CN113198418B - Method for preparing efficient phosphorus removal activated carbon by using edible fungus residues - Google Patents
Method for preparing efficient phosphorus removal activated carbon by using edible fungus residues Download PDFInfo
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- 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
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- 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
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
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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
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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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention relates to a method for preparing efficient phosphorus removal activated carbon by using edible fungus residues. The method comprises the following steps: A. taking edible fungus residue, removing sand, stone and soil, drying, pulverizing, and sieving with 20-60 mesh sieve; B. grinding and mixing the bacterial slag powder and an activating agent, carbonizing and activating for 1-3 hours at the temperature of 650-800 ℃ under the protection of inert gas, and cooling to obtain a reactant solid; C. carrying out acid washing on the reactant solid, then washing the reactant solid to be neutral by using deionized water, and drying to obtain a dried substance; D. taking the dried substance, adding lanthanum ion solution which is 8-12 times of the weight of the dried substance, drying the dried substance under the condition of continuous stirring, and then calcining the dried substance at the temperature of 350-450 ℃ for 2-8 hours to obtain the catalyst. The invention has the characteristics of convenient use, easy material taking, lower cost, safety and practicability.
Description
Technical Field
The invention belongs to the field of resource utilization of emerging industrial solid wastes, and particularly relates to a method for preparing efficient phosphorus removal activated carbon by using edible fungus residues
Background
According to statistics, the edible fungus yield of China accounts for 75% of the global total yield, and the edible fungus residues generated each year exceed 6000 million tons. The Guizhou edible fungus industry is started late, but has been vigorously supported and developed as a poverty-relief industry in recent years. The yield of the edible fungi in Guizhou province in 2019 is about 110 ten thousand tons, and the yield of the edible fungi residues reaches 175 ten thousand tons, and the number of the edible fungi residues is further increased along with the rapid development of the edible fungi industry. The edible fungus residues are used as byproducts of emerging industries, and how to reasonably treat and dispose the edible fungus residues becomes a current troublesome environmental problem.
The edible fungus residues are used as typical biomass-based solid wastes, are natural, rich in carbon, green and renewable, and can be used as high-quality raw materials for preparing carbon materials such as activated carbon and the like. However, the research on the preparation of the activated carbon by using the edible fungus residues is limited at present, and the preparation of the activated carbon is carried outThe regulation and control of the process and the exploration of potential application are quite lacking. For example, "Preparation of activated carbon from edge bacteria residue by microwave assisted K2CO3 activation-Application in reactive black 5adsorption from aqueous solution" (Xiao et al, 2012, Bioresource Technology) reports that the edible fungus residue is carbonized and activated in a microwave reactor by using K2CO3 as an activator, and the specific surface area and the total pore volume of the obtained activated carbon are 683.76m 2 (iv)/g and 0.591cm 3 (ii) in terms of/g. Similarly, a method for preparing biochar from edible fungus dregs (CN201911179545) sequentially uses ZnCl in the edible fungus dregs 2 And H 2 SO 4 +H 3 PO 4 The mixed solution is treated and then hydrothermally carbonized to obtain activated carbon with the specific surface area of 962m 2/g. Generally, the specific surface area of the edible fungi residue activated carbon reported at present is relatively low, and the reason may be that the traditional method for preparing the activated carbon, especially the selection of an activating agent and a reaction process, is suitable for biomass such as coconut shells, sisal hemp, wood chips, straws and the like, and the edible fungi residue is a byproduct obtained after a series of processes such as sterilization, edible fungi growth and the like of the biomass. Therefore, the activated carbon with large specific surface area, developed pores and rich active sites can be obtained only by developing a proper activating agent and activating process based on the special physicochemical characteristics of the edible fungus residues. On the other hand, phosphorus is the key to cause water eutrophication, and the water eutrophication can be effectively relieved by reducing the input of phosphorus-containing wastewater (such as breeding wastewater, farmland drainage, domestic sewage and the like). Among various physical and chemical treatment processes, the adsorption method has attracted extensive attention because of low equipment requirements and strong operability. However, at present, the development of cheap, green and efficient adsorbents becomes an important bottleneck for phosphorus removal by an adsorption method. Researches on the adsorption application of the edible fungus residue activated carbon include a method for preparing a high-performance activated carbon organic pollutant adsorbent by using the edible fungus residue (CN201911007061.X) for adsorbing organic chlorobenzene and dichloromethane, and a high-efficiency method for adsorbing the organic chlorobenzene and dichloromethane by using the edible fungus residueA preparation method (CN201710785849.8) of charcoal adsorbent for removing heavy metal lead and cadmium Pleurotus ostreatus residue is used for adsorbing heavy metal lead and cadmium. However, in general, the development of the application function of the activated carbon of the edible fungus residue is relatively limited, and particularly, the activated carbon is used as an adsorbent for removing heavy metals, organic matters, phosphorus and the like in a water body.
