CN103861866A - Fixed enrichment method for city life compost heavy metals through modified nanocarbon - Google Patents
Fixed enrichment method for city life compost heavy metals through modified nanocarbon Download PDFInfo
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Abstract
The invention discloses a fixed enrichment method for city life compost heavy metals through modified nanocarbon. The fixed enrichment method comprises the following steps: modifying the modified nanocarbon with the grain diameter of 20-70nm before being applied so as to obtain various types of modified nanocarbon; then sealing a layer of cotton cloth and a nylon net at the lower end of a PVC (polyvinyl chloride) tube, uniformly and proportionally mixing garbage compost with the modified nanocarbon, wherein each tube is filled with150g of a mixed material; setting the temperature during experiments to be 19-27 DEG C and the relative humidity to be 60% to 72%, and supplementing water for the compost every day, so that the content of water of the compost reaches about 70% of field moisture capacity; sampling 45d for cultivation later, and carrying out morphological analysis on the heavy metals, wherein the addition of the modified nanocarbon is 1-5%(w/w) of the weight of the garbage compost. Experimental results show that the modified nanocarbon is added so that the contents of the heavy metals in a residual form are increased, the conversion of the compost heavy metals from a plant easily-absorbed state to a difficultly-absorbed state is promoted, and the method provides a basis for the application of the modified nanocarbon on passivation and plant enrichment of the heavy metals in garbage compost.
Description
Technical field
The invention belongs to environmental protection technical field, relate to urban afforestation, particularly the fixing enrichment method of modified Nano carbon to urban life compost heavy metal.
Background technology
Nano material is because its huge specific area, high active site position and good photoelectric properties more and more come into one's own and become new study hotspot in contaminated environment reparation research.The special physico-chemical character of nano material depends on its specific area, distribution and purity, and therefore, nano material as magnetic, the aspect such as optical, electrical, hot and common material have a great difference, has the new features such as absorption, catalysis, radiation, absorption in physical property.Nano particle, due to its a large amount of micro-interfaces and microporosity, can be strengthened various interfacial reactions, as counterweight metallic surface and obligate adsorption reaction etc., in heavy-metal contaminated soil improvement and sewage purification, will bring into play remarkable effect.Chang etc. (2005) repair polycyclic aromatic hydrocarbon pollution in applying nano Zero-valent Iron and have obtained very good effect; The investigative test that Nanjing Soil Inst., Chinese Academy of Sciences administers heavy-metal contaminated soil by Nanoscale Iron has confirmed that it reduces the effect of heavy metal validity.Carbon black is that the volatile ingredient of organism or fossil feedstock is transformed in the time of imperfect combustion or high temperature pyrolysis, is the product of gaseous process.Under normal circumstances, carbon black is porous nano material, and diameter is 30～50 nm, has large specific area and high active site position.
In the eighties in 20th century, the annual carbon black producing in the whole world is greatly about 50-270Tg(Tg=10
12g) left and right, wherein about 80% is to come from burning.Most carbon black directly enters soil, accumulates gradually, becomes the important component of the soil organism, and another part is kicked up in atmosphere by wind.Due to the inertia of carbon black, it is very little after its depositional stage, being subject to photochemical reaction and microbial action.This means carbon black can long-term existence in environment, for the slow carbon storehouse of circulation on the earth, there is important contribution.
The absorption of nano-sized carbon can be divided into physical absorption and chemisorbed.Physical absorption mainly occurs in the micropore that nano-sized carbon is abundant, for removing the impurity of water and air, the molecular diameter of these impurity must be less than the aperture of nano-sized carbon, and chemisorbed is mainly because functional group is contained on the surface of nano-sized carbon, with the material generation chemical reaction being adsorbed.Impurity in medium constantly enters by physical absorption and chemisorbed in the loose structure of nano-sized carbon and makes nano-sized carbon absorption saturated, and adsorption effect declines.The nano-sized carbon of adsorbing after saturated need to be carried out activating and regenerating, recovers its adsorption capacity, reuses, and adsorption capacity is larger, and adsorption effect is just better.Generally believe that at present nano-sized carbon is the superpower adsorbent of organic pollution.It can strong adsorption polycyclic aromatic hydrocarbon, Polychlorinated biphenyls, many chloros dibenzo dioxin, many chloros dibenzofurans and PBDE, pesticide diuron, 3-chlorophenol and the various organic pollutions such as luxuriant and rich with fragrance.In fact, nano-sized carbon also has certain suction-operated to heavy metal.Wu Cheng etc. find that carbon black can strong adsorption Hg
2+, As
3+, Pb
2+and Cd
2+, and to Pb
2+maximal absorptive capacity is much larger than to other several heavy metal species.Carbon black and commercial activated carbon that Qiu etc. (2008) form the burning of wheat straw and rice straw relatively find, carbon black is to Pb
2+adsorption capacity stronger.
