CN106698582A - Method for treating industrial wastewater containing heavy metal contaminants by utilizing industrial fly ash and nano iron - Google Patents
Method for treating industrial wastewater containing heavy metal contaminants by utilizing industrial fly ash and nano iron Download PDFInfo
- Publication number
- CN106698582A CN106698582A CN201710052212.8A CN201710052212A CN106698582A CN 106698582 A CN106698582 A CN 106698582A CN 201710052212 A CN201710052212 A CN 201710052212A CN 106698582 A CN106698582 A CN 106698582A
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- flyash
- industrial
- iron
- metal contaminants
- 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.)
- Pending
Links
Classifications
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
Abstract
The invention discloses a method for treating industrial waste water containing heavy metal contaminants by utilizing industrial fly ash and nano iron. The method comprises the following steps of: firstly, fully mixing industrial fly ash and a ferric chloride solution at room temperature; and secondly, dropwise adding sodium cyanoborohydride to the mixed solution to reduce trivalent iron ions to zero-valent nano iron, and loading onto fly ash particles to obtain a fly ash-nano iron composite material. The fly ash-nano iron composite material is added to the industrial wastewater containing heavy metal contaminants, and is treated and recovered at normal temperature. The precipitated supernatant can meet the relevant integrated wastewater discharge standards to be directly discharged, wherein the zero-valent nano iron accounts for 10% of the composite material in mass, the concentration of the wastewater containing heavy metal contaminants is less than or equal to 100 mg / L, and the pH value of the wastewater containing heavy metal is 5.6 to 9. The method has the advantages of making full use of nano-sized silica particles with a large specific surface area in fly ash, improving the removal rate of the industrial wastewater containing heavy metal contaminants, solving the problems that the nano iron is easily oxidized and agglomerated, and adsorbents are difficultly recovered and the like, improving efficiency and saving cost, and achieving the purpose of water environmental pollution reduction and recovery and comprehensive utilization of resources.
Description
The application obtains the money of Universities in Tianjin " young and middle-aged backbone's innovation personnel training plan " (ZX110GG019) problem
Help.
Technical field
The invention belongs to environmental technology field, it is related to Industrial Wastewater Treatment and solid waste to comprehensively utilize, more particularly to one
Plant using industrial flyash and nanometer iron composite material method of the treatment containing heavy metal contaminants industrial wastewater.
Background technology
With the development of social economy and being continuously increased for population, discharged volume of industrial waste water is also sharply increased, substantial amounts of heavy
Metal pollutant has been discharged in environment.Wherein the industrial wastewater discharge environmental pollution containing cadmium heavy metal is more and more serious, cadmium
With bioconcentration and toxicity, and difficult degradation, health is threatened, pollution of the toxic heavy metal to water environment is increasingly becoming
Global problem, early in industrial revolution period, just there occurs a series of Environment Pollution Event, in the overall situation contaminated matter of the world ten
In part, the sixties in 20th century, world-shaking Japanese nuisance disease itai-itai, was caused by cadmium wastewater polluted-water.Cadmium is
A kind of linen metal, cadmium plating can provide a kind of protective layer of corrosion resistance for steel, iron etc., with excellent adsorption and plating
The features such as layer is uniform bright and clean.Therefore, industrial 90% cadmium is used for the row such as plating, pigment, stabilizer for plastics, alloy and battery
The life of the industries such as industry, the selecting and purchasing of the source also including metal mine of cadmium wastewater, smelting, electrolysis, agricultural chemicals, medicine, textile printing and dyeing
During product, the heavy metal contaminants being discharged into environment can not be degraded by microorganisms, can only be transferred, dilute, accumulating or
Change its form, so be also just difficult to eliminate its harm by self-purification of waters disappear, toxic heavy metal can be with environment is long
Extended stationary periods are simultaneously accumulated, and being enriched with amplification toxicity step by step by food chain causes it to constitute a threat to human health, causes people wide
General attention.Cadmium is human body non-essential element, is the known noxious material most easily accumulated in vivo, and the continuous accumulation of cadmium can
Contactee is set to produce various lesions.If cadmium wastewater is without strict treatment, easily cause the slow poisoning of organism, endanger larger,
Its Poisoning maximum is caddy.The processing method of cadmium wastewater mainly include chemical precipitation method, iron oxidizing process, absorption method,
Ion-exchange, membrane separation process and bioanalysis, the thinking of heavy metals removal mainly has two in current water, and one is by absorption etc.
Method makes pollutant be completely removed from water body, and two is the Transport And Transformation ability for reducing pollutant.
Absorption method is most widely used method, and flyash can be used for the absorption of heavy metal in water, flyash have compared with
Big specific surface area and ion exchange capacity, absorption property preferably, can be used for the adsorption treatment of heavy metal in waste water.Though flyash
Can be used for the fields such as architectural engineering industry, but its scientific and technological content is relatively low, and silica and alumina composition are contained in flyash, is
A kind of physical resources.Flyash goes heavy metal mechanism mainly suction-operated in water removal.The suction-operated of flyash mainly has thing
Reason absorption and chemisorbed.Physical absorption refers to the absorption produced by intermolecular force between flyash and adsorbate,
Material will not change original property in adsorption process, and the adsorption effect of flyash is compared with the duct point for depending primarily on adsorbent
Cloth structure and specific surface area.With the increase of porosity and specific surface area, adsorption capacity is consequently increased.Chemisorbed refers to powder
There is substantial amounts of aluminium, iron, silicon isoreactivity group, the adsorption process that can be produced by chemical bond with adsorbate in coal ash.