Disclosure of Invention
The invention aims to provide a method for preparing efficient phosphorus removal activated carbon by using edible fungus residues, which is used for preparing the efficient phosphorus removal activated carbon, realizes resource utilization of the edible fungus residues, which are new industrial solid wastes, and development of a cheap efficient phosphorus removal activated carbon adsorbent, has important economic and environmental significance, and has huge market prospects. .
The purpose of the invention is realized by the following technical scheme:
the method for preparing the efficient phosphorus removal activated carbon by using the edible fungus residues comprises the following steps:
A. taking edible fungus residue, removing sand, stone and soil, drying, pulverizing, and sieving with 20-60 mesh sieve;
B. grinding and mixing the bacterial slag powder prepared in the step A and an activating agent, gradually heating to 650-800 ℃ under the protection of inert gas, carbonizing and activating for 1-3 hours at 650-800 ℃, and naturally cooling to room temperature to obtain a reactant solid; wherein the activating agent is a mixture of potassium hydroxide and potassium oxalate;
C. carrying out acid washing on the reactant solid, filtering, washing the acid-washed filtrate to be neutral by using deionized water, and further drying to obtain a dried product;
D. taking the dried substance, adding lanthanum ion solution which is 8-12 times of the weight of the dried substance, drying at 60-90 ℃ under the condition of continuously stirring, and then calcining at 350-450 ℃ for 2-8 hours to obtain the catalyst.
The lanthanum ion-containing solution is a lanthanum chloride solution or a lanthanum nitrate solution.
The concentration of lanthanum ions in the lanthanum ion solution is 0.05-0.3 mol/L.
The acid washing process in the step C comprises the following steps: adding 0.08-0.2mol/L hydrochloric acid which is 3-10 times of the weight of the solid of the reactant, placing the mixture in a water bath constant temperature shaking table for reaction for 4-10 hours, and then filtering and repeatedly washing the mixture by using deionized water until the filtrate is neutral.
The method for drying the edible fungus dregs in the step A comprises the following steps: the mushroom dregs are naturally dried and then dried for 3 to 10 hours at a temperature of between 80 and 110 ℃.
In the step B, the weight ratio of the mushroom dreg powder to the activating agent is 5:1-1: 5.
And the weight ratio of the potassium hydroxide to the potassium oxalate in the activating agent in the step B is 3:1-1: 3.
The heating process in the step B is carried out in a pyrolysis reactor.
In the step B, the temperature rise rate is 5-20 ℃/min in the process of gradually raising the temperature to 650-800 ℃.
The edible fungus dreg source comprises: auricularia, Tremella, Lentinus Edodes, Pleurotus ostreatus, Coprinus comatus, Pleurotus eryngii, and Volvariella volvacea.
