CN108033571B - A kind of preparation method and applications of composite nano materials - Google Patents
A kind of preparation method and applications of composite nano materials Download PDFInfo
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- CN108033571B CN108033571B CN201711141954.4A CN201711141954A CN108033571B CN 108033571 B CN108033571 B CN 108033571B CN 201711141954 A CN201711141954 A CN 201711141954A CN 108033571 B CN108033571 B CN 108033571B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/341—Consortia of bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/347—Use of yeasts or fungi
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a kind of preparation method and applications of composite nano materials, by the way that the EM calcium activated with flocculation and nano material are combined, EM calcium activated liquid is immobilized on the porous carrier made of composite nano materials, achievees the effect that remove free state heavy metal ion and soluble small molecule organically combine state heavy metal in water body based on the obligate sticking of physical chemistry and bioflocculation and package.Composite nano materials good purification prepared by the present invention, function is more, has the advantages that quickly available heavy metal passivation in water body to remove the toxic heavy metal ion in sewage.
Description
Technical field
The present invention relates to water-treatment technology fields, and in particular to a kind of preparation method and application of composite Nano ball.
Background technique
Heavy metal pollution of water body is always to be difficult to solve and endanger one of huge pollution, it is easy to cause human diseases or
It is dead.The method of microorganism and nano material processing sewage has a extensive future, and is then with nano material immobilized microorganism
Primary good improvement on microorganism and nano material processing Technology of Sewage, related application research have phase both at home and abroad at present
Close report.Although immobilized microorganism technique achieves certain effect in specific water body, to heavy-metal ion removal
Correlative study and patent be not much, especially that there are stability is poor for microorganism used therefor, it is easily dead the disadvantages of, there are also immobilization materials
Material can not meet the optimum condition of microbial growth well.
Summary of the invention
Goal of the invention: it is exceeded for certain heavy metal ions in sewage contents, to solve problems of the prior art,
The present invention by microbial fermentation technology combined with composite nano materials in the way of, EM calcium activated liquid, which is immobilized onto diameter, is
A kind of composite nano materials are obtained on the nanoporous support of 10-20mm, which can effectively remove toxic heavy metal in sewage
Ion.
Technical solution: to realize the above-mentioned technical purpose, the preparation method of composite nano materials proposed by the present invention, including such as
Lower step:
(1) EM stoste, glucose, calcium carbonate and deionized water are pressed into 4~6%:3~5%:3~5%:80~90%
Mass percent mixing, and move it into fermentation flask, the 7-8 that ferments in confined conditions is put into 35~37 DEG C of constant incubators
It, EM calcium activated liquid is made in shaking speed 180-200r/min；
(2) by nano grade iron powder, nanoscale silicon powder and kaolin powder with the quality hundred of 20-30%:25-35%:35-55%
Divide than mixing, washes with water and be placed in temperature control furnace, started to warm up from 100 DEG C, with 10~20 DEG C per minute of heating rate liter
Temperature is kept for temperature constant state 24-36 hours to 700-800 DEG C, cooling, obtains composite nanometre powder；
(3) composite nanometre powder that step (2) obtains is put into the EM calcium activated liquid of step (1) preparation and is impregnated 2-3 days,
It is pelletizing after taking-up, is obtaining composite Nano carrier, composite Nano carrier is being subjected to high temperature sintering, cooling is spare, then will be above-mentioned
Composite Nano carrier impregnates 2~3 days in EM calcium activated liquid again, and room temperature 1~2 day is after taking-up up to composite Nano material
Material.
Preferably, in step (2), the diameter of the composite Nano carrier obtained after granulation is 10-20mm.
Preferably, the condition of high temperature sintering is to be sintered at 550-600 DEG C, and sintering time is 24-36 hours
The property wherein pelletized be spherical shape, spheroid shape, it is cylindrical in any one.Spherical shape is more preferred shape,
However the purpose of the present invention also may be implemented in other shapes.
The glucose, calcium carbonate are that analyze pure, described EM stoste be to like that peaceful happy environment friendly biological technology (Nanjing) has
The production of limit company, contains the complex microorganisms such as photosynthetic bacteria, lactic acid bacteria, saccharomycete, actinomyces.
Nanometer iron powder partial size is between 50-55nm, and nano silica fume partial size is between 20-40nm, the huge ratio of nano material
Surface area and preferable biocompatibility and adsorptivity enable it to the more microorganisms of more effective immobilization.Kaolin its
The caking property that carrier ball can be increased is allowed to be not easily broken, convenient for calcining molding.
The composite nano materials obtained by above-mentioned preparation method are also within protection scope of the present invention.
