AU2021103819A4 - Modified biochar and preparation method and application thereof - Google Patents
Modified biochar and preparation method and application thereof Download PDFInfo
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- AU2021103819A4 AU2021103819A4 AU2021103819A AU2021103819A AU2021103819A4 AU 2021103819 A4 AU2021103819 A4 AU 2021103819A4 AU 2021103819 A AU2021103819 A AU 2021103819A AU 2021103819 A AU2021103819 A AU 2021103819A AU 2021103819 A4 AU2021103819 A4 AU 2021103819A4
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- soil
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002689 soil Substances 0.000 claims abstract description 90
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 70
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000011068 loading method Methods 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims description 61
- 239000002028 Biomass Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 239000003575 carbonaceous material Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000000197 pyrolysis Methods 0.000 claims description 13
- 150000000703 Cerium Chemical class 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- 239000003610 charcoal Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- 239000011572 manganese Substances 0.000 abstract description 21
- 229910052748 manganese Inorganic materials 0.000 abstract description 18
- 238000002161 passivation Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 238000005067 remediation Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 238000011282 treatment Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009418 agronomic effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical class [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical class O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000001676 hydride generation atomic fluorescence spectroscopy Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052957 realgar Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention provides modified biochar and a preparation method as well as
application thereof; said invention belongs to the technical field of heavy metal
remediation of soil and a water body; manganese and cerium are loaded on said
biochar, and loading of manganese and cerium can greatly improve the adsorption and
fixation capacity of said biochar for arsenic; meanwhile, loading of manganese and
cerium improves the specific surface area of the biochar, and the adsorption effect of
the modified biochar for arsenic is improved; data of embodiment indicates that the
specific surface area of the provided modified biochar is 6.10-8.36 m(2) g(-1), and the
arsenic adsorption capacity can reach 96.13 mg/g; when said modified biochar is used
for removing arsenic from soil, the addition amount of the modified biochar is 1-10%
of the soil weight, the passivation efficiency of red soil is 70.59-94.72%, the
passivation efficiency of yellow soil is 75.24-98.35%, and the passivation efficiency
of purple soil is 76.53-99.61%.
1
Description
[0001] The invention relates to the technical field of soil and water heavy metal
restoration, in particular to a modified biochar and its preparation method and
application.
[0002] Arsenic is a kind of carcinogenic trace metal that has long been regarded as the
main hazard to human health thus has attracted global attention; people feeding on
water and food that contains excessive amounts of arsenic in long term can cause
disease and cancer in human organs; China is one of the countries seriously polluted
by arsenic, and there are large areas of low-to-medium polluted soils, such as Shimen
city in Hunan province, Chenzhou city in Yunnan province, Wenshan city in Guangxi
province, and Hechi city in Guangxi province; the Ministry of Environmental
Protection and the Ministry of Land and Resources jointly issued a national pollution
survey bulletin in 2014; said survey basically grasped the overall status of the soil
environment in China, said survey results indicated that the national soil environment
is worrisome; some areas are seriously polluted and the quality of cultivated land is
not in optimistic status; therefore, the soil problems are prominent; national total soil
point over-standard rate reached 16.1%, and the over-standard rate of arsenic points in
the inorganic pollutant index reached 2.7%; in the face of severe arsenic pollution,
restoration of arsenic pollution cannot be underestimated.
[0003] At present, there are two approaches to treat soil polluted by heavy metals; one
is to remove the pollutants, namely, to decontaminate; the other is to change the form
of heavy metals in the soil by fixing them, reducing the activity of said pollutants, and
reduce the mobility and bioavailability of pollutants in the soil, namely, stabilization;
around these two approaches, different treatment measures and methods have
emerged, mainly including engineering measures, electric remediation methods,
chemical leaching methods, bioremediation methods, agronomic measures and in-situ
passivation methods; however, since each method has certain limitations, none of
them has become an ideal repair measure; for example, although engineering
measures have a thorough and stable advantage in the treatment of heavy metal
contaminated soil, however it has disadvantages like high in cost and time-consuming
as well as labor-intensive, thus it is difficult to promote and can cause damage to the
soil structure, and soil fertility to decline; electric remediation method is limited to
soil remediation in a small area; chemical leaching method is likely to cause a large
amount of soil nutrients to be leached at the same time, leaching waste liquid can
increase subsequent treatment costs, and is restricted by soil texture, leaching agent
type, and water source; although the bioremediation method can achieve the purpose
of decontamination, but it needs a long remediation period, and is greatly affected by
climate and soil conditions, and the remediation efficiency is low; compared with
many other soil pollution remediation methods, the in-situ passivation method is
suitable for large-scale promotion due to its low cost, strong operability, remarkable
effect, and environmental friendliness, especially for the large area of medium and
low pollution farmland in China today; the application prospect of this technology is
good, and it has attracted the attention of the majority of scientific researchers in
recent years.
