CN105753608A - Preparation method and application of novel iron-based biochar - Google Patents
Preparation method and application of novel iron-based biochar Download PDFInfo
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- CN105753608A CN105753608A CN201610324435.0A CN201610324435A CN105753608A CN 105753608 A CN105753608 A CN 105753608A CN 201610324435 A CN201610324435 A CN 201610324435A CN 105753608 A CN105753608 A CN 105753608A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of preparation and application of novel iron-based biochar, in particular to a preparation method for a novel iron-based biochar repair material which is used for treating polluted soil. The preparation method is characterized by comprising the following steps: performing anaerobic dry distillation on a biomass raw material which is carried with an iron oxide in a dry distillation furnace; performing reducing, cracking and polymerizing reactions on the biomass to generate energy conversion; separating reductive gases, namely CO and H2; under a proper temperature, gradually reducing part iron oxide which is loaded on the surface of the biomass into zero-valent iron. Electrode potential difference exists between iron and carbon, so that a micro primary cell can be formed in soil solution; moreover, the iron oxide which remains on the surface of the biochar has a very good removal capacity to arsenic, so that the treatment effect on the pollutants in soil is enhanced very well; according to the preparation method and the application of the novel iron-based biochar, environmental effects of the biochar, the zero-valent iron and the iron oxide are combined, so that the problem of repair function loss of the biochar is solved; the repair efficiency is improved; the application potential of the novel iron-based biochar in the aspect of soil body pollution control is expanded.
Description
Technical field
The present invention relates to the preparation of a kind of new iron-based charcoal and application thereof, particularly to the preparation method of the new iron-based charcoal repair materials processed for contaminated soil.
Background technology
The material base that soil is agricultural production and the mankind depend on for existence, but soil pollution has become as one of whole world environmental problem urgently to be resolved hurrily, in per capita cultivated land's occupancy volume China lower than world average level, soil contamination problem is more prominent, relevant ministries and commissions of in April, 2014 country issue " whole nation Soil Pollution Investigation publication ", the display whole nation total exceeding standard rate of soil has reached 16.1%, the farm land area of heavy metal pollution about 25,000,000 square metres, cause grain drop in production more than up to 1,000 ten thousand tons because of heavy metal pollution, add up to economic loss at least 200 hundred million yuan;The great environmental problem that soil pollution has become to be affected agricultural product security, restrict agricultural Sustainable Healthy Development, involve the interests of the state and the people, causes extensive concern both domestic and external.
At present, the method for domestic process soil pollution is numerous, and wherein, charcoal is extensively praised highly as the effective soil remediation material of one.Charcoal wide material sources, containing abundant organic macromolecule and space, and have the structure of height aromatization, and containing a large amount of phenol alkyl, carboxyl and carbonyl, these fundamental propertys make charcoal possess good characterization of adsorption and stability.Heavy metal in soil, organic pollution can be played absorption, fixation by using of charcoal, reduce its biological effectiveness, can strengthen the activity of Soil Microorganism, thus also enhancing the microorganism degradation capability to organic pollution simultaneously.
Owing to charcoal is undesirable to the fixed effect of pollutant in soil, therefore, if directly charcoal being applied to contaminated soil, often make large usage quantity, and the soil application of charcoal is an irreversible process, although applying substantial amounts of charcoal can be effectively reduced the biological effectiveness of pollutant, but cost also can improve, and owing to charcoal has the stability of height, can long-term existence in soil, it is possible to cause the reduction of soil fertility and to the vegeto-animal murder by poisoning of soil.In addition, there are some researches show: in soil, add charcoal can improve As transfer ability, as the researchs such as Zheng find, after charcoal is applied to the paddy soil of heavy metal pollution, Cd in rice root, Zn and Pb concentration have dropped 98%, 83% and 72% respectively, and the concentration of arsenic adds 327%.Therefore, how modification biological charcoal so that it is the removal effect of pollutant (particularly arsenic) various in soil is got a promotion and becomes next step research emphasis of people.
Zero-valent Iron is a kind of material being widely used in polluted underground water and soil treatment, owing to it has stronger reproducibility and electronegativity, can with the multiple pollutant generation reduction reaction including chlorobenzene class and heavy metal class, thus reach remove pollutant purpose;Meanwhile, iron oxides/hydroxides owing to there being higher affinity to receive more concern to arsenic.Therefore, how charcoal, Zero-valent Iron being combined with the environmental activity of iron oxides/hydroxides, prepare iron-based charcoal composite, thus promoting the removal effect of various pollutant in soil, having great importance.
