CN112827475B - Preparation method and application of artificial humic acid functionalized colloid-like magnetic biochar - Google Patents

Preparation method and application of artificial humic acid functionalized colloid-like magnetic biochar Download PDF

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CN112827475B
CN112827475B CN202011643294.1A CN202011643294A CN112827475B CN 112827475 B CN112827475 B CN 112827475B CN 202011643294 A CN202011643294 A CN 202011643294A CN 112827475 B CN112827475 B CN 112827475B
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humic acid
biochar
artificial humic
magnetic
colloid
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CN112827475A (en
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杨帆
杜庆
程魁
隋龙
赵莹
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Northeast Agricultural University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J20/28002—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 physical properties
    • B01J20/28009—Magnetic properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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Abstract

A preparation method and application of artificial humic acid functionalized colloid-like magnetic biochar relate to a preparation method of colloid-like magnetic biochar. The invention aims to solve the problems that the magnetic iron oxide of the existing magnetic biochar material is aggregated on the surface of the biochar, the specific surface area of the biochar is reduced, the dispersibility of magnetic biochar particles in water is poor, and the adsorption capacity of heavy metals in sewage is limited. The method comprises the following steps: 1. preparing a mixture composite material; 2. firstly, charcoal/Fe 2+ /Fe 3+ Mixing the mixed solution of (2) with artificial humic acid solution, performing hydrothermal reaction, cleaning, and finally dispersing by using deionized water to obtain the artificial humic acid functionalized colloid-like magnetic biochar. The invention can obtain the artificial humic acid functionalized colloid-like magnetic biochar.

Description

Preparation method and application of artificial humic acid functionalized colloid-like magnetic biochar
Technical Field
The invention relates to a preparation method of colloid-like magnetic biochar.
Background
Magnetic Biochar (MBC) is a composite material containing magnetic iron oxides, commonly used as adsorbents or catalysts for heavy metals and organic pollutants, which can be separated by permanent magnets after treatment. However, because the agglomeration phenomenon of the magnetic iron oxide on the surface of the biochar, the magnetic iron oxide causes the empty blockage of the biochar to reduce the specific surface area of the biochar, the magnetic biochar particles have poor dispersibility in water, and the preparation and use processes are complex, so that the application of the magnetic biochar particles in water treatment is limited.
The existing magnetic biochar has poor magnetic iron oxide dispersibility on the surface and poor magnetic biochar dispersibility in water as a whole, and has poor functional group content, so that the adsorption capacity for heavy metals in sewage is limited, and the adsorption capacity for removing cadmium ions is 7.4mg (Cd)/g-33.81 mg (Cd)/g, thereby preventing the biochar from being applied to water treatment.
Disclosure of Invention
The invention aims to solve the problems that the magnetic iron oxide of the existing magnetic biochar material is aggregated on the surface of the biochar, the specific surface area of the biochar is reduced, the dispersibility of magnetic biochar particles in water is poor, and the heavy metal adsorption capacity in sewage is limited, and provides a preparation method and application of the artificial humic acid functionalized colloid-like magnetic biochar.