This process is often irreversible, and flyash contains porous vitreum, porous carbon granules, porous cellular tissue, specific surface
Product is larger, while active group, with adsorption activity higher.
Flyash is carried out rationally to be modified and can improve adsorption efficiency, there is sour modified, alkali to change the modified main of flyash
Property, salt it is modified and surfactant-modified etc..In it is prosperous etc. have studied flyash to mine water in heavy metal ion adsorption effect,
Research finds that flyash is to Cu in water under strongly acidic conditions2+、Pb2+、Zn2+Clearance 50% or so, and in pH=3.5
It is most strong to these three ion adsorption capacities when~4, it is 4 in pH, when adsorption time is 6h, flyash is to Pb2+Clearance it is reachable
The research of 80%, Sen Asitk etc. finds that pH value is to influence flyash to Hg in waste water2+The most important parameter of adsorption effect, in pH
It is 3.4~4.5 to be worth, the reaction time be 3h under conditions of, with flyash process contain Hg2+Preferably, as a result showing can be with for waste water effect
Removal concentration is l0mg/L containing Hg completely2+Waste water.Zhu Hongtao is modified using salt acid soak flyash 24h, will be modified
Flyash treatment simulated wastewater in Cr6+Research, as a result shows, using the Cr in modified coal ash treatment waste water6+Compared to not
Modified fine coal adsorption rate improves about 42%.Zuo Jicheng etc. have studied with the NaOH solution of 3mol/L to after flyash modified, right
Concentration is 50mg/L containing Cd2+The removal effect of simulated wastewater, as a result shows, to Cd2+Clearance by the 40% of former flyash
More than 80% is brought up to, is significantly increased by the adsorption capacity of NaOH modified flyash.The CaO such as king main forces is used as modified
Agent is modified to flyash, studies it to containing Zn2+The removal effect of waste water, result of study shows with 2.0g modified coal ash
Reason l00mL concentration is l00mg/L containing Zn2+Waste water, the reaction time is more than 40min, Zn2+Clearance be higher than 97%, water outlet is low
In discharge standard, this method can directly process the zinc-containing water that pH value is 4~11, wide to acidity accommodation.
Flyash and NaOH are that Material synthesis zeolite is studied as the sorbent material of low cost by Somerset etc., for inhaling
Pb in attached waste water2+And Hg2+, result of study shows that result of the test shows, when synthetic zeolite dosage for 5-20g/L is added to acid
Property mine drainage（AMD）Waste water in, Pb2+And Hg2+The concentration in water accordingly reduce, pH value be 4.5 when, synthetic zeolite
To Hg2+And Pb2+And Hg2+Clearance is respectively 95% and 30%.The wide material sources of flyash, it is cheap, using flyash to useless
Water is processed, and can play the treatment of wastes with processes of wastes against one another, is prevented the pollution of the environment and cost-effective purpose, but, directly using fine coal
Than relatively low, process time is long, consumption is big and can not realize qualified discharge etc. for heavy metal removing rate and adsorption rate in ash treatment water
Shortcoming.
Nano zero valence iron (Nanoscale Zero-valent Iron, nZVI) has that particle diameter is small, specific surface area big, strong also
The features such as originality, particle diameter is in the range of 1 ~ 100nm.NZVI has reducing activity and absorption property higher, can improve Zero-valent Iron
The reactivity and treatment effeciency of particle.NZVI is one of nano adsorption material of adsorbing metal ions better performances, Chen Yu etc.
Domestic and foreign scholars carry out the treatment of electroplating wastewater and effluent containing heavy metal ions using Zero-valent Iron.Result shows that nZVI removals are with much money
Category pollutant effect is good, and removal efficiency is high, and process is simple, operating cost is low, practical.Its cutting mechanisms can substantially be summarized as
Reduction and suction-operated.But domestic and international many scholars are simultaneously it has also been found that nZVI removal heavy metal contaminants there is also many lacking
, such as there is agglomeration, oxidizable, long-time heavy metal and there is dissolution phenomenon and be not easy to reclaim in point.
Therefore, this research and utilization flyash-supporting nanometer iron can not only play flyash by precipitation and flocculation
In nano level silica and aluminum oxide effect, so as to improve its adsorption capacity and clearance, when can also reduce reaction
Between, make up nZVI easily reunite, deficiency that is oxidizable and reclaiming difficulty etc..
The content of the invention
To achieve the above object, heavy metal pollution is contained using industrial flyash and Nanoscale Iron treatment the invention discloses one kind
The method of thing industrial wastewater, it is characterised in that carried out by the steps：
（1）Industrial flyash and ferric chloride solution composition are mixed at normal temperatures first, then in mixed solution and dripping boron cyanogen
Change sodium, ferric ion is reduced into nano zero valence iron, and load on flyash, be combined so as to obtain flyash-Nanoscale Iron
Material；Wherein the ratio of weight and number of flyash and nano zero valence iron is 1:0.11(1:0.05~1:0.25)；The industrial flyash
Particle diameter is 0.5 ~ 10 μm, and the particle diameter of nano zero valence iron is 80 ~ 120 nm；The consumption of boron Cymag is 20.8g/ (100g composite woods
Material).
（2）Then added in composite and reacted containing the industrial wastewater of heavy metal contaminants, stirring at normal temperatures and
Fully reaction, reacts 5-60 min, after staticly settling, obtains supernatant and sediment；Wherein composite with containing heavy metal-polluted
The ratio of weight and number for contaminating the industrial wastewater of thing is 5g/L ~ 20g/L；The content of wherein nano zero valence iron accounts for the mass ratio of composite
It is 10%（w/w）；Concentration containing heavy metal contaminants waste water is≤100 (mg/L), and the pH value containing heavy metal contaminants waste water is
5.6~9；
（3）Processed waste water is capable of achieving solid through precipitation and liquid is directly separated, and supernatant realizes qualified discharge, and sediment is through dry
Solid mixture can be obtained after dry, and is rationally disposed.
