CN101570377A - Processing method of waste water containing heavy metal and dye - Google Patents
Processing method of waste water containing heavy metal and dye Download PDFInfo
- Publication number
- CN101570377A CN101570377A CNA2008100668915A CN200810066891A CN101570377A CN 101570377 A CN101570377 A CN 101570377A CN A2008100668915 A CNA2008100668915 A CN A2008100668915A CN 200810066891 A CN200810066891 A CN 200810066891A CN 101570377 A CN101570377 A CN 101570377A
- Authority
- CN
- China
- Prior art keywords
- waste water
- dyestuff
- heavy metal
- sorbent material
- treatment process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a processing method of waste water containing heavy metal and dye. In the method, a sorbent is utilized to process the waste water containing heavy metal and dye, and the sorbent contains ferroferric oxide micro-magnetic particles and laccase. The laccase is hydroquinone dioxygen oxidoreductase containing copper, and the class number is EC 1.10.3.2. The ferroferric oxide micro-magnetic particles and the lasscase are in cross-linkage combination through assistance of a cross linkage agent. Heavy metal and dye in the waste water can be fast adsorbed and recovered with high efficiency by the ferroferric oxide micro-magnetic particles and the laccase, thereby the waste water containing heavy metal and dye is effectively processed, and the environment is protected.
Description
[technical field]
The present invention relates to field of waste water treatment, especially about a kind of treatment process that contains heavy metal and waste water from dyestuff.
[background technology]
Heavy metal is a kind of harmful material, particularly cadmium, sexavalent chrome, and heavy metal toxicities such as mercury are bigger, can cause direct injury to human body.Particularly the threat of water resources is serious day by day to environment from the heavy metal wastewater thereby of Electroplate Factory and circuit board plant, and has become global environment problem.Therefore administer heavy metal wastewater thereby and more and more attracted attention by the whole world, various countries drop into a large amount of manpower and materials for this reason and carry out extensive studies, and obtain certain achievement in research and patent of invention.Up to the present, be used to administer the method for heavy metal wastewater thereby mainly based on chemical precipitation method, the chemical precipitation ratio juris is to make the heavy metal that is dissolved state in the waste water change water-fast heavy metal compound into by chemical reaction, with separating throw out is removed by filtering from the aqueous solution, comprised neutralization precipitation method, sulphide precipitation, ferrite coprecipitation method.Though chemical method is the most general technology of using at present, owing to be subjected to the influence of precipitation agent and envrionment conditions, the precipitator method often go out water concentration and do not reach requirement, need be for further processing, and the throw out of generation must be handled and dispose well, otherwise can cause secondary pollution.In addition, handle the waste residue that is produced in the heavy metal wastewater thereby with chemical precipitation method and contain a large amount of heavy metals, these heavy metals must reclaim, otherwise can cause severe contamination to environment.And from waste residue, reclaim the heavy metal technical sophistication, and can not carry out at the scene, the department or the business unit that must transport to statutory regulation recycle, and transportation and tooling cost are all very high, and are difficult to reclaim thoroughly.Except that chemical precipitation method, also has some other technology sequential use in heavy metal containing wastewater treatment, these comprise: electrolytic process, physisorphtion, ion exchange method, membrane separation process comprise that liquid membrane separates, electrodialysis and diaphragm electrolysis, though these technology all have certain advantage separately to handling chromium metal waste water, but still there are shortcomings such as the too high or reliability of cost is not enough.Membrane separation process has bigger potentiality and application prospect but must overcome the too high resistance that brings of cost in these technology.
Except heavy metal wastewater thereby, also be an important source to pollution of waterhead from the dyeing waste water of dyeing.The dyeing waste water not only water yield is big, and the colourity height, and complicated component also contains slurry, auxiliary agent, acid, alkali, heavy metal and inorganic salt etc. except residual dye; And heavy metal elements such as amino-complex in this body structure of dyestuff and copper, chromium, zinc, arsenic have bigger toxicity.In addition, dyeing waste water pollutes the toxic substance that contains bio-refractories such as aromatic halide, aromatic nitro compound, biphenyl in the organism, and it is very harmful to enter water body.Because the complicated component of dyeing waste water, intractability is big, and treatment of dyeing wastewater faces various technical barriers always for many years.What treatment of dyeing wastewater was the most frequently used at present is the coagulation decoloration method, and its process is to close reaction by residual dye generation complexing in flocculation agent and the waste water or huge legendary turtle to form precipitation, thereby removes dyestuff.The shortcoming of Coagulation Method is, decolouring and COD remove not thorough, produce a large amount of mud, easily cause secondary pollution, facility takes up an area of big simultaneously, technology is consuming time longer, and other various technology are also attempted in the wastewater of dyeing and printing industry treatment project in succession or used, comprising the physical adsorption decoloring method, the oxidative decoloration method, ion-exchange decolouring, technology such as membrane sepn decolouring and biochemical decolouring, these technology or undesirable or all do not obtain widespread use because of cost is too high because of effect.A kind of synthetic macromolecular cpd that is called as cucurbit urea (cucurbituril) of the external report beginning of this century can be used as the regenerable sorbent of dyestuff contaminant, this sorbent material is to regenerate by the oxidizing reaction that ozone participates in, it should be the ideal sorbent material, but because application surface is narrow, only effective to reactive dyestuffs, simultaneously cost is too high, so far large-scale application not as yet.
