CN113198431A - Preparation and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar - Google Patents
Preparation and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar Download PDFInfo
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- CN113198431A CN113198431A CN202110657434.9A CN202110657434A CN113198431A CN 113198431 A CN113198431 A CN 113198431A CN 202110657434 A CN202110657434 A CN 202110657434A CN 113198431 A CN113198431 A CN 113198431A
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- manganese
- iron
- salt solution
- sodium alginate
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 47
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 47
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 19
- 239000011572 manganese Substances 0.000 title claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 49
- 150000002500 ions Chemical class 0.000 claims abstract description 45
- 238000001035 drying Methods 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims description 48
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 28
- 238000001179 sorption measurement Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- -1 manganese (II) ions Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical class [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 15
- 240000000225 Euphorbia hirta Species 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000002910 solid waste Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002689 soil Substances 0.000 abstract description 10
- 150000001450 anions Chemical class 0.000 abstract description 6
- 150000001768 cations Chemical class 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 24
- 240000002791 Brassica napus Species 0.000 description 18
- 235000006008 Brassica napus var napus Nutrition 0.000 description 18
- 241000037488 Coccoloba pubescens Species 0.000 description 18
- 238000007873 sieving Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 229910052793 cadmium Inorganic materials 0.000 description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910052785 arsenic Inorganic materials 0.000 description 7
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229960001126 alginic acid Drugs 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 239000000783 alginic acid Substances 0.000 description 4
- 229920000615 alginic acid Polymers 0.000 description 4
- 150000004781 alginic acids Chemical class 0.000 description 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 241000219793 Trifolium Species 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003621 irrigation water Substances 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
Classifications
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/103—Arsenic 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
- C02F2101/105—Phosphorus 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
-
- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Soil Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar, wherein the preparation method of the carbonized sodium alginate-coated biochar comprises the following steps: s1, adding a biochar precursor into a 2 wt% sodium alginate solution, fully mixing and wrapping, and drying to obtain solid particles; s2, sintering and carbonizing the solid particles obtained in the step S1 at the temperature of 900 ℃ of 300-. The composite material obtained by the preparation method can improve the treatment of heavy metal anions and cations and phosphorus, realize the fixation of heavy metal ions and the retention of phosphorus in water and soil, and has wide application prospect in environmental management.
Description
Technical Field
The invention relates to the field of environmental management, in particular to preparation and application of carbonized sodium alginate-coated biochar and iron/manganese crosslinked sodium alginate-modified biochar.
Background
China is a large country for producing and using chemical fertilizers, and about 35 percent of chemical fertilizer production all over the world comes from China, wherein the phosphate fertilizer is mainly in the soil in an anion form and is easy to enter a water environment along with irrigation water and rainwater, so that water eutrophication is caused. Meanwhile, heavy metal anions and cations and phosphorus exist together in the environment. Therefore, it is necessary to develop a rapid and efficient adsorbent to realize efficient adsorption of heavy metals and efficient retention of phosphorus in the environment.
Disclosure of Invention
The invention mainly aims to provide a preparation method, an application method and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar.
The technical problem of the invention is solved by the following technical scheme:
a preparation method of a carbonized alginic acid coated biochar composite material comprises the following steps:
s1, adding a biochar precursor into a 2 wt% sodium alginate solution, fully mixing and wrapping, and drying to obtain solid particles;
s2, sintering and carbonizing the solid particles obtained in the step S1 at the temperature of 900 ℃ of 300-.
Preferably, in the step S1, the mass ratio of the added biochar precursor to sodium alginate is 1: 3.
Preferably, the biochar precursor is prepared from garden solid waste, preferably is prepared from euphorbia hirta, and more preferably is prepared from dark green euphorbia hirta which is dried, crushed and sieved by a 60-mesh sieve after being washed.
