CN103394699B - The preparation method of nano iron particles and application thereof - Google Patents
The preparation method of nano iron particles and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of nano iron particles, by the iron particulate feed material of 1-10 micron and water and dispersant, enter grinder, abrading-ball is filled in grinder, through rotor axis mechanical extruding mixing, grinding 5-7 hour, gained particle sieves through filter membrane, namely obtain the tiny nano iron particles of satisfactory dispersed, the underproof particle that sieves continues again to enter grinder together with water and dispersant and repeats above process; 1-10 micron iron particulate feed material accounts for 20-50%, dispersant accounts for 1-10%, all the other are water, its gross weight meet 100%; The input power of grinder is 1.5-1.8kw.h/L, and grinding temperature is 20-55
oc, rotating shaft rotating speed is 2200-2400RPM.Effluent quality of the present invention is effective and reliable and stable, cost of investment and operating cost lower.Nanometer water treatment process and series of products effectively can overcome the stable complex compound heavy metal ion remaval efficiency that the inorganic ligands such as the high chloride ion in waste water, high sulfate ion, high ammonia nitrogen and heavy metal ion form solubility, and water treatment effect does not affect by it completely.
Description
Technical field
The present invention relates to preparation method and the application thereof of a kind of Nanoscale Iron (1-1000nm) particle.
Background technology
Nanometer is a dimensional units, and a nanometer equals part per billion meter.Illustrate, the diameter of hairline is about 100,000 nanometers (100 microns), a common bacterium (E
0coli) diameter is about 1000 nanometers.
Nanometer technology refers to the material synthesis on nano-level, the production of processing and micro devices and use.Nanometer technology is not singly subtitle substance synthesis and produces, and the more important thing is and utilizes strange biology, physics, chemistry and environment sex character.Illustrate, carbon is a conventional non-conductive material, but CNT (diameter about 1.4 nanometer) is a fabulous conductor.Gold is a very stable inert metal, but nanogold particle (<10 nanometer) is then a very active chemical reaction catalyst.
As everyone knows, iron is a common more active metal, and iron can react with water and oxygen:
2Fe + 0
2 + 4H
+ → 2Fe
2+ + 2H
2O (1)
Fe + H
2O → Fe
2+ + H
2 + 2OH
-(2)
Above reaction is actually common iron rot reaction, and metallic iron is a reducing agent (electronics donor) the role of above-mentioned reaction:
Fe → Fe
2+ + 2e
- (3)
Be oxidized each iron atom and can discharge 2 or 3 electronics.
Fe
2+ → Fe
3+ +e
- (4)
When environmental condition is simple, oxygen or hydrone are the acceptors of electronics.
The electronics that iron discharges when the application of environment is to utilize Fe forms is for reducing environment pollutant.Illustrate, nickel ion (Ni
2+) can be reduced by metallic iron:
Fe + Ni
2+ → Fe
2+ + Ni (5)
Equally, iron may be used for reducing a lot of organic pollution, and chlorination carbon can be become methane by Fe3+ reduction.Such as:
4Fe + CCl
4+ 4H
+ → 4Fe
2+ + CH
4 + 4Cl
- (6)
Above-mentioned reaction all has report on document, and the advantage of nano iron particles has in addition:
1, bigger serface.The specific area of particle and its diameter are inversely proportional to, and particle is larger, and specific area is less.Illustrate, compare the particle of 1 millimeter and 1 nanometer, diameter is that the particle of 1 nanometer is by larger than the surface area of 1 mm granules 1,000,000 times.The effect of high surface area is large reaction table, and that is little particle can produce high reactivity.This point is very important for the conversion of environmental contaminants and process;
2, material service efficiency is improved.The iron atom being positioned at outer surface as everyone knows directly participates in chemical reaction for bulky grain, only has the atom of small part to be positioned at particle surface.Concerning nano particle, then there is sizable a part of atomic energy directly to participate in chemical reaction, thus substantially increase reaction speed and efficiency;
3, dispersed and suspension.The feature that the another one of nano particle is obvious is dispersiveness highly and suspension.When particle diameter is less than 100 nanometer, the effect of Brownian movement is just more obvious, and the precipitation produced by gravity then seems not too important.Bulky grain precipitation is very fast, and therefore, comparatively speaking, it is possible for preparing more stable suspension with nano particle.The dispersiveness of height, stable suspension, make nano particle have a lot of novelty teabag, such as Nanoscale Iron can inject underground water easily, mixes with contaminated soil, to join in sewage etc.And due to the great surface area of nano particle, as long as just likely process relatively large sewage and mud with a small amount of nano particle.