[summary of the invention]
Technical problem to be solved by this invention is, overcomes the deficiencies in the prior art, provide a kind of rapidly and efficiently, nontoxic, cost is low and the treatment process that contains heavy metal and waste water from dyestuff of applied range.
The technical solution adopted for the present invention to solve the technical problems is: a kind of treatment process that contains heavy metal and waste water from dyestuff, and utilize a kind of sorbent treatment to contain heavy metal and waste water from dyestuff, this sorbent material contains ferroferric oxide micro-magnetic grain and laccase.
Described laccase is a kind of copper bearing to diphenol dioxy oxydo-reductase, and classification number is EC1.10.3.2.
Described ferroferric oxide micro-magnetic grain and described laccase are to assist to take place crosslinked bonded by a kind of linking agent.
Described linking agent is a glutaraldehyde, and its molecular formula is C
5H
8O
2
Described sorbent material is to reach capacity by the substep dilatation to the absorption of hexavalent chromium.
The method of adsorbing hexavalent chromium ions comprises the steps:
A), under waste water meta-acid condition, add described sorbent material;
B), normal temperature stirs down;
C), post precipitation, filter or magnet absorption makes solid-liquid separation, the solid material of collection is used further to adsorbing hexavalent chromium ions behind the sorbent material dilation process;
D), under the situation of wash-out metal ion not, repetitive operation at least twice.
In the described a) step, the pH value scope of described waste water is 1.5～6.0; Described b) in the step, normal temperature stirred two minutes down; Described d) in the step, under the situation of wash-out metal ion not, repetitive operation ten times.
The dilation process of described sorbent material is realized by replenishing ferrous iron.
Described ferrous iron is a ferrous salt.
Described ferrous salt is an iron protochloride, and the method for replenishing described iron protochloride is, is that 25% solution of ferrous chloride adds and adsorbed in the hygrometric state sorbent material that contains chromium ion also thorough mixing by 1: 10 ratio with concentration.
Described treatment process comprises absorption and reclaims, the heavy metal ion of this absorption includes copper, nickel and other metal ion, the method of absorbing copper, nickel or other metal ion is, pH value with metallic cation waste water such as cupric, nickel transfers to more than 8 earlier, add an amount of described sorbent material, normal temperature stirred 2 minutes down, and by precipitation, filtration or magnet absorption make solid-liquid separation; The dyestuff of this absorption includes acidity, alkalescence, substantive dyestuff and other dyestuff, absorption is acid, the method of alkalescence, substantive dyestuff or other dyestuff is, pH value with waste water containing dye transfers to 6～7 earlier, add an amount of described sorbent material, normal temperature stirred 2 minutes down, and by precipitation, filtration or magnet absorption make solid-liquid separation.
The approach of the heavy metal of described recovery is to pass through elution process, the method of this wash-out is, by 0.2 times of volume concentrated nitric acid is added in the hygrometric state sorbent material of adsorbing metal ions and mixes, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration, belong to the ionic trace with 0.2 equivalent concentration dilute nitric acid solution washing sorbent material to the acomia cash of 1: 1 volume; The approach of the dyestuff of described recovery is to pass through elution process, the method of this wash-out is, in 1: 1.5 ratio the 0.2M sodium hydroxide solution is added in the hygrometric state sorbent material of absorbing dye and mixes, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration, with the 50mM sodium hydroxide washing of 1: 1 volume till do not have a color.
The invention has the beneficial effects as follows: by ferroferric oxide micro-magnetic grain and laccase in can absorption waste water rapidly and efficiently heavy metal and dyestuff and it is reclaimed, thereby handled the waste water that contains heavy metal and dyestuff effectively, protected environment.
[description of drawings]
Fig. 1 is the dynamic adsorption amount synoptic diagram of the present invention to three kinds of different heavy metal ion;
Fig. 2 is the variation synoptic diagram of the present invention to accumulative total adsorptive capacity in 10 continuous adsorption of hexavalent chromium.
[embodiment]
As depicted in figs. 1 and 2, a kind of treatment process that contains heavy metal and waste water from dyestuff of the present invention, utilize a kind of novel sorbent material to handle and contained heavy metal and waste water from dyestuff, this sorbent material contains ferroferric oxide micro-magnetic grain and laccase, described laccase is a kind of copper bearing to diphenol dioxy oxydo-reductase, and classification number is EC 1.10.3.2; Ferroferric oxide micro-magnetic grain in the sorbent material and laccase are to be C by a kind of molecular formula
5H
8O
2, name is called the linking agent of glutaraldehyde and assists to take place crosslinked bonded.
