CN103084153A - Method for preparing nano black carbon passivator for repairing heavy metal contaminated soil - Google Patents
Method for preparing nano black carbon passivator for repairing heavy metal contaminated soil Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of novel materials and relates to a method for preparing a nano black carbon passivator for repairing heavy metal contaminated soil. The method comprises the following steps of: weighing nano black carbon raw materials and putting the raw materials in a glass container, adding HNO3 and KMnO4, uniformly mixing so as to obtain a mixed oxidant, putting the nano black carbon and the mixed oxidant in a ventilating kitchen, and standing at room temperature so as to obtain the pre-oxidized nano black carbon; heating the pre-oxidized nano black carbon by utilizing a constant temperature water bath kettle, thus obtaining the oxidized nano black carbon; centrifuging the oxidized nano black carbon in a centrifugal machine, and pouring the supernatant; adding distilled water, and repeatedly centrifuging until the pH value of the centrifuged supernatant is more than 5.5, thus obtaining the washed modified nano black carbon; and controlling the temperature of the washed modified nano black carbon to be 105 DEG C, and drying in a dryer, thus obtaining the product. The method is simple in process principle, low in preparation cost, high in product quality, environment-friendly in production, high in economic benefits, wide in product application range and good in a using effect.
Description
Technical field:
The invention belongs to technical field of new material preparation, relate to a kind of nano black carbon passivator preparation method who is applied to the novel preparation process, particularly a kind of heavy-metal contaminated soil reparation use of the nano black carbon surface modification passivator that the heavy-metal contaminated soil passivation repairs.
Background technology:
China's heavy metal pollution of soil problem is increasingly serious, especially the farmland area of aobvious outstanding and slight heavy metal pollution of Pb, Cd, Cu, Hg and combined pollution day thereof constantly enlarges, and the passivation recovery technique becomes slight heavy-metal contaminated soil, and especially the heavy-metal composite pollution soil remediation has one of technology of application prospect most.The key of this technology successful Application is exactly to prepare that remediation efficiency is high, the stable strong passivator of passivation.The volatile matter that black carbon (Black Carbon) is organism or fossil feedstock changes into when imperfect combustion or high temperature pyrolysis, is the product of gaseous process, and the black carbon surface that generally forms is long-pending is 89 ± 2m
2/ g; Diameter is 30-50nm, and density is 1.8-2.0g/cm
3Element set becomes C (87%-92.5%), H (1.2%-1.6%), O (6.0%-11%); Architectural characteristic with aromatic compound has many carboxyls, phenolic hydroxyl group, carbonyl etc. to contain the oxygen functional group.Therefore, black carbon belongs to the nano material of porous aromatic compound structure, have stronger from environment the ability of adsorbent.Exactly because the specific area that nano black carbon is larger, high active site position and good photoelectric properties, its in the application prospect in pollution control field by people's extensive concern.But nano black carbon is hydrophobic non-polar adsorbent, nonpolar organic matter had stronger affinity, can the 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, and to the adsorptivity of polarity heavy metal ion a little less than.There are some researches show: black carbon is to Pb
2+Maximal absorptive capacity is much smaller than mineral and humic acid.Therefore, must carry out surface modification to it, making it has stronger absorption passivation ability to the polarity heavy metal.
In the prior art, nano black carbon is by oxidation modification, can increase C=C and O-H functional group, and newly introduce the functional groups such as O=C-OH, C-O and CNO, thereby weakened it to the absorption of weak organic substance of polarity, strengthened the absorption to the polarity heavy metal ion.Simultaneously, due to nano black carbon ubiquity in soil, and to germination and not significantly harm of plant growth.Therefore, nano black carbon after Surface Oxidation Modification, is the eco-friendly passivator that a kind of heavy-metal contaminated soil is repaired.At present, to the modification of nano black carbon surface highly acid oxidant commonly used, strong oxidizer modification meeting goes to pot its micropore architecture, and transitional pore is to increase, and absorption property obviously reduces.In addition, high concentration strong acid oxidation modification nano black carbon also is faced with the problems such as the after-treatment of modification waste water and passivator production cost height, will affect applying of this technology.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seeking to design provides a kind of nano black carbon of heavy-metal contaminated soil reparation use passivator preparation method, take business nano black carbon as raw material, adopt low concentration nitric acid and potassium permanganate hybrid oxidant and two-section low-temperature oxidizing process thereof to prepare the black carbon passivator of modified Nano, for the slight passivation reparation of heavy-metal contaminated soil or heavy-metal composite pollution soil provides efficient passivator.
