 4.Under pneumatic ultrasound condition, (frequency is 20kHz, ultrasonic power is 300W), press nano ferriferrous oxide concentration 0.5g/L, nano nickel concentration 0.5g/L, to the compound adsorbent that adds nano ferriferrous oxide and nano nickel in above-mentioned waste water, pneumatic ultrasonic 5min under 20-25 ℃, use magnet adsorption, isolate composite nano adsorbent from waste water.
Record in the industrial wastewater after processing, trivalent chromic ion concentration is 0mg/L, adsorbance △=5mg/L.
Embodiment 4:
The industrial wastewater that is 30mg/L to trivalent chromic ion concentration is processed:
In the industrial wastewater that is 30mg/L to trivalent chromic ion concentration, adding NaOH and sulphur acid for adjusting pH is 5.Under pneumatic ultrasound condition, (frequency is 50kHz, ultrasonic power is 1000W), press nano ferriferrous oxide concentration 2.1g/L, nanometer cobalt concentration 0.9g/L, to the compound adsorbent that adds nano ferriferrous oxide and nanometer cobalt in above-mentioned waste water, pneumatic ultrasonic 20min under 20-25 ℃, use magnet adsorption, isolate composite nano adsorbent from waste water.
Record in the industrial wastewater after processing, trivalent chromic ion concentration is 0.5mg/L, adsorbance △=29.5mg/L.
Embodiment 5:
The industrial wastewater that is 20mg/L to trivalent chromic ion concentration is processed:
In the industrial wastewater that is 20mg/L to trivalent chromic ion concentration, adding NaOH and sulphur acid for adjusting pH is 5.Under pneumatic ultrasound condition, (frequency is 35kHz, ultrasonic power is 500W), press nano ferriferrous oxide concentration 0.6g/L, Nanoscale Iron concentration 1.4g/L, to the compound adsorbent that adds nano ferriferrous oxide and Nanoscale Iron in above-mentioned waste water, pneumatic ultrasonic 40min under 20-25 ℃, use magnet adsorption, isolate composite nano adsorbent from waste water.
Record in the industrial wastewater after processing, trivalent chromic ion concentration is 0.4mg/L, adsorbance △=19.6mg/L.
Claims (4)
1. a trivalent chromic ion compound adsorbent, it is characterized in that: described compound adsorbent, by nano ferriferrous oxide and nano simple substance particle, ratio cooperation for 7:3~3:7 forms in mass ratio, wherein, the nano simple substance particle is selected from one or both compositions in nano nickel, nanometer cobalt, nano iron particles.
2. compound adsorbent as claimed in claim 1, the method of trivalent chromic ion in absorption waste water, it is characterized in that: described adsorption method is, the pH that regulates the waste water that the trivalent chromic ion initial concentration is 5-50mg/L is 4-6, under pneumatic ultrasound condition, the amount by composite nano adsorbent with 0.5-4g/L, put in this waste water, react 5-60min under 20-25 ℃, finally from solution, isolate composite nano adsorbent.
3. adsorption method as claimed in claim 2, it is characterized in that: in described pneumatic ultrasound condition, supersonic frequency is 20-50kHz, and ultrasonic power is 20-1000W.
4. adsorption method as claimed in claim 2, it is characterized in that: in described adsorption process, add dispersant in reaction system, dispersant is selected from one or both mixing organic matters in ethanol, polyethylene glycol, glycerine, cyclohexanol, glucose, and the mass ratio of dispersant and composite nano adsorbent is 0.1-1.
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CN104163462A (en) * | 2014-06-26 | 2014-11-26 | 中山大学 | Application of municipal sludge for removal of arsenic |
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