This sorbent material reaches capacity by the substep dilatation to the absorption of hexavalent chromium, the method of adsorbing hexavalent chromium ions comprises the steps: a), under waste water meta-acid condition, the pH value scope that is waste water is under 1.5～6.0 the condition, to add described sorbent material; B), normal temperature stirred general two minutes down; C), by precipitation, filter or magnet absorption makes solid-liquid separation, the solid material of collection is used further to adsorbing hexavalent chromium ions (Cr behind the sorbent material dilation process
6+); D), under the situation of wash-out metal ion not, possible repetitive operation ten times.
The dilation process of this sorbent material is realized by replenishing ferrous iron, ferrous iron can be iron protochloride or other ferrous salts, the method of replenishing iron protochloride is, is that 25% solution of ferrous chloride adds and adsorbed in the hygrometric state sorbent material that contains chromium ion also thorough mixing by 1: 10 ratio with concentration.
This sorbent material may be used to adsorb each metal ion species and dyestuff, thereby may be used to contain the processing of heavy metal or waste water containing dye, also may be used for the recovery of heavy metal and dyestuff, and described sorbent material also may be used for the recovery of other wastewater treatment and pollutent.The method of this sorbent treatment waste water comprises absorption and reclaims that the approach of recovery is to pass through elution process.
The heavy metal ion of absorption includes copper, nickel and metal ion, the method of absorbing copper, nickel or other metallic cation is, pH value with metallic cation waste water such as cupric, nickel transfers to more than 8 earlier, add an amount of described sorbent material, normal temperature stirred 2 minutes down, by precipitation, filtration or magnet absorption make solid-liquid separation; The method of this wash-out is, by 0.2 times of volume concentrated nitric acid is added in the hygrometric state sorbent material of adsorbing metal ions and mixes, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration, belong to the ionic trace with 0.2 equivalent concentration dilute nitric acid solution washing sorbent material to the acomia cash of 1: 1 volume.
The dyestuff of absorption includes acidity, alkalescence, substantive dyestuff and other dyestuff, absorption is acid, the method of alkalescence, substantive dyestuff or other dyestuff is, pH value with waste water containing dye transfers to 6～7 earlier, add an amount of described sorbent material, normal temperature stirred 2 minutes down, and by precipitation, filtration or magnet absorption make solid-liquid separation; The method of this wash-out is, in 1: 1.5 ratio the 0.2M sodium hydroxide solution is added in the hygrometric state sorbent material of absorbing dye and mixes, at room temperature reacted 20 minutes, and made its solid-liquid separation by vacuum filtration, with the 50mM sodium hydroxide washing of 1: 1 volume till do not have a color.
Can adopt application number about the manufacture method of ferroferric oxide micro-magnetic grain and process is the Chinese patent of 200710075261.X, also can use the produced ferroferric oxide micro-magnetic grain of additive method; Can adopt application number about the manufacture method of laccase (EC 1.10.3.2) and process is the Chinese patent of 200710076988.X, also can use the produced laccase of additive method (EC1.10.3.2).The present invention is the effect by the glutaraldehyde cross-linking agent, and laccase (EC 1.10.3.2) is linked to little magnetic grain surface, allows its curing, forms a kind of composite structure.Laccase (EC 1.10.3.2) has the feature of polyphenol oxidase reductase enzyme, under certain condition can the catalysis phenols or the redox reaction of non-phenolic compound, can also play the electron transport effect, and itself various ions or ionic group are had adsorption simultaneously.Formed complex body still has the feature of magnetic.The present invention is high-efficiency adsorbents of a kind of contaminated wastewater thing through a series of novel materials of being made up of ferroferric oxide micro-magnetic grain and laccase that experiment showed,, can not only be used for the waste water decontamination, can also be used for the recovery of valuable waste material.
The present invention is adsorbed various heavy metal ion by a kind of sorbent material in waste water solution, comprise sexavalent chrome, copper, nickel etc., and dyestuff.By elution process heavy metal ion and the dyestuff that is adsorbed reclaimed again.Specifically, adsorption process is exactly that described sorbent material forms a kind of water-fast complex body with the heavy metal ion and the dyestuff that are dissolved in the water; Elution process is exactly that the heavy metal ion and the dyestuff that are adsorbed are peeled away from adsorbent surface, and is soluble in water again, and sorbent material still keeps insoluble state, thereby respectively with the two separation, reclaims heavy metal ion and dyestuff.
This sorbent material is that the capacity that described adsorbents adsorb contains chromium ion is to replenish ferrous iron by substep, thereby makes the sorbent material activation that its loading capacity is progressively increased, up to saturated to the absorption that contains hexavalent chromium and the key problem in technology of recovery; Again by acid treatment separate sorbent and the chromium ion that contains that is adsorbed.Strictly speaking, this sorbent material will just can reach the state of saturation to chromium ion absorption through 9 dilatations.
