AU2021103100A4 - Method for preparing modified biochar adsorption material and application thereof - Google Patents
Method for preparing modified biochar adsorption material and application thereof Download PDFInfo
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- biochar
- adsorption material
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 38
- 150000002500 ions Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000002028 Biomass Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 19
- 239000002351 wastewater Substances 0.000 claims description 16
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 12
- 244000105624 Arachis hypogaea Species 0.000 claims description 12
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 12
- 235000018262 Arachis monticola Nutrition 0.000 claims description 12
- 235000020232 peanut Nutrition 0.000 claims description 12
- 238000000197 pyrolysis Methods 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- 239000011833 salt mixture Substances 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 244000280244 Luffa acutangula Species 0.000 claims description 2
- 235000009814 Luffa aegyptiaca Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 235000009973 maize Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 230000035939 shock Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims 1
- 238000007885 magnetic separation Methods 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- -1 Pb2+ ions Chemical class 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- DCPMPXBYPZGNDC-UHFFFAOYSA-N hydron;methanediimine;chloride Chemical compound Cl.N=C=N DCPMPXBYPZGNDC-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 210000004789 organ system Anatomy 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002699 waste material 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
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/008—Pyrolysis reactions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
-
- 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
-
- 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 present invention provides a method for preparing a modified biochar
adsorption material. The method comprises the following steps: treating a raw
material; preparing biochar; preparing a modified biochar adsorption material; and
adding the biochar, a modifier and a solvent that are ground into a round-bottom flask,
heating and stirring a mixture, adding a catalyst after cooling, adjusting a pH of a
reaction liquid, continuing a reaction, conducting filtration after the reaction, and
drying and grinding a solid after the solid is washed to obtain the modified biochar
adsorption material. The material has advantages of that the preparation method
thereof is cost-effective and that it has a high adsorption speed and adsorption efficacy,
and it can adsorb heavy metal ions selectively and can enable a preparation method of
fast solid-liquid separation of the modified magnetic biochar adsorption material, such
that the material can be applied to selectively removing heavy metal ions in a water
body.
Description
TECHNICAL FIELD The present invention relates to preparation of biochar adsorption materials by
pyrolysis of agricultural and forest residues, belongs to the novel technical field of
environment function materials and water treatment, and in particular relates to a
method for preparing a modified biochar adsorption material and preferential
adsorption of heavy metal ions in water.
With rapid development of economy and continuous advancement of industrial
progress, discharge of industrial wastewater is also increased year by year, and some
heavy metal ions, together with industrial wastewater, are discharged to an
environment, resulting in increasing serious environmental pollution. Intake of
excessive heavy metal ions may cause damage to organ systems such as nerve,
hematopoiesis, reproductive development and skeleton of human body, and thereby,
the human health is threatened severely. It is particularly important to treat heavy
metal polluted wastewater, which is helpful to protect the water environment and the
public health. There are many conventional methods for treating heavy metal
pollution and one of the most common effective methods is an adsorption method.
Biochar featuring in wide source of raw materials, low cost, simple preparation
method, porous structure, abundant functional groups, high specific surface area and
the like is widely researched and applied in the field of governing heavy metal
polluted water. However, there are some problems in heavy metal pollution governing
application as biomass is directly pyrolyzed to obtain original biochar. First, the
specific surface area and the pore volume of the original biochar are relatively small
and the adsorption process is relatively slow, such that the balance time of heavy metal adsorption is longer, resulting in low adsorption and removal efficiency of heavy metals. Second, as the pH value of wastewater containing the heavy metal ions discharged by a plant is relatively low and the original biochar is usually quite weak in adsorption capacity on the heavy metal ions under a condition of a low pH value, it is needed to increase an extra process flow to adjust the pH value of the wastewater.
