CN103464101A - Resource utilization method of plant bamboo reed after restoring heavy metal contaminated soil - Google Patents
Resource utilization method of plant bamboo reed after restoring heavy metal contaminated soil Download PDFInfo
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- CN103464101A CN103464101A CN2013104065814A CN201310406581A CN103464101A CN 103464101 A CN103464101 A CN 103464101A CN 2013104065814 A CN2013104065814 A CN 2013104065814A CN 201310406581 A CN201310406581 A CN 201310406581A CN 103464101 A CN103464101 A CN 103464101A
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- heavy metal
- contaminated soil
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Abstract
The invention discloses a resource utilization method of plant bamboo reed after restoring heavy metal contaminated soil. The method comprises the following steps: air-drying and crushing the harvested plant bamboo reed used for restoring heavy metal contaminated soil, adding a catalytic modifier under a condition of controlling oxygen atmosphere, calcining the plant bamboo reed at 200-800 DEG C for 0.5-4 h, and cooling the plant bamboo reed to obtain charcoal, wherein the yield of the bamboo reed charcoal is 25-75%. When the bamboo reed charcoal is used for adsorbing heavy metals and compounds thereof in contaminated soil, wastewater or waste gases, the adsorption capacity reaches 0.4-6.0 mg/g; meanwhile, the bamboo reed charcoal can be used as an energy source raw material or a reducing agent to be comprehensively utilized by metallurgy enterprises. The invention provides an engineering approach for biomass resource utilization of contaminated soil restoring plants and solving the problem of potential secondary pollution.
Description
Technical field
The present invention relates to reclamation of solid wastes comprehensive utilization field.Particularly, the present invention relates to a kind of standby charcoal of biomass-making that utilizes the rehabilitation plant giantreed of gathering in the crops on heavy-metal contaminated soil, with charcoal, come heavy metal in adsorption fouling soil, waste water or waste gas, conduct to relate to the method for heavy enterprise energy material or reducing agent simultaneously.
Background technology
Giantreed is the perennial grass that extensively is distributed in the south China area, and fast growth, biomass are large.The giantreed living beings contain a large amount of celluloses and lignin, have higher combustion heat value.Giantreed living beings most of component after calcining is charcoal.The researchs such as Yang Haiping show that in the biomass carbon preparation process, separating out of material volatile matter mainly concentrates on 300-600 ℃; At high temperature (> 800 ℃) biomass carbon mainly contains carbon and a small amount of oxygen, almost do not have protium residual.Biomass carbon has flourishing pore structure and abundant surface group, and make it to heavy metal and organic matter (especially heavy metal), removal effect preferably all be arranged, and stablize anticorrosive difficult decomposition, be a kind of desirable adsorbent.Simultaneously, charcoal or a kind of reducing agent preferably, the reports such as Wang Yongbin, biomass reduction magnetization limonite effect is compared with brown coal reduction magnetization limonite, the reduction magnetization effect of living beings is better, and reduction temperature can reduce more than 100 ℃ and (is down to 650 ℃ of left and right).