The method for the treatment of of the present invention, wherein iron chloride are referred to：98%（w/w）Iron chloride（With FeCl3Meter）,
The described industrial wastewater containing heavy metal contaminants refers to the industrial wastewater containing Cd, Cr, Cu, Pb and Zn.
The present invention further discloses using flyash and Nanoscale Iron method of the treatment containing heavy metal contaminants industrial wastewater
Application in terms of the clearance containing heavy metal contaminants waste water is improved.Particularly reduce nZVI be oxidized, agglomeration and
Flyash-nanometer iron composite material is reclaimed, and reduces the application in terms of leaching ability of heavy metal.
The results show：
（1）The method of the present invention improves the clearance aspect of heavy metals in industrial wastewater：Clearance can reach 99.99%, even if
Under sour environment（pH=5.6）Industrial waste water containing Cd to 5ppm can also reach 99.99% clearance.
（2）The method of the present invention significantly reduces nZVI agglomerations, reduces leaching ability of heavy metal：Through flyash-receive
The industrial wastewater of rice iron composite material treatment, by after 24h, not producing heavy metal dissolution phenomenon again；
（3）Can be used in normal circumstances, without in N2Protection forms anaerobic environment.
At present for the treatment containing heavy metal industrial effluent, typically：The processing method of cadmium wastewater mainly has chemistry
The precipitation method, ion-exchange, electrolysis, absorption method, membrane separation process and bioanalysis etc..
Chemical precipitation method is a kind of main method for processing cadmium wastewater, in the basic conditions, by cadmium wastewater
Adding mixed precipitant makes the cadmium of dissolved state change into the sediment of the indissolubles such as cadmium carbonate and cadmium hydroxide and stabilization, precipitating reagent
Source than wide, conventional main have sulfide, lime, hydroxide and the mixing by several precipitant mix
Precipitating reagent.The advantage of the precipitation method is can to remove the most of cadmium ion in waste water, simple to operate, but the sediment containing cadmium of generation
Easily cause secondary pollution, and when the comparison of ingredients of pollutant is complicated, other ions may be to the precipitation of cadmium ion
Journey produces influence, and the pH value of waste water is larger on sedimentation effect influence.
Ion-exchange mainly uses ion exchange resin that ion exchange process occurs to remove the cadmium in water removal, resin
Performance determines the quality of removal effect, and ion-exchange is typically using acid cation exchange resin the cadmium ion in waste water
Exchange in ion exchanger, regeneration of hydrochloric acid is used afterwards.The resin types for processing cadmium wastewater are various, and exchange material mainly has the moon
Ion exchange resin, Humic Acid Resin, chelating resin etc..Ion-exchange has the advantages that degree of purification is high, is easy to regeneration, may be used also
To reclaim cadmium, and without secondary pollution.But ion exchange resin is expensive, and vulnerable to pollution or oxidation deactivation, treatment
It is relatively costly.
Electrolysis is the Ji Li using electrolysis, basis removal of Cadmium from wastewater is passed through electrolytic process and divides on positive and negative the two poles of the earth
Fa Sheng not aoxidize and reduction reaction, cadmium ion is processed after being enriched with, the method to realize purification of waste water.Electrolysis removes cadmium
The clearance of ion is high, technical maturity, it is not necessary to largely expends chemical agent, operates at normal temperatures and pressures, and management is easy, such as in waste water
Pollutant concentration is changed, method that can be by adjusting voltage and current, it is ensured that stable effluent quality, and processing unit is taken up an area
Area is little.But the consumption of power consumption and electrode metal is larger when a large amount of waste water are processed, the deposit isolated is difficult place
Reason is utilized, and cost is higher, limits the application of electrolysis.
Absorption method adsorbs the pollutant of cadmium wastewater using porous sorbing material, to remove pollutant, so that waste water
The method being purified.The operation of absorption method unit generally includes three steps.First it is to contact waste water and solid absorbent, gives up
Pollutant in water is adsorbed by adsorbent；The adsorbent that second step will be adsorbed with pollutant is separated with waste water；Finally adsorbed
The regeneration or renewal of agent.Sorbing material is the key of absorption method, and adsorbent wide material sources, species mainly includes inorganic, You Jihe
Biological adsorption agent, main active charcoal, zeolite, slag, improvement fiber, activated alumina etc..These sorbent treatments are useless containing cadmium
The mechanism of water is not quite similar, but good to the removal effect of cadmium, and current adsorption technology is widely used in wastewater treatment, but absorption
Method treatment containing every electroplating wastewater control condition it is relatively more, such as the addition of adsorbent, waste water containing cadmium concentration, pH value, meeting
Increase the difficulty of practical operation.
Processing method of the invention is by the use of flyash as carrier, and the silica SiO in flyash2（>55%）And aluminum oxide
Al2O3（>25%）, SiO2It is many to exist with particle diameter as the nano particle form of 80 ~ 120nm, the specific surface in adsorbent is increased, change
The performance of kind Nanoscale Iron sorbing material product.This experimental technique method is simple, and the presence of flyash widely realizes waste
Recycle, and energy consumption is small, production cost is relatively low.