Third, the wastewater discharged from the plant usually contains various heavy metal
ions, and the original biochar cannot adsorb the heavy metal ions selectively. Fourth,
it is hard to realize fast solid-liquid separation aft the original biochar adsorbs the
heavy metal ions in the water. Therefore, it is a necessity to research and develop an
improved biochoar adsorption material, such that the improved biochoar adsorption
material is used under a wider pH value condition, and can remove the heavy metal
ions in the water efficiently and selectively. After adsorption, solid-liquid separation
can be realized quickly, and thereby, secondary pollution is reduced.
Aiming at defects in the prior art, the present invention provides a material. The
material has advantages of that the preparation method thereof is cost-effective and
that it has a high adsorption speed and adsorption efficacy, and it can adsorb heavy
metal ions selectively and can enable a preparation method of fast solid-liquid
separation of the modified magnetic biochar adsorption material, such that the
material can be applied to selectively removing heavy metal ions in a water body.
A method for preparing a high-selective modified biochar adsorption material,
including the following steps:
(1) treatment of a raw material: airing and crushing a biomass raw material, and
drying the biomass raw material for 3h in an oven under a condition of 75°C; and then
placing the biomass raw material in a saturated activator aqueous solution, stirring and
soaking the biomass raw material for 2h, filtering the solution and taking out the
biomass raw material, and naturally airing the biomass raw material for later use;
(2) preparation of biochar: placing the treated raw material in an atmospheric
furnace, introducing protecting gas, conducting high-temperature anaerobic pyrolysis
for a certain time, stopping heating, and continuing to introduce the protecting until a
temperature in the atmospheric furnace is reduced to a room temperature; and taking
out the biomass material, washing the biomass material for three times with deionized
water, and drying the biomass material in an oven for 3h under the condition of 75°C
for later use;
(3) preparation of the modified biochar adsorption material: dissolving a certain
amount of chitosan in an acetum, adding the biochar and ferric salt mixture
respectively under a stirring condition, and then slowly dropwise adding alkali liquor
into a system after continuously stirring the solution for 2h; and conducting filtration
after a reaction, washing a solid to neutrality, drying the solid in a 75°C oven, and
grinding the solid for later use; and
(4) adding the biochar, a modifier and a solvent that are ground into a round
bottom flask, heating and stirring a mixture, adding a catalyst after cooling, adjusting
a pH of a reaction liquid, continuing a reaction, conducting filtration after the reaction,
and drying and grinding a solid after the solid is washed to obtain the modified
biochar adsorption material, and grinding the modified biochar adsorption material for
later use.
According to the present invention, a further defined technical scheme is as
follows:
the biomass material in the step (1) is one of or a mixture of more of maize
straws, cotton straws, peanut straws, rice hulls, peanut hulls and loofah sponges and is
crushed to 1-3 mm.
The selected activator is one of or a mixture of more of sodium hydrogen
carbonate, calcium hydrogen carbonate and potassium hydrogen carbonate, preferably
potassium hydrogen carbonate.
According to the present invention, the protecting gas introduced for pyrolysis in
the step (2) is nitrogen, argon and the like, preferably, nitrogen.
A pyrolysis temperature is 300-850°C, further preferably 700-750°C.
A heating rate during the pyrolysis process is 3-15°C/min, further preferably 5
8°C/min; and a pyrolysis time is 1-5h, further preferably 2-3h.
According to the present invention, a degree of deacetylation of the chitosan used
in the step (3) is greater than or equal to 95%, and a viscosity of the chitosan is 100
200 mpa.s.
A concentration of the acetum is 1-5%, preferably 2%.
The ferric salt mixture is a mixture of a soluble trivalent ferric salt and a bivalent
ferric salt, preferably, FeCl3•6H 20 and FeCl2•4H 20; a mass ratio of the soluble
trivalent ferric salt to the bivalent ferric salt is (3.3-2.9): (1.1-1.6), preferably (3.3-2.9):
(1.168-1.325).
In the preparation method, the mass ratio of biochar to the chitosan to the ferric
salt mixture is (4.7-5.2): (0.4-2.7): (0.4-2.3), preferably, (4.7-5.2): (0.95-1.68): (0.6
1.27).