Nano iron particles refers to metallic iron [Fe (the 0)] particle that diameter is less than 100 nanometers, has following three kinds of methods to may be used for synthesis of nano iron particle:
First method: sodium borohydride reduction
Boron hydride is a kind of stronger reducing agent, can reduce the iron ion of divalence and trivalent.
4Fe
3+ + 3BH
4 - + 9H
2O → 4Fe↓ + 3H
2BO
3 - + 12H
+ + 6H
2 (7)
The iron be reduced normally is less than the spheric granules of 200 nanometers.
Second method: Fe (CO)
5decompose
Fe (CO)
5a unstable organoiron compound, under the condition of high temperature (200 DEG C to 300 DEG C), Fe (CO)
5iron and carbon monoxide can be resolved into:
Fe(CO)
5 → Fe + 5CO (8)
Utilize above-mentioned thermal decomposition manner can synthesize the spherical iron particles of minimum (<10 nanometer), but be less than iron particle less stable in water of 10 nanometers, easily oxidized.Usually can replace water with organic solvent, thus stable nano iron particles can be obtained.
The third method: mechanical milling method
Recent years, precise finiss machinery has had very fast progress, and new ball mill utilizes the ball particle of the high strength of less (<0.2 millimeter) can smash the iron particle of 1-10 micron, makes the iron particle being less than 100 nanometers.The iron particle that mechanical means produces has irregular shape usually.
Have in scientific and technical literature much about the report of Nanoscale Iron.But, nearly all research is all that the method for the above-mentioned chemical synthesis of application and crystal growth prepares nano particle.Chemical synthesis will use number of chemical reagent usually, and much reagent is all poisonous compound.Chemical synthesis generally all wants multiple production stage to carry out synthesis of solid particle.In general, chemical synthesis process cost is higher, complex process.It is few that current mechanical milling method production is seen at home, do not see relevant report.
Summary of the invention
The object of the invention is to the preparation method and the application thereof that propose a kind of nano iron particles.
The preparation method of the nano iron particles that the present invention proposes, concrete steps are as follows:
By the iron particulate feed material of 1-10 micron and water and dispersant, enter grinder, stainless steel steel ball is filled as abrading-ball in grinder, through rotor axis mechanical extruding mixing, milling time is 5-7 hour, gained particle sieves through filter membrane, namely obtains the tiny nano iron particles of satisfactory dispersed, and the underproof particle that sieves continues again to enter grinder together with water and dispersant and repeats above process; Wherein:
The iron particulate feed material addition of 1-10 micron is 20-50%, the addition of dispersant is 1-10%, and all the other are water, and its gross weight meets 100%;
The input power of grinder is 1.5-1.8kw.h/L, and grinding temperature is 20-55
oc, rotating shaft rotating speed is 2200-2400RPM.
In the present invention, described dispersant adopts any one in polyvinyl alcohol (Polyvinly Alcohol), polyacrylic acid (Polyacrylic Acid), polymethylacrylic acid (Polymethacrylic Acid), polyacrylamide (Polyacrylamide), poly-ethylene methacrylic ether (Polyvinyl methyl ether), POLYPROPYLENE GLYCOL (Polypropylene) or polyvinyl acetate (Polyvinyl acetate).Preferably, described dispersant adopts any one in polyvinyl alcohol, polyacrylic acid or polymethylacrylic acid.