The preparation method of the artificial humic acid functionalized colloid-like magnetic biochar is specifically completed according to the following steps:
1. preparing a mixture composite material:
(1) washing biomass with deionized water, drying, cutting and crushing the dried biomass, washing the crushed biomass with distilled water, drying, and sieving to obtain biomass powder;
(2) uniformly mixing a certain amount of biomass powder with a pore-forming activator to obtain a mixture; placing the mixture into a tube furnace, introducing inert gas into the tube furnace, heating the tube furnace to 700-900 ℃ under the protection of the inert gas, and pyrolyzing the mixture under the protection of the inert gas at 700-900 ℃ to obtain a reaction product; cleaning a reaction product by using hydrochloric acid, removing a pore-forming activator, and finally cleaning the reaction product to be neutral by using deionized water to obtain biochar;
the mass ratio of the biomass powder to the pore-forming activator in the step one (2) is 1:1;
(3) uniformly mixing a certain amount of biomass powder with KOH particles and ultrapure water to obtain a mixed solution; placing the mixed solution into an autoclave, then carrying out continuous hydrothermal humification reaction for 20-24 hours in the autoclave at the temperature of 200-240 ℃, cooling to room temperature, filtering, and removing solids to obtain a liquid reaction product; adjusting the pH value of the liquid reaction product to 1 by using hydrochloric acid, centrifuging, and removing upper layer centrifugate to obtain a solid substance; washing the solid matters to be neutral by using distilled water to obtain artificial humic acid solid;
the mass ratio of the biomass powder to the KOH particles in the step one (3) is (20 g-30 g) (3 g-5 g);
the volume ratio of the mass of the biomass powder to the ultrapure water in the step one (3) is (20 g-30 g) (180 mL-280 mL);
(4) immersing biochar into Fe 2+ And Fe (Fe) 3+ In the mixed solution of (2) to obtain the biochar/Fe 2+ /Fe 3+ Is a mixed solution of (a) and (b); dissolving artificial humic acid solids into ammonia water, and then performing ultrasonic dispersion to obtain an artificial humic acid solution;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ Wherein the mixed solution of ferrous salt, ferric salt and deionized water is mixed solution of Fe 2+ And Fe (Fe) 3+ The mass ratio of (2) is 1:1;
the biochar and Fe in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ And Fe (Fe) 3+ The ratio of the total mass is 2:1;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ The concentration of (2) is 2.0 g/L-3.0 g/L;
the volume ratio of the mass of the artificial humic acid solid in the step one (4) to the ammonia water is (20 mg-100 mg) 20mL;
2. biochar/Fe 2+ /Fe 3+ Mixing the mixed solution of (2) with an artificial humic acid solution, and stirring to obtain a mixture; placing the mixture into an autoclave with the temperature of 100-200 ℃ for 10-24 hours, and cooling to room temperature to obtain a solid product; washing the solid product to be neutral by using deionized water, and finally dispersing the solid product by using deionized water to obtain artificial humic acid functionalized colloid-like magnetic biochar;
biochar/Fe as described in step two 2+ /Fe 3+ The volume ratio of the mixed solution of (2) and the artificial humic acid solution is 3:1;
the concentration of the artificial humic acid functionalized colloid-like magnetic biochar in the second step is 15 g/L-20 g/L.
The principle and the advantages of the invention are that:
1. according to the invention, the biochar skeleton and the artificial humic acid are prepared from biomass, the loading of the magnetic iron oxide on the biochar and the activation of the functional group of the humic acid are realized by a one-step hydrothermal method of the biochar, the simple preparation of the material is realized, and the magnetic biochar colloid iron oxide prepared by the method is uniformly distributed on the surface of the biochar through SEM result analysis, so that the aggregation of the magnetic iron oxide on the surface of the biochar and the current situation of blocking of biochar holes are relieved;
2. the artificial humic acid is used as a functional group activator to improve the dispersibility of the iron oxide on the surface of the biochar, the magnetic biochar is uniformly dispersed in water by combining the artificial humic acid and the iron oxide through the interaction between the functional groups, and the magnetic biochar can be kept in a better dispersion state in water after being placed for 20 days, so that a state similar to colloid is formed;
3. the concentration of the artificial humic acid functionalized colloid-like magnetic biochar is measured and prepared by a weighing method, the quantitative measurement is directly used for sewage treatment, the energy loss caused in the drying process of the artificial humic acid functionalized colloid-like magnetic biochar and the performance of removing heavy metal ions in sewage are reduced, the maximum capacity of the prepared artificial humic acid functionalized colloid-like magnetic biochar for removing Cd ions in sewage is 169.68mg/g, and the maximum capacity of the prepared artificial humic acid functionalized colloid-like magnetic biochar for removing Cd ions in sewage is 70.61mg/g which is far greater than that of the dried artificial humic acid functionalized colloid-like magnetic biochar;
4. biomass materials (such as corn stalks) are used as agricultural wastes, and the cost of the synthetic materials is reduced due to the fact that the biomass materials are cheap and easy to obtain;
5. the invention simultaneously completes the uniform loading of the magnetic iron oxide on the biochar skeleton and the functionalization of the magnetic biochar by the artificial humic acid, improves the provision of more functional group binding sites for heavy metal ions, and is convenient for the separation of the heavy metal ions by using a permanent magnet after the heavy metal ions are removed;
6. 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 mass synthesis and preparation; the artificial humic acid functionalized colloid-like magnetic biochar prepared by the invention is used for removing heavy metal ions in sewage.
