CN113559858B - Preparation method and application of biochar-based composite material - Google Patents
Preparation method and application of biochar-based composite material Download PDFInfo
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- CN113559858B CN113559858B CN202110909806.2A CN202110909806A CN113559858B CN 113559858 B CN113559858 B CN 113559858B CN 202110909806 A CN202110909806 A CN 202110909806A CN 113559858 B CN113559858 B CN 113559858B
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010902 straw Substances 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000002028 Biomass Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 238000001354 calcination Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 150000003254 radicals Chemical class 0.000 abstract description 5
- 239000012298 atmosphere Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 239000010949 copper Substances 0.000 description 27
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000002386 leaching Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 206010019851 Hepatotoxicity Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007686 hepatotoxicity Effects 0.000 description 1
- 231100000304 hepatotoxicity Toxicity 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- -1 sawdust Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B01J35/33—
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The application discloses a preparation method and application of a biochar-based composite material, which takes straw, sawdust and the like as raw materials for preparing biochar, grows hydrotalcite-like compounds (LDHs) in situ on the basis, and performs inert atmosphere calcination at high temperature to prepare the magnetic biochar-based composite material. The degradation experiment result of TBBPA shows that the biochar-based composite material can effectively activate PMS to generate free radical to degrade TBBPA, and the TBBPA removal effect can reach more than 90% within 60min, thus being an ideal material for preparing good catalysts.
Description
Technical Field
The application relates to the technical field of pollutant degradation, in particular to a preparation method and application of a biochar-based composite material.
Background
Tetrabromobisphenol a (TBBPA) is an important brominated flame retardant, and is the most widely used BFRs with the largest current use, and accounts for about 60% of the BFRs market. TBBPA is mainly used for synthesizing brominated epoxy resins and polycarbonate resins, which are raw materials for printed circuit boards. With the widespread use of TBBPA, these numbers may continue to grow in recent years and the environmental impact will continue to deepen.
TBBPA has high lipophilicity and durability, and researches show that the TBBPA has potential hepatotoxicity, cytotoxicity and immune toxicity, thereby causing serious harm to the environmental ecological system and even threatening the health of human bodies. Therefore, it is necessary and important to develop an efficient TBBPA treatment process.
Advanced oxidation technology (SR-AOPs) based on sulfate has become an indispensable technology for water purification. SO (SO) 4 ·- Generally, the persulfate is generated by activating the persulfate, so that the activation method of the persulfate is a hot spot of the current SR-AOPs technical research. Among these activation methods, the transition metal catalyst has a good effect of activating PMS, and the operation is simple. However, the application of the method is greatly limited by the problems of difficult leaching and recycling of harmful metal ions and the like.
Research shows that the catalyst carrier material with special structure and performance, such as carbon-based material, clay material, perovskite-like material, etc. can raise the activity and stability of catalyst effectively and inhibit the leaching of active components. As a large agricultural country, about 7 hundred million tons of crop straws are produced annually in China, the crop straws are cheap and easy to obtain, and the straws contain a large amount of carbon elements, so that the crop straws are excellent raw materials for preparing biochar economically and environmental protection. Biochar is widely applied to the field of chemical catalysis as a matrix material with excellent thermal stability and excellent chemical stability, has surface active groups with high specific surface area and strong controllability, and is a green catalyst carrier material. Because of the insufficient capability of degrading organic pollutants in the biochar material, researchers have carried out a great deal of modification work on the biochar material to improve the catalytic performance of the biochar material.
The present application has been made in view of this.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a preparation method of a biochar-based composite material, which is characterized in that biomass materials such as sawdust, straw, rice husk and the like are used for preparing biochar, hydrotalcite-like compounds (LDHs) are grown in situ on the basis, and the magnetic biochar-based composite material is prepared by calcining in an inert atmosphere at high temperature, so that the biochar-based composite material has good stability and magnetism, solves the problem of difficult ion leaching and recovery, and is beneficial to the efficient recycling of the composite material.
Another object of the application is the use of a biochar based composite to activate PMS to produce free radical degrading TBBPA.