A preparation method of an iron/manganese crosslinked sodium alginate modified biochar composite material comprises the following steps:
s1, mixing and fully stirring a metal salt solution and a biochar precursor, dropwise adding a 2 wt% sodium alginate solution, forming fine granular substances on the surface of the biochar precursor through a crosslinking reaction, washing, recovering solid particles, and drying; wherein the metal salt solution is at least one of a manganese (II) salt solution and an iron (II) salt solution;
s2, sintering and carbonizing the solid particles obtained in the step S1 at the temperature of 900 ℃ of 300-.
Preferably, the method further comprises the following steps: the manganese (II) salt solution is a manganese sulfate solution; the iron (II) salt solution is a ferrous sulfate solution; the screening in the step S2 means screening by a 60-mesh screen.
Preferably, the volume ratio of the sodium alginate solution to the metal salt solution in the step S1 is 3:2, and the mass concentration of the biochar precursor in the metal salt solution is 15 mg/mL.
Preferably, when the metal salt solution in the step S1 is an iron (II) salt solution or a manganese (II) salt solution, the molar concentration of iron (II) ions in the iron (II) salt solution is 1.5mol/L, and the molar concentration of manganese (II) ions in the manganese (II) salt solution is 1.5 mol/L; when the metal salt solution in the step S1 is a mixed solution of an iron (II) salt solution and a manganese (II) salt solution, the molar concentrations of iron (II) ions and manganese (II) ions in the mixed solution satisfy one of the following conditions: (1) the molar concentration of iron (II) ions was 1.5mol/L and the molar concentration of manganese (II) ions was 0.75 mol/L; (2) the molar concentration of iron (II) ions is 1.5mol/L and the molar concentration of manganese (II) ions is 1.5 mol/L; (3) the molar concentration of iron (II) ions was 0.75mol/L and the molar concentration of manganese (II) ions was 1.5 mol/L.
A composite material prepared by the preparation method.
The application of the composite material in treating heavy metal ions and/or phosphorus is provided.
Preferably, the heavy metal ions are at least one of As (III) ions, As (V) ions, Cr (VI) ions, Cd (II) ions.
Preferably, the application refers to the adsorption of Cd (II) ions by the carbonized alginic acid coated biochar composite material prepared by the preparation method.
Preferably, the application refers to the adsorption of at least one of As (III) ions, As (V) ions, Cr (VI) ions, Cd (II) ions and phosphorus on the iron/manganese crosslinked sodium alginate modified biochar composite material prepared by the preparation method.
The beneficial effects of the invention include: the composite material obtained by the preparation method can improve the treatment of heavy metal anions and cations and phosphorus, realize the fixation of heavy metal ions and the retention of phosphorus in water and soil, and has wide application prospects in the environment.
Drawings
FIG. 1 is a graph showing the comparison of the adsorption of arsenic and phosphorus by the composite materials prepared in examples 1 to 5 of the present invention.
FIG. 2 is a graph comparing the adsorption of hexavalent chromium and divalent cadmium to composite materials prepared in examples 1-5 of the present invention.
FIG. 3 shows the adsorption capacity for cadmium of the composite material prepared in example 6 of the present invention.
Figure 4 is an XRD pattern of the composite material prepared in example 5 of the present invention.
FIG. 5 is a FT-IR plot of a composite prepared in example 5 of the present invention.
FIG. 6 is an SEM image of a composite material prepared in example 5 of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings and preferred embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The embodiment of the invention provides a preparation method of a carbonized alginic acid coated biochar composite material, which comprises the following steps: s1, adding a biochar precursor into a 2 wt% sodium alginate solution, fully mixing and wrapping, and drying to obtain solid particles; s2, sintering and carbonizing the solid particles obtained in the step S1 at the temperature of 900 ℃ of 300-.
The sodium alginate consists of 1-4 chain block polymers of polyglucuronic acid and polymannuronic acid, and can effectively adsorb divalent metal ions, the carbonized sodium alginate-coated charcoal composite material obtained by the technical scheme can realize high-efficiency adsorption of high-concentration heavy metal cations, and the carbonized sodium alginate-coated charcoal greatly improves the adsorption capacity of the charcoal and further improves the practical applicability of the composite material.