The invention can obtain the artificial humic acid functionalized colloid-like magnetic biochar.
Drawings
FIG. 1 is a scanning electron microscope photograph of an artificial humic acid functionalized colloid-like magnetic biochar prepared in example I;
FIG. 2 is an XRD spectrum of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example I;
fig. 3 is a dispersion performance test and a magnetic test chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one, wherein a is a photo chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one, b is a photo chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one after being left for 20 days, c is a photo chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one after being separated by a magnet for 30 minutes.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the artificial humic acid functionalized colloid-like magnetic biochar is specifically completed according to the following steps:
1. preparing a mixture composite material:
(1) washing biomass with deionized water, drying, cutting and crushing the dried biomass, washing the crushed biomass with distilled water, drying, and sieving to obtain biomass powder;
(2) uniformly mixing a certain amount of biomass powder with a pore-forming activator to obtain a mixture; placing the mixture into a tube furnace, introducing inert gas into the tube furnace, heating the tube furnace to 700-900 ℃ under the protection of the inert gas, and pyrolyzing the mixture under the protection of the inert gas at 700-900 ℃ to obtain a reaction product; cleaning a reaction product by using hydrochloric acid, removing a pore-forming activator, and finally cleaning the reaction product to be neutral by using deionized water to obtain biochar;
the mass ratio of the biomass powder to the pore-forming activator in the step one (2) is 1:1;
(3) uniformly mixing a certain amount of biomass powder with KOH particles and ultrapure water to obtain a mixed solution; placing the mixed solution into an autoclave, then carrying out continuous hydrothermal humification reaction for 20-24 hours in the autoclave at the temperature of 200-240 ℃, cooling to room temperature, filtering, and removing solids to obtain a liquid reaction product; adjusting the pH value of the liquid reaction product to 1 by using hydrochloric acid, centrifuging, and removing upper layer centrifugate to obtain a solid substance; washing the solid matters to be neutral by using distilled water to obtain artificial humic acid solid;
the mass ratio of the biomass powder to the KOH particles in the step one (3) is (20 g-30 g) (3 g-5 g);
the volume ratio of the mass of the biomass powder to the ultrapure water in the step one (3) is (20 g-30 g) (180 mL-280 mL);
(4) immersing biochar into Fe 2+ And Fe (Fe) 3+ In the mixed solution of (2) to obtain the biochar/Fe 2+ /Fe 3+ Is a mixed solution of (a) and (b); dissolving artificial humic acid solids into ammonia water, and then performing ultrasonic dispersion to obtain an artificial humic acid solution;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ Wherein the mixed solution of ferrous salt, ferric salt and deionized water is mixed solution of Fe 2+ And Fe (Fe) 3+ The mass ratio of (2) is 1:1;
the biochar and Fe in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ And Fe (Fe) 3+ The ratio of the total mass is 2:1;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ The concentration of (2) is 2.0 g/L-3.0 g/L;
the volume ratio of the mass of the artificial humic acid solid in the step one (4) to the ammonia water is (20 mg-100 mg) 20mL;
2. biochar/Fe 2+ /Fe 3+ Mixing the mixed solution of (2) with an artificial humic acid solution, and stirring to obtain a mixture; placing the mixture into an autoclave with the temperature of 100-200 ℃ for 10-24 hours, and cooling to room temperature to obtain a solid product;washing the solid product to be neutral by using deionized water, and finally dispersing the solid product by using deionized water to obtain artificial humic acid functionalized colloid-like magnetic biochar;
biochar/Fe as described in step two 2+ /Fe 3+ The volume ratio of the mixed solution of (2) and the artificial humic acid solution is 3:1;
the concentration of the artificial humic acid functionalized colloid-like magnetic biochar in the second step is 15 g/L-20 g/L.
