CN112456491A - Production process of environment-friendly regenerated activated carbon - Google Patents
Production process of environment-friendly regenerated activated carbon Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a production process of environment-friendly regenerated active carbon, which belongs to the technical field of active carbon recovery and comprises the following steps of grinding after micro-oxidation of the surface of hot air, vacuum extraction, and then sequentially immersion-washing with acid-alkali liquor to obtain a recovered material, heating the recovered material, rapidly immersing the heated recovered material into low-temperature liquid nitrogen, loading potassium ferrate, performing high-temperature activation, mixing with weakly caking coal powder, performing compression molding, and performing secondary activation to obtain the active carbon; the invention separates and desorbs the adsorbate on the active carbon through grinding and refining and vacuum extraction, decomposes and recovers the active carbon pore structure by low-temperature liquid nitrogen and pore channel loaded potassium ferrate, realizes the reutilization of the waste active carbon, and has important significance for the comprehensive utilization efficiency of resources.
Description
Technical Field
The invention relates to the technical field of activated carbon regeneration, in particular to a production process of environment-friendly regenerated activated carbon.
Background
Activated carbon is one of the most important industrial adsorbents. It has hydrophobic property and developed pore structure and specific surface, so that it is widely used in chemical industry, petroleum, light industry, food, environment protection, national defense and other fields. The performance of the activated carbon is mainly determined by two aspects of the pore structure and the surface chemical property of the activated carbon, generally, the activated carbon rich in micropores has strong advantages in the aspects of adsorbing gas and small molecules in liquid, however, with the continuous improvement of the manufacturing technology and the performance of the activated carbon, the demand of the activated carbon is continuously increased, and the activated carbon product rich in pores is increasingly needed in the fields of water and sewage treatment, chemical products and food decoloration, catalyst carriers, double electric layer capacitors, blood purification and the like.
At present, the activated carbon is basically made of wood, coal or petroleum semi-finished products, the cost consumption is high, the preparation process is complex, the sustainable development of the environment is not facilitated, along with the increasing consumption of the activated carbon, more and more waste activated carbon is generated, the adsorption capacity of the coal-based activated carbon is recovered through regeneration, and the cyclic recycling of a large amount of waste coal-based activated carbon is necessary. However, the conventional activated carbon regeneration methods have common defects, such as large loss of activated carbon in the regeneration process, obvious reduction of the adsorption capacity of the regenerated activated carbon, and the like, besides their respective disadvantages, so that it is of great significance to improve the comprehensive utilization efficiency of resources by the conventional regeneration technology.
Disclosure of Invention
Aiming at the problems, the invention provides a production process of environment-friendly regenerated activated carbon.
The purpose of the invention is realized by adopting the following technical scheme:
the production process of the environment-friendly regenerated activated carbon comprises the following steps:
s1, pretreatment
Cleaning the recovered waste activated carbon after impurity removal, drying by hot air and simultaneously carrying out surface micro-oxidation, grinding after cooling, wherein the grinding granularity is 200-300 meshes, putting the recovered activated carbon obtained by grinding into a pressure-resistant container, pumping air by a vacuum pump until the absolute air pressure in the container reaches 300-500Pa, keeping the air pressure for 1-3h, taking out, then respectively adding the obtained product into 1mol/L hydrochloric acid solution and 4mol/L sodium hydroxide solution to soak and remove redundant impurities, rinsing by clear water, and drying for multiple times by using drying equipment to obtain a recovered material;
s2, processing of multiple holes
Heating the recycled material to 180 ℃, preserving the temperature until the temperature of the recycled material is stable, quickly immersing the high-temperature recycled material into low-temperature liquid nitrogen for cooling, and repeatedly heating and cooling for 2-3 times;
s3, activation
Under the protection atmosphere of nitrogen or argon, heating the treated activated carbon to 800 ℃, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product, adding the prepared calcined product into 0.1mol/L hydrochloric acid solution to soak for removing redundant impurities, and washing with deionized water to obtain an activated product;
s4, preparing the ingredients
Mixing the activated product with weakly-sticky coal powder according to the weight part ratio of 100 (5-20), wherein the particle size of the weakly-sticky coal powder is 200-300 meshes, mechanically stirring or air stirring uniformly to obtain a mixture, adding a binder accounting for 1-3% of the weight of the mixture, stirring uniformly again, putting the mixture into a forming device for compression forming to obtain a forming material, and drying the forming material until the moisture content is less than 2%;
s5, secondary activation
Activating by adopting a gas activation method, wherein the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 30-72h to obtain a secondary activation product;
s6, post-processing
And (2) screening the secondary activation product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, adding the finished product into the treatment solution, stirring and reacting for 1-5h under the condition of 70 ℃ water bath, filtering out, rinsing with clear water, and drying for multiple times by using drying equipment to obtain the environment-friendly regenerated activated carbon.