In order to achieve the above purpose, the present application provides the following technical solutions: the application of the biochar-based composite material for activating PMS to degrade TBBPA comprises the following steps:
adding PMS and a biochar-based composite material into the TBBPA solution, and starting a reaction;
the PMS concentration is 0.1-5 mM, the TBBPA concentration is 5-50 mg/L, and the adding amount of the biochar-based composite material is 0.075-0.25 g/L;
the biochar-based composite material is an M/N hydrotalcite modified biochar-based composite material, wherein M is a divalent metal ion, N is a mixture of trivalent metal ions Fe and Al, the molar ratio of M/N is 2-4, and Fe 3+ And Al 3+ The molar ratio of (2) is 1/3-3.
The preparation method of the biochar-based composite material comprises the following specific steps:
s1: cleaning and drying biomass raw materials, crushing and grinding, and sieving to obtain biomass powder for later use; weighing the biomass powder after treatment, and adding the biomass powder into an alkaline solution to prepare a biochar mixed system;
s2: will contain divalent metal cations M 2+ And solution A containing trivalent metal cations N 3+ Dissolving the solution B in deionized water to prepare a mixed salt solution, and fully dissolving and complexing the mixed salt solution;
s3: dropwise adding the mixed salt solution prepared in the step S2 into an alkaline solution under the condition of continuous stirring, and performing aging treatment;
s4: carrying out suction filtration and washing on the mixed solution aged in the step S3, and then drying to obtain a hydrotalcite-like/biochar composite material;
s5: and (3) placing the hydrotalcite-like/biochar composite material obtained in the step (S4) in a tube furnace in a nitrogen atmosphere for high-temperature calcination to obtain the M/N hydrotalcite-modified biochar-based composite material.
Preferably, in the step S4, the mass fraction of the biochar is 5-30%, the concentration of acetic acid is 0.5-3%, and the stirring and dissolving time is more than 10 hours.
Preferably, in step S2, the divalent metal cation M 2+ Is Co 2+ 、Ni 2+ 、Mn 2+ 、Cu 2+ One or more than two of them.
Preferably, in the step S3, the pH value of the alkaline solution is controlled to be 8-12, and the aging time is more than 4 hours.
Preferably, the suction filtration and washing process in step S4 is specifically as follows: repeatedly washing the mixed solution with deionized water until the pH value of the filtrate is 6-7 under the condition of suction filtration, washing the filtrate with ethanol once when the filtrate is about to be dried, and pumping to obtain a precipitate; the obtained precipitate was placed in a vessel containing ethanol and vigorously stirred at room temperature, after 2 hours, suction filtration was performed and the filter cake was repeatedly washed with ethanol.
Preferably, the biomass raw material is one or more than two of sawdust, straw and rice hulls.
Preferably, the high temperature calcination temperature in step S5 is 300 ℃ to 700 ℃.
Preferably, the high temperature calcination temperature in step S6 is 500-700 ℃.
The beneficial effects of the application are as follows:
1. hydrotalcite-like compound grows on the biochar material in situ, and is calcined in an inert atmosphere at high temperature to prepare the magnetic biochar-based composite material. The hydrotalcite-like compound grows on the surface of the biochar carrier material with larger specific surface area in situ, under certain conditions, a composite material with certain morphological characteristics is generated on the surface of the biochar carrier through chemical health between the hydrotalcite-like compound and the biochar carrier material, compared with simple physical mixing, the method for growing in situ is generally uniform, the coverage and the dispersibility of surface particles are better, the hydrotalcite-like compound with a lamellar structure grows on the surface of the biochar through the method, the hydrotalcite-like compound has high dispersibility and catalytic activity, nano particles consisting of simple substances and other oxides formed after anaerobic high-temperature calcination have the advantages of small particles, high dispersity, strong catalytic activity and the like, and meanwhile, the biochar matrix generated by calcined straws improves the specific surface area and the stability of the catalyst.
2. The method takes hydrotalcite-like compound as a precursor, can be regulated and controlled, and the calcined catalyst contains simple substances and oxide nano particles with activity and magnetism, and the formed iron oxide enables the catalyst to have magnetism, so that the functional treatment on the biochar enhances the catalytic activity and magnetism of the whole catalyst, can be highly dispersed on an atomic level, exposes more active sites and generates more free radicals, and can have good degradation effect even under low dosage and low PMS concentration, thereby achieving the purpose of efficiently degrading TBBPA in water.
