CN104785207A - High-adsorption performance biochar for heavy metal ions and preparation method for high-adsorption-performance biochar - Google Patents
High-adsorption performance biochar for heavy metal ions and preparation method for high-adsorption-performance biochar Download PDFInfo
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Abstract
The invention discloses a high-adsorption performance biochar for heavy metal ions. The high-adsorption performance biochar is prepared by using sorghum residues, rice residues, glutinous rice residues, wheat residues and corn residues which are obtained after wine is brewed as raw materials and performing anaerobic pyrolysis; the high-adsorption performance biochar is characterized by being prepared by uniformly mixing the sorghum residues, the rice residues, the glutinous rice residues, the wheat residues and the corn residues which are crushed to a certain particle size in a certain mass ratio; adding a suitable amount of a rubidium chloride solution with an appropriate concentration; sealing and standing for 12 hours; performing high-temperature anaerobic pyrolysis on a mixture after the solution is dried naturally; soaking the mixture which is subjected to the high-temperature anaerobic pyrolysis by utilizing a mixed solution of HCl/HF; washing the mixture to neutral by utilizing distilled water. According to the biochar prepared by the preparation method, the content of lead, chromium, zinc and copper in water can be effectively reduced; the highest removal rates of the lead, the chromium, the zinc and the copper in the water can reach 99.2 percent, 85.3 percent, 82.9 percent and 85.9 percent.
Description
Technical field
The present invention relates to contaminated environment administering method, particularly a kind of preparation method of heavy metal ion high absorption property charcoal.
Background technology
Along with developing rapidly of industry, the diffusate of various industry (as smelting, plating, mining etc.) waste water and solid waste directly enters water body, causes Heavy Metals in Waters content more and more higher.Heavy metal can natural degradation or biodegradation unlike organic compound, is often dissolved in water body or deposits to water bottom, or is absorbed by water plant (phytoplankton, emergent aquactic plant), and healthy by food chain accumulation infringement animals and humans.Therefore, be badly in need of carrying out purified treatment to the heavy metal in waste water.
Processing method is simple, adsorption efficiency advantages of higher to utilize charcoal absorption process heavy metal-containing waste water to have.But utilize charcoal treatment heavy metal-containing waste water cost higher, cannot widely use.Charcoal is biological material pyrolysis under anoxic or limited oxygen condition, removes the gentle rear remaining solid matter of oil in living beings.Because its hole is flourishing, specific area is large and ion-exchange capacity unique physicochemical properties such as strong, the heavy metal ion in waste water directly can be adsorbed preferably.At present, organic materials is utilized to prepare the research of biological carbon both at home and abroad more, as Lanzhou University of Science & Technology Zhang Jiyi etc. utilizes wheat stalk to prepare, biological carbon is oldly brightly again prepared with rice straw by biological carbon, Zhejiang University, University of Science & Technology, Beijing makes widely known and prepares biological carbon etc. with corncob, but existing research prepares charcoal mainly with single raw material, and it is less to prepare the research of charcoal with mixed material, especially lack and targetedly combination is optimized to multiple biomass material, to prepare the charcoal that heavy metal ion has high absorption property.
Summary of the invention
The object of this invention is to provide and multiple abandoned biomass can be utilized to mix, the charcoal that heavy metal ion has stronger absorption property is prepared in anaerobism pyrolysis, can promote the recycling of waste material further, realize the object of the treatment of wastes with processes of wastes against one another.Multiple living beings are mixed with charcoal, the high absorption property of the charcoal prepared can be guaranteed, improve charcoal to the clean-up effect of heavy metal-containing waste water.
Another object of the present invention is to provide a kind of preparation method of charcoal of heavy metal ion high absorption property.
Concrete technical scheme of the present invention is:
A kind of heavy metal ion high absorption property charcoal, this charcoal comprises following living beings, namely Chinese sorghum slag, paddy slag, glutinous rice slag, wheat grit and maize pulp after wine brewing, wherein Chinese sorghum slag: paddy slag: glutinous rice slag: wheat grit: maize pulp mass ratio is 4 ~ 6:7 ~ 8:3 ~ 4:3 ~ 4:1.