The principle and the advantages of the embodiment are that:
1. according to the embodiment, the biochar skeleton and the artificial humic acid are prepared from biomass, the loading of the magnetic iron oxide on the biochar and the activation of the functional group of the humic acid are realized by a one-step hydrothermal method of the biochar, the simple preparation of the material is realized, and the magnetic biochar colloid iron oxide prepared by the embodiment is uniformly distributed on the surface of the biochar through SEM result analysis, so that the aggregation of the magnetic iron oxide on the surface of the biochar and the current situation of blocking of biochar holes are relieved;
2. the artificial humic acid is used as a functional group activator to improve the dispersibility of the iron oxide on the surface of the biochar, the magnetic biochar is uniformly dispersed in water by combining the artificial humic acid and the iron oxide through the interaction between the functional groups, and the magnetic biochar can be kept in a better dispersion state in water after being placed for 20 days, so that a state similar to colloid is formed;
3. the concentration of the artificial humic acid functionalized colloid-like magnetic biochar is measured and prepared by a weighing method, the quantitative measurement is directly used for sewage treatment, the energy loss caused in the drying process of the artificial humic acid functionalized colloid-like magnetic biochar and the performance of removing heavy metal ions in sewage are reduced, the maximum capacity of the artificial humic acid functionalized colloid-like magnetic biochar prepared by the embodiment for removing Cd ions in sewage is 169.68mg/g, and the maximum capacity of the artificial humic acid functionalized colloid-like magnetic biochar is 70.61mg/g far greater than that of the dried artificial humic acid functionalized colloid-like magnetic biochar for removing Cd ions in sewage;
4. biomass materials (such as corn stalks) are used as agricultural wastes, and the cost of the synthetic materials is reduced due to the fact that the biomass materials are cheap and easy to obtain;
5. the method can simultaneously complete uniform loading of the magnetic iron oxide on the biochar skeleton and functionalization of the magnetic biochar by the artificial humic acid, so that more functional group binding sites are provided for heavy metal ions, and the heavy metal is conveniently removed and separated by using a permanent magnet;
6. the preparation method of the embodiment is simple and convenient, and the raw materials are cheap and easy to obtain, so that the method is suitable for mass synthesis and preparation; the artificial humic acid functionalized colloid-like magnetic biochar prepared by the embodiment is used for removing heavy metal ions in sewage.
The embodiment can obtain the artificial humic acid functionalized colloid-like magnetic biochar.
The second embodiment is as follows: the present embodiment differs from the specific embodiment in that: the biomass in the step one (1) is one or a mixture of more than one of corn straw, leaves, rice hulls, sawdust and bamboo poles; washing biomass for 3-5 times by using deionized water, drying at 50-80 ℃, cutting and crushing the dried biomass, washing the crushed biomass for 3-5 times by using distilled water, drying at 50-80 ℃, and finally sieving to obtain biomass powder; the particle size of the biomass powder is 40-100 meshes. The other steps are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the pore-forming activator in the step one (2) is KHCO 3 KOH, naOH or ZnCl 2 . The other steps are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: one difference between this embodiment and the first to third embodiments is that: the inert gas in the first step (2) is nitrogen or argon. The other steps are the same as those of the first to third embodiments.
Fifth embodiment: one to four differences between the present embodiment and the specific embodiment are: in the first step (2), the temperature rising rate of the tube furnace is 5-15 ℃ per minute when the tube furnace is heated to 700-900 ℃ from room temperature under the protection of inert gas. Other steps are the same as those of the first to fourth embodiments.
Specific embodiment six: the present embodiment differs from the first to fifth embodiments in that: the pyrolysis time in the step one (2) is 1 to 2 hours; the concentration of the hydrochloric acid in the step one (2) is 0.5mol/L to 1.0mol/L. Other steps are the same as those of the first to fifth embodiments.
Seventh embodiment: one difference between the present embodiment and the first to sixth embodiments is that: the concentration of the hydrochloric acid in the step one (3) is 1 mol/L-4 mol/L; the speed of the centrifugation in the step one (3) is 4000r/s to 10000r/s. Other steps are the same as those of embodiments one to six.
Eighth embodiment: one difference between the present embodiment and the first to seventh embodiments is that: the ultrasonic time in the step one (4) is 10-15 min, and the ultrasonic power is 800-1200W; the mass fraction of the ammonia water in the step one (4) is 6%. The other steps are the same as those of embodiments one to seven.
Detailed description nine: one of the differences between this embodiment and the first to eighth embodiments is: the ferrous salt in the step one (4) is FeSO 4 、Fe(NO 3 ) 2 Or FeCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The ferric salt in the step one (4) is Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Or FeCl 3 The method comprises the steps of carrying out a first treatment on the surface of the The stirring speed in the second step is 500-1000 r/min, and the stirring time is 15-30 min. Other steps are the same as those of embodiments one to eight.