3. The catalyst of the application effectively activates PMS to generate SO 4 · - And OH, compared with the metal oxide component, the simple substance component generated in the catalyst has higher oxidation-reduction potential, can effectively promote electron transfer in the reaction, quicken the reaction rate of activating PMS and more quickly and effectively catalyze and degrade TBBPA.
Drawings
FIG. 1 Cu before and after calcination 2 Fe 0.5 Al 0.5 -an X-ray diffraction pattern of a biochar based composite;
FIG. 2.Cu 2 Fe 0.5 Al 0.5 -the degradability of the biochar-based composite material to TBBPA;
FIG. 3.M 2+ /M 3+ Molar ratio of (c) to Cu 2 Fe 0.5 Al 0.5 -the influence of biochar based composite properties;
FIG. 4 hydrotalcite-like compound/straw mass ratio Cu 2 Fe 0.5 Al 0.5 -biochar based composite activity effect;
FIG. 5 calcination temperature vs. Cu 2 Fe 0.5 Al 0.5 -the influence of biochar based composite properties;
FIG. 6 Cu 2 Fe 0.5 Al 0.5 The added amount of the biochar-based composite material influences the degradation effect of TBBPA;
FIG. 7 Cu 2 Fe 0.5 Al 0.5 -copper ion leaching pattern of biochar based composite material;
FIG. 8 Cu 2 Fe 0.5 Al 0.5 -a TEM image of a biochar based composite.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
Cu 2 Fe 0.5 Al 0.5 Preparation method of biochar-based composite material
S1: cleaning and drying 1g of straw, crushing and grinding, and sieving to obtain straw powder for later use; weighing the treated straw powder, and adding 1.33g of Na 2 CO 3 Uniformly mixing the mixture in 100mL of solution to prepare a biochar mixed system solution;
s2: 3.02g of Cu (NO) 3 ) 2 ·3H 2 O，1.26g Fe(NO 3 ) 3 ·9H 2 O and 1.17g Al (NO) 3 ) 3 ·9H 2 O is dissolved in 100mL of deionized water to prepare mixed salt solution, and the mixed solution is added into Na containing straw in the step S1 drop by drop 2 CO 3 In the solution, magnetic stirring is carried out all the time during the dropwise adding, meanwhile, 4mol/L NaOH solution is used for maintaining the pH value of the system to be 10, and the stirring is continued for 12 hours after the dropwise adding is finished;
s3: filtering the aged mixed solution in the step S3, washing with deionized water until the pH of the filtrate is neutral (measured by pH test paper), and washing with ethanol; placing the precipitate after suction filtration in a blast oven at 60 ℃ for overnight drying, and grinding into powder to obtain Cu 2 Fe 0.5 Al 0.5 Hydrotalcite-like/straw precursor with an X-ray diffraction spectrum as shown in figure 1.
S4: the prepared Cu 2 Fe 0.5 Al 0.5 Hydrotalcite-like compound/straw in a tube furnace at N 2 Calcining at 600 deg.C in atmosphereCalcining for 3 hours to obtain Cu 2 Fe 0.5 Al 0.5 Biochar-based composite material with an X-ray diffraction spectrum as shown in figure 1.
Comparative example 1
The straw biochar is prepared by adopting a high-temperature calcination method and is used as a control catalyst.
An application of a biochar-based composite material:
at room temperature (25 ℃) 130rpm in a glass bottle of an air bath shaking box;
200mL of the prepared TBBPA solution was taken, 200. Mu.L of PMS and 20mg of Cu prepared in example 1 were added to the solution 2 Fe 0.5 Al 0.5 -a biochar-based composite catalyst to initiate the reaction;
1mL of the sample was taken at a time interval and immediately quenched with 1mL of methanol, then filtered through a 0.22 μm filter to remove the catalyst, and assayed using a high performance liquid chromatograph.
The experimental conditions are as follows: the initial concentration of TBBPA is 15mg/L, the solid-liquid ratio is 0.1g/L, the pH is 8.5, and the PMS concentration is 0.1-2 mM.
The method for degrading TBBPA by using the straw biochar prepared in the comparative example is the same as that of example 1.
