CN104941575A - Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method - Google Patents
Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method Download PDFInfo
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Abstract
The invention provides a preparation method of an ethylenediamine grafted modified biomass carbon composite material for selectively fixing metal mercury (II), chromium (III) and lead (II) in soil, aiming at solving the actual problems that an existing passivant has small adsorption capacity on heavy metal of the soil, low selectivity and bad safety. The novel multi-amino biomass carbon composite material agent takes common substances including agricultural straw biomass, hydrochloric acid, nitric acid, ethylenediamine and the like as raw materials and is prepared through carbonization, carboxylation and molecule copolycondensation, and has abundant pore channels and abundant content of surface multi-amino groups; and the product has large fixed capacity and good selectivity on mercury (II), chromium (III) and lead (II) in the heavy metal polluted soil, has the advantages of simple process, easiness for implementation and the like, and can be produced in a large batch.
Description
Technical field
The invention belongs to safety of soil environment and resource reutilization technical field, be specifically related to a kind ofly select mercury in heavy metal-passivated contaminated soil, chromium, plumbous polyamines based biomass carbon composite and preparation method thereof.
Background technology
Soil is one of mankind's Main Natural Resources of depending on for existence, is also the important component part of human ecological environment.Along with China's economy is growing, commercial production scale constantly expands, heavy metal pollution of soil become China's contaminated area the widest, endanger one of maximum environmental problem.According to the incomplete investigation statistics of State Environmental Protection Administration, about there are 0.1 hundred million hm in Chinese contaminated arable land
2, sewage irrigation arable land 216.67hm
2, solid waste is stored up and is taken up an area and ruin field 13.33 ten thousand hm
2, add up to and account for more than 1/10 of total cultivated area.Since 2009, a series of heavy metal pollution events caused a sensation throughout the country such as the lead contamination of Fengxiang, Shaanxi, liuyang hunan cadmium poisoning, the arsenic pollution of Linyi, Shandong, highlight the sternness of China's heavy metal pollution situation more.Heavy metal pollution of soil has chronicity, latency, cumulative bad and transitivity, causes multiple harm to health, economical production, ecological environment etc., has become the key factor of restriction China's sustainable development and construction of harmonious society.For this reason, research remediation of heavy metal-contaminated soil, the efficient heavy metal-polluted soil passivating material of development of new, effectively administers pollution of area source heavy metal pollution of soil, ensures the sustainable use of land resource, becomes problem demanding prompt solution.
Heavy metal-polluted soil recovery technique mainly contains soil moved in improve the original, leaching, extraction, heat treatment, phytoremediation, chemical passivation etc., wherein utilize passivator repairing heavy metal in soil to pollute and there is economy, the feature such as easy to implement, in, in slight agricultural area source heavy metal pollution of soil reparation, there is great potential.It is reported, the new materials such as biomass carbon, nano black carbon, molecular sieve, carbon nanotube, due to its huge specific area, special surface texture, superpower absorption property, demonstrate obvious advantage in the fixing reparation of heavy-metal contaminated soil.Straw biomass charcoal has large specific area, pore volume and adjustable pore passage structure, be easy to activation modification, also effectively can not only fix restoration of soil polluted by heavy metal behind field, voidage and the water holding capacity of soil can also be increased, reduce the soil weight, strengthen the carbon solidification effect of soil, have good soil ecological conditions.Biomass carbon surface is containing various active groups such as hydroxyl, sulfydryl, carboxyl, amino, and these groups can form ionic bond or covalent bond with the metal ion of absorption, thus reach the object of fixing heavy metal ion.China's farm crop straw organism matter aboundresources, enormous amount, amount usable more than 5.6 hundred million tons, but wherein has 43% directly burned by as fuel or in field.If above-mentioned stalk resource to be prepared into the passivator of efficient fixing heavy metal polluted soil of farmland, can not only effectively alleviate because burning the air pollution brought, and can effective restoration of soil polluted by heavy metal.
The present invention by with agricultural biomass stalk and ethylenediamine for presoma, by the method such as charing, activation, carboxylated and amination the multiporous biological matter charcoal of preparation and polyamine molecule react poly-and, prepare the composite passivated material of modified polyamine biomass carbon of the efficient fixing soil heavy metal of energy.Novel carbon based composites after ethylenediamine grafting hydridization, not only significantly can strengthen the fixed capacity of biomass carbon to Mercury in Soil (II), chromium (III), plumbous (II), and effectively can improve based composite material of carbon to Mercury in Soil, chromium, plumbous selectivity.