Detailed description ten: the embodiment is a colloid-like magnetic biochar functionalized by artificial humic acid, which is used for removing heavy metal ions in sewage.
The present invention will be described in detail with reference to the accompanying drawings and examples.
Embodiment one: the preparation method of the artificial humic acid functionalized colloid-like magnetic biochar is specifically completed according to the following steps:
1. preparing a mixture composite material:
(1) washing corn stalks for 4 times by using deionized water, drying at 60 ℃, cutting and crushing the dried biomass, washing the crushed biomass for 4 times by using distilled water, drying at 60 ℃, and finally sieving to obtain biomass powder; the particle size of the biomass powder is 100 meshes;
(2) taking a certain amount of biomass powder and KHCO 3 Uniformly mixing to obtain a mixture; putting the mixture into a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 800 ℃ under the protection of the argon, and pyrolyzing the tubular furnace for 2 hours under the protection of the argon atmosphere at 800 ℃ to obtain a reaction product; washing the reaction product with 1mol/L hydrochloric acid to remove KHCO 3 Finally, washing the reaction product to be neutral by using deionized water to obtain biochar;
biomass powder and KHCO as described in step one (2) 3 The mass ratio of (2) is 1:1;
in the first step (2), the temperature rising rate of the tube furnace is 5 ℃/min when the tube furnace is heated to 800 ℃ from room temperature under the protection of inert gas;
(3) uniformly mixing a certain amount of biomass powder with KOH particles and ultrapure water to obtain a mixed solution; placing the mixed solution into an autoclave, then carrying out continuous hydrothermal humification reaction for 24 hours in the autoclave at the temperature of 200 ℃, cooling to room temperature, filtering, and removing solids to obtain a liquid reaction product; adjusting the pH value of the liquid reaction product to 1 by using hydrochloric acid with the concentration of 2mol/L, centrifuging at the centrifuging speed of 6000r/s, and removing the upper layer of centrifugate to obtain a solid substance; washing the solid matters to be neutral by using distilled water to obtain artificial humic acid solid;
the mass ratio of the biomass powder to the KOH particles in the step one (3) is 24g to 4.8g;
the volume ratio of the mass of the biomass powder in the step one (3) to the ultrapure water is 24g to 220mL;
(4) immersing biochar into Fe 2+ And Fe (Fe) 3+ In the mixed solution of (2) to obtain the biochar/Fe 2+ /Fe 3+ Is a mixed solution of (a) and (b); dissolving artificial humic acid solids into ammonia water with the mass fraction of 6%, and then performing ultrasonic dispersion to obtain an artificial humic acid solution;
the ultrasonic time in the step one (4) is 15min, and the ultrasonic power is 1200W;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ Is FeSO 4 、Fe 2 (SO 4 ) 3 And deionized mixed solution, wherein Fe 2+ And Fe (Fe) 3+ The mass ratio of (2) is 1:1;
the biochar and Fe in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ And Fe (Fe) 3+ The ratio of the total mass is 2:1;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ Is 2.083g/L;
the volume ratio of the mass of the artificial humic acid solid in the step one (4) to the ammonia water is 20 mg/20 mL;
2. biochar/Fe 2+ /Fe 3+ Mixing the mixed solution of (2) with an artificial humic acid solution, and stirring to obtain a mixture; placing the mixture into an autoclave with the temperature of 120 ℃ for 20 hours, and cooling to room temperature to obtain a solid product; and (3) cleaning the solid product to be neutral by using deionized water, and finally dispersing the solid product by using deionized water to obtain the artificial humic acid functionalized colloid-like magnetic biochar.
The stirring speed in the second step is 800r/min, and the stirring time is 30min;
biochar/Fe as described in step two 2+ /Fe 3+ The volume ratio of the mixed solution of (2) and the artificial humic acid solution is 60mL:20mL;
the concentration of the artificial humic acid functionalized colloid-like magnetic biochar in the second step is 15.733g/L.
