CN110240233B - Preparation method and application of modified bamboo charcoal - Google Patents
Preparation method and application of modified bamboo charcoal Download PDFInfo
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- CN110240233B CN110240233B CN201910527830.2A CN201910527830A CN110240233B CN 110240233 B CN110240233 B CN 110240233B CN 201910527830 A CN201910527830 A CN 201910527830A CN 110240233 B CN110240233 B CN 110240233B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
- C02F2001/46157—Perforated or foraminous electrodes
- C02F2001/46161—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a preparation method and application of modified bamboo charcoal. A large amount of high-valence metal elements such as copper, tin, cobalt or manganese loaded on the modified bamboo charcoal obtained by the method can increase potential difference in iron-carbon micro-electrolysis reaction, so that iron is oxidized into iron ions more quickly, the iron ion generation reaction is promoted, the iron-carbon micro-electrolysis reaction process can be promoted, the catalytic effect on the iron-carbon micro-electrolysis reaction is good, the water treatment effect is good, and the problem that the existing modified bamboo charcoal is not suitable for iron-carbon micro-electrolysis is solved. The method has the advantages of simple and easy process, rich and cheap raw material sources, low cost, easy realization of large-scale industrial production and good economic benefit.
Description
Technical Field
The invention relates to the technical field of water treatment materials, in particular to a preparation method and application of modified bamboo charcoal.
Background
Iron-carbon microelectrolysis is a good process for treating wastewater by using a metal corrosion principle method to form a primary battery, and is also called an internal electrolysis method, an iron scrap filtration method and the like. In order to improve the electrochemical reaction activity, an additional carbon-based material is adopted to increase the cathode, and the selection of the carbon-based material determines the water treatment effect of the process to a certain extent. Due to the special structure of bamboo, bamboo charcoal has developed large and medium pores, so that the bamboo charcoal has strong adsorbability, can improve the water treatment effect, and has the characteristics of low cost and environmental protection, and therefore the bamboo charcoal is an ideal carbon-based material.
The prior method for preparing bamboo charcoal comprises a direct firing method by heating in an earth kiln, a dry distillation thermal cracking firing method and the like, for example, the invention patent CN201610641743.6 discloses a firing method for a bamboo charcoal desiccant in an earth kiln, wherein bamboo is stacked in the earth kiln to be heated, the bamboo is subjected to fumigation pre-drying treatment for 3 to 5 days, the bamboo is subjected to drying treatment for 5 to 7 days, and the bamboo is subjected to pre-carbonization treatment for 5 to 7 days; the bamboo is carbonized for 5 to 7 days, and is calcined for 5 to 7 days, but the method wastes time and labor, consumes more energy and causes serious pollution. The invention patent CN201810380966.0 discloses a preparation method of an iron-bamboo charcoal composite material, which comprises the steps of mixing bamboo charcoal with an acid reagent for first modification treatment to obtain acid-modified bamboo charcoal; mixing the acid modified bamboo charcoal with an iron reagent for second modification treatment to obtain iron modified bamboo charcoal; mixing the iron-modified bamboo charcoal and a water hyacinth leaf extracting solution, adjusting the pH value of the obtained reaction material to be 6-6.8, and carrying out reduction reaction to obtain an iron-bamboo charcoal composite material, wherein the combination of iron and bamboo charcoal in the obtained composite material mainly depends on physical adsorption and is unstable, so that the iron-bamboo charcoal composite material is poor in stability, slow in purification effect and poor in water treatment effect when used for iron-carbon micro-electrolysis, and has no effect of catalytically strengthening the iron-carbon micro-electrolysis reaction process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of modified bamboo charcoal and application thereof, and solves the problems of high energy consumption, long time consumption, serious pollution, poor stability in iron-carbon micro-electrolysis, slow reaction, poor water treatment effect and the like in the existing bamboo charcoal preparation.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of modified bamboo charcoal comprises the following steps:
1) soaking the bamboo material in a dilute acid solution for 24-48 h, cleaning and drying to remove organic matters on the surface of the bamboo material and roughen the surface of the bamboo material;
2) crushing the bamboo material pretreated in the step 1), sieving to obtain bamboo charcoal powder, adding a pore-forming agent, water and a binder into the bamboo charcoal powder, stirring uniformly, twisting into small balls with the diameter of 3-5 mm, and calcining the small balls in a muffle furnace to obtain porous bamboo charcoal small balls; the small balls with the diameter of 3-5 mm ensure the recycling of bamboo charcoal after iron-carbon micro-electrolysis.
