CN110935421A - Method for adsorption treatment of hexavalent chromium-containing wastewater by bismuth ferrite modified charcoal compound - Google Patents

Method for adsorption treatment of hexavalent chromium-containing wastewater by bismuth ferrite modified charcoal compound Download PDF

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CN110935421A
CN110935421A CN201911299885.9A CN201911299885A CN110935421A CN 110935421 A CN110935421 A CN 110935421A CN 201911299885 A CN201911299885 A CN 201911299885A CN 110935421 A CN110935421 A CN 110935421A
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hexavalent chromium
containing wastewater
bismuth ferrite
modified biochar
bismuth
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张娅
许姗
王宏归
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Yangzhou University
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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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention relates to a method for adsorbing and treating hexavalent chromium-containing wastewater by using a bismuth ferrite modified biochar compound, which comprises the steps of firstly cleaning pomegranate shells by using hydrochloric acid, washing the pomegranate shells clean, cutting the pomegranate shells into pieces, putting the pomegranate shells into a furnace for carbonization, dispersing the carbonized pomegranate shells in a zinc chloride solution, reacting under high-temperature vigorous stirring, carrying out suction filtration, washing, drying, then carbonizing at high temperature in a nitrogen atmosphere to obtain activated biochar, and washing by using hydrochloric acid; weighing activated charcoal, bismuth nitrate hexahydrate, ferric nitrate nonahydrate and polyvinylpyrrolidone, dissolving in deionized water, stirring uniformly, dropwise adding potassium hydroxide to adjust pH, and continuing stirring; finally transferring the mixture into a high-pressure reaction kettle for reaction, and cleaning the mixture with ethanol and deionized water after centrifugal separation; drying to obtain a finished product of the bismuth ferrite modified biochar compound; adding the prepared sample into wastewater containing hexavalent chromium, stirring uniformly, adsorbing, and measuring the adsorption capacity of the prepared sample on the hexavalent chromium. By the invention, the capacity of the bismuth ferrite modified biochar compound for adsorbing hexavalent chromium is large, the treatment cost is low, and the method is environment-friendly.

Description

Method for adsorption treatment of hexavalent chromium-containing wastewater by bismuth ferrite modified charcoal compound
Technical Field
The invention relates to a method for adsorbing and treating hexavalent chromium-containing wastewater by using a bismuth ferrite modified biochar compound, and belongs to the technical field of sewage treatment.
Background
In recent years, with the increasing awareness of the public on environmental protection, various new water treatment technologies have been developed. Adsorption technology is considered to be one of new water treatment technologies with great development potential. The method has the advantages of simple operation, quick response, capability of designing and recycling the adsorbent, environmental friendliness and the like, and can be widely applied to treatment of the hexavalent chromium-containing wastewater. The vigorous development of the industries such as metallurgical industry, metal processing, electroplating, tanning, paint, printing and dyeing, pigment and the like causes the gradual increase of waste water containing heavy metal chromium discharged into the environment, and poses great threat to the environment. The hexavalent chromium-containing wastewater is difficult to biodegrade after being discharged into a water body, and can cause potential harm and even carcinogenesis to aquatic animals, plants and human beings. The adsorbent can effectively reduce the toxicity of chromium. However, the adsorption methods commonly used in China all have certain defects, such as high material price, small adsorption capacity, and the like, and the selective adsorption property needs to be improved.
Bismuth ferrite is an excellent multiferroic material that exhibits ferroelectricity and antiferromagnetism at room temperature. The magnetic, ferroelectric and optical properties of bismuth ferrite have been widely studied in different fields of application, such as in the spintronics direction of magnetic memories, ferroelectric memories, etc. In recent years, the use of bismuth ferrite in environmental applications, particularly in sewage treatment, has attracted the attention of researchers. Pomegranate hull is a common biological waste, and a plurality of documents prove that the pomegranate hull can be used as a template material; the pomegranate shells can be activated into the biochar through proper treatment, and the prepared biochar belongs to a multilayer material, has good adsorption performance, and can effectively improve the specific surface area of the template material. Therefore, the activated charcoal and the bismuth ferrite are compounded, so that the novel application of the pomegranate hull can be developed, and the adsorbent with good adsorption performance can be obtained.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a treatment method of hexavalent chromium-containing wastewater, in particular to a method for treating hexavalent chromium-containing wastewater by adsorbing a bismuth ferrite modified charcoal compound, wherein the compound has excellent adsorption performance.