The ferrous iron that the reactivation process of this sorbent material is added refers to iron protochloride (FeCl
2), also can be other divalent iron salt.Replenish ferrous process and be meant, press ratio iron protochloride (FeCl
2) the hygrometric state sorbent material (water content is about 75%) that contains chromium ion that adsorbs of solution and recovery mixes and can use; Specifically, be that 25% solution of ferrous chloride adds and adsorbed in the hygrometric state sorbent material that contains chromium ion and thorough mixing gets final product in 1: 10 ratio with concentration exactly.
This sorbent material should carry out under the meta-acid condition the adsorption process of chromium ion; Specifically, the pH value of aqueous solution scope that requires to contain heavy metal chromium is 1.5～6.0, generally contain chromium electroplating wastewater all in this scope, so needn't adjust; Refer to by acid treatment separate sorbent and the chromium ion that contains that is adsorbed, with concentrated nitric acid (HNO
3) handle and adsorbed the sorbent material that contains chromium ion, thereby being dissolved in again, chromium ion reaches isolating purpose in the water.This process is defined as elution process, specifically, is exactly with concentrated nitric acid (HNO by 0.2 times of volume
3) be added to and adsorb in the hygrometric state sorbent material that contains chromium ion and mix, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration again, with the 0.2 equivalent concentration dilute nitric acid solution washing sorbent material of 1: 1 volume to there not being the trace of finding chromium ion.
This sorbent material is different from containing the absorption of hexavalent chromium the absorption of copper, nickel metallic cation.The former does not need the substep dilatation, but settle the state of reaching capacity at one go, and copper, the disposable absorption of nickel metallic cation reached capacity the loading capacity of state much larger than to the loading capacity of chromium ion under same state, 989 milligrams/gram of the former difference and 1080 milligrams/gram, and the latter only is 95 milligrams.Yet the loading capacity to copper, nickel to the loading capacity of chromium and the disposable state that reaches capacity through dilatation progressively and when reaching final state of saturation is suitable substantially.Adsorption process to copper, nickel metallic cation should carried out under the alkali condition partially, and specifically, the pH value scope that requires cupric, nickel waste water solution is more than 8.The electroplating wastewater of general cupric, nickel metal all is lower than this scope, must be adjusted to suitable scope before absorption.The method of separating the copper be adsorbed, nickel metallic cation is the same with the separating metal chromium ion, by concentrated nitric acid solution its wash-out is finished; Be exactly with concentrated nitric acid (HNO by 0.2 times of volume
3) be added in the hygrometric state sorbent material of adsorbing metal ions and mix, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration, belong to the ionic trace with 0.2 equivalent concentration dilute nitric acid solution washing sorbent material to the acomia cash of 1: 1 volume.
This adsorbents adsorb dyestuff refers to, to matching stain, the absorption of three class dyestuffs such as basic dyestuff and substantive dyestuff, specifically, just be meant following 6 kinds of dyestuffs: Basic Violet 5BN, Acid Red B G (red 37), alkalescent light green (green 4), Acid Light Yellow G (yellow 11), alkali blue B (blue 5), direct black BN (black 38).
This sorbent material is to the absorption of dyestuff, and its process does not have big difference with absorption to heavy metal, and different is to the absorption of dyestuff is to carry out under the nearly neutrallty condition of pH value; Carry out in the scope of pH value 6～7 exactly.To similar to the adsorpting characteristic of copper, nickel metallic cation; This sorbent material also is the disposable state that reaches capacity to the absorption of dyestuff, and the loading capacity of its state of saturation is 86～95 a milligrams/gram.
This sorbent material is different with the wash-out of metal ion to the wash-out of the dyestuff that is adsorbed, and the former is by the concentrated acid wash-out, and the latter is by the dilute alkaline soln wash-out; Specifically, 0.2M sodium hydroxide (NaOH) solution is added in the hygrometric state sorbent material of absorbing dye in 1: 1.5 ratio exactly and mixes, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration, with 50mM sodium hydroxide (NaOH) washing of 1: 1 volume till do not have a color.The rate of adsorption of this sorbent material is very fast, no matter is to each heavy metal species or to dyestuff, the adsorption process state that all reached capacity in 2 minutes.
By elution process, heavy metal or dyestuff can be reclaimed, simultaneously sorbent material is reclaimed.Sorbent material can be reused after reclaiming.
