CN114073939A - Three-dimensional biochar carrier based on enzymatic hydrolysis method and preparation method thereof - Google Patents
Three-dimensional biochar carrier based on enzymatic hydrolysis method and preparation method thereof Download PDFInfo
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- 238000006047 enzymatic hydrolysis reaction Methods 0.000 title claims abstract description 33
- 230000007071 enzymatic hydrolysis Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 108010059892 Cellulase Proteins 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940106157 cellulase Drugs 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- XTUROJFGMGASDK-UHFFFAOYSA-N dodecyl acetate;sodium Chemical compound [Na].CCCCCCCCCCCCOC(C)=O XTUROJFGMGASDK-UHFFFAOYSA-N 0.000 claims abstract description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 7
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 7
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000007853 buffer solution Substances 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims description 27
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical class [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 239000003610 charcoal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 239000000017 hydrogel Substances 0.000 claims description 5
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- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 3
- 238000004132 cross linking Methods 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910001437 manganese ion Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract 1
- 238000004108 freeze drying Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
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- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
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- 238000009792 diffusion process Methods 0.000 description 1
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002699 waste material Substances 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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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
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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
- B01J20/28014—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 form
- B01J20/28047—Gels
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
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- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to the technical field of materials, and discloses a three-dimensional biochar carrier based on an enzymatic hydrolysis method and a preparation method thereof. The method comprises the following steps: 1) drying, crushing and sieving fruit tree chips, adding a mixed solution of potassium permanganate, iron powder and dilute sulfuric acid for impregnation modification, filtering the obtained raw materials to be colorless and neutral, and then drying and calcining to obtain modified biochar; 2) taking a proper amount of modified biochar, microcrystalline cellulose, acrylamide, N-methylene bisacrylamide and deionized water, and carrying out ball milling and mixing; 3) adding sodium dodecyl acetate, tetramethylethylenediamine and sodium persulfate into the obtained slurry while stirring, and injecting the slurry into a mold after foaming; 4) placing the obtained three-dimensional biochar carrier in deionized water, adding a cellulase buffer solution and a cellulase solution, oscillating in a constant-temperature water bath, and taking out; 5) and repeatedly cleaning the three-dimensional biochar carrier subjected to enzymatic hydrolysis by using alcohol and water, and freeze-drying to obtain the three-dimensional biochar carrier based on the enzymatic hydrolysis method.
Description
Technical Field
The invention relates to the technical field of biochar materials, in particular to a three-dimensional biochar carrier based on an enzymatic hydrolysis method and a preparation method thereof.
Background
The problem of heavy metal pollution is always an environmental problem concerned by the public due to the random disposal of heavy metal wastewater. Adsorption is considered to be the most effective technology for removing heavy metals in wastewater, and the low separation efficiency of the nano adsorbent can cause the increase of operation cost and potential threat to the natural environment, thereby greatly limiting the practical application of the nano adsorbent. The low cost and large adsorption capacity of the adsorbent is in short supply in the actual adsorption process.
Polymer hydrogels are typically soft solid materials with a three-dimensional network structure, with high water permeability. Conventional hydrogels are often too fragile to be widely used. Recently, double-network hydrogels have been developed for high-strength mechanical fields, and their high permeability completely exposes their internal adsorption sites to metal ions. The double-net type biochar/acrylamide gel as a three-dimensional biochar carrier has good mechanical strength and can be repeatedly used.
Disclosure of Invention
The invention aims to provide a three-dimensional biochar carrier based on an enzymatic hydrolysis method and a preparation method thereof, the preparation method is simple, and the material acquisition approach is wide; the recycling of agricultural and forestry wastes is realized by using the biochar as an adsorbing material; the modification of the biochar improves the problems of low adsorption capacity and difficult solid-liquid separation of the original biochar directly used as an adsorption material.
The invention also aims to provide a three-dimensional biochar carrier based on an enzymatic hydrolysis method, which has large adsorption capacity and good adsorption effect and does not pollute the natural environment when adsorbing pollutants in high-concentration organic wastewater.
