CN106542625A - The preparation of composite flocculation agent and the processing method of the mine tailing wastewater of Organic substance containing heavy metal - Google Patents
The preparation of composite flocculation agent and the processing method of the mine tailing wastewater of Organic substance containing heavy metal Download PDFInfo
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- CN106542625A CN106542625A CN201611055924.7A CN201611055924A CN106542625A CN 106542625 A CN106542625 A CN 106542625A CN 201611055924 A CN201611055924 A CN 201611055924A CN 106542625 A CN106542625 A CN 106542625A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention provides the processing method of the preparation of composite flocculation agent and the mine tailing wastewater of Organic substance containing heavy metal, magnesium copper zinc ferrite and distilled water are mixed, ultrasonic disperse, then the sodium carboxymethyl cellulose solution that Deca is excessive, stirring reaction, generate magnesium copper zinc ferrite carboxymethyl cellulose, with polyethyleneimine as parent, under conditions of polypeptide reagent is initiator, excessive TGA is added, carry out amidation process, you can mercaptoacetyl polyethyleneimine is obtained；Excessive mercaptoacetyl aq. polyethyleneimine is added in magnesium copper zinc ferrite carboxymethyl cellulose, is stirred, be added dropwise over excessive glutaraldehyde water solution, stirring reaction, washing is composite flocculation agent after being dried.Catch volume and sweep and chelation using the sulfur end group and carbonyl, the net of amino amphiprotic group of close heavy metal in the sulfydryl of novel high polymer composite flocculation agent, the low-concentration heavy metal and organic contamination in effective process compound wastewater, and stable performance.
Description
Technical field
The invention belongs to water-treatment technology field, is related to the mine tailing wastewater of Organic substance containing heavy metal, and in particular to composite flocculation
The preparation of agent and the processing method of the mine tailing wastewater of Organic substance containing heavy metal.
Background technology
Mine tailing wastewater discharge capacity is big, complicated component, the slaine only not dissolved, sludge, remaining beneficiation reagent, also contains
The heavy metal ion of various low concentrations such as copper, lead, chromium.These pollutant permeate the ground or flow into river nearby, polluted underground water
And water source, the heavy metal penetrated in environment is easily accumulated difficult degradation, there is persistency to endanger ecological environment, and it is strong to endanger the mankind
Health.
In general conventional high polymer coagulant can remove most Organic substance and metal during flocculating sedimentation
Insoluble matter, it is impossible to effectively remove the heavy metal of the dissolved, the sequestering power of heavy metal ion is relatively low, it is impossible to effective process mining area
Compound wastewater.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a kind of preparation method of composite flocculation agent,
Process for the mine tailing wastewater of Organic substance containing heavy metal provides the composite flocculation agent of high treating effect.
Another object of the present invention is to a kind of processing method of the mine tailing wastewater of Organic substance containing heavy metal is provided, for low dense
The mine tailing wastewater of Organic substance containing heavy metal of degree, the removal problem of the heavy metal and Organic substance of effectively solving wherein low concentration.