Summary of the invention
The present invention is directed to the practical problem that existing biomass carbon is little to heavy metal-polluted soil adsorption capacity, selectivity is low, provide one can select the preparation method of ethylenediamine modified biomass carbon composite of passivation heavy metal-polluted soil mercury (II), chromium (III), plumbous (II).This New Polyamine based biomass carbon composite agent with Common materials such as agricultural stalk living beings and phosphoric acid, nitric acid, ethylenediamines for raw material, obtained by charing, oxidation and molecule copolycondensation, have that duct is many, specific area is large, surperficial polyamine group rich content, in heavy metal contaminated soil, the fixed capacity of mercury (II), chromium (III), plumbous (II) is large, selectivity good, and there is the advantages such as technique is simple, easy to implement, can be mass-produced.
Object of the present invention can be reached by following measures:
A kind of New Polyamine grafting biomass carbon soil heavy metal passivant utilizing agricultural biomass and polyamine molecule to produce and preparation method thereof, comprises the steps:
A), by the agricultural biomass such as cotton stalk, wheat stalk, rice straw, maize straw of maturation gather in, clean, air-dry rear pulverizer pulverizes, powder particle diameter is less than 200 orders, and preferable particle size is 50 ~ 100 orders.
B), above-mentioned agricultural biomass powder of straw is prepared the high surface area porous biomass carbon of rich surface containing oxyacid functional group by physics or chemical activation;
C), by above-mentioned activated carbon from activated sludge with 10% hydrochloric acid solution 60 DEG C stir 5 hours, the nitric acid that purified active carbon powder adds 10 ~ 50% of 100 ~ 500ml again stirs 1 ~ 10 hour, after completion of the reaction that product washing is extremely neutral, filtering drying obtains the multiporous biological matter charcoal being rich in carboxylic acid group.
D), take the above-mentioned carboxylated biomass carbon of 5g, be distributed in 50 ~ 200ml ethylenediamine, to be mixed evenly after, add 5 grams of N, N '-dicyclohexylcarbodiimide, back flow reaction 48 hours.
E), by above-mentioned product first slightly wash with ethanol, then with ether cleaning, then namely obtain new soil heavy metal biological matter charcoal passivating material 80-800 DEG C of oven dry.
Excellent results of the present invention is as follows:
1, heavy metal has the ethylenediamine molecule of stronger complexing to be grafted on straw biomass charcoal by the present invention, prepare polyamines graft modification biomass carbon heavy metal-polluted soil passivating material, achieve and repair the selection of heavy metal-polluted soil mercury (II), chromium (III), plumbous (II) is fixing, develop the soil heavy metal passivant of a kind of low cost high power capacity high selectivity energy.
2, raw materials derives from agricultural biomass stalk, widely distributed in farmland, inexpensive, the preparation method of the biomass carbon adopted is ripe, cost is low, polymerisation grafting polyamine method technique is simple, effective, the polyamines graft modification biomass carbon adsorption capacity adopting said method to prepare is large, by force selective.
3, biomass carbon extensively exists in soil, green non-poisonous, pollution-free in the process preparing active carbon, not welding.Polyamines material
4, simple, the economy of preparation technology of the present invention, environmental protection, meet the needs of recycling economy development, have large-scale production and application prospect.
Accompanying drawing explanation
Fig. 1. the infrared spectrogram of biomass composite before and after amination modifying
Fig. 2. pH value of solution on polyamines change raw biomass carbon composite Adsorption of Mercury (II), chromium (III), plumbous (II) impact (solution concentration of mercury (II), chromium (III), plumbous (II) is 50mg/L, liquor capacity 100mL, quantity of sorbent is 0.10g, adsorption time 1h)
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but be not limited thereto.
Example 1:
By the bagasse powder after clean oven dry and phosphoric acid with 1: 1 mass ratio soak 12 hours; bagasse powder after soaking is placed in 60 DEG C of baking ovens; pre-carbonization 10 hours; put into microwave reactor; under the protection of the nitrogen stream of 50ml/min, under the condition of 900W, constant temperature activates 22 minutes and obtains bagasse biomass carbon.By above-mentioned 5g biomass carbon mass fraction be 10% HCl solution stir purifying 5 hours at 60 DEG C, then the nitric acid biological powdered carbon after purifying being added 32.5% of 300ml stirs 5 hours, take the powdered carbon 5g after above-mentioned nitric acid oxidation, add the ethylenediamine of 100ml, after agitating heating is even, add 5 grams of N, N '-dicyclohexylcarbodiimide, back flow reaction 48 hours.By product washes clean, after oven dry, obtain New Polyamine based biomass carbon composite.Before and after amination modifying, the infrared spectrogram of biomass carbon material as shown in Figure 1.Absworption peak relatively, can find out that amination modifying artifact matter charcoal contains more significantly nitrogen base group, show that modified ethylenediamine has successfully been guided on mesoporous carbon sample I3.