In the present invention, described filter membrane is nanoscale.
In the present invention, the diameter of described abrading-ball is 100 microns, and the quality of size to product of abrading-ball has a great impact.Normally the smaller the better.Experience tells us, and grinder can produce the particle being less than 1000 times of abrading-balls.That is, if use the abrading-ball of 200 microns, the product of 200 nanometers can be produced.China only has the abrading-ball of 200-400 micron at present on the market.Then there is the abrading-ball of 100 microns in the U.S..
In the present invention, described abrading-ball adopts steel ball.Iron is a kind of metal of high strength, than the 7.8g/cm that weighs
3, usually high to the requirement of abrading-ball, consume also fast.We used steel ball, the cross pollution that other materials causes can also be eliminated like this.
Principle of the present invention is as follows:
In stable suspension, zero-valent iron particle can be in high degree of dispersion state, has high reaction activity, and the mobility of height.Key of the present invention is the size reducing Zero-valent Iron, is reduced to nanoscale, applies effective dispersant to prepare stable suspension simultaneously from millimeter or micron.After preparation, this water treatment agent is applied to also progressively industrialization in the improvement of relevant environment pollution prevention.
(1) the size of particle
In water, a particle is subject to the effect of many kinds of force.Usually downward gravity is had, buoyancy upwards, and irregular Brownian movement.
For the solid particle of proportion more than 1, when diameter is greater than 1 micron, gravity then plays an important role.That is, particle may be settled out water body soon.
When diameter is less than 0.1 micron, the energy of Brownian movement is higher than the energy of gravity.Solid particle then likely suspends in water.
Only having had nano iron particles, is to form stable water slurry.Because tiny iron particle easily forms larger group (aggregates) sedimentation in water.
Prepare a stable suspension to need to balance a series of factor.The size of solid particle generally can not exceed several micron.To the size requirements of the solid particle of density too high (>2.5) lower (being less than a micron).The surface nature of particle has conclusive effect to the stability of colloid equally.Weak charge between particle interacts and usually can cause the cohesion of particle.Particle is less, and surface area is larger, causes the trend of cohesion stronger.As there is no enough electrostatic repulsions between fruit granule, then can not form stable colloid.
The suspension of preparation zero-valent iron particle, the largest diameter of iron particle is no more than 10 microns, and suspension comprises a kind of and multiple organic polymer.Polymer has one or more functional groups.Functional group comprises hydrophilic and hydrophobic grouping.The effect of dispersant is not only to disperse Zero-valent Iron in process of production, and prior function is conducive to Zero-valent Iron to comprise transmission in underground water and migration in water environment.These functional groups are the dispersant comprising one or more organic polymers.
The method applied in the present invention adds a small amount of charged organic polymer to reach the object increasing iron Particle surface charge.In general, organic acid is likely as effective dispersant:
R-COOH
R-COO
-+ H
+
Many organic polymers are had to be used as dispersant.As adopted polyvinyl alcohol (Polyvinly Alcohol), polyacrylic acid (Polyacrylic Acid), polymethylacrylic acid (Polymethacrylic Acid), polyacrylamide (Polyacrylamide), poly-ethylene methacrylic ether (Polyvinyl methyl ether), POLYPROPYLENE GLYCOL (Polypropylene), polyvinyl acetate (Polyvinyl acetate) etc.
The sodium rice iron particle that employing the present invention prepares is for heavy mental treatment.
Many heavy metal ion have important impact to biological growth, and particularly excessive heavy metal can produce the negative interaction serious to health.Environmental legislation has clear and definite and strict regulation to the content of beary metal in water, air, soil and food.