[0004] Said passivating agents for soil heavy metal pollution restoration mainly
include phosphorus-containing substances, silicon-calcium compounds, organic
materials, clay minerals, metals and metal oxides, and biochar and other functional
materials; many cases related with the use of biochar and metal oxides to successfully
carrying out arsenic pollution remediation have been reported.
[0005] Biochar is a carbon-rich and stable solid product obtained by pyrolysis of
organic materials such as crop straw and wood under hypoxia or anaerobic conditions;
it is an environmentally friendly passivation material; it has the advantages of porosity,
large specific surface area, rich surface active functional groups, and has the effect of
carbon fixation and emission reduction; it is an environmentally friendly material with easy-to-obtain raw materials; however, more and more studies have shown that biochar has a limited ability to fix arsenic; adsorption performance of biochar for heavy metals not only depends on its pore structure, but also closely related to the chemical properties of its surface; modifying the surface of biochar or treating it with chemical reagents to improve its adsorption capacity has become a new research hotspot.
[0006] Many studies in recent years have shown that surface modification of biochar and effective loading of metals and metal oxides, such as manganese, iron, etc., can greatly improve the ability of biochar to adsorb and fix arsenic; Chinese patent CN107824612A discloses a preparation method of Fe 3 0 4 -based biochar soil passivation agent, which can improve the stability of heavy metals Pb and Cd thus prevent heavy metals from being absorbed by crops, but the method does not mention the effect of As; Chinese patent CN108816188A discloses a goethite modified biochar and its preparation method and application; said modified biochar provided by it has a relatively low adsorption capacity for arsenic.
[0007] This invention aims to provide a modified biochar and its preparation method as well as its application; said biochar provided by this invention has high arsenic adsorption capacity, high removal rate and low processing cost, and can be applied to repair arsenic-contaminated sites and arsenic-contaminated farmland.
[0008] With intention to achieve said aim, technical solution of this invention is introduced as follow:
[0009] A modified biochar is provided by this invention, wherein said modified biochar is biomass charcoal stacked in flakes and granular cerium oxide and manganese oxide loaded on the surface of said biomass charcoal; loading amount of said manganese element is 2.85-4.63% of the mass of the modified biochar; loading amount of cerium element is 7.65~-45.82% of the mass of the modified biochar; said specific surface area of said modified biochar is 6.10-8.35m 2 -g -1.
[0010] Preparation method of said modified biochar has steps as followed:
[0011] Carbonize biomass raw materials to obtain carbonized composites;
[0012] Mix said carbonized composite with a hydrochloric acid solution to perform a first reaction to obtain a carbon material;
[0013] Mix said carbon material, potassium permanganate, water-soluble cerium salt, and water to perform a second reaction to obtain a carbon composite;
[0014] Said carbon composite is subjected to anaerobic pyrolysis to obtain the modified biochar.
[0015] Preferred, temperature of said carbonization temperature is 600-800°C, and the time is 2-8 hours.
[0016] Preferred, solid-to-liquid ratio of the carbonized composite to the hydrochloric acid solution is 1 g: (2-10) mL; concentration of said hydrochloric acid solution is 0.5-1.5 mol/L..
[0017] Preferred, temperature of said first reaction is 25-35°C, and the time is 12-18 hours.
[0018] Preferred, amount ratio of the carbon material, potassium permanganate and water-soluble cerium salt is Ig: 0.0002 to 0.003 mol: 0.0005 to 0.015 mol.
[0019] Preferred, temperature of said second reaction is room temperature, and the time is 1 to 5 hours.
[0020] Preferred, temperature of said anaerobic pyrolysis is 600-800°C, and the time is 2-8 hours.
[0021] This invention also provide preparation method of said modified biochar and its application to remove arsenic in water or soil body.
[0022] Preferred, when said modified biochar is used to remove arsenic from water bodies, the solid-to-liquid ratio of the modified biochar to the arsenic-containing water body is 5-20 g/L.
[0023] This invention provides a modified biochar, said modified biochar is biomass charcoal stacked in flakes and granular cerium oxide and manganese oxide loaded on the surface of said biomass charcoal; loading amount of said manganese element is
2.85-4.63% of the mass of the modified biochar; loading amount of cerium element is 7.65~-45.82% of the mass of the modified biochar; said specific surface area of said modified biochar is 6.10-8.35m 2 -g -1.