To achieve these goals, specific embodiment of the present invention comprises the following steps:
(1) pre-oxidation: take nano black carbon raw material (g), be placed in glass container, add 3.17mol/LHNO
3With 0.1mol/LKMnO
4(or weight percent concentration is 20%HNO
3With 1.58%KMnO
4Mix) even mixed hybrid oxidant (mL), the mass volume ratio=1g:10mL of nano black carbon and hybrid oxidant is placed in ventilating kitchen, and the standing 24h of room temperature obtains the nano black carbon after pre-oxidation;
(2) oxidation: nano black carbon after pre-oxidation is utilized thermostat water bath heating, and temperature is controlled at 90 ± 2 ℃, and oxidation reaction 3 hours gets the nano black carbon after oxidation;
(3) washing: with the nano black carbon after oxidation in centrifuge with 4000 rev/mins centrifugal 15 minutes, outwell supernatant; Add distilled water, controlling centrifuge speed is 180 rev/mins, reciprocating vibration 10 minutes, the centrifugal supernatant of removing again; Again add again distilled water, repeat centrifugally, until the supernatant pH after centrifugal＞5.5, get the black carbon of modified Nano after washing;
(4) oven dry: the black 105 ℃ of oven dry of carbon temperature control of the modified Nano after washing are placed in drier standby, namely make product.
After the imperfect combustion that nano black carbon raw material of the present invention is coal, oil and natural gas or decomposes, formed black carbon powder end, adopt conventional oven process, channel process or pyrolysis method to prepare nano black carbon, and nano black carbon iodine absorption value is 700-900g/kg; The BDP absorption value is 400 * 10
-5-500 * 10
-5m
3/ kg; The nitrogen adsorption specific surface area is 800 * 10
3-900 * 10
3m
2/ kg; Heating loss (max)=1%; The powder resistance rate is 0.12 Ω .cm; Average grain diameter is 30-40nm; Ash content≤5-8%.
The preparation weight percent concentration of the hybrid oxidant that the present invention relates to is the red fuming nitric acid (RFNA) (HNO of 50%-70%
3) and the potassium permanganate of weight percent concentration 〉=99% mix, first red fuming nitric acid (RFNA) is diluted to weight percent concentration and is 20% salpeter solution, put into glass container or plastic containers are standby; Be 20% HNO again with weight percent concentration
3Solution dissolving potassium permanganate, every liter of 20%HNO
3Solution dissolving 15.8g KMnO
4, be mixed into hybrid oxidant.
Centrifugal process or decompress filter method are adopted repeatedly in the washing of the nano black carbon after the oxidation modification that the present invention relates to.
The present invention compared with prior art, its technological principle is simple, preparation cost is low, good product quality, production environment is friendly, economic benefit is high, the product applied range, result of use is good.
Description of drawings:
Fig. 1 is the CB that the present invention relates to and the infrared spectrum line chart of OCB, wherein, CB and OCB be respectively oxidation repair before and repair after nano black carbon, below agree.
Fig. 2 is the CB that the present invention relates to and the Zeta potential curve map of OCB.
Fig. 3 is the amplification comparison diagram of the SEM figure of the CB that the present invention relates to and OCB, and wherein a is that CB amplifies 350 times, and b is that OCB amplifies 350 times, and c is that CB amplifies 2500 times, and d is that OCB amplifies 2500 times.
Fig. 4 is that the OCB DTPA in heavy-metal contaminated soil that the present invention relates to extracts the attitude impact.
Fig. 5 is the OCB rye grass biomass impact in heavy-metal contaminated soil that the present invention relates to.
Fig. 6 is that the OCB rye grass in heavy-metal contaminated soil that the present invention relates to absorbs the impact of heavy metal amount.
The specific embodiment:
Also the invention will be further described by reference to the accompanying drawings below by embodiment.
The specific embodiment of the present embodiment comprises the following steps:
(1) pre-oxidation: take nano black carbon raw material (g), be placed in glass container, add 3.17mol/LHNO
3-0.1mol/LKMnO
4(or 20%HNO
3-1.58%KMnO
4) hybrid oxidant (mL), make mass volume ratio=1g:10mL, be placed in ventilating kitchen, the standing 24h of room temperature obtains the nano black carbon after pre-oxidation;
(2) oxidation: nano black carbon after pre-oxidation is utilized thermostat water bath heating, and temperature is controlled at 90 ± 2 ℃, and oxidation reaction 3 hours gets the nano black carbon after oxidation;
(3) washing: the nano black carbon after oxidation at 4000 rev/mins, centrifugal 15 minutes, is outwelled supernatant.Add distilled water, being controlled at rotating speed is 180 rev/mins again, reciprocating vibration 10 minutes, the centrifugal supernatant of removing; Again add again distilled water, repeat centrifugally, until the supernatant pH after centrifugal＞5.5, get the black carbon of modified Nano after washing;
(4) oven dry: the black carbon of the modified Nano after cleaning is placed in drier standby in 105 ℃ of oven dry, namely make product.