As shown in FIG. 2, the experimental results show that Cu was present in 60min 2 Fe 0.5 Al 0.5 The removal rate of TBBPA by the biochar-based composite catalyst can reach 90%, which shows Cu 2 Fe 0.5 Al 0.5 The biochar-based composite catalyst can activate PMS to oxidize and degrade TBBPA more efficiently. The straw biochar catalyst can only remove 30% of TBBPA, which shows Cu 2 Fe 0.5 Al 0.5 The biochar-based composite material can activate PMS to oxidize and degrade TBBPA more efficiently.
Example 2
Cu x Fe 0.5 Al 0.5 The biochar-based composite, method for activating PMS oxidation to remove TBBPA is identical to example 1, except that this example looks at M 2+ /N 3+ When the molar ratio x is 1-4, cu is prepared x Fe 0.5 Al 0.5 Living biological carbon base composite materialAnd (3) performance of degrading TBBPA by using PMS.
As a result of measurement, as shown in FIG. 3, when M 2+ /N 3+ When the molar ratio x is 1-4, different catalytic effects are shown in the process of activating PMS and oxidizing to remove TBBPA under the same experimental condition, and when x in the catalyst is 2, the removal efficiency of TBBPA can reach 90%, which indicates that the composite material has excellent thermal stability.
Example 3
Hydrotalcite-like compound/straw mass comparison Cu 2 Fe 0.5 Al 0.5 Biological carbon based composite Activity Effect
Hydrotalcite-like compounds (LDHs) are considered to be good precursors for the preparation of highly dispersible mixed metal oxides. According to the methods of example 1 and example 2, the application examines the influence of activated PMS of the prepared biochar-based composite material on the degradation performance of TBBPA when the mass fraction of added straws is 30% -80%.
As shown in FIG. 4, the measurement results show that Cu prepared by adding hydrotalcite-like compounds with different contents 2 Fe 0.5 Al 0.5 The biochar-based composite material shows different catalytic effects in the process of activating PMS to degrade TBBPA; when the mass fraction of the added straw in the composite material is 50%, the removal efficiency of TBBPA can reach 90%.
Example 4
Calcination temperature vs. Cu 2 Fe 0.5 Al 0.5 Biological carbon based composite Activity Effect
In the preparation process of the catalyst, the calcination temperature is a key factor for the formation of the active components of the catalyst, and indirectly affects the activity of the catalyst. The thermal stability of the catalyst can be reflected by examining the influence of the calcination temperature, which is a very important parameter for evaluating the recycling property of the catalyst in actual working conditions. According to the methods of example 1 and example 2, the application examines the performance of activated PMS degradation TBBPA of the biochar-based composite material prepared at the calcination temperature of 500-700 ℃.
As shown in FIG. 5, the measurement results indicate Cu prepared by different calcination temperatures 2 Fe 0.5 Al 0.5 Biochar-based composite materialThe activated PMS shows good degradation effect in the process of removing TBBPA; when the calcination temperature is 500-700 ℃, the removal efficiency of TBBPA can reach more than 88% under the same experimental condition, which shows that the composite material has excellent thermal stability.
Example 5
Cu 2 Fe 0.5 Al 0.5 Influence of added amount of biochar-based composite material on degradation effect of TBBPA
In water treatment applications, the amount of catalyst added is an important parameter affecting the purification effect. Under the same conditions, the higher the addition amount of the catalyst, the more serious the ion leaching problem in water. According to the methods of example 1 and example 2, the application examines the influence of activated PMS of the biochar-based composite material on the degradation performance of TBBPA when the adding amount of the composite material is 0.075-0.25 g/L.
As shown in FIG. 6, the experimental results indicate Cu 2 Fe 0.5 Al 0.5 The increase of the adding amount of the biochar-based composite material has remarkable promoting effect on the degradation of TBBPA, and the degradation effect is more than 87 percent; with the increase of the adding amount of the catalyst, more free radicals are generated in the reaction system, so that the interaction between the free radicals and TBBPA is further promoted, and the TBBPA is effectively degraded.