[0024] Manganese and cerium are loaded on said biochar in this invention, and loading of manganese and cerium can greatly improve the adsorption and fixation capacity of said biochar for arsenic; meanwhile, loading of manganese and cerium improves the specific surface area of the biochar, and the adsorption effect of the modified biochar for arsenic is improved; data of embodiment indicates that the specific surface area of the provided modified biochar is 6.10-8.35m 2/g, and the arsenic adsorption capacity can reach 96.13 mg/g; when said modified biochar is used to remove arsenic from the soil, it has a strongfixation/passivation effect on the arsenic in the soil,
when the addition amount of the modified biochar is 1-10% of the soil weight, the passivation efficiency of red soil is 70.59-94.72%, the passivation efficiency of yellow soil is 75.24-98.35%, and the passivation efficiency of purple soil is 76.53-99.61%.
[0025] This invention also provides the preparation method of said modified biochar, which is easy to provide said preparation method, strong operability and application adaptability; meanwhile, the raw material source is wide and the adaptability is wide.
[0026] FIG. 1 refers to 10,000 times SEM image of the carbonized composite (a) and modified biochar (b) obtained in embodiment 1;
[0027] FIG. 2 refers to 10,000 times SEM image of the modified biochar obtained in embodiment 1;
[0028] FIG. 3 refers to XRD spectrum of cerium oxide, manganese oxide, and carbonized composite (BC) obtained in embodiment 1 and the modified biochar (MBC).
[0029] This invention provides a modified biochar, said modified biochar is biomass
charcoal stacked in flakes and granular cerium oxide and manganese oxide loaded on
the surface of said biomass charcoal; loading amount of said manganese element is
2.85-4.63% of the mass of the modified biochar; loading amount of cerium element is
7.65~-45.82% of the mass of the modified biochar; said specific surface area of said
modified biochar is 6.10-8.35m 2 -g -1.
[0030] Manganese and cerium are loaded on said biochar in this invention, and
loading of manganese and cerium can greatly improve the adsorption and fixation
capacity of said biochar for arsenic; meanwhile, loading of manganese and cerium
improves the specific surface area of the biochar, and the adsorption effect of the
modified biochar for arsenic is improved
[0031] Preparation method of said modified biochar is provided, wherein steps are
listed below:
[0032] Carbonize biomass raw materials to obtain carbonized composites;
[0033] Mix said carbonized composite with a hydrochloric acid solution to perform a
first reaction to obtain a carbon material;
[0034] Mix said carbon material, potassium permanganate, water-soluble cerium salt,
and water to perform a second reaction to obtain a carbon composite;
[0035] Said carbon composite is subjected to anaerobic pyrolysis to obtain the
modified biochar.
[0036] This invention carbonizes biomass raw materials to obtain a carbonized
composite.
[0037] In the present invention, particle size of the biomass raw material is preferably
100 to 400 mesh, more preferably 150 to 350 mesh, more preferably 200 to 300 mesh,
and even more preferably 250 mesh; In said invention, the biomass raw material is
preferably one or more of wheat straw, cotton stalk, rice straw and corn stalk, and
more preferably wheat stalk or cotton stalk.
[0038] Said biomass raw material is preferably prepared by a method including the
following steps: said biomass raw material is washed, dried and pulverized to obtain the biomass raw material; said invention does not specifically limit the washing parameters, as long as the biomass raw materials can be washed clean; in the present invention, the drying method is preferably drying, and the drying temperature is preferably 80°C; said invention does not specifically limit the pulverization parameters, as long as the particle size of the biomass raw material remains 100~400 mesh.
[0039] In the present invention, said carbonization temperature is preferably 600-800°C, more preferably 650-780°C, more preferably 700-750°C; the rate of heating to the carbonization temperature is preferably 10-20°C/min , further preferably °C/min; the carbonization time is preferably 2-8h.
[0040] After said carbonization is completed, this invention preferably further includes cooling the obtained carbonized product to room temperature and then taking it out, grinding and passing it through a 100-mesh screen to obtain a carbonized composite.
[0041] After said carbonized composite is obtained, mix the carbonized composite with a hydrochloric acid solution to perform a first reaction to obtain a carbon material.
[0042] In the present invention, the solid-to-liquid ratio of the carbonized composite to the hydrochloric acid solution is preferably lg:(2-10)mL, more preferably lg:5mL; the concentration of the hydrochloric acid solution is preferably 0.5-1.5mol/L, more preferably 0.6 to 1.2 mol/L, and more preferably 0.8 to 1.0 mol/L.