Many heavy metal ion have important impact to biological growth, and particularly excessive heavy metal can produce the negative interaction serious to health.Environmental legislation has clear and definite and strict regulation to the content of beary metal in water, air, soil and food.
Iron is a kind of quite active element, can the multiple comparatively inactive heavy metal element of precipitate reduction.Such as bivalent cupric ion [Cu (II)] can be reduced to zerovalent copper by metallic iron, and zerovalent copper is water insoluble, and the copper be reduced so just can be separated from water:
Cu
2+ + Fe → Fe
2+ + Cu↓ （9）
Table 1: metallic element standard electrode potential (E
0) (25 DEG C)
| Metal species | E0（V） | |
| Barium (Ba) | Ba 2++2e - ?Ba | -2.90 |
| Zinc (Zn) | Zn 2++2e - ?Zn | -0.76 |
| Iron (Fe) | Fe 2++2e - ?Fe | -0.41 |
| Cadmium (Cd) | Cd 2++2e - ?Cd | -0.40 |
| Nickel (Ni) | Ni 2++2e - ?Ni | -0.24 |
| Plumbous (Pb) | Pb 2++2e - ?Pb | -0.13 |
| Copper (Cu) | Cu 2++2e - ?Cu | 0.34 |
| Silver (Ag) | Ag ++2e - ?Ag | 0.80 |
| Mercury (Hg) | Hg 2++2e - ?Hg | 0.86 |
| Chromium (Cr) | Cr 2O 7 2-+14H ++6e ?2Cr 3++7H 2O | 1.36 |
As the normal potential in table one shows: many kinds of metal ions (cadmium, nickel, lead, copper, silver, mercury, chromium) can by Fe3+ reduction, and zinc and barium are then more active than iron, then can not by Fe3+ reduction.
The sodium rice iron particle that employing the present invention prepares is for hexavalent chromium-treatments.
Chromium is a kind of metal having extensive use.Plating, alloy material, leather process, the industry such as dyestuff all widely use chromium.Research shows that chromium is to health, and other animal and many plants all may have negative interaction, and chromium is a kind of known carcinogenic substance.
Chromium has trivalent (Cr (III)) and sexavalence (Cr (VI)) two kinds of main valence states in water.Cr VI (CrO
4 2-, HCrO
4 -) be anion, there is very high solubility, therefore in water, have very high mobility; Trivalent chromium is then not too water-soluble, usually can form comparatively stable sediment [Cr (OH)
3], the mobility thus in water is very little.Common processing method is water-fast trivalent chromium hexavalent chrome reduction, and Nanoscale Iron can reduction of hexavalent chromium effectively rapidly.
2CrO
4 2- + 3Fe + 10H
+ → 2Cr(OH)
3↓ + 3Fe
2+ + 2H
2O （10）
The sodium rice iron particle that employing the present invention prepares is for halogenated organic matters process.
Chloro-carbon solvent (trichloro-ethylene, tetrachloromethane etc.) has commercial Application very widely.Chlorine organic is had also to be groundwater pollutant the most common.These pollutants are very stable in water, have great impact to environment and health.
Nanoscale Iron is a kind of very effective reducing agent, and such as tetrachloro-ethylene can be reduced to ethene by Nanoscale Iron:
Ⅰ） C
2Cl
4 + 4Fe + 4H
+ → C
2H
4 + 4Fe
2+ + 4Cl
-
Tetrachloromethane can be reduced to methane effectively:
Ⅱ） CCl
4 + 4Fe + 4H
+ → CH
4 + 4Fe
2+ + 4Cl
-
Other chlorinated organics also can be reduced by Nanoscale Iron similarly.
The sodium rice iron particle that employing the present invention prepares is for organic dyestuff process.
Dyestuff is important industrial materials, and according to statistics, annual global organic dyestuff output is more than 1,000,000 tons.Not hard to imagine, dyestuff has also become common and environmental contaminants widely.