The specific technical scheme of the invention is as follows: the three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof comprise the following steps: 1. cleaning crushed fruit tree scraps with deionized water, putting the cleaned fruit tree scraps into a drying oven at 105 ℃ for drying for 12 hours, taking the fruit tree scraps out, crushing the fruit tree scraps by a crusher, sieving the crushed fruit tree scraps by a sieve with 100 meshes, mixing a proper amount of fruit tree powder with a potassium permanganate solution (0.1 mol/L), iron powder and dilute sulfuric acid (0.4 mol/L) in a 2L beaker for carrying out impregnation modification, filtering the mixture to obtain an impregnated and modified iron-manganese modified charcoal raw material, and adjusting the impregnated and modified iron-manganese modified charcoal raw material to be colorless and neutral by using a NaOH solution; the obtained ferro-manganese modified biocharThe raw materials are put into a 105 ℃ oven to be dried for 12h, taken out and put into a quartz boat, and the temperature rise rate is 5 ℃/min and N2Introducing into a tubular furnace with the speed of 100ml/min for calcination, keeping 30min at the calcination temperature of 400-500 ℃, and cooling the taken-out iron-manganese modified biochar to the room temperature in a dryer.
2. And (3) mixing the cooled ferro-manganese modified biochar, microcrystalline cellulose, acrylamide, N-methylene bisacrylamide and deionized water according to the mass ratio of (10-15): (0.05-0.15): (1-3): (0.2-0.5): and 20, placing the mixture into a ball milling tank, and grinding the mixture for 2-3 hours by using a ball mill to obtain mixed slurry.
3. And (2) taking 20-40 g of the obtained slurry, carrying out rapid magnetic stirring, sequentially adding 0.05-0.1 g of sodium dodecyl acetate, 1-2 ml of tetramethylethylenediamine and 5-10 ml of sodium persulfate solution (10-15 wt%) in the stirring process, and injecting the obtained foamed slurry into a mold.
4. And placing the obtained three-dimensional biochar carrier in a beaker containing deionized water, adding 12.5-15 ml of cellulase buffer solution and 0.0125-0.02625 g of cellulase, oscillating in a thermostatic water bath at 50 ℃ for 2h, and taking out.
5. Repeatedly cleaning the three-dimensional biochar carrier subjected to enzymatic hydrolysis by using alcohol and water, placing the washed three-dimensional biochar carrier in a freezer at the temperature of-20 ℃ for 12 hours, taking out the three-dimensional biochar carrier after freezing, placing the three-dimensional biochar carrier in a vacuum freeze dryer, and drying until the moisture is completely lost to obtain the three-dimensional biochar carrier based on the enzymatic hydrolysis method.
The three-dimensional biochar carrier based on the enzymatic hydrolysis method is prepared by the preparation method of the three-dimensional biochar carrier based on the enzymatic hydrolysis method.
Has the advantages that: 1. according to the invention, a three-dimensional biochar carrier based on an enzymatic hydrolysis method is prepared by using biochar obtained by modifying and calcining fruit tree powder as a raw material, acrylamide as a monomer, N, N-methylene bisacrylamide as a cross-linking agent, sodium dodecyl acetate as a foaming agent, tetramethylethylenediamine as a catalyst and sodium persulfate as an initiator, and is used for adsorbing pollutants of high-concentration organic wastewater.
2. Compared with the method of directly using the primary biochar as the adsorbing material, the adsorbing material prepared by the invention is convenient to transport, has certain mechanical strength, is convenient to stack, and avoids dust pollution.
3. According to the invention, the biochar is modified, so that the problems of low adsorption capacity and difficult solid-liquid separation of the original biochar as an adsorption material are solved, and meanwhile, heavy metal adsorption active sites are introduced, so that a large number of active centers are provided for pollutant adsorption, and the adsorption effect on heavy metals is effectively improved.
4. In the invention, sodium lauryl acetate is an anionic surfactant, can dissociate anions with surface activity in water, and can greatly improve the adsorption effect and the diffusion of heavy metal cations in the material in the process of adsorbing heavy metals by the adsorption material.
5. In the invention, in the process of continuous magnetic stirring, the time interval of adding the reagent every time is at least 40min, so that the medicine is fully reacted in the solution. After the initiator is added, the foamed slurry is poured into a mold prepared in advance, and the slurry starts to gel.