The preparation method of the new iron-based charcoal of the present invention, mainly puts into the biomass material being loaded with iron oxides and carries out anaerobism dry distilling in gas retort, and biomass, through reduction, cracking and polyreaction, produce energy conversion, isolate reducibility gas CO and H2, at moderate temperatures, fractional load is progressively reduced to Zero-valent Iron at the iron oxides of biological surface;Owing to there is difference in Electrode Potential between ferrum, carbon, the soil liquid can be formed micro-galvanic element, and arsenic is had good removal ability by the iron oxides remaining in charcoal surface, thus well enhancing the treatment effect to pollutant in soil;Charcoal, Zero-valent Iron are combined by the present invention with the environmental activity of iron oxides, the problem both having overcome charcoal repair function disappearance, improve again remediation efficiency, expand its application potential in soil pollution improvement.
Utilizing the method that iron-based charcoal is prepared in biomass material and iron oxides anaerobism dry distilling to have not been reported at home, the present invention is as starting point, it is proposed that the preparation method of a kind of new iron-based charcoal.
Summary of the invention
It is desirable to provide a kind of for new iron-based charcoal improving pollutant in soil treatment effect and preparation method thereof, to solve the deficiency that current material exists.
The preparation method of described new iron-based charcoal comprises the following steps:
A. the preparation of biomass material: at 50~90 DEG C, (includes sawdust, wood shavings, branch, the wooden class of trunk forestry waste by biomass material;The stalks such as Caulis et Folium Oryzae, wheat straw, millet straw, corn straw) dry 5~10h, size-reduced 1~20mm powder that is machined to, standby.
B. biomass material pretreatment: by a certain amount of iron oxides (Fe2O3/Fe3O4) be dissolved in ethanol and in the system (V (alcohol): V (water)=8:2) of water, mix homogeneously with appropriate above-mentioned powdered biological raw material, impregnate 1~5h under ultrasound condition;Low temperature (70~90 DEG C) adds heat abstraction solvent and dries subsequently, by the ferrum oxide load of precipitation on biological material surface, subsequently, crosses 50 mesh sieves and removes unsupported croci, stand-by.
C. the preparation of new iron-based charcoal: by powdered biological raw material complete for pretreatment, puts into and carries out anaerobism dry distilling in gas retort.When in-furnace temperature slows down programming rate after reaching 300~400 DEG C, temperature reaches insulation 1~2h when 500 DEG C;1~2h it is incubated after being to slowly warm up to 500~600 DEG C more subsequently, same insulation 1~2h after being warming up to 800~1000 DEG C, namely prepare new iron-based charcoal.In this process, biomass, through reduction, cracking and polyreaction, produce energy conversion, isolate reducibility gas CO and H2, at moderate temperatures, fractional load is progressively reduced to Zero-valent Iron at the ferrum oxide of biological surface.
Preferably, in the process of described preparation iron oxide solution, ultra-pure water is used to prepare.
Preferably, described gas retort adopts " the biomass energy wind formula gas retort " that Beijing core standing grain great achievement bioenergy Science and Technology Ltd. produces.
Preferably, the complete powdered biological raw material of described pretreatment passes into nitrogen about 10min before carrying out anaerobism dry distilling.
The invention have the advantages that
1, charcoal, Zero-valent Iron are combined by the present invention with the environmental activity of iron oxides, the problem both having overcome charcoal repair function disappearance, improve again remediation efficiency, expand its application potential in soil pollution improvement.
2, the present invention can form the composite bed of Zero-valent Iron and iron oxides on charcoal surface, owing to there is difference in Electrode Potential between ferrum, carbon, the soil liquid can be formed micro-galvanic element, and arsenic is had good repair ability by iron oxides, thus enhancing the treatment effect to pollutant in soil.
3, the preparation method technical process of a kind of new iron-based charcoal of the present invention is simple and reliable, it is easy to control;And with low cost, it is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope comparison diagram of the new iron-based charcoal of the present invention and charcoal.
Fig. 2 is the present invention new iron-based charcoal removal curve chart to DCBP.
Fig. 3 is the removal curve chart of the new iron-based charcoal heavy metal arsenic of the present invention.
Detailed description of the invention
Present disclosure has been carried out further detailed description by specific examples below, is only specific embodiments of the invention, is not limited to the present invention.
Embodiment 1:
A kind of new iron-based charcoal and preparation method thereof, this material with charcoal for carrier, area load iron oxides and Zero-valent Iron, its concrete preparation process is as follows:
A. the preparation of biomass material: at 70 DEG C, (includes sawdust, wood shavings, branch, the wooden class of trunk forestry waste by biomass material;The stalks such as Caulis et Folium Oryzae, wheat straw, millet straw, corn straw) dry 5h, size-reduced 1~20mm powder that is machined to, standby.