Have many industrial dyes to have molecular structure roughly the same, red yellowish green dyestuff is all containing (-N=N-) nitrogen double bond.Nitrogen double bond can be decomposed by Nanoscale Iron.Such as orange (Orange II) can be decoloured by Nanoscale Iron effectively.
Adopt the commercial application of sodium rice iron particle in wastewater from chemical industry that the present invention prepares.
Beneficial effect of the present invention is:
1. effluent quality is effective and reliable and stable, cost of investment and operating cost lower;
2. nanometer water treatment process and series of products effectively can overcome the stable complex compound heavy metal ion remaval efficiency that the inorganic ligands such as the high chloride ion in waste water, high sulfate ion, high ammonia nitrogen and heavy metal ion form solubility, and water treatment effect does not affect by it completely;
3. sludge settling performance is good, and sludge quantity comparatively traditional handicraft at least reduces by more than 50%;
4. floor space is little, and operational management is convenient, and have certain capacity of resisting impact load (impact of resistance to water quality, the water yield), water quality fluctuates within the specific limits does not affect water treatment effect;
5. effluent quality is better than state emission standard.
Accompanying drawing explanation
Fig. 1 is Brownian movement schematic diagram.
Fig. 2 is the inventive method operative installations structural diagrams.
Number in the figure: 1 is rotating shaft, and 2 is machine casing, and 3 is abrading-ball, and 4 is shaft.
Detailed description of the invention
The present invention is further illustrated below by embodiment.
embodiment 1:
Adopt an import high accuracy grinder.Operational factor is as follows:
1. the Milling volume of 0.6 liter,
2. the abrading-ball of 80-85% is filled,
3. 20-50% iron particle (1-10 micron),
4. 1.5-1.8kwh/L input power,
5. rotating speed 2200-2400 RPM,
6. grinding temperature <55
oc(water wherein plays cooling effect),
We have tried out the grinder that volume is 10,25 and 60 liters respectively, and its result is all similar.Above-described grinder can use different abrading-balls, such as iron, steel, aluminium, zirconium (Zivconia), talcum (Steatite), silicon nitride (Silicon Nitride), carborundum (Silicon Carbon) and tungsten carbide tool (Tungsten Carbon).Finally we used steel ball, the cross pollution that other materials causes can be eliminated like this.Steel ball as abrading-ball belongs to same metal with the Nanoscale Iron finally produced.
In production base, according to the laboratory experience of inventor, the needs of Bound moisture processing item, can produce the particle stabilized suspension of iron of different Nano grade.
The abrading-ball of 80% is filled in grinder, described abrading-ball adopts steel ball, the diameter of abrading-ball is 100 microns, the iron particle of 10 microns will be less than, dispersant and water mix according to the weight ratio of 40:8:52 and add in grinder, described dispersant adopts polyvinyl alcohol, in the Milling volume of 0.6 liter, debug power output is 1.5kwh/L, rotating speed 2200 RPM, by adding water in batches in process, temperature-controllable is built in less than 50 degree, approximately pass through six hours process of lapping out first product, adopt the filter membrane of 220 nanometers to determine to be less than in mixture the ratio of the iron particle of 200 nanometers, the particle that particle diameter meets Nano grade can be by the product in the suspension of filter membrane, unsanctioned explanation particle diameter is larger, do not meet Nano grade, again return production line to carry out second time and produce grinding together with new raw material.Remarks: the iron particle of Nano grade belongs to dangerous material, so operating process is taken care, necessarily does droplet measurement by form of suspension.