Present invention further proposes application of the above-mentioned composite nano materials in heavy-metal ion removal.
Specifically, when for heavy metal ion when removing, the composite nano materials are straight in the ratio of 0.5-2g/L
It connects and is invested in polluted-water to be processed.The composite nano materials are recyclable when dystopy processing, can utilize again after pickling,
It is not recycled generally when in-situ treatment.
The utility model has the advantages that compared with prior art, the present invention has the advantage that
(1) composite nano materials (ball) good purification that preparation method of the present invention is prepared, can quickly improve water quality
And remove Heavy Metals in Waters ion；
(2) compound EM strain used in has very strong stability, and oxidation resistance is strong, multiple functional, significant effect, fits
Should be able to power it is stronger, after biological nano purifying ball enters water body, microorganism therein can adapt to external environment, and energy faster
It is enough that environment conditioning is carried out to water body；
It (3), can be by the hole of nano particle honeycomb shape using composite nano materials and kaolin as the making material of carrier
Gap and huge specific surface area (750~850m2/ g) and preferable biocompatibility and sticking, reach preferably fixed micro- life
Object forms the effect of biomembrane, can not only preferably purify water, heavy-metal ion removal, moreover it is possible to which preferably absorption fixation is micro-
Biology；And be different from other process for fixation, the present invention using 2 kinds of nano materials and kaolin as microorganism composite carrier,
Strain used is with very strong stability, and oxidation resistance is strong and can generate having for biological flocculant and causes EM flora, can be by
The hole of nano particle honeycomb shape and huge specific surface area and preferable biocompatibility and sticking, reach better fixation
Microorganism forms the effect of biomembrane, and composite nano materials combine effective microbial activity calcium liquid functionally can be mutually complementary
It fills, effect more better than other methods can be reached in removal Heavy Metals in Waters ions.
Specific embodiment
Below by specific embodiment, the present invention will be described in detail.Wherein, EM stoste is to like peaceful happy environment friendly biological technology (south
Capital) Co., Ltd's production；Nanometer iron powder, nano silica fume are purchased from Shanghai great achievement nano material Co., Ltd, kaolin be from
Longyan Gaolingtu Co., Ltd's purchase.
Embodiment 1
EM stoste, glucose, calcium carbonate and deionized water are mixed by the mass percent of 4%:3%:3%:90%, and
It moves it into fermentation flask, is put into 35 DEG C of constant incubators and ferments in confined conditions 7 days, shaking speed 200r/min,
EM calcium activated liquid is made.Laboratory is by mass percentage by nano grade iron powder and nanoscale silicon powder and kaolin powder with 25%:
The ratio of 30%:45% mixes, and washes with water and is placed in temperature control furnace, start to warm up from 100 DEG C, with 10 DEG C of heating per minute
Rate is warming up to 750 DEG C, is kept for temperature constant state 36 hours, cooling, obtains composite nanometre powder.The above composite nanometre powder is put
Enter in EM calcium activated liquid and impregnate 3 days, be granulated after taking-up in pan-type pelletizer, the carrier ball that diameter is 20mm is obtained, by carrier ball
It is sintered and cooled at 600 DEG C spare.Carrier ball is impregnated 3 days in EM calcium activated liquid, is made within room temperature 2 days after taking-up
At composite Nano ball.And sewage of the 10L containing heavy metal is configured, heavy metal ions in sewage Cd2+、Cu2+、Zn2+、As3+、Pb2+,
Each heavy metal mass concentration is all 10mg/L.PH is that 8, DO content is 2mg/L.Put into 20g composite Nano ball, nano-carrier ball
(impregnating 3 days not in EM calcium activated liquid) and equivalent EM calcium activated liquid, monitored water quality after 10 days, each to handle heavy metal removing rate such as
Shown in table 1:
1 difference of table adds object counterweight metal purification Contrast on effect
Embodiment 2
EM stoste, glucose, calcium carbonate and deionized water are mixed by the mass percent of 4%:3%:3%:90%, and
It moves it into fermentation flask, is put into 35 DEG C of constant incubators and ferments in confined conditions 7 days, shaking speed 180r/min,
EM calcium activated liquid is made.Laboratory is by mass percentage by nano grade iron powder and nanoscale silicon powder and kaolin powder with 30%:
The ratio of 30%:40% mixes, and washes with water and is placed in temperature control furnace, start to warm up from 100 DEG C, with 10 DEG C of heating per minute
Rate is warming up to 800 DEG C, is kept for temperature constant state 36 hours, cooling, obtains composite nanometre powder.By the above composite nanometre powder
It is put into EM calcium activated liquid and impregnates 3 days, be granulated after taking-up in pan-type pelletizer, the carrier ball that diameter is 15mm is obtained, by carrier
Ball is sintered and cooled spare at 600 DEG C.Carrier ball is impregnated 3 days in EM calcium activated liquid, is made within room temperature 2 days after taking-up
Composite Nano ball is made.10L sewage, major pollutant and quality in sewage are acquired in a certain sewage treatment plant forebay in Nanjing
Concentration is respectively ammonia nitrogen 50mg/L, total nitrogen 57mg/L, total phosphorus 24mg/L, COD 520mg/L, pH 8, and DO content is 1mg/L,
Heavy metal ion Cd2+、Cu2+、 Zn2+、As3+、Pb2+Mass concentration is respectively 5.2mg/L, 12mg/L, 24mg/L, 3.2mg/L and
53mg/L.20g composite Nano purifying ball, bamboo charcoal ball and active carbon ball and equivalent EM calcium activated liquid are put into respectively, are monitored after 10 days
Water quality, heavy metal removing rate are as shown in table 2:
2 difference of table adds object and compares to wastewater purifying efficiency
In terms of the purified treatment effect of Tables 1 and 2, in the case where same dosage, composite Nano ball of the invention is wanted
Significantly better than other processing.Illustrate that the composite Nano ball has preferable removal effect to the heavy metal ion in sewage.