A preparation method for heavy metal ion high absorption property charcoal, comprises the following steps:
(1) the living beings natural air drying will collected, in air-dry artifact matter, the weight percentage of water is 1%-5%, pulverizes 20-100 mesh sieve after removing abiotic matter component;
(2) living beings after above-mentioned pulverizing mixed in proportion, add the rubidium chloride solution mixing sealing and standing 12h that 5ml concentration is 0.05-1.5mol/L, the mass percentage shared by natural air drying to water is 3%-10%;
(3) living beings of above-mentioned process are placed in porcelain crucible compacting, cover lid carries out anaerobism pyrolysis, namely obtains rough charcoal after pyrolytic reaction terminates, and is cooled to after room temperature takes out until crucible.Described rough charcoal anaerobism pyrolysis temperature is 400 ~ 700 DEG C, and pyrolysis time is 60-300min, and programming rate is 5-15 DEG C/min.
(4) the HCl/HF mixed solution that the rough charcoal of above-mentioned preparation mixes with 10 milliliters of 0.5-2.0mol/L isoconcentrations is mixed, shake 2h in an oscillator and take out, with the centrifugal 10min of 4000r/min, repeat aforesaid operations 5 times; Be washed with distilled water to neutrality again, namely obtain the charcoal of high absorption property; The HCl/HF mixed solution concentration of described isoconcentration mixing is 0.5-2.0mol/L.
Described living beings comprise following composition: the Chinese sorghum slag after wine brewing, paddy slag, glutinous rice slag, wheat grit and maize pulp, and its mixing is counted according to mass ratio: Chinese sorghum slag: paddy slag: glutinous rice slag: wheat grit: maize pulp=5:7:4:3:1.Selected living beings need first pulverize 20-100 mesh sieve, then add the mixing of rubidium chloride solution in the material of mixing, and sealing and standing 12h, natural air drying, the molar concentration of rubidium chloride solution is 0.05-1.5mol/L.
Chinese sorghum slag, paddy slag, glutinous rice slag, wheat grit and maize pulp are the discarded object after brewing spirit, are commercially available prod, also can adopt the vinasse after Qionglai City's winery brewing spirit.
Good effect of the present invention is embodied in:
(1) utilize multiple abandoned biomass mixed pyrolysis to prepare heavy metal ion and there is charcoal compared with high absorption property, the recycling of waste material can be promoted further, realize the object of the treatment of wastes with processes of wastes against one another.
(2) multiple living beings are mixed with charcoal, the high absorption property of the charcoal prepared can be guaranteed, improve the clean-up effect of charcoal.
(3) charcoal prepared can reach 99.2%, 85.3%, 82.9% and 85.9% to the highest clearance of lead, chromium, zinc, copper in water.
Detailed description of the invention
A kind of heavy metal ion high absorption property charcoal, this charcoal comprises following living beings, Chinese sorghum slag, paddy slag, glutinous rice slag, wheat grit and maize pulp, in mass, Chinese sorghum slag: paddy slag: glutinous rice slag: wheat grit: maize pulp=4 ~ 6:7 ~ 8:3 ~ 4:3 ~ 4:1.
A preparation method for heavy metal ion high absorption property charcoal, comprises the following steps:
(1) the living beings natural air drying will collected, in air-dry artifact matter, the weight percentage of water is 2%, carries out pulverizing 20-100 mesh sieve after removing the abiotic matter components such as silt;
(2) living beings after above-mentioned pulverizing mixed in proportion, add the rubidium chloride solution mixing sealing and standing 12h that 5ml concentration is 0.05-1.5mol/L, natural air drying, in air-dry artifact matter, the weight percentage of water is 4%;
(3) living beings of above-mentioned process are placed in porcelain crucible compacting, cover lid carries out anaerobism pyrolysis, after pyrolytic reaction terminates, be cooled to after room temperature until crucible and take out, obtain rough charcoal, described biomass anaerobic pyrolysis temperature is 400 ~ 700 DEG C, and pyrolysis time is 60-300min, and programming rate is 5-15 DEG C/min;
(4) the HCl/HF mixed solution that the rough charcoal of above-mentioned preparation mixes with isoconcentration is mixed, shake 2h in an oscillator to take out, with the centrifugal 10min of 4000r/min, repeat aforesaid operations 5 times, be washed with distilled water to neutrality again, namely obtain the charcoal of high absorption property, the HCl/HF mixed solution concentration of described isoconcentration mixing is 0.5-2.0mol/L.
