CN108722356B - Preparation method of nano zero-valent iron-loaded hydrophilic porous biochar composite material - Google Patents
Preparation method of nano zero-valent iron-loaded hydrophilic porous biochar composite material Download PDFInfo
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- CN108722356B CN108722356B CN201810599359.3A CN201810599359A CN108722356B CN 108722356 B CN108722356 B CN 108722356B CN 201810599359 A CN201810599359 A CN 201810599359A CN 108722356 B CN108722356 B CN 108722356B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 69
- 150000003839 salts Chemical class 0.000 claims abstract description 55
- 238000000197 pyrolysis Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000010902 straw Substances 0.000 claims abstract description 13
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 7
- 235000005822 corn Nutrition 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 55
- 239000002994 raw material Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000011261 inert gas Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000005067 remediation Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 239000002154 agricultural waste Substances 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 2
- 241000209149 Zea Species 0.000 abstract 2
- 239000003610 charcoal Substances 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
- B01J20/02—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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- 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
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
A preparation method of a nano zero-valent iron-loaded hydrophilic porous biochar composite relates to a preparation method of a hydrophilic porous biochar composite. The invention aims to solve the problems that the existing matrix loaded with metal particles is high in cost, nano zero-valent iron is unstable and easy to agglomerate, and the performance is lower in the process of removing heavy metals by adsorption. The method comprises the following steps: firstly, biomass pyrolysis molten salt activation; secondly, preparing a hydrophilic porous biochar material; and thirdly, loading the nano zero-valent iron to obtain the nano zero-valent iron loaded hydrophilic porous biochar composite. The specific surface area of the nano zero-valent iron-loaded hydrophilic porous biochar composite material prepared by the invention can reach 603.4m2·g‑1. Because the corn straws are agricultural wastes with low cost and wide sources, the corn straws are pyrolyzed to be used as a matrix material, so that the cost of the synthesis process is reduced. The nano zero-valent iron-loaded hydrophilic porous biochar composite material prepared by the invention is used in the field of environmental pollutant remediation.
Description
Technical Field
The invention relates to a preparation method of a hydrophilic porous biochar composite material.
Background
The nanometer zero-valent iron is an environment-friendly material and has the advantages of small particle size, large surface area, strong reduction capability, high reaction speed and the like. Therefore, the nano zero-valent iron is widely applied to the field of water body restoration. However, the nano zero-valent iron has poor stability in air and high storage difficulty, and is easy to react with water or oxygen in a surrounding medium, so that an oxide layer is formed to inhibit further reaction with pollutants. In addition, due to the high surface energy, the nano zero-valent iron is easy to agglomerate into larger particles, so that the reaction activity is reduced, and therefore, the utilization rate of the nano zero-valent iron is low.
In recent years, the stability of the nano zero-valent iron can be effectively improved by using materials such as silicon dioxide, polymers, clay minerals, activated carbon, graphene and carbon nanotubes as carriers. However, these carriers are costly and have been used for adsorption removal of heavy metalsThe performance in the process is lower. Studies have reported the removal of heavy metals Pb from groundwater by using sepiolite-loaded nanoscale zero-valent iron2+The maximum adsorption capacity is 44.05 mg/g; zero-valent iron is loaded on SiC nano particles and used for Pb in aqueous solution2+The maximum adsorption capacity of the material to lead is 178.57 mg/g.
Disclosure of Invention
The invention aims to solve the problems that the existing matrix loaded with metal particles is high in cost, nano zero-valent iron is unstable and easy to agglomerate, and the performance is lower in the process of removing heavy metals by adsorption, and provides a preparation method of a nano zero-valent iron loaded hydrophilic porous biochar composite material.