[0043] After the first reaction is completed, the present invention preferably includes post-processing the obtained first reaction liquid; the post-processing preferably includes the following steps:
[0044] In the present invention, the solid-liquid separation method is preferably vacuum filtration; the washing reagent is preferably deionized water; the present invention does not specifically limit the number of washings, as long as the solid matter can be washed to the middle sex is enough; in the present invention, the drying method is preferably drying; the drying temperature is preferably 70-80°C; the present
invention does not specifically limit the drying time, as long as the solid matter can be
dried.
[0045] In the present invention, said first reaction can remove the ash in the
carbonized composite; at the same time, some alkaline substances in the carbonized
composite react with acid to generate soluble salt substances for removal in the
post-treatment process.
[0046] In the present invention, the amount ratio of the carbon material, potassium
permanganate and the water-soluble cerium salt is preferably lg: 0.0002~0.003mol:
0.0005 ~ 0.015mol; the molar ratio of the potassium permanganate and the
water-soluble cerium salt is preferably 1:1 to 1:5, more preferably 1:2 to 1:4, and
more preferably 1:2.5 to 1:3.
[0047] In the present invention, the water-soluble cerium salt is preferably cerium
chloride.
[0048] In the present invention, the manner of mixing the carbon material, potassium
permanganate, water-soluble cerium salt, and water is preferably: sequentially mixing
the carbon material with an aqueous potassium permanganate solution and a
water-soluble cerium salt aqueous solution; in the present invention, the concentration
of the potassium permanganate aqueous solution is preferably 0.1-0.5 mol/L; the
concentration of the water-soluble cerium salt aqueous solution is preferably 0.2-1.0
mol/L.
[0049] In the present invention, temperature of the second reaction is preferably room
temperature, namely, no additional heating or cooling is required; the time of the
second reaction is preferably 1 to 5 hours; in the present invention, the second
reaction is preferably performed under ultrasound conditions; this invention does not
specifically limit the parameters of the ultrasound.
[0050] After the second reaction is over, this invention preferably includes
post-processing the obtained second reaction liquid; said post-processing preferably
includes the following steps:
[0051] Said obtained second reaction liquid is evaporated to dryness in a constant
temperature water bath to obtain a mud cake; the obtained mud cake is washed and
separated into solid and liquid, and the obtained solid matter is dried and ground to
obtain a carbon composite.
[0052] In the present invention, temperature for drying in the constant temperature
water bath is preferably 95C; the time for drying in the constant temperature water
bath is preferably 8-12 hours; and the drying in the constant temperature water bath is
preferably carried out in a water bath.
[0053] In the present invention, said washing reagent is preferably deionized water;
the number of times of washing is preferably 3 to 5 times; in the present invention, the
washing can wash away potassium permanganate and water-soluble cerium salt that
are not loaded on the carbon material.
[0054] In the present invention, said solid-liquid separation method is preferably
vacuum filtration; the drying temperature is preferably 80°C; the present invention
does not specifically limit the drying time, as long as the moisture can be completely
removed; this invention does not specifically limit the grinding parameters, as long as
the grinding product can be made to be 100-400 mesh.
[0055] In the present invention, said second reaction can load cerium and manganese
elements on the carbon material in the form of oxides and hydrates thereof.
[0056] After the carbon composite is obtained, this invention performs anaerobic
pyrolysis of the carbon composite to obtain modified biochar.
[0057] In the present invention, temperature of the anaerobic pyrolysis is preferably
600-800°C, more preferably 700°C; the rate of heating to the temperature of the
anaerobic pyrolysis is preferably 10-20°C/min; oxygen pyrolysis time is preferably
2-8h; said anaerobic pyrolysis is preferably performed under a protective atmosphere;
protective atmosphere is preferably nitrogen; flow rate of the nitrogen is preferably
600 cm 3 -min -1; in the present invention, oxygen-free pyrolysis is preferably carried
out in a muffle furnace.
[0058] In the present invention, said anaerobic pyrolysis can finally convert the
manganese and cerium hydrates in the carbon composite into stable manganese and
cerium oxides, which are more firmly supported on the surface of the biochar in the
form of needle-like particles.
[0059] This invention also provides the application of the modified biochar to remove
arsenic from water bodies or soil.
[0060] In the present invention, when said modified biochar is used to remove arsenic
from water bodies, the solid-to-liquid ratio of said modified biochar to the
arsenic-containing water body is preferably 5-20 g/L.
[0061] In the present invention, when said modified biochar is used to remove arsenic
from the soil, the dosage of said modified biochar is preferably 200-2000 kg/mu.
