CN117160405A - Calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar, preparation method and application - Google Patents
Calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar, preparation method and application Download PDFInfo
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 title claims abstract description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 70
- 239000001301 oxygen Substances 0.000 title claims abstract description 70
- 239000001110 calcium chloride Substances 0.000 title claims abstract description 67
- 229910001628 calcium chloride Inorganic materials 0.000 title claims abstract description 67
- 230000003647 oxidation Effects 0.000 title claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 13
- 235000014676 Phragmites communis Nutrition 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004519 grease Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 13
- 239000011574 phosphorus Substances 0.000 abstract description 13
- 230000004913 activation Effects 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 24
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005273 aeration Methods 0.000 description 10
- 238000000197 pyrolysis Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
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- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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Abstract
The application relates to a calcium chloride activated biochar with adsorption-catalysis oxygen oxidation characteristics, which has excellent adsorption-catalysis oxygen oxidation characteristics, has stronger adsorption capacity on organic pollutants in water, and can catalyze oxygen to degrade the organic matters; compared with the original biochar, the adsorption-catalytic oxygen oxidation characteristic biochar activated by calcium chloride improves the removal efficiency of organic pollutants by 3-5 times. The preparation method of the activated adsorption-catalytic oxygen oxidation characteristic biochar for preparing the calcium chloride changes the pore size distribution and the specific surface area of the biochar to a certain extent, and changes the aromaticity and the defect degree of a carbon product, so that the biochar has good adsorption and catalytic oxygen oxidation characteristics; in addition, the preparation method does not depend on the phosphorus activation technology, and the defects brought by the phosphorus activation technology are avoided.
Description
Technical Field
The application relates to the technical field of environmental protection, in particular to calcium chloride activated biochar with adsorption-catalytic oxygen oxidation characteristics, a preparation method and application thereof.
Background
Organic pollutants are one of the main problems of current water pollution, and about 4 hundred million tons of organic pollutants enter the water environment every year in the world and form serious threat to human health and ecological environment. Therefore, the development of an effective and economical organic pollutant removal material is of great importance to the environmental protection field.
Biochar is a solid product prepared from biomass resources (such as agricultural and forestry waste) through pyrolysis, has good adsorption performance, and is widely applied to the field of environmental protection, in particular to the aspect of removing organic pollutants in water. The adsorption performance of the biochar is closely related to the properties of pore size distribution, specific surface area, aromaticity, defect degree and the like, and the properties are closely connected with the preparation process of the biochar.
However, current biochar preparation and application rely primarily on phosphorus activation technology, which has its obvious limitations: first, phosphorus activated biochar relies primarily on physical adsorption for removal of organic contaminants, requiring replacement or regeneration after saturation of adsorption, which increases operational complexity and cost; secondly, phosphorus is a limited non-renewable resource and has potential negative effects on the environment, and the preparation cost of phosphorus activated biochar is about 10000-20000 yuan per ton according to statistics, and the treatment of waste phosphorus is also an environmental protection problem. Therefore, searching for a preparation technology of the biochar for replacing phosphorus activation and improving the organic pollutant removal capability of the biochar is an important subject in the current environment-friendly field.
Disclosure of Invention
In view of the above, the application provides a method for preparing activated adsorption-catalytic oxygen oxidation biochar by preparing calcium chloride, which does not depend on a phosphorus activation technology, avoids the defects caused by the phosphorus activation technology, and has strong adsorption capacity on organic pollutants in water, and can catalyze oxygen to realize degradation of the organic matters.