The invention aims to realize the method for adsorbing and treating the hexavalent chromium-containing wastewater by using the bismuth ferrite modified biochar compound, and is characterized by comprising the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1-2 hours at 600-800 ℃ in a nitrogen atmosphere, cooling, and adjusting the pH to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑼ modification of 5-10 mg bismuth ferriteAdding the finished product of the sex biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of the hexavalent chromium-containing wastewater0Adding the bismuth ferrite modified biochar composite finished product obtained in the step ⑻ and 30mL of hexavalent chromium-containing wastewater into a glass container, and sealing;
⑽, putting the glass container in the step ⑼ into a reactor, stirring the finished product of the bismuth ferrite modified biochar composite and the hexavalent chromium-containing wastewater for 60-150 minutes to obtain a second mixture, and controlling the temperature to be room temperature;
⑾ shaking the second mixture obtained in step ⑽ in a constant temperature oscillator at room temperature, extracting 5mL of the adsorbed wastewater at set time intervals, and filtering to obtain clear solution;
⑿ taking 2mL of clear liquid, measuring the absorbance of the treated hexavalent chromium by using an ultraviolet spectrophotometry, and calculating the concentration by using a standard curve;
calculation of adsorption Capacity
Figure BDA0002321591850000031
qtThe adsorption capacity is expressed in mg/g; c0The initial concentration of the hexavalent chromium-containing wastewater is mg/L; ctThe unit of the concentration of hexavalent chromium in the adsorbed hexavalent chromium-containing wastewater is mg/L; v is the volume of the solution, and the unit is L; w is the mass of the finished product of the bismuth ferrite modified biochar composite, and the unit is g.
In step ⑴, the pomegranate hull has a mass of 15 grams.
In step ⑵, the high temperature carbonization temperature was 400 ℃.
Step ⑶, weighing 5 g carbonized pomegranate hull, adding 7.5 g zinc chloride into deionized water, and stirring at 80 ℃ for 6 hours under the condition that the dipping ratio is 1.5.
In steps ⑶, ⑸, ⑹, the stirring frequency is not less than 200 rpm.
In step ⑷, the filtrate was filtered and calcined at 700 ℃ for 1.5 hours under nitrogen atmosphere.
In step ⑸, 0.99 g of bismuth nitrate hexahydrate, 0.9 g of ferric nitrate nonahydrate, 0.2 g of activated charcoal and 0.75 g of polyvinylpyrrolidone (PVP, K30) were weighed, and the above bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) were added to 40 ml of deionized water solution.
In step ⑺, the first mixture obtained in step ⑹ was transferred to a 100 ml autoclave and reacted at 180 ℃ for 9 hours.
Compared with the prior art, the method for adsorbing and treating the hexavalent chromium-containing wastewater by the bismuth ferrite modified biochar compound provided by the invention has the following beneficial effects:
① the impregnation ratio of step ⑵ and step ⑷ must be controlled within a proper range to obtain activated charcoal.
② the activated charcoal is added into the bismuth ferrite synthesis system to improve the performance of the charcoal and promote the bismuth ferrite modified charcoal compound to have larger specific surface area and better dispersion performance, during the adsorption process, the activated charcoal and the bismuth ferrite have synergistic effect, and the rough material and the wrinkled, loose and porous structure of the wrinkled surface are beneficial to the adsorption of hexavalent chromium and provide more exposed active binding sites for the hexavalent chromium.
③ the weight ratio of the activated biochar to the bismuth ferrite in the bismuth ferrite modified biochar composite prepared by the invention is about (0.2-0.5): 1, the composite has excellent performance of adsorbing hexavalent chromium in water, is low in cost, has very high adsorption capacity when being used for adsorbing wastewater containing hexavalent chromium, and has high potential industrial application value, for the wastewater containing hexavalent chromium with initial concentration of 50-250 mg/L and pH value of 1.05-9.21, the hexavalent chromium-containing wastewater containing the initial concentration of 50-250 mg/L is put into 30mL of wastewater according to 6mg of the bismuth ferrite modified biochar composite, and after shaking for 150 minutes, the adsorption capacity can reach about 200mg/g at most.