The alkali liquor used in the preparation method is one or two of a sodium
hydroxide solution, a potassium hydroxide solution and an ammonia water solution,
preferably, potassium hydroxide and ammonia water.
A mass concentration of the alkali liquor is ranged from 2% to 25%.
The pH is adjusted to 8-11 after adding the alkali liquor, further preferably 9-9.5.
The modifier used in the preparation method is one or more of ethylene diamine
tetraacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid, diethyltriamine
pentacarboxylic acid and dimercaptobutyric polycarboxyl compounds.
The catalyst used in the preparation method is one of N,N'
dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide
hydrochloride and N,N-biisopropyl carbodiimide, preferably 1-(3
dimethylaminopropyl)-3-ethylcarbodiimidehydrochloride.
In the preparation method, the mass ratio of biochar to the modifier to the
catalyst is (4.7-5.2): (4.0-5.5): (2.5-3.3), preferably, (4.7-5.2): (4.63-5.17): (2.96-3.28).
In the preparation method, the heating means heating to 55-65°C, preferably 58
62°C; and a temperature when the catalyst is added is 35-45°C, preferably 38-40°C.
In the preparation method, the pH of the reaction liquid is adjusted to 4.5-6.0
after the catalyst is added, preferably 5-5.3.
According to the present invention, an application of the modified biochar
adsorption material prepared by the method in removing heavy metal ions in waste
water.
According to the application of the present invention, the step of removing the
heavy metal ions in the wastewater includes the following steps:
adding the modified biochar adsorption material into the wastewater containing
the heavy metals, conducting rotary shock adsorption and conducting magnetic
separation of the adsorption material by an external magnetic field after adsorption.
According to the application of the present invention, preferably, a ratio of a
mass of the modified biochar adsorption material to a volume of the wastewater is 8.
0.5-1.5 g/L, preferably 0.8-1.2g/L; and when the pH of the wastewater is adjusted to
5-6, preferably 5.8-6, the removal effect is more excellent.
According to the present invention, the modified biochar adsorption material can
be applied to treating various heavy metal combined pollution in the water body;
when the modified biochar adsorption material is applied to treating Cu2+ and Cd2+
combined polluted water, Cu2+ is adsorbed preferably until saturation adsorption is
attained, and if the saturation adsorption is not attained, Cd2+ is then adsorbed again.
The characteristic can be applied to separating and recovering two metal ions.
According to the present invention, the adsorption material adsorbing the heavy
metal ions are recovered under an external applied magnetic field condition. 1mol/1 of
HCl solution is stirred and desorbed, the solution is filtered and is washed for several times with deionized water until a filtrate is neutral, and a filter cake is dried and can be recycled.
Innovation points of the present invention primarily lie in that
As a current biochar adsorption material is featured on low adsorption amount,
long adsorption time, narrow pH value required by adsorption, difficulty in selective
adsorption in treating the composite heavy metal pollution and separating the heavy
metals quickly after adsorption in the heavy metal removal process, the present
invention provides a method for preparing modified biochar which is large in
adsorption amount, short in adsorption time, wide in pH value required by adsorption,
selective to adsorption of heavy metals and capable of being separated and recycled
quickly after adsorption and an application thereof. By taking biomass as a raw
material, activated by an activator, the specific surface area and the pore volume of
the biochar can be increased greatly. Magnetic endowment and preliminary
modification can be conducted on the activated biochar, the mixed ferric salt and
chitosan in a specific proportion in a one pot reaction, such that obtained product
magnetic particles are stable and hard to fall off, and the surface functional groups are
increased greatly. The surface of the biochar is more stable and more characteristic
functional groups are increased by secondary modification, such that the material is
selective to adsorb heavy metal ions, and thereby, the adsorption rate is increased, and
a pH range suitable for a wastewater solution is wider. Compared with original
common biochar, according to the modified biochar, the specific surface area and the
pore volume of the biochar are improved, and the quantity of the surface functional
groups is improved greatly, such that the adsorption capacity to the heavy metal
pollutants is improved, and the adsorption balance time is shortened. Solid-liquid
separation is realized quickly under the action of the external applied magnetic field.