In order to solve above-mentioned technical problem, the present invention is adopted the following technical scheme that and is achieved：
A kind of preparation method of composite flocculation agent, the method are comprised the following steps：
Step one, the nitrate solution of hybrid metal ion is added in preheating sodium hydroxide solution, precipitant is made, is adjusted
Section pH value is stood to 10.5, uses distilled water cyclic washing, sucking filtration to be dried to constant weight in vacuum drying oven, you can obtain magnesium copper
Zn ferrite；
The nitrate solution of described hybrid metal ion is the mixing nitre of magnesium ion, copper ion, zinc ion and iron ion
Acid salt solution；
Step 2, magnesium copper zinc ferrite and distilled water is mixed, ultrasonic disperse 20min, adjusts pH to 6, then Deca excess
Sodium carboxymethyl cellulose solution, take while ultrasonic vibration, at room temperature
Continue constant speed mechanical agitation 10min, generate magnesium copper zinc ferrite-carboxymethyl cellulose, with Magnet by magnesium copper zinc ferrite-carboxylic first
Base cellulose is separated from system, and distilled water wash is standby after mixing；
Step 3, with polyethyleneimine as parent, under conditions of polypeptide reagent is initiator, adds excessive sulfydryl second
Acid, carries out amidation process, adjusts pH=1.0～3.0, stirring reaction 12h at 30 DEG C～50 DEG C, you can mercaptoacetyl is obtained
Polyethyleneimine；
Described polypeptide reagent is 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride；
Step 4, adds excessive mercaptoacetyl polyethyleneimine water-soluble in magnesium copper zinc ferrite-carboxymethyl cellulose
Liquid, adopts mechanical agitation 30min while ultrasonic vibration, stop ultrasound afterwards, after continuing mechanical agitation 10min at room temperature,
Be added dropwise over excessive glutaraldehyde water solution, using ultrasound is stopped after mechanical agitation 30min while acoustic shock is swung, at room temperature after
After continuous mechanical agitation 10min, product is separated from system with Magnet, and use distilled water cyclic washing, used after being washed till neutrality again
Absolute ethanol washing, is dried to constant weight, obtains final product yellow-brown solid, as composite flocculation agent.
The present invention also has following distinguishing feature：
In step one, magnesium ion, copper ion, zinc ion and iron ion in the nitrate solution of described hybrid metal ion
Between mol ratio be 1：1：1：1；
The nitrate solution of described hybrid metal ion is 0.5 with the total moles ratio of sodium hydroxide：2；
Described preheating temperature is 50 DEG C.
In step 2, the concentration of described sodium carboxymethyl cellulose solution is 5g/L.
In step 3, the mol ratio between polyethyleneimine, TGA and polypeptide reagent is 1:(1～3):(0.1～
0.3)。
In step 4, the mass concentration of described mercaptoacetyl aq. polyethyleneimine is 10%.
A kind of processing method of the mine tailing wastewater of Organic substance containing heavy metal, the method are obtained using preparation method as above
Composite flocculation agent the mine tailing wastewater of Organic substance containing heavy metal is processed.
Specifically, in described Organic substance containing heavy metal mine tailing wastewater, the total concentration≤200mg/L of heavy metal particles has
COD≤the 200mg/L of machine thing.
Preferably, in described Organic substance containing heavy metal mine tailing wastewater, heavy metal particles Pb2+、Cu2+、Cd2+And Cr6+It is total
Concentration is 40.169mg/L, and the COD of Organic substance is 132.4mg/L.
Specifically, the detailed process of described processing method is：Organic substance containing heavy metal mine tailing wastewater was specifically processed
Cheng Wei：The pH=6.1 of the mine tailing wastewater of Organic substance containing heavy metal is adjusted, and compound wadding is added in the mine tailing wastewater of Organic substance containing heavy metal
Solidifying agent is adsorbed；
The mine tailing wastewater of Organic substance containing heavy metal correspondence per 10L adds the composite flocculation agent of 5g～30g.
Preferably, the mine tailing wastewater of Organic substance containing the heavy metal correspondence per 10L adds the composite flocculation agent of 15g～20g, absorption
Time is 90min～120min.Specific test effect is as described below.
The present invention compared with prior art, has the following technical effect that：
(I) composite flocculation agent of the invention is incorporated into the strong dentate of heavy metal ion in high polymer coagulant, synthesizes
The new macromolecule heavy metal flocculant containing chelating functional group, realizes the synchronization of heavy metal and turbidity by Flocculation Settling Process
Remove, improve the integrated treatment performance of high polymer coagulant.Magnesium copper zinc ferrite is grafted to using sodium carboxymethyl cellulose (CMC)
Surface, then MAPEI is linked on the ferrite after assembling with glutaraldehyde, prepare containing carbonyl, amino, sulfydryl and height
The novel high polymer composite flocculation agent of magnetic property.On the one hand due to possessing the sulfydryl of close heavy metal on its molecule, can be with a huge sum of money
Category forms multiple strong coordinating groups such as the amido of stable coordinate bond, imido grpup, carboxylic epoxide.On the other hand, itself and heavy metal ion
Generate the minimum chelate of solubility product and precipitation occurs, so as to reach the good result of heavy-metal ion removal.
