CN107442066B - Microwave carbonized persimmon peel biological adsorbent and preparation method and application thereof - Google Patents
Microwave carbonized persimmon peel biological adsorbent and preparation method and application thereof Download PDFInfo
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- CN107442066B CN107442066B CN201710668207.XA CN201710668207A CN107442066B CN 107442066 B CN107442066 B CN 107442066B CN 201710668207 A CN201710668207 A CN 201710668207A CN 107442066 B CN107442066 B CN 107442066B
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- 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
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- 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
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a microwave carbonized persimmon peel biological adsorbent and a preparation method and application thereof, wherein the raw material of the biological adsorbent is agricultural waste, the raw material has almost no cost, the source is rich, and the cost for preparing the adsorbent is low; the prepared biological adsorbent is used for removing heavy metal ions in the wastewater, follows the concept of 'resource, environment, circulation and sustainable development', and achieves the purpose of 'treating waste by waste'; the preparation method is simple and feasible, energy-saving and efficient, the conditions are easy to control, no wastewater, waste gas or waste is generated, the requirement on equipment is not high, and the industrial application is convenient to realize; the adsorption capacity and efficiency of the biological adsorbent to heavy metal ions are less influenced by the environmental temperature and the initial concentration, the temperature control is not needed in the adsorption process, ions in a larger concentration range can be efficiently adsorbed, and the biological adsorbent is suitable for treating large-volume low-concentration heavy metal wastewater; after adsorption, the heavy metal ions can be eluted by dilute acid, the concentration degree is high, the adsorbent can be recycled, and secondary pollution can not be caused.
Description
Technical Field
The invention belongs to the field of natural product biological adsorbents, and particularly relates to a microwave carbonized persimmon peel biological adsorbent and a preparation method and application thereof.
Background
The rapid development of modern industry generates a large amount of wastewater containing heavy metals, which poses a great threat to the environment and human life because it is not degradable and is easily enriched in the organism through the food chain. Toxic and harmful heavy metals such as lead, copper, nickel and the like are generally from industrial wastewater such as electroplating, battery processing and recycling, mineral mining and refining. The methods for treating the wastewater containing heavy metal ions are more, and the researches are mainly carried out by a chemical precipitation method, an electrochemical method, an ion exchange method, a solvent extraction method, a membrane separation method and the like. Although these methods have high treatment efficiency, they have disadvantages of high treatment cost, high energy consumption, generation of a large amount of sludge by adding chemical agents, and the like.
Biosorption refers to a method for removing heavy metals by the adsorption of organisms and their derived materials on heavy metal ions in water, and is regarded as an effective, cheap, simple, convenient and practical method for environmental remediation. The commonly used biosorbents are bacteria, fungi, yeast, brown algae or some natural polymers such as cellulose, chitosan, etc., but the cost is still high.
Persimmon (Diospyros kaki Thunb.) is originally produced in China, has a cultivation history of more than 2000 years, and has extremely rich germplasm resources. Persimmon is one of the large fruits in China, the total output of the persimmon in 2013 nationwide is the eighth of the main fruits, the persimmon is widely planted in 23 provinces, cities and regions in China at present, the persimmon with ten large yields in Guangxi, Shaanxi, Hebei and the like in China, and about half of the persimmon fruits harvested every year are processed into dried persimmon. 176.9 million tons is used as raw material for processing, and 17.7 million tons of persimmon peels can be produced in the process, calculated as 353.9 million tons of persimmons in 2013. Most of the persimmon peels produced by persimmon processing enterprises are directly buried or burned as wastes, so that the persimmon peels cannot be used to the full extent, but the environmental pollution is aggravated, and the treatment cost is increased. Therefore, if the relevant waste can be utilized, it is expected that the use thereof for producing the biosorbent will have a double advantage to the environment, and the cost may be further reduced. Also, there is a need to develop bioadsorbents with good selectivity for certain metal ions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a microwave carbonization persimmon peel biological adsorbent, which contains crosslinked and cured persimmon tannin, wherein the mass percentage content of the crosslinked and cured persimmon tannin is 2.0-15.0%.
According to the invention, the specific surface area of the biological adsorbent is 220-2/g。
According to the invention, the pore volume of the biosorbent is between 0.200 and 0.380m3/g。
According to the invention, the characteristic peak of the infrared absorption spectrum of the biological adsorbent is 3417cm-1，1604cm-1And 1196cm-1。
Preferably, the biosorbent has an infrared absorption spectrum substantially as shown in figure 2.
The invention also provides a preparation method of the microwave carbonized persimmon peel biological adsorbent, which comprises the following steps:
(1) mixing persimmon peel with a phosphoric acid aqueous solution to obtain a mixture;
(2) and (2) carrying out microwave heating on the mixture obtained in the step (1) to prepare the biological adsorbent.
According to the present invention, the persimmon peel may be in any form, and for example, may be persimmon peel powder, persimmon peel granules, persimmon peel fragments, or a mixture of two or more thereof.