Compare with traditional cadmium wastewater processing method, flyash-nanometer iron composite material has water process higher
Energy.Be swift in response, clearance it is high（99.99%）Reclaim easy with flyash-nanometer iron composite material, containing heavy metal contaminants
Waste water in have larger advantage.
A preferred method of wastewater treatment containing Cd of the invention：
A kind of method that utilization industrial flyash and nanometer iron composite material process cadmium wastewater, it is first at normal temperatures（20℃）
To be sufficiently mixed using ferric chloride solution and industrial flyash, then in mixed solution and dripping boron Cymag by ferric ion
Zeroth order Nanoscale Iron is reduced into, and is loaded on flyash.Flyash-Nanoscale Iron composite wood is added in containing industrial wastewaters such as cadmiums
Material is stirred, fully reacts at normal temperatures, precipitate and separate after reacting 5 minutes, and reclaims flyash-nanometer iron composite material,
The integrated wastewater discharge standard that supernatant after precipitation can meet correlation is directly discharged；The content of wherein nano zero valence iron accounts for multiple
The mass ratio of condensation material is 10%；The concentration of cadmium wastewater is≤100 (mg/L), and the pH value of cadmium wastewater is 5.6 ~ 9.
The more detailed handling process of the present invention（As a example by processing the industrial wastewater containing heavy metal cadmium）
（1）The physicochemical property of industrial wastewater：
The physicochemical property of the industrial wastewater of table 1
（2）The physicochemical property of industrial flyash：
（3）Technological process
Technological process refers to accompanying drawing 1.First, a certain amount of flyash is placed in the reactor with agitating device, adds water simultaneously
Stirring flyash, by determining the pH value of dissolution liquid, by ferric chloride solution addition reactor, stirs abundant Fe ionic adsorptions
On middle fly ash grain, ferric ion is then reduced into zeroth order nano iron particles in mixed solution and dripping boron Cymag,
Realization is loaded on flyash.
Add flyash-nanometer iron composite material to be stirred at normal temperatures in containing industrial wastewaters such as cadmiums, it is fully anti-
Should, precipitate and separate after reacting 5 minutes, and flyash-nanometer iron composite material is reclaimed, supernatant after precipitation can meet correlation
Integrated wastewater discharge standard directly discharge；The mass ratio that the content of wherein nano zero valence iron accounts for composite is 10%；It is useless containing cadmium
The concentration of water is≤100 (mg/L), and the pH value of cadmium wastewater is 5.6 ~ 9
During being adsorbent, treatment heavy metal contaminants waste water using flyash-nanometer iron composite material.Emphasis pair
Influence the factor of flyash-nanometer iron composite material absorption property --- absorption agent dose, industrial wastewater heavy metal contaminants
Concentration, the pH value of industrial wastewater and reaction temperature etc. have carried out research and condition optimizing：
（1）Influence of the pH value to absorption property in industrial wastewater：
Before flyash-nanometer iron composite material is added, the pH value of industrial wastewater is adjusted by HCl or NaOH, set 4
Individual gradient（PH value is 3,5.6,7 and 9）Obtain optimal pH（Accompanying drawing 2）.As pH value increases, the clearance of Cd in industrial wastewater
Also increasing, when pH value is 7, clearance reaches maximum, hereafter pH value increases little on performance of the adsorbent influence.20mg/L's
In industrial wastewater, pH value >=7 are optimum condition, and when pH value is 5.6 in the industrial wastewater of 5mg/L, clearance can also reach
To 100%.
（2）Influence of the reaction temperature to composite absorption property：
Flyash-nanometer iron composite material is added in the industrial wastewater containing 5 mg/L Cd（5g/L, containing 10% nZVI）, pH
It is 5.6 to be worth, and sets 3 thermogrades（288K, 298K and 308K）, the reaction time be 1 it is small in the case of, study reaction temperature
Accompanying drawing 3 is shown in influence to performance of the adsorbent.When the clearance of Cd starts（5min）Slightly increase with the increase of reaction temperature.
Hereafter, subsequent temperature is limited to the performance impact of adsorbent.It is considered that temperature is to flyash-nanometer iron composite material absorption
Performance impact is little.Therefore, this composite can be used at normal temperatures, and the temperature of industrial wastewater is improved without heating.
（3）Shadow noon of the Cd concentration to absorption property in industrial wastewater：
Using concentration containing Cd be 5,20,100 and the industrial wastewater of 200mg/L is contrast experiment, and the pH value in waste water is 7, reaction
Temperature is 298K, in about l hours reaction time, studies shadow noon (accompanying drawing 4 and accompanying drawing 5) of the different Cd concentration to clearance.By attached
Fig. 4 can be seen that clearance and be reduced with the increase of Cd contents, and as Cd concentration≤100mg/L, clearance reaches
100%, and when Cd concentration reaches 200mg/L, the clearance of Cd has reached 80%.The suction of Cd when being can be seen that by accompanying drawing 5
Attached amount increases as the concentration of Cd increases, and peak value is reached when Cd concentration reaches 200mg/L, and adsorbance reaches 316mgCd/g
nZVI。
ESEM (SEM) and projection Electronic Speculum before and after industrial flyash and nanometer iron composite material treatment cadmium wastewater
(TEM) result is shown in accompanying drawing 6 and accompanying drawing 7.From the result of ESEM, preceding 80 ~ 100 nm SiO are adsorbed2Nano particle, absorption
After there are many flocculent substances.From the result of projection Electronic Speculum, it is possible to find, Nanoscale Iron nZVI is almost evenly distributed in powder before absorption
The surface of coal ash particle, and by forming the compound of Fe after absorption.From X-ray photoelectron spectroscopic analysis（XPS）Can find to pass through
After crossing absorption, the crest of Cd is occurred in that（Accompanying drawing 7）, show Cd absorption on the surface of composite.