FIG. 1 is a scanning electron microscope photograph of an artificial humic acid functionalized colloid-like magnetic biochar prepared in example I;
as can be seen from FIG. 1, the addition of artificial humic acid results in uniform dispersion of granular magnetic iron oxide on the biochar skeleton, thereby reducing agglomeration of magnetic iron oxide on the biochar surface.
FIG. 2 is an XRD spectrum of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example I;
the XRD spectrum of fig. 2 shows that the crystal structure corresponds to Fe at 2θ=30.10° (2 2 0), 35.42 ° (3 1), 43.05 ° (4 0), 53.39 ° (4 2), 56.94 ° (5 1) and 62.51 ° (4 4 0) for the artificial humic acid functionalized colloid-like magnetic biochar 3 O 4 (JCPDS No. 19-0629), corresponding to γfe at 2θ=30.24° (2 2 0), 35.63 ° (3 1), 43.28 ° (4 0), 53.73 ° (4 2), 57.27 ° (5 1) and 62.92 ° (4 4 0) 2 O 3 (JCPDS No. 39-1346) shows that the artificial humic acid can be beneficial to Fe 2+ And Fe (Fe) 3+ Forming magnetic iron oxide with good crystal form.
Fig. 3 is a dispersion performance test and a magnetic test chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one, wherein a is a photo chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one, b is a photo chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one after being left for 20 days, c is a photo chart of the artificial humic acid functionalized colloidal-like magnetic biochar prepared in example one after being separated by a magnet for 30 minutes.
From fig. 3, it is understood that the addition of artificial humic acid can make the magnetic biochar have more excellent dispersibility in water to form a magnetic biochar similar to a colloid.
The artificial humic acid functionalized colloid-like magnetic biochar prepared in the embodiment I is directly used for Cd in sewage 2+ The maximum removal capacity of the artificial humic acid is (169.68 (Cd) mg/g), the artificial humic acid functionalized colloid-like magnetic biochar prepared in the first embodiment is dried to obtain the dried artificial humic acid functionalized colloid-like magnetic biochar prepared in the first embodiment, and the dried artificial humic acid functionalized colloid-like magnetic biochar is used for Cd in sewage 2+ The result shows that the dried magnetic biochar solid is used for Cd in sewage 2+ Maximum capacity (70.61 (Cd) mg/g) removed.
According to IUPAC Classification, example one prepared ArtificialThe humic acid functionalized colloid-like magnetic biochar can lead the granular magnetic iron oxide to be uniformly dispersed on the biochar skeleton after the artificial humic acid is added, reduce the agglomeration condition of the magnetic iron oxide on the surface of the biochar, and be beneficial to Fe after the artificial humic acid is added 2+ And Fe (Fe) 3+ The magnetic iron oxide with good crystal form is formed and the magnetic biochar can have more excellent dispersibility in water to form the magnetic biochar similar to colloid. Clearly, the excellent dispersibility provides the magnetic biochar with a richer active site for heavy metal adsorption and a more colored adsorption capacity (169.68 (Cd) mg/g).

Claims (10)

1. The preparation method of the artificial humic acid functionalized colloid-like magnetic biochar is characterized by comprising the following steps of:
1. preparing a mixture composite material:
(1) washing biomass with deionized water, drying, cutting and crushing the dried biomass, washing the crushed biomass with distilled water, drying, and sieving to obtain biomass powder;
(2) uniformly mixing a certain amount of biomass powder with a pore-forming activator to obtain a mixture; placing the mixture into a tubular furnace, introducing inert atmosphere into the tubular furnace, heating the tubular furnace to 700-900 ℃ under the protection of the inert atmosphere, and pyrolyzing the tubular furnace under the protection of the inert atmosphere at 700-900 ℃ to obtain a reaction product; cleaning a reaction product by using hydrochloric acid, removing a pore-forming activator, and finally cleaning the reaction product to be neutral by using deionized water to obtain biochar;
the mass ratio of the biomass powder to the pore-forming activator in the step one (2) is 1:1;
(3) uniformly mixing a certain amount of biomass powder with KOH particles and ultrapure water to obtain a mixed solution; placing the mixed solution into an autoclave, then carrying out continuous hydrothermal humification reaction for 20-24 h in the autoclave with the temperature of 200-240 ℃, cooling to room temperature, filtering, and removing solids to obtain a liquid reaction product; adjusting the pH value of the liquid reaction product to 1 by using hydrochloric acid, centrifuging, and removing upper layer centrifugate to obtain a solid substance; washing the solid matters to be neutral by using distilled water to obtain artificial humic acid solid;