B. biomass material pretreatment: by a certain amount of iron oxides (Fe2O3/Fe3O4) be dissolved in ethanol and in the system (V (alcohol): V (water)=7:3) of water, mix homogeneously with appropriate above-mentioned powdered biological raw material, impregnate 1~5h under ultrasound condition;Low temperature (60 DEG C) adds heat abstraction solvent and dries subsequently, by the ferrum oxide load of precipitation on biological material surface, subsequently, crosses 50 mesh sieves and removes unsupported croci, stand-by.
C. the preparation of new iron-based charcoal: by powdered biological raw material complete for pretreatment, puts into and carries out anaerobism dry distilling in gas retort.When in-furnace temperature slows down programming rate after reaching 400 DEG C, temperature reaches insulation 1h when 500 DEG C;It is incubated 1h after being to slowly warm up to 600 DEG C more subsequently, after being warming up to 900 DEG C, is incubated 1h equally, namely prepare new iron-based charcoal.In this process, biomass, through reduction, cracking and polyreaction, produce energy conversion, isolate reducibility gas CO and H2, at moderate temperatures, fractional load is progressively reduced to Zero-valent Iron at the ferrum oxide of biological surface.
Use scanning electron microscope that described new iron-based charcoal is scanned, it is observed that material surface is uneven, and there is substantial amounts of space, relatively charcoal can be seen that one layer of uniform particle layer of new iron-based charcoal area load, and this particle layer is exactly the coating (such as Fig. 1) of Zero-valent Iron and iron-based oxide.
Embodiment 2:
The new iron-based charcoal present invention prepared carries out the clearance test of DCBP in soil.Weigh the contaminated simulation soil sample (initial concentration 500ug/kg) that 7 parts of quality are 2.0g respectively, it is separately added into the new iron-based charcoal of 0.1g, humidity is regulated by 2ml ultra-pure water, put in indoor without direct sunlit position, keep room temperature 20 DEG C, it is 1h, 2h, 3h, 5h, 12h, 24h and 36h in the response time respectively, filters, filtering residue is put in that to be placed in freezer dryer dry.Treat that it is completely dried to grind afterwards to sieve, weigh 1.0g soil sample in 50ml centrifuge tube, it is added thereto to 1.5g anhydrous sodium sulfate dewater, add normal hexane-acetone mixed solution 20ml (volume ratio is 1:1), carry out microwave extracting 40min, extraction is centrifugal after terminating, and takes its supernatant and rotates evaporation, carries out upper machine analysis after being evaporated to 1ml.Experimental result is as shown in Figure 2, it will thus be seen that DCBP is had good removal effect by described material prepared by the present invention, and is swift in response, and within 24h, the degradation rate of DCBP just can reach more than 95%.
Embodiment 3:
The new iron-based charcoal present invention prepared carries out heavy metal arsenic clearance test.Take the arsenic solution of 150ml2mg/L, add new iron-based charcoal 0.3g, point three groups of parallel tests, put it in the constant temperature oscillation case of 30 DEG C and react, the clearance of sampling and measuring Heavy Metals in Waters arsenic at set intervals, obtains the heavy metals removal curve of described material.As can be seen from Figure 3: acid gorgeous indigo plant is had good removal effect by described material prepared by the present invention, and is swift in response, the clearance of nearly 80% can be reached after 30min.
Claims (5)
1. a preparation method for new iron-based charcoal, is characterised by, described preparation method comprises the following steps:
1) preparation of biomass material
2) biomass material pretreatment
3) preparation of new iron-based charcoal.
2. the method for claim 1, it is characterised in that in step 1) described in biomass material include the wooden classes such as sawdust, wood shavings, branch, trunk forestry waste;The stalks such as Caulis et Folium Oryzae, wheat straw, millet straw, corn straw.
3. the method for claim 1, it is characterised in that in step 2) described in iron oxides be Fe2O3Or Fe3O4。
4. the method for claim 1, it is characterised in that in step 3) described in retort process in-furnace temperature Changing Pattern be: in-furnace temperature slows down programming rate after reaching 300~400 DEG C, temperature reaches insulation 1~2h when 500 DEG C;1~2h it is incubated, same insulation 1~2h after being warming up to 800~1000 DEG C after being to slowly warm up to 500~600 DEG C more subsequently.