The application aims to achieve the aim, and the aim is achieved by the following technical scheme:
the application provides a preparation method of calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar, which comprises the following preparation steps:
s1: dissolving calcium chloride in water;
s2: uniformly mixing the dissolved calcium chloride solution with reed powder;
s3: drying the mixed sample;
s4: transferring the dried sample to a heating furnace, and before heating, ensuring the atmosphere to be high-purity nitrogen through multiple times of air suction and nitrogen inflation;
s5: under nitrogen atmosphere, heating to 190-210 deg.C at the rate of 9-11 deg.C/min, heating to 440-460 deg.C at the rate of 1.5-3.5 deg.C/min, heating to 790-810 deg.C at the rate of 9-11 deg.C/min, and maintaining t 1 Hours;
s6: stopping heating, and naturally cooling the sample to room temperature;
s7: fully washing the cooled sample with hydrochloric acid and deionized water to remove ash and grease;
s8: and drying the washed sample to obtain the calcium chloride activated biochar with adsorption-catalytic oxygen oxidation characteristics.
In some embodiments of the application, the water in step S1 is deionized water.
In some embodiments of the present application, the weight part of the calcium chloride in the step S2 is 9-250 parts, and the weight part of the reed powder is 25 parts.
In some embodiments of the application, the reed powder has a particle size of 40 mesh or less.
In some embodiments of the application, the temperature of the drying in step S3 is 100 ℃ to 120 ℃ and the drying time is 24 hours or more.
In some embodiments of the application, the temperature of the drying in step S3 is 105 ℃ and the drying time is 24 hours.
In some embodiments of the application, the heating furnace in step S4 is a tube furnace.
In some embodiments of the application, 1.ltoreq.t in step S5 1 ≤3。
In some embodiments of the application, the specific operation of step S5 is: under nitrogen atmosphere, the temperature is raised to 200 ℃ at a speed of 10 ℃/min, then to 450 ℃ at a speed of 2.5 ℃/min, finally to 800 ℃ at a speed of 10 ℃/min, and the temperature is kept for 1 hour.
In some embodiments of the present application, in step S7, the hydrochloric acid concentration is 1-5mmol/L, the deionized water conductivity is 20mΩ×cm or more, and the sufficient washing criterion is that the washing solution resistivity is 5mΩ×cm or more.
In some embodiments of the application, the temperature of the drying in step S8 is 100 ℃ to 120 ℃ and the drying time is 24 hours or more.
In some embodiments of the application, the temperature of the drying in step S8 is 105 ℃ and the drying time is 24 hours.
The application also provides the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar prepared by any one of the above methods.
In some embodiments of the application, the biochar has the property of catalyzing the oxidation of contaminants by oxygen.
The application also provides application of the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar in the aspect of treating organic pollutants in water.
The preparation method of the activated adsorption-catalytic oxygen oxidation characteristic biochar of calcium chloride provided by the application can enable the calcium chloride to actively capture pyrolysis gas and pyrolysis oil which are dissipated by pyrolysis in a specific stage, and fix the specific functional groups in the biochar in a higher temperature stage. The activated adsorption-catalytic oxygen oxidation characteristic biochar prepared by the method has strong adsorption capacity on organic pollutants in water, can catalyze oxygen to degrade the organic matters, and improves the efficiency of removing the organic pollutants by 3-5 times compared with that of the original biochar; in addition, the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar prepared by the modification process has the capability of further oxidizing and degrading pollutants under the aeration condition.
Compared with the prior art, the application has the beneficial effects that:
(1) Improving the adsorption capacity: the biochar activated by calcium chloride has stronger adsorption capacity to organic pollutants.
(2) Innovative removal mechanism: the activated adsorption-catalytic oxygen oxidation characteristic biochar of the calcium chloride can adsorb organic pollutants, can catalyze oxygen to degrade the organic pollutants, and can further reduce the concentration of the organic pollutants by aerating the biochar into water after the biochar is saturated in adsorption of the organic pollutants.
(3) Changing the properties of biochar: by calcium chloride activation, the pore size distribution, specific surface area, aromaticity and defect degree of the activated adsorption-catalysis oxygen oxidation characteristic biochar are changed, and the changes are beneficial to improving the adsorption-catalysis oxygen oxidation performance of the biochar.