3) Uniformly mixing the porous bamboo charcoal pellets obtained in the step 2), metal salt and a pH control agent to enable the pH value of a reaction system to be 8-9, then placing the reaction system in an ultrasonic constant-temperature water bath at 15-70 ℃ to fully react for 1-2 hours, and then washing and drying the product to obtain the modified bamboo charcoal.
Preferably, the mass ratio of the pore-forming agent, the binder, the water and the bamboo charcoal powder is 0.01-0.05: 0.10-0.30: 0.1-0.4: 1.
preferably, the mass ratio of the porous bamboo charcoal small balls to the metal salt is 1: 0.01 to 0.05.
Preferably, the bamboo material is trunk and branch of bamboo plant such as arrowroot bamboo, single bamboo, mottled bamboo, water bamboo, brown bamboo, phyllostachys pubescens, arhat bamboo, phoenix tail bamboo or giant dragon bamboo, and products made from the same. Phyllostachys pubescens belongs to Phyllostachys of Gramineae, is a large-area bamboo planted in China, has the characteristics of high elasticity, high rigidity, high hardness, long fiber and the like, can be used for materials, eating, medicine, appreciation and the like, and is an ideal material for preparing bamboo charcoal.
Preferably, the dilute acid solution is a dilute sulfuric acid solution, a dilute nitric acid solution, a dilute hydrochloric acid solution or an acetic acid solution with the mass fraction of 10-50%, the weak acid solution can effectively remove organic matters on the surface of the bamboo material and ensure that the bamboo material is not damaged, and on the basis, the weak acid solution also has the effect of improving the original pore structure of the bamboo material or increasing the pores of the bamboo material. The dilute nitric acid has oxidizing effect on organic matters, is weaker in acidity than dilute sulfuric acid and dilute hydrochloric acid, can reduce corrosion on the main material, and is a good reagent for conditioning the bamboo material.
The soaking time is 24-48 hours, so that organic matters on the surfaces of the bamboo chips are sufficiently removed, and the surfaces of the bamboo chips are rough. Soaking the bamboo material in dilute nitric acid solution for 24h to remove organic matters such as mud and dust naturally remaining on the surface of the bamboo material, ensure the subsequent bamboo charcoal firing quality, increase and improve the surface pores of the main material and increase the porosity.
Preferably, the pore-forming agent is ammonium bicarbonate, benzoic acid, phenolic resin, flour, graphene, ps microspheres, PMMA microspheres or polyethylene glycol, and the pore-forming agent forms pores in sintering due to burnout of pore-forming agent particles in a high-temperature calcination process under an aerobic condition, so that a uniform microporous structure is formed on the surface and inside of the bamboo charcoal microspheres, for example, sodium bicarbonate starts to decompose at a temperature of more than 50 ℃, and completely decomposes at a temperature of 270 ℃ to generate sodium carbonate, water and carbon dioxide. In the firing process of the bamboo material, the temperature exceeds 270 ℃, and the sodium bicarbonate can be completely decomposed, so that fine pores are left in the small balls, and the porosity of the bamboo charcoal is increased.
The binder is sodium silicate, epoxy resin, polyurethane, polyimide, amino resin, methyl acrylate, polyurethane acrylate or alkyl acrylate. The polyimide binder includes polyimide fluoride, polyimide with ketone anhydride (BTDA) as a monomer, polyamide-imide and the like. The binding agent is a high-temperature-resistant high-molecular binding agent, and due to high-temperature resistance and good binding property, the binding agent can not be decomposed at high temperature, effectively binds bamboo powder, ensures the strength of the bamboo powder in the firing process, and finally enables the bamboo charcoal to be fired and molded.
Preferably, the metal salt is one or more of copper chloride, tin chloride, manganese chloride, cobalt chloride, chromium chloride, copper nitrate, tin nitrate, manganese nitrate, cobalt nitrate, chromium nitrate, copper sulfate, manganese sulfate, tin sulfate and cobalt sulfate; the pH control agent is a sodium hydroxide solution, a calcium hydroxide solution, a sodium carbonate solution, a calcium oxide solution, a sodium phosphate solution or a sodium bicarbonate solution, and the mass fraction of the pH control agent is 10-25%. The acid-base change in the loading process can be relieved and lightened to a certain extent, the pH value is relatively stable at 8-9, and the loading process is guaranteed to be carried out stably.