embodiment 2:the abrading-ball of 85% is filled in grinder, described abrading-ball adopts steel ball, the diameter of abrading-ball is 100 microns, the iron particulate feed material of 1-10 micron and water and dispersant being mixed according to the weight ratio of 20:3:77 adds in grinder, described dispersant adopts polymethylacrylic acid, through rotor axis mechanical extruding mixing, milling time is 5 hours, gained particle sieves through the filter membrane of 200 nanometers, unsanctioned explanation particle diameter is larger, do not meet Nano grade, again return production line and carry out second time and produce grinding together with new raw material.Namely obtain the tiny nano iron particles of satisfactory dispersed, the underproof particle that sieves continues again to enter grinder together with water and dispersant and repeats above process.Wherein: the input power of grinder is 1.8kw.h/L, and grinding temperature is 20-55oC, and rotating shaft rotating speed is 2400RPM.
embodiment 3: the nano iron particles of embodiment 1 gained is used for somewhere Tong Ye company process complex multi-metal waste water project
project profile
After the waste water-heavy copper of this project treatment, liquid derives from the factory effluent in certain factory one workshop (noble metal workshop), mainly by the multiply waste water composition such as liquid, pretreatment supernatant, secondary pretreatment supernatant, dynamic wave liquid, gold and silver waste water, a silver-colored excessive reducing solution after tower liquid, copper leached solution, displacement.Waste water characteristic:
(1) wastewater source is complicated, and wastewater flow rate and waste water quality fluctuation are greatly;
(2) waste component is complicated, containing Various Complex heavy metal (arsenic, copper, cadmium, gold, silver etc.);
(3) in waste water, chloride ion content high (can reach 60 ~ 150g/L), salinity high (concentration is about 15% ~ 25%), sulfite ion, COD etc. are also higher.
Liquid after in April ,-2011 in August, 2010 successively to this factory's sulfuric acid plant gypsum filtrate waste water, sulfuric acid plant western factory waste water, a workshop secondary purification, a workshop sink liquid after copper and have carried out laboratory lab scale and field pilot test test.Lab scale and pilot plant test result show: nanometer pharmaceutical techniques effectively can overcome the impact of the inorganic coordination such as chlorion, sulfate ion in waste water, have good removal effect to heavy metal ion such as Cu, As, Cd, Pb, Zn, the Ni in waste water, stable effluent quality reaches and is better than the water pollutions concentration of emission limit value of " copper, nickel, cobalt emission of industrial pollutants standard " (GB25467-2010) middle table 2 regulation.
one workshop sinks liquid pilot scale after copper
Test period: on March 6,1 day ~ 2011 March in 2011
Test waste water takes from liquid after heavy copper; Test water yield 10L/h=240L/d.
Table 2 sinks liquid waste water quality situation-(unit: mg/L) after copper
Pilot scale water outlet testing result is as table 3:
Table 3 to sink after copper liquid water quality situation-(unit: mg/L) after liquid-nanotechnology treatments
Table 3 pilot scale water outlet testing result shows: nanometer medicament patented technology sinks the pollutant such as Cu, Zn, As, Cd, Pb of liquid after copper to a workshop have good treatment effect, and water outlet reaches national grade one discharge standard.
one workshop sinks liquid lab scale after copper
Test period: in November, 2011
After test waste water takes from heavy copper, liquid is in table 4:
Table 4: in lab scale water outlet and former water, content of beary metal contrasts-(unit: mg/L)
embodiment 4: the product that embodiment 1 obtains is used for certain smeltery of company second relieving haperacidity Sewage Treatment Project
the supernatant effluent heavy metal process of smeltery of the said firm second is tested
Test period: on November 16 ,-2011 years on the 10th November in 2011.
Test waste water takes from supernatant effluent after the Wastewater from Acid Preparation lime iron salt method process of the second smeltery.