A preparation method of a nano zero-valent iron-loaded hydrophilic porous biochar composite material comprises the following steps:
firstly, biomass pyrolysis molten salt activation:
cutting and crushing a biochar raw material, cleaning the biochar raw material for 5-10 times by using distilled water, drying the biochar raw material at the temperature of 70-90 ℃, and sieving the dried biochar raw material by using a 100-200-mesh sieve to obtain fine biochar raw material powder;
secondly, grinding and mixing fine powder of the raw biochar material and metal salt to obtain a reactant; placing the reactant in a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 700-900 ℃ under the protection of the inert gas, and then pyrolyzing the reactant at the temperature of 700-900 ℃ for 1-3 h under the protection of the inert gas atmosphere to obtain a pyrolyzed and carbonized porous biochar material;
the inert gas in the first step is nitrogen or argon;
the mass ratio of the fine powder of the biochar raw material to the metal salt in the first step is (1-10) to 1;
secondly, putting the porous biochar material subjected to pyrolysis carbonization into distilled water for cleaning, and taking out the porous biochar material subjected to pyrolysis carbonization;
secondly, repeating the second step for 5 to 10 times, drying at the temperature of between 70 and 90 ℃, immersing the dried product into an acidic oxidant solution, heating in a water bath for 3 to 24 hours, taking out the product, washing the product with distilled water for 5 to 10 times, and drying at the temperature of between 70 and 90 ℃ to obtain a hydrophilic porous biochar material;
thirdly, under the protection of inert gas, soaking the hydrophilic porous biochar material in an iron salt aqueous solution, stirring for 2-10 h at the stirring speed of 1000-1500 r/min, keeping the stirring speed unchanged, dropwise adding a reducing solution, continuously stirring for reaction for 2-10 h, then performing centrifugal separation, and performing vacuum drying on solid matters obtained by centrifugal separation at the temperature of 50-70 ℃ to obtain the nano zero-valent iron-loaded hydrophilic porous biochar composite material;
the inert gas in the third step is nitrogen or argon;
the mass ratio of the ferric salt in the ferric salt water solution to the reducing agent in the reducing solution in the third step is 1 (0.1-0.5).
The principle and the advantages of the invention are as follows:
the nano zero-valent iron-loaded hydrophilic porous biochar composite material prepared by taking biochar raw materials as raw materials and adopting the combination of molten salt assistance and chemical reduction has a large specific surface area, and the specific surface area of the nano zero-valent iron-loaded hydrophilic porous biochar composite material prepared by the method can reach 603.4m2·g-1. The nano zero-valent iron can be highly and uniformly dispersed on the surface of the hydrophilic porous charcoal material, so that the utilization efficiency of the nano zero-valent iron in the environment is improved;
secondly, when the hydrophilic porous charcoal material is mixed with ferrous ions, the ferrous ions are adsorbed on the surface of the hydrophilic porous charcoal material by the oxygen-containing functional groups on the surface of the hydrophilic porous charcoal material, so that the dispersity of the generated nano zero-valent iron on the surface of the porous charcoal material is improved. The synergistic effect of the nano zero-valent iron and the porous charcoal material improves the utilization efficiency of the nano zero-valent iron in the environment;
and thirdly, the raw material of the biochar is used as cheap and easily-obtained agricultural waste, and the biochar is pyrolyzed to be used as a matrix material, so that the synthesis cost is reduced. The nano zero-valent iron-loaded hydrophilic porous charcoal composite material is prepared by a method combining the nano zero-valent iron with metal salt mixing pyrolysis and chemical reduction, so that the dispersity of the nano zero-valent iron is effectively improved, and the utilization value of the nano zero-valent iron in the field of environmental remediation is improved;
fourthly, the nano zero-valent iron-loaded hydrophilic porous biochar composite material prepared by the invention removes heavy metal Pb2+The adsorption amount of (B) was 174.5mg g-1~195.0mg·g-1(ii) a Removal of heavy metals Cu2+The adsorption amount of (B) was 68.8mg g-1~161.9mg·g-1Removal of the heavy metal Zn2+The adsorption amount of (B) was 62.1mg g-1~109.7mg·g-1;
And fifthly, the preparation method is simple and convenient, and the raw materials are cheap and easy to obtain, so that the preparation method is suitable for large-batch synthesis and preparation.
The nano zero-valent iron-loaded hydrophilic porous biochar composite material prepared by the invention is used in the field of environmental pollutant remediation.