6. In the invention, the obtained three-dimensional biochar carrier is placed in the cellulase liquid, so that cellulose in the adsorbing material is subjected to an enzymatic hydrolysis reaction, the pore density in the gel can be increased, the appearance of the adsorbing material is improved, and the adsorbing performance of the adsorbing material is greatly improved.
Drawings
FIG. 1 is a flow chart of the preparation of the three-dimensional biochar carrier based on the enzymatic hydrolysis method of the present invention.
FIG. 2 is a graph showing adsorption isotherms of Cd (II) on modified biochar and a three-dimensional biochar carrier based on an enzymatic hydrolysis method as described in example 1 of the present invention.
Detailed Description
The three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof of the present invention are described below by specific embodiments. The following description is only a preferred embodiment of the present invention, and the specific implementation method is illustrative and not intended to limit the scope of the present invention, which is defined by the claims.
Example 1: a three-dimensional biochar carrier based on an enzymatic hydrolysis method and a preparation method thereof are carried out according to the following steps.
1) Cleaning crushed fruit tree scraps with deionized water, putting the cleaned fruit tree scraps into a drying oven at 105 ℃ for drying for 12 hours, taking the fruit tree scraps out, crushing the fruit tree scraps by a crusher, sieving the crushed fruit tree scraps by a sieve with 100 meshes, mixing a proper amount of fruit tree powder with a potassium permanganate solution (0.1 mol/L), iron powder and dilute sulfuric acid (0.4 mol/L) in a 2L beaker for carrying out impregnation modification, filtering the mixture to obtain an impregnated and modified iron-manganese biochar raw material, and adjusting the impregnated and modified iron-manganese biochar raw material to be colorless and neutral by using a NaOH solution; putting the obtained iron-manganese modified biochar raw material into a 105 ℃ oven to be dried for 12h, taking out the biochar raw material, putting the biochar raw material into a quartz boat, and heating at the temperature rise rate of 5 ℃/min and N2Calcining in a tubular furnace at the rate of 100ml/min, keeping the calcining temperature at 450 ℃ for 30min, and cooling the taken-out iron-manganese modified biochar to room temperature in a dryer.
2) Putting the obtained manganese-iron modified biochar, microcrystalline cellulose, acrylamide, N-methylene bisacrylamide and deionized water into a ball milling tank according to the mass ratio of 13:0.05:1:0.2:20, and grinding for 2.5 hours by using a ball mill to obtain mixed slurry.
3) Taking 20g of the obtained slurry, carrying out rapid magnetic stirring, and sequentially adding 0.07g of sodium dodecyl acetate, 1.5ml of tetramethylethylenediamine and 7ml of sodium persulfate solution (10 wt%) in the stirring process to obtain foamed slurry, and injecting the foamed slurry into a mold; .
4) And placing the obtained three-dimensional biochar carrier in a beaker containing deionized water, adding 12.5ml of cellulase buffer solution and 0.0125g of cellulase, oscillating in a thermostatic water bath at 50 ℃ for 2h, and taking out.
5) Repeatedly cleaning the three-dimensional biochar carrier subjected to enzyme hydrolysis with alcohol and water, placing the cleaned three-dimensional biochar carrier in a freezer at the temperature of-20 ℃ for 12 hours, taking out the washed three-dimensional biochar carrier after freezing, placing the washed three-dimensional biochar carrier in a vacuum freeze dryer, and drying the three-dimensional biochar carrier until the water is completely lost.
Example 2: this example is the same as example 1 except that in step 2), the mass ratio of the ferrimanganic modified biochar, microcrystalline cellulose, acrylamide, N-methylenebisacrylamide and deionized water was 10:0.15:1:0.2:20, and the obtained adsorbent had lower mechanical strength than that of example 1.
Example 3: in this example, the same as example 1, except that in step 2), the mass ratio of the ferrimanganic modified biochar, microcrystalline cellulose, acrylamide, N-methylenebisacrylamide and deionized water was 15:0.15:1:0.2:20, the obtained adsorbent had higher mechanical strength than that of example 1.
Comparative example 1: the three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof are carried out according to the following steps.