The invention has the positive effects that:
the invention utilizes the edible fungus dregs as the by-product of biomass raw material after crushing, sterilizing and fermenting and the growth of edible fungus, the original structure of the biomass can be destroyed in the growth process of the edible fungus, the components such as cellulose and lignin are degraded and absorbed as nutrient and carbon source, the obtained edible fungus dregs are fluffy and soft, and have larger difference in physical and chemical characteristics with the original biological preparation, so the edible fungus dregs can be used as the raw material for preparing the active carbon
Based on the unique physicochemical characteristics of the edible fungus residues, the invention innovatively adopts a mixed catalyst and couples the traditional potassium hydroxide activator with violent reaction and the emerging moderate potassium oxalate activator. The potassium hydroxide is mainly beneficial to etching a carbon structure and growing macropores and mesopores, and the potassium oxalate is mild in action and mainly promotes the growth of the mesopores and the micropores in the macroporous structure. Under the synergistic effect of the mixed activator, the edible fungus dregs can be converted into activated carbon with larger specific surface area, more developed pores and more abundant mesopores and micropores, which is superior to the products in the prior art.
In the invention, the potassium hydroxide-potassium oxalate mixed activator can activate fungi residues including agaric, tremella, mushroom, oyster mushroom, coprinus comatus, pleurotus eryngii, straw mushroom and the like to prepare activated carbon, and the application range is wide.
The specific surface area of the activated carbon prepared by the method is up to 2628.27m2/g, and the total pore volume is 1.67cm3/g (wherein, the sum of the micropore volume and the mesopore volume is 2.08cm 3/g).
According to the invention, the activated carbon with high specific surface area is prepared by using the waste edible fungus residues, and then the activated carbon is used as a carrier to load the active component lanthanum for removing phosphorus, so that the high-efficiency phosphorus-removing activated carbon is obtained, and the multi-win effect of treating wastes with wastes is realized, and under the preferable working condition, the adsorption amount of the edible fungus residue activated carbon loaded with lanthanum to phosphorus in the simulated wastewater is up to 76.58 mg/g.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that the examples of the present invention are for illustrative purposes and not intended to limit the present invention. Simple modifications of the invention in accordance with its spirit fall within the scope of the claimed invention.
Example 1
The method for preparing the efficient phosphorus removal activated carbon by using the edible fungus residues comprises the following steps:
A. removing gravels and mud from the white fungus residues, naturally drying, drying at 100 deg.C for 4 hr, drying the edible fungus residues, pulverizing, and sieving with 20 mesh sieve;
B. grinding and mixing the bacterial slag powder prepared in the step A and an activating agent according to the weight ratio of 5:1, gradually heating to 650 ℃ at the heating rate of 5 ℃/min under the protection of inert gas, carbonizing and activating for 1 hour at 650 ℃, and naturally cooling to room temperature to obtain a reactant solid; wherein the activating agent is a mixture of potassium hydroxide and potassium oxalate in a weight ratio of 3: 1;
C. taking reactant solid, adding 0.08mol/L hydrochloric acid which is 3 times of the weight of the reactant solid, carrying out acid washing for 4 hours, removing residual activating agent and other mineral substances, immediately washing the reactant solid to be neutral by using deionized water, and further drying to obtain a dried substance;
D. taking the dried substance, adding 0.1mol/L lanthanum nitrate solution which is 8 times of the weight of the dried substance, drying at 60 ℃ under the condition of continuously stirring, and then calcining for 2 hours at 350 ℃ to obtain the catalyst.
Example 2
The method for preparing the efficient phosphorus removal activated carbon by using the edible fungus residues comprises the following steps:
A. removing gravels and soil from Pleurotus eryngii fungus residues, naturally air drying, drying at 90 deg.C for 10 hr, drying edible fungus residues, pulverizing, and sieving with 60 mesh sieve;
B. grinding and mixing the bacterial residue powder prepared in the step A and an activating agent according to the weight ratio of 1:5, gradually heating to 800 ℃ at the heating rate of 20 ℃/min under the protection of inert gas, carbonizing and activating for 3 hours at 800 ℃, and naturally cooling to room temperature to obtain a reactant solid; wherein the activating agent is a mixture of potassium hydroxide and potassium oxalate in a weight ratio of 1: 3;
C. taking reactant solid, adding 0.2mol/L hydrochloric acid which is 10 times of the weight of the reactant solid, carrying out acid washing for 10 hours, removing residual activating agent and other mineral substances, immediately washing the reactant solid to be neutral by using deionized water, and further drying to obtain a dried substance;
D. taking the dried substance, adding 0.2mol/L lanthanum nitrate solution which is 12 times of the weight of the dried substance, drying at 60 ℃ under the condition of continuously stirring, and then calcining for 4 hours at 450 ℃ to obtain the catalyst.