In a preferred embodiment, in the step S1, the mass ratio of the added biochar precursor to sodium alginate is 1: 3.
In a preferred embodiment, the biochar precursor is prepared from garden solid waste, preferably the biochar precursor is prepared from euphorbia hirta, and more preferably the biochar precursor is prepared from dark green euphorbia hirta which is dried, crushed and sieved by a 60-mesh sieve after being washed.
In a preferred embodiment, the sintering carbonization is performed under an inert gas atmosphere.
In a preferred embodiment, the sinter carbonization is a sinter carbonization at 600 ℃ for 2 h.
The embodiment of the invention also provides a preparation method of the iron/manganese crosslinked sodium alginate modified biochar composite material, which comprises the following steps: s1, mixing and fully stirring a metal salt solution and a biochar precursor, dropwise adding a 2 wt% sodium alginate solution, forming fine granular substances on the surface of the biochar precursor through a crosslinking reaction, washing, recovering solid particles, and drying; wherein the metal salt solution is at least one of a manganese (II) salt solution and an iron (II) salt solution; s2, sintering and carbonizing the solid particles obtained in the step S1 at the temperature of 900 ℃ of 300-.
The iron and/or manganese modified biochar can promote the adsorption effect of the biochar on heavy metal anions and cations, can improve the electron transfer capacity of the biochar, and further improve the catalytic effect of the composite material, for example, high-toxicity trivalent arsenic can be oxidized into low-toxicity pentavalent arsenic, and high-toxicity hexavalent chromium can be reduced into low-toxicity trivalent chromium, so that the toxicity of heavy metal ions is reduced. However, the fixation of the iron/manganese element on the surface of the biochar can be difficult to realize by using the modified biochar loaded with the pure iron and/or manganese, so that the technical scheme provides that the iron/manganese element is fixed on the surface of the biochar through sodium alginate cross-linking, the iron/manganese element immobilization and carbon loading are realized, the adsorption of heavy metal cations and anions and phosphorus by the iron/manganese is further improved, and the fixation of heavy metals in water and soil and the retention of the phosphorus are realized.
In a preferred embodiment, the method further comprises the following steps: the manganese (II) salt solution is a manganese sulfate solution.
In a preferred embodiment, the iron (II) salt solution is an iron (II) sulfate solution.
In a preferred embodiment, said sieving in said step S2 is 60 mesh sieving.
In a preferred embodiment, the volume ratio of the sodium alginate solution to the metal salt solution in step S1 is 3:2, and the mass concentration of the biochar precursor in the metal salt solution is 15 mg/mL.
In a preferred embodiment, when the metal salt solution in the step S1 is an iron (II) salt solution or a manganese (II) salt solution, the molar concentration of iron (II) ions in the iron (II) salt solution is 1.5mol/L, and the molar concentration of manganese (II) ions in the manganese (II) salt solution is 1.5 mol/L; when the metal salt solution in the step S1 is a mixed solution of an iron (II) salt solution and a manganese (II) salt solution, the molar concentrations of iron (II) ions and manganese (II) ions in the mixed solution satisfy one of the following conditions: (1) the molar concentration of iron (II) ions was 1.5mol/L and the molar concentration of manganese (II) ions was 0.75 mol/L; (2) the molar concentration of iron (II) ions is 1.5mol/L and the molar concentration of manganese (II) ions is 1.5 mol/L; (3) the molar concentration of iron (II) ions was 0.75mol/L and the molar concentration of manganese (II) ions was 1.5 mol/L.
In a preferred embodiment, the sintering carbonization of step S2 is performed under the protection of inert gas.
In a preferred embodiment, the sintering carbonization of step S2 is sintering carbonization at 600 ℃ for 2 h.
In a preferred embodiment, the dropping of step S1 refers to dropping by using a peristaltic pump with a rotation speed of 3 mL/min.
The embodiment of the invention also provides a composite material prepared by the preparation method.
The embodiment of the invention also provides application of the composite material in treatment of heavy metal ions and/or phosphorus.