(II) mine tailing wastewater processing method of the invention, using close heavy metal in the sulfydryl of novel high polymer composite flocculation agent
Sulfur end group and carbonyl, the net of amino amphiprotic group catch volume and sweep and chelation, the low concentration in effective process compound wastewater
Heavy metal and organic contamination, and stable performance.
(III) composite flocculation agent of the invention is short to the optimal flocculation time of mining tailing wasteland waste water, and dosage is few, Optimal pH
Wide ranges, good stability are difficult dissolution in water body, and secondary pollution is little.
(IV), after composite flocculation agent of the invention is to mine tailing wastewater process, the flco residue for obtaining can be effectively soaked with acid solution
Go out, each ion also effectively can be leached, and then recycle.Composite flocculation agent Magneto separate is faster than the speed of standing sedimentation, efficiency
Height, can effectively reduce waste water finishing time, reduce Financial cost.
Description of the drawings
Fig. 1 is the infrared spectrum of three kinds of different composite things.
Fig. 2 is the transmission electron microscope picture of Ferrite.
Fig. 3 is the transmission electron microscope picture of Ferrite-CMC-MAPEI.
Fig. 4 is the Zeta potential of Ferrite and Ferrite-CMC-MAPEI.
Fig. 5 is impact of the dosage to ion remaval rate.
Fig. 6 is the impact of adsorption time heavy metal ion remaval rate.
Explanation is further explained in detail to the particular content of the present invention with reference to embodiments.
Specific embodiment
Reagent：Sodium carboxymethyl cellulose (Li Anlongbohua medical chemistries company limited), polyethyleneimine (Aladdin), mercapto
Guanidine-acetic acid (Aladdin), polypeptide reagent (EDCHCL) (Aladdin), glutaraldehyde (Aladdin), medicine are all that analysis is pure.
Instrument：Atomic absorption spectrophotometer (manufacture of Beijing Fourth Ring scientific instrument factory), MAGGNA-IR560 type infrared lights
Spectrometer (Nicolet companies of the U.S.), X-ray diffractometer (Rigaku Rugaku Instrument Ltd.), transmission electron microscope (Holland
Philips-PEI companies).
The specific embodiment of the present invention given below, implement it should be noted that is the invention is not limited in detail below
Example, all equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1：
The present embodiment provides a kind of preparation method of composite flocculation agent, and the method is comprised the following steps：
Nitrate solution solution of the total concentration for the hybrid metal ion of 0.5mol/L is added 2mol/L preheatings by step one
In sodium hydroxide solution, precipitant is made, be added slowly with stirring hybrid metal solion, be 10% with mass concentration
Ammonia adjusts pH value to 10.5, stands, and uses distilled water cyclic washing, sucking filtration to be dried at 90～110 DEG C in vacuum drying oven
To constant weight, you can obtain magnesium copper zinc ferrite (Mg0.25Cu0.25Zn0.5Fe2O4, abbreviation Ferrite).
The nitrate solution of described hybrid metal ion is the mixing nitre of magnesium ion, copper ion, zinc ion and iron ion
Acid salt solution；Rubbing between magnesium ion, copper ion, zinc ion and iron ion in the nitrate solution of described hybrid metal ion
You are than being 1：1：1：1；
The nitrate solution of described hybrid metal ion is 0.5 with the total moles ratio of sodium hydroxide：2；
Described preheating temperature is 50 DEG C.