But nano-sized carbon is hydrophobic non-polar adsorbent, and nonpolar organic matter is had to stronger affinity, and to polar substances, although can adsorb, adsorption capacity a little less than.There are some researches show, nano-sized carbon is to Pb
2+maximal absorptive capacity much smaller than mineral and humic acid.Regulate surperficial acidic-group content by oxidation modification, can obviously strengthen it to Pb
2+, Cr
3+the absorption of the material that isopolarity is stronger, weakens the suction of weak organic substance of polarity.Therefore, on purpose nano-sized carbon being carried out to surface modification, give its some special surface chemical properties, is practicable thereby change its absorption property.
Mainly contain chemical modification, physical modification, chemistry and physical union modification, plasma modification and electrochemical modification etc. for the method for nano-sized carbon surface modification.Chemical modification is divided into again oxidation modification, modified with reduction, loaded metal ion modification, adds the hetero atom modifications such as N, F, Cl.Wherein the oxidation modification of nano-sized carbon is mainly to utilize strong oxidizer, under proper temperature, oxidation processes is carried out in nano-sized carbon surface, thereby improves the content of black carbon surface oxyacid group, strengthens surface polarity.At present, the modifier that improves activated carbon surface acidic-group by oxidation modification mainly contains HNO
3, H
2o
2, H
2sO
4, HCl, HClO, HF and O
3deng oxygen oxidized black, introduce Suo Ji, its content is 6%.The people (2002) such as Katsumi kamegawa adopt nitric acid oxidation carbon black, have obtained the carbon black of high-load oxygen, are insoluble matter but wherein have most of, have affected the dispersion of carbon black in water.A large amount of oxy radicals has been introduced on the carbon black CBO surface making with nitric acid oxidation, as-COOH ,-OH etc., make black carbon surface be acid, and these polar groups have strengthened its dispersive property in water greatly.The research that nano-sized carbon is curbed environmental pollution as repair materials is not also a lot, has research H
2sO
4the absorption of the carbon black of modification to ionic state pentavalent As, result shows that the carbon black of modification can reach 62.52mgg to the maximal absorptive capacity of As
-1.Use KMnO
4carbon black is carried out to oxidation modification, make it to Pb
2+eliminating rate of absorption reach 94%.In soil, add respectively 1%, 3%, 5% use HNO
3after the nano-sized carbon of modification, soil available Cu has reduced respectively 47.26%, 72.01%, 80.89%, and Effective Zinc has reduced respectively 3.00%, 17.71%, 43.61 %.
In a word, the application study of nano material at present focuses mostly on aspect water treatment, trial multi-focus aspect the improvement of soil pollution is in organic material contaminated soil, and Application of micron, in the fixing enrichment reparation of heavy metal from consumer garbage compost aspect, also there is no bibliographical information.
The research of up to the present, administering for compost nano-sized carbon as repair materials lacks very much.Obviously, the feature of nano-sized carbon high-specific surface area, high reaction activity and strong characterization of adsorption etc., is greater than the sorbing material of general particle diameter to the absorption crystallized ability of heavy metal.Nano-sized carbon is applied in the fixing enrichment reparation of compost heavy metal, can avoids bringing harmful effect to compost, this is incomparable as passivator ground method using lime, frog stone, zeolite etc.This will develop into the technology of a kind of low cost and eco-friendly in-situ passivation heavy metal, for the application of nano-sized carbon in environmental pollution improvement provides new development space.
Along with the develop rapidly of industrialization and urbanization, heavy metal pollution of soil has become the outstanding environmental problem can not be ignored.China is subject to nearly 2,000 ten thousand hm of the cultivated area of heavy metal pollution
2, account for 1/5th of total area under cultivation.Heavy metal pollution can cause soil productivity to decline, and causes underground water and crop pollution, directly or indirectly endangers human and livestock health.Heavy metal ion exists with various forms in lawn matrix, wherein has ambulant Heavy Metals plant growth is had to significant impact.In the time that the heavy metal concentration that can be absorbed and used by plants in matrix is too high, be necessary to take certain measure, reduce plant to its absorption and accumulation.The fixing recovery scenario of original position is by the adding of various additives, and makes heavy metal biological available state be converted into the not available form of biology.There is carbon black through the material that is often used as heavy metal in soil fixative, the excess sludge in quick lime, phosphate and wastewater treatment, and some other trade wastes.