Preferably, the calcining temperature is 600-800 ℃; the calcination time is 4-8 h, so that the bamboo material is completely converted into carbonized particles, and the sintering and scorching phenomena are avoided. The calcination temperature and time of the porous bamboo charcoal pellets determine the strength and porosity of the formed bamboo charcoal. If the temperature is too low and the firing time is too short, the bamboo materials cannot be completely converted into carbonized particles, so that the final bamboo charcoal component is impure and the porosity is low; on the contrary, if the temperature is too high and the firing time is too long, the bamboo charcoal is burnt, loose components (ash content) are increased, and finally the strength of the bamboo charcoal is reduced.
Preferably, the ultrasonic power is 0.5-1 KW, and the ultrasonic frequency is 17.5-22 KHZ. When ultrasonic wave acts on the aqueous solution, on one hand, micro bubbles (cavitation) are formed in the water, so that the impact action among particles is enhanced, and a good stirring effect can be achieved. Therefore, under the action of ultrasonic waves, the metal salt can be forced to vibrate, the probability of entering the bamboo charcoal pores is greatly increased, and the metal salt is uniformly distributed inside and on the surfaces of the bamboo charcoal pores; on the other hand, the ultrasonic energy generates a heat effect, so that the metal and the carbon generate chemical reaction to generate carbide or generate oxide or oxycarbide in cooperation with oxygen, and the bamboo charcoal and the metal are firmly combined through the synergistic effect of high temperature and ultrasonic wave.
Preferably, the drying temperature is 50-70 ℃, and the time is 12-24 h.
The invention also provides application of the modified bamboo charcoal in iron-carbon micro-electrolysis. A large amount of high valence metal elements such as copper, tin, cobalt or manganese loaded on the modified bamboo charcoal can increase potential difference in iron-carbon micro-electrolysis reaction, so that iron is oxidized into iron ions more quickly, the iron ion generation reaction is promoted, and the iron-carbon micro-electrolysis reaction process can be promoted.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method comprises the steps of firstly carrying out functionalization treatment on bamboo materials to obtain porous bamboo charcoal particles, then taking the porous bamboo charcoal as a carrier, uniformly distributing metal salt inside and on the surfaces of pores of the bamboo charcoal under the action of ultrasonic waves, and firmly combining the metal salt with the bamboo charcoal in a chemical bond and physical mode to prepare the modified bamboo charcoal. A large amount of high-valence metal elements such as copper, tin, cobalt or manganese loaded on the modified bamboo charcoal obtained by the method can increase potential difference in iron-carbon micro-electrolysis reaction, so that iron is oxidized into iron ions more quickly, the iron ion generation reaction is promoted, the iron-carbon micro-electrolysis reaction process can be promoted, the catalytic effect on the iron-carbon micro-electrolysis reaction is good, the water treatment effect is good, the treatment effect on high-salinity organic wastewater is particularly remarkably improved, and the problem that the existing modified bamboo charcoal is not suitable for iron-carbon micro-electrolysis is solved.
2. The method has the advantages of simple and easy process, abundant and cheap raw material sources, low cost, easy realization of large-scale industrial production, provision of new theoretical guidance and technical support for efficiently catalyzing iron-carbon micro-electrolysis reaction and good economic benefit.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation method of modified bamboo charcoal
Example 1
1) Soaking 50g of bamboo material in 500ml of 20% dilute nitric acid solution for 24h, cleaning and naturally drying, removing organic matters on the surface of the bamboo material and making the surface rough;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving with a 50-mesh sieve to obtain 46.7g of bamboo charcoal powder.
3) Adding 40g of bamboo charcoal powder, 8g of polyimide, 2g of sodium bicarbonate and 12ml of deionized water into a reaction device, uniformly stirring, twisting into small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at the temperature of 800 ℃ for firing for 2 hours, after firing, taking out the fired and molded bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 52.5g of porous bamboo charcoal pellets and 2.6g of copper chloride into a reaction container, adding 500ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of the reaction system to reach 8-9, then placing the reaction system in an ultrasonic constant-temperature water bath at 30 ℃ for fully reacting for 1h, wherein the ultrasonic power is 0.2kw and the ultrasonic frequency is 16KHZ, and washing and drying the product for multiple times at 70 ℃ for 4h to obtain the Cu-bamboo charcoal.