[0062] Said modified biochar in the present invention has a higher specific surface
area and a higher adsorption capacity for arsenic in soil and water; at the same time,
the loading of manganese and cerium greatly improves the adsorption and fixation
capacity of the biomass charcoal to arsenic.
[0063] Said modified biochar provided in the present invention and its preparation
method and application will be described in detail below in conjunction with
embodiments, but they should not be understood as limiting the protection scope of
the present invention.
[0064] Embodiment 1
[0065] Wash the wheat straw, dry it at 80°C, pulverize it through 100-mesh screen,
and obtain a biomass raw material; place said biomass raw material in a muffle
furnace at 600°C for 2 hours, cool it to room temperature, take it out, and grind it
through 100 mesh screen to obtain a carbonized composite.
[0066] Take 100g of the carbonized composite obtained and treat it with 500mL
1.Omol-L -1 HCl for 12 hours; use vacuum pump to separate the solid from the liquid
by vacuum filtration to obtain the solid material; said solid material is washed
repeatedly with deionized water; after neutralization, it is dried and sieved at 70°C to
obtain a carbon material.
[0067] Take 1OOg of carbon material, add 500mL of potassium permanganate solution
with a concentration of 0.2mol-L -1 and 500mL of cerium chloride solution with a
concentration of 0.5mol-L -1 in sequence, put it in a digital ultrasonic instrument for
ultrasonic dispersion for 2 hours, then put it in a water bath at a constant temperature
(95°C) and evaporate to dryness in a water bath, and cool to room temperature to
obtain a mud cake; wash the mud cake with deionized water 3 times, use a vacuum
pump, and use vacuum filtration to separate solid and liquid; said material was dried
at 80°C and ground through a 100 mesh sieve to obtain a carbon composite.
[0068] Put said carbon composite into muffle furnace, use nitrogen (600cm 3 -min -1)
as protective gas, pyrolyze it at 600°C for 2 hours without oxygen, and then take it out
after cooling to room temperature to obtain the modified biochar; ratio of cerium to
manganese is 2.5:1; loading amount of Mn element in the modified biochar is 3.16%
of the mass of said modified biochar, and the loading amount of Ce element is 22.31%
of the mass of said modified biochar.
[0069] The specific surface area of said modified biochar obtained in this embodiment
is 6.88m 2 -g -1, which is 24.54% higher than that of the unmodified carbonized
composite; increase of the specific surface area increases the adsorption sites on the
surface of the modified biochar, which is beneficial to improve the adsorption
performance of the modified biochar to arsenic.
[0070] FIG. 1 is a 10,000 times SEM image of the carbonized composite (a) and
modified biochar (b) obtained in this embodiment; FIG. 2 is a 30,000 times SEM
image of the modified biochar obtained in this embodiment; it can be seen from FIG.
1 and FIG. 2 that said modified biochar is stacked in flakes, and a large number of
needle-like particulate materials are formed on the surface.
[0071] FIG. 3 shows the XRD spectra of cerium oxide, manganese oxide, and the
carbonized composite (BC) and modified biochar (MBC) obtained in this embodiment,
where BC refers to the unmodified carbonized composite and MBC refers to the
modified biochar; it can be seen from the FIG. 3 that the cerium and manganese in
said modified biochar mainly exist in the form of oxides.
[0072] Embodiment 2
[0073] Difference indicated here: take 100g of carbon material, add 500mL of
potassium permanganate solution with a concentration of 0.2mol-L -1 and 500mL of
cerium chloride solution with a concentration of 0.2mol-L -1 in sequence, the rest are
the same as in embodiment 1; ratio of cerium to manganese is 1:1; loading amount of
Mn element in the modified biochar obtained in this embodiment is 3.15% of the
mass of the modified biochar, and the loading amount of Ce element is 8.94% of the
mass of said modified biochar; specific surface area of the obtained modified biochar
is 6.95 m 2 -g -1.
[0074] Embodiment 3
[0075] Difference indicated here: take 100g of carbon material, add 500mL of
potassium permanganate solution with a concentration of 0.2mol-L -1 and 500mL of
cerium chloride solution with a concentration of Imol-L -1 in sequence, the rest are
the same as in embodiment 1; ratio of cerium to manganese is 5:1; loading amount of
Mn element in the modified biochar obtained in this embodiment is 3.08% of the
mass of the modified biochar, and the loading amount of Ce element is 43.26% of the
mass of said modified biochar; specific surface area of the obtained modified biochar
is 7.48 m 2 -g -1.