Embodiment 1: the screening of oxidant
The present embodiment first selects five kinds of oxidants (concentration of oxidant sees Table 1) that red fuming nitric acid (RFNA), sulfuric acid, potassium permanganate, sulfuric acid+potassium permanganate and nitric acid+potassium permanganate forms respectively as a comparison, take respectively again 5 groups of nano black carbon, every group of 20g is in the 250ml conical flask, add the 200ml oxidant in each bottle, after being put in respectively the interior standing 24h of ventilating kitchen, carry out oxidation reaction, below by the operation of technical process step, prepare respectively the black carbon passivator of five kinds of modified Nanos under the oxidant oxidizing condition; Then take respectively some parts of the black carbon of 0.1g modified Nano, be placed in respectively centrifuge tube, add respectively the Cu(NO of 20ml
3)
2Solution, its concentration is respectively 30mg/L, 50mg/L, 70mg/L, 100mg/L, 130mg/L, 160mg/L, 200mg/L, in 25 ℃ of constant temperature oscillation 2h, is placed in 25 ℃ of thermostatic drying chambers and keeps 24h, get supernatant centrifugal 15min under 4000r/min, measure the Cu of supernatant
2+Content, minusing calculates adsorbance, triplicate, result shows: the adsorption capacity to Cu after nitric acid+potassium permanganate hybrid oxidant modification is the strongest, as table 1.
The different oxidants of table 1 are on the impact of the black carbon of modified Nano on heavy metal adsorption
| The oxidant kind | Maximal absorptive capacity (mg/g) to Cu |
| 69% red fuming nitric acid (RFNA) | 38.98 |
| The 1:1 concentrated sulfuric acid | 5.48 |
| 10% potassium permanganate | 15.13 |
| 1:2 sulfuric acid+1.58% potassium permanganate | 9.57 |
| 20% nitric acid+1.58% potassium permanganate | 83.33 |
Embodiment 2: nitric acid+potassium permanganate oxidant oxidation technology parameter
(1) oxidant concentration determines
20%HNO
3Respectively with the KMnO of 0.05～0.20mol/L
4Solution is made a series of nitric acid-potassium permanganate hybrid oxidant; Below by the operation of technical process step, prepare respectively the black carbon passivator of modified Nano under variable concentrations nitric acid-potassium permanganate hybrid oxidant oxidizing condition; As shown in Table 2: when potassium permanganate concentration is 0.10mol/L, to Cu
2+Adsorbance maximum;
Table 2 potassium permanganate concentration is on the impact of the black carbon of modified Nano on heavy metal adsorption
| Potassium permanganate concentration/(mol/L) | Adsorbance (mg/g) to Cu |
| 0.05 | 13.51 |
| 0.10 | 15.85 |
| 0.20 | 15.13 |
(2) oxidization time determines
With 20%HNO
3-1.58%KMnO
4Be hybrid oxidant, oxidization time is selected respectively 0.5～4h, and other operation is prepared respectively the black carbon passivator of modified Nano under different oxidization time conditions by the operation of technical process step; By being 3h when the reaction time as seen from Table 3, to Cu
2+Adsorbance reach 14.50mg/g, increasing the reaction time, adsorbance increases little, therefore the selection reaction time is 3h;
Table 3 oxidation time is on the impact of the black carbon of modified Nano on heavy metal adsorption
| Oxidation time | Adsorbance (mg/g) to Cu |
| 0.5h | 11.95 |
| 1.0h | 12.04 |
| 1.5h | 13.07 |
| 2.0h | 13.08 |
| 2.5h | 13.62 |
| 3.0h | 14.50 |
| 3.5h | 14.53 |
| 4.0h | 14.60 |
(3), oxidizing temperature determines
With 20%HNO
3-1.58%KMnO
4Be hybrid oxidant, oxidizing temperature is selected respectively 20 ℃～90 ℃, and other operation is prepared respectively the black carbon passivator of modified Nano under different oxidizing reaction temperature spares by the operation of technical process step; Increase with reaction temperature as shown in Table 4, passivator increases the adsorbance of Cu in solution, therefore select 90 ℃ to be reaction temperature;
Table 4 oxidizing reaction temperature is on the impact of the black carbon of modified Nano on heavy metal adsorption
| Oxidization time | Adsorbance (mg/g) to |
| 20℃ | 11.41 |
| 40℃ | 13.18 |
| 60℃ | 12.37 |
| 80℃ | 13.58 |
| 90℃ | 14.46 |
(4), system acidity determines
0.10mol/L KMnO
4Respectively with 10%-45%HNO
3Solution is made the nitric acid of different acidity-potassium permanganate hybrid oxidant; Below by the operation of technical process step, prepare respectively the black carbon passivator of modified Nano under different acidity nitric acid-potassium permanganate hybrid oxidant oxidizing condition; As shown in Table 5: when the nitric acid addition was 20%, passivator had reached 14.10mg/g to the adsorbance of Cu in solution, then increases concentration of nitric acid, and adsorbance increases little; Therefore, selecting weight percent concentration is that 20% nitric acid is as the acidity of reaction system;