Giantreed impoverishment tolerant, drought-enduring waterlogging, have the advantages such as strong stress resistance.Giantreed has had relevant research report both at home and abroad to heavy metal tolerance and enrichment performance.Papazoglou studies and shows, giantreed is at 973.8mg kg
– 1cd and 2543.3mg kg
– 1show good tolerance while growing in the soil of Ni.Mirza studies and shows, giantreed can be 600 μ g L in As concentration
– 1normal growth in nutrient solution, show good tolerance and cumulative bad.The researchs such as Han Zhiping show, giantreed is 100mgkg in concentration respectively
-1cu
2+, Ni
2+, Cd
2+, Pb
2+, Zn
2+, Hg
2+and 50mgkg
-1following Cr
6+all can normally survive in 7 kinds of contaminated environment, show the tolerance stronger to single high-load Heavy-metal Polluted Environment; At 105mg kg
– 1cu, 103mg kg
– 1ni, 55mg kg
– 1cr also all can normal growth under affecting separately.The researchs such as Guo Chaohui show, at As53.2, Cd31.9, Pb728.4, Zn968mg kg
– 1multiple metal soil on the giantreed overground part year biomass of growing reach 3000kg/ mu, and can absorb As in soil, Cd, Pb and Zn, contaminated soil is had to certain repair.Above-mentioned research shows, giantreed can be used as the rehabilitation plant of heavy-metal contaminated soil and carries out contaminated soil reparation application.Yet, contain a certain amount of heavy metal in the giantreed cutting after reparation, as unreasonable disposal may cause the secondary pollution of heavy metal.But do not consider the living beings such as the giantreed problem how safety comprehensive utilizes containing heavy metal in currently available technology.The present invention is intended to utilize the heavy metal pollution giantreed to prepare charcoal, and charcoal is continued on for reducing available state content in contaminated soil, processes waste water or waste gas containing heavy metal, finally send and relate to heavy enterprise as biomass energy or reducing agent, reach the purpose of the treatment of wastes with processes of wastes against one another, comprehensive utilization.
Summary of the invention
The present invention is in order effectively to utilize the giantreed living beings of repairing heavy-metal contaminated soil, produce charcoal as raw material, the waste water or the waste gas that contain heavy metal for reducing Heavy Metals in Contaminated Soils available state content, processing, finally send and relate to heavy enterprise as biomass energy or reducing agent, reach the purpose of the treatment of wastes with processes of wastes against one another, comprehensive utilization.
A kind of method of repairing the plant giantreed recycling of heavy-metal contaminated soil comprises the following steps:
1) to the giantreed of repairing heavy-metal contaminated soil cradled, air-dry, broken;
2) the catalytic modification material of one or both combinations in the molysite of the interpolation of the giantreed powder after fragmentation 0.5wt%-5wt%, aluminium salt, calcium salt, sodium salt is calcined calcining heat 200-800 ℃, calcination time 0.5-4h in the calcining furnace of controlling the oxygen atmosphere; In calcination process, adopt negative pressure system condensation recovery volatile matter to realize charcoal end de-oiling, or the mass ratio according to 1:5-10 wash de-oiling by charcoal end and alcohol mix and blend after calcining is cooling; Charcoal end briquet group or excellent bar, obtain charcoal;
3) adopt heavy metal and compound thereof in charcoal adsorption fouling soil, waste water or waste gas, Heavy Metals in Contaminated Soils available state content is significantly reduced, purify liquid waste or waste gas;
4) by step 2) charcoal that obtains or by having adsorbed the charcoal of heavy metal in contaminated soil, waste water or waste gas and compound thereof in step 3), send the utilization of non-ferrous metal metallurgy Enterprise Integrated as energy and material or reducing agent.
Described heavy metal comprises one or more in As, Cd, Cr, Cu, Hg, Ni, Pb, Zn.
The described fragmentation of step 1) is to adopt broken facility that air-dry giantreed cutting is broken into to 1-2cm following rod-short fritter or Powdered thing.
Step 2) described catalytic modification material, first be mixed with solution or emulsion, before calcining or during calcining, is sprayed at equably on the giantreed powder.
Step 2) described control oxygen atmosphere is to control calcining furnace to be anoxic or to approach anaerobic atmosphere.(adopt the calcining furnace such as Muffle furnace, tube furnace, elevator furnace of logical nitrogen, argon gas or through specialized designs, can regulate and control the reacting furnace that oxygen enters, control calcining furnace and be anoxic or approach anaerobic atmosphere.）
Adopt said method, the charcoal productive rate is generally at 25%-75%.
Adopt said method, in charcoal adsorption fouling soil, waste water or waste gas, the adsorption capacity of heavy metal and compound thereof can reach 0.4-6.0mg/g.
The moulding measure adopted in said method, adopt the biomass carbon powder common press compressed to slugs group or stub bar exactly.