[0076] Weigh 2g of the modified biochar obtained in embodiment 1 to 3 and the
carbonized composite obtained in embodiment 1, and mix them into 40g soil samples
contaminated by heavy metals, maintaining 70% of the field water holding capacity
for cultivation; after 15 days of incubation, samples were taken to measure the content
of available heavy metals.
[0077] Calculation formula for the fixation efficiency q of biochar material to soil As
is:
[0078] q=(C 0 -C e )/C 0 x100 %
[0079] In the formula, C 0 and C e are the effective As content (mg-kg -1) of the
blank soil sample and the soil sample with biochar material, respectively.
[0080] Table 1: Comparison of passivation efficiency of the modified biochar
obtained in embodiment 1 to 3 and the carbonized composite obtained in embodiment
1 on soil heavy metals
[0081] Note: CK is a blank soil sample without adding any materials, Ce is the
effective As content in the soil, and is thefixation efficiency; a negative value
indicates that the heavy metal is activated, and "/" indicates no value.
[0082] Table 1 indicates that when the molar ratio of cerium to manganese is 2.5:1,
the modified biochar can achieve the best passivation effect on arsenic in the soil;
moreover, it not only has a good fixation effect on arsenic, but also has a certain
passivation effect on copper and lead in the soil.
[0083] Adsorption performance of biochar materials for arsenic in solution
[0084] Weigh 0.100g unmodified carbonized composite and modified biochar
obtained in embodiment 1 respectively; put them in a 50mL centrifuge tube, and add
mL of As(V) solution with a concentration of 50mg-L -1 respectively; oscillate at a
constant speed of 180r-min -1 at room temperature; after shaking for 2min, 5min,
min, 30min, 60min, 120min, 240min, 360min, 480min and 720mn, finish the
centrifugal separation; after filtering the supernatant, said arsenic content was
measured with an atomic fluorescence spectrometer, and the adsorption amount was
calculated based on the difference with the initial concentration; each treatment was
repeated 3 times; results are shown in table 2; table 2 indicates the adsorption capacity
of carbonized composite and modified biochar for arsenic.
[0085] Table 2: Comparison of arsenic adsorption capacity of carbonized composite
and modified biochar
[0086] Table 2 indicates that adsorption capacity of carbonized composite for arsenic
is 0.79mg-kg -1, and the adsorption capacity of modified biochar for arsenic is
79.73g-kg -1; arsenic adsorption capacity of the modified biochar provided by this
invention is 98.01 times higher than that of the unmodified carbonized composite.
[0087] Biochar's ability to remove arsenic from polluted water
[0088] Weigh 0.100g carbonized composite and modified biomass charcoal in
embodiment 1 and place them in 50mL centrifuge tubes respectively; add 20mL As(V)
solution with concentrations of 5mg-L -1, 10mg-L -1, 20mg-L -1, 50mg-L -1, 100mg-L -1, 150mg-L -1, 200mg-L -1 respectively; repeat each treatment 3 times;
after shaking at room temperature for 12 hours, take out said solution for centrifugal
filtration, measure the concentration of arsenic in the filtrate; removal rate of arsenic
in polluted water was compared between the two biochar materials; results are
indicated as table 3; table 3 indicates removal rate of arsenic in polluted water by
carbonized composite and modified biochar.
[0089] Table 3 indicates that when the concentration of arsenic in the water body is
-20mg-L -1, the removal rate of arsenic by modified biochar is over 99.95%, while
the removal rate of unmodified carbonized composite for arsenic in water body is
3.28-9.03%; with increase of the concentration of arsenic in the water body, removal
rates of arsenic by the modified biochar and the carbonized composite are in a
downward trend, but the modified biochar has better removal function than that of
said carbonized composite; Langmuir isotherm curve indicates that the maximum
adsorption capacity of modified biochar for arsenic is 96.13mg-g -1, while the
maximum adsorption capacity of unmodified carbonized composite for arsenic is only
1.23mg-g -1; it can be seen that removal rate of arsenic by modified biochar is greatly
improved, and its ability to remove arsenic from water bodies is greatly increased.
[0090] Table 4 indicates adsorption capacity of arsenic in polluted water by
carbonized composite and modified biochar
[0091] Table 4 indicates adsorption capacity of arsenic in polluted water by
carbonized composite and modified biochar; table 4 indicates that adsorption capacity
of modified biochar to arsenic is much higher than that of carbonized composite.