Table 5 oxidation reaction acidity is on the impact of the black carbon of modified Nano on heavy metal adsorption
| Concentration of nitric acid (mass percent) | Adsorbance (mg/g) to |
| 10% | 11.18 |
| 20% | 14.10 |
| 35% | 14.30 |
| 45% | 14.38 |
Embodiment 3: the black carbon passivator appearance structure of modified Nano and surface characteristic
(1), oxidation modification rear surface oxygen-containing functional group increases
Fig. 1 is the infrared spectrogram of (CB and OCB) before and after the modification of nano black carbon passivator, and before modification, (CB's) goes out the peak position at 1619cm
-1And 3450cm
-1Locate, be respectively the stretching vibration of C=C stretching vibration and O-H; After modification on the infrared spectrum of (OCB) except this two place peak area increases, 1244.0cm has newly appearred
-1, 1721.6cm
-1, 447.3cm
-1At the peak, be respectively the stretching vibration of C-O, the stretching vibration of C=O and the flexural vibrations of CNO group; CB is described after oxidation modification, except C=C and O-H functional group increase than CB, has also increased C-O, C=O and CNO functional group newly on the OCB surface; Increasing of surface oxygen functional group is conducive to nano carbon black to the absorption of polarity heavy metal;
(2), oxidation modification rear surface negative electrical charge increases
Fig. 2 as can be known, OCB is all electronegative in the scope of pH2-9, carried charge increases with the rising of pH, and is linear correlation (Y=-7.03X-2.22, r=0.98, P＜0.05); During by pH=3-when 20mV is reduced to pH=8-60mV; The Zeta potential of CB and pH be linear (Y=-7.41X+26.48, r=0.99, P＜0.05) also, and the carried charge of OCB is greater than the carried charge of CB under identical pH; Passivator surface how much charged, the positive and negative size that determines its charge neutrality effect; Infer thus, OCB may be stronger to the adsorption capacity of positively charged ion than CB;
(3), hole, oxidation modification rear surface increases
Fig. 3 is respectively that before and after oxidation modification, nano black carbon amplifies respectively ESEM (SEM) photo of 350 and 2500 times, observing its surface appearance feature finds, the more smooth rule of nano black carbon surface before modification, and after oxidation modification, it is uneven that the surface becomes, roughness increases, and the hole showed increased is conducive to its Adsorption of Heavy Metals.
Embodiment 4: the repairing effect of the black carbon passivator of modified Nano
(1), to the adsorption effect of heavy metal in solution
Table 6 is Cu
2+And Cd
2+Adsorption isotherm on CB and OCB, both can well use Langmuir equation and Freundlich equation model, R
2Difference 0.935-0.992; The Langmuir equation model goes out Cu
2+And Cd
2+Maximal absorptive capacity is respectively 83.333gkg on OBC
-1And 10.309gkg
-1, maximal absorptive capacity has increased respectively 5.17 times and 1.81 times before than oxidation modification;
Table 6CB and OCB to heavy metal adsorption isotherm
(2), to the passivation effect of heavy metal in soil
Add OCB and cultivate after 30 days in heavy-metal contaminated soil, along with the increase of OCB addition, each processes soil available Cu and Zn content reduces (Fig. 4) gradually; The OCB addition is respectively 1%, 3%, 5% processing, and soil available Cu has reduced respectively 31.34%, 60.98%, 71.17% compared with the control; The comparison of soil available Zn content is taken a picture and has been reduced by 20.24%, 35.76%, 44.05% than respectively; Illustrate that OCB has stronger passivation ability to heavy metal in soil;
(3), to the passivation effect of heavy metal in soil-botanical system
Add OCB in heavy-metal contaminated soil and significantly increased rye grass on the ground and the biomass of underground part, and increase (Fig. 4) with the increase of MCB addition; Interpolation 1%OCB, 3%OCB, 5%OCB make the biomass of rye grass overground part increase by 71.6%, 172.8% and 413.2% than CK respectively; The underground part biomass has increased by 49.1%, 220.1% and 435.6% than CK respectively.Heavy metal pollution is added OCB and has significantly been reduced rye grass overground part Cu and Zn content, and reduces (Fig. 5) with increase rye grass overground part Cu and the Zn content of OCB addition; With the contrastive ratio, greater than 1% the time, rye grass overground part Cu content reduces and reaches the level of signifiance (p＜0.05) when the OCB addition; Greater than 3% the time, rye grass overground part Zn content reduces and reaches the level of signifiance (p＜0.05) when the OCB addition; Illustrate add OCB can the passivation heavy metal in soil, reduce plant to the absorption of heavy metal, thereby improved the biomass of plant.