Example 3
The method for preparing the efficient phosphorus removal activated carbon by using the edible fungus residues comprises the following steps:
A. removing gravels and soil from the straw mushroom dregs, naturally drying, drying at 80 ℃ for 5 hours, drying the edible mushroom dregs, crushing, and sieving with a 30-mesh sieve;
B. grinding and mixing the bacteria residue powder prepared in the step A and an activating agent according to the weight ratio of 5:1-1:5, gradually heating to 650-800 ℃ at the heating rate of 5-20 ℃/min under the protection of inert gas, carbonizing and activating for 1-3 hours at 650-800 ℃, and naturally cooling to room temperature to obtain a reactant solid; wherein the activating agent is a mixture of potassium hydroxide and potassium oxalate in a weight ratio of 3:1-1: 3;
C. taking reactant solid, adding 0.12mol/L hydrochloric acid which is 6 times of the weight of the reactant solid, carrying out acid washing for 5 hours, removing residual activating agent and other mineral substances, immediately washing the reactant solid to be neutral by using deionized water, and further drying to obtain a dried substance;
D. taking the dried substance, adding 0.1mol/L lanthanum nitrate solution which is 12 times of the weight of the dried substance, drying at 60 ℃ under the condition of continuously stirring, and then calcining at 400 ℃ for 6 hours to obtain the catalyst.
Example 4
A. Cleaning impurities such as sand, soil and the like from the collected mushroom fungus residues, naturally drying in air, transferring the mushroom fungus residues into a baking oven for baking for 6 hours at 105 ℃, then crushing, and sieving by a 40-mesh sieve;
B. weighing 10g of mushroom dreg powder, placing the powder in a mortar, adding potassium hydroxide and potassium oxalate, grinding and mixing. Wherein the mass ratio of the bacteria residue to the mixed catalyst (potassium hydroxide + potassium oxalate) is 2:1, and the mass ratio of the potassium hydroxide to the potassium oxalate is 1: 1.5; transferring the ground mixture into a vertical fixed bed, introducing nitrogen of 0.1m3/min, starting heating the reactor at the heating rate of 5 ℃/min after 30min to 800 ℃, maintaining the current temperature for 2 hours, cutting off the power of the reactor after finishing, keeping the circulation of the nitrogen, and naturally cooling the reactor to the room temperature;
C. taking the reactant solid, adding 0.1mol/L hydrochloric acid which is 7 times of the weight of the reactant solid, carrying out acid cleaning for 4 hours, removing residual activating agent and other mineral substances, then washing the reactant solid to be neutral by using deionized water, and further drying to obtain a dried substance, namely the mushroom residue activated carbon (sample 1). Nitrogen adsorption/desorption analysis showed that the specific surface area of the obtained activated carbon was 1809.88m2/g, and the total pore volume was 1.12cm3/g (see Table 1 for details).
Example 5
A. Cleaning impurities such as sand, soil and the like from the collected oyster mushroom residues, naturally drying, transferring the oyster mushroom residues into an oven for baking for 10 hours at 110 ℃, then crushing, and sieving with a 80-mesh sieve;
B. weighing 10g of oyster mushroom residue powder, placing the powder in a mortar, adding potassium hydroxide and potassium oxalate, grinding and mixing. Wherein the mass ratio of the bacteria residue to the mixed catalyst (potassium hydroxide + potassium oxalate) is 1:2, and the mass ratio of the potassium hydroxide to the potassium oxalate is 1: 1; transferring the ground mixture into a horizontal tubular furnace, introducing nitrogen of 0.1m3/min, starting heating the reactor at the heating rate of 10 ℃/min after 30min to 750 ℃, maintaining the current temperature for 2 hours, cutting off the power of the reactor after finishing, keeping the circulation of the nitrogen, and naturally cooling the reactor to room temperature;
C. taking the solid reactant, adding 0.2mol/L hydrochloric acid which is 8 times of the weight of the solid reactant, carrying out acid washing for 5 hours, removing residual activating agent and other mineral substances, then washing the solid reactant to be neutral by using deionized water, and further drying to obtain a dried substance, namely the oyster mushroom residue activated carbon (sample 2). Nitrogen adsorption/desorption analysis showed that the specific surface area of the obtained activated carbon was 1628.90m2/g, and the total pore volume was 1.04cm3/g (see Table 1 for details).