Preferably, the temperature of the hot air is between 120 ℃ and 160 ℃, and the heat treatment time is between 30 and 50 min.
Preferably, the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate in the treatment solution are 2mol/L, 0.5mol/L and 0.4mol/L, respectively.
Preferably, the mixture further comprises carbon nanotubes, and the addition amount of the carbon nanotubes is 2-5% of the activated product.
Preferably, before the activation treatment after the secondary pore treatment, the production process further comprises a load treatment, and the specific steps are as follows:
weighing potassium ferrate and tween-60, dissolving in deionized water to obtain a solution A, wherein the mass concentration of the potassium ferrate in the solution A is 3-6g/L, the mass concentration of the tween-60 is 0.2-0.5g/L, adding the solution A into the treated activated carbon, the addition amount is 1g/10ml, fully and uniformly stirring, standing overnight, filtering, and carrying out vacuum drying at 70-80 ℃ for 8-12h to obtain the reclaimed material loaded with the potassium ferrate.
Preferably, the binder is a modified phenolic resin.
Preferably, the modified phenolic resin consists of water-soluble phenolic resin, modified filler and diluent, wherein the weight ratio of the water-soluble phenolic resin to the modified filler to the diluent is (10-20): (1-3): 100, the modified filler is a composition of modified bryophyte fibers and carboxymethyl chitosan hydrogel.
Preferably, the preparation method of the modified filler comprises the following steps:
s1 modified bryophyte fiber
Washing moss with clear water for several times to remove soil impurities on the surface, drying the cleaned moss until the moisture content is less than 10%, weighing 1 part by weight of the dried moss, adding 100 parts by weight of deionized water, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite, heating in a 75 ℃ water bath for 1h under stirring, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, continuing to stir and heat for 1h, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, stirring, filtering out precipitates, leaching with an acetic acid solution, soaking the precipitates in a mixed water solution of hydrogen peroxide and acetic acid according to a liquid-material ratio of 50ml/g for 20-30min, transferring into a reaction kettle with a polytetrafluoroethylene substrate, heating in a 140 ℃ water bath for 12-24h, cooling to room temperature, centrifuging the suspension, and freeze-drying at-60 ℃, mechanically pulverizing, micronizing, and sieving to obtain micropowder with particle size of 40-70 μm to obtain modified bryophyte fiber;
s2 preparation of hydrogel
Weighing 1 part by weight of polyvinyl alcohol, dissolving the polyvinyl alcohol in deionized water, wherein the mass part of the polyvinyl alcohol is 2-5%, adjusting the pH value of the solution to 5 with glacial acetic acid, adding 12-15 parts of carboxymethyl chitosan, mixing and stirring, introducing nitrogen into the mixed solution to obtain a uniform and transparent precursor solution, adding deionized water with the same volume as the precursor solution, stirring to obtain a viscous solution, standing for 24 hours, soaking for 72-120 hours with the deionized water, changing water once every 12 hours, performing forced air drying at 80 ℃ for 12 hours after soaking is completed, performing vacuum drying at 60 ℃ for 24 hours, mechanically crushing for micronization, and screening to obtain micro powder with the particle size of 40-70 mu m, thereby preparing the carboxymethyl chitosan hydrogel;
s3, proportioning
And mixing the modified bryophyte fibers with the carboxymethyl chitosan hydrogel according to a ratio to prepare the modified filler.
Preferably, in the mixed aqueous solution of hydrogen peroxide and acetic acid, the mass fractions of hydrogen peroxide and acetic acid are 10 wt.% and 10 wt.%, respectively.