Drawings
FIG. 1 is a scanning electron microscope image of a nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in step three of the example;
FIG. 2 is a transmission electron microscope image of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in step three of the example;
FIG. 3 is an XRD spectrum of the nano zero-valent iron-supported hydrophilic porous biochar composite prepared in step three of the example;
FIG. 4 is a diagram of N of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the embodiment2Adsorption-desorption spectra.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment is a preparation method of a nano zero-valent iron-loaded hydrophilic porous biochar composite material, which is specifically completed according to the following steps:
firstly, biomass pyrolysis molten salt activation:
cutting and crushing a biochar raw material, cleaning the biochar raw material for 5-10 times by using distilled water, drying the biochar raw material at the temperature of 70-90 ℃, and sieving the dried biochar raw material by using a 100-200-mesh sieve to obtain fine biochar raw material powder;
secondly, grinding and mixing fine powder of the raw biochar material and metal salt to obtain a reactant; placing the reactant in a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 700-900 ℃ under the protection of the inert gas, and then pyrolyzing the reactant at the temperature of 700-900 ℃ for 1-3 h under the protection of the inert gas atmosphere to obtain a pyrolyzed and carbonized porous biochar material;
the inert gas in the first step is nitrogen or argon;
the mass ratio of the fine powder of the biochar raw material to the metal salt in the first step is (1-10) to 1;
secondly, putting the porous biochar material subjected to pyrolysis carbonization into distilled water for cleaning, and taking out the porous biochar material subjected to pyrolysis carbonization;
secondly, repeating the second step for 5 to 10 times, drying at the temperature of between 70 and 90 ℃, immersing the dried product into an acidic oxidant solution, heating in a water bath for 3 to 24 hours, taking out the product, washing the product with distilled water for 5 to 10 times, and drying at the temperature of between 70 and 90 ℃ to obtain a hydrophilic porous biochar material;
thirdly, under the protection of inert gas, soaking the hydrophilic porous biochar material in an iron salt aqueous solution, stirring for 2-10 h at the stirring speed of 1000-1500 r/min, keeping the stirring speed unchanged, dropwise adding a reducing solution, continuously stirring for reaction for 2-10 h, then performing centrifugal separation, and performing vacuum drying on solid matters obtained by centrifugal separation at the temperature of 50-70 ℃ to obtain the nano zero-valent iron-loaded hydrophilic porous biochar composite material;
the inert gas in the third step is nitrogen or argon;
the mass ratio of the ferric salt in the ferric salt water solution to the reducing agent in the reducing solution in the third step is 1 (0.1-0.5).
The first step of the embodiment is to perform pyrolysis: the metal salt is melted at high temperature to activate the biomass to prepare the porous biochar, and the porous biochar material obtained after pyrolysis has an obvious hierarchical porous structure.
In the second step of the embodiment, the hydrophilic capacity of the porous biochar material is enhanced by immersing the porous biochar material in an acidic oxidant solution, so that the porous biochar material can be better dissolved in water; and the number of oxygen-containing functional groups on the surface of the porous biochar material can be increased by the treatment in the process, so that the application range of the material is favorably enlarged.
The purpose of dropping the reducing solution in step three of the present embodiment is: reducing ferrous iron adsorbed on the surface of the hydrophilic porous charcoal material to zero-valent iron in situ, and highly dispersing the reduced nano zero-valent iron on the surface of the hydrophilic porous charcoal material.
The principle and advantages of the embodiment are as follows:
according to the embodiment, a biological carbon raw material is used as a raw material, the nano zero-valent iron-loaded hydrophilic porous biological carbon composite material prepared by combining molten salt assistance and chemical reduction has a large specific surface area, and the specific surface area of the nano zero-valent iron-loaded hydrophilic porous biological carbon composite material prepared by the embodiment can reach 603.4m2·g-1. The nano zero-valent iron can be highly and uniformly dispersed on the surface of the hydrophilic porous charcoal material, so that the utilization efficiency of the nano zero-valent iron in the environment is improved;
secondly, when the hydrophilic porous charcoal material is mixed with ferrous ions, the ferrous ions are adsorbed on the surface of the hydrophilic porous charcoal material by the oxygen-containing functional groups on the surface of the hydrophilic porous charcoal material, so that the dispersity of the generated nano zero-valent iron on the surface of the porous charcoal material is improved. The synergistic effect of the nano zero-valent iron and the porous charcoal material improves the utilization efficiency of the nano zero-valent iron in the environment;
and thirdly, the raw material of the biochar is used as cheap and easily-obtained agricultural waste, and the biochar is pyrolyzed to be used as a matrix material, so that the synthesis cost is reduced. The nano zero-valent iron-loaded hydrophilic porous charcoal composite material is prepared by a method combining the nano zero-valent iron with metal salt mixing pyrolysis and chemical reduction, so that the dispersity of the nano zero-valent iron is effectively improved, and the utilization value of the nano zero-valent iron in the field of environmental remediation is improved;
and fourthly, the preparation method is simple and convenient, and the raw materials are cheap and easy to obtain, so that the method is suitable for large-batch synthesis and preparation.