It is disclosed by the invention:The method and existing skill of cadmium wastewater are processed using industrial flyash and nanometer iron composite material
Art is compared to had good effect：
The method of the present invention is used to process has following advantage containing industrial wastewaters such as cadmiums：
（1）Clearance is high, can reach 99.9%, and the concentration of cadmium is less than 0.001 mg/L in water outlet, can meet sewage drainage standard straight
Run in and put；Process time is short（≤60 min）, can be completed in 5min, it is particularly well-suited to the emergency processing of cadmium wastewater.
（2）Easily flyash-nanometer iron composite material is reclaimed, can be separated by precipitation.
（3）Low cost, compared with the methods such as charcoal absorption, what the industrial flyash fire coal used in this method was produced consolidates
Body waste, big with amount, distribution is wide, is not required to cost, while can also be silica, nanometer using main component in flyash
Level SiO2Particle has bigger serface.The method can improve the clearance of heavy metal-containing waste water, while improving Nanoscale Iron
Easily oxidation, reunite and adsorbent is the problems such as reclaim, and efficiency and cost-effective can be improved, reached reduction water environment pollution and
The purpose of resource reclaim comprehensive utilization.
Brief description of the drawings
The industrial flyash of accompanying drawing 1 and nanometer iron composite material are prepared and technological process of the treatment containing Cd waste water；
Influence of the pH value to Cd clearances in a industry plating wastewaters of accompanying drawing 2；
Influence of the temperature to Cd clearances in the b industry plating wastewaters of accompanying drawing 3；
Influence of the concentration of Cd to its clearance in the c industry plating wastewaters of accompanying drawing 4；
Influence of the concentration of Cd to its adsorbance in the d industry plating wastewaters of accompanying drawing 5；
SEM the and TEM results of accompanying drawing 6 (a-d) composite；
SEM the and TEM results of accompanying drawing 7 (a-b) composite；
The effect of the different materials of accompanying drawing 8 removal industrial waste water containing Cd compares.
Specific embodiment
Illustrate the present invention with reference to embodiment, the scheme of embodiment described here does not limit the present invention, this area it is special
Industry personnel can be made improvements and change according to spirit of the invention, and described such modifications and variations are regarded as at this
In the range of invention, the scope of the present invention and essence are defined by the claims.Industrial flyash belongs to the solid of coal-burning power plant
Discarded object, with little need for cost.Other raw materials used in the present invention, reagent are commercially available.
Embodiment 1
（1）Weigh a certain amount of industrial flyash (I grades) at normal temperatures first, and after flyash is soaked in water, add 10%
Iron chloride（In terms of Fe）After being sufficiently mixed, the amount that boron Cymag is added dropwise is 20.8g/ (100g composites）By ferric ion also
Original is loaded on flyash into zeroth order Nanoscale Iron.In the industrial wastewater containing heavy metal contaminants such as cadmiums add flyash-
Nanometer iron composite material is stirred, fully reacts at normal temperatures, precipitate and separate after reacting 5 minutes, and reclaims flyash-nanometer
Iron composite material, the integrated wastewater discharge standard that supernatant after precipitation can meet correlation is directly discharged；Wherein flyash and
The ratio of weight and number of nano zero valence iron is 1:0.11；The particle diameter of industrial flyash is 0.5 ~ 10 μm, nano zero valence iron particle diameter 80 ~
120 nm；
The mass ratio that the content of nano zero valence iron accounts for composite is 10%；The concentration of cadmium wastewater is≤100 (mg/L), containing cadmium
The pH value of waste water is 7.
The Cd concentration of water outlet is less than 0.001mg/L wherein after Industrial Wastewater Treatment；Clearance reaches 99.99%.
（2）Industrial flyash-Nanoscale Iron composite products can be directly as adsorbent, for electroplating at waste water containing Cd
The emergency management of reason or the leakage of waste water containing Cd etc. closes disposal, and after precipitate and separate, supernatant can direct qualified discharge, and work
Industry flyash-nanometer iron composite material can quickly be reclaimed and rationally disposed.
Embodiment 2
Using flyash and nanometer iron composite material method of the treatment containing heavy metal contaminants industrial wastewater：
（1）Industrial flyash and ferric chloride solution composition are mixed at normal temperatures first, then in mixed solution and dripping boron cyanogen
The consumption for changing sodium is 20.8g/ (100g composites）Ferric ion is reduced into nano zero valence iron, and loads to flyash
On, so as to obtain flyash-nanometer iron composite material；Wherein the ratio of weight and number of flyash and nano zero valence iron is 1:0.11；
The industrial flyash particle diameter is 0.5 ~ 10 μm, and the particle diameter of nano zero valence iron is 80 ~ 120 nm；
（2）Then the industrial wastewater containing heavy metal contaminants is added in composite（Pb and Zn）Reacted, stirred at normal temperatures
Fully reaction is mixed and stirred, 5min is stood（~60 min）, obtain supernatant and sediment；Wherein composite with contain heavy metal pollution
The ratio of weight and number of the industrial wastewater of thing is 5g：1L（5g/L）；The content of wherein nano zero valence iron accounts for the mass ratio of composite
It is 10%（w/w）；Concentration containing heavy metal contaminants waste water is≤100 (mg/L), and the pH value containing heavy metal contaminants waste water is 7；
（3）Processed waste water is capable of achieving solid through precipitation and liquid is directly separated, and supernatant realizes qualified discharge, and sediment is through dry
Solid mixture can be obtained after dry.