Preferably, the mass mixing ratio of the modified bryophyte fibers to the hydrogel micropowder (3-6): 1.
the invention has the beneficial effects that:
(1) the desorption and separation of adsorbates on the activated carbon can be promoted through grinding and refining and vacuum extraction, and the adsorbates are further dissolved and absorbed through acid-alkali liquor washing, so that the pore structure of the activated carbon is preliminarily recovered.
(2) The recycled material is expanded after being heated and then quickly immersed into low-temperature liquid nitrogen, the ultra-strong permeability of the liquid nitrogen can quickly permeate into pores of the recycled material, the high-temperature recycled material enables the liquid nitrogen in the pores to be vaporized, the vaporized nitrogen plays a role in expanding and restoring the pores in the pores, the pore structure of the activated carbon is restored, no organic solvent is needed in treatment, the period is short, the energy consumption is low, and the process is clean and environment-friendly.
(3) The alkaline treatment solution can further remove acid-insoluble metal oxides and silicon oxide, and meanwhile, based on good metal complexing performance of sodium hexametaphosphate, the alkaline treatment solution can be added into the treatment solution to further reduce the metal content in the activated carbon, so that the ash content is reduced, and the quality of the activated carbon is improved.
Detailed Description
The invention is further described with reference to the following examples.
The embodiment of the invention relates to a production process of environment-friendly regenerated activated carbon, which comprises the following steps:
s1, pretreatment
Cleaning the recovered waste activated carbon after impurity removal, drying by hot air and simultaneously carrying out surface micro-oxidation, grinding after cooling, wherein the grinding granularity is 200-300 meshes, putting the recovered activated carbon obtained by grinding into a pressure-resistant container, pumping air by a vacuum pump until the absolute air pressure in the container reaches 300-500Pa, keeping the air pressure for 1-3h, taking out, then respectively adding the obtained product into 1mol/L hydrochloric acid solution and 4mol/L sodium hydroxide solution to soak and remove redundant impurities, rinsing by clear water, and drying for multiple times by using drying equipment to obtain a recovered material;
s2, processing of multiple holes
Heating the recycled material to 180 ℃, preserving the temperature until the temperature of the recycled material is stable, quickly immersing the high-temperature recycled material into low-temperature liquid nitrogen for cooling, and repeatedly heating and cooling for 2-3 times;
s3, activation
Under the protection atmosphere of nitrogen or argon, heating the treated activated carbon to 800 ℃, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product, adding the prepared calcined product into 0.1mol/L hydrochloric acid solution to soak for removing redundant impurities, and washing with deionized water to obtain an activated product;
s4, preparing the ingredients
Mixing the activated product with weakly-sticky coal powder according to the weight part ratio of 100 (5-20), wherein the particle size of the weakly-sticky coal powder is 200-300 meshes, mechanically stirring or air stirring uniformly to obtain a mixture, adding a binder accounting for 1-3% of the weight of the mixture, stirring uniformly again, putting the mixture into a forming device for compression forming to obtain a forming material, and drying the forming material until the moisture content is less than 2%;
s5, secondary activation
Activating by adopting a gas activation method, wherein the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 30-72h to obtain a secondary activation product;
s6, post-processing
And (2) screening the secondary activation product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, adding the finished product into the treatment solution, stirring and reacting for 1-5h under the condition of 70 ℃ water bath, filtering out, rinsing with clear water, and drying for multiple times by using drying equipment to obtain the environment-friendly regenerated activated carbon.
The invention promotes desorption and separation of adsorbate on the active carbon through grinding refinement and vacuum extraction, and the desorption is further dissolved and absorbed by washing with acid-alkali liquor, so as to initially recover the pore structure of the active carbon;
the recycled material is heated and then expanded, and then quickly immersed in low-temperature liquid nitrogen, the ultra-strong permeability of the liquid nitrogen can quickly permeate into pores of the recycled material, meanwhile, the high-temperature recycled material vaporizes the liquid nitrogen in the pores, the vaporized nitrogen plays a role in expanding and restoring the pores in the pores, the pore structure of the activated carbon is recovered, an organic solvent is not needed in the treatment, the period is short, the energy consumption is low, and the process is clean and environment-friendly;
the alkaline treatment solution can further remove acid-insoluble metal oxides and silicon oxide, and meanwhile, based on good metal complexing performance of sodium hexametaphosphate, the alkaline treatment solution can be added into the treatment solution to further reduce the metal content in the activated carbon, so that the ash content is reduced, and the quality of the activated carbon is improved;
preferably, the temperature of the hot air is between 120 ℃ and 160 ℃, and the heat treatment time is between 30 and 50 min.