④ the hexavalent chromium containing wastewater with the initial concentration of 209mg/L and the pH value of 6.68 is put into 30mL wastewater according to 6mg of the bismuth ferrite modified biochar compound, the adsorption capacity can reach 186.45585mg/g after shaking for more than 150 minutes, the hexavalent chromium containing wastewater with the initial concentration of 50-250 mg/L and the pH value of 1.05-9.21 mg/L is put into 30mL wastewater according to 6mg of the bismuth ferrite modified biochar compound, and after shaking for 150 minutes, the adsorption capacity exceeds 112 mg/g.
In summary, the invention relates to a method for treating hexavalent chromium-containing wastewater by adsorption of a bismuth ferrite modified biochar compound. The method comprises the following steps: washing pomegranate shells with hydrochloric acid, cutting cleaned pomegranate shells, carbonizing the cleaned pomegranate shells in a furnace, dispersing the carbonized pomegranate shells in a zinc chloride solution, reacting for several hours under high-temperature vigorous stirring, filtering, washing, drying, carbonizing at high temperature in a nitrogen atmosphere to obtain activated charcoal, and cleaning with hydrochloric acid; weighing a proper amount of activated charcoal, bismuth nitrate hexahydrate, ferric nitrate nonahydrate and polyvinylpyrrolidone, dissolving in deionized water, uniformly stirring, dropwise adding potassium hydroxide to adjust the pH value, and continuously stirring; finally transferring the mixture into a high-pressure reaction kettle for reaction, and cleaning the mixture with ethanol and deionized water after centrifugal separation; drying to obtain a finished product of the bismuth ferrite modified biochar compound; adding the mixture into hexavalent chromium-containing wastewater with the initial concentration of 50-250 mg/L, uniformly stirring, adsorbing for more than 2 hours, and measuring the adsorption capacity of the prepared sample on hexavalent chromium. The bismuth ferrite modified biochar compound has large hexavalent chromium adsorption capacity, low treatment cost and environmental friendliness.
Drawings
FIG. 1 is a scanning electron microscope image of the bismuth ferrite modified biochar composite of example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the bismuth ferrite modified biochar composite of example 4 of the present invention.
FIG. 3 is a scanning electron microscope image of the bismuth ferrite modified biochar composite of example 6 of the present invention.
FIG. 4 is a scanning electron microscope image of the bismuth ferrite modified biochar composite of example 9 of the present invention.
FIG. 5 is a graph showing the effect of different initial concentrations of bismuth ferrite modified biochar complexes on hexavalent chromium adsorption in accordance with the present invention.
FIG. 6 is a graph showing the effect of the bismuth ferrite modified biochar composite of the invention on photo-adsorption of hexavalent chromium as a function of the pH of the solution.
Detailed Description
Example 1
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewaterInitial concentration C of hexavalent chromium052mg/L, the pH value is 4.69, ⑵ adding the hexavalent chromium-containing wastewater of the bismuth ferrite modified biochar compound obtained in the step ⑴ into a glass container, sealing, ⑶ placing the glass container of the step ⑵ into a constant-temperature oscillator to shake, stirring for 150 minutes, controlling the temperature to be room temperature, after ⑷ stirring is finished, extracting 5mL of hexavalent chromium-containing wastewater of the step ⑶, filtering, ⑸ taking 2mL of clear liquid, and measuring the concentration C of the treated hexavalent chromium by an ultraviolet spectrophotometry methodt25.6mg/L, ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000051
Example 2
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0105mg/L, the pH value is 4.7, ⑵ adding the hexavalent chromium-containing wastewater of the bismuth ferrite modified biochar compound obtained in the step ⑴ into a glass container, sealing, ⑶ placing the glass container of the step ⑵ into a constant-temperature oscillator to shake, stirring for 150 minutes, controlling the temperature to be room temperature, after ⑷ stirring is finished, extracting 5mL of hexavalent chromium-containing wastewater of the step ⑶, filtering, ⑸ taking 2mL of clear liquid, and measuring the concentration C of the treated hexavalent chromium by an ultraviolet spectrophotometry methodt74.7mg/L, ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000061
Example 3