(4) The cost is reduced: compared with phosphorus activated biochar, the preparation method of the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar does not need phosphorus, and avoids the problems of high cost and environmental pollution caused by limited phosphorus resources.
(5) Catalytic oxygen oxidation: at present, the existing biochar has a catalytic oxidation function, but needs to be additionally added with an oxidant, so that the cost is high, and secondary pollution is easy to cause; the activated adsorption-catalytic oxygen oxidation characteristic biochar of the calcium chloride can realize the capability of catalyzing oxygen to oxidize pollutants through aeration, has low cost and does not cause secondary pollution.
Drawings
Fig. 1 is a schematic diagram of a preparation principle of biochar, wherein 1 is calcium chloride, 2 is a biomass matrix, 3 is an oxygen-containing compound fixed by the calcium chloride in a catalytic biomass pyrolysis process, 4 is coke, 5 is an oxygen-containing functional group and a pore structure formed by pyrolysis, 6 is a carbocycle main body of the biochar, and 7 is an acid washing or water washing process;
FIG. 2 is data from an electron paramagnetic resonance spectrometer for capturing active components generated by calcium chloride activated adsorption-catalytic oxygen oxidation characteristics biochar in different solvents;
FIG. 3 is a chart comparing Fourier infrared spectra of activated adsorption-catalytic oxygen oxidation characteristics biochar with unactivated biochar and calcium chloride;
FIG. 4 is a graph of nitrogen adsorption and desorption tests for activated adsorption-catalytic oxygen oxidation characteristics biochar with unactivated biochar and calcium chloride;
FIG. 5 is a graph showing comparison test of adsorption effects of biochar prepared by different temperature increasing programs;
FIG. 6 is data of the two-stage degradation of organic contaminants by biochar adsorption-catalyzed oxygen oxidation characteristics of calcium chloride activation.
Detailed Description
The application will be further described with reference to the accompanying drawings and specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1: preparation of calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar
Firstly, 0.1mol of calcium chloride is dissolved in 100ml of deionized water, and then the dissolved calcium chloride solution is mixed with 20g of reed powder; drying the mixed sample in an oven at 105 ℃ for 24 hours; transferring the dried sample to a tube furnace, and ensuring the atmosphere to be high-purity nitrogen through repeated air suction and nitrogen inflation before the pyrolysis procedure starts; under the nitrogen filling atmosphere, firstly heating to 200 ℃ at the speed of 10 ℃/min, then heating to 450 ℃ at the speed of 2.5 ℃/min, finally heating to 800 ℃ at the speed of 10 ℃/min, and keeping for 1 hour; stopping heating, and naturally cooling the sample to room temperature; fully washing the cooled biochar sample with 0.05mol/L HCl and deionized water to remove ash and grease; and (3) putting the washed biochar sample into a baking oven, drying the biochar sample at 105 ℃ for 24 hours, and sealing the dried biochar sample for later use.
Example 2: capture test of calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar
The activated adsorption-catalytic oxygen oxidation characteristic biochar prepared in example 1 was added to pure water, dimethyl sulfoxide and methanol solvent in an aerated state for aeration, and the mixture in the system was sampled, and the catalytically generated active species were captured by 5, 5-dimethyl-1-pyrroline-N-oxide, and after capturing, the signal and type of the active species were analyzed by using an electron paramagnetic resonance spectrometer.
The test results are shown in figure 2.
The test results show that the OH signal is stably generated and distributed in the solution in the reaction system. The production of OH may be related to a Fenton-like oxidation process. Thereby capturing H in dimethyl sulfoxide and methanol 2 O 2 Related O 2 - The OOH signal. CH (CH) 3 The C (=o) OO signal is captured in both water and dimethyl sulfoxide, indicating the presence of an electron transfer process product in the redox reaction. No signal was captured in methanol solution, indicating CH 3 C (=o) OO-undergoes a quenching reaction with methanol, masking the signal peak. Further illustrates the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar with the capability of further oxidizing and degrading pollutants under the aeration condition.