Carbon black is that the volatile ingredient of organism or fossil feedstock is transformed in the time of imperfect combustion or high temperature pyrolysis, is the product of gaseous process.Under normal circumstances, carbon black is porous nano material, and diameter is 30～50 nm, and the specific area that it is larger and stronger adsorption ability make its application in heavy-metal contaminated soil is administered become possibility.Black carbon surface has acidic functionality and alkaline oxygen-containing functional group.Acidic functionality makes carbon black have polarity, is conducive to adsorb the compound that various polarity is stronger; Basic functionality easily adsorbs the weak or apolar substance of polarity.Someone finds after to the oxidation modification of Chinese tallow tree seed shell active carbon: surface oxygen functional group quantity is than the left and right that do not double of the active carbon of oxidation processes, high nearly 4 times of the light base ratio of shuttle, and carbon surface polarity increases, and has the Adsorption of solute capacity of certain polarity to increase to some.Illustrate that the functional group of black carbon surface, through oxidation processes, can improve the content of surperficial oxyacid group, strengthen surperficial polarity, thereby improve the adsorption effect to polar substances.
Summary of the invention
The object of the present invention is to provide the fixing enrichment method of a kind of modified Nano carbon to urban life compost heavy metal.
The present invention is on the basis of Optimal Experimental, by adopting certain density sulfuric acid, nitric acid and potassium permanganate carry out Surface Oxidation Modification to nano-sized carbon, and mix as matrix proportional to itself and compost, carry out indoor culture experiment, studied modified Nano carbon heavy metal biological available state in compost changed, with and on growth of Festuca elata and the impact to Festuca Arundinacea migration by compost on heavy metal, for the application of modified Nano carbon in heavy metal pollution reparation provides the foundation of science.
For achieving the above object, the invention provides following technical scheme:
The fixing enrichment method of modified Nano carbon to urban life compost heavy metal, is characterized in that being undertaken by following step:
(1) processing of material:
Before experiment, garbage compost is carried out to pretreatment, removes the bulk foreign material such as plastic sheeting, brick and tile, stone and glass wherein, air-dry after, cross 2 mm and sieve, for subsequent use; Garbage compost physicochemical property is: pH 7.62, the content of organic matter 221.25 gkg
-1, full nitrogen 13.48 gkg
-1, available phosphorus 0.078 gkg
-1, C/N is 8.37, saturation moisture content 0.76 mLg
-1, unit weight 0.85 gmL
-1; Heavy metal (Cr, Cu, Pb, Zn) content is respectively 67.00,238.73,172.11 and 496.38 mgkg
-1;
Plants selection Festuca Arundinacea (
festuca arundinaceal
.);
Nano-sized carbon particle diameter 20-70 nm, specific area is 1.2 × 10
5m
2kg
-1, pH value is 7, uses front it to be carried out to modification, obtains respectively KMnO
4, H
2sO
4or HNO
3the nano-sized carbon of modification;
(2) experimental technique:
1) at the pvc pipe of high 25 cm of diameter 3 cm, lower end is sealed with one deck cotton and nylon wire, and garbage compost and each modified Nano carbon are mixed in proportion, and packs composite material 150g in every pipe into; After passivation 7 d, every pipe sowing 0.2 g tall fescue seed, experimental session temperature is 19-27 DEG C, relative humidity is 60%-72%, and keep the skin wet every day to compost, makes compost moisture reach field capacity 70%, at laboratory balance 30d, carry out Speciation Analysis of Heavy Metals; The addition of wherein said each modified Nano carbon is the 1-5%(w/w of garbage compost weight).
In garbage compost of the present invention, add respectively the percetage by weight of the nano-sized carbon of modification to be: 1%, 3% or 5%(w/w).Wherein in garbage compost, add respectively 1%, 3%, 5% H
2sO
4modified Nano carbon; In garbage compost, add respectively 1%, 3%, 5% HNO
3modified Nano carbon; In garbage compost, add respectively 1%, 3%, 5% KMnO
4modified Nano carbon.
The present invention further discloses modified Nano carbon the fixing enrichment method of urban life compost heavy metal is being improved to Festuca Arundinacea to the application aspect heavy metal accumulation, described modified Nano carbon refers to HNO
3or H
2sO
4modified Nano carbon.
The present invention further disclose modified Nano carbon to the fixing enrichment method of urban life compost heavy metal in the application improving aspect its absorption property.Wherein KMnO
4the specific area of nano-sized carbon is increased.
The present invention further discloses modified Nano carbon the fixing enrichment method of urban life compost heavy metal is being strengthened the application aspect the passivation of heavy metal, wherein said KMnO
4the addition of modified Nano carbon is the 5%(w/w of garbage compost weight).Oxidation modification has changed the surface chemical property of nano-sized carbon in this case, has increased the content of its surface acidity group, has improved its chemisorbed performance, and HNO
3and KMnO
4the more notable surperficial carboxyl-content that has improved nano-sized carbon of modification, has strengthened its absorption to polar substances, is conducive to the passivation to heavy metal.
The present invention further discloses modified Nano carbon increases organic matter and sulfide in conjunction with the application aspect state content to the fixing enrichment method of urban life compost heavy metal at the content that reduces heavy metal Fe/Mn oxidizable in compost; Wherein said KMnO
4, H
2sO
4or HNO
3the addition of modified Nano carbon is the 5%(w/w of garbage compost weight).