In a preferred embodiment, the heavy metal ions are at least one of As (III) ions, As (V) ions, Cr (VI) ions, Cd (II) ions.
In a preferred embodiment, the application refers to the adsorption of Cd (II) ions by the carbonized alginic acid coated biochar composite material prepared by the preparation method.
In a preferred embodiment, the application refers to that the iron/manganese crosslinked sodium alginate modified biochar composite material prepared by the preparation method adsorbs at least one of As (III) ions, As (V) ions, Cr (VI) ions, Cd (II) ions and phosphorus.
The present invention is further illustrated by the following specific examples.
Example 1
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from green to dark green, putting 30g of the dried large-leaf oilseed rape into a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water along with ultrasonic waves, repeating the steps for a plurality of times until cleaning liquid is free of soil, then putting the cleaning liquid into an oven for drying for 24h at 60 ℃, crushing by using a small crusher, sieving by using a 60-mesh sieve, and finally putting the drying liquid into a drying oven for storage.
Taking 300mmol of FeSO4Dissolving the extract in 200mL of distilled water, adding 3g of the treated euphorbia hirta, uniformly stirring (1 mL of nitric acid solution can be further added to assist dissolution and oxidation resistance), performing ultrasonic treatment for 30min, and dropwise adding 300mL of 2 wt% sodium alginate solution through a peristaltic pump (the rotating speed is 3mL/min) to form tiny particles on the surface of the euphorbia hirta so as to realize the fixation of iron (II) ions. And (3) recovering and washing the prepared composite material, and drying the washed composite material in an oven at 90 ℃ until the weight is constant to obtain solid particles.
And taking out the dried solid particles, putting the solid particles into a porcelain crucible, reacting for 2h at 600 ℃ in a muffle furnace, naturally cooling, washing with deionized water until the last washing liquid is colorless, drying for 24h in an oven at 80 ℃, grinding with an agate mortar, ball-milling with a ball mill at the rotating speed of 220rpm for 15min to recover powder, grinding with the agate mortar and sieving with a 60-mesh sieve to obtain the iron crosslinked sodium alginate modified biochar (shown as Fe-SA @ BC-1, namely the material numbered as No. 1 in figures 1 and 2).
Example 2
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from green to dark green, putting 30g of the dried large-leaf oilseed rape into a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water along with ultrasonic waves, repeating the steps for a plurality of times until cleaning liquid is free of soil, then putting the cleaning liquid into an oven for drying for 24h at 60 ℃, crushing by using a small crusher, sieving by using a 60-mesh sieve, and finally putting the drying liquid into a drying oven for storage.
Taking 300mmol of FeSO4And 150mmol of MnSO4Dissolving the extract in 200mL of distilled water, adding 3g of the treated euphorbia hirta, uniformly stirring, adding 1mL of nitric acid solution, performing ultrasonic treatment for 30min, and dropwise adding 300mL of 2 wt% sodium alginate solution through a peristaltic pump (the rotating speed is 3mL/min) to form tiny particles on the surface of the euphorbia hirta so as to fix manganese (II) Ions and Iron (II) ions. And (3) recovering and washing the prepared composite material, and drying the washed composite material in an oven at 90 ℃ until the weight is constant to obtain solid particles.
Taking out the dried solid particles, putting the solid particles into a porcelain crucible, reacting for 2h at 600 ℃ in a muffle furnace, naturally cooling, washing with deionized water until the last washing liquid is colorless, drying for 24h in an oven at 80 ℃, grinding with an agate mortar, ball-milling with a ball mill at the rotating speed of 220rpm for 15min to recover powder, grinding with the agate mortar and sieving with a 60-mesh sieve to obtain the iron-manganese crosslinked sodium alginate modified biochar (expressed as Fe/Mn-SA @ BC-2, namely the material numbered as No. 2 in figures 1 and 2).
Example 3
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from green to dark green, putting 30g of the dried large-leaf oilseed rape into a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water along with ultrasonic waves, repeating the steps for a plurality of times until cleaning liquid is free of soil, then putting the cleaning liquid into an oven for drying for 24h at 60 ℃, crushing by using a small crusher, sieving by using a 60-mesh sieve, and finally putting the drying liquid into a drying oven for storage.