5. the new iron-based charcoal that preparation method according to claim 1 obtains, it is characterized in that charcoal, Zero-valent Iron are combined by the present invention with the environmental activity of iron oxides, both the problem having overcome charcoal repair function disappearance, improve again remediation efficiency, expand its application potential in soil pollution improvement.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107936972A (en) * | 2017-11-24 | 2018-04-20 | 广西博世科环保科技股份有限公司 | A kind of composite passivant and its application method of remediating heavy metal combined pollution agricultural land soil |
CN108199057A (en) * | 2017-12-20 | 2018-06-22 | 武汉豪岩照明电子有限公司 | A kind of ecology accumulation of energy ground battery |
CN108854951A (en) * | 2018-06-05 | 2018-11-23 | 南昌大学 | The method that one-step method prepares charcoal nano zero valence iron nickel composite |
CN110404539A (en) * | 2019-07-15 | 2019-11-05 | 上海应用技术大学 | A kind of oxidation restorative procedure of iron-based biological Pd/carbon catalyst and contaminated soil |
CN110548483A (en) * | 2019-05-25 | 2019-12-10 | 北京化工大学 | preparation method and application of biochar/nano ferroferric oxide composite material |
CN110548879A (en) * | 2019-06-04 | 2019-12-10 | 北京化工大学 | Preparation method and application of green synthetic novel iron-carbon material |
CN111662728A (en) * | 2020-07-29 | 2020-09-15 | 杨凌职业技术学院 | Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof |
CN112354532A (en) * | 2020-10-27 | 2021-02-12 | 东北农业大学 | Preparation method and application of zero-valent iron-loaded biochar material |
CN112427014A (en) * | 2020-11-04 | 2021-03-02 | 清华大学 | Method for preparing zero-valent iron-biochar material |
CN114433610A (en) * | 2020-10-30 | 2022-05-06 | 中国环境科学研究院 | Water and soil co-treatment method for composite pollution region |
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CN104549155A (en) * | 2015-01-23 | 2015-04-29 | 中国科学院生态环境研究中心 | Biological activated carbon composite material and application thereof |
CN104587958A (en) * | 2015-01-23 | 2015-05-06 | 中国科学院生态环境研究中心 | Composite biological carbon material loading iron oxide as well as preparation method and application of composite biological carbon material |
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CN103406095A (en) * | 2013-07-16 | 2013-11-27 | 复旦大学 | Activation method and application of biomass liquefaction residue |
CN104549155A (en) * | 2015-01-23 | 2015-04-29 | 中国科学院生态环境研究中心 | Biological activated carbon composite material and application thereof |
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Cited By (12)
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CN107936972A (en) * | 2017-11-24 | 2018-04-20 | 广西博世科环保科技股份有限公司 | A kind of composite passivant and its application method of remediating heavy metal combined pollution agricultural land soil |
CN108199057A (en) * | 2017-12-20 | 2018-06-22 | 武汉豪岩照明电子有限公司 | A kind of ecology accumulation of energy ground battery |
CN108854951A (en) * | 2018-06-05 | 2018-11-23 | 南昌大学 | The method that one-step method prepares charcoal nano zero valence iron nickel composite |
CN108854951B (en) * | 2018-06-05 | 2021-04-02 | 南昌大学 | Method for preparing biochar nano zero-valent iron-nickel compound by one-step method |
CN110548483A (en) * | 2019-05-25 | 2019-12-10 | 北京化工大学 | preparation method and application of biochar/nano ferroferric oxide composite material |
CN110548879A (en) * | 2019-06-04 | 2019-12-10 | 北京化工大学 | Preparation method and application of green synthetic novel iron-carbon material |
CN110404539A (en) * | 2019-07-15 | 2019-11-05 | 上海应用技术大学 | A kind of oxidation restorative procedure of iron-based biological Pd/carbon catalyst and contaminated soil |
CN111662728A (en) * | 2020-07-29 | 2020-09-15 | 杨凌职业技术学院 | Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof |
CN111662728B (en) * | 2020-07-29 | 2021-12-21 | 杨凌职业技术学院 | Walnut branch biochar-based fertilizer soil remediation agent and preparation method and application thereof |
CN112354532A (en) * | 2020-10-27 | 2021-02-12 | 东北农业大学 | Preparation method and application of zero-valent iron-loaded biochar material |
CN114433610A (en) * | 2020-10-30 | 2022-05-06 | 中国环境科学研究院 | Water and soil co-treatment method for composite pollution region |
CN112427014A (en) * | 2020-11-04 | 2021-03-02 | 清华大学 | Method for preparing zero-valent iron-biochar material |
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