Embodiment 3
A kind of utilization industrial flyash and nanometer iron composite material method of the treatment containing heavy metal contaminants industrial wastewater：
（1）Industrial flyash and ferric chloride solution composition are mixed at normal temperatures first, then in mixed solution and dripping boron cyanogen
Change sodium and ferric ion is reduced into nano zero valence iron, and load on flyash, so as to obtain industrial flyash-Nanoscale Iron
Composite；Wherein the quality parts ratio of industrial flyash and nano zero valence iron is 1:0.22；The particle diameter of industrial flyash is 0.5
~ 10 μm, 80 ~ 120nm of nano zero valence iron particle diameter；The consumption of boron Cymag is 41.6g/ (100g composites.
（2）Then added in composite and contain heavy metal contaminants（Containing Cd, Cr, Cu, Pb and Zn）Industrial wastewater carry out
Reaction, fully stirring at normal temperatures and reaction, stands 30 min, obtains supernatant and sediment；Wherein composite with containing weight
The ratio of weight and number of the industrial wastewater of metal pollutant is 10g/L；The content of wherein nano zero valence iron accounts for the quality of composite
Than being 10%（w/w）；Concentration containing heavy metal contaminants waste water is≤100 (mg/L), and the pH value containing heavy metal contaminants waste water is
7；
（3）Processed waste water is capable of achieving solid through precipitation and liquid is directly separated, and supernatant realizes qualified discharge, and sediment is through dry
Solid mixture can be obtained after dry, and is rationally disposed.Wherein iron chloride and boron Cymag is referred to：With FeCl3Meter, 98%（w/
w）Iron chloride and with NaBH4Meter, 98%（w/w）NaBH4, described industrial wastewater containing heavy metal contaminants refer to containing Cd,
The industrial wastewater of Cr, Cu, Pb and Zn.
Embodiment 4
Typical practical application-clearance comparative experiments that cadmium wastewater is processed using the method for the present invention：
In room temperature（20℃）Under experiment condition, using different adsorbents（Flyash-Nanoscale Iron and activated carbon）To a certain acidity
Cadmium wastewater is processed.The specific water quality index of waste water is：PH value is 5.6, and cadmium concentration is 5 ppm.
1L waste water is taken in reactor, the flyash-nano-iron material of 5g is added（10%nZVI）, with 30 revs/min at a slow speed
Electromagnetic agitation, the first sub-sampling after 5min, then sampled with the interval of 10min, until stopping stirring, standing sedimentation 30min after 2h
Afterwards, by supernatant and sediment（Flyash-nanometer iron composite material）Separate.And appropriate supernatant is taken, determine the dense of its cadmium
Degree.
Under same experiment condition, 1L waste water is taken in reactor, add the activated carbon of same amount, with 30 revs/min of electromagnetism at a slow speed
Stirring, the first sub-sampling after 5min, then sampled with the interval of 10min, until stop stirring after 2h, and after standing sedimentation 30min, will
Supernatant and sediment（Activated carbon）Separate.And appropriate supernatant is taken, determine the concentration of its cadmium.
Experimental result is shown in accompanying drawing 8 and table 3.From accompanying drawing 8, under pH=5.6 acid conditions, flyash-Nanoscale Iron
Composite has reached 99% to the clearance of industrial waste water containing Cd, and activated carbon and nano-iron material are respectively 80% and 20%, master
Under wanting reason and being acid condition, nano iron particles and acid H+Reaction is generated, so clearance is not high, and is passed through and industrial fine coal
After ash is compound, the clearance of cadmium is significantly improved.
The absorption property of the different adsorbents of table 3 compares
Compared by the absorption property of the adsorbent of table 3 it can be found that flyash-nZVI is than with work in the experiment of cadmium in removing waste water
Property charcoal and flyash to get well, while low cost than activated carbon on the market, saving expense, and flyash-Nanoscale Iron
Have the advantages that to be swift in response and settle fast and supernatant and adsorbent is easily separated.
Claims (4)
1. a kind of method that utilization industrial flyash and the treatment of nanometer iron composite material contain heavy metal contaminants industrial wastewater, it is special
Levy is to be carried out by the steps：
（1）Industrial flyash and ferric chloride solution composition are mixed at normal temperatures first, then in mixed solution and dripping boron cyanogen
Change sodium and ferric ion is reduced into nano zero valence iron, and load on flyash, be combined so as to obtain flyash-Nanoscale Iron
Material；Wherein the quality parts ratio of industrial flyash and nano zero valence iron is 1:0.11~1:0.25；The particle diameter of industrial flyash is
0.5 ~ 10 μm, the nm of nano zero valence iron particle diameter 80 ~ 120；The consumption of boron Cymag is 100g composites 20.8g/；
（2）Then add the industrial wastewater containing heavy metal contaminants to be reacted in composite, stir at normal temperatures and abundant
Reaction, after reaction 5-60 min, staticly settles, and obtains supernatant and sediment；Wherein composite with contain heavy metal contaminants
Industrial wastewater ratio of weight and number be 5 g/L ~ 20 g/L；The mass ratio that the content of wherein nano zero valence iron accounts for composite is
10%~20%（w/w）；Concentration containing heavy metal contaminants waste water is≤100 (mg/L), and the pH value containing heavy metal contaminants waste water is
5.6~9；
（3）Processed waste water is capable of achieving solid through precipitation and liquid is directly separated, and supernatant realizes qualified discharge, and sediment is through dry
Solid mixture can be obtained after dry, and is rationally disposed.
