CN115814768A - Process method for preparing honeycomb-shaped recyclable magnetic biochar and applying honeycomb-shaped recyclable magnetic biochar to cadmium removal of sewage - Google Patents
Process method for preparing honeycomb-shaped recyclable magnetic biochar and applying honeycomb-shaped recyclable magnetic biochar to cadmium removal of sewage Download PDFInfo
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- 239000010865 sewage Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 53
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 108
- 239000000243 solution Substances 0.000 claims description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000002114 nanocomposite Substances 0.000 claims description 16
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- 235000001759 Citrus maxima Nutrition 0.000 claims description 13
- 244000131522 Citrus pyriformis Species 0.000 claims description 13
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010298 pulverizing process Methods 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 230000001413 cellular effect Effects 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 2
- 240000008790 Musa x paradisiaca Species 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 13
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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Abstract
The invention discloses a process method for preparing honeycomb-shaped recyclable magnetic biochar and applying the honeycomb-shaped recyclable magnetic biochar to cadmium removal of sewage, which comprises the following steps: mixing and reacting raw material sewage with the prepared magnetic biochar, and adjusting the dosage, the reaction PH value and the reaction temperature of the magnetic biochar to remove cadmium elements in the sewage. The method aims at the technical method that the magnetic biochar has poor recycling performance, easy collapse of the structure, small specific surface area and low adsorption efficiency, and the honeycomb-shaped recyclable magnetic biochar is applied to the cadmium removal of the sewage, has high removal rate, stable structure and good recycling performance, and is suitable for large-scale application.
Description
Technical Field
The invention belongs to the technical field of sewage solution treatment, and particularly relates to a process method for preparing honeycomb-shaped recyclable magnetic biochar and applying the honeycomb-shaped recyclable magnetic biochar to sewage cadmium removal.
Background
The waste water solution generated in the process of chemical industry and pharmaceutical industry contains certain metal ions, and due to the continuous improvement of the requirements of environmental protection policies in recent years, the requirement of waste water discharge is more and more strict, the ecological environment is seriously polluted due to the overhigh content of the metal ions, particularly, the metal cadmium has toxicity and carcinogenicity, and the metal cadmium can seriously cause harmful effects on the health of human bodies after being contacted for a long time.
At present, methods for removing cadmium ions from wastewater solutions mainly comprise chemical precipitation methods, biological treatment methods, electrochemical treatment methods and ion exchange methods, however, the application of the technologies in the aspect of removing metal cadmium has certain limitations. The chemical precipitation method may introduce new impurity elements while removing cadmium, the biological treatment method has low cost, but the development and utilization of the technology are limited by special pH and temperature conditions and long removal time, and the high capital and operating cost are main limiting factors for removing cadmium metal by adopting the electrochemical technology. Therefore, adsorption using biochar is a method that does not introduce impurities and can remove cadmium elements.
In addition, the existing preparation process of the magnetic biochar composite material has low removal efficiency for cadmium element, and the biochar structure is easy to collapse when the cadmium element is removed, so that secondary recycling cannot be carried out, and economic loss is caused. Therefore, the development of a process method for preparing the honeycomb-shaped recyclable magnetic biochar and applying the process method to the cadmium removal of the sewage is very important.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a process method for preparing honeycomb-shaped recyclable magnetic biochar applied to cadmium removal from sewage, wherein the honeycomb-shaped recyclable magnetic biochar contains a large amount of micropores and nitrogen in an active center, the specific surface area of a honeycomb structure is large, the adsorption effect is good, and the structure is not easy to collapse after adsorption is completed. The specific scheme is as follows:
a process method for preparing honeycomb-shaped recyclable magnetic biochar and applying the biochar to cadmium removal of sewage comprises the following steps:
drying raw materials, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C for 5 hr at 5 deg.C/min, granulating with 25 mesh sieve, and chemically synthesizing to obtain biochar/Fe 3 O 4 Cellular magnetic nanocomposite formed by reacting CO (NO) 3 ) 2 .6H 2 Dissolving O in methanol solution, adding biochar/Fe 3 O 4 Stirring the honeycomb-shaped magnetic nano composite material at normal temperature to obtain a mixture, dissolving the ZIF-67 zeolite imidazolate framework material in a methanol solution, adding the mixture into the mixture, magnetically stirring, standing at room temperature, and using a magnet to prepare the ZIF-67/biochar/Fe 3 O 4 Separating the composite material from the methanol solution, washing with deionized water, and drying; mixing the sewage with the prepared ZIF-67/biochar/Fe 3 O 4 Mixing and reacting the composite material, and removing cadmium elements in the sewage by adjusting the dosage, the reaction PH value and the reaction temperature of the composite material; the biochar/Fe 3 O 4 The preparation method of the cellular magnetic nano composite material comprises the following steps:
(1) Adding the granulated biochar to FeCl 3 And FeCl 2 In the mixed solution, magnetic stirring is used;
(2) Adding a sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring at 80-90 ℃;
(3) And (3) externally separating the solution obtained in the step (2) by using a magnet, and drying.