The biochar desorbed can be recycled, is a green, cheap and effective adsorption
material, and can be actually applied to emergent treatment of heavy metal polluted
water.
Compared with the prior art, the present invention has the advantages that
1. By taking agricultural and forest residues as the raw material, the
environmental pollution problem caused by random accumulation and incineration of
the agricultural and forest residues can be reduced effectively while the cost is saved,
and thereby, resource utilization of the agricultural and forest residues is realized.
Furthermore, a preparation process of the adsorption material is simple and easy to
operate and popularize.
2. As an adsorbent to treat the heavy metal polluted water, the modified biochar
prepared by the present invention is obvious in adsorption effect, wide in demand on
pH of the water environment and is relatively stable and high in adsorption capacity
when the pH is lower.
3. The modified biochar prepared by the present invention can achieve
adsorption balance of various heavy metals within 10-30 min substantially, such that
the reaction time is shortened, and the modified biochar can be applied to emergent
treatment of the heavy metal polluted water.
4. The modified biochar prepared by the present invention can be recovered
under the action of the external applied magnetic field after adsorbing various heavy
metals, can be recycled after being desorbed, does not generate secondary pollution
and is green and environmental-friendly.
Fig. 1 is a scanning electron microscope diagram of the modified biochar
adsorption material prepared in the embodiment 1 of the present invention.
Fig. 2 is a separation effect diagram of the magnetic adsorption material prepared
in the embodiment 1 of the present invention under the external applied magnetic field
condition.
Further detailed description will be made on the present invention below, but the
claimed scope of protection of the present invention is not limited to the scope
represented by the embodiments.
Example 1
A method for preparing a high-selective modified biochar adsorption material,
including the following steps:
(1) treatment of a raw material: lOg of peanut hulls are aired naturally and
crushed to about 2 mm, and the peanut hulls are dried for 3h under a condition of 75°C;
and then the peanut hulls are placed in a saturated activator aqueous solution, the
peanut hulls are stirred and soaked for 2h, the solution is filtered and the peanut hulls
are taken out and are naturally aired the for later use;
(2) preparation of biochar: the treated maize corns are placed in an atmospheric
furnace, protecting gas is introduced, high-temperature anaerobic pyrolysis is
conducted for a certain time, heating is stopped, and the protecting gas introduced
continuously until a temperature in the atmospheric furnace is reduced to a room
temperature; and the biomass material is taken out, the biomass material is washed for
three times with deionized water, and the biomass material dried in an oven for 3h
under the condition of 75°C for later use;
(3) preparation of the modified biochar adsorption material: 1.06g of chitosan is
solved in a 2% acetum, 4.89g of biochar, 0.782g of FeCl 3•6H 20 and 0.309g of
FeCl2 •4H2 0 are added respectively under a stirring condition, and then a potassium
hydroxide and stronger ammonia water solution is slowly dropwise added into a
system till the pH of the system is 9.3 after continuously stirring the solution for 2h,
and the solution is stirred at a normal temperature overnight; filtration is conducted
after a reaction, a solid is washed to neutrality, the solid is dried in a 75°C oven, and
the solid is ground and screened by a 100-mesh sieve for later use; and
5.08g of the ground biochar, 4.83g of ethylene diamine tetraacetic acid and
500ml of deionized water into a round-bottom flask, heating is conducted to 60°C and
the mixture is stirred for 4h, 3.16g of 1-(3-dimethylaminopropyl)-3-ethyl
carbodiimide hydrochloride is added after the temperature is reduced to 38°C, the pH
of a reaction liquid is adjusted to 5.3, a reaction is continued for 4h, filtration is
conducted after the reaction, and a solid is dried and ground by the 100-mesh sieve
after being washed to obtain the modified biochar adsorption material.