Taking 300mmol of FeSO4And 300mmol of MnSO4Dissolving the extract in 200mL of distilled water, adding 3g of the treated euphorbia hirta, uniformly stirring, adding 1mL of nitric acid solution, performing ultrasonic treatment for 30min, and dropwise adding 300mL of 2 wt% sodium alginate solution through a peristaltic pump (the rotating speed is 3mL/min) to form tiny particles on the surface of the euphorbia hirta so as to fix manganese (II) Ions and Iron (II) ions. And (3) recovering and washing the prepared composite material, and drying the washed composite material in an oven at 90 ℃ until the weight is constant to obtain solid particles.
And taking out the dried solid particles, putting the solid particles into a porcelain crucible, reacting for 2h at 600 ℃ in a muffle furnace, naturally cooling, washing with deionized water until the last washing liquid is colorless, drying for 24h in an oven at 80 ℃, grinding with an agate mortar, ball-milling with a ball mill at the rotating speed of 220rpm for 15min to recover powder, and grinding the powder with the agate mortar and sieving with a 60-mesh sieve to obtain the iron-manganese crosslinked sodium alginate modified biochar (expressed as Fe/Mn-SA @ BC-3, namely the material numbered as No. 3 in figures 1 and 2).
Example 4
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from green to dark green, putting 30g of the dried large-leaf oilseed rape into a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water along with ultrasonic waves, repeating the steps for a plurality of times until cleaning liquid is free of soil, then putting the cleaning liquid into an oven for drying for 24h at 60 ℃, crushing by using a small crusher, sieving by using a 60-mesh sieve, and finally putting the drying liquid into a drying oven for storage.
150mmol of FeSO4And 300mmol of MnSO4Dissolving in 200mL of distilled waterAdding 3g of the treated euphorbia hirta into water, uniformly stirring, adding 1mL of nitric acid solution, performing ultrasonic treatment for 30min, and dropwise adding 300mL of 2 wt% sodium alginate solution through a peristaltic pump (the rotating speed is 3mL/min), so that tiny particles are formed on the surface of the euphorbia hirta, and the fixation of manganese (II) Ions and Iron (II) ions is realized. And (3) recovering and washing the prepared composite material, and drying the washed composite material in an oven at 90 ℃ until the weight is constant to obtain solid particles.
And taking out the dried solid particles, putting the solid particles into a porcelain crucible, reacting for 2h at 600 ℃ in a muffle furnace, naturally cooling, washing with deionized water until the last washing liquid is colorless, drying for 24h in an oven at 80 ℃, grinding with an agate mortar, ball-milling with a ball mill at the rotating speed of 220rpm for 15min to recover powder, and grinding the powder with the agate mortar and sieving with a 60-mesh sieve to obtain the iron-manganese crosslinked sodium alginate modified biochar (expressed as Fe/Mn-SA @ BC-4, namely the material numbered as No. 4 in figures 1 and 2).
Example 5
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from green to dark green, putting 30g of the dried large-leaf oilseed rape into a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water along with ultrasonic waves, repeating the steps for a plurality of times until cleaning liquid is free of soil, then putting the cleaning liquid into an oven for drying for 24h at 60 ℃, crushing by using a small crusher, sieving by using a 60-mesh sieve, and finally putting the drying liquid into a drying oven for storage.
Taking 300mmol of MnSO4Dissolving the extract in 200mL of distilled water, adding 3g of the treated tall clover, uniformly stirring, adding 1mL of nitric acid solution, performing ultrasonic treatment for 30min, and dropwise adding 300mL of 2 wt% sodium alginate solution through a peristaltic pump (the rotating speed is 3mL/min) to form tiny particles on the surface of the tall clover and realize the fixation of manganese (II) ions. And (3) recovering and washing the prepared composite material, and drying the washed composite material in an oven at 90 ℃ until the weight is constant to obtain solid particles.