The raw material is banana peel, lemon peel or shaddock peel.
The concentration of cadmium in the sewage is 0-20mg/L.
The FeCl 3 And FeCl 2 In the mixed solution, the molar ratio between the two is 1.
The sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction PH value is 2-8 when the composite material is mixed and reacted.
The sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction pH value is 6 when the composite material is mixed and reacted.
The sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction temperature is 25-50 ℃ when the composite material is mixed and reacted.
The sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction temperature is 25 ℃ when the composite material is mixed and reacted.
The sewage and the prepared ZIF-67/biochar/Fe 3 O 4 ZIF-67/biochar/Fe in composite material mixing reaction 3 O 4 The dosage of the composite material is 0.5-4.0g/L.
The invention has at least the following gain effects:
(1) According to the invention, a large number of micropores of the ZIF-67 structure and nitrogen of an active center are utilized, so that the adsorption effect of the magnetic biochar is improved, and the removal rate of cadmium ions is improved.
(2) The specific surface area of the whole biological carbon can be improved by preparing the magnetic biological carbon into a honeycomb shape, the adsorption capacity can be greatly improved under the condition of the same quality, and meanwhile, the structure of the honeycomb structure is not easy to collapse when the honeycomb structure is repeatedly used, so that the cyclic utilization rate of the magnetic biological carbon is improved.
Drawings
FIG. 1 is a flow chart of the preparation of the magnetic biochar applied to the process method for removing cadmium from sewage by using the honeycomb-shaped recyclable magnetic biochar.
Detailed Description
Example 1
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the structure of the magnetic biochar is flat-layer.
Example 2
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nano composite material at normal temperature for 2h to obtain a mixture, dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture, magnetically stirring for 30min, standing at room temperature for 24h, and mixing the prepared ZIF-67/biochar/Fe by using a magnet 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 1
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, gradient heating at 400 deg.C at 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Stirring the honeycomb-shaped magnetic nano composite material at normal temperature for 2 hours to obtain a mixture, then dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture into the mixture, stirring the mixture by magnetic force for 30 minutes, standing the mixture at room temperature for 24 hours, and using a magnet to prepare ZIF-67/biochar/Fe 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 2.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and determining the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar has a honeycomb structure.