Example 3: fourier infrared spectrum contrast test of unactivated biochar and calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar
The unactivated biochar and the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar prepared in the example are respectively mixed and ground with potassium bromide, and then projected scanning is carried out through a Fourier infrared spectrometer to identify the type difference of the surface chemical functional groups of the two biochars. The unactivated biochar is prepared by directly heating reed powder to 800 ℃ under the same condition after drying, and keeping the temperature at 800 ℃ for 1h at a heating rate of 10 ℃/min.
The test results are shown in FIG. 3.
The test result shows that the main position of the change in the biological carbon sample with the adsorption-catalytic oxygen oxidation characteristics activated by calcium chloride is 880cm -1 And 1500cm -1 Nearby, the activated calcium chloride shows that the biochar generates CH in methyl peroxy radical 3 O-O bond stretching vibration and aromatic changes.
Example 4: nitrogen adsorption and desorption test of unactivated biochar and calcium chloride activated adsorption-catalytic oxygen oxidation-specific biochar
The adsorption-catalytic oxygen oxidation characteristic biochar activated by unactivated biochar and calcium chloride is subjected to nitrogen adsorption and desorption test, and comparison of adsorption and desorption curves shows that calcium chloride modification has an influence on the distribution of micropores and mesopores of the biochar. The unactivated biochar is prepared by directly heating reed powder to 800 ℃ under the same condition after drying, and keeping the temperature at 800 ℃ for 1h at a heating rate of 10 ℃/min.
The test results are shown in FIG. 4.
The test result shows that the adsorption-catalytic oxygen oxidation characteristic biochar nitrogen adsorption-desorption curve activated by calcium chloride has obvious hysteresis, and the contents of mesopores and micropores in the biochar are obviously improved.
Example 5: elemental distribution and defect level testing of unactivated and varying amounts of calcium chloride activated biochar
One group is unactivated biochar, namely reed powder is directly heated to 800 ℃ under the same condition after being dried, the heating rate is 10 ℃/min, and the temperature is kept at 800 ℃ for 1h, so as to prepare the unactivated biochar; the same method as in example 1 was used for preparing biochar in the other five groups, and the only variable to be changed in the different groups was the use amount of calcium chloride, which was 0.01mol, 0.03mol, 0.05mol, 0.07mol and 0.1mol, respectively, to prepare calcium chloride activated biochar.
The test results are shown in the following table one, and it is clear from the test results that the activated adsorption-catalytic oxygen oxidation characteristic biochar of calcium chloride prepared in example 1, which is different from the unactivated biochar and the activated biochar of different amounts of calcium chloride, has a significant change in element distribution and defect degree.
List one
Example 6: calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar and other biochar adsorption capacity comparison test
Four biochar adsorption capacities were tested: the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar prepared in example 1, the original biochar directly prepared from reed powder, the biochar prepared by changing only the temperature elevation procedure in the preparation method of example 1 (instead maintaining at room temperature of 10 c/min to 800 c for one hour), and the commercially available phosphoric acid activated carbon purchased.
As a result of the test, the adsorption capacity of the unactivated original biochar was 10.7mg/g, and the temperature was directly raised to obtain a calcium chloride activated biochar adsorption capacity of 18.68mg/g, a commercial phosphoric acid activated active carbon adsorption capacity of 51.64mg/g, and a calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar adsorption capacity of 87.53mg/g, which was prepared in example 1.
Example 7: biochar prepared by different heating programs and adsorption effect comparison test of different biochars
Preparing activated standard-temperature-rising biochar, direct-temperature-rising biochar, non-constant-temperature-rising biochar and 700-DEG C-temperature-rising biochar according to different temperature-rising programs:
the other preparation steps were the same as those of example 1 except for the difference in temperature elevation program.