The test water yield: 10m
3/ d.
supernatant effluent water quality index
Table 5: supernatant effluent water quality index-(unit: mg/L)
| Project | pH | Pb | Cd | Cu | As |
| Supernatant 1111-1500 | 12 | 34.72 | 0.73 | 0.042 | 4.22 |
| Supernatant 1112-0800 | 5 | 4.47 | 0.94 | 4.47 | 8.56 |
| Supernatant 1112-1500 | 13 | 84.4 | 0.59 | 0.051 | 0.078 |
| Supernatant 1113-0800 | 7 | 67.91 | 6.16 | 0.091 | 15.06 |
| Supernatant 1113-1500 | 5 | 13.75 | 2.9 | 0.038 | 1.76 |
| Supernatant 1114-1500 | 5 | 3.72 | 0.019 | 0.89 | 0.54 |
| Supernatant 1115-0800 | 6 | 2.52 | 0.88 | 0.043 | 0.22 |
| Supernatant 1115-1500 | 5 | 3.88 | 1.19 | 0.04 | 0.93 |
| Supernatant 1116-0800 | 8 | 4.14 | 3.83 | 0.042 | 1.63 |
water quality index after 2 supernatant effluent nanometer pharmaceutical techniques process
Water sample send Institute of Analysis of Fudan University and Tongji University's Environmental capacity and Resource analysis National Key Laboratory to detect, and testing result is as follows:
Table 6: supernatant effluent detects data-(unit: mg/L) after the process of nanometer pharmaceutical techniques
(detection of Institute of Analysis of Fudan University)
| Project | Pb | Cd | As |
| Discharge standard | ≤0.5 | ≤0.05 | ≤0.3 |
| Liquid 1112-1500 after process | ＜0.05 | ＜0.02 | ＜0.05 |
| Liquid 1113-0800 after process | ＜0.05 | ＜0.02 | ＜0.05 |
Table 7: supernatant effluent detects data-(unit: mg/L) after the process of nanometer pharmaceutical techniques
(Tongji University's Environmental capacity and Resource analysis National Key Laboratory are detected)
| Project | Pb | Cd | Cu | As | Zn |
| Discharge standard | ≤0.5 | ≤0.05 | ≤0.5 | ≤0.3 | ≤1.5 |
| Liquid 1112-1500 after process | 0.00 | 0.00 | 0.00 | 0.00 | 0.03 |
| Liquid 1113-0800 after process | 0.00 | 0.00 | 0.00 | 0.00 | 0.08 |
| Liquid 1113-1500 after process | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Liquid 1114-0800 after process | 0.01 | 0.00 | 0.01 | 0.00 | 0.00 |
| Liquid 1114-1500 after process | 0.00 | 0.00 | 0.01 | 0.00 | 0.00 |
Field pilot test water outlet testing result shows: nanometer pharmaceutical techniques has good place to go effect to heavy metal ion such as Cu, As, Zn, Cd, the Pb in supernatant effluent, and effluent quality reaches and is better than the water pollutions concentration of emission limit value that in " plumbous, Zn Cr coating pollutant emission standard " (GB25466-2010), table 2 specifies.
embodiment 5: embodiment 2 products obtained therefrom is used for rare your factory of certain company heavy metal comprehensive wastewater processing item
1 laboratory lab scale
Test period: in September, 2011.
After getting sulfuration, liquid waste water carries out nanometer pharmaceutical techniques laboratory lab scale at Tongji University's Environmental capacity and Resource analysis National Key Laboratory, and test water outlet testing result is as follows:
Table 8: liquid wastewater treatment experimental result after sulfuration
| Pollutant project | Liquid (former water) (mg/L) after sulfuration | Liquid (mg/L) after the process of nanometer pharmaceutical techniques | Discharge standard (mg/L) |
| As | 482.010 | 0.194 | 0.5 |
| Zn | 0.470 | 0.000 | 1.5 |
| Ni | 0.980 | 0.000 | 0.5 |
| Cu | 2.010 | 0.002 | 0.5 |
Experimental result shows: nanometer pharmaceutical techniques effectively can overcome the impact of the inorganic coordination such as chlorion in waste water, sulfate ion, ammonia nitrogen, good place to go effect is had, the water pollutions concentration of emission limit value that during effluent quality is better than " copper, nickel, cobalt emission of industrial pollutants standard " (GB25467-2010), table 2 specifies to heavy metal ion such as Cu, As, Zn, the Ni in waste water.
field pilot test
Test period: on November 4 ,-2011 years on the 22nd October in 2011.