The principle of work of explaining little magnetic grain-laccase sorbent material needs certain theoretical support.The present invention proposes two kinds of possible theoretical patterns:
One, redox complex body pattern: be exactly the ferrous iron (Fe in the contained Z 250 magnet of sorbent material
2+) be free on ion or ionic group generation redox reaction in the aqueous solution, form complex body and be fixed on adsorbent surface.To containing sexavalent chrome (Cr
2O
7 2-) ionic absorption meets this pattern.Ferrous iron (Fe in the redox reaction process
2+) be sexavalent chrome (Cr
2O
7 2-) electronics is provided and makes it be reduced to trivalent chromium (CrO
2 -), and form the ferrochrome complex compound.Laccase may play the electron transport effect in this process, thereby has quickened this process.Ferrous iron (Fe in little magnetic grain
2+) after the useful space taken, sorbent material reached interim state of saturation.In this state, the adsorption function that recover sorbent material must allow Z 250 (Fe
3O
4) little magnetic grain provides more ferrous iron (Fe
2+).By directly replenishing ferrous iron (Fe
2+) and achieve the goal, process is simplified greatly, and shortens the time greatly.
Two, ion-catching pattern: by the active group in electrostatic attraction and the sorbent material ion or the ionic group that are free in the aqueous solution are caught exactly.Absorption to copper, nickel metallic cation and dyestuff may meet this pattern.Sorbent material may form powerful electrostatic field and can effectively catch ion under the certain pH value condition.Described chemical group refer to contain can with the chemical group of the chemical bond of ionic bond, as contain-the O key ,-group of chemical bonds such as H key, polyphenoloxidase comprises laccase, contains a large amount of active groups that can catch ion or ionic group in the biological enzyme molecules such as manganese enzyme and peroxidase.
The invention has the beneficial effects as follows that this new sorbent material can adsorb in the waste water deleterious heavy metal ion or dyestuff and effectively with its recovery, thereby can handle waste water effectively, the protection environment increases economic benefit simultaneously.
For beneficial effect of the present invention is described, done following experiment:
Testing used little magnetic grain-laccase sorbent material is to be made by following method: containing 0.5 mole of iron(ic) chloride (FeCl
3) and iron protochloride (FeCl
2) 1 liter of solution (pH=2) in, add the sodium hydroxide that concentration is 1 mol (NaOH) while stirring lentamente and rise to 7.5 until the pH value.At this moment all iron(ic) chloride (FeCl
3) and iron protochloride (FeCl
2) all be converted into the Z 250 (Fe that does not allow and be black basically
3O
4) particulate.By the action of a magnetic field by Z 250 (Fe
3O
4) little magnetic grain precipitates rapidly, remove supernatant liquor after, the pH value is transferred to 6.0, adding 20 milliliters of units activity is 2,000IU/ milliliter laccase enzyme liquid, and the back that stirs adds 100 milliliter of 2.5% glutaraldehyde, under the room temperature, handled 2 hours in slowly stirring, collect by vacuum filtration at last.
Table 1: handle after 5 minutes sorbent material to the sexavalent chrome (Cr of three kinds of different concns
6+), copper, the isoionic adsorptive capacity * of nickel
* data are the mean number of three repeated experiments in the table
As shown in Table 1, prove by experiment that this sorbent material can be finished each heavy metal species of absorption and various dyestuff composition respectively in 2 minutes.The disposable maximum capacity of every gram over dry sorbent material can adsorb 95 milligrams of chromium respectively, 989 milligrams of copper, 1080 milligrams in nickel.
The yield and the rate of recovery of table 2 metals such as chromium, copper, nickel after wash-out is handled
The experiment of experiment 4, usefulness sorbent treatment waste water containing dye, carry out as follows: from the following waste water from dyestuff that contains 250 mg/litre respectively: Basic Violet 5BN, Acid Red B G (red 37), alkalescent light green (green 4), Acid Light Yellow G (yellow 11), alkali blue B (blue 5), direct black BN (black 38), getting 500 milliliters, to pour capacity into be in 1000 ml beakers, the pH value is transferred to 6～7, adding over dry heavily is 1 gram sorbent material, and normal temperature stirred 2 minutes down.Sampling is once handled after 2 minutes when handling 1 minute, and a fast magnet is placed under the beaker, is all inhaled toward beaker bottom after when solid material, pours out supernatant liquor, and the detection dyestuff content of taking a sample, and it is for referencial use to detect the sample of taking a sample in 1 minute simultaneously.Calculate adsorptive capacity with the content difference of measuring dyestuff in the next absorption front and back waste water.Then carry out wash-out with the solid material of staying beaker bottom.The step of dyestuff wash-out is, in 1: 1.5 ratio 0.2M sodium hydroxide (NaOH) solution is added in the hygrometric state sorbent material of absorbing dye and mixes, at room temperature stirred 20 minutes, make its solid-liquid separation by vacuum filtration, with 50mM sodium hydroxide (NaOH) washing of 1: 1 volume till do not have a color.Table 3 result displayed shows that with described adsorbents adsorb matching stain, basic dyestuff and substantive dyestuff are effectively, the adsorptive capacity of six kinds of dyestuffs are distributed in the scope of 86～95 milligrams/gram.1 minute adsorptive capacity illustrates when being adsorbed on 1 minute near saturated very near 2 minutes adsorptive capacity.The dyestuff of the overwhelming majority can reclaim behind wash-out, and the rate of recovery is all greater than 95%.