The nano zero-valent iron-loaded hydrophilic porous biochar composite material prepared by the embodiment is used for the field of environmental pollutant remediation.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the biochar raw material in the first step is one or a mixture of more of corn straw, wheat straw, soybean straw, rice straw and rice hull. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the metal salt in the first step is KHCO3Or NaHCO3. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: step one, the temperature rise rate of the middle-tube furnace is 8-11 ℃/min when the temperature rises to 700-900 ℃. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: grinding and mixing fine biochar raw material powder and metal salt to obtain a reactant; and putting the reactants in a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 700-800 ℃ under the protection of the inert gas, and pyrolyzing the tubular furnace for 1-2 hours at the temperature of 700-800 ℃ under the protection of the inert gas atmosphere to obtain the pyrolyzed and carbonized porous biochar material. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the mass ratio of the fine powder of the biochar raw material to the metal salt in the first step is (1-5): 1. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the temperature of the water bath heating in the second step is 50-70 ℃. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the acidic oxidant solution in the second step is (NH)4)2S2O8And 10-20% sulfuric acid; in the acidic oxidizing agent solution (NH)4)2S2O8And H2SO4The molar ratio of (1) to (5). The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: the ferric salt aqueous solution in the third step is ferrous nitrate, ferrous sulfate solution or ferrous chloride, and the concentration of the ferric salt aqueous solution is 0.02 mol.L-1~0.2mol·L-1. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the reducing solution in the third step is NaBH4The concentration of the solution, the reducing solution is 0.1 mol.L-1~1mol·L-1。
The other is the same as one of the first to ninth embodiments.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The first embodiment is as follows: a preparation method of a nano zero-valent iron-loaded hydrophilic porous biochar composite material comprises the following steps:
firstly, biomass pyrolysis molten salt activation:
cutting and crushing a biochar raw material, cleaning for 7 times by using distilled water, drying at the temperature of 80 ℃, and sieving the dried biochar raw material by using a 100-mesh sieve to obtain fine biochar raw material powder;
the biochar raw material in the first step is corn straw;
secondly, grinding and mixing fine powder of the raw biochar material and metal salt to obtain a reactant; placing the reactant in a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 800 ℃ under the protection of the nitrogen, and pyrolyzing the reactant for 2 hours at the temperature of 800 ℃ under the protection of nitrogen atmosphere to obtain a pyrolyzed and carbonized porous biochar material;
the metal salt in the first step is KHCO3;
The mass ratio of the fine powder of the biochar raw material to the metal salt in the first step is 1: 1;
step one, the temperature rise rate of the middle-tube furnace is 10 ℃/min when the temperature rises to 800 ℃;
secondly, putting the porous biochar material subjected to pyrolysis carbonization into distilled water for cleaning, and taking out the porous biochar material subjected to pyrolysis carbonization;
secondly, repeating the second step for 7 times, drying at the temperature of 80 ℃, immersing the dried product into an acidic oxidant solution, heating in a water bath for 8 hours, taking out the product, washing the product with distilled water for 7 times, and drying at the temperature of 80 ℃ to obtain a hydrophilic porous charcoal material;
the temperature of the water bath heating in the second step is 60 ℃;
the acidic oxidant solution in the second step is (NH)4)2S2O8And 17.5 percent of sulfuric acid by mass; in the acidic oxidizing agent solution (NH)4)2S2O8And H2SO4In a molar ratio of 1: 2;
thirdly, under the protection of inert gas, soaking the hydrophilic porous biochar material in an iron salt aqueous solution, stirring for 4 hours at the stirring speed of 1200r/min, keeping the stirring speed unchanged, dropwise adding a reducing solution, continuously stirring for reaction for 5 hours, performing centrifugal separation, and performing vacuum drying on solid matters obtained by centrifugal separation at the temperature of 60 ℃ to obtain a nano zero-valent iron-loaded hydrophilic porous biochar composite material;
the inert gas in the third step is nitrogen;
the ferric salt aqueous solution in the third step is ferrous sulfate solution, and the concentration of the ferric salt aqueous solution is 0.075 mol.L-1;
The reducing solution in the third step is NaBH4The concentration of the solution, the reducing solution is 0.3 mol.L-1;
The mass ratio of the ferric salt in the ferric salt aqueous solution in the third step to the reducing agent in the reducing solution is 1: 0.27.
In the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the embodiment, the mass ratio of the nano zero-valent iron to the hydrophilic porous biochar material is 1: 1.