Example 6
A. And cleaning impurities such as sand, soil and the like from the collected coprinus comatus mushroom residues, naturally drying, transferring to an oven for baking for 8 hours at 80 ℃, then crushing, and sieving with a 20-mesh sieve.
B. Weighing 10g of coprinus comatus mushroom dreg powder, placing the coprinus comatus mushroom dreg powder into a mortar, adding potassium hydroxide and potassium oxalate, grinding and mixing. Wherein, the mass ratio of the bacteria residue to the mixed catalyst (potassium hydroxide + potassium oxalate) is 1:2, and the mass ratio of the potassium hydroxide to the potassium oxalate is 1: 3. Transferring the ground mixture to a horizontal fixed bed, introducing nitrogen of 0.1m3/min, starting heating the reactor at the heating rate of 5 ℃/min after 30min to 800 ℃, maintaining the current temperature for 2 hours, cutting off the power of the reactor after finishing, keeping the circulation of the nitrogen, and naturally cooling the reactor to the room temperature.
C. Taking the reactant solid, adding 0.08mol/L hydrochloric acid which is 10 times of the weight of the reactant solid, carrying out acid washing for 8 hours, removing residual activating agent and other mineral substances, then washing the reactant solid to be neutral by using deionized water, and further drying to obtain a dried product, namely the coprinus comatus mushroom dreg activated carbon (sample 3). Nitrogen adsorption/desorption analysis showed that the specific surface area of the obtained activated carbon was 2628.27m2/g, and the total pore volume was 1.67cm3/g (see Table 1 for details).
D. And taking the dried substance, adding 0.2mol/L lanthanum chloride solution which is 6 times of the weight of the dried substance, drying at 80 ℃ under the condition of continuously stirring, and calcining at 450 ℃ for 4 hours to obtain the lanthanum-loaded agaric fungi residue activated carbon. 0.1g of lanthanum-loaded coprinus comatus mushroom residue activated carbon is put into 50mL of simulated wastewater with the phosphorus concentration of 200mg/L and reacted for 2 hours at room temperature. Through detection, the adsorption capacity of the lanthanum-loaded coprinus comatus dreg activated carbon to phosphorus can reach 76.58 mg/g.
Example 7
A. And cleaning impurities such as sand, soil and the like from the collected agaricus bisporus residues, naturally drying, transferring to an oven for baking for 4 hours at 100 ℃, then crushing, and sieving by a 40-mesh sieve.
B. 10g of agaric residue powder is weighed and placed in a mortar, and potassium hydroxide and potassium oxalate are added simultaneously for grinding and mixing. Wherein the mass ratio of the bacteria residue to the mixed catalyst (potassium hydroxide + potassium oxalate) is 1:1, and the mass ratio of the potassium hydroxide to the potassium oxalate is 1:1. Transferring the ground mixture into a vertical fixed bed, introducing nitrogen at 0.1m3/min, heating the reactor at a heating rate of 20 ℃/min after 30min to 700 ℃, maintaining the current temperature for 3 hours, cutting off the reactor after the temperature is up, keeping the circulation of the nitrogen, and naturally cooling the reactor to room temperature.
C. Taking the reactant solid, adding 0.2mol/L hydrochloric acid which is 10 times of the weight of the reactant solid, carrying out acid washing for 10 hours, removing residual activating agent and other mineral substances, then washing the reactant solid to be neutral by using deionized water, and further drying to obtain a dried substance, namely the agaric mushroom residue activated carbon (sample 4). Nitrogen adsorption/desorption analysis showed that the specific surface area of the obtained activated carbon was 2126.34m2/g, and the total pore volume was 1.38cm3/g (see Table 1 for details).