Comparative example 2
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, gradient heating at 400 deg.C at 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nano composite material at normal temperature for 2h to obtain a mixture, dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture, magnetically stirring for 30min, standing at room temperature for 24h, and mixing the prepared ZIF-67/biochar/Fe by using a magnet 3 O 4 Separating the composite material from the methanol solution, cleaning the composite material by using deionized water,drying was carried out at 80 ℃.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 4.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 3
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at the temperature of 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nano composite material at normal temperature for 2h to obtain a mixture, dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture, magnetically stirring for 30min, standing at room temperature for 24h, and mixing the prepared ZIF-67/biochar/Fe by using a magnet 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 8.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 4
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nano composite material at normal temperature for 2h to obtain a mixture, dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture, magnetically stirring for 30min, standing at room temperature for 24h, and mixing the prepared ZIF-67/biochar/Fe by using a magnet 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
The method comprises the steps of putting 0.5g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 5
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biocharAddition to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nano composite material at normal temperature for 2h to obtain a mixture, dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture, magnetically stirring for 30min, standing at room temperature for 24h, and mixing the prepared ZIF-67/biochar/Fe by using a magnet 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
The method comprises the steps of putting 1.5g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 6
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, gradient heating at 400 deg.C at 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nano composite material at normal temperature for 2h to obtain a mixture, dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture, magnetically stirring for 30min, standing at room temperature for 24h, and mixing the prepared ZIF-67/biochar/Fe by using a magnet 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
Putting 3.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 25 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 7
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nanocomposite with the above mixture at room temperature for 2 hr to obtain a mixture, dissolving 1.3g ZIF-67 zeolite imidazolate framework material in 100ml methanol solution, adding, and mixingMagnetically stirring for 30min, standing at room temperature for 24 hr, and mixing the prepared ZIF-67/biochar/Fe with magnet 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 35 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 8
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Stirring the honeycomb-shaped magnetic nano composite material at normal temperature for 2 hours to obtain a mixture, then dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture into the mixture, stirring the mixture by magnetic force for 30 minutes, standing the mixture at room temperature for 24 hours, and using a magnet to prepare ZIF-67/biochar/Fe 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 45 ℃, reacting for 30min, filtering and measuring the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar is honeycomb-shaped.
Comparative example 9
The preparation method of the magnetic biochar comprises the following steps:
drying raw materials of banana peel, lemon peel or shaddock peel at 100 deg.C for 24 hr, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C with gradient of 5 deg.C/min for 5 hr, and granulating the prepared biochar with No. 25 sieve
(1) 2g of granulated biochar was added to 100ml FeCl 3 And FeCl 2 In the mixed solution, the molar ratio of the two is 1;
(2) Adding 30ml of 3mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring for 50min at 80-90 ℃;
(3) The solution obtained in step (2) was externally separated with a magnet and dried at 105 ℃ for 24 hours.
1.2g of CO (NO) 3 ) 2 .6H 2 O was dissolved in 100ml of methanol solution, and 1g of the biochar/Fe prepared above was added 3 O 4 Mixing the honeycomb magnetic nano composite material at normal temperature for 2h to obtain a mixture, dissolving 1.3g of ZIF-67 zeolite imidazolate framework material in 100ml of methanol solution, adding the mixture, magnetically stirring for 30min, standing at room temperature for 24h, and mixing the prepared ZIF-67/biochar/Fe by using a magnet 3 O 4 The composite was separated from the methanol solution and washed with deionized water and dried at 80 ℃.
Putting 4.0g of magnetic biochar into 1L of raw sewage (the concentration of cadmium element is 20 mg/L), adjusting the pH value to 6.0, raising the reaction temperature to 50 ℃, reacting for 30min, filtering and determining the content of cadmium ions in the sewage solution after the reaction is finished, wherein the magnetic biochar has a honeycomb structure.
The following examples 1-2 were identical except that magnetic biochar was prepared, as specified in the following table:
| process for the preparation of a coating | Magnetic biochar type | Type of construction | Removal ratio of cadmium (%) |
| Example 1 | Fe 3 O 4 Biochar | Layer-like | 90.34 |
| Example 2 | ZIF-67/Fe 3 O 4 Biochar | Honeycomb shape | 99.71 |
The following comparative examples 1 to 3 were the same as in example 2 except that the pH of the mixed solution was adjusted as a reaction, and are specifically as follows:
| process for the preparation of a coating | pH value | Removal ratio of cadmium (%) |
| Example 2 | 6.0 | 99.71 |
| Comparative example 1 | 2.0 | 36.65 |
| Comparative example 2 | 4.0 | 68.12 |
| Comparative example 3 | 8.0 | 95.45 |
The following comparative examples 4 to 6 were otherwise identical to example 2, except that the amount of the magnetic biochar added was varied as specified in the following table:
| process for the preparation of a coating | Dosage (g/L) of magnetic charcoal | Removal ratio of cadmium (%) |
| Example 2 | 4.0 | 99.71 |
| Comparative example 4 | 0.5 | 52.74 |
| Comparative example 5 | 1.5 | 79.46 |
| Comparative example 6 | 3.0 | 90.88 |
The following comparative examples 7 to 9 were identical to example 2 except that the temperature of the mixed solution was varied during the reaction, and are specifically as follows:
| process for the preparation of a coating | Temperature (. Degree.C.) | Removal ratio of cadmium (%) |
| Example 2 | 25 | 99.71 |
| Comparative example 7 | 35 | 98.67 |
| Comparative example 8 | 45 | 95.98 |
| Comparative example 9 | 50 | 93.28 |
The above-mentioned embodiments are only used for explaining the inventive concept of the present invention, and do not limit the protection of the claims of the present invention, and any insubstantial modifications of the present invention using this concept shall fall within the protection scope of the present invention.