Comparative example 1
A method for preparing an unmodified original biochar adsorption material,
including the following steps:
1Og of peanut hulls are aired naturally and crushed to about 3mm, and the peanut
hulls are dried for 3h under a condition of 75°C; and the peanut hulls are placed in an
atmospheric furnace, the protecting gas is introduced, heating is conducted to 700°C at
5°C/min, heating is stopped after constant temperature is kept for 2h, and the
protecting gas introduced continuously until a temperature in the atmospheric furnace
is reduced to a room temperature; and the mixture is taken out and is washed for three
times with deionized water, and the mixture is dried in an oven for 3h under the
condition of 75°C to obtain the unmodified biochar adsorption material.
Example 2
The modified biochar adsorption material prepared by the method of the present
invention is used for removing heavy metal ions in waste water.
The embodiment inspects the adsorption capacities and the adsorption balance
times of the modified biochar and the unmodified biochar on the heavy metal ions.
25mg of prepared modified biochar and 25mg of prepared unmodified biochar
are respectively added into a 25ml 200 mg/L conical flask of a single heavy meat ion
solution, the pH of which is 6, vibration is conducted in a 150r/m constant
temperature table at a rotating speed of 25°C, sampling is conducted at every different
times, a concentration of the residual heavy metal ions in the solution is measured by flame atomic absorption, the adsorption amount is calculated and the adsorption balance time is determined when the adsorption amount is invariable substantially. Metal Adsorption amount (mg/g) Balance time (min) ions Example 1 Comparative Example 1 Comparative example 1 example 1 C 55.8 7.7 25 600 u2+ C 68.6 8.2 25 480 d2+ Ni 50.6 6.3 25 720 2+ Pb 168.2 13.6 30 720 2+
Example 3
The modified biochar adsorption material prepared by the method of the present
invention is used for removing heavy metal ions in waste water.
The embodiment inspects influence of the pH values of Pb2+ ions of the modified
biochar and the unmodified biochar on the adsorption amount.
25mg of prepared modified biochar and 25mg of prepared unmodified biochar
are respectively added into a 25ml 300mg/L conical flask of a Pb2+ solution, the pH of
which is 2 and 6, vibration is conducted for 24h in a 150r/m constant temperature
table at a rotating speed of 25°C, a concentration of the residual Pb2+ in the solution is
measured by flame atomic absorption, and the adsorption amount is calculated. pH value Adsorption amount (mg/g)
Example 1 Comparative example 1 2 156.9 0.58
6. 168.2 13.8
Claims (9)
1. A method for preparing a high-selective modified biochar adsorption material,
characterized by comprising the following steps:
(1) treatment of a raw material: airing and crushing a biomass raw material, and
drying the biomass raw material in an oven for 3h under a condition of 75°C; and then
placing the biomass raw material in a saturated activator aqueous solution, stirring and
soaking the biomass raw material for 2h, filtering the solution and taking out the
biomass raw material, and naturally airing the biomass raw material for later use;
(2) preparation of biochar: placing the treated raw material in an atmospheric
furnace, introducing protecting gas, conducting high-temperature anaerobic pyrolysis
for a certain time, stopping heating, and continuing to introduce the protecting until a
temperature in the atmospheric furnace is reduced to a room temperature; and taking
out the biomass material, washing the biomass material for three times with deionized
water, and drying the biomass material in an oven for 3h under the condition of 75°C
for later use;
(3) preparation of the modified biochar adsorption material: dissolving a certain
amount of chitosan in an acetum, adding the biochar and ferric salt mixture
respectively under a stirring condition, and then slowly dropwise adding alkali liquor
into a system after continuously stirring the solution for 2h; and conducting filtration
after a reaction, washing a solid to neutrality, drying the solid in a 75°C oven, and
grinding the solid for later use; and
(4) adding the biochar, a modifier and a solvent that are ground into a round
bottom flask, heating and stirring a mixture, adding a catalyst after cooling, adjusting
a pH of a reaction liquid, continuing a reaction, conducting filtration after the reaction,
and drying and grinding a solid after the solid is washed to obtain the modified
biochar adsorption material.