The conclusion that the present invention reaches by test is as follows:
(1) use 3 kinds of oxidants to carry out oxidation modification meeting to nano-sized carbon its specific area is changed, wherein HNO
3modification reduces nano-sized carbon specific area, and KMnO
4the specific area of nano-sized carbon is increased, be conducive to improve its absorption property.
(2) oxidation modification has changed the surface chemical property of nano-sized carbon, has increased the content of its surface acidity group, has improved its chemisorbed performance, and HNO
3and KMnO
4the more notable surperficial carboxyl-content that has improved nano-sized carbon of modification, has strengthened its absorption to polar substances, is conducive to the passivation to heavy metal.
(3) interpolation mass ratio is 1%, 3%, 5% modified Nano carbon, and the effectively heavy metal in passivation compost, reduces its available state content, wherein to add mass ratio as 5% modified Nano carbon effect optimum.
The more detailed preparation method of the present invention is as follows:
1 materials and methods
1.1 for examination material
Consumer garbage compost, from Tianjin little Dian garbage compost treatment plant.Before experiment, garbage compost is carried out to pretreatment, removes the bulk foreign material such as plastic sheeting, brick and tile, stone and glass wherein, air-dry after, cross 2 mm and sieve, for subsequent use.Compost physicochemical property is: pH 7.62, the content of organic matter 221.25 gkg
-1, full nitrogen 13.48 gkg
-1, available phosphorus 0.078 gkg
-1, C/N is 8.37, saturation moisture content 0.76 mLg
-1, unit weight 0.85 gmL
-1; Heavy metal (Cr, Cu, Pb, Zn) content is respectively 67.00,238.73,172.11 and 496.38 mgkg
-1.Lawn plant select Festuca Arundinacea (
festuca arundinaceal
.).
Be purchased from real carbon plant of Tianjin autumn for examination nano-sized carbon, particle diameter 20-70 nm, specific area is 1.2 × 10
5m
2kg
-1, pH value is 7, uses front it to be carried out to modification.
The preparation of 1.2 modified Nano carbon
KMnO
4modification: take nano-sized carbon 10 g in 250 mL conical flasks, add 100 mL0.03 molL
-1kMnO
4solution, leaves standstill after 10 min, is put in boiling reflux 1 h on general-purpose electric heater.After cooling, repeatedly rinse by deionized water, no longer muddiness and pH are stable to make solution.Be transferred to beaker, under 110 DEG C of conditions, dry to constant weight.
H
2sO
4modification: the H that takes 10 g nano-sized carbon and join 250 mL 20%
2sO
4in solution, under 110 DEG C of conditions, heat 90 min.After cooling, repeatedly rinse by deionized water, no longer muddiness and pH are stable to make solution.Under 110 DEG C of conditions, dry to constant weight.
HNO
3modification: take 10 g nano-sized carbon and join in the salpeter solution of 150 mL 65%, be placed in 110 DEG C of oxidation reaction 2 h on the heating plate of fume hood.After cooling, repeatedly rinse by deionized water, no longer muddiness and pH are stable to make solution.Under 110 DEG C of conditions, dry to constant weight.
1.3 experimental design
13 processing are established in experiment altogether: only compost (CK); In compost, add respectively 1%, 3%, 5%(mass ratio) unmodified nano-sized carbon (CB), in compost, add respectively 1%, 3%, 5% H
2sO
4modified Nano carbon; In compost, add respectively 1%, 3%, 5% HNO
3modified Nano carbon; In compost, add respectively 1%, 3%, 5% KMnO
4modified Nano carbon.The pvc pipe that uses high 25 cm of diameter 3 cm, lower end is sealed with one deck cotton and nylon wire, and compost is mixed than with modified Nano carbon with different quality, and every pvc pipe packs composite material 150 g into, and contrast is 150 g compost, and each processing repeats for 3 times.Passivation one week (7 d) after, every pipe sowing 0.2 g tall fescue seed.Experimental session temperature is 19-27 DEG C, and relative humidity is 60%-72%, and keep the skin wet every day to compost, makes compost moisture reach field capacity 70% left and right, and at laboratory balance 30d, experiment amounts to 37 d.