Described living beings comprise following composition: the Chinese sorghum slag after wine brewing, paddy slag, glutinous rice slag, wheat grit and maize pulp, and its mixing is counted according to mass ratio: Chinese sorghum slag: paddy slag: glutinous rice slag: wheat grit: maize pulp=4 ~ 6:7 ~ 8:3 ~ 4:3 ~ 4:1.Its preferred mass is than being 5:7:4:3:1.Anaerobic environment during for guaranteeing pyrolysis and pyrolysis effect, selected living beings need pulverize 20-100 mesh sieve in advance, then add the mixing of rubidium chloride solution, sealing and standing 12h in the material of mixing, natural air drying, the molar concentration of rubidium chloride solution is 0.05-1.5mol/L.
Below in conjunction with embodiment, the present invention is further described, but do not limit the scope of the invention.
embodiment 1:
One, a heavy metal ion high absorption property charcoal, obtains as follows:
1, biomass material pretreatment
By Chinese sorghum slag, paddy slag, glutinous rice slag, wheat grit, maize pulp natural air drying after the wine brewing of collection, in air-dry artifact matter, the weight percentage of water is 1%, pulverizes 80 mesh sieves after removing the abiotic matter components such as silt.
2, preparation method
(1) by the Chinese sorghum slag after above-mentioned pulverizing, paddy slag, glutinous rice slag, wheat grit, maize pulp be in mass ratio 4:6:4:3:1 ratio mixing, add 0.1mol/L rubidium chloride solution 5ml and mix, sealing and standing 12h, natural air drying.
(2) biomass material of above-mentioned process is placed in porcelain crucible compacting, cover lid, pyrolysis 120min under 500 DEG C of conditions, pyrolysis programming rate is 10 DEG C/min.After pyrolytic reaction terminates, be cooled to after room temperature until crucible and take out.
(3) be that the HCl/HF mixed liquor that 0.5mol/L isoconcentration mixes mixes by the charcoal of above-mentioned preparation and concentration, shake 2h in an oscillator to take out, with the centrifugal 10min of 4000r/min, repeat aforesaid operations 5 times, with distilled water, the charcoal after process is washed to neutral again, namely obtain the charcoal of high absorption property.
Two, above-mentioned obtained charcoal is used for purified treatment heavy metal-containing waste water
Get 100mL and simulate heavy metal wastewater thereby (preparing by deionized water) in 250ml beaker, add a certain amount of homemade charcoal, 3h is shaken with 200r/min under 20 DEG C of conditions, take out with the centrifugal 20min of 4000r/min, measuring content of beary metal in water by after supernatant membrane filtration with ICP-MAS, the clearance of charcoal to heavy metal in waste water can be drawn by calculating.
Three, experimental result
1, to the removal of lead
Charcoal dosage 1.5131g, lead concentration is 9.50mg/L, and charcoal is 99.2% to clearance plumbous in water.
2, to the removal of chromium
Charcoal dosage 1.5028g, chromium concn is 7.35mg/L, and charcoal is 84.6% to the clearance of chromium in water.
3, to the removal of zinc
Charcoal dosage 1.5021g, zinc concentration is 9.25mg/L, and charcoal is 79.2% to the clearance of zinc in water.
4, to the removal of copper
Charcoal dosage 1.5115g, copper concentration is 10.25mg/L, and charcoal is 85.9% to the clearance of copper in water.
embodiment 2:
One, a heavy metal ion high absorption property charcoal, obtains as follows:
1, biomass material pretreatment: by Chinese sorghum slag, paddy slag, glutinous rice slag, wheat grit, maize pulp natural air drying after the wine brewing of collection, in air-dry artifact matter, the weight percentage of water is 1%, pulverized 80 mesh sieves after removing the abiotic matter components such as silt.
2, preparation method
(1) by the Chinese sorghum slag after above-mentioned pulverizing, paddy slag, glutinous rice slag, wheat grit, maize pulp be in mass ratio 5:8:4:4:1 ratio mixing, add 0.1mol/L rubidium chloride solution 5ml to mix, sealing and standing 12h, natural air drying, in air-dry artifact matter, the weight percentage of water is 5%.