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C0 of hexavalent chromium in the hexavalent chromium-containing wastewater is 159mg/L, the pH value is 4.72, ⑵ adding the hexavalent chromium-containing wastewater of the bismuth ferrite modified biochar compound obtained in the step ⑴ into a glass container, sealing the glass container, ⑶ placing the glass container in the step ⑵ into a constant-temperature oscillator to shake the glass container, stirring the glass container for 150 minutes, controlling the temperature to be room temperature, after the ⑷ stirring is finished, extracting 5mL of the hexavalent chromium-containing wastewater in the step ⑶, filtering the hexavalent chromium-containing wastewater, ⑸ taking 2mL of clear liquid, and measuring the concentration C luminosity of the treated hexavalent chromium by an ultraviolet spectrometryt122.4mg/L, ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000071
Example 4
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
the method for adsorbing the hexavalent chromium-containing wastewater by adopting the bismuth ferrite modified biochar compound comprises the following steps⑴ adding 6mg of bismuth ferrite modified biochar complex finished product into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0209mg/L of waste water with pH value of 4.68, ⑵ adding the waste water containing hexavalent chromium of the bismuth ferrite modified biochar compound obtained in the step ⑴ into a glass container, sealing, ⑶ placing the glass container in the step ⑵ into a constant temperature oscillator to shake, stirring for 150 minutes, controlling the temperature to be room temperature, after the stirring of ⑷ is finished, extracting 5mL of waste water containing hexavalent chromium in the step ⑶, filtering, ⑸ taking 2mL of clear liquid, measuring the concentration Ct of the treated hexavalent chromium to be 171.9mg/L by an ultraviolet spectrophotometry, and ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000081
Example 5
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0254mg/L, pH 4.65, ⑵ adding the waste water containing hexavalent chromium of the bismuth ferrite modified biochar complex obtained in the step ⑴ into a glass container, sealing, ⑶ placing the glass container in the step ⑵ into a constant temperature oscillator to shake, stirring for 150 minutes, controlling the temperature to be room temperature, after ⑷ stirring is finished, extracting 5mL of waste water containing hexavalent chromium in the step ⑶, filtering, ⑸ taking 2mL of clear liquid, measuring the concentration Ct of the treated hexavalent chromium to be 216.8mg/L by an ultraviolet spectrophotometry, and ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000082
Example 6
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0202mg/L, the pH value is 1.05, ⑵ adding the hexavalent chromium-containing wastewater of the bismuth ferrite modified biochar compound obtained in the step ⑴ into a glass container, sealing, ⑶ placing the glass container of the step ⑵ into a constant-temperature oscillator to shake, stirring for 150 minutes, controlling the temperature to be room temperature, after the stirring of ⑷ is finished, extracting 5mL of the hexavalent chromium-containing wastewater of the step ⑶, filtering, ⑸ taking 2mL of clear liquid, measuring the concentration Ct of the treated hexavalent chromium to be 160.3mg/L by an ultraviolet spectrophotometry, and ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000091
Example 8
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0202mg/L, the pH value is 3.32, ⑵ adding the hexavalent chromium-containing wastewater of the bismuth ferrite modified biochar compound obtained in the step ⑴ into a glass container, sealing, ⑶ placing the glass container of the step ⑵ into a constant-temperature oscillator to shake, stirring for 150 minutes, controlling the temperature to be room temperature, after the stirring of ⑷ is finished, extracting 5mL of the hexavalent chromium-containing wastewater of the step ⑶, filtering, ⑸ taking 2mL of clear liquid, measuring the concentration Ct of the treated hexavalent chromium to be 162.8mg/L by an ultraviolet spectrophotometry, and ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000101
Example 9
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0202mg/L, the pH value is 5.22, ⑵ adding the hexavalent chromium-containing wastewater of the bismuth ferrite modified biochar compound obtained in the step ⑴ into a glass container, sealing, ⑶ placing the glass container of the step ⑵ into a constant-temperature oscillator to shake, stirring for 150 minutes, controlling the temperature to be room temperature, after the stirring of ⑷ is finished, extracting 5mL of the hexavalent chromium-containing wastewater of the step ⑶, filtering, ⑸ taking 2mL of clear liquid, measuring the concentration Ct of the treated hexavalent chromium to be 164.2mg/L by an ultraviolet spectrophotometry, and ⑺ calculating the removal rate after photocatalysis
Figure BDA0002321591850000111
Example 10