1.4 analytical method
The specific area of modified Nano carbon adopts internationally recognized nitrogen physisorption BET method, and the detection of functional group adopts Boehm titration.In compost, heavy metal biological available state content adopts TCLP method to extract, the buffer solution of formulating different pH values according to the difference of compost acid-base value and buffering capacity is as extract, but pH value of compost is less than 5 in this experiment, preparation extractant is that 5.7 mL glacial acetic acid are in 500 mL distilled water, add again 64.3 mL1 mol/L NaOH, be settled to 1 L with distilled water, guarantee reagent pH value is 4.93 ± 0.05, the HNO of 1.0 mol/L for the pH value of buffer solution
3regulate with 1.0 mol/L NaOH, the consumption of buffer solution is 20 times of compost, and water-water reactor is fertile in being 20:1.With the speed of (30 ± 2) r/min (18 ± 2) h that vibrates at normal temperatures, centrifugal, filter.In plant, the content of Cu and Zn is cleared up with red fuming nitric acid (RFNA)-perchloric acid.
It is pure that experiment agents useful for same is analysis, vessel used 2 molL
-1nitric acid clean, and by washed with de-ionized water 3 times, then in fume hood, dry.Filtrate is through Filter paper filtering, and in filtrate, content of beary metal adopts TAS-990 atomic absorption detecting.
1.5 data processing
In literary composition, data are all mean value and the standard deviations repeating for 3 times, adopt SPSS 11.5 softwares to compare the single factor ANOVA statistical analysis in average to the data obtained.
2 development results analyses
2.1 add H
2sO
4the impact of modified Nano carbon on Festuca Arundinacea heavy metal accumulation
Add the H of different quality ratio
2sO
4modified Nano carbon can reduce plant shoot and divide heavy metal accumulation concentration, for Cd, and Cr, Cu, Zn, Pb five heavy metal species, add mass ratio and be 3% and 5% modified Nano carbon all with contrast generation significant difference, adding 5% modified Nano carbon processed group reduces at most, compare according to group and reduced respectively 64.89%, 30.63%, 30.85%, 34.60%, 29.63%.
From table 1, we can find out, add H
2sO
4modified Nano carbon on the impact of Festuca Arundinacea aerial part heavy metal accumulation amount with its on heavy metal accumulation concentration to affect trend consistent, wherein add mass ratio and be 5% H
2sO
4modified Nano carbon processed group compares according to group and has reduced respectively 60.00%, 20.37%, 20.77%, 25.57%, 19.84%.We can find out thus, although control group Festuca Arundinacea ground biomass is significantly less than each processed group Festuca Arundinacea ground biomass, but control group heavy metal accumulation amount, still higher than processed group heavy metal accumulation amount, illustrates that the modified Nano carbon of certain mass ratio is remarkable to the harm effect of minimizing heavy metal on plants aerial part.
Table 1 adds H
2sO
4modified Nano carbon is on Festuca Arundinacea overground part heavy metal accumulation concentration and enriching quantity impact
Note: with the different letter representation significant differences of column data (
p<0.05); Lower same.
2.2 add HNO
3the impact of modified Nano carbon on Festuca Arundinacea heavy metal accumulation
As can be seen from Table 2, add the HNO of different quality ratio
3modified Nano carbon all can reduce Festuca Arundinacea overground part heavy metal Cd, Cr, and Cu, Zn, Pb enrichment concentration, wherein adds mass ratio and is 3% and 5% HNO
3modified Nano carbon processed group and control group produce significant difference, reduce effect best be the mass ratio modified Nano carbon processed group that is 5%, five heavy metal species enrichment concentration have reduced by 79.79%, 40.39% than control group respectively, 37.98%, 43.87%, 34.66%.
Add the HNO of different quality ratio
3modified Nano carbon all can reduce Festuca Arundinacea overground part heavy metal Cd, Cr, Cu, Zn, the impact of Pb enriching quantity and enrichment concentration are different, and it is high that the Festuca Arundinacea overground part heavy metal accumulation amount of the modified Nano carbon processed group that interpolation mass ratio is 1% is compared control group, but not remarkable; And the Festuca Arundinacea overground part heavy metal accumulation amount of to add mass ratio be 5% modified Nano carbon processed group is compared control group and significantly reduced, heavy metal accumulation amount has all reduced by 70.00%, 28.70%, 25.70%, 33.06%, 22.22% than control group in five.
Table 2 adds HNO
3modified Nano carbon is on Festuca Arundinacea overground part heavy metal accumulation concentration and enriching quantity impact
Note: with the different letter representation significant differences of column data (
p<0.05); Lower same.
2.3 add KMnO
4the impact of modified Nano carbon on Festuca Arundinacea heavy metal accumulation
Add the HNO of different quality ratio
3modified Nano carbon can reduce plant shoot and divide heavy metal accumulation concentration, for Cd, and Cr, Cu, Zn, Pb five heavy metal species, add mass ratio and be 3% and 5% modified Nano carbon all with contrast generation significant difference, adding 5% modified Nano carbon processed group reduces at most, relative comparison group is respectively 78.72%, 39.36%, and 36.03%, 41.51%, 36.60%.