Step 2,1g magnesium copper zinc ferrite and 50mL distilled water is added in 250ml three-neck flasks, ultrasonic disperse 20min,
With salt acid for adjusting pH to 6, then in good time sodium carboxymethyl cellulose (CMC) aqueous solution of the excessive 5g/L of Deca, ultrasonic vibration it is same
When take, continue constant speed mechanical agitation 10min at room temperature, generate magnesium copper zinc-iron
Magnesium copper zinc ferrite-carboxymethyl cellulose is separated from system, distilled water wash by oxysome-carboxymethyl cellulose with Magnet, is mixed
It is standby after even.
Step 3, with polyethyleneimine (PEI) as parent, under conditions of polypeptide reagent (EDCHCL) is for initiator,
TGA is added, amidation process is carried out, and pH=3.0 is adjusted with hydrochloric acid, lower stirring reaction 12h at 50 DEG C, you can be obtained
Mercaptoacetyl polyethyleneimine.
Described polypeptide reagent is 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride (EDCHCl).
Mol ratio between polyethyleneimine, TGA and polypeptide reagent is 1:3:0.3.
TGA (TGA) is accessed by polyethyleneimine macromolecular chain by amidation process, heavy metal ion is introduced
Strong coordinating group sulfydryl-SH, you can prepare while having the mercaptoacetyl polyethyleneimine of trap heavy metals ion and turbidity removal
(MAPEI).Reaction equation is as described below：
In formula：N=18～22.
Step 4, magnesium copper zinc ferrite-carboxymethyl cellulose is placed in 250ml three-neck flasks, the excessive quality of Deca
Concentration is 10% mercaptoacetyl aq. polyethyleneimine, adopts mechanical agitation 30min, stop while ultrasonic vibration afterwards
Ultrasound, after continuing mechanical agitation 10min at room temperature, is added dropwise over the glutaraldehyde water solution that excessive mass concentration is 25%,
Using ultrasound is stopped after mechanical agitation 30min while acoustic shock is swung, at room temperature after continuation mechanical agitation 10min, will with Magnet
Product is separated from system, and uses distilled water cyclic washing, is done with vacuum at absolute ethanol washing, with 45 DEG C after being washed till neutrality again
It is dry to constant weight, obtain final product yellow-brown solid, as composite flocculation agent (Ferrite-CMC-MAPEI).
The structural formula of the CMC-MAPEI in composite flocculation agent is as described below：
Wherein：M=100～2000：N=18～22.
The preparation of CMC-MAPEI：200mL concentration is added in there-necked flask for the sodium carboxymethyl cellulose solution of 5g/L
And the MAPEI aqueous solutions that 15mL mass concentrations are 10%, continue machinery after ultrasonic vibration constant speed mechanical agitation 30min and stir
Mix, while it is 25% glutaraldehyde water solution to be added dropwise over 2mL mass concentrations, take out after continuing constant speed mechanical agitation 6h at room temperature
Filter, and distilled water wash is used, it is vacuum dried at 45 DEG C, obtains yellow-brown solid, grinding is uniform, as CMC-MAPEI.
The Infrared Characterization of composite flocculation agent：As seen in Figure 1, the polymer substance for introducing on magnesium copper zinc ferrite contains
Amount is relatively low, and sulfhydryl content is too low in MAPEI chains, and infrared spectrum does not detect the characteristic peak 2512cm-1 of sulfydryl；
The infrared spectrogram of Ferrite-CMC-MAPEI occurs in that-stretching vibration absworption peak 1661cm of C=N-1, there is not primary amine
Stretching vibration absworption peak 3420cm-1, illustrate that the carbonyl in glutaraldehyde there occurs reaction with the amino in MAPEI molecules；
1125cm-1Place occurs in that characteristic absorption peak, the stretching vibration absworption peak for having O-C-O-C in illustrating molecule, it was demonstrated that carboxymethyl cellulose
Hydroxyl on plain sodium there occurs aldolisation with the carbonyl in glutaraldehyde.As a result show that CMC and MAPEI is introduced by the Success in Experiment
To on ferrite, the novel high polymer composite flocculation agent containing carbonyl, amino, sulfydryl and high magnetic characteristics has been prepared
Ferrite-CMC-MAPEI。
The tem analysis of magnesium copper zinc ferrite and composite flocculation agent：Fig. 2 is schemed for the TEM of Ferrite, and Fig. 3 is Ferrite-
The TEM figures of CMC-MAPEI, it can be seen that the complex microsphere good dispersion in Fig. 3, but there is agglomeration between complex microsphere
Exist, but compared with the ferrite microsphere of Fig. 2, hence it is evident that improved.Occur agglomeration between microsphere and be because compound iron oxygen
Macromolecular chain on body powder body there occurs bridge linking effect with the strand on multiple ferrite particles.