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0202mg/L, the pH value is 7.56, ⑵ is carried out by adding the hexavalent chromium-containing waste water of bismuth ferrite modified biochar compound obtained in step ⑴ into a glass container, sealing, ⑶ is carried out by placing the glass container of step ⑵ into a constant temperature oscillator, shaking, stirring for 150 minutes, controlling the temperature to room temperature, ⑷ is carried out after stirring, 5mL of hexavalent chromium-containing waste water of step ⑶ is extracted, filtering is carried out, ⑸ is carried out by taking 2mL of clear liquid, and purple is used for clear liquidThe concentration Ct of the treated hexavalent chromium is 171.2mg/L measured by an external spectrophotometry, ⑺ the removal rate after photocatalysis is calculated
Figure BDA0002321591850000121
Example 11
The invention discloses a method for adsorbing hexavalent chromium-containing wastewater by a bismuth ferrite modified biochar compound, which comprises the following steps of:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1 to 2 hours at the temperature of 600 to 800 ℃ in a nitrogen atmosphere, cooling the calcined filtrate, and adjusting the pH value to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑴ adding 6mg of finished product of the bismuth ferrite modified biochar compound into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration C of hexavalent chromium in the hexavalent chromium-containing wastewater is0202mg/L, the pH value is 9.21, ⑵ is carried out by adding the hexavalent chromium-containing waste water of bismuth ferrite modified biochar compound obtained in step ⑴ into a glass container, sealing, ⑶ is carried out by placing the glass container of step ⑵ into a constant temperature oscillator, agitating for 150 minutes, controlling the temperature to room temperature, after ⑷ agitating, extracting 5mL of hexavalent chromium-containing waste water of step ⑶, filtering, ⑸ is carried out by taking 2mL of clear liquid, measuring the concentration Ct of treated hexavalent chromium by ultraviolet spectrophotometry to be 179.5mg/L, ⑺ is carried out by calculating the removal rate after photocatalysis
Figure BDA0002321591850000131
The data for examples 1-10 are summarized in the following table, and are plotted in FIG. 5 according to the data for examples 1-5 and FIG. 6 according to the data for examples 4, 6-10.
Figure BDA0002321591850000132
As can be seen from the summary table and FIG. 5, the hexavalent chromium-containing wastewater with an initial concentration of 50 to 250mg/L and a pH value of 4.65 to 4.72 is added into 30mL of wastewater according to 6mg of the bismuth ferrite modified biochar complex, and the adsorption capacity is 130mg/g or more after shaking for 150 minutes.
As can be seen from the summary table and fig. 6, the removal rate is gradually reduced by increasing the pH of the bismuth ferrite modified biochar composite within a certain range at different pH values; as can be seen from the summary table and FIG. 5, under the condition that the adding amount of the bismuth ferrite modified biochar composite is the same, the removal rate is the highest when the material concentration is about 200mg/L and the pH value is between 1.05 and 5.22.
It is not stated that the percentages are by weight. The adsorption reactor can be an sh-yz-B type photocatalytic reactor of Shanghai Bilang laboratory instruments Co., Ltd, and the light source is removed.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention. In addition to the above examples, the present invention may have other embodiments, for example, the mass and volume of each component may be scaled up several times. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention. Technical features of the present invention which are not described may be implemented by or using the prior art, and will not be described herein.

Claims (8)

1. A method for treating hexavalent chromium-containing wastewater by adsorption of a bismuth ferrite modified biochar compound is characterized by comprising the following steps:
⑴ weighing 10-20 g pomegranate hull, adding into 0.5mol/L hydrochloric acid solution, cleaning, drying and chopping for later use;
⑵ carbonizing the cut pomegranate hull dried in step ⑴ at 400-500 deg.C in nitrogen atmosphere for 2 hours;
⑶ weighing 5-10 g of carbonized pomegranate shells, adding 5-10 g of zinc chloride into deionized water, stirring for 5-10 hours at 80-100 ℃ under the condition that the impregnation ratio is 1-3, and performing suction filtration to obtain a filtrate;
⑷, filtering to obtain a filtrate, calcining the filtrate for 1-2 hours at 600-800 ℃ in a nitrogen atmosphere, cooling, and adjusting the pH to 6 by using 0.5mol/L hydrochloric acid;