Test waste water to take from behind a workshop waste water in liquid bath; The test water yield: 10m
3/ d.
liquid raw water quality index after sulfuration
Table 9: liquid raw water quality index-(unit: mg/L) after sulfuration
Note:
\represent that this element is not analyzed (lower same).
water quality index after the process of liquid nanometer pharmaceutical techniques after sulfuration
Field pilot test water outlet testing result shows: nanometer pharmaceutical techniques effectively overcomes the impact of the inorganic coordination such as chlorion in waste water, sulfate ion, ammonia nitrogen, have good place to go effect to heavy metal ion such as Cu, As, Zn, Ni, Cd, Pb, the Hg in waste water, effluent quality reaches and is better than the water pollutions concentration of emission limit value of " copper, nickel, cobalt emission of industrial pollutants standard " (GB25467-2010) middle table 2 regulation.
Table 10: water quality index-(unit: mg/L) after liquid-nanometer pharmaceutical techniques process after sulfuration
Claims (8)
1. a preparation method for nano iron particles, is characterized in that concrete steps are as follows:
By the iron particulate feed material of 1-10 micron and water and dispersant, enter grinder, stainless steel steel ball is filled as abrading-ball in grinder, through rotor axis mechanical extruding mixing, milling time is 5-7 hour, gained particle sieves through filter membrane, namely obtains the tiny nano iron particles of satisfactory dispersed, and the underproof particle that sieves continues again to enter grinder together with water and dispersant and repeats above process; Wherein:
The iron particulate feed material addition of 1-10 micron is 20-50%, the addition of dispersant is 1-10%, and all the other are water, and its gross weight meets 100%;
The input power of grinder is 1.5-1.8kw.h/L, and grinding temperature is 20-55
oc, rotating shaft rotating speed is 2200-2400RPM
;
Described dispersant adopts any one in polyvinyl alcohol, polyacrylic acid or polymethylacrylic acid.
2. the preparation method of nano iron particles according to claim 1, is characterized in that described filter membrane is nanoscale.
3. the preparation method of nano iron particles according to claim 1, is characterized in that the diameter of described abrading-ball is 100 microns, and described abrading-ball adopts steel ball.
4. one kind as claimed in claim 1 the sodium rice iron particle that obtains of preparation method for heavy mental treatment.
5. one kind as claimed in claim 1 the sodium rice iron particle that obtains of preparation method for hexavalent chromium-treatments.
6. one kind as claimed in claim 1 the sodium rice iron particle that obtains of preparation method for halogenated organic matters process.
7. one kind as claimed in claim 1 the sodium rice iron particle that obtains of preparation method for organic dyestuff process.
8. the commercial application of sodium rice iron particle in wastewater from chemical industry that obtain of preparation method as claimed in claim 1.
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| CN201310360854.6A CN103394699B (en) | 2013-08-19 | 2013-08-19 | The preparation method of nano iron particles and application thereof |
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| CN106957100B (en) * | 2017-04-07 | 2020-05-22 | 北京工业大学 | Method for rapid reductive degradation of alkaline dye alkaline brown G wastewater |
| CN112139508A (en) * | 2020-09-23 | 2020-12-29 | 中国科学院地理科学与资源研究所 | Amphoteric surface micron zero-valent iron, and preparation method and application thereof |
| CN112591928A (en) * | 2020-11-03 | 2021-04-02 | 同济大学 | Simple method for quickly decoloring dye wastewater |
| CN114749656A (en) * | 2020-12-28 | 2022-07-15 | 航天神舟生物科技集团有限公司 | Preparation method of metal nano iron/nano copper particle solution and working solution |
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