Can be found out by table 3, add the HNO of different quality ratio
3modified Nano carbon is different from enrichment concentration affects rule to Festuca Arundinacea overground part heavy metal accumulation amount, except the control group heavy metal accumulation amount of heavy metal Zn higher than processed group, other heavy metals be all mass ratio be 1% modified Nano carbon processed group heavy metal accumulation amount higher than control group, but not remarkable; Mass ratio be 5% modified Nano carbon processed group Festuca Arundinacea aerial part heavy metal accumulation amount significantly lower than control group, heavy metal Cd, Cr, Cu, Zn, Pb enriching quantity has all reduced by 70.00%, 26.85% than control group, 22.54%, 36.44%, 23.81%.
Table 3 adds KMnO
4modified Nano carbon on the impact of Festuca Arundinacea overground part heavy metal accumulation concentration and enriching quantity (
μg/g)
Note: with the different letter representation significant differences of column data (
p<0.05); Lower same.
2.4 add H
2sO
4modified Nano carbon affects compost available heavy metal
Add H
2sO
4modified Nano carbon has reduced available heavy metal content in compost, from table 4, we can find out, except available state heavy metal Cr, only have and add modified Nano carbon group and the control group generation significant difference that mass ratio is 5%, available heavy metal Cu processed group all produces significant difference with control group, add 3% and 5% modified Nano carbon and all make available heavy metal Cd, Zn, the content of Pb and control group produce significant difference.Wherein 5% processed group effect of 5 kinds of available heavy metals is best, available heavy metal Cd, and Cr, Cu, Zn, Pb has all reduced by 30.00%, 22.45% than control group, and 27.87%, 28.35%, 22.06%.
Table 4 adds H
2sO
4modified Nano carbon to compost available heavy metal enrichment concentration affects (
μg/g)
Note: with the different letter representation significant differences of column data (P<0.05); Lower same.
2.5 add HNO
3modified Nano carbon affects compost available heavy metal
From table 5, we can find out, add the HNO of different quality ratio
3modified Nano carbon all can reduce available heavy metal content in compost, and except available state heavy metal Zn, processed group all produces significant difference with control group; 3% and 5% modified Nano carbon and processed group all make available heavy metal Cd, Cr, Cu, the heavy content of Pb available state is significantly lower than control group, and wherein 5% processed group effect of 5 kinds of available heavy metals is best, available heavy metal Cd, Cr, Cu, Zn, Pb has all reduced by 35.14% than control group, 26.81%, 32.99%, 28.59%, 35.24%.
Table 5 adds HNO
3modified Nano carbon to compost available heavy metal enrichment concentration affects (
μg/g)
Note: with the different letter representation significant differences of column data (
p<0.05); Lower same
2.6 add KMnO
4modified Nano carbon affects compost available heavy metal
From table 6, we can find out, add the KMnO of different quality ratio
4modified Nano carbon all can reduce available heavy metal content in compost, except available state heavy metal Cd and Cr, adds 3% and 5% modified Nano carbon processed group and control group and produces significant difference, available heavy metal Cu, Zn, the processed group of Pb all produces significant difference with control group, wherein 5% processed group effect of 5 kinds of available heavy metals is best, available heavy metal Cd, Cr, Cu, Zn, Pb has all reduced by 39.19% than control group, 35.22%, 34.78%, 29.52%, 39.32%.
Table 6 adds KMnO
4modified Nano carbon to compost available heavy metal enrichment concentration affects (
μg/g)
Note: with the different letter representation significant differences of column data (
p<0.05); Lower same.
2.7 the impact contrast of three kinds of different modified Nano carbon of interpolation 5% on compost heavy metal accumulation amount
Add mass ratio and be 1%, 3% and 5% modified Nano carbon all can reduce available heavy metal enrichment concentration in compost.Wherein three kinds of modified Nano carbon is that to add 5% quality more best than effect, and we are summarized as table 7 and find, removing heavy metals Cd is with H
2sO
4modified Nano carbon processed group effect is best, and three kinds of modified Nano carbon are KMnO to the passivation effect of compost heavy metal
4modification > HNO
3modification > H
2sO
4modification.
In the time that being contrasted, nano-carbon modified front and back specific area finds KMnO
4the specific area of modified Nano carbon is all higher than other 2 kinds of modified Nano carbon, and high specific area can improve the absorption property of carbon black.But, HNO
3the specific area minimum of modified Nano carbon, even compares former carbon black and decreases, and heavy metal passivation effect amount is but better than H
2sO
4modified Nano carbon.HNO
3the carboxyl-content of modified Nano carbon and acid total group content are all higher than other two kinds of modified Nano carbon, and the increase of the acidic-group that this polarity of surperficial carboxyl is stronger, can improve the adsorption strength of active carbon to polar substances, from this aspect, HNO
3modified Nano carbon has some superiority.
The modified Nano carbon that three kinds of mass ratioes of table 7 are 5% for the impact of available heavy metal enriching quantity in compost (
μg/g)
Note: with the different letter representation significant differences of column data (
p<0.05); Lower same.