⑸ weighing 0.5-1 g of bismuth nitrate hexahydrate, 0.5-1 g of ferric nitrate nonahydrate, 0.1-1 g of activated charcoal and 0.5-1 g of polyvinylpyrrolidone (PVP, K30), adding all the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated charcoal and polyvinylpyrrolidone (PVP, K30) into 40-80 ml of deionized water solution, and then placing the solution on a magnetic stirrer to stir for 30min until the solution is uniform;
⑹ dropwise adding 2mol/L potassium hydroxide while stirring, adjusting the pH to 10-12, and continuously stirring for at least 1 hour to obtain a first mixture;
⑺, transferring the first mixture obtained in the step ⑹ into a 100 ml high-pressure reaction kettle, and reacting at 180 ℃ for 8-10 hours;
⑻, after centrifugally separating the reaction product obtained in the step ⑺ to remove moisture, firstly cleaning the reaction product with ethanol to remove unreacted polyvinylpyrrolidone, then cleaning the reaction product with deionized water to remove unreacted inorganic ions, placing the cleaned reaction product in an oven, and drying the reaction product at 50-70 ℃ for 10-20 hours to obtain a finished product of the bismuth ferrite modified biochar composite;
⑼ adding 5-10 mg of bismuth ferrite modified biochar compound finished product into 30mL of hexavalent chromium-containing wastewater, wherein the initial concentration of the hexavalent chromium-containing wastewater is C0Adding the bismuth ferrite modified biochar composite finished product obtained in the step ⑻ and 30mL of hexavalent chromium-containing wastewater into a glass container, and sealing;
⑽, putting the glass container in the step ⑼ into a reactor, stirring the finished product of the bismuth ferrite modified biochar compound and the hexavalent chromium-containing wastewater for 60-150 minutes to obtain a second mixture, and controlling the temperature to be room temperature;
⑾ shaking the second mixture obtained in step ⑽ in a constant temperature oscillator at room temperature, extracting 5mL of the adsorbed wastewater at set time intervals, and filtering to obtain clear solution;
⑿ taking 2mL of clear liquid, measuring the absorbance of the treated hexavalent chromium by using an ultraviolet spectrophotometry, and calculating the concentration by using a standard curve;
calculation of adsorption Capacity
Figure FDA0002321591840000021
qtThe adsorption capacity is expressed in mg/g; c0The initial concentration of the hexavalent chromium-containing wastewater is mg/L; ctThe unit of the concentration of hexavalent chromium in the adsorbed hexavalent chromium-containing wastewater is mg/L; v is the volume of the solution, and the unit is L; w is the mass of the finished product of the bismuth ferrite modified biochar composite, and the unit is g.
2. The method for the adsorption treatment of hexavalent chromium-containing wastewater by using the bismuth ferrite modified biochar composite according to claim 1, wherein in the step ⑴, the mass of pomegranate shells is 15 g.
3. The method for the adsorption treatment of hexavalent chromium-containing wastewater by using the bismuth ferrite modified biochar composite according to claim 1, wherein the high-temperature carbonization temperature in step ⑵ is 400 ℃.
4. The method for the adsorption treatment of hexavalent chromium-containing wastewater by using the bismuth ferrite modified biochar composite according to claim 1, wherein in step ⑶, 5 g of carbonized pomegranate husk is weighed, 7.5 g of zinc chloride is added into deionized water, and the mixture is stirred at 80 ℃ for 6 hours under the condition that the impregnation ratio is 1.5.
5. The method for the adsorption treatment of hexavalent chromium-containing wastewater by using the bismuth ferrite modified biochar composite according to claim 1, wherein in the steps ⑶, ⑸ and ⑹, the stirring frequency is not less than 200 rpm.
6. The method for the adsorption treatment of hexavalent chromium-containing wastewater by using the bismuth ferrite modified biochar composite according to claim 1, wherein in the step ⑷, the filtrate obtained by suction filtration is calcined at 700 ℃ for 1.5 hours in a nitrogen atmosphere.
7. The method for adsorbing hexavalent chromium-containing wastewater by using the bismuth ferrite-modified biochar complex as claimed in claim 1, wherein in step ⑸, 0.99 g of bismuth nitrate hexahydrate, 0.9 g of ferric nitrate nonahydrate, 0.2 g of activated biochar, and 0.75 g of polyvinylpyrrolidone (PVP, K30) are weighed, and the weighed bismuth nitrate hexahydrate, ferric nitrate nonahydrate, activated biochar, and polyvinylpyrrolidone (PVP, K30) are added to 40 ml of deionized water solution.
8. The method for the adsorption treatment of hexavalent chromium-containing wastewater by using the bismuth ferrite modified biochar complex as claimed in claim 1, wherein the first mixture obtained in the step ⑹ is transferred to a 100 ml autoclave and reacted at 180 ℃ for 9 hours in the step ⑺.
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