The Zeta potential of composite flocculation agent is determined：Zeta potential instrument detection magnetic particle surface electricity at various ph values
Position, in condition determination, different pH value are respectively 2,4,6,8,10,12, and the nano-complex particle solution concentration of preparation is 1g/L,
0.1mmol/L NaCl adjust the pH value of suspension with HCl, NaOH solution adjusting the ionic strength of suspension.Determine gained
As a result it is as shown in Figure 4.Find out in determining from the Zeta potential of magnesium copper zinc ferrite, the magnesium copper zinc ferrite isoelectric point, IP after being combined from
Before compound, isoelectric pH=3.8 are displaced to pH=6.1, and Ferrite-CMC-MAPEI is a kind of new polyampholyte, its
Not only sulfydryl base had been contained on strand but also had contained amino, sulfydryl-SH had been dissociated into-S when pH gradually rises-, pH is gradually lowered the time-division
Amino-NH in subchain2Proton formation-NH can be received3 +.Work as pH<pHiepWhen (isoelectric point, IP), complex macromolecular chain is with cation
Form is present, the increase of electrical charge rejection effect；pH>pHiepWhen, complex macromolecular chain loses proton, exists with anion form, electricity
Lotus repelling effect increases；PH=pHiepWhen, complex macromolecular chain is present with electric neutrality state, and net charge is zero, and electric charge is mutually arranged
Repulsion reduces, into salt number of keys at most, in most strong with metal ion chelating capacity in aqueous solution therefore follow-up flocculating experiment,
Experiment is selected pH and typically adopts pH=6.10 ± 0.05.
Embodiment 2：
The present embodiment provides a kind of preparation method of composite flocculation agent, and the method is comprised the following steps：
Step one is identical with the step of embodiment 11.
Step 2 is identical with the step of embodiment 12.
Step 3, step 3, with polyethyleneimine (PEI) as parent, is initiator in polypeptide reagent (EDCHCL)
Under the conditions of, excessive TGA is added, amidation process is carried out, and pH=2.0 is adjusted with hydrochloric acid, the lower stirring reaction at 40 DEG C
12h, you can mercaptoacetyl polyethyleneimine is obtained.
Described polypeptide reagent is 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride (EDCHCl).
Mol ratio between polyethyleneimine, TGA and polypeptide reagent is 1:2:0.2.
Step 4, it is essentially identical with the step of embodiment 1 four.
Obtained in the present embodiment, the characterization result of composite flocculation agent Ferrite-CMC-MAPEI is same as Example 1.
Embodiment 3：
The present embodiment provides a kind of preparation method of composite flocculation agent, and the method is comprised the following steps：
Step one is identical with the step of embodiment 11.
Step 2 is identical with the step of embodiment 12.
Step 3, step 3, with polyethyleneimine (PEI) as parent, is initiator in polypeptide reagent (EDCHCL)
Under the conditions of, excessive TGA is added, amidation process is carried out, and pH=1.0, the stirring reaction at 30 DEG C is adjusted with hydrochloric acid
12h, you can mercaptoacetyl polyethyleneimine is obtained.
Described polypeptide reagent is 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride (EDCHCl).
Mol ratio between polyethyleneimine, TGA and polypeptide reagent is 1:1:0.1.