2. the method for the treatment described in claim 1, wherein iron chloride is referred to：With FeCl3Meter, 98%（w/w）Iron chloride, institute
The industrial wastewater containing heavy metal contaminants stated refers to the industrial wastewater containing Cd, Cr, Cu, Pb and Zn.
3. application of the processing method described in claim 1 in terms of the clearance containing heavy metal contaminants industrial wastewater is improved.
4. the processing method described in claim 1 is in reduction Nanoscale Iron (nZVI) easily oxidized, easy agglomeration, and reduces a huge sum of money
Application in terms of category Leaching rule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710052212.8A CN106698582A (en) | 2017-01-24 | 2017-01-24 | Method for treating industrial wastewater containing heavy metal contaminants by utilizing industrial fly ash and nano iron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710052212.8A CN106698582A (en) | 2017-01-24 | 2017-01-24 | Method for treating industrial wastewater containing heavy metal contaminants by utilizing industrial fly ash and nano iron |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106698582A true CN106698582A (en) | 2017-05-24 |
Family
ID=58909529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710052212.8A Pending CN106698582A (en) | 2017-01-24 | 2017-01-24 | Method for treating industrial wastewater containing heavy metal contaminants by utilizing industrial fly ash and nano iron |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106698582A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108555015A (en) * | 2018-05-09 | 2018-09-21 | 河北工业大学 | A kind of electric repair method in situ and equipment of portable contaminated soil |
| CN109985599A (en) * | 2019-04-10 | 2019-07-09 | 苏州科技大学 | A kind of method and in-situ remediation method of the nano zero valence iron synthesizing fly ash loading |
| KR20190141950A (en) * | 2018-06-15 | 2019-12-26 | 건국대학교 산학협력단 | Zerovalent iron catalyst supported on surface of coal combustion by-product modified by alkaline treatment and manufacturing method thereof |
| CN110773195A (en) * | 2019-11-06 | 2020-02-11 | 合肥学院 | Nano zero-valent metal composite material prepared based on meteorite, and preparation method and application thereof |
| CN110902800A (en) * | 2019-12-05 | 2020-03-24 | 中国人民大学 | Granular bacterial cellulose loaded nano zero-valent iron composite material and preparation method and application thereof |
| CN112456597A (en) * | 2020-10-21 | 2021-03-09 | 北京工业大学 | Method for removing hexavalent chromium in underground water by loading nano zero-valent iron on modified cellulose filter paper |
| CN112560323A (en) * | 2020-12-08 | 2021-03-26 | 宁波诺丁汉新材料研究院有限公司 | Industrial wastewater screening method for promoting fine particulate matter agglomeration |
| CN112845563A (en) * | 2020-12-18 | 2021-05-28 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Modified fly ash and preparation method and application thereof |
| CN113198416A (en) * | 2021-03-26 | 2021-08-03 | 同济大学 | Preparation method and application of zero-valent iron/mesoporous silica composite material |
| CN113292130A (en) * | 2021-05-11 | 2021-08-24 | 中南林业科技大学 | Preparation method and application of nano iron sulfide modified composite material based on heavy metal polluted wastewater remediation |
| CN114275868A (en) * | 2022-01-18 | 2022-04-05 | 长沙千河环保科技有限责任公司 | Heavy metal targeted remover and preparation method and application thereof |
| CN114835231A (en) * | 2022-06-30 | 2022-08-02 | 北京博泰至淳生物科技有限公司 | Nano flocculant for realizing in-situ energy expansion and preparation method thereof |
| CN114950343A (en) * | 2022-07-04 | 2022-08-30 | 辽宁工程技术大学 | Fly ash loaded nano FeS, preparation method thereof and application of fly ash loaded nano FeS in removing Cr in water |
| CN116002919A (en) * | 2023-01-10 | 2023-04-25 | 天津大学 | Method for treating acidic mine wastewater by using fly ash |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880113A (en) * | 2014-04-14 | 2014-06-25 | 北京矿冶研究总院 | Method for circularly treating heavy metal ion wastewater by using modified fly ash |
| CN104084125A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Nano-iron-loaded sintered active carbon as well as preparation method and application thereof |
| CN104174355A (en) * | 2014-08-19 | 2014-12-03 | 中国地质科学院水文地质环境地质研究所 | Zeolite-loaded nano-iron material for removing heavy metals in water and preparation method of zeolite nano-iron material for removing heavy metals in water |
-
2017
- 2017-01-24 CN CN201710052212.8A patent/CN106698582A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880113A (en) * | 2014-04-14 | 2014-06-25 | 北京矿冶研究总院 | Method for circularly treating heavy metal ion wastewater by using modified fly ash |
| CN104084125A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Nano-iron-loaded sintered active carbon as well as preparation method and application thereof |
| CN104174355A (en) * | 2014-08-19 | 2014-12-03 | 中国地质科学院水文地质环境地质研究所 | Zeolite-loaded nano-iron material for removing heavy metals in water and preparation method of zeolite nano-iron material for removing heavy metals in water |
Non-Patent Citations (1)
| Title |
|---|
| 陈震等编著: "《土壤资源环境研究》", 31 August 1997, 中国农业科技出版社 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108555015A (en) * | 2018-05-09 | 2018-09-21 | 河北工业大学 | A kind of electric repair method in situ and equipment of portable contaminated soil |
| KR20190141950A (en) * | 2018-06-15 | 2019-12-26 | 건국대학교 산학협력단 | Zerovalent iron catalyst supported on surface of coal combustion by-product modified by alkaline treatment and manufacturing method thereof |