Preferably, the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate in the treatment solution are 2mol/L, 0.5mol/L and 0.4mol/L, respectively.
Preferably, the mixture further comprises carbon nanotubes, and the addition amount of the carbon nanotubes is 2-5% of the activated product.
Preferably, before the activation treatment after the secondary pore treatment, the production process further comprises a load treatment, and the specific steps are as follows:
weighing potassium ferrate and tween-60, dissolving in deionized water to obtain a solution A, wherein the mass concentration of the potassium ferrate in the solution A is 3-6g/L, the mass concentration of the tween-60 is 0.2-0.5g/L, adding the solution A into the treated activated carbon, the addition amount is 1g/10ml, fully and uniformly stirring, standing overnight, filtering, and carrying out vacuum drying at 70-80 ℃ for 8-12h to obtain the reclaimed material loaded with the potassium ferrate.
The potassium ferrate has strong oxidizability, the ferrate root is colloidal in the solution, can aggregate suspended matters in water to form precipitate, can efficiently remove fine suspended matters in the water, has the water purification effect of chlorine and alum, and is a novel green water purifier; the method comprises the steps of loading potassium ferrate on micropores of active carbon, then carrying out high-temperature activation, decomposing the potassium ferrate into potassium hydroxide and ferric hydroxide by heating at high temperature, etching carbon by potassium compounds generated by the potassium hydroxide at high temperature to form carbon dioxide and carbon monoxide gas to generate a pore structure, and carrying out Fe (OH)3Reacting with a carbon material at high temperature to generate iron particles, and converting amorphous carbon into graphitized carbon by catalysis, so that the pore structure of the activated carbon is further recovered;
preferably, the binder is a modified phenolic resin.
Preferably, the modified phenolic resin consists of water-soluble phenolic resin, modified filler and diluent, wherein the weight ratio of the water-soluble phenolic resin to the modified filler to the diluent is (10-20): (1-3): 100, the modified filler is a composition of modified bryophyte fibers and carboxymethyl chitosan hydrogel.
The binder used in the prior art is generally an asphalt binder, mainly coal tar pitch, is suitable for producing binders of coal-based columnar activated carbon and honeycomb activated carbon, but can be melted and volatilized after being heated, so that the strength of a final product is not high, and in the production of the activated carbon, residues of the asphalt can block pores of the activated carbon and are not beneficial to improving the quality of the activated carbon; the modified phenolic resin is used as the binder, the carbon content is high, the binding property is good, the coking rate is high in the pyrolysis process, a part of the active carbon is formed after pyrolysis, the adsorption capacity is good, the influence on a pore structure is small, and the forming mechanical strength is high;
preferably, the preparation method of the modified filler comprises the following steps:
s1 modified bryophyte fiber
Washing moss with clear water for several times to remove soil impurities on the surface, drying the cleaned moss until the moisture content is less than 10%, weighing 1 part by weight of the dried moss, adding 100 parts by weight of deionized water, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite, heating in a 75 ℃ water bath for 1h under stirring, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, continuing to stir and heat for 1h, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, stirring, filtering out precipitates, leaching with an acetic acid solution, soaking the precipitates in a mixed water solution of hydrogen peroxide and acetic acid according to a liquid-material ratio of 50ml/g for 20-30min, transferring into a reaction kettle with a polytetrafluoroethylene substrate, heating in a 140 ℃ water bath for 12-24h, cooling to room temperature, centrifuging the suspension, and freeze-drying at-60 ℃, mechanically pulverizing, micronizing, and sieving to obtain micropowder with particle size of 40-70 μm to obtain modified bryophyte fiber;
s2 preparation of hydrogel
Weighing 1 part by weight of polyvinyl alcohol, dissolving the polyvinyl alcohol in deionized water, wherein the mass part of the polyvinyl alcohol is 2-5%, adjusting the pH value of the solution to 5 with glacial acetic acid, adding 12-15 parts of carboxymethyl chitosan, mixing and stirring, introducing nitrogen into the mixed solution to obtain a uniform and transparent precursor solution, adding deionized water with the same volume as the precursor solution, stirring to obtain a viscous solution, standing for 24 hours, soaking for 72-120 hours with the deionized water, changing water once every 12 hours, performing forced air drying at 80 ℃ for 12 hours after soaking is completed, performing vacuum drying at 60 ℃ for 24 hours, mechanically crushing for micronization, and screening to obtain micro powder with the particle size of 40-70 mu m, thereby preparing the carboxymethyl chitosan hydrogel;
s3, proportioning
And mixing the modified bryophyte fibers with the carboxymethyl chitosan hydrogel according to a ratio to prepare the modified filler.