Step 4, it is essentially identical with the step of embodiment 1 four.
Obtained in the present embodiment, the characterization result of composite flocculation agent Ferrite-CMC-MAPEI is same as Example 1.
Embodiment 4：
The present embodiment provides a kind of processing method of the mine tailing wastewater of Organic substance containing heavy metal, and the method adopts claim 1
In preparation method obtained in composite flocculation agent the mine tailing wastewater of Organic substance containing heavy metal is processed.
In the handled mine tailing wastewater of Organic substance containing heavy metal, the total concentration≤200ppmmg/L of heavy metal particles is organic
COD≤the 200mg/L of thing, is super low concentration Organic substance containing heavy metal mine tailing wastewater.
Testing the handled mine tailing wastewater of Organic substance containing heavy metal is：The deionized water of four groups of 1L is taken, is added respectively certain
Amount Pb2+、Cu2+、Cd2+、Cr6+Slaine, the design concentration that adds for making each ion is 10mg/L, and in water sample, the design load of COD value is
130mg/L, takes each metal ion content in atomic absorption measuring waste water afterwards, determines COD, detection using potassium dichromate method
Value such as table 1.I.e. specific to the present embodiment, in following tests, in the handled mine tailing wastewater of Organic substance containing heavy metal, heavy metal grain
Sub- Pb2+、Cu2+、Cd2+And Cr6Total concentration be 40.169ppm mg/L, the COD of Organic substance is 132.4mg/L.
Table 1 tests the handled mine tailing wastewater related test results of Organic substance containing heavy metal
The concrete processing procedure of the mine tailing wastewater of Organic substance containing heavy metal is：Adjust the pH of the mine tailing wastewater of Organic substance containing heavy metal
=6.1, composite flocculation agent is added in the mine tailing wastewater of Organic substance containing heavy metal adsorbed.Organic substance containing heavy metal per 10L
Mine tailing wastewater correspondence adds the flocculant of 5g～30g.Adsorption time is 90min～120min.The specific following institute of test effect
State.
The impact of dosage heavy metal ion remaval rate：
In pH=6.1,5g, 10g, 15g, 20g, 25g, 30g composite flocculation agent is added in the mine tailing wastewater of 10L and wadded a quilt with cotton
Solidifying experiment, determines the concentration of each ion in solution with Flame Atomic Absorption Spectrometry instrument after flocculation sediment, according to solution before and after absorption respectively from
Sub- concentration difference calculates adsorption capacity.As a result it is as shown in Figure 5.As a result show, composite flocculation agent Ferrite-CMC-MAPEI is to mine tailing
In waste water all there is optimal coagulant dose in each metal ion, be 15g and 20g, and before optimum, the clearance of ion is relatively low,
And clearance increases as dosage increases；After optimum, such as continue to increase dosage, clearance declines on the contrary.
This is primarily due to dissociation of the MAPEl molecules due to sulfydryl (- SH) with substantial amounts of negative charge, metal ion and MAPEl molecules
In part-S- there is chelation and form fine particles, on microgranule, superfluous negative charge makes to there is electrostatic between chelating body
Repulsion, is allowed to be unable to coagulation, so as to cause clearance to reduce.So the optimal coagulant dose of composite flocculation agent is 15g～20g.
In this process of the test, the organic cod of residual is less than 1.3mg/L, and the clearance of Organic substance is more than 99%.
The impact of time heavy metal ion remaval rate：
In pH=6.1, in the mine tailing wastewater of 10L the composite flocculation agent of 20g is added to carry out flocculating experiment, be spaced (5min,
10min, 20min, 30min, 60min, 90min, 120min, 150min, 180min, 240min) sampling, with fire after flocculation sediment
The concentration of each ion in flame atomic absorption measuring solution.As a result it is as shown in Figure 6.As a result show, within 125min, with suction
The increase of attached time, the clearance of each ion gradually increase, Cu2+In 90min, clearance is maximum, Pb2+、Cd2+、Cr6+Ion
Clearance reach maximum in 120min.After 125min, each ion remaval rate is declined slightly, it may be possible to ion concentration
Reduce, cause ionic strength to change, cause the functional group on composite flocculation agent macromolecular chain that dissociation occurs.Comprehensive four kinds from
The removal situation of son, preferred adsorption time are 90min～120min.