Example 2
1) Soaking 100g of bamboo material in 1000ml of 30% dilute nitric acid solution for 24h, cleaning, naturally drying, removing organic matters on the surface of the bamboo material, and roughening the surface of the bamboo material;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving with a 70-mesh sieve to obtain 73.5g of bamboo charcoal powder.
3) Adding 60g of bamboo charcoal powder, 18g of polyimide, 3g of sodium bicarbonate and 20ml of deionized water into a reaction device, uniformly stirring, twisting into small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at the temperature of 750 ℃ for firing for 2.5h, after firing, taking out the fired and molded bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 60g of porous bamboo charcoal pellets and 1.8g of manganese nitrate into a reaction container, adding 600ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of a reaction system to reach 8-9, then placing the reaction system in an ultrasonic constant-temperature water bath at 30 ℃ to fully react for 1h, wherein the ultrasonic power is 0.25kw and the ultrasonic frequency is 17KHZ, washing the product for multiple times, and drying the product at 65 ℃ for 5h to obtain the Mn-bamboo charcoal.
Example 3
1) Soaking 50g of bamboo material in 500ml of dilute nitric acid solution with the mass fraction of 35% for 30h, cleaning, drying at 50 ℃ for 12h, removing organic matters on the surface of the bamboo material, and roughening the surface of the bamboo material;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving with a 60-mesh sieve to obtain 43.7g of bamboo charcoal powder.
3) Adding 40g of bamboo charcoal powder, 12g of sodium silicate, 2g of PPM microspheres and 12ml of deionized water into a reaction device, uniformly stirring, twisting into small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at 900 ℃ for firing for 2 hours, after firing, taking out the fired and formed bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 45g of porous bamboo charcoal pellets and 1.4g of cobalt nitrate into a reaction container, adding 500ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of a reaction system to reach 8-9, then placing the reaction system in 30 ℃ ultrasonic constant-temperature water bath for fully reacting for 1h, wherein the ultrasonic power is 0.5kw and the ultrasonic frequency is 15.5KHZ, washing the product for multiple times, and drying the product for 6h at 60 ℃ to obtain the Co-bamboo charcoal.
Example 4
1) Soaking 70g of bamboo material in 700ml of dilute nitric acid solution with the mass fraction of 40% for 24h, cleaning, drying at 30 ℃ for 24h, removing organic matters on the surface of the bamboo material, and roughening the surface of the bamboo material;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving with a 70-mesh sieve to obtain 65.7g of bamboo charcoal powder.
3) Adding 50g of bamboo charcoal powder, 10g of sodium silicate, 2.5g of benzoic acid and 10ml of deionized water into a reaction device, uniformly stirring, twisting to obtain small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at 900 ℃ for firing for 2 hours, after firing, taking out the fired and molded bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 40g of porous bamboo charcoal pellets and 1.6g of tin nitrate into a reaction container, adding 400ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of a reaction system to reach 8-9, then placing the reaction system in 30 ℃ ultrasonic constant-temperature water bath for fully reacting for 1h, wherein the ultrasonic power is 0.5kw and the ultrasonic frequency is 16.5KHZ, washing the product for multiple times, and drying the product for 4h at 65 ℃ to obtain the Sn-bamboo charcoal.
Example 5
1) Soaking 50g of bamboo material in 500ml of dilute nitric acid solution with the mass fraction of 30% for 30h, cleaning, drying at 60 ℃ for 8h, removing organic matters on the surface of the bamboo material, and roughening the surface of the bamboo material;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving by a 60-mesh sieve to obtain 47.8g of bamboo charcoal powder.
3) Adding 40g of bamboo charcoal powder, 8g of epoxy resin, 2g of PS microspheres and 12ml of deionized water into a reaction device, uniformly stirring, twisting into small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at the temperature of 600 ℃ for firing for 3 hours, after firing, taking out the fired and molded bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 40g of porous bamboo charcoal pellets and 2g of nickel nitrate into a reaction container, adding 40ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of a reaction system to reach 8-9, then placing the reaction system in 30 ℃ ultrasonic constant-temperature water bath for full reaction for 1h, wherein the ultrasonic power is 0.3kw and the ultrasonic frequency is 16KHZ, washing the product for multiple times, and drying the product at 70 ℃ for 5h to obtain the Ni-modified bamboo charcoal.