Technique effect
The present invention is that after the reparation of solution heavy-metal contaminated soil engineering, the recycling of large giantreed cutting has proposed practicable Engineering Approach.First the living beings that contain the heavy metals such as a small amount of As, Cd, Pb, Zn passed through to control the oxygen atmosphere and add the catalytic modification material, obtain containing the charcoal of a small amount of heavy metal under low calcining heat and be used for the adsorption fouling heavy metal in soil, preventing the diffusion of heavy metal contaminants; Adsorb low-concentration heavy metal and compound in waste water or waste gas, realize the deep purifying of waste water or waste gas; Deliver to metallurgical technology as energy raw material, thermal source is provided, or create reducing atmosphere or direct-reduction metal oxide as reducing agent, effectively realized the comprehensive utilization containing heavy metal biological matter.
The present invention adds the catalytic modification material in containing the giantreed living beings calcination process of heavy metal, can significantly improve productive rate and the surface-active number of functional groups thereof of giantreed charcoal, improve charcoal adsorption capacity, reduce after excessive mistake in calcination process of heavy metal in giantreed and calcining the leaching rate of heavy metal in the giantreed charcoal, efficiently solve the potential secondary pollution problem that the giantreed charcoal containing heavy metal exists in the comprehensive utilization process.
The present invention carries out the de-oiling processing to the charcoal of preparing, can further improve its adsorption capacity, be used for the adsorption effect of heavy metal and compound in efficient adsorption contaminated soil, waste water or waste gas, Heavy Metals in Contaminated Soils available state content is significantly reduced, and in waste water or waste gas, heavy metal reaches the discharge standard requirement after adsorption cleaning.
The accompanying drawing explanation
Fig. 1 is process chart of the present invention;
The SEM photo that Fig. 2 is charcoal of the present invention;
(a) unwashed charcoal; (b) charcoal after the alcohol washing;
The adsorption effect of Fig. 3 giantreed charcoal to As, Cd, Pb in waste water.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, and unrestricted the present invention.
Embodiment 1: utilize the plant giantreed of repairing heavy-metal contaminated soil to prepare charcoal
Giantreed aerial part from heavy metal pollution place soil results containing heavy metal, cut into the 1-2cm fritter after cutting is cleaned by running water and deionized water successively, oven dry under 105 ℃ of 30min that complete, 60 ℃.The giantreed fritter of oven dry is put into to the tubular type elevator furnace; spray into the sodium hydroxide solution of 1mol/L simultaneously; make NaOH account for the 0.5wt% of giantreed powder; under nitrogen protection, heat; control 300 ℃ of calcining 2h of calcining heat; be crushed to after cooling below 20 orders, obtain the giantreed charcoal containing heavy metal.Under this calcination condition, giantreed charcoal productive rate is about 55%, and the charcoal calorific value reaches 29.53kJ/g.There are a large amount of holes and oil droplet in the charcoal surface of above-mentioned preparation, and (Fig. 2 a); With after alcohol washing 30min, charcoal surface oil droplet disappears, and a large amount of holes (Fig. 2 b) occur; Wherein heavy metal is cleared up, measured to the charcoal concentrated acid, and in charcoal, As, Cd, Pb, Zn equal size are followed successively by 16-33,0.9-15,21-80,106-263mg/kg, show in this charcoal to contain a certain amount of heavy metal.Simultaneously, select in the tubular type elevator furnace of giantreed under nitrogen protection of gathering in the crops on uncontaminated soil and calcine, 300 ℃ of calcining heats, calcination time 2h, prepare untainted giantreed charcoal.Under this calcination condition, untainted giantreed charcoal productive rate is about 35%, and in charcoal, As, Cd, Pb, Zn equal size are followed successively by 0.21-7.26,0.03-0.50,0.22-3.62,15-96.66mg/kg.Showing to repair content of beary metal in charcoal prepared by the plant giantreed cutting of heavy-metal contaminated soil obviously improves.