Table 3 sorbent material is to the adsorptive capacity of six kinds of different dyes
In table 4 pilot experiment through the detected result of sorbent treatment rear section water sample
Pilot-scale experiment shows can the disposable discharging standards that reaches to the processing from the heavy metal wastewater thereby of Electroplate Factory.Heavy metal that is adsorbed and dyestuff be effectively wash-out recovery all, and eluting rate reaches 96～99%, and behind the wash-out absorbate, sorbent material can be reused, and effect is constant.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (11)
1. treatment process that contains heavy metal and waste water from dyestuff, it is characterized in that: utilize a kind of sorbent treatment to contain heavy metal and waste water from dyestuff, this sorbent material contains ferroferric oxide micro-magnetic grain and laccase.
2. the treatment process that contains heavy metal and waste water from dyestuff according to claim 1 is characterized in that: described laccase is a kind of copper bearing to diphenol dioxy oxydo-reductase, and classification number is EC1.10.3.2.
3. the treatment process that contains heavy metal and waste water from dyestuff according to claim 1, it is characterized in that: described ferroferric oxide micro-magnetic grain and described laccase are to assist to take place crosslinked bonded by a kind of linking agent, described linking agent is a glutaraldehyde, and its molecular formula is C
5H
8O
2
4. the treatment process that contains heavy metal and waste water from dyestuff according to claim 1 is characterized in that: described sorbent material is to reach capacity by the substep dilatation to the absorption of hexavalent chromium.
5. the treatment process that contains heavy metal and waste water from dyestuff according to claim 4 is characterized in that: the method for adsorbing hexavalent chromium ions comprises the steps:
A), under waste water meta-acid condition, add described sorbent material;
B), normal temperature stirs down;
C), post precipitation, filter or magnet absorption makes solid-liquid separation, the solid material of collection is used further to adsorbing hexavalent chromium ions behind the sorbent material dilation process;
D), under the situation of wash-out metal ion not, repetitive operation at least twice.
6. the treatment process that contains heavy metal and waste water from dyestuff according to claim 5 is characterized in that: in the described a) step, the pH value scope of described waste water is 1.5～6.0; Described b) in the step, normal temperature stirred two minutes down; Described d) in the step, under the situation of wash-out metal ion not, repetitive operation ten times.
7. according to each described treatment process that contains heavy metal and waste water from dyestuff in the claim 4～6, it is characterized in that: the dilation process of described sorbent material is realized by replenishing ferrous iron.
8. the treatment process of heavy metal according to claim 7 and waste water from dyestuff is characterized in that: described ferrous iron is a ferrous salt.
9. the treatment process of heavy metal according to claim 8 and waste water from dyestuff, it is characterized in that: described ferrous salt is an iron protochloride, the method of replenishing described iron protochloride is, is that 25% solution of ferrous chloride adds and adsorbed in the hygrometric state sorbent material that contains chromium ion also thorough mixing by 1: 10 ratio with concentration.
10. according to the treatment process of each described heavy metal and waste water from dyestuff in the claim 1～3, it is characterized in that: described treatment process comprises absorption and reclaims, the heavy metal ion of this absorption includes copper, nickel and other metal ion, the method of absorbing copper, nickel or other metal ion is, pH value with metallic cation waste water such as cupric, nickel transfers to more than 8 earlier, adds an amount of described sorbent material, and normal temperature stirred 2 minutes down, by precipitation, filtration or magnet absorption make solid-liquid separation; The dyestuff of this absorption includes acidity, alkalescence, substantive dyestuff and other dyestuff, absorption is acid, the method of alkalescence, substantive dyestuff or other dyestuff is, pH value with waste water containing dye transfers to 6～7 earlier, add an amount of described sorbent material, normal temperature stirred 2 minutes down, and by precipitation, filtration or magnet absorption make solid-liquid separation.