Example 6
1) Soaking 100g of bamboo material in 1000ml of dilute nitric acid solution with the mass fraction of 10% for 48h, cleaning, drying at 70 ℃ for 6h, removing organic matters on the surface of the bamboo material, and roughening the surface of the bamboo material;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving with a 100-mesh sieve to obtain 60.7g of bamboo charcoal powder.
3) Adding 60g of bamboo charcoal powder, 12g of sodium silicate, 2g of sodium bicarbonate and 18ml of deionized water into a reaction device, uniformly stirring, twisting into small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at 900 ℃ for firing for 2 hours, after firing, taking out the fired and molded bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 50g of porous bamboo charcoal pellets, 1g of lead chloride and 1g of nickel nitrate into a reaction container, adding 500ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of the reaction system to reach 8-9, then placing the reaction system in an ultrasonic constant-temperature water bath at 30 ℃ for fully reacting for 1h, wherein the ultrasonic power is 0.2kw and the ultrasonic frequency is 18KHZ, washing the product for multiple times, and drying the product at 70 ℃ for 5h to obtain the Ni and Pb-modified bamboo charcoal.
Second, application test
Adding the modified bamboo charcoal prepared in the embodiment 1-6 and iron powder into an iron-carbon micro-electrolysis reaction tank, wherein the adding mass ratio of the iron powder to the bamboo charcoal is 2: 1, the COD of the original wastewater is 3000-100000 mg/L, the ammonia nitrogen is 30-500 mg/L, the total nitrogen is 30-600 mg/L, the salt content is 0-18%, an iron-carbon micro-electrolysis reaction device is started to carry out iron-carbon micro-electrolysis reaction, effluent is obtained after 2 hours of treatment, then the effluent is detected, the removal rate of wastewater pollutants is obtained, and the results are shown in Table 1.
TABLE 1
| Product(s) | Removal rate of COD (%) | Removal ratio of Ammonia Nitrogen (%) | Removal ratio of Total Nitrogen (%) |
| Example 1 | 73.5 | 69.5 | 75.9 |
| Example 2 | 68.7 | 65.4 | 68.9 |
| Example 3 | 75.7 | 67.9 | 70.5 |
| Example 4 | 71.2 | 76.4 | 75.3 |
| Example 5 | 73.5 | 71.2 | 67.7 |
| Example 6 | 76.8 | 77.5 | 70.9 |
| Commercial product 1 (activated carbon and iron filings) | 30.5 | 17.9 | 22.0 |
| Commercial product 2 (active carbon and scrap iron) | 23.8 | 15.8 | 22.9 |
As can be seen from Table 1, compared with the commercial products, the method provided by the invention has the advantages that the iron-carbon micro-electrolysis process is catalyzed and strengthened by loading the active metal component, and the removal efficiency of COD, ammonia nitrogen and total nitrogen is higher. Especially, the method has better COD removal effect aiming at high-concentration organic wastewater and high-salinity organic wastewater, and can obviously improve the biodegradability of the wastewater. And the iron-carbon micro-electrolysis using conventional activated carbon and scrap iron has a low removal rate of COD, has a poor degradation effect on high-molecular organic matters, and has a worse treatment effect on high-salinity organic wastewater. The catalytic strengthening method of the invention can obviously improve the treatment effect on high-salinity organic wastewater.
The above description is only exemplary of the present invention and should not be taken as limiting, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. The application of the modified bamboo charcoal in iron-carbon micro-electrolysis is characterized in that copper loaded on the modified bamboo charcoal increases potential difference in iron-carbon micro-electrolysis reaction, so that iron is oxidized into iron ions more quickly, the iron ion generation reaction is promoted, and the iron-carbon micro-electrolysis reaction process can be promoted;
the preparation method of the modified bamboo charcoal comprises the following steps:
1) soaking 50g of bamboo material in 500ml of 20% dilute nitric acid solution for 24h, cleaning and naturally drying, removing organic matters on the surface of the bamboo material and making the surface rough;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving with a 50-mesh sieve to obtain 46.7g of bamboo charcoal powder;
3) adding 40g of bamboo charcoal powder, 8g of polyimide, 2g of sodium bicarbonate and 12ml of deionized water into a reaction device, uniformly stirring, twisting into small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at the temperature of 800 ℃ for firing for 2 hours, after firing, taking out the fired and molded bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 52.5g of porous bamboo charcoal pellets and 2.6g of copper chloride into a reaction container, adding 500ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of the reaction system to reach 8-9, then placing the reaction system in an ultrasonic constant-temperature water bath at 30 ℃ for fully reacting for 1h, wherein the ultrasonic power is 0.2kw and the ultrasonic frequency is 16KHZ, and washing and drying the product for multiple times at 70 ℃ for 4h to obtain the Cu-bamboo charcoal.