The scanning electron microscope photo of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the example is shown in fig. 1;
the transmission electron microscope photograph of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the example is shown in fig. 2.
FIG. 1 is a scanning electron microscope image of a nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in step three of the example;
as can be seen from fig. 1, the nano zero-valent iron particles are uniformly dispersed on the surface of the hydrophilic porous biochar material.
FIG. 2 is a transmission electron microscope image of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in step three of the example;
as can be seen from FIG. 2, the nano zero-valent iron particles have no agglomeration phenomenon, and have an average particle size of about 100nm and are uniformly dispersed on the surface of the hydrophilic porous biochar material;
FIG. 3 is an XRD spectrum of the nano zero-valent iron-supported hydrophilic porous biochar composite prepared in step three of the example;
from fig. 3, the crystal properties of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the example can be analyzed. The broad and weak diffraction peak centered at 21.6 ° in the XRD pattern is attributed to carbon element and exists mainly in amorphous form.The sample shows three strong diffraction peaks of 44.7 degrees, 65.0 degrees and 82.3 degrees, which respectively correspond to the nanometer zero-valent iron (Fe)0) (JCPDS, NO.87-0721)) of (100), (200) and (211). These results indicate that the well-crystallized nano zero-valent iron has been successfully loaded on the surface of the hydrophilic porous biochar material.
FIG. 4 is a diagram of N of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the embodiment2Adsorption-desorption spectra.
As can be seen from FIG. 4, the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the example has the characteristics of type II isotherm under medium relative pressure (P/P)00.4-0.95) generated by capillary condensation, and an H4 type hysteresis loop exists, indicating that the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the example has a micropore and mesopore structure.
The specific surface area of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the embodiment can reach 603.4m2·g-1。
Example two: a preparation method of a nano zero-valent iron-loaded hydrophilic porous biochar composite material comprises the following steps:
firstly, biomass pyrolysis molten salt activation:
cutting and crushing a biochar raw material, cleaning for 7 times by using distilled water, drying at the temperature of 80 ℃, and sieving the dried biochar raw material by using a 100-mesh sieve to obtain fine biochar raw material powder;
the biochar raw material in the first step is corn straw;
secondly, grinding and mixing fine powder of the raw biochar material and metal salt to obtain a reactant; placing the reactant in a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 800 ℃ under the protection of the nitrogen, and pyrolyzing the reactant for 2 hours at the temperature of 800 ℃ under the protection of nitrogen atmosphere to obtain a pyrolyzed and carbonized porous biochar material;
the metal salt in the first step is KHCO3;
The mass ratio of the fine powder of the biochar raw material to the metal salt in the first step is 1: 1;
step one, the temperature rise rate of the middle-tube furnace is 10 ℃/min when the temperature rises to 800 ℃;
secondly, putting the porous biochar material subjected to pyrolysis carbonization into distilled water for cleaning, and taking out the porous biochar material subjected to pyrolysis carbonization;
secondly, repeating the second step for 7 times, drying at the temperature of 80 ℃, immersing the dried product into an acidic oxidant solution, heating in a water bath for 8 hours, taking out the product, washing the product with distilled water for 7 times, and drying at the temperature of 80 ℃ to obtain a hydrophilic porous charcoal material;
the temperature of the water bath heating in the second step is 60 ℃;
the acidic oxidant solution in the second step is (NH)4)2S2O8And 17.5 percent of sulfuric acid by mass; in the acidic oxidizing agent solution (NH)4)2S2O8And H2SO4In a molar ratio of 1: 2;
thirdly, under the protection of inert gas, soaking the hydrophilic porous biochar material in an iron salt aqueous solution, stirring for 4 hours at the stirring speed of 1200r/min, keeping the stirring speed unchanged, dropwise adding a reducing solution, continuously stirring for reaction for 5 hours, performing centrifugal separation, and performing vacuum drying on solid matters obtained by centrifugal separation at the temperature of 60 ℃ to obtain a nano zero-valent iron-loaded hydrophilic porous biochar composite material;
the inert gas in the third step is nitrogen;
the ferric salt aqueous solution in the third step is ferrous sulfate solution, and the concentration of the ferric salt aqueous solution is 0.035 mol.L-1;
The reducing solution in the third step is NaBH4The concentration of the solution, the reducing solution is 0.15 mol.L-1;
The mass ratio of the ferric salt in the ferric salt aqueous solution in the third step to the reducing agent in the reducing solution is 1: 0.27.