Claims (3)
1. the nano black carbon passivator preparation method of a heavy-metal contaminated soil reparation use, is characterized in that specific embodiment comprises the following steps:
(1) pre-oxidation: take nano black carbon raw material, be placed in glass container, add the even mixed hybrid oxidant of 3.17mol/L nitric acid and 0.1mol/L potassium permanganate, mass volume ratio=the 1g:10mL of nano black carbon and hybrid oxidant, be placed in ventilating kitchen, the standing 24h of room temperature obtains the nano black carbon after pre-oxidation;
(2) oxidation: nano black carbon after pre-oxidation is utilized thermostat water bath heating, and temperature is controlled at 90 ± 2 ℃, and oxidation reaction 3 hours gets the nano black carbon after oxidation;
(3) washing: with the nano black carbon after oxidation in centrifuge with 4000 rev/mins centrifugal 15 minutes, outwell supernatant; Add distilled water, controlling centrifuge speed is 180 rev/mins, reciprocating vibration 10 minutes, the centrifugal supernatant of removing again; Again add again distilled water, repeat centrifugally, until the supernatant pH after centrifugal＞5.5, get the black carbon of modified Nano after washing;
(4) oven dry: the black 105 ℃ of oven dry of carbon temperature control of the modified Nano after washing are placed in drier standby, namely make product.
2. the nano black carbon passivator preparation method of heavy-metal contaminated soil reparation use according to claim 1, it is characterized in that the nano black carbon raw material that adopts is formed black carbon powder end after the imperfect combustion of coal, oil and natural gas or decomposes, adopt conventional oven process, channel process or pyrolysis method to prepare nano black carbon, nano black carbon iodine absorption value is 700-900g/kg; The BDP absorption value is 400 * 10
-5-500 * 10
-5m
3/ kg; The nitrogen adsorption specific surface area is 800 * 10
3-900 * 10
3m
2/ kg; Heating loss max=1%; The powder resistance rate is 0.12 Ω .cm; Average grain diameter is 30-40nm; Ash content≤5-8%.
3. the nano black carbon passivator preparation method of heavy-metal contaminated soil reparation use according to claim 1, the preparation weight percent concentration that it is characterized in that the hybrid oxidant that relates to is that the red fuming nitric acid (RFNA) of 50%-70% and the potassium permanganate of weight percent concentration 〉=99% mix, first red fuming nitric acid (RFNA) is diluted to weight percent concentration and is 20% salpeter solution, put into glass container or plastic containers are standby; Be 20% salpeter solution dissolving potassium permanganate with weight percent concentration again, every liter of 20% salpeter solution dissolving 15.8g potassium permanganate is mixed into hybrid oxidant.
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| CN105523840A (en) * | 2015-12-29 | 2016-04-27 | 芜湖市创源新材料有限公司 | An organic fertilizer specially used for grapes |
| CN105879838A (en) * | 2016-06-12 | 2016-08-24 | 山东师范大学 | Method for preparing efficient heavy metal adsorbent from modified cotton stalk biomass charcoal |
| CN109158411A (en) * | 2018-06-26 | 2019-01-08 | 昆明理工大学 | The method of one heavy metal species soil modification |
| CN109158412A (en) * | 2018-06-26 | 2019-01-08 | 昆明理工大学 | A kind of method of harmless treatment heavy metal soil |
| CN110038514A (en) * | 2019-03-29 | 2019-07-23 | 山东师范大学 | A kind of nanometer hydroxyapatite dry method modification nano black carbon heavy metal absorbent and the preparation method and application thereof |
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