The bonding strength of the resin can be further improved by adding the modified filler, on one hand, the modified moss plant fibers and the carboxymethyl chitosan hydrogel can provide partial bonding force, have stronger water retention capacity, can reduce the permeation of the binder in the microporous structure of the activated carbon, and reduce the influence of the permeation of the binder on the quality of the activated carbon, on the other hand, the modified moss plant fibers and the carboxymethyl chitosan hydrogel have high carbon content and good porous structure, can form a part of the activated carbon after pyrolysis and carbonization, have good adsorption capacity, and can maintain the microporous structure of the pressed activated carbon to the maximum extent;
preferably, in the mixed aqueous solution of hydrogen peroxide and acetic acid, the mass fractions of hydrogen peroxide and acetic acid are 10 wt.% and 10 wt.%, respectively.
Preferably, the mass mixing ratio of the modified bryophyte fibers to the hydrogel micropowder (3-6): 1.
example 1
The production process of the environment-friendly regenerated activated carbon comprises the following steps:
s1, pretreatment
Cleaning the recovered waste activated carbon after impurity removal, drying by hot air and simultaneously carrying out surface micro-oxidation, wherein the temperature of the hot air is 150 ℃, the heat treatment time is 30-50min, after cooling, grinding is carried out, the grinding granularity is 200-300 meshes, the recovered activated carbon obtained by grinding is put into a pressure-resistant container, a vacuum pump exhausts air until the absolute air pressure in the container reaches 300-500Pa, the recovered activated carbon is taken out after keeping the air pressure for 1-3h, then the recovered activated carbon is respectively and sequentially added into 1mol/L hydrochloric acid solution and 4mol/L sodium hydroxide solution to be soaked to remove redundant impurities, rinsed by clear water, and dried by drying equipment for many times to obtain a recovered material;
s2, processing of multiple holes
Heating the recycled material to 180 ℃, preserving the temperature until the temperature of the recycled material is stable, quickly immersing the high-temperature recycled material into low-temperature liquid nitrogen for cooling, and repeatedly heating and cooling for 2-3 times;
s3, activation
Under the protection atmosphere of nitrogen or argon, heating the treated activated carbon to 800 ℃, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product, adding the prepared calcined product into 0.1mol/L hydrochloric acid solution to soak for removing redundant impurities, and washing with deionized water to obtain an activated product;
s4, preparing the ingredients
Mixing an activated product and weakly caking coal powder according to the weight part ratio of 100:15, wherein the particle size of the weakly caking coal powder is 200-300 meshes, adding carbon nano tubes accounting for 3% of the activated product by mass, mechanically stirring or air stirring until the mixture is uniform to obtain a mixture, adding a modified phenolic resin binder accounting for 3% of the mixture by weight, stirring again until the mixture is uniform, putting the mixture into a forming device for compression forming to obtain a forming material, and drying the forming material until the moisture content is less than 2%;
s5, secondary activation
Activating by adopting a gas activation method, wherein the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 48h to obtain a secondary activation product;
s6, post-processing
Screening the secondary activation product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, adding the finished product into the treatment solution, wherein the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate are respectively 2mol/L, 0.5mol/L and 0.4mol/L, stirring and reacting for 4 hours under the water bath condition of 70 ℃, filtering out, rinsing with clear water, and drying for multiple times by using drying equipment to prepare the environment-friendly regenerated activated carbon;
the modified phenolic resin consists of water-soluble phenolic resin, modified filler and diluent, wherein the weight ratio of the water-soluble phenolic resin to the modified filler to the diluent is 12: 3: 100, the modified filler is a composition of modified bryophyte fibers and carboxymethyl chitosan hydrogel;
the preparation method of the modified filler comprises the following steps:
s1 modified bryophyte fiber
Washing moss for a plurality of times by using clean water, removing soil impurities on the surface, drying the cleaned moss until the moisture content is less than 10%, weighing 1 part by weight of the dried moss, adding 100 parts by weight of deionized water, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite, heating in a 75 ℃ water bath for 1h under the stirring condition, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, continuing to stir and heat for 1h, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, stirring, filtering out precipitates, leaching by using an acetic acid solution, soaking the precipitates into a mixed aqueous solution of hydrogen peroxide and acetic acid according to the liquid-material ratio of 50ml/g, wherein the mass fractions of the hydrogen peroxide and the acetic acid in the mixed aqueous solution of the hydrogen peroxide and the acetic acid are respectively 10 wt.%, and the soaking time is 20-30min, then transferring the mixture into a reaction kettle with a polytetrafluoroethylene substrate, heating the mixture in water bath at 140 ℃ for 12-24h, cooling the mixture to room temperature, centrifuging the suspension, freeze-drying the suspension at-60 ℃, mechanically crushing the suspension into micropowder with the particle size of 40-70 mu m, and screening the micropowder to obtain the modified moss plant fiber;