11. the treatment process of heavy metal according to claim 10 and waste water from dyestuff, it is characterized in that: the approach of the heavy metal of described recovery is to pass through elution process, the method of this wash-out is, by 0.2 times of volume concentrated nitric acid is added in the hygrometric state sorbent material of adsorbing metal ions and mixes, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration, belong to the ionic trace with 0.2 equivalent concentration dilute nitric acid solution washing sorbent material to the acomia cash of 1: 1 volume; The approach of the dyestuff of described recovery is to pass through elution process, the method of this wash-out is, in 1: 1.5 ratio the 0.2M sodium hydroxide solution is added in the hygrometric state sorbent material of absorbing dye and mixes, at room temperature reacted 20 minutes, make its solid-liquid separation by vacuum filtration, with the 50mM sodium hydroxide washing of 1: 1 volume till do not have a color.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100668915A CN101570377B (en) | 2008-04-29 | 2008-04-29 | Processing method of waste water containing heavy metal and dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100668915A CN101570377B (en) | 2008-04-29 | 2008-04-29 | Processing method of waste water containing heavy metal and dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101570377A true CN101570377A (en) | 2009-11-04 |
| CN101570377B CN101570377B (en) | 2011-09-21 |
Family
ID=41229881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100668915A Expired - Fee Related CN101570377B (en) | 2008-04-29 | 2008-04-29 | Processing method of waste water containing heavy metal and dye |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101570377B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817622A (en) * | 2010-04-29 | 2010-09-01 | 南京神克隆科技有限公司 | Ozone pre-oxidation and laccase advanced water treatment method |
| CN102078840A (en) * | 2010-11-24 | 2011-06-01 | 深圳市港艺金塑胶有限公司 | Liquid-slag separation device, metal ion waste liquid treatment system and using method thereof |
| CN102548910A (en) * | 2009-10-16 | 2012-07-04 | 株式会社御牧工程 | Waste water cleaning system, washing device, and ink jet printer system |
| CN102728602A (en) * | 2011-03-29 | 2012-10-17 | 栗田工业株式会社 | Processing method of solid objects having heavy metal |
| CN103910429A (en) * | 2014-04-09 | 2014-07-09 | 厦门科霖达环保科技有限公司 | Preparation process of biological complex breaking agent for treating electroplating wastewater containing heavy metal complex |
| CN104370392A (en) * | 2014-12-03 | 2015-02-25 | 广州蓝涛水处理有限公司 | Treatment method for smelting waste water containing sulfuric acid and heavy metal |
| CN107352676A (en) * | 2017-07-04 | 2017-11-17 | 中国科学院生态环境研究中心 | The processing method of the waste water containing heavy-metal stain |
| CN107381926A (en) * | 2017-08-31 | 2017-11-24 | 广州大学 | A kind of purification of waste water containing thallium and the enriching and recovering method and its application of thallium element |
| CN107930605A (en) * | 2017-11-30 | 2018-04-20 | 重庆精创联合环保工程有限公司 | Adsorbent for electroplating wastewater adsorption treatment |
| CN107983312A (en) * | 2017-11-30 | 2018-05-04 | 重庆精创联合环保工程有限公司 | For removing the adsorbent composition of heavy metals in industrial wastewater ion |
| CN108061681A (en) * | 2017-12-25 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | The detection method of Manganese in Waste Water ion |
-
2008
- 2008-04-29 CN CN2008100668915A patent/CN101570377B/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102548910A (en) * | 2009-10-16 | 2012-07-04 | 株式会社御牧工程 | Waste water cleaning system, washing device, and ink jet printer system |
| CN101817622A (en) * | 2010-04-29 | 2010-09-01 | 南京神克隆科技有限公司 | Ozone pre-oxidation and laccase advanced water treatment method |
| CN102078840B (en) * | 2010-11-24 | 2013-04-10 | 深圳市港艺金塑胶有限公司 | Liquid-slag separation device, metal ion waste liquid treatment system and using method thereof |
| CN102078840A (en) * | 2010-11-24 | 2011-06-01 | 深圳市港艺金塑胶有限公司 | Liquid-slag separation device, metal ion waste liquid treatment system and using method thereof |
| WO2012068943A1 (en) * | 2010-11-24 | 2012-05-31 | 深圳市港艺金塑胶有限公司 | Liquid-slag separation device, metal ion waste liquid treatment system, and method of use thereof |
| CN102728602B (en) * | 2011-03-29 | 2015-10-14 | 栗田工业株式会社 | Containing the processing method of the solid of heavy metal |
| CN102728602A (en) * | 2011-03-29 | 2012-10-17 | 栗田工业株式会社 | Processing method of solid objects having heavy metal |
| CN103910429A (en) * | 2014-04-09 | 2014-07-09 | 厦门科霖达环保科技有限公司 | Preparation process of biological complex breaking agent for treating electroplating wastewater containing heavy metal complex |
| CN104370392A (en) * | 2014-12-03 | 2015-02-25 | 广州蓝涛水处理有限公司 | Treatment method for smelting waste water containing sulfuric acid and heavy metal |
| CN107352676A (en) * | 2017-07-04 | 2017-11-17 | 中国科学院生态环境研究中心 | The processing method of the waste water containing heavy-metal stain |
| CN107381926A (en) * | 2017-08-31 | 2017-11-24 | 广州大学 | A kind of purification of waste water containing thallium and the enriching and recovering method and its application of thallium element |