| KR102126227B1 (en) * | 2018-06-15 | 2020-06-24 | 건국대학교 산학협력단 | Zerovalent iron catalyst supported on surface of coal combustion by-product modified by alkaline treatment and manufacturing method thereof |
| CN109985599A (en) * | 2019-04-10 | 2019-07-09 | 苏州科技大学 | A kind of method and in-situ remediation method of the nano zero valence iron synthesizing fly ash loading |
| CN110773195B (en) * | 2019-11-06 | 2022-06-17 | 合肥学院 | Nano zero-valent metal composite material prepared based on meteorite, and preparation method and application thereof |
| CN110773195A (en) * | 2019-11-06 | 2020-02-11 | 合肥学院 | Nano zero-valent metal composite material prepared based on meteorite, and preparation method and application thereof |
| CN110902800A (en) * | 2019-12-05 | 2020-03-24 | 中国人民大学 | Granular bacterial cellulose loaded nano zero-valent iron composite material and preparation method and application thereof |
| CN112456597A (en) * | 2020-10-21 | 2021-03-09 | 北京工业大学 | Method for removing hexavalent chromium in underground water by loading nano zero-valent iron on modified cellulose filter paper |
| CN112560323A (en) * | 2020-12-08 | 2021-03-26 | 宁波诺丁汉新材料研究院有限公司 | Industrial wastewater screening method for promoting fine particulate matter agglomeration |
| CN112845563A (en) * | 2020-12-18 | 2021-05-28 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Modified fly ash and preparation method and application thereof |
| CN113198416A (en) * | 2021-03-26 | 2021-08-03 | 同济大学 | Preparation method and application of zero-valent iron/mesoporous silica composite material |
| CN113292130A (en) * | 2021-05-11 | 2021-08-24 | 中南林业科技大学 | Preparation method and application of nano iron sulfide modified composite material based on heavy metal polluted wastewater remediation |
| CN114275868A (en) * | 2022-01-18 | 2022-04-05 | 长沙千河环保科技有限责任公司 | Heavy metal targeted remover and preparation method and application thereof |
| CN114835231A (en) * | 2022-06-30 | 2022-08-02 | 北京博泰至淳生物科技有限公司 | Nano flocculant for realizing in-situ energy expansion and preparation method thereof |
| CN114950343A (en) * | 2022-07-04 | 2022-08-30 | 辽宁工程技术大学 | Fly ash loaded nano FeS, preparation method thereof and application of fly ash loaded nano FeS in removing Cr in water |
| CN116002919A (en) * | 2023-01-10 | 2023-04-25 | 天津大学 | Method for treating acidic mine wastewater by using fly ash |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106698582A (en) | Method for treating industrial wastewater containing heavy metal contaminants by utilizing industrial fly ash and nano iron | |
| WO2015109899A1 (en) | Method for quickly and effectively removing heavy metals in water body | |
| CN105731624B (en) | A method of utilizing heterogeneous Fenton-like reaction catalytic oxidation treatment reverse osmosis concentrated water | |
| CN106076261B (en) | A kind of adsorbent for heavy metal and preparation method and application | |
| CN101348297B (en) | Processing method for heavy metal ion-containing waste water | |
| Cai et al. | Advanced treatment of piggery tail water by dual coagulation with Na+ zeolite and Mg/Fe chloride and resource utilization of the coagulation sludge for efficient decontamination of Cd2+ | |
| CN106750356A (en) | A kind of method that metal-organic framework materials of utilization UiO 66 purify selenium-containing wastewater | |
| Yan et al. | Synchronous removal of Cr (VI) and phosphates by a novel crayfish shell biochar-Fe composite from aqueous solution: Reactivity and mechanism | |
| Ju et al. | Removal of chelated Cu (II) from aqueous solution by adsorption–coprecipitation with iron hydroxides prepared from microelectrolysis process | |
| Brewster et al. | Use of electrochemical iron generation for removing heavy metals from contaminated groundwater | |
| CN102476836A (en) | Method for treating arsenic-containing wastewater | |
| CN101811795A (en) | Processing method and processing system thereof for acidic waste water containing heavy metals | |
| CN106336038A (en) | Treatment method for heavy metal-containing polluted wastewater | |
| CN104445675A (en) | Method for treating mercury-containing wastewater by virtue of demercuration adsorbent material | |
| CN114275868A (en) | Heavy metal targeted remover and preparation method and application thereof | |
| CN101148297A (en) | Method for processing surface treatment integrated waste water | |
| CN104478055A (en) | Sewage treatment complexing agent as well as preparation method and application method thereof | |
| CN110117108A (en) | A kind of processing method of high concentration cadmium wastewater | |
| CN106242013B (en) | Method for treating heavy metal ion-containing wastewater by mixing natural pyrrhotite and zero-valent iron | |
| CN116161834A (en) | Heavy metal wastewater treatment method based on zero-valent iron packed bed system | |
| CN111072153A (en) | Desulfurization microbial inoculum and sewage treatment technology applying same | |
| CN102476860B (en) | Mercury removal agent for treating waste water containing mercury | |
| CN109012571B (en) | Modified electrolytic manganese waste residue, preparation method thereof and industrial wastewater treatment method | |
| CN111001389A (en) | Preparation and use methods of renewable nano zero-valent iron-loaded waste clay-based activated carbon for removing heavy metals in water | |
| CN106007057B (en) | Treatment method of COD (chemical oxygen demand) and ammonia nitrogen mixed waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170524 |
|
| WD01 | Invention patent application deemed withdrawn after publication |