s2 preparation of hydrogel
Weighing 1 part by weight of polyvinyl alcohol, dissolving the polyvinyl alcohol in deionized water, wherein the mass part of the polyvinyl alcohol is 2-5%, adjusting the pH value of the solution to 5 with glacial acetic acid, adding 12-15 parts of carboxymethyl chitosan, mixing and stirring, introducing nitrogen into the mixed solution to obtain a uniform and transparent precursor solution, adding deionized water with the same volume as the precursor solution, stirring to obtain a viscous solution, standing for 24 hours, soaking for 72-120 hours with the deionized water, changing water once every 12 hours, performing forced air drying at 80 ℃ for 12 hours after soaking is completed, performing vacuum drying at 60 ℃ for 24 hours, mechanically crushing for micronization, and screening to obtain micro powder with the particle size of 40-70 mu m, thereby preparing the carboxymethyl chitosan hydrogel;
s3, proportioning
Mixing the modified bryophyte fibers with the carboxymethyl chitosan hydrogel according to a mass ratio of 4: 1, mixing to obtain the modified filler.
Example 2
The production process of the environment-friendly regenerated activated carbon comprises the following steps:
s1, pretreatment
Cleaning the recovered waste activated carbon after impurity removal, drying by hot air and simultaneously carrying out surface micro-oxidation, wherein the temperature of the hot air is 150 ℃, the heat treatment time is 30-50min, after cooling, grinding is carried out, the grinding granularity is 200-300 meshes, the recovered activated carbon obtained by grinding is put into a pressure-resistant container, a vacuum pump exhausts air until the absolute air pressure in the container reaches 300-500Pa, the recovered activated carbon is taken out after keeping the air pressure for 1-3h, then the recovered activated carbon is respectively and sequentially added into 1mol/L hydrochloric acid solution and 4mol/L sodium hydroxide solution to be soaked to remove redundant impurities, rinsed by clear water, and dried by drying equipment for many times to obtain a recovered material;
s2, processing of multiple holes
Heating the recycled material to 180 ℃, keeping the temperature until the temperature of the recycled material is stable, quickly immersing the high-temperature recycled material into low-temperature liquid nitrogen for cooling, repeatedly heating and cooling for 2-3 times, carrying out load treatment, weighing potassium ferrate and tween-60, dissolving in deionized water to prepare a solution A, wherein the mass concentration of the potassium ferrate in the solution A is 5g/L, the mass concentration of the tween-60 is 0.4g/L, adding the solution A into the treated activated carbon, the addition amount of the solution A is 1g/10ml, fully stirring uniformly, standing overnight, filtering, and carrying out vacuum drying at 70-80 ℃ for 8-12 hours;
s3, activation
Under the protection atmosphere of nitrogen or argon, heating the treated activated carbon to 800 ℃, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product, adding the prepared calcined product into 0.1mol/L hydrochloric acid solution to soak for removing redundant impurities, and washing with deionized water to obtain an activated product;
s4, preparing the ingredients
Mixing an activated product and weakly caking coal powder according to the weight part ratio of 100:15, wherein the particle size of the weakly caking coal powder is 200-300 meshes, adding carbon nano tubes accounting for 3% of the activated product by mass, mechanically stirring or air stirring until the mixture is uniform to obtain a mixture, adding a modified phenolic resin binder accounting for 3% of the mixture by weight, stirring again until the mixture is uniform, putting the mixture into a forming device for compression forming to obtain a forming material, and drying the forming material until the moisture content is less than 2%;
s5, secondary activation
Activating by adopting a gas activation method, wherein the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 48h to obtain a secondary activation product;
s6, post-processing
Screening the secondary activation product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, adding the finished product into the treatment solution, wherein the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate are respectively 2mol/L, 0.5mol/L and 0.4mol/L, stirring and reacting for 4 hours under the water bath condition of 70 ℃, filtering out, rinsing with clear water, and drying for multiple times by using drying equipment to prepare the environment-friendly regenerated activated carbon;
the modified phenolic resin adhesive is the same as in example 1.