(2) biomass material of above-mentioned process is placed in porcelain crucible compacting, cover lid, pyrolysis 120min under 500 DEG C of conditions, pyrolysis programming rate is 10 DEG C/min.After pyrolytic reaction terminates, be cooled to after room temperature until crucible and take out.
(3) be that the HCl/HF mixed liquor that 0.5mol/L isoconcentration mixes mixes by the charcoal of above-mentioned preparation and concentration, shake 2h in an oscillator to take out, with the centrifugal 10min of 4000r/min, repeat aforesaid operations 5 times, with distilled water, the charcoal after process is washed to neutral again, namely obtain the charcoal of high absorption property.
Two, above-mentioned obtained charcoal is used for purified treatment heavy metal-containing waste water
Get 100mL and simulate heavy metal wastewater thereby (preparing by deionized water) in 250ml beaker, add a certain amount of homemade charcoal, 3h is shaken with 200r/min under 20 DEG C of conditions, take out with the centrifugal 20min of 4000r/min, measuring content of beary metal in water by after supernatant membrane filtration with ICP-MAS, the clearance of charcoal to heavy metal in waste water can be drawn by calculating.
Three, experimental result
1, to the removal of lead
Charcoal dosage 1.5006g, lead concentration is 9.50mg/L, and charcoal is 93.6% to clearance plumbous in water.
2, to the removal of chromium
Charcoal dosage 1.5219g, chromium concn is 7.35mg/L, and charcoal is 85.3% to the clearance of chromium in water.
3, to the removal of zinc
Charcoal dosage 1.5117g, zinc concentration is 9.25mg/L, and charcoal is 81.2% to the clearance of zinc in water.
4, to the removal of copper
Charcoal dosage 1.5231g, copper concentration is 10.25mg/L, and charcoal is 83.9% to the clearance of copper in water.
embodiment 3:
One, a heavy metal ion high absorption property charcoal, obtains as follows:
1, biomass material pretreatment: by Chinese sorghum slag, paddy slag, glutinous rice slag, wheat grit, maize pulp natural air drying after the wine brewing of collection, in air-dry artifact matter, the weight percentage of water is 1%, pulverized 80 mesh sieves after removing the abiotic matter components such as silt.
2, preparation method
(1) by the Chinese sorghum slag after above-mentioned pulverizing, paddy slag, glutinous rice slag, wheat grit, maize pulp be in mass ratio 9:14:7:6:1 ratio mixing, add 0.1mol/L rubidium chloride solution 5ml to mix, sealing and standing 12h, natural air drying, in air-dry artifact matter, the weight percentage of water is 4%.
(2) biomass material of above-mentioned process is placed in porcelain crucible compacting, cover lid, pyrolysis 120min under 500 DEG C of conditions, pyrolysis programming rate is 10 DEG C/min.After pyrolytic reaction terminates, be cooled to after room temperature until crucible and take out.
(3) be that the HCl/HF mixed liquor that 0.5mol/L isoconcentration mixes mixes by the charcoal of above-mentioned preparation and concentration, shake 2h in an oscillator to take out, with the centrifugal 10min of 4000r/min, repeat aforesaid operations 5 times, with distilled water, the charcoal after process is washed to neutral again, namely obtain the charcoal of high absorption property.
Two, above-mentioned obtained charcoal is used for purified treatment heavy metal-containing waste water
Get 100mL and simulate heavy metal wastewater thereby (preparing by deionized water) in 250ml beaker, add a certain amount of homemade charcoal, 3h is shaken with 200r/min under 20 DEG C of conditions, take out with the centrifugal 20min of 4000r/min, measuring content of beary metal in water by after supernatant membrane filtration with ICP-MAS, the clearance of charcoal to heavy metal in waste water can be drawn by calculating.
Three, experimental result
1, to the removal of lead
Charcoal dosage 1.5128g, lead concentration is 9.50mg/L, and charcoal is 91.7% to clearance plumbous in water.
2, to the removal of chromium
Charcoal dosage 1.5242g, chromium concn is 7.35mg/L, and charcoal is 83.6% to the clearance of chromium in water.