Example 2:
By the cotton cane powder after clean oven dry and 80% potassium hydroxide with 1: 2 mass ratio soak 12 hours; cotton cane powder after immersion is put into after vacuum desiccator is dried and insert tube furnace; under the protection of the nitrogen stream of 50ml/min; 400 DEG C are warmed up to 5 DEG C/min; and constant temperature carbonizes 2 hours at such a temperature, be then warmed up to 700 DEG C with 10 DEG C/min and activate to obtain cotton stalk biomass carbon.Stirred 5 hours at 60 DEG C by above-mentioned 5g biomass carbon powder 10%HCl solution, the nitric acid that purified charcoal powder adds 32.5% of 300ml again stirs 5 hours, then it is washed till neutral dry for standby.Take above-mentioned powder 5g, add the ethylenediamine of 100ml, after agitating heating, add N, N '-dicyclohexylcarbodiimide, back flow reaction 48 hours.By product washes clean, after oven dry, obtain New Polyamine based biomass carbon composite.
Example 3:
By the water wheat cane powder after clean oven dry and 30% phosphoric acid with 2: 1 mass ratio soak 12 hours; insert in tube furnace after water wheat cane powder after immersion is dried; under the protection of the nitrogen stream of 50ml/min; 500 DEG C are warmed up to 5 DEG C/min; and constant temperature carbonizes 1.5 hours at such a temperature, being washed till PH with distilled water after cooling is 7.0.Finally, clean product is put into baking oven with 105 DEG C of oven dry.Stirred 5 hours at 60 DEG C by above-mentioned for 10g biomass carbon powder 200ml10%HCl solution, the nitric acid that purified charcoal powder adds 32.5% of 200ml again stirs 3 hours, then it is washed till neutral oven dry.The ethylenediamine of 200ml is added in above-mentioned sample.After agitating heating, add N, N '-dicyclohexylcarbodiimide, back flow reaction 36 hours.By product washes clean, after oven dry, obtain New Polyamine based biomass carbon composite.
Example 4:
By the water wheat cane powder after clean oven dry and 60% phosphoric acid with 2: 3 mass ratio soak 12 hours; insert in tube furnace after water wheat cane powder after immersion is dried; under the protection of the nitrogen stream of 50ml/min; 450 DEG C are warmed up to 5 DEG C/min; and constant temperature carbonizes 1 hour at such a temperature, being washed till PH with distilled water after cooling is 7.0.Finally, clean product is put into baking oven with 105 DEG C of oven dry.Stirred 5 hours at 60 DEG C by above-mentioned for 10g biomass carbon powder 200ml10%HCl solution, the nitric acid that purified charcoal powder adds 35% of 300ml again stirs 2 hours, then it is washed till neutral oven dry.The ethylenediamine of 250ml is added in above-mentioned sample.After agitating heating, add N, N '-dicyclohexylcarbodiimide (DCC), back flow reaction 36 hours.By product washes clean, after oven dry, obtain New Polyamine based biomass carbon composite.
Example 5:
By the water wheat cane powder after clean oven dry and 60% phosphoric acid with 2: 3 mass ratio soak 12 hours; insert in tube furnace after water wheat cane powder after immersion is dried; under the protection of the nitrogen stream of 50ml/min; 450 DEG C are warmed up to 5 DEG C/min; and constant temperature carbonizes 1 hour at such a temperature; then pass into carbon dioxide constant temperature activation 10min with the flow velocity of 5ml/min, being washed till PH with distilled water after cooling is 7.0.Finally, clean product is put into baking oven with 105 DEG C of oven dry.Stirred 5 hours at 60 DEG C by above-mentioned for 10g biomass carbon powder 200ml10%HCl solution, the nitric acid that purified charcoal powder adds 32.5% of 200ml again stirs 2 hours, then it is washed till neutral oven dry.The ethylenediamine of 250ml is added in above-mentioned sample.After agitating heating, add N, N '-dicyclohexylcarbodiimide, back flow reaction 48 hours.By product washes clean, after oven dry, obtain New Polyamine based biomass carbon composite.