Embodiment 2: the toxicity characteristic leaching procedure that contains the giantreed charcoal of heavy metal
Utilize the giantreed charcoal of embodiment 1 preparation to carry out the toxicity leaching experiment.Leaching experiment is with reference to " the horizontal succusion of solid waste Leaching leaching method (HJ557-2010) " method, adopt water logging and acidleach to carry out toxicity characteristic leaching procedure: to get in the 20mL deionized water, regulating pH is 2.5 and 5.5, add again 0.2g to contain the giantreed charcoal of heavy metal, under room temperature in water bath with thermostatic control vibration case after vibration 24h, centrifugal filtration, the content of As, Cd, Pb, Zn in the measurement supernatant.Simultaneously, do blank test (not adding charcoal) and carry out the Elimination test error.As can be seen from Table 1, in untainted giantreed charcoal leachate, content of beary metal is extremely low; Containing the giantreed charcoal of heavy metal under neutral and acid condition in leachate As, Cd, Pb, Zn concentration also far below Leaching standard authenticating value (GB5085.3-2007), adsorption treatment that can safety applications heavy metal in contaminated soil, waste water and waste gas.
As, Cd, Pb, Zn concentration in table 1 giantreed charcoal leachate
*in Leaching standard authenticating value (GB5085.3-2007), the heavy metal authenticating value is all in its total amount." ND " means not detect.
Embodiment 3: contain the adsorption capacity test of the giantreed charcoal of heavy metal
Utilize the giantreed charcoal (raw material is the giantreed containing heavy metal from heavy metal pollution place soil results) of embodiment 1 preparation to carry out heavy metal adsorption test in simulated wastewater.The test operation process is as follows: the series analog waste water containing As, Cd, Pb that the compound concentration gradient is 5mg/L, 10mg/L, 25mg/L, 50mg/L.Add the 0.2g charcoal in the 20ml simulated wastewater, the 24h that then at room temperature vibrates, measure the rear heavy metal ions concentration in solution of absorption, utilizes the suction-operated of the poor calculating charcoal of solution concentration to As, Cd, Pb in waste water.Experimental result shows (Fig. 3), and the giantreed charcoal has certain suction-operated to waste water A s, Cd, Pb, and suction-operated increases with the increase of As, Cd, Pb concentration in waste water.In trial stretch, its adsorbance reaches respectively 4.08,1.30,0.86mg/g.
Claims (5)
1. a method of repairing the plant giantreed recycling of heavy-metal contaminated soil, is characterized in that, comprises the following steps:
1) to the giantreed of repairing heavy-metal contaminated soil cradled, air-dry, broken;
2) the catalytic modification material of one or both combinations in the molysite of the interpolation of the giantreed powder after fragmentation 0.5wt%-5wt%, aluminium salt, calcium salt, sodium salt is calcined calcining heat 200-800 ℃, calcination time 0.5-4h in the calcining furnace of controlling the oxygen atmosphere; In calcination process, adopt negative pressure system condensation recovery volatile matter to realize charcoal end de-oiling, or the mass ratio according to 1:5-10 wash de-oiling by charcoal end and alcohol mix and blend after calcining is cooling; Charcoal end briquet group or excellent bar, obtain charcoal;
3) adopt heavy metal and compound thereof in charcoal adsorption fouling soil, waste water or waste gas, Heavy Metals in Contaminated Soils available state content is significantly reduced, purify liquid waste or waste gas;
4) by step 2) charcoal that obtains or by having adsorbed the charcoal of heavy metal in contaminated soil, waste water or waste gas and compound thereof in step 3), send the utilization of non-ferrous metal metallurgy Enterprise Integrated as energy and material or reducing agent.
2. method according to claim 1, is characterized in that, described heavy metal comprises one or more in As, Cd, Cr, Cu, Hg, Ni, Pb, Zn.
3. method according to claim 1, is characterized in that, the described fragmentation of step 1) is to adopt broken facility that air-dry giantreed cutting is broken into to 1-2cm following rod-short fritter or Powdered thing.
4. method according to claim 1, is characterized in that step 2) described catalytic modification material, first be mixed with solution or emulsion, before calcining or calcining the time be sprayed at equably on the giantreed powder.
5. method according to claim 1, is characterized in that step 2) described control oxygen atmosphere is to control calcining furnace to be anoxic or to approach anaerobic atmosphere.
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