Comparative example 1
The binder was a coal tar binder as in example 1.
Examples of the experiments
The basic performance indexes of the activated carbon described in example 1, example 2 and comparative example 1 were measured, and the measurement results are as follows:
| performance index | Measurement method | Example 1 | Example 2 | Comparative example 1 |
| Ash content | GB/T7702.15-2008 | 3.2％ | 3.4％ | 3.5％ |
| Iodine adsorption number | GB/T7702.7-2008 | 675mg/g | 839mg/g | 541mg/g |
| Methylene blue adsorption number | GB/T7702.6-2008 | 180mg/g | 196mg/g | 153mg/g |
| Mechanical strength | GB/T7702.3-2008 | 97.2％ | 97.5％ | 86.4％ |
| Specific surface area | GB/T7702.20-2008 | 759m2/g | 828m2/g | 533m2/g |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The production process of the environment-friendly regenerated activated carbon is characterized by comprising the following steps of:
s1, pretreatment
Cleaning the recovered waste activated carbon after impurity removal, drying by hot air and simultaneously carrying out surface micro-oxidation, grinding after cooling, wherein the grinding granularity is 200-300 meshes, putting the recovered activated carbon obtained by grinding into a pressure-resistant container, pumping air by a vacuum pump until the absolute air pressure in the container reaches 300-500Pa, keeping the air pressure for 1-3h, then taking out, sequentially adding the recovered activated carbon into 1mol/L hydrochloric acid solution and 4mol/L sodium hydroxide solution, soaking to remove redundant impurities, rinsing by clear water, and drying for multiple times by using drying equipment to obtain a recovered material;
s2, processing of multiple holes
Heating the recycled material to 180 ℃, preserving the temperature until the temperature of the recycled material is stable, quickly immersing the high-temperature recycled material into low-temperature liquid nitrogen for cooling, and repeatedly heating and cooling for 2-3 times;
s3, activation
Under the protection atmosphere of nitrogen or argon, heating the activated carbon obtained by the multiple hole treatment to 700-800 ℃, carrying out thermal insulation pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product, adding the prepared calcined product into a 0.1mol/L hydrochloric acid solution, soaking to remove redundant impurities, and washing with deionized water to obtain an activated product;
s4, preparing the ingredients
Mixing the activated product with weakly-sticky coal powder according to the weight part ratio of 100 (5-20), wherein the particle size of the weakly-sticky coal powder is 200-300 meshes, mechanically stirring or air stirring uniformly to obtain a mixture, adding a binder accounting for 1-3% of the weight of the mixture, stirring uniformly again, putting the mixture into a forming device for compression forming to obtain a forming material, and drying the forming material until the moisture content is less than 2%;
s5, secondary activation
Activating by adopting a gas activation method, wherein the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 30-72h to obtain a secondary activation product;
s6, post-processing
And (2) screening the secondary activation product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, adding the finished product into the treatment solution, stirring and reacting for 1-5h under the condition of 70 ℃ water bath, filtering out, rinsing with clear water, and drying for multiple times by using drying equipment to obtain the environment-friendly regenerated activated carbon.