2. The application of the modified bamboo charcoal in iron-carbon micro-electrolysis is characterized in that cobalt loaded on the modified bamboo charcoal increases potential difference in iron-carbon micro-electrolysis reaction, so that iron is oxidized into iron ions more quickly, the iron ion generation reaction is promoted, and the iron-carbon micro-electrolysis reaction process can be promoted; the preparation method of the modified bamboo charcoal comprises the following steps:
1) soaking 50g of bamboo material in 500ml of dilute nitric acid solution with the mass fraction of 35% for 30h, cleaning, drying at 50 ℃ for 12h, removing organic matters on the surface of the bamboo material, and roughening the surface of the bamboo material;
2) putting the bamboo material pretreated in the step 1) into a crusher to be crushed, repeatedly crushing for 3 times, taking out the crushed powder, and sieving with a 60-mesh sieve to obtain 43.7g of bamboo charcoal powder;
3) adding 40g of bamboo charcoal powder, 12g of sodium silicate, 2g of PPM microspheres and 12ml of deionized water into a reaction device, uniformly stirring, twisting into small balls with the diameter of 3mm, then placing the small balls into a muffle furnace, calcining at 900 ℃ for firing for 2 hours, after firing, taking out the fired and formed bamboo charcoal small balls after the muffle furnace is cooled to room temperature, and placing the small balls into water for washing to obtain porous bamboo charcoal small balls;
4) adding 45g of porous bamboo charcoal pellets and 1.4g of cobalt nitrate into a reaction container, adding 500ml of deionized water and 25% by mass of sodium hydroxide solution, uniformly mixing to enable the pH value of a reaction system to reach 8-9, then placing the reaction system in 30 ℃ ultrasonic constant-temperature water bath for fully reacting for 1h, wherein the ultrasonic power is 0.5kw and the ultrasonic frequency is 15.5KHZ, washing the product for multiple times, and drying the product for 6h at 60 ℃ to obtain the Co-bamboo charcoal.
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| CN114210970B (en) * | 2021-12-28 | 2023-09-22 | 北京建工环境修复股份有限公司 | Coated iron-carbon composite material, preparation method, modification method and sewage treatment method |
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| CN102040263A (en) * | 2010-11-17 | 2011-05-04 | 北京航空航天大学 | Method for modifying micro-electrolytic fillers |
| CA2873040A1 (en) * | 2012-05-07 | 2013-11-14 | Biogenic Reagents Ventures, Llc | Biogenic activated carbon and methods of making and using same |
| CN104003483A (en) * | 2014-06-19 | 2014-08-27 | 福州大学 | Bamboo charcoal-based microelectrolysis porous ceramsite filler and preparing method thereof |
| CN104707566A (en) * | 2015-02-17 | 2015-06-17 | 中国海洋大学 | Charcoal sphere as well as preparation method and application thereof |
| CN105056884A (en) * | 2015-07-23 | 2015-11-18 | 南通名物电子商务有限公司 | Preparation method for activated carbon material for drinking water purification |
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| CN102040263A (en) * | 2010-11-17 | 2011-05-04 | 北京航空航天大学 | Method for modifying micro-electrolytic fillers |
| CA2873040A1 (en) * | 2012-05-07 | 2013-11-14 | Biogenic Reagents Ventures, Llc | Biogenic activated carbon and methods of making and using same |
| CN104003483A (en) * | 2014-06-19 | 2014-08-27 | 福州大学 | Bamboo charcoal-based microelectrolysis porous ceramsite filler and preparing method thereof |
| CN104707566A (en) * | 2015-02-17 | 2015-06-17 | 中国海洋大学 | Charcoal sphere as well as preparation method and application thereof |
| CN105056884A (en) * | 2015-07-23 | 2015-11-18 | 南通名物电子商务有限公司 | Preparation method for activated carbon material for drinking water purification |
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