The different temperature rise programs are respectively as follows:
direct heating: heating to 800 ℃ at 10 ℃/min, and then keeping the temperature for 1 hour;
two-stage heating: heating to 200 ℃ at 10 ℃/min, keeping for 1 hour, heating to 800 ℃ at 10 ℃/min, and keeping the temperature for 1 hour;
standard temperature rise: heating to 200 ℃ at 10 ℃/min, heating to 450 ℃ at 2.5 ℃/min, heating to 800 ℃ at 10 ℃ per min, and keeping the temperature for 1 hour;
heating at 700 ℃): heating to 200 ℃ at 10 ℃/min, keeping for 1 hour, heating to 700 ℃ at 10 ℃/min, and keeping the temperature for 1 hour;
no constant temperature heating: heating to 200 ℃ at 10 ℃/min, heating to 450 ℃ at 2.5 ℃/min, heating to 800 ℃ at 10 ℃/min, and immediately cooling.
In addition, charcoal was prepared according to the method of example 1, but without adding calcium chloride for activation, and other preparation steps were the same, to prepare standard warming charcoal; biochar was prepared according to the method of example 1 without adding calcium chloride for activation, changing the temperature program, and directly heating to prepare the original biochar.
In addition, commercial plant-based activated carbon is commercially available.
The prepared and purchased biochar is subjected to a pollutant removal effect comparison test, and the test method comprises the following steps: bisphenol S is dissolved in deionized water to prepare bisphenol S solution for adsorption experiments. All adsorption experiments were performed under blank conditions and repeated three times in parallel to ensure accuracy. Adsorption experiments were performed by adding 0.1g of charcoal powder to 10-100mg/L bisphenol S solution in a 100mL Erlenmeyer flask. The flask was shaken in a constant temperature shaking chamber at 180rpm for 24 hours. The adsorption kinetics were determined by placing 1 gram of biochar powder into 1 liter of 50 mg/liter bisphenol S solution. Sampling is carried out for multiple times until the adsorption equilibrium is reached. All samples were filtered using a 0.45 μm filter. The concentration of bisphenol S was measured by 278 nm spectrophotometry. The limit of quantitation (LOQ) was 0.1 mg/L with a linear range of 1-50 mg/L (R) 2 ＝0.9996)。
The test results are shown in FIG. 5.
Test results show that the activated standard temperature-rising biochar, namely the activated adsorption-catalytic oxygen oxidation characteristic biochar of calcium chloride prepared by the application, has the best adsorption effect.
Example 8: calcium chloride activated adsorption-catalytic oxygen oxidation characteristics biochar adsorption-catalytic oxygen oxidation two-stage organic pollutant degradation reaction process test
First, high-purity N is introduced into 30mg/L bisphenol S (BPS) solution 2 The gas was subjected to deoxidation treatment for 5 minutes to reduce the dissolved oxygen concentration in the solution to 0.3mg/L or less. Then, 100mL of the completely deoxygenated BPS solution was poured into a 100mL conical flask, the conical flask was sealed with a paraffin-coated glass stopper, and the flask body was wrapped with aluminum foil to prevent light; the calcium chloride activated adsorption-catalytic oxygen oxidation-property biochar prepared in example 1 was added to a conical flask and stirring was started.
Samples of the solution were taken at various time points and, after passing through a 0.22 μm filter, 0.01mmol Ascorbic Acid (AA) was immediately added for radical scavenging treatment. The concentration of BPS in the solution was determined by High Performance Liquid Chromatography (HPLC) at each time point.
Stirring was continued for 24 hours under anaerobic conditions to allow the reaction to proceed completely; then enters an aeration stage, when the aeration stage starts, the reaction solution in the conical flask is poured into a 150mL high-neck beaker, stirred and aerated under the protection of shading, al is used 2 O 3 And (5) performing aeration treatment by an aeration screen.
The solution was removed at various times during the aeration phase and filtered, and the BPS concentration and intermediates were determined by liquid chromatography-mass spectrometry (HPLC-MS).