| CN107381926B (en) * | 2017-08-31 | 2020-09-18 | 广州大学 | Thallium-containing wastewater purification and thallium element enrichment recovery method and application thereof |
| CN107930605A (en) * | 2017-11-30 | 2018-04-20 | 重庆精创联合环保工程有限公司 | Adsorbent for electroplating wastewater adsorption treatment |
| CN107983312A (en) * | 2017-11-30 | 2018-05-04 | 重庆精创联合环保工程有限公司 | For removing the adsorbent composition of heavy metals in industrial wastewater ion |
| CN107983312B (en) * | 2017-11-30 | 2020-10-13 | 重庆精创联合环保工程有限公司 | Adsorbent composition for removing heavy metal ions in industrial wastewater |
| CN107930605B (en) * | 2017-11-30 | 2021-05-04 | 重庆精创联合环保工程有限公司 | Adsorbent for adsorption treatment of electroplating wastewater |
| CN108061681A (en) * | 2017-12-25 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | The detection method of Manganese in Waste Water ion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101570377B (en) | 2011-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101570377B (en) | Processing method of waste water containing heavy metal and dye | |
| CN102603097B (en) | Advanced treatment and recycling process for wastewater containing heavy metal ions | |
| CN101269871B (en) | Method for processing chrome wastewater | |
| CN101570372B (en) | Method for purifying electroplating wastewater and comprehensively utilizing resources | |
| CN101348297B (en) | Processing method for heavy metal ion-containing waste water | |
| CN103553249B (en) | In electroplating effluent, acid is separated and heavy metal collection method | |
| CN103043844A (en) | Method and device for removing heavy metals in industrial sewage by electromagnetic stirring paddle | |
| CN103482783A (en) | Treatment process for plumbic acid waste water generated in production process of lead storage batteries | |
| CN101734815A (en) | Electronic electroplating wastewater recycling advanced treatment technology | |
| CN108249623B (en) | Electroplating nickel-containing wastewater treatment process and system | |
| CN113307438A (en) | Treatment method of nickel-cobalt smelting heavy metal wastewater | |
| CN109516629A (en) | Electroplating wastewater zero treatment process | |
| CN108264164A (en) | A kind of nickel-containing wastewater treatment technology | |
| CN103754952A (en) | Preparation method and application of iron-based material for removing heavy metal in wastewater synchronously | |
| CN204803171U (en) | Electroplating wastewater treatment device | |
| CN111003853A (en) | Electroplating waste liquid treatment method | |
| CN101172688B (en) | Method for removing heavy metal in electroplating waste | |
| CN104150570B (en) | A kind of method extracting chromium from chrome waste liquid | |
| CN101444716B (en) | Heavy metal bioadsorbent and method for adsorbing heavy metal in electroplating wastewater by same | |
| CN108866337B (en) | A method of processing metal sludge | |
| CN108483760B (en) | Advanced treatment method for heavy metal sewage | |
| CN107768760A (en) | A kind of lithium resource and salt alkali reclaiming method | |
| Namasivayam et al. | Removal of lead (II) by adsorption onto" waste" iron (III)/chromium (III) hydroxide from aqueous solution and radiator manufacturing industry wastewater | |
| CN108585339A (en) | A kind of processing of chromate waste water and waste liqouor method | |
| CN111253004B (en) | Multi-group chelating type magnetic hypha water purifying agent circulating treatment process and treatment system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: MO SIYUAN Owner name: HE SUXIA Free format text: FORMER OWNER: BIO SCIENTIFIC (SHENZHEN) LIMITED Effective date: 20110609 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 518000 YONGXING BUILDING, NO. 222, BAOSHI EAST ROAD, SHUITIAN VILLAGE, SHIYAN TOWN, SHENZHEN CITY, GUANGDONG PROVINCE TO: 523000 13A, TOWER D, CUIJINGXUAN, FUMIN GARDEN, HUMEN TOWN, DONGGUAN CITY, GUANGDONG PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20110609 Address after: 523000 Guangdong province Dongguan city Humen town gate Fumin garden Cui Jingxuan block D 13A Applicant after: He Suxia Co-applicant after: Mo Siyuan Address before: 518000 Yongxing building, 222 precious stone road east, Shiyan Town, Shiyan City, Guangdong, Shenzhen Applicant before: Bio Scientific (Shenzhen) Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: GUANGZHOU LANTAO WATE TREATMENT CO., LTD. Free format text: FORMER OWNER: HE SUXIA Effective date: 20121025 Free format text: FORMER OWNER: MO SIYUAN Effective date: 20121025 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 523000 DONGGUAN, GUANGDONG PROVINCE TO: 510000 GUANGZHOU, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20121025 Address after: 510000 Guangdong city of Guangzhou province Panyu District Shiji Street Zhushan village Yiyuan Cui Bamboo Garden No. 51 Patentee after: GUANGZHOU LANTAO WATER TREATMENT CO., LTD. Address before: 523000 Guangdong province Dongguan city Humen town gate Fumin garden Cui Jingxuan block D 13A Patentee before: He Suxia Patentee before: Mo Siyuan |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110921 Termination date: 20180429 |