[0092] Table 4 indicates adsorption capacity of arsenic in polluted water by
carbonized composite and modified biochar
[0093] When solid-to-liquid ratio of the modified biochar obtained in embodiments 1
to 3 to the arsenic-containing waste liquid is 5-20g/L, such as 6g/L, 8g/L, 10g/L,
12g/L or 18g/L, removal efficiency of said modified biochar for arsenic in the
arsenic-containing waste liquid is still higher than the corresponding removal rate
indicated in table 3.
[0094] Fixation effect of biochar materials on soil arsenic
[0095] (1) Test soil
[0096] Three types of test soil were collected from red soil developed by slate shale in
Shimen county, Hunan province, yellow soil developed by granite in Sanmen county,
Fujian province, and purple soil developed by purple sand shale in Suining city,
Sichuan province; said collected soil samples are naturally air-dried and passed
through a 2mm sieve for use; take 1OOg of soil and pass it through a 0.149mm sieve,
and determine the relevant indicators according to the conventional soil agricultural
chemistry analysis method; said red soil is the As-contaminated vegetable soil near
the Shimen realgar mining area; total As content is 162.2mg-kg -1, and the
water-soluble As content is 0.19mg-kg -1; said yellow and purple soil come from
vegetable soil and are artificially simulated As contaminated soil; they are prepared by
adding a certain concentration of Na 3 AsO 5 solution to aging for 3 months, and then
receive air-drying, grinding and sieving; total As content of yellow soil and purple soil
were 148.5 mg-kg -1 and 156.8 mg-kg -1, respectively, and the water-soluble As
content was 1.75 mg-kg -1 and 5.43 mg-kg -1 respectively; basic soil properties are as
follow: said red soil, yellow soil and purple soil have pH values of 5.65, 4.14 and 7.43
respectively; total N content is 0.90, 0.86 and 0.39g-kg -1 respectively; total P content
is 0.73, 0.68 and 0.61g-kg -1 respectively; total K content is 14.56, 5.83 and 9.Olg-kg
-1 respectively; organic carbon content is 11.90, 12.38 and 7.52g-kg -1 respectively.
[0097] (2) Test materials
[0098] Use carbonized composite and modified biochar obtained in embodiment 1
[0099] (3) Soil cultivation experiment
[0100] Use said 3 types of soil for cultivation experiment; accurately weigh 120g of
said red, yellow and purple soil and place them in 250mL beakers, and then apply the
carbonized composite and modified biochar into the soil at a mass ratio of 1 %, 5%, and 10%, respectively; mix said carbonized composite and modified biochar with said
soil thoroughly; set blank control check (CK) treatment for said soil samples at the
same time; all treatments maintain 70% field water holding capacity and place them
in a constant temperature incubator for cultivation; repeat said treatments for three
time respectively; supplement water by constant weight method to maintain 70% of
the field water holding capacity for cultivation; samples were taken when the
cultivation was carried out to 1, 3, 5, 7, 15, and 30 days to analyze the effective As
content in the soil.
[0101] Above-mentioned arsenic content was tested by hydride generation-atomic
fluorescence spectroscopy (HG-AFS 9120, Beijing Jitian Instrument, detection limit
<0.024g-L -1 ).
[0102] Table 5 indicates fixation efficiency of arsenic by carbonized composite and
modified biochar with different addition amount after 30 days of cultivation.
[0103] Table 5 indicates that after applying the unmodified carbonized composite, the
water-soluble As content in the red soil has increased significantly, and it continues to
increase with the increase in the amount; after the application of modified biochar, the
water-soluble As content in the red soil decreased significantly, and the reduction
range was 70.59-94.72%, and with the increase of the modified biochar application,
said water-soluble As content decreased more.
[0104] For yellow soil, although low application of said unmodified carbonized
composite indicates slight fixation effect for the As in the soil; release of As was also
significantly increased with the increase in the amount of said composite, especially at
addition amount of 10%; when it was cultured for 30 days, said water-soluble As
content increased by 119.77% compared with the control in the same period; however,
after the application of modified biochar, content of soil water-soluble As was greatly
reduced, and reduction range of addition amount treatment in 1% was 43.00-75.36%;
with increase in the addition amount of modified biochar, reduction range of soil
water-soluble As increased; fixation efficiency of As in yellow soil treated with 10%
addition amount at 30 days was 98.35%.
[0105] Unmodified carbonized composite promotes the activation of As in purple soil;
after applying modified biochar, content of active As in purple soil is greatly reduced;
when it was cultivated for 30 days, modified biochar treatment in 1% reduces the
water-soluble As content by 80.45% compared with the soil of the control period; as
the application amount of modified biochar increases, fixation efficiency of As in soil increases; addition amount treatment in 10% was 99.61% lower than the control over
the same period; compared with the addition amount treatment in 1%, fixation efficiency was greatly improved.