In this process of the test, the organic cod of residual is less than 1.3mg/L, and the clearance of Organic substance is more than 99%.
The stability of metal ion and recovery in flco residue：
According to upper two groups of experimental results, optimal coagulant dose 20g and optimal adsorption time 120min is taken, to 100L mine tailing wastewaters
Flocculated, separated with Magnet after flocculating sedimentation, filtered, drying is weighed, and is soaked with 100L deionized waters, is spaced one section
Timing supernatant intermediate ion concentration, calculates each ion leaching rate, as a result such as table 2.
2 flco residue intermediate ion leaching rate testing result of table
As a result show, in the deionized water immersion process of 15 days, each metal ion only has minimal amount of dissolution, shows wadding
The residue stability of solidifying agent is higher, and Stability of Chelate is good, is not likely to produce secondary pollution, this is because polymer composite flocculant
In mercapto functional group atomic radius it is larger, electronegativity is little, easy polarization deformation produces more stable covalent type compound, while sulfur
Atom forms four-membered ring chelate with metal ion, and steric configuration tension force is little, also so that Stability of Chelate is good.
Optimal coagulant dose 20g and optimal adsorption time 120min is taken, 100L mine tailing wastewaters is flocculated, after flocculating sedimentation
Separated with Magnet, filtered, drying is weighed, uses 50L soak with hydrochloric acid, determined supernatant intermediate ion concentration at set intervals,
Leaching rate is calculated, as a result as shown in table 3.
3 flco residue intermediate ion of table reclaims result
As a result show, after with acid soak 15 days, the dissolution rate of each ion is all higher, wherein the leaching rate to Cu2+
Reach as high as 69.1%, it can be seen that the metal ion in the residue of composite flocculation agent effectively can be reclaimed.
The Magneto separate effect of flco residue and waste water：
Optimal coagulant dose 20g and optimal adsorption time 120min is taken, two groups of 100L mine tailing wastewaters is flocculated, is adopted respectively
Take standing separation and Magnet draws separate mode, determine Cu in supernatant at set intervals2+Ion concentration, as a result such as 4 institute of table
Show.
The Magneto separate effect of 4 flco residue of table and waste water
As a result show, when Magneto separate mode carries out settling of floccus lock out operation, in magnetic suck 60s, flco is just complete
When separating with clear liquid, and taking standing mode to carry out flco free settling, when 10min is stood, flco has not still been settled
Entirely, its supernatant intermediate ion concentration remaining is larger.As can be seen here, experiment prepares the magnetic point of the Ferrite-CMC-MAPEI of gained
Fast, the efficiency high from speed, can effectively reduce overall flocculation time, improve the efficiency of wastewater treatment, can more effectively process low
Concentration heavy metal and Organic substance compound wastewater.