1) Cleaning crushed fruit tree scraps with deionized water, putting the cleaned fruit tree scraps into a drying oven at 105 ℃ for drying for 12 hours, taking the fruit tree scraps out, crushing the fruit tree scraps by a crusher, sieving the crushed fruit tree scraps by a sieve with 100 meshes, mixing a proper amount of fruit tree powder with a potassium permanganate solution (0.1 mol/L), iron powder and dilute sulfuric acid (0.4 mol/L) in a 2L beaker for carrying out impregnation modification, filtering the mixture to obtain an impregnated and modified iron-manganese biochar raw material, and adjusting the impregnated and modified iron-manganese biochar raw material to be colorless and neutral by using a NaOH solution; putting the obtained iron-manganese modified biochar raw material into a 105 ℃ oven to be dried for 12h, taking out the biochar raw material, putting the biochar raw material into a quartz boat, and heating at the temperature rise rate of 5 ℃/min and N2Calcining in a tubular furnace at the rate of 100ml/min, staying at the calcining temperature of 450 ℃ for 30min, and cooling the extracted iron-manganese modified biochar to room temperature in a dryer.
2) The mass ratio of the obtained manganese iron modified biochar to acrylamide to N, N-methylene bisacrylamide to deionized water is 13: 0.15: placing the mixture in a ball milling tank at a ratio of 1:0.2:20, and grinding the mixture for 2.5 hours by using a ball mill to obtain mixed slurry.
3) 20g of the obtained slurry is taken for rapid magnetic stirring, 0.07g of sodium dodecyl acetate, 1.5ml of tetramethylethylenediamine and 7ml of sodium persulfate solution (10 wt%) are sequentially added in the stirring process, and the obtained foamed slurry is injected into a mold.
4) And placing the obtained three-dimensional biochar carrier in deionized water, adding 15ml of cellulase buffer solution and 0.02625g of cellulase, oscillating in a thermostatic water bath at 50 ℃ for 2h, and taking out.
5) Repeatedly cleaning the three-dimensional biochar carrier subjected to enzyme hydrolysis with alcohol and water, placing the cleaned three-dimensional biochar carrier in a freezer at the temperature of-20 ℃ for 12 hours, taking out the washed three-dimensional biochar carrier after freezing, placing the washed three-dimensional biochar carrier in a vacuum freeze dryer, and drying the three-dimensional biochar carrier until the water is completely lost.
Adsorption experiment conditions are as follows: the isothermal adsorption experiment of Cd (II) was carried out on the modified biochar and the three-dimensional biochar carrier prepared in example 1 based on the enzymatic hydrolysis method, and the specific operation steps are as follows.
Into 8 Erlenmeyer flasks were added 8 parts of 30mL of an aqueous solution having a Cd (II) ion concentration of 20mg/L, respectively. 2 parts of 0.01g of the three-dimensional charcoal carrier prepared in examples 1 to 2 and comparative example 1, which was based on the enzymatic hydrolysis method, were weighed into each part of the aqueous solution, and then put into a constant temperature shaking chamber at a rotation speed of 200rpm and a temperature of 25 ℃ for shaking for 72 hours. 5mL of the aqueous solution was taken out of one of the portions at different time periods (15 minutes, 30 minutes, 1 hour, 2 hours, 4 hours), respectively. The obtained sample was subjected to Cd (II) concentration measurement using ICP-OES, and the unit adsorption amount of the material was calculated.
In summary, the isothermal adsorption experiments of the modified biochar and the three-dimensional biochar carrier prepared in example 1 on cd (ii) based on the enzymatic hydrolysis method all conform to the Freundlich model, so that the adsorption processes of the modified biochar and the three-dimensional biochar carrier on cd (ii) are similar to the multi-molecular-layer adsorption process. Compared with modified charcoal, the maximum adsorption capacity of the three-dimensional charcoal carrier based on the enzymatic hydrolysis method to Cd (II) is about 10 times that of the three-dimensional charcoal carrier, and the adsorption capacity is obviously improved.