It is to provided by the present invention a kind of for removing the composite Nano ball and its system of heavy metal ions in sewage above
Preparation Method is described, and specific example is combined to explain the effect of product removal Heavy Metals ion of the invention
It states, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas；Meanwhile for this field
Those skilled in the art, according to the thought of the present invention, there will be changes in the specific implementation manner and application range, this explanation
Book content should not be construed as limiting the invention.
Claims (6)
1. a kind of preparation method of composite nano materials, which comprises the steps of:
(1) EM stoste, glucose, calcium carbonate and deionized water is mixed by 4 ~ 6%:3 ~ 5%:3 ~ 5%:80 ~ 90% mass percent
It closes, and moves it into fermentation flask, be put into 35 ~ 37oC constant incubator and ferment in confined conditions 7-8 days, shaking speed is
EM calcium activated liquid is made in 180-200r/min；
(2) nano grade iron powder, nanoscale silicon powder and kaolin powder are mixed with the mass percent of 20-30%:25-35%:35-55%
It is even, it washes with water and is placed in temperature control furnace, started to warm up from 100 DEG C, 700- is warming up to 10 ~ 20 DEG C of heating rate per minute
It 800 DEG C, is kept for temperature constant state 24-36 hours, it is cooling, obtain composite nanometre powder；
(3) composite nanometre powder that step (2) obtains is put into the EM calcium activated liquid of step (1) preparation and is impregnated 2-3 days, taken out
It pelletizes again afterwards, obtains composite Nano carrier, composite Nano carrier is subjected to high temperature sintering, the condition of high temperature sintering is 550-600
It is sintered at DEG C, sintering time is 24-36 hours, and cooling is spare, then by above-mentioned composite Nano carrier again in EM calcium activated liquid
Middle to impregnate 2 ~ 3 days, room temperature 1 ~ 2 day is after taking-up up to composite nano materials, wherein the glucose, calcium carbonate are point
It analyses pure；The nanometer iron powder partial size is between 50-55nm, and nano silica fume partial size is between 20-40nm.
2. preparation method according to claim 1, which is characterized in that in step (2), the composite Nano obtained after granulation is carried
The diameter of body is 10-20mm.
3. preparation method according to claim 1, which is characterized in that the property of granulation is spherical shape, in spheroid shape, cylinder
Any one.
4. the composite nano materials that described in any item preparation methods obtain according to claim 1 ~ 3.
5. application of the composite nano materials as claimed in claim 4 in heavy-metal ion removal.
6. application according to claim 5, which is characterized in that, will be described compound when for heavy metal ion when removing
Nano material is directly invested in polluted-water to be processed in the ratio of 0.5-2g/L.
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| CN108033571B true CN108033571B (en) | 2019-08-02 |
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| US20050029198A1 (en) * | 2003-08-08 | 2005-02-10 | Frederick Tepper | Heavy metals absorbent and method of use |
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Patent Citations (7)
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| JP2005144304A (en) * | 2003-11-14 | 2005-06-09 | Seisui:Kk | Sludge degrading or water purifying agent, and purification method |
| CN101274174A (en) * | 2007-12-25 | 2008-10-01 | 吉林大学 | Nano granule water purifying material for removing heavy metal and preparation thereof |
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