The test results are shown in FIG. 6.
According to the test result, after the adsorption of the calcium chloride activated adsorption-catalysis oxygen oxidation characteristic biochar reaches equilibrium, oxygen is triggered to catalyze the surface of the calcium chloride activated adsorption-catalysis oxygen oxidation characteristic biochar to generate oxidation active species by aerating a reaction system, so that the concentration of water environment pollutants is further reduced, and further water quality purification is completed, namely the calcium chloride activated adsorption-catalysis oxygen oxidation characteristic biochar prepared by the method can effectively adsorb bisphenol S which is an organic pollutant and realize oxidative degradation of bisphenol S in an aeration stage. The calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar prepared by the method has high efficiency for removing organic pollutants in water, and provides a new and effective solution for the environmental protection field.
The above description is only illustrative of the preferred embodiments of the present application and of the principles of the technology employed. It will be appreciated by persons skilled in the art that the scope of the application referred to in the present application is not limited to the specific combinations of the technical features described above, but also covers other technical features formed by any combination of the technical features described above or their equivalents without departing from the inventive concept. Such as the features described above, have similar functions to those disclosed in the present application (but are not limited to).
Claims (10)
1. The preparation method of the calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar is characterized by comprising the following preparation steps:
s1: dissolving calcium chloride in water;
s2: uniformly mixing the dissolved calcium chloride solution with reed powder;
s3: drying the mixed sample;
s4: transferring the dried sample to a heating furnace, and before heating, ensuring the atmosphere to be high-purity nitrogen through multiple times of air suction and nitrogen inflation;
s5: under nitrogen atmosphere, heating to 190-210 deg.C at the rate of 9-11 deg.C/min, heating to 440-460 deg.C at the rate of 1.5-3.5 deg.C/min, heating to 790-810 deg.C at the rate of 9-11 deg.C/min, and maintaining t 1 Hours;
s6: stopping heating, and naturally cooling the sample to room temperature;
s7: fully washing the cooled sample with hydrochloric acid and deionized water to remove ash and grease;
s8: and drying the washed sample to obtain the calcium chloride activated biochar with adsorption-catalytic oxygen oxidation characteristics.
2. The method for preparing activated adsorption-catalytic oxygen oxidation biochar according to claim 1, wherein the weight part of calcium chloride in step S2 is 9-250 parts and the weight part of reed powder is 25 parts.
3. The method for preparing calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar according to claim 2, wherein the particle size of reed powder is less than or equal to 40 mesh.
4. The method for preparing calcium chloride activated adsorption-catalytic oxygen oxidation biochar according to claim 1, wherein the temperature of the drying in step S3 is 100 ℃ to 120 ℃ and the drying time is 24 hours or more; and S8, the temperature of the drying in the step is 100-120 ℃, and the drying time is more than or equal to 24 hours.
5. The method for preparing calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar according to claim 1, wherein the heating furnace in step S4 is a tube furnace.
6. The method for preparing calcium chloride activated adsorption-catalytic oxygen oxidation characteristic biochar according to claim 1, wherein t is 1-t in step S5 1 ≤3。
7. The method for preparing activated calcium chloride adsorption-catalytic oxygen oxidation biochar according to claim 1, wherein in step S7, the concentration of hydrochloric acid is 1-5mmol/L, the conductivity of deionized water is 20mΩ/cm or more, and the sufficient washing standard is that the resistivity of the washing solution is 5mΩ/cm or more.
8. The calcium chloride activated adsorption-catalytic oxygen oxidation biochar prepared by the method of any one of claims 1-8.
9. The calcium chloride activated adsorption-catalytic oxygen oxidation biochar of claim 8, having the property of catalyzing the oxidation of contaminants by oxygen.
10. Use of the calcium chloride activated adsorption-catalytic oxygen oxidation biochar according to claim 8 for the treatment of organic pollutants in water.
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