In the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the second step and the third step of the embodiment, the mass ratio of the nano zero-valent iron to the hydrophilic porous biochar material is 1: 2.
Example three: a preparation method of a nano zero-valent iron-loaded hydrophilic porous biochar composite material comprises the following steps:
firstly, biomass pyrolysis molten salt activation:
cutting and crushing a biochar raw material, cleaning for 7 times by using distilled water, drying at the temperature of 80 ℃, and sieving the dried biochar raw material by using a 100-mesh sieve to obtain fine biochar raw material powder;
the biochar raw material in the first step is corn straw;
secondly, grinding and mixing fine powder of the raw biochar material and metal salt to obtain a reactant; placing the reactant in a tubular furnace, introducing nitrogen into the tubular furnace, heating the tubular furnace to 800 ℃ under the protection of the nitrogen, and pyrolyzing the reactant for 2 hours at the temperature of 800 ℃ under the protection of nitrogen atmosphere to obtain a pyrolyzed and carbonized porous biochar material;
the metal salt in the first step is KHCO3;
The mass ratio of the fine powder of the biochar raw material to the metal salt in the first step is 1: 1;
step one, the temperature rise rate of the middle-tube furnace is 10 ℃/min when the temperature rises to 800 ℃;
secondly, putting the porous biochar material subjected to pyrolysis carbonization into distilled water for cleaning, and taking out the porous biochar material subjected to pyrolysis carbonization;
secondly, repeating the second step for 7 times, drying at the temperature of 80 ℃, immersing the dried product into an acidic oxidant solution, heating in a water bath for 8 hours, taking out the product, washing the product with distilled water for 7 times, and drying at the temperature of 80 ℃ to obtain a hydrophilic porous charcoal material;
the temperature of the water bath heating in the second step is 60 ℃;
the acidic oxidant solution in the second step is (NH)4)2S2O8And 17.5 percent of sulfuric acid by massThe mixed solution of (1); in the acidic oxidizing agent solution (NH)4)2S2O8And H2SO4In a molar ratio of 1: 2;
thirdly, under the protection of inert gas, soaking the hydrophilic porous biochar material in an iron salt aqueous solution, stirring for 4 hours at the stirring speed of 1200r/min, keeping the stirring speed unchanged, dropwise adding a reducing solution, continuously stirring for reaction for 5 hours, performing centrifugal separation, and performing vacuum drying on solid matters obtained by centrifugal separation at the temperature of 60 ℃ to obtain a nano zero-valent iron-loaded hydrophilic porous biochar composite material;
the inert gas in the third step is nitrogen;
the ferric salt aqueous solution in the third step is ferrous sulfate solution, and the concentration of the ferric salt aqueous solution is 0.15 mol.L-1;
The reducing solution in the third step is NaBH4The concentration of the solution, the reducing solution is 0.6 mol.L-1;
The mass ratio of the ferric salt in the ferric salt aqueous solution in the third step to the reducing agent in the reducing solution is 1: 0.27.
The mass ratio of the nanoscale zero-valent iron to the hydrophilic porous biochar material in the nanoscale zero-valent iron-loaded hydrophilic porous biochar composite material prepared in the third step of the embodiment is 2: 1.
Example three steps of preparation of nano zero-valent iron-loaded hydrophilic porous biochar composite for removing heavy metal Pb2+、Cu2+And Zn2+The adsorption capacity is 192.8mg g-1,125.4mg·g-1And 73.8mg g-1And the porous charcoal material obtained in the first step of the embodiment after pyrolysis and carbonization is used for adsorbing heavy metal Pb2+、Cu2+And Zn2+The adsorption capacity is respectively 108.1mg g-1,50.8mg·g-1And 33.5mg g-1And the adsorption effect is obviously lower than that of the nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the embodiment.