D. And taking the dried substance, adding 0.1mol/L lanthanum nitrate solution which is 10 times of the weight of the dried substance, drying at 60 ℃ under the condition of continuously stirring, and calcining at 350 ℃ for 6 hours to obtain the lanthanum-loaded agaric fungi residue activated carbon. 0.1g of lanthanum-loaded agaric fungi residue activated carbon is respectively put into 50mL of agricultural dewatering, breeding wastewater and domestic sewage samples, the corresponding phosphorus concentrations are respectively 2.14mg/L, 98.72mg/L and 6.18mg/L, and the reaction is carried out for 2 hours at room temperature. Through detection, the lanthanum-loaded agaric fungi residue activated carbon has the phosphorus removal rate of 85-100% in three samples.
Examples of the experiments
Comparison of specific surface area and pore volume of inventive and Prior Art samples
Firstly, sample preparation of the application:
the samples of examples 4-7 were used as samples 1-4, and the specific preparation procedure was as described above.
Secondly, sample preparation in the prior art:
1. preparation of sample 5:
A. cleaning impurities such as sand, soil and the like from the collected oyster mushroom residues, naturally drying, transferring the oyster mushroom residues into an oven for baking for 10 hours at 110 ℃, then crushing, and sieving with a 80-mesh sieve;
B. 10g of oyster mushroom residue powder is weighed, placed in a mortar, and added with potassium oxalate for grinding and mixing. Wherein the mass ratio of the bacterial residues to the single potassium oxalate catalyst is 1: 2. Transferring the ground mixture into a horizontal tubular furnace, introducing nitrogen of 0.1m3/min, starting heating the reactor at the heating rate of 10 ℃/min after 30min to 750 ℃, maintaining the current temperature for 2 hours, cutting off the power of the reactor after finishing, keeping the circulation of the nitrogen, and naturally cooling the reactor to room temperature;
C. taking the solid reactant, adding 0.2mol/L hydrochloric acid which is 8 times of the weight of the solid reactant, carrying out acid washing for 5 hours, removing residual activating agent and other mineral substances, then washing the solid reactant to be neutral by using deionized water, and further drying to obtain a dried substance, namely the oyster mushroom residue activated carbon (sample 5). Nitrogen adsorption/desorption analysis showed that the specific surface area of the obtained activated carbon was 286.14m2/g, and the total pore volume was 0.16cm3/g (see Table 1 for details).
2. Preparation of sample 6:
A. and (3) cleaning impurities such as sand, soil and the like from the collected coprinus comatus mushroom residues, naturally drying in air, transferring into a baking oven, baking for 8 hours at 80 ℃, then crushing, and sieving by a 20-mesh sieve.
B. 10g of coprinus comatus mushroom dreg powder is weighed and placed in a mortar, and potassium hydroxide is added for grinding and mixing. Wherein the mass ratio of the bacterial residues to the single catalyst potassium hydroxide is 1: 2. Transferring the ground mixture to a horizontal fixed bed, introducing nitrogen of 0.1m3/min, starting heating the reactor at the heating rate of 5 ℃/min after 30min to 800 ℃, maintaining the current temperature for 2 hours, cutting off the power of the reactor after finishing, keeping the circulation of the nitrogen, and naturally cooling the reactor to the room temperature.
C. Taking the reactant solid, adding 0.08mol/L hydrochloric acid which is 10 times of the weight of the reactant solid, carrying out acid washing for 8 hours, removing residual activating agent and other mineral substances, then washing the reactant solid to be neutral by using deionized water, and further drying to obtain a dried product, namely the coprinus comatus mushroom dreg activated carbon (sample 6). Nitrogen adsorption/desorption analysis showed that the specific surface area of the obtained activated carbon was 836.68m2/g, and the total pore volume was 0.36cm3/g (see Table 1 for details).