And taking out the dried solid particles, putting the solid particles into a ceramic crucible, reacting for 2h at 600 ℃ in a muffle furnace, naturally cooling, washing with deionized water until the last washing liquid is colorless, drying for 24h in an oven at 80 ℃, grinding with an agate mortar, ball-milling with a ball mill at the rotating speed of 220rpm for 15min to recover powder, grinding with the agate mortar and sieving with a 60-mesh sieve to obtain the manganese crosslinked sodium alginate modified biochar (Mn-SA @ BC-5, namely the material numbered in 5 in figures 1 and 2).
FIG. 4 is an XRD pattern of the composite material prepared in example 5 of the present invention, from which the formation of MnO can be seen. Fig. 5 is an FT-IR diagram of the composite material prepared in example 5 of the present invention, which fully demonstrates that the organic functional group on the surface of the biochar can realize the high-efficiency loading of the metal oxide, the immobilization of the nanomaterial and the carbon loading. Fig. 6 is an SEM image of the composite material prepared in example 5 of the present invention, which shows that when the carbonized Mn crosslinked sodium alginate is attached to the surface of the biochar, the large specific surface area of the biochar provides attachment sites for the Mn crosslinked sodium alginate microspheres.
Example 6
Collecting harvested large-leaf oilseed rape from a Qinghua garden of Xili university of Shenzhen, Guangdong province, naturally drying under the irradiation of sunlight until the leaves of the large-leaf oilseed rape are changed from green to dark green, putting 30g of the dried large-leaf oilseed rape into a 2L beaker, carrying out ultrasonic cleaning for 20min by using deionized water along with ultrasonic waves, repeating the steps for a plurality of times until cleaning liquid is free of soil, putting the cleaning liquid into an oven for drying for 24h at 60 ℃, crushing by using a small crusher, sieving by using a 60-mesh sieve, and finally putting the drying liquid into a drying oven for storage.
Dissolving 3g of sodium alginate in 150mL of distilled water, stirring completely, adding 1g of the treated tall clover, stirring uniformly, wrapping completely, performing ultrasonic treatment for 30min, and drying in an oven at 90 ℃ for 24h to obtain solid particles.
And taking out the dried solid particles, putting the solid particles into a ceramic crucible, reacting for 2h at 600 ℃ in a muffle furnace, naturally cooling, washing with deionized water until the last washing liquid is colorless, drying for 24h in an oven at 80 ℃, grinding with an agate mortar, ball-milling for 15min at a rotating speed of 220rpm by using a ball mill, recovering the powder, grinding with the agate mortar and sieving with a 60-mesh sieve to obtain the sodium alginate-coated biochar (shown as SA-BC).
The adsorption performance of trivalent arsenic, pentavalent arsenic, phosphorus, hexavalent chromium and divalent cadmium was measured on the composite materials prepared in examples 1 to 5, and the adsorption performance was measured by adding 15mg of the composite material prepared in examples 1 to 5 to 30mL of a solution containing 20mg/L of heavy metal ions or a solution containing 20mg/L of phosphorus. From fig. 1, it can be found that the adsorption of trivalent arsenic, pentavalent arsenic and phosphorus can be promoted by the iron/manganese crosslinked sodium alginate modified charcoal, wherein the removal efficiency of phosphorus by the manganese single crosslinked sodium alginate modified charcoal (No. 5) is the best. From FIG. 2, it can be found that the sample No. 3 has the best effect of removing hexavalent chromium, i.e., the removal effect of hexavalent chromium is that the sample No. 3 is more than 4 and more than 5 and more than 2 and more than 1; the sample No. 5 has the best adsorption effect on the divalent cadmium and the removal effect on the divalent cadmium, wherein No. 5 is more than No. 1 and more than No. 4 is more than No. 3 and more than No. 2. It was determined that the material of example 6 has a poor adsorption effect on As (III) ions, As (V) ions, Cr (VI) ions and phosphorus (not shown in FIGS. 1 and 2), and therefore, compared with example 6, the iron/manganese crosslinked sodium alginate modified biochar can improve the adsorption performance of the composite material on As (III) ions, As (V) ions, Cr (VI) ions and phosphorus.