3 development conclusions
(1) use 3 kinds of oxidants to carry out oxidation modification meeting to nano-sized carbon its specific area is changed, wherein HNO
3modification reduces nano-sized carbon specific area, and KMnO
4the specific area of nano-sized carbon is increased, be conducive to improve its absorption property.
(2) oxidation modification has changed the surface chemical property of nano-sized carbon, has increased the content of its surface acidity group, has improved its chemisorbed performance, and HNO
3and KMnO
4the more notable surperficial carboxyl-content that has improved nano-sized carbon of modification, has strengthened its absorption to polar substances, is conducive to the passivation to heavy metal.
(3) interpolation mass ratio is 1%, 3%, 5% modified Nano carbon, and the effectively heavy metal in passivation compost, reduces its available state content, wherein to add mass ratio as 5% modified Nano carbon effect optimum.
Detailed description of the invention:
Below in conjunction with specific embodiment, the present invention will be further described, and following each embodiment is not only limitation of the present invention for the present invention is described.Wherein chemical reagent used all has commercially available.
Embodiment 1
Modified Nano carbon is undertaken by following step the fixing enrichment method of urban life compost heavy metal:
(1) processing of material:
Before experiment, garbage compost is carried out to pretreatment, removes the bulk foreign material such as plastic sheeting, brick and tile, stone and glass wherein, air-dry after, cross 2 mm and sieve, for subsequent use; Garbage compost physicochemical property is: pH 7.62, the content of organic matter 221.25 gkg
-1, full nitrogen 13.48 gkg
-1, available phosphorus 0.078 gkg
-1, C/N is 8.37, saturation moisture content 0.76 mLg
-1, unit weight 0.85 gmL
-1; Heavy metal (Cr, Cu, Pb, Zn) content is respectively 67.00,238.73,172.11 and 496.38 mgkg
-1;
Plants selection Festuca Arundinacea (
festuca arundinaceal
.);
Nano-sized carbon particle diameter 20nm, specific area is 1.2 × 10
5m
2kg
-1, pH value is 7, uses front it to be carried out to modification, obtains respectively KMnO
4, H
2sO
4or HNO
3the nano-sized carbon of modification;
(2) experimental technique:
At the pvc pipe of high 25 cm of diameter 3 cm, lower end is sealed with one deck cotton and nylon wire, and garbage compost and each modified Nano carbon are mixed in proportion, and packs composite material 150g in every pipe into; After passivation 7 d, every pipe sowing 0.2 g tall fescue seed, experimental session temperature is 19 DEG C, and relative humidity is 60%-72%, and keep the skin wet every day to compost, makes compost moisture reach field capacity 70%, at laboratory balance 30d, carries out Speciation Analysis of Heavy Metals; The addition of wherein said each modified Nano carbon is the 1%(w/w of garbage compost weight).
Embodiment 2
The fixing enrichment method of modified Nano carbon to urban life compost heavy metal, is undertaken by following step:
(1) processing of material:
Before experiment, garbage compost is carried out to pretreatment, removes the bulk foreign material such as plastic sheeting, brick and tile, stone and glass wherein, air-dry after, cross 2 mm and sieve, for subsequent use; Garbage compost physicochemical property is: pH 7.62, the content of organic matter 221.25 gkg
-1, full nitrogen 13.48 gkg
-1, available phosphorus 0.078 gkg
-1, C/N is 8.37, saturation moisture content 0.76 mLg
-1, unit weight 0.85 gmL
-1; Heavy metal (Cr, Cu, Pb, Zn) content is respectively 67.00,238.73,172.11 and 496.38 mgkg
-1;
Plants selection Festuca Arundinacea (
festuca arundinaceal
.);
Nano-sized carbon particle diameter 70 nm, specific area is 1.2 × 10
5m
2kg
-1, pH value is 7, uses front it to be carried out to modification, obtains respectively KMnO
4, H
2sO
4or HNO
3the nano-sized carbon of modification;
(2) experimental technique:
At the pvc pipe of high 25 cm of diameter 3 cm, lower end is sealed with one deck cotton and nylon wire, and garbage compost and each modified Nano carbon are mixed in proportion, and packs composite material 150g in every pipe into; After passivation 7 d, every pipe sowing 0.2 g tall fescue seed, experimental session temperature is 27 DEG C, and relative humidity is 60%, and keep the skin wet every day to compost, makes compost moisture reach field capacity 70%, at laboratory balance 30d, carries out Speciation Analysis of Heavy Metals; The addition of wherein said each modified Nano carbon is the 3%(w/w of garbage compost weight).