Example two-step three-prepared nano zero-valent iron-loaded hydrophilic porous biochar compositeRemoval of heavy metals Pb2+、Cu2+And Zn2+The adsorption capacity is respectively 174.5mg g-1,68.8mg·g-1And 62.1mg g-1。
The nano zero-valent iron-loaded hydrophilic porous biochar composite prepared in the third step of the embodiment removes heavy metal Pb2+、Cu2+And Zn2+The adsorption capacity is 195.0mg g-1,161.9mg·g-1And 109.7mg g-1。
Claims (7)
1. A preparation method of a nano zero-valent iron-loaded hydrophilic porous biochar composite material is characterized in that the preparation method of the nano zero-valent iron-loaded hydrophilic porous biochar composite material is specifically completed according to the following steps:
firstly, biomass pyrolysis molten salt activation:
cutting and crushing a biochar raw material, cleaning the biochar raw material for 5-10 times by using distilled water, drying the biochar raw material at the temperature of 70-90 ℃, and sieving the dried biochar raw material by using a 100-200-mesh sieve to obtain fine biochar raw material powder;
secondly, grinding and mixing fine powder of the raw biochar material and metal salt to obtain a reactant; placing the reactant in a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 700-900 ℃ under the protection of the inert gas, and then pyrolyzing the reactant at the temperature of 700-900 ℃ for 1-3 h under the protection of the inert gas atmosphere to obtain a pyrolyzed and carbonized porous biochar material;
the inert gas in the first step is nitrogen or argon;
the mass ratio of the fine powder of the biochar raw material to the metal salt in the first step is (1-10) to 1;
secondly, putting the porous biochar material subjected to pyrolysis carbonization into distilled water for cleaning, and taking out the porous biochar material subjected to pyrolysis carbonization;
secondly, repeating the second step for 5 to 10 times, drying at the temperature of between 70 and 90 ℃, immersing the dried product into an acidic oxidant solution, heating in a water bath for 3 to 24 hours, taking out the product, washing the product with distilled water for 5 to 10 times, and drying at the temperature of between 70 and 90 ℃ to obtain a hydrophilic porous biochar material;
the acidic oxidant solution in the second step is (NH)4)2S2O8And 10-20% sulfuric acid; in the acidic oxidizing agent solution (NH)4)2S2O8And H2SO4The molar ratio of (1) to (5);
thirdly, under the protection of inert gas, soaking the hydrophilic porous biochar material in an iron salt aqueous solution, stirring for 2-10 h at the stirring speed of 1000-1500 r/min, keeping the stirring speed unchanged, dropwise adding a reducing solution, continuously stirring for reaction for 2-10 h, then performing centrifugal separation, and performing vacuum drying on solid matters obtained by centrifugal separation at the temperature of 50-70 ℃ to obtain the nano zero-valent iron-loaded hydrophilic porous biochar composite material;
the ferric salt aqueous solution in the third step is ferrous nitrate, ferrous sulfate solution or ferrous chloride, and the concentration of the ferric salt aqueous solution is 0.02 mol.L-1~0.2mol·L-1;
The reducing solution in the third step is NaBH4The concentration of the solution, the reducing solution is 0.1 mol.L-1~1mol·L-1;
The inert gas in the third step is nitrogen or argon;
the mass ratio of the ferric salt in the ferric salt water solution to the reducing agent in the reducing solution in the third step is 1 (0.1-0.5).
2. The preparation method of the nano zero-valent iron-loaded hydrophilic porous biochar composite material according to claim 1, characterized in that the biochar raw material in the first step is one or a mixture of several of corn straw, wheat straw, soybean straw, rice straw and rice hull.
3. The preparation method of the nano zero-valent iron-loaded hydrophilic porous biochar composite material according to claim 1The method is characterized in that the metal salt in the first step is KHCO3Or NaHCO3。
4. The preparation method of the nano zero-valent iron-loaded hydrophilic porous biochar composite material according to claim 1, characterized in that the heating rate of the first step of heating the medium-tube furnace to 700-900 ℃ is 8-11 ℃/min.
5. The preparation method of the nano zero-valent iron-loaded hydrophilic porous biochar composite material according to claim 1, characterized in that in the first step, fine biochar raw material powder and metal salt are ground and mixed to obtain a reactant; and putting the reactants in a tubular furnace, introducing inert gas into the tubular furnace, heating the tubular furnace to 700-800 ℃ under the protection of the inert gas, and pyrolyzing the tubular furnace for 1-2 hours at the temperature of 700-800 ℃ under the protection of the inert gas atmosphere to obtain the pyrolyzed and carbonized porous biochar material.
6. The preparation method of the nano zero-valent iron-loaded hydrophilic porous biochar composite material according to claim 1, wherein the mass ratio of the biochar raw material fine powder to the metal salt in the first step is (1-5): 1.
7. The preparation method of the nano zero-valent iron-loaded hydrophilic porous biochar composite material according to claim 1, characterized in that the temperature of water bath heating in the second step is 50-70 ℃.
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