Relative to Cu 1 Fe 0.5 Al 0.5 The LDO catalyst is prepared by taking the straw as a raw material, and the hydrotalcite-like material grows in situ on the basis, so that waste is changed into valuable, the recycling is realized, and the preparation cost of the catalyst can be effectively reduced. Importantly, the composite material can further reduce leaching of metal ions while ensuring high activity of the catalyst. As shown in FIG. 7, after 3 times of cyclic use, the ion leaching of the composite material is only 0.36mg/L, which is far lower than Cu 1 Fe 0.5 Al 0.5 LDO (0.74 mg/L), shows higher stability, and avoids the problem of secondary pollution in the water pollution purification process. As shown in FIG. 8, the activated nano particles in the biochar-based composite material have high dispersion degree and uniform size, and are about 20-50 nm, which is also the catalytic activity of the biochar-based composite materialOne of the reasons for the higher sex.
To sum up, when M x Fe 0.5 Al 0.5 When x in the biochar-based composite material is 1-4, the prepared composite material has high degradation performance on TBBPA and good magnetism and stability.
The method grows hydrotalcite-like compound in situ on the biochar material, namely, the hydrotalcite-like compound in situ grows on the surface of the biochar carrier material with larger specific surface area, grows hydrotalcite-like compound with a flaky structure on the surface of the biochar, has high dispersibility and catalytic activity, and performs inert atmosphere calcination at high temperature to prepare the magnetic biochar-based composite material. The nano particles formed by simple substances and other oxides after oxygen-free high-temperature calcination have the advantages of small particles, high dispersity, strong catalytic activity and the like, and meanwhile, the biochar matrix generated by the calcined straws improves the specific surface area and the stability of the catalyst.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (5)
1. The application of the biochar-based composite material is characterized in that the biochar-based composite material is used for activating PMS to degrade TBBPA, and the specific degradation method is as follows:
adding PMS and a biochar-based composite material into the TBBPA solution, and starting a reaction;
the PMS concentration is 0.1-5 mM, the TBBPA concentration is 5-50 mg/L, and the addition amount of the biochar-based composite material is 0.075-0.25 g/L;
the biochar-based composite material is an M/N hydrotalcite modified biochar-based composite material, wherein M is bivalent metal ion Cu 2+ N is a trivalent metalIon Fe 3+ And Al 3+ In a molar ratio of M/N of 2 to 4, fe 3+ And Al 3+ The mol ratio of (3) is 1/3-3;
the preparation method of the biochar-based composite material comprises the following specific steps:
s1: cleaning and drying biomass raw materials, crushing and grinding, and sieving to obtain biomass powder for later use; weighing the biomass powder after treatment, and adding the biomass powder into an alkaline solution to prepare a biochar mixed system;
s2: will contain divalent metal cations M 2+ And solution A containing trivalent metal cations N 3+ Dissolving the solution B in deionized water to prepare a mixed salt solution, and fully dissolving and complexing the mixed salt solution;
s3: dropwise adding the mixed salt solution prepared in the step S2 into an alkaline solution under the condition of continuous stirring, and performing aging treatment;
s4: carrying out suction filtration and washing on the mixed solution aged in the step S3, and then drying to obtain a hydrotalcite-like/biochar composite material;
s5: and (3) placing the hydrotalcite-like/biochar composite material obtained in the step (S4) in a tube furnace in a nitrogen atmosphere for high-temperature calcination to obtain the M/N hydrotalcite-modified biochar-based composite material.
2. The use according to claim 1, wherein the alkaline solution in step S3 has a pH of 8 to 12 and the aging time is greater than 4 hours.
3. The use according to claim 1, wherein the suction filtration and washing in step S4 is performed as follows: repeatedly washing the mixed solution with deionized water until the pH value of the filtrate is 6-7 under the condition of suction filtration, washing the filtrate with ethanol once when the filtrate is about to be dried, and pumping to obtain a precipitate; the obtained precipitate was placed in a vessel containing ethanol and vigorously stirred at room temperature, after 2 hours, suction filtration was performed and the filter cake was repeatedly washed with ethanol.
4. The use according to claim 1, wherein the biomass raw material is one or more of sawdust, straw, rice hulls.
5. The use according to claim 1, wherein the high temperature calcination temperature in step S5 is 300 ℃ to 700 ℃.
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