Embodiment 3
The fixing enrichment method of modified Nano carbon to urban life compost heavy metal, is undertaken by following step:
(1) processing of material:
Before experiment, garbage compost is carried out to pretreatment, removes the bulk foreign material such as plastic sheeting, brick and tile, stone and glass wherein, air-dry after, cross 2 mm and sieve, for subsequent use; Garbage compost physicochemical property is: pH 7.62, the content of organic matter 221.25 gkg
-1, full nitrogen 13.48 gkg
-1, available phosphorus 0.078 gkg
-1, C/N is 8.37, saturation moisture content 0.76 mLg
-1, unit weight 0.85 gmL
-1; Heavy metal (Cr, Cu, Pb, Zn) content is respectively 67.00,238.73,172.11 and 496.38 mgkg
-1;
Plants selection Festuca Arundinacea (
festuca arundinaceal
.);
Nano-sized carbon particle diameter 60 nm, specific area is 1.2 × 10
5m
2kg
-1, pH value is 7, uses front it to be carried out to modification, obtains respectively KMnO
4, H
2sO
4or HNO
3the nano-sized carbon of modification;
(2) experimental technique:
At the pvc pipe of high 25 cm of diameter 3 cm, lower end is sealed with one deck cotton and nylon wire, and garbage compost and each modified Nano carbon are mixed in proportion, and packs composite material 150g in every pipe into; After passivation 7 d, every pipe sowing 0.2 g tall fescue seed, experimental session temperature is 25 DEG C, and relative humidity is 60%, and keep the skin wet every day to compost, makes compost moisture reach field capacity 70%, at laboratory balance 30d, carries out Speciation Analysis of Heavy Metals; The addition of wherein said each modified Nano carbon is the 5%(w/w of garbage compost weight).
Claims (7)
1. the fixing enrichment method of modified Nano carbon to urban life compost heavy metal, is characterized in that being undertaken by following step:
(1) processing of material:
Before experiment, garbage compost is carried out to pretreatment, removes foreign material wherein, air-dry after, cross 2 mm and sieve, for subsequent use; Plants selection Festuca Arundinacea (
festuca arundinaceal
.); Nano-sized carbon particle diameter 20-70 nm, specific area is 1.2 × 10
5m
2kg
-1, pH value is 7, uses front it to be carried out to modification, obtains respectively KMnO
4, H
2sO
4or HNO
3the nano-sized carbon of modification;
(2) experimental technique:
At the pvc pipe of high 25 cm of diameter 3 cm, lower end is sealed with one deck cotton and nylon wire, and garbage compost and each modified Nano carbon are mixed in proportion, and packs composite material 150g in every pipe into; After passivation 7 d, every pipe sowing 0.2 g tall fescue seed, experimental session temperature is 19 ~ 27 DEG C, relative humidity is 60%-72%, and keep the skin wet every day to compost, makes compost moisture reach field capacity 70%, at laboratory balance 30d, carry out Speciation Analysis of Heavy Metals; The addition of wherein said each modified Nano carbon is the 1-5%(w/w of garbage compost weight).
2. preparation method claimed in claim 1, wherein adds respectively the percetage by weight of the nano-sized carbon of modification to be in garbage compost: 1%, 3% or 5%(w/w).
3. preparation method claimed in claim 1, wherein adds respectively 1%, 3%, 5% H in garbage compost
2sO
4modified Nano carbon; In garbage compost, add respectively 1%, 3%, 5% HNO
3modified Nano carbon; In garbage compost, add respectively 1%, 3%, 5% KMnO
4modified Nano carbon.
4. described in claim 1, modified Nano carbon is improving Festuca Arundinacea to the application aspect heavy metal accumulation to the fixing enrichment method of urban life compost heavy metal, and described modified Nano carbon refers to HNO
3or H
2sO
4modified Nano carbon.
Described in claim 1 modified Nano carbon to the fixing enrichment method of urban life compost heavy metal at the application improving aspect its absorption property, wherein KMnO
4the specific area of nano-sized carbon is increased.
6. described in claim 1, modified Nano carbon is strengthening the application aspect the passivation of heavy metal, wherein said KMnO the fixing enrichment method of urban life compost heavy metal
4the addition of modified Nano carbon is the 5%(w/w of garbage compost weight), oxidation modification has changed the surface chemical property of nano-sized carbon in this case, has increased the content of its surface acidity group, has improved its chemisorbed performance, and HNO
3and KMnO
4the more notable surperficial carboxyl-content that has improved nano-sized carbon of modification, has strengthened its absorption to polar substances, is conducive to the passivation to heavy metal and fixes.
7. described in claim 1, modified Nano carbon increases organic matter and sulfide in conjunction with the application aspect state content to the fixing enrichment method of urban life compost heavy metal at the content that reduces heavy metal Fe/Mn oxidizable in compost; Wherein said KMnO
4, H
2sO
4or HNO
3the addition of modified Nano carbon is the 5%(w/w of garbage compost weight).
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