Claims (10)
1. a kind of preparation method of composite flocculation agent, it is characterised in that the method is comprised the following steps：
Step one, the nitrate solution of hybrid metal ion is added in preheating sodium hydroxide solution, precipitant is made, pH is adjusted
It is worth to 10.5, stands, uses distilled water cyclic washing, sucking filtration to be dried to constant weight in vacuum drying oven, you can obtain magnesium copper zinc-iron
Oxysome；
The nitrate solution of described hybrid metal ion is the mixed nitrate of magnesium ion, copper ion, zinc ion and iron ion
Solution；
Step 2, magnesium copper zinc ferrite and distilled water is mixed, ultrasonic disperse 20min, adjusts pH to 6, then the carboxylic that Deca is excessive
Methylcellulose sodium water solution, stops ultrasound after taking constant speed mechanical agitation 30min, continue while ultrasonic vibration at room temperature
Constant speed mechanical agitation 10min, generates magnesium copper zinc ferrite-carboxymethyl cellulose, magnesium copper zinc ferrite-carboxymethyl is fine with Magnet
Dimension element is separated from system, and distilled water wash is standby after mixing；
Step 3, with polyethyleneimine as parent, under conditions of polypeptide reagent is initiator, adds excessive TGA,
Amidation process is carried out, pH=1.0～3.0, stirring reaction 12h at 30 DEG C～50 DEG C is adjusted, you can mercaptoacetyl is obtained and is gathered
Aziridine；
Described polypeptide reagent is 1- ethyls-(3- dimethylaminopropyls) carbodiimide hydrochloride；
Step 4, adds excessive mercaptoacetyl aq. polyethyleneimine in magnesium copper zinc ferrite-carboxymethyl cellulose, surpasses
While acoustic shock is swung adopt mechanical agitation 30min, afterwards stop ultrasound, at room temperature continue mechanical agitation 10min after, dropwise plus
Enter excessive glutaraldehyde water solution, using ultrasound is stopped after mechanical agitation 30min while acoustic shock is swung, continue machinery at room temperature
After stirring 10min, product is separated from system with Magnet, and use distilled water cyclic washing, after being washed till neutrality, use anhydrous second again
Alcohol is washed, and is dried to constant weight, is obtained final product yellow-brown solid, as composite flocculation agent.
2. preparation method as claimed in claim 1, it is characterised in that in step one, the nitric acid of described hybrid metal ion
Mol ratio in saline solution between magnesium ion, copper ion, zinc ion and iron ion is 1：1：1：1；
The nitrate solution of described hybrid metal ion is 0.5 with the total moles ratio of sodium hydroxide：2；
Described preheating temperature is 50 DEG C.
3. preparation method as claimed in claim 1, it is characterised in that in step 2, described sodium carboxymethyl cellulose is water-soluble
The concentration of liquid is 5g/L.
4. preparation method as claimed in claim 1, it is characterised in that in step 3, polyethyleneimine, TGA and polypeptide
Mol ratio between reagent is 1:(1～3):(0.1～0.3).
5. preparation method as claimed in claim 1, it is characterised in that in step 4, described mercaptoacetyl polyethyleneimine
The mass concentration of aqueous solution is 10%.
6. a kind of processing method of the mine tailing wastewater of Organic substance containing heavy metal, it is characterised in that the method using as claim 1 to
Composite flocculation agent obtained in preparation method described in 5 any claims is processed to the mine tailing wastewater of Organic substance containing heavy metal.
7. processing method as claimed in claim 6, it is characterised in that in the described mine tailing wastewater of Organic substance containing heavy metal,
Total concentration≤the 200mg/L of heavy metal particles, the COD≤200mg/L of Organic substance.
8. processing method as claimed in claim 7, it is characterised in that in the described mine tailing wastewater of Organic substance containing heavy metal,
Heavy metal ion Pb2+、Cu2+、Cd2+And Cr6+Total concentration be 40.169mg/L, the COD of Organic substance is 132.4mg/L.
9. processing method as claimed in claim 8, it is characterised in that the detailed process of described processing method is：Containing a huge sum of money
Category Organic substance mine tailing wastewater concrete processing procedure be：The pH=6.1 of the mine tailing wastewater of Organic substance containing heavy metal is adjusted, to containing a huge sum of money
Composite flocculation agent is added in category Organic substance mine tailing wastewater to be processed；
The mine tailing wastewater of Organic substance containing heavy metal correspondence per 10L adds the composite flocculation agent of 5g～30g.
10. processing method as claimed in claim 9, it is characterised in that the mine tailing wastewater pair of Organic substance containing heavy metal per 10L
The composite flocculation agent of 15g～20g should be added, adsorption time is 90min～120min.Specific test effect is as described below.
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Application publication date: 20170329 |