2. The method according to claim 1, characterized in that the biomass material in
the step (1) is one of or a mixture of more of maize straws, cotton straws, peanut straws, rice hulls, peanut hulls and loofah sponges and is crushed to 1-3 mm; and the activator is one of or a mixture of more of sodium hydrogen carbonate, calcium hydrogen carbonate and potassium hydrogen carbonate.
3. The method according to claim 1, characterized in that the protecting gas
introduced in the step (2) for pyrolysis is nitrogen and argon, wherein a pyrolysis
temperature is 300-850°C, a heating rate during a pyrolysis process is 3-15 °C/min and
a pyrolysis time is 1-5h.
4. The method according to claim 1, characterized in that the degree of
deacetylation of the chitosan used in the step (3) is greater than or equal to 95%, and a
viscosity of the chitosan is 100-200 mpa.s; and a concentration of the acetum is 1-5%.
5. The method according to claim 1, characterized in that the ferric salt mixture
is a mixture of a soluble trivalent ferric salt and a bivalent ferric salt, wherein a mass
ratio of the soluble trivalent ferric salt to the bivalent ferric salt is (3.3-2.9): (1.1-1.6);
the mass ratio of biochar to the chitosan to the ferric salt mixture is (4.7-5.2):
(0.4-2.7): (0.4-2.3);
the alkali liquor is one or two of a sodium hydroxide solution, a potassium
hydroxide solution and an ammonia water solution; a mass concentration of the alkali
liquor is 2-25%; the pH is adjusted to 8-11 after the alkali liquor is dropwise added;
the modifier is one or more of ethylene diamine tetraacetic acid, ethylene glycol
diethyl ether diamine tetraacetic acid, diethyltriamine pentacarboxylic acid and
dimercaptobutyric polycarboxyl compounds; the catalyst is one of N,N'
dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide
hydrochloride and N,N-biisopropyl carbodiimide; the mass ratio of biochar to the
modifier to the catalyst is (4.7-5.2): (4.0-5.5): (2.5-3.3);
the heating means heating to 55-65°C; a temperature when the catalyst is added is
-45°C, preferably 38-40°C; and
the pH of the reaction liquid is adjusted to 4.5-6.0 after the catalyst is added.
6. An application of the modified biochar adsorption material prepared by the
method according to one of claims 1-5 in removing heavy metal ions in waste water.
7. The application according to claim 6, characterized in that the step of
removing heavy metal ions in wastewater comprises the following steps: adding the
modified biochar adsorption material into the wastewater containing the heavy metals,
conducting rotary shock adsorption and conducting magnetic separation of the
adsorption material by an external magnetic field after adsorption.
8. The application according to claim 7, characterized in that a ratio of a mass of
the modified biochar adsorption material to a volume of the wastewater is 0.5-1.5 g/L,
and a pH of the wastewater is adjusted to 5-6.
9. The application according to claim 7, characterized in that the modified
biochar adsorption material can be applied to treating various heavy metal combined
pollution in a water body; when the modified biochar adsorption material is applied to
treating Cu2+ and Cd2+ combined polluted water, Cu2+ is adsorbed until saturation
adsorption is attained, and if the saturation adsorption is not attained, Cd2+ is then
adsorbed again.
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| CN113786803A (en) * | 2021-08-24 | 2021-12-14 | 福州大学 | Charcoal adsorbent with carbon defect site structure and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113786803A (en) * | 2021-08-24 | 2021-12-14 | 福州大学 | Charcoal adsorbent with carbon defect site structure and preparation method and application thereof |
| CN114477683A (en) * | 2022-01-25 | 2022-05-13 | 安徽工程大学 | Pigment sludge treatment method |
| CN114477683B (en) * | 2022-01-25 | 2023-08-18 | 安徽工程大学 | Pigment sludge treatment method |
| CN115843631A (en) * | 2023-03-02 | 2023-03-28 | 潍坊科技学院 | Cultivation method for improving taste type tomato quality |
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