Claims (9)
1. A process method for preparing honeycomb-shaped recyclable magnetic biochar and applying the biochar to cadmium removal of sewage is characterized by comprising the following steps:
drying raw materials, pulverizing and grinding into 1-3mm with grinder, heating at 400 deg.C for 5 hr at 5 deg.C/min, granulating with 25 mesh sieve, and chemically synthesizing to obtain biochar/Fe 3 O 4 Cellular magnetic nanocomposite material of carbon monoxide (CO) (NO) 3 ) 2 .6H 2 Dissolving O in methanol solution, adding biochar/Fe 3 O 4 Stirring the honeycomb-shaped magnetic nano composite material at normal temperature to obtain a mixture, dissolving the ZIF-67 zeolite imidazolate framework material in a methanol solution, adding the mixture into the mixture, magnetically stirring, standing at room temperature, and using a magnet to prepare the ZIF-67/biochar/Fe 3 O 4 Separating the composite material from the methanol solution, washing with deionized water, and drying; mixing the sewage with the prepared ZIF-67/biochar/Fe 3 O 4 Mixing and reacting the composite material, and removing cadmium elements in the sewage by adjusting the dosage, the reaction PH value and the reaction temperature of the composite material; the biochar/Fe 3 O 4 The preparation method of the cellular magnetic nano composite material comprises the following steps:
(1) Adding the granulated biochar to FeCl 3 And FeCl 2 In the mixed solution, magnetic stirring is used;
(2) Adding a sodium hydroxide solution into the mixed solution obtained in the step (1), and stirring at 80-90 ℃;
(3) And (3) externally separating the solution obtained in the step (2) by using a magnet, and drying.
2. The process method for preparing the honeycomb-shaped recoverable magnetic biochar applied to cadmium removal from the sewage according to claim 1 is characterized in that: the raw materials are banana peel, lemon peel or shaddock peel.
3. The process method for preparing the honeycomb-shaped recoverable magnetic biochar applied to cadmium removal from the sewage according to claim 1 is characterized in that: the concentration of cadmium in the sewage is 0-20mg/L.
4. The process method for preparing the honeycomb-shaped recoverable magnetic biochar applied to cadmium removal from the sewage according to claim 1 is characterized in that: the FeCl 3 And FeCl 2 In the mixed solution, the molar ratio between the two is 1.
5. The process method for preparing the honeycomb-shaped recoverable magnetic biochar applied to cadmium removal from the sewage according to claim 1 is characterized in that: the sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction PH value is 2-8 when the composite material is mixed and reacted.
6. The process method for preparing the honeycomb-shaped recoverable magnetic biochar applied to cadmium removal from sewage according to claim 5, which is characterized by comprising the following steps: the sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction pH value is 6 when the composite material is mixed and reacted.
7. The process method for preparing the honeycomb-shaped recoverable magnetic biochar applied to cadmium removal from the sewage according to claim 1 is characterized in that: the sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction temperature is 25-50 ℃ when the composite material is mixed and reacted.
8. The process method for preparing the honeycomb-shaped recoverable magnetic biochar applied to cadmium removal from sewage according to claim 7, which is characterized by comprising the following steps: the sewage and the prepared ZIF-67/biochar/Fe 3 O 4 The reaction temperature is 25 ℃ when the composite material is mixed and reacted.
9. The process method for preparing the honeycomb-shaped recyclable magnetic biochar for cadmium removal from sewage according to claim 1 is characterized by comprising the following steps: the sewage and the prepared ZIF-67/biochar/Fe 3 O 4 ZIF-67/biochar/Fe in composite material mixing reaction 3 O 4 The dosage of the composite material is 0.5-4.0g/L.
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