3, to the removal of zinc
Charcoal dosage 1.5038g, zinc concentration is 9.25mg/L, and charcoal is 82.9% to the clearance of zinc in water.
4, to the removal of copper
Charcoal dosage 1.5109g, copper concentration is 10.25mg/L, and charcoal is 82.6% to the clearance of copper in water.
Through checking, this test is equally applicable to the heavy metal polluted waste water under equal conditions, also has good adsorption effect to it.
Claims (6)
1. a heavy metal ion high absorption property charcoal, it is characterized in that this charcoal comprises following living beings: Chinese sorghum slag, paddy slag, glutinous rice slag, wheat grit and maize pulp, in mass, Chinese sorghum slag: paddy slag: glutinous rice slag: wheat grit: maize pulp=4 ~ 6:7 ~ 8:3 ~ 4:3 ~ 4:1.
2. a preparation method for heavy metal ion high absorption property charcoal as claimed in claim 1, is characterized in that comprising following
Step:
(1) the living beings natural air drying will collected, pulverizes and sieves after removing abiotic matter component;
(2) living beings after above-mentioned pulverizing are mixed in proportion, add the rubidium chloride solution mixing sealing and standing 12h that 5ml concentration is 0.05-1.5mol/L, natural air drying;
(3) living beings after above-mentioned process are placed in porcelain crucible compacting, cover lid carries out anaerobism pyrolysis, after pyrolytic reaction terminates, is cooled to after room temperature takes out until crucible;
(4) be that the HCl/HF mixed liquor that 0.5-2.0mol/L isoconcentration mixes mixes by the rough charcoal of above-mentioned preparation and 10 ml concentration, then shake 2h in an oscillator to take out, with the centrifugal 10min of 4000r/min, repeat aforesaid operations 5 times, be washed with distilled water to neutrality again, namely obtain the charcoal of high absorption property.
3. heavy metal ion high absorption property charcoal according to claim 1, it is characterized in that: in mass, the proportionate relationship of described living beings is: Chinese sorghum slag: paddy slag: glutinous rice slag: wheat grit: maize pulp=5:7:4:3:1.
4. the preparation method of charcoal according to claim 2, it is characterized in that: selected living beings need pulverize 20-100 mesh sieve in advance, then add the mixing of rubidium chloride solution, sealing and standing 12h in the material of mixing, natural air drying, the molar concentration of rubidium chloride solution is 0.05-1.5mol/L.
5. the preparation method of charcoal according to claim 2, it is characterized in that: described biomass anaerobic pyrolysis temperature is 400-700 DEG C, pyrolysis time is 60-300min, and programming rate is 5-15 DEG C/min.
6. the preparation method of charcoal according to claim 2, is characterized in that: the HCl/HF mixed solution concentration of described isoconcentration mixing is 0.5-2.0mol/L.
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| CN105858739A (en) * | 2016-04-21 | 2016-08-17 | 东北农业大学 | Water purification agent for removing heavy metal in wastewater and preparation method thereof |
| CN106219724A (en) * | 2016-08-17 | 2016-12-14 | 安徽科技学院 | Utilize charcoal absorption and the method for the catalysis persulfate orange II waste water from dyestuff of degraded |
| CN108745300A (en) * | 2018-05-23 | 2018-11-06 | 北京林业大学 | A kind of natural soapberry air purification medium and preparation method thereof |
| CN110183257A (en) * | 2019-06-21 | 2019-08-30 | 中国科学院成都生物研究所 | A kind of complete utilization method of Maotai-flavor liquor distillage anaerobic digestion coupling hydrothermal carbonization |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105148842A (en) * | 2015-09-07 | 2015-12-16 | 河北师范大学 | Preparing method of manganese oxide-charcoal composite adsorbent |
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| CN110183257A (en) * | 2019-06-21 | 2019-08-30 | 中国科学院成都生物研究所 | A kind of complete utilization method of Maotai-flavor liquor distillage anaerobic digestion coupling hydrothermal carbonization |
| CN116282387A (en) * | 2023-01-04 | 2023-06-23 | 哈尔滨工业大学 | Method for preparing straw carbon-hydroxypropyl membrane electrode by melting pyrolysis with cadmium removal |
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