Example 6:
1. pH value of solution is on the impact of New Polyamine based biomass carbon composite Adsorption of Mercury (II), chromium (III), plumbous (II).Take example 1 sample 0.10g respectively, to add the volume filling different pH value be 20mL concentration is in the triangular flask of the mercury (II) of 50mg/L, chromium (III), plumbous (II), vibrate 1h at 25 DEG C, measure the content of metal with ICP-OES, under recording different solutions pH, composite on the clearance impact of mercury (II), chromium (III), plumbous (II) as shown in Figure 2.Fig. 2 shows, pH value of solution has considerable influence to composite Adsorption of Mercury (II), chromium (III), plumbous (II), when pH≤4, the eliminating rate of absorption of composite to mercury (II), chromium (III), plumbous (II) increases with the increase of pH value of solution, when pH >=4, the clearance of composite to mercury (II), chromium (III), plumbous (II) is substantially constant with the increase of pH value of solution.
2. New Polyamine based biomass carbon composite is to the adsorbance of mercury in the aqueous solution (II), chromium (III), plumbous (II).By the mercury (II) of 100mL variable concentrations (10mg/L ~ 300mg/L), chromium (III), plumbous (II) solution 0.1mol/L
-1hCl and 0.1mol/LNH
3.H
2o is adjusted to pH=6, then the biomass carbon composite taking example 1 sample 0.10g is respectively added, constant temperature oscillation 1h at 25 DEG C, measure the content of metal with ICP-OES, use Langumir Isothermal Model to record the Langumir maximal absorptive capacity of material B AC-TETA to mercury in the aqueous solution (II), chromium (III), plumbous (II) as calculated and be respectively 10.7mg/g, 63.7mg/g and 53.2mg/g.
Example 7:
Coexisting ion is on the impact of composite Adsorption mercury (II), chromium (III), plumbous (II).Regulate pH value of solution=6, and be (K (I), the Na (I) of 2000 times, Ca (II), Mg (II), NH in the mixed solution of 1000 μ g/L mercury (II), chromium (III), plumbous (II) filling 20mL concentration
4(I) with Zn (II), Cd (II), Mn (II), Ni (II), Cu (II), Co (II) ion coexist of 100 times), add composite BAC-TETA0.020g respectively, vibration absorption 20min at 25 DEG C, in the lower example 2 of mensuration, composite BAC-TETA is to the Adsorption situation of mercury (II), chromium (III), plumbous (II).Table 1 be when pH value of solution=6 in solution containing the Adsorption situation of composite BAC-TETA during coexisting ion to mercury (II), chromium (III), plumbous (II).Table 1 data show, at the K of 2000 times (I), Na (I), Ca (II) and Zn (II), the Cd (II) of 100 times, Mn (II), Ni (II), Cu (II) ion coexist in case, the effect of coexisting ion composite Adsorption mercury (II), chromium (III), plumbous (II) does not have a significant effect.
Table 1 coexisting ion is on the impact of lmg/L mercury (II), chromium (III), plumbous (II) solution removal rate
The solution concentration of note: Cr (III), Fe (III) and Pb (II) is 1000 μ g/L, liquor capacity 20mL, and quantity of sorbent is 0.020g, adsorption time 20min, temperature 25 DEG C
Example 8:
The air-dry soil sample (soil takes from farm, Agricultural University Of Nanjing Jiangpu) taking 1mm aperture sieve is placed in beaker with for trying the common 100g of material, and the ratio in 3% is mixed and applied the obtained bio-based carbon composite of example 1.Consider the soil moisture content scope of crop normal growth, water by 80% of relative water content, add Cr
3+, Fe
3+and pb
2+, making Mercury in Soil (II), chromium (III), plumbous (II) concentration be 300mg/kg, being placed in 25 DEG C of insulating boxs, respectively at determining that time sampling is to be measured.Heavy metal in soil effective content adopts TCLP extract extraction and determination (method reference literature: Sun Yefang, Xie Zhengmiao, Xu Jianming, wait .TCLP method to evaluate the Ecological Environment Risk [J] of mining soil heavy metal. environmental science, 2005,26 (3): 152-156).Result of the test shows, and add biomass carbon based composites obtained in example 1 in the heavy-metal contaminated soil of pH=6 after, the effective content of mercury in soils (II), chromium (III), plumbous (II) significantly reduces.When cultivation proceeds to 60d, after applying the obtained biomass carbon based composites of example 1, the content of soil available mercury (II), chromium (III), plumbous (II) respectively comparatively control treatment reduce 52.1%, 36.2%, 43.2%.