D. And taking the dried substance, adding 0.2mol/L lanthanum chloride solution which is 6 times of the weight of the dried substance, drying at 80 ℃ under the condition of continuously stirring, and calcining at 450 ℃ for 4 hours to obtain the lanthanum-loaded agaric fungi residue activated carbon. 0.1g of lanthanum-loaded coprinus comatus mushroom residue activated carbon is put into 50mL of simulated wastewater with the phosphorus concentration of 200mg/L and reacted for 2 hours at room temperature. Through detection, the adsorption capacity of the lanthanum-loaded coprinus comatus dreg activated carbon to phosphorus is 25.37mg/g, which is far lower than that of the activated carbon prepared in the embodiment 6 of the application.
3. The specific surface area and pore volume data for each sample are shown in Table 1 below
TABLE 1 specific surface area and pore volume of the samples
Claims (8)
1. A method for preparing efficient phosphorus removal activated carbon by using edible fungus residues is characterized by comprising the following steps:
A. taking edible fungus residue, removing sand, stone and soil, drying, pulverizing, and sieving with 20-60 mesh sieve;
B. grinding and mixing the bacterial slag powder prepared in the step A and an activating agent, gradually heating to 650-800 ℃ under the protection of inert gas, carbonizing and activating for 1-3 hours at 650-800 ℃, and naturally cooling to room temperature to obtain a reactant solid; wherein the activating agent is a mixture of potassium hydroxide and potassium oxalate;
C. carrying out acid washing on the reactant solid, filtering, washing the acid-washed filtrate to be neutral by using deionized water, and further drying to obtain a dried product;
D. taking the dried material, adding lanthanum ion solution which is 8-12 times of the weight of the dried material, drying at 60-90 ℃ under the condition of continuously stirring, and then calcining at 350-450 ℃ for 2-8 hours to obtain the catalyst;
in the step B, the weight ratio of the prepared mushroom dreg powder to the activating agent is 5:1-1: 5;
and the weight ratio of the potassium hydroxide to the potassium oxalate in the activating agent in the step B is 3:1-1: 3.
2. The method for preparing high-efficiency phosphorus removal activated carbon by using edible fungus residues as claimed in claim 1, wherein the method comprises the following steps: the lanthanum ion solution is a lanthanum chloride solution or a lanthanum nitrate solution.
3. The method for preparing high-efficiency phosphorus removal activated carbon by using edible fungus residues as claimed in claim 1, wherein the method comprises the following steps: the concentration of lanthanum ions in the lanthanum ion solution is 0.05-0.3 mol/L.
4. The method for preparing high-efficiency phosphorus removal activated carbon by using edible fungus residues as claimed in claim 1, wherein the acid washing process in the step C is as follows: adding 0.08-0.2mol/L hydrochloric acid which is 3-10 times of the weight of the solid of the reactant, placing the mixture in a water bath constant temperature shaking table for reaction for 4-10 hours, and then filtering and repeatedly washing the mixture by using deionized water until the filtrate is neutral.
5. The method for preparing high-efficiency phosphorus removal activated carbon by using edible fungus residues as claimed in claim 1, wherein the method comprises the following steps: the method for drying the edible fungus dregs in the step A comprises the following steps: the mushroom dregs are naturally dried and then dried for 3 to 10 hours at a temperature of between 80 and 110 ℃.
6. The method for preparing high-efficiency phosphorus removal activated carbon by using edible fungus residues as claimed in claim 1, which is characterized in that: the heating process in the step B is carried out in a pyrolysis reactor.
7. The method for preparing high-efficiency phosphorus removal activated carbon by using edible fungus residues as claimed in claim 1, which is characterized in that: in the step B, the temperature rise rate is 5-20 ℃/min in the process of gradually raising the temperature to 650-800 ℃.
8. The method for preparing high-efficiency phosphorus removal activated carbon from edible fungus dregs as claimed in claim 1, wherein the edible fungus dregs are derived from the following raw materials: auricularia, Tremella, Lentinus Edodes, Pleurotus ostreatus, Coprinus comatus, Pleurotus eryngii, and Volvariella volvacea.
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