[0106] In general, compared with said three types of soil, said modified biochar all showed good fixation performance for As in soil, and thefixation efficiency order was as follow: purple soil>yellow soil>red soil; when the addition amount of modified biochar is 10%, fixation efficiency of modified biochar to As in soil is above 95%.
[0107] Table 5: Fixation efficiency of arsenic by carbonized composite and modified biochar with different addition amount after 30 days of cultivation
[0108] Therefore, application of modified biochar greatly reduces the effective arsenic contained by different types of soil, thereby fixing the active arsenic in the soil to a certain extent.
[0109] Above mentioned are only the preferred embodiments of the present invention; it should be pointed out that for those of ordinary skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications are also regarded as the protection scope of the present invention.
Claims (9)
1.A modified biochar is characterized in that, said modified biochar is biomass charcoal stacked in flakes and granular cerium oxide and manganese oxide loaded on the surface of said biomass charcoal; loading amount of said manganese element is 2.85-4.63% of the mass of the modified biochar; loading amount of cerium element is 7.65~-45.82% of the mass of the modified biochar; said specific surface area of said modified biochar is 6.10-8.35m 2 -g -1.
2. Preparation method of said modified biochar as claimed in claim 1, wherein steps are listed below: Carbonize biomass raw materials to obtain carbonized composites; Mix said carbonized composite with a hydrochloric acid solution to perform a first reaction to obtain a carbon material; Mix said carbon material, potassium permanganate, water-soluble cerium salt, and water to perform a second reaction to obtain a carbon composite; Said carbon composite is subjected to anaerobic pyrolysis to obtain the modified biochar.
3.Preparation method as claimed in claim 2, wherein temperature of said carbonization temperature is 600-800°C, and the time is 2-8 hours.
4.Preparation method as claimed in claim 2, wherein the solid-to-liquid ratio of the carbonized composite to the hydrochloric acid solution is 1 g: (2-10) mL; concentration of said hydrochloric acid solution is 0.5-1.5 mol/L..
5.Preparation method as claimed in claim 2, wherein the temperature of said first reaction is 25-35°C, and the time is 12-18 hours.
6.Preparation method as claimed in claim 2, wherein the amount ratio of the carbon material, potassium permanganate and water-soluble cerium salt is Ig: 0.0002 to 0.003 mol: 0.0005 to 0.015 mol.
7.Preparation method as claimed in claim 2, wherein the temperature of said second reaction is room temperature, and the time is 1 to 5 hours.
8.Preparation method as claimed in claim 2, wherein the temperature of said anaerobic pyrolysis is 600-800°C, and the time is 2-8 hours.
9.Modified biochar as claimed in claim 1 and claim 2-8, wherein the application of the modified biomass charcoal obtained by any one of the preparation methods in removing arsenic from water bodies and soil. 1.Application as claimed in claim 9, wherein when the modified biochar is used to remove arsenic from water bodies, the solid-to-liquid ratio of the modified biochar to the arsenic-containing water body is 5-20 g/L.
D R AW I N G S 02 Jul 2021 2021103819
FIG. 1
FIG. 2
D R AW I N G S 02 Jul 2021 2021103819
FIG. 3
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114082771A (en) * | 2021-11-17 | 2022-02-25 | 山东农业大学 | Safe cultivation method for weakly alkaline cadmium-polluted soil |
| CN114101310A (en) * | 2021-11-04 | 2022-03-01 | 生态环境部南京环境科学研究所 | Method for passivating lead-cadmium polluted farmland soil based on biochar-attapulgite compounding |
| CN114891515A (en) * | 2022-04-15 | 2022-08-12 | 西南石油大学 | Rare earth tailing doped biomass-based carrier soil heavy metal passivation material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114101310A (en) * | 2021-11-04 | 2022-03-01 | 生态环境部南京环境科学研究所 | Method for passivating lead-cadmium polluted farmland soil based on biochar-attapulgite compounding |
| CN114101310B (en) * | 2021-11-04 | 2022-08-26 | 生态环境部南京环境科学研究所 | Method for passivating lead-cadmium polluted farmland soil based on biochar-attapulgite compounding |
| CN114082771A (en) * | 2021-11-17 | 2022-02-25 | 山东农业大学 | Safe cultivation method for weakly alkaline cadmium-polluted soil |
| CN114891515A (en) * | 2022-04-15 | 2022-08-12 | 西南石油大学 | Rare earth tailing doped biomass-based carrier soil heavy metal passivation material and preparation method thereof |
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