Claims (6)
1. The three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof are characterized in that: the method comprises the following steps: 1) cleaning crushed fruit tree scraps with deionized water, putting the cleaned fruit tree scraps into a drying oven at 105 ℃ for drying for 12 hours, taking the fruit tree scraps out, crushing the fruit tree scraps by a crusher, sieving the crushed fruit tree scraps by a sieve with 100 meshes, mixing a proper amount of fruit tree powder with a potassium permanganate solution (0.1 mol/L), iron powder and dilute sulfuric acid (0.4 mol/L) in a 2L beaker for carrying out impregnation modification, filtering the mixture to obtain an impregnated and modified iron-manganese modified charcoal raw material, and adjusting the impregnated and modified iron-manganese modified charcoal raw material to be colorless and neutral by using a NaOH solution; putting the obtained iron-manganese modified biochar raw material into a 105 ℃ oven to be dried for 12h, taking out the biochar raw material, putting the biochar raw material into a quartz boat, and heating at the temperature rise rate of 5 ℃/min and N2Introducing into a tubular furnace with the speed of 100ml/min for calcination, keeping 30min at the calcination temperature of 400-500 ℃, and cooling the taken-out iron-manganese modified biochar to room temperature in a dryer; 2) and (3) mixing the cooled ferro-manganese modified biochar, microcrystalline cellulose, acrylamide, N-methylene bisacrylamide and deionized water according to the mass ratio of (10-15): (0.05-0.15): (1-3): (0.2-0.5): 20 is placed in a ball milling pot to ensure thatGrinding for 2-3 h by using a ball mill to obtain mixed slurry; 3) taking 20-40 g of the obtained slurry, carrying out rapid magnetic stirring, sequentially adding 0.05-0.1 g of sodium dodecyl acetate, 1-2 ml of tetramethylethylenediamine and 5-10 ml of sodium persulfate solution (10-15 wt%) in the stirring process, and injecting the obtained foamed slurry into a mold; 4) placing the obtained three-dimensional biochar carrier in a beaker containing deionized water, adding 12.5-15 ml of cellulase buffer solution and 0.0125-0.02625 g of cellulase, oscillating in a thermostatic water bath at 50 ℃ for 2h, and taking out; 5) repeatedly cleaning the three-dimensional biochar carrier subjected to enzymatic hydrolysis by using alcohol and water, placing the washed three-dimensional biochar carrier in a freezer at the temperature of-20 ℃ for 12 hours, taking out the three-dimensional biochar carrier after freezing, placing the three-dimensional biochar carrier in a vacuum freeze dryer, and drying until the moisture is completely lost to obtain the three-dimensional biochar carrier based on the enzymatic hydrolysis method.
2. The three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof according to claim 1, are characterized in that: in the step 1), the molar ratio of the potassium permanganate solution to the iron powder to the dilute sulfuric acid solution is 3:5:12, the particle size of the iron powder is 1-2 mm, and the potassium permanganate solution, the iron powder and the dilute sulfuric acid solution are added in sequence; 5-9 wt% of NaOH solution, and deionized water can also be used.
3. The three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof according to claim 1, are characterized in that: in the step 1), the fruit tree powder is subjected to iron and manganese ion attachment and calcined to obtain the iron and manganese modified biochar, so that heavy metal adsorption sites can be increased in the prepared three-dimensional biochar carrier, and the organic wastewater treatment capacity of the three-dimensional biochar carrier is improved.
4. The three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof according to claim 1, are characterized in that: in the step 3), sodium lauryl acetate is used as an anionic surfactant, and the anionic surfactant is added to improve the adsorption capacity of the adsorption material on heavy metal cations; the tetramethylethylenediamine is a catalyst for a crosslinking reaction, and the catalyst is added to improve the reaction rate; the sodium persulfate solution is an initiator of a crosslinking reaction and comprises a persulfate solution.
5. The three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof according to claim 1, are characterized in that: in the step 3), in the process of continuous magnetic stirring, the time interval of adding the reagent every time is at least 40min, and the rotating speed of the rapid magnetic stirring is 1200-2000 rpm.
6. The three-dimensional biochar carrier based on the enzymatic hydrolysis method and the preparation method thereof according to claim 1, are characterized in that: in the step 4), the volume of the cellulase buffer solution and the mass ratio of the cellulase to the cellulose are (500-600): (2-6): (0.6-1.25), the cellulase liquid is added to perform an enzymatic hydrolysis reaction with the microcrystalline cellulose mixed in the hydrogel so as to increase the porosity and the specific surface area inside the hydrogel.
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