Example 9:
The air-dry soil sample (soil takes from farm, Agricultural University Of Nanjing Jiangpu) taking 1mm aperture sieve is placed in beaker with for trying the common 300g of material, add mercury (II), chromium (III), plumbous (II), make Mercury in Soil (II), chromium (III), plumbous (II) concentration is 50mg/kg, ratio in 5% is mixed and is applied the obtained bio-based carbon composite of example 2, add 40% of deionized water guarantee maximum field capacity again, keep soil pH=5 time at 25 DEG C, to cultivate reaction 60 days.In soil, exchangeable species mercury (II), chromium (III), plumbous (II) content are measured by Tessier continuous extration.Result of the test shows, and after adding biomass carbon based composites obtained in example 1 in heavy-metal contaminated soil, in soil, the effective content of exchangeable species mercury (II), chromium (III), plumbous (II) significantly reduces.When cultivation proceeds to 60d, after applying the obtained biomass carbon based composites of example 1, the content of soil exchangeable species mercury (II), chromium (III), plumbous (II) respectively comparatively control treatment reduce 15.2%, 13.5%, 13.3%.
Claims (8)
1. select the polyamines based biomass carbon composite of mercury (II), chromium (III), plumbous (II) in fixing restoration of soil polluted by heavy metal and preparation method thereof for one kind, it is characterized in that taking agricultural biomass as raw material, with phosphoric acid, nitric acid, ethylenediamine for modifier, prepare a kind of polyamines based biomass carbon composite selecting heavy metal Hg (II), chromium (III), plumbous (II) in fixing repairing polluted soil by steps such as charing, carboxylated and molecule copolycondensations.
2. one selects the biomass carbon composite of mercury (II), chromium (III), plumbous (II) in fixing restoration of soil polluted by heavy metal and preparation method thereof according to claim 1, it is characterized in that the method comprises biomass material collection, charing, purifying, carboxylated, amination, cleaning, oven dry, concrete steps are as follows:
A), agricultural biomass harvesting, cleaning, the air-dry rear pulverizers such as cotton stalk, wheat stalk, rice straw, maize straw are pulverized and sieved;
B), above-mentioned agricultural biomass powder of straw is added a certain amount of activator carbonize under the effect of inert gas, cleaning, drying, the obtained biomass carbon had compared with bigger serface and pore volume;
C), by above-mentioned B) in the obtained certain density hydrochloric acid solution of agricultural biomass charcoal, at 60 DEG C, stir 5 hours purifying;
D) add certain density salpeter solution in the biomass carbon powder, after above-mentioned purifying, add thermal agitation, after question response, product washing is extremely neutral, filtering drying;
E), take a certain amount of through step D) straw biomass carbon powder after nitric acid oxidation, be distributed in a certain amount of ethylenediamine solution, to be mixed evenly after, add N, N '-dicyclohexylcarbodiimide, back flow reaction a period of time;
F), by above-mentioned product first slightly wash with ethanol, then with ether cleaning, dry at a certain temperature to constant weight.
3. a kind ofly according to claim 2 select the biomass carbon composite of mercury (II), chromium (III), plumbous (II) in fixing restoration of soil polluted by heavy metal and preparation method thereof, it is characterized in that A) described in agricultural biomass cane be bagasse, cotton stalk, maize straw, shuck, cocoanut shell, water Wheat Straw, rice straw or bark.
4. one selects the biomass carbon composite of mercury (II), chromium (III), plumbous (II) in fixing restoration of soil polluted by heavy metal and preparation method thereof according to claim 2, it is characterized in that B) described in physically activated method comprise phosphoric acid chemical activation, microwave radiation technology steam activation, the steam activation of potash auxiliary water, the Carbon Materials mesopore content >35% of preparation.
5. a kind of polyamines based biomass carbon composite selecting mercury, chromium and lead in fixing restoration of soil polluted by heavy metal and preparation method thereof according to claim 2, it is characterized in that D) described in concentration of nitric acid be 10 ~ 50%, the mass ratio of biomass carbon and this salpeter solution is 1: (10 ~ 100).
6. a kind ofly according to claim 2 select the polyamines based biomass carbon composite of mercury (II), chromium (III), plumbous (II) in fixing restoration of soil polluted by heavy metal and preparation method thereof, it is characterized in that E) described in the ratio of carboxylated biomass carbon and ethylenediamine be 1: (10 ~ 50).
7. one selects the biomass carbon composite of mercury (II), chromium (III), plumbous (II) in fixing restoration of soil polluted by heavy metal and preparation method thereof according to claim 2, it is characterized in that E) described in reflux time be 24 ~ 96h, preferred 48h.
8. one selects the biomass carbon composite of mercury (II), chromium (III), plumbous (II) in fixing restoration of soil polluted by heavy metal and preparation method thereof according to claim 2, it is characterized in that E) in the mass ratio of N, N '-dicyclohexylcarbodiimide and biomass carbon be 0.5-2.
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