The adsorption capacity of divalent cadmium was measured for the composite material prepared in example 6 by adding 15mg of the composite material to 30mL of a solution of 50-600mg/L of divalent cadmium. According to the graph 3, the adsorption capacity of the biochar to heavy metal cadmium can be obviously increased by wrapping the biochar with the sodium alginate carbide, the adsorption capacity of the composite material to divalent heavy metal ions is greatly improved, and the composite material is verified to be capable of rapidly and efficiently adsorbing the divalent heavy metal ions.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.
Claims (10)
1. A preparation method of a carbonized sodium alginate-coated biochar composite material is characterized by comprising the following steps:
s1, adding a biochar precursor into a 2 wt% sodium alginate solution, fully mixing and wrapping, and drying to obtain solid particles;
s2, sintering and carbonizing the solid particles obtained in the step S1 at the temperature of 900 ℃ of 300-.
2. The method of claim 1, wherein: in the step S1, the mass ratio of the added biochar precursor to sodium alginate is 1: 3.
3. The method of claim 1, wherein: the biochar precursor is prepared from garden solid waste, preferably is prepared from euphorbia hirta, and more preferably is prepared from dark green euphorbia hirta which is dried, crushed and sieved by a 60-mesh sieve after being washed.
4. A preparation method of an iron/manganese crosslinked sodium alginate modified biochar composite material is characterized by comprising the following steps:
s1, mixing and fully stirring a metal salt solution and a biochar precursor, dropwise adding a 2 wt% sodium alginate solution, forming fine granular substances on the surface of the biochar precursor through a crosslinking reaction, washing, recovering solid particles, and drying; wherein the metal salt solution is at least one of a manganese (II) salt solution and an iron (II) salt solution;
s2, sintering and carbonizing the solid particles obtained in the step S1 at the temperature of 900 ℃ of 300-.
5. The method of claim 4, wherein: also comprises the following steps: the manganese (II) salt solution is a manganese sulfate solution; the iron (II) salt solution is a ferrous sulfate solution; the screening in the step S2 means screening by a 60-mesh screen.
6. The method of claim 4, wherein:
the volume ratio of the sodium alginate solution to the metal salt solution in the step S1 is 3:2, and the mass concentration of the biochar precursor in the metal salt solution is 15 mg/mL.
7. The method of claim 4, wherein:
when the metal salt solution in the step S1 is an iron (II) salt solution or a manganese (II) salt solution, the molar concentration of iron (II) ions in the iron (II) salt solution is 1.5mol/L, and the molar concentration of manganese (II) ions in the manganese (II) salt solution is 1.5 mol/L;
when the metal salt solution in the step S1 is a mixed solution of an iron (II) salt solution and a manganese (II) salt solution, the molar concentrations of iron (II) ions and manganese (II) ions in the mixed solution satisfy one of the following conditions: (1) the molar concentration of iron (II) ions was 1.5mol/L and the molar concentration of manganese (II) ions was 0.75 mol/L; (2) the molar concentration of iron (II) ions is 1.5mol/L and the molar concentration of manganese (II) ions is 1.5 mol/L; (3) the molar concentration of iron (II) ions was 0.75mol/L and the molar concentration of manganese (II) ions was 1.5 mol/L.
8. A composite material produced by the production method according to claim 1 or 4.
9. Use of the composite material of claim 8 for the treatment of heavy metal ions and/or phosphorus.
10. The use of claim 9, wherein: the heavy metal ions are at least one of As (III) ions, As (V) ions, Cr (VI) ions and Cd (II) ions; preferably, the application refers to the adsorption of Cd (II) ions by the composite material prepared by the preparation method in the claim 1; preferably, the application refers to the adsorption of at least one of As (III) ion, As (V) ion, Cr (VI) ion, Cd (II) ion and phosphorus element by the composite material prepared by the preparation method of claim 4.
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