the mass ratio of the biomass powder to the KOH particles in the step (3) is (20 g-30 g) (3 g-5 g);
the volume ratio of the mass of the biomass powder to the ultrapure water in the first step (3) is (20 g-30 g) (180 mL-280 mL);
(4) immersing biochar into Fe 2+ And Fe (Fe) 3+ In the mixed solution of (2) to obtain the biochar/Fe 2+ /Fe 3+ Is a mixed solution of (a) and (b); dissolving artificial humic acid solids into ammonia water, and then performing ultrasonic dispersion to obtain an artificial humic acid solution;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ The mixed solution of ferrous salt, ferric salt and deionized water, wherein Fe 2+ And Fe (Fe) 3+ The mass ratio of (2) is 1:1;
the ferrous salt in the step one (4) is FeSO 4 、Fe(NO 3 ) 2 Or FeCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The ferric salt in the step one (4) is Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Or FeCl 3 ；
The biochar and Fe in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ And Fe (Fe) 3+ The ratio of the total mass is 2:1;
fe as described in the step one (4) 2+ And Fe (Fe) 3+ Fe in the mixed solution of (2) 2+ The concentration of (2.0 g/L) - (3.0 g/L);
the volume ratio of the mass of the artificial humic acid solid in the step one (4) to the ammonia water is (20 mg-100 mg) 20mL;
2. biochar/Fe 2+ /Fe 3+ Mixing the mixed solution of (2) with an artificial humic acid solution, and stirring to obtain a mixture; placing the mixture into an autoclave with the temperature of 100-200 ℃ for 10-24 hours, and cooling to room temperature to obtain a solid product; washing the solid product to be neutral by using deionized water, and finally dispersing the solid product by using deionized water to obtain artificial humic acid workAn functionalized colloid-like magnetic biochar;
biochar/Fe as described in step two 2+ /Fe 3+ The volume ratio of the mixed solution of (2) and the artificial humic acid solution is 3:1;
the concentration of the artificial humic acid functionalized colloid-like magnetic biochar in the second step is 15 g/L-20 g/L.
2. The method for preparing artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the biomass in the step one (1) is one or a mixture of several of corn stalks, leaves, rice hulls, sawdust and bamboo poles; washing biomass 3-5 times by using deionized water, drying at 50-80 ℃, cutting and crushing the dried biomass, washing the crushed biomass 3-5 times by using distilled water, drying at 50-80 ℃, and finally sieving to obtain biomass powder; the particle size of the biomass powder is 40-100 meshes.
3. The method for preparing artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the pore-forming activator in the step one (2) is KHCO 3 KOH, naOH or ZnCl 2 。
4. The method for preparing artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the inert atmosphere in the step one (2) is nitrogen or argon.
5. The preparation method of the artificial humic acid functionalized colloid-like magnetic biochar, which is characterized in that in the step one (2), the temperature rising rate of the tubular furnace is 5-15 ℃ per minute when the temperature of the tubular furnace is raised from room temperature to 700-900 ℃ under the protection of inert atmosphere.
6. The method for preparing artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the pyrolysis time in the step one (2) is 1-2 h; the concentration of the hydrochloric acid in the step one (2) is 0.5 mol/L-1.0 mol/L.
7. The method for preparing the artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the concentration of hydrochloric acid in the step one (3) is 1 mol/L-4 mol/L; the centrifugal speed in the step one (3) is 4000 r/s-10000 r/s.
8. The method for preparing artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the ultrasonic time in the step one (4) is 10-15 min, and the ultrasonic power is 800-1200W; the mass fraction of the ammonia water in the step one (4) is 6%.
9. The method for preparing the artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the stirring speed in the second step is 500-1000 r/min, and the stirring time is 15-30 min.
10. The method for preparing the artificial humic acid functionalized colloid-like magnetic biochar according to claim 1, wherein the artificial humic acid functionalized colloid-like magnetic biochar is used for removing heavy metal ions in sewage; artificial humic acid functionalized colloid-like magnetic biochar directly used for Cd in sewage 2+ The removal maximum capacity of (2) was 169.68mg/g.
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