2. The process for producing environment-friendly regenerated activated carbon as claimed in claim 1, wherein the temperature of the hot air is 120-160 ℃ and the heat treatment time is 30-50 min.
3. The process for producing environment-friendly regenerated activated carbon according to claim 1, wherein the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate in the treatment solution are 2mol/L, 0.5mol/L and 0.4mol/L respectively.
4. The process for producing environment-friendly regenerated activated carbon according to claim 1, wherein the mixture further comprises carbon nanotubes in an amount of 2-5% of the activated product.
5. The production process of the environment-friendly regenerated activated carbon according to claim 1, characterized in that the production process further comprises a loading treatment before the activation treatment after the secondary pore treatment, and the specific steps are as follows:
weighing potassium ferrate and tween-60, dissolving in deionized water to obtain a solution A, wherein the mass concentration of the potassium ferrate in the solution A is 3-6g/L, the mass concentration of the tween-60 is 0.2-0.5g/L, adding the solution A into activated carbon obtained by porous treatment, the addition amount is 1g/10ml, fully and uniformly stirring, standing overnight, filtering, and carrying out vacuum drying at 70-80 ℃ for 8-12h to obtain the reclaimed material loaded with the potassium ferrate.
6. The process for producing environment-friendly regenerated activated carbon according to claim 1, wherein the binder is modified phenolic resin.
7. The production process of the environment-friendly regenerated activated carbon according to claim 6, wherein the modified phenolic resin is composed of water-soluble phenolic resin, modified filler and diluent, wherein the weight ratio of the water-soluble phenolic resin to the modified filler to the diluent is (10-20): (1-3): 100, the modified filler is a composition of modified bryophyte fibers and carboxymethyl chitosan hydrogel.
8. The production process of the environment-friendly regenerated activated carbon as claimed in claim 7, wherein the preparation method of the modified filler comprises the following steps:
s1 modified bryophyte fiber
Washing moss with clear water for several times to remove soil impurities on the surface, drying the cleaned moss until the moisture content is less than 10%, weighing 1 part by weight of the dried moss, adding 100 parts by weight of deionized water, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite, heating in a 75 ℃ water bath for 1h under stirring, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, continuing to stir and heat for 1h, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, stirring, filtering out precipitates, leaching with an acetic acid solution, soaking the precipitates in a mixed water solution of hydrogen peroxide and acetic acid according to a liquid-material ratio of 50ml/g for 20-30min, transferring into a reaction kettle with a polytetrafluoroethylene substrate, heating in a 140 ℃ water bath for 12-24h, cooling to room temperature, centrifuging the suspension, and freeze-drying at-60 ℃, mechanically pulverizing, micronizing, and sieving to obtain micropowder with particle size of 40-70 μm to obtain modified bryophyte fiber;
s2 preparation of hydrogel
Weighing 1 part by weight of polyvinyl alcohol, dissolving the polyvinyl alcohol in deionized water, wherein the mass part of the polyvinyl alcohol is 2-5%, adjusting the pH value of the solution to 5 with glacial acetic acid, adding 12-15 parts of carboxymethyl chitosan, mixing and stirring, introducing nitrogen into the mixed solution to obtain a uniform and transparent precursor solution, adding deionized water with the same volume as the precursor solution, stirring to obtain a viscous solution, standing for 24 hours, soaking for 72-120 hours with the deionized water, changing water once every 12 hours, performing forced air drying at 80 ℃ for 12 hours after soaking is completed, performing vacuum drying at 60 ℃ for 24 hours, mechanically crushing for micronization, and screening to obtain micro powder with the particle size of 40-70 mu m, thereby preparing the carboxymethyl chitosan hydrogel;
s3, proportioning
And mixing the modified bryophyte fibers with the carboxymethyl chitosan hydrogel according to a ratio to prepare the modified filler.
9. The process for producing environment-friendly regenerated activated carbon according to claim 8, wherein the mass fractions of hydrogen peroxide and acetic acid in the mixed aqueous solution of hydrogen peroxide and acetic acid are 10 wt.% and 10 wt.%, respectively.
10. The production process of the environment-friendly regenerated activated carbon as claimed in claim 8, wherein the mass mixing ratio of the modified bryophyte fibers to the hydrogel micropowder (3-6): 1.
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