According to the present invention, the persimmon peel may be further pretreated before being mixed with the phosphoric acid aqueous solution. Preferably, the pre-treatment may comprise the steps of:
(1-1) washing and drying the persimmon peel raw material with water;
(1-2) pulverizing dried persimmon peel.
The drying may be constant temperature drying or vacuum freeze drying.
Preferably, the dried persimmon peels are pulverized into particles. Preferably, the crushed particles can also be sieved by a 60-100 mesh sieve.
According to the present invention, the persimmon peel raw material may be, for example, persimmon peel waste generated in the production of dried persimmons.
According to the invention, the constant-temperature drying temperature is 50-85 ℃, and the constant-temperature drying time is 1-24 h.
According to the invention, the vacuum degree of the vacuum freeze drying is 0-1 MPa; the vacuum freeze-drying time is 4-36 h.
According to the invention, the comminution is preferably carried out with a high-speed mill.
According to the present invention, preferably, in step (1): the phosphoric acid aqueous solution may have a mass percentage concentration of 10-85%.
The mass molar ratio of the persimmon peel to the phosphoric acid is 1 (2-6) g/mol.
Mixing the persimmon peel with phosphoric acid water solution to dehydrate and activate the persimmon peel.
The temperature of the dehydration activation may be 15-65 ℃, for example room temperature; the time for the dehydration activation may be 30min to 24h, for example 2 h.
The dehydration activation is preferably carried out under stirring conditions, for example under magnetic or mechanical stirring conditions.
According to the invention, in the step (2), the microwave heating time is 5-40 min; the microwave power is not particularly limited, and is, for example, 600-900W.
According to the invention, during the microwave heating process, the persimmon peel can be carbonized.
Preferably, curing crosslinking also occurs during the carbonization process of step (2).
For example, persimmon tannin is cured and crosslinked in the carbonization process of the step (2).
According to the invention, the preparation method of the microwave carbonized persimmon peel biological adsorbent further comprises the following steps:
(3) and (3) washing the biological adsorbent in the step (2) with water (such as deionized water), NaOH aqueous solution and water (such as deionized water) to be neutral, drying, crushing and sieving to obtain the biological adsorbent. As an example, the water can be washed 1-3 times, then washed with NaOH aqueous solution, and then washed with water to neutral.
According to the present invention, preferably, in step (3):
the concentration of the NaOH aqueous solution is 0.01-0.50 mol/L;
the drying temperature can be 50-85 ℃, and the drying time can be 2-24 h;
the crushing and sieving are preferably carried out by sieving with a 60-100 mesh sieve after crushing.
According to the invention, the preparation method further comprises the following steps:
(4) in the microwave heating process, phosphoric acid loses partial water at high temperature to form pyrophosphoric acid, and metaphosphoric acid is obtained after further dehydration; after the microwave heating is completed, pyrophosphoric acid and metaphosphoric acid are hydrolyzed to produce phosphoric acid.
Preferably, the phosphoric acid can be recycled.
The invention also provides the use of the biosorbent for adsorbing metal ions.
Preferably, the metal ions are selected from one or more mixtures of lead, copper, nickel, manganese, magnesium, calcium, and the like.
Preferably, the metal ions may be selected from heavy metal ions, such as a mixture of one or more of lead, copper, nickel, manganese, and the like.
Preferably, the biosorbent is used to adsorb metal ions, preferably heavy metal ions, in a solution containing the metal ions.
Preferably, the pH of the solution containing metal ions is in the range of 2.0 to 7.0.
Preferably, the pH of the solution containing metal ions is in the range of 3.0 to 6.0, such as 5.0 to 6.0.
The invention also provides a method for removing metal ions, comprising contacting the biosorbent with metal ions, such as heavy metal ions.
Preferably, the method may comprise the steps of:
a) optionally adjusting or not adjusting the pH of the solution containing the metal ions;
b) adding the biological adsorbent into the solution containing the metal ions in the step a) to adsorb the heavy metal ions.
According to the present invention, the method for removing metal ions further comprises the steps of:
c) after the adsorption is finished, mixing the adsorbent adsorbed with the metal ions in the step b) with the nitric acid aqueous solution to desorb the metal ions adsorbed on the adsorbent.
According to the invention, the concentration of heavy metal ions in the solution containing metal ions may be 10 to 150mg/L, preferably 30 to 60 mg/L.
Preferably, the metal ions are selected from one or more mixtures of lead, copper, nickel, manganese, magnesium, calcium, and the like.
Preferably, the metal ions may be selected from heavy metal ions, such as a mixture of one or more of lead, copper, nickel, manganese, and the like.
According to the invention, in step a), the pH of the solution containing metal ions is preferably in the range of 2.0 to 7.0, or after pH adjustment, the pH of the solution containing metal ions is in the range of 2.0 to 7.0.
Preferably, the pH is in the range of 3.0 to 6.0, for example 5.0 to 6.0.
According to the invention, in step a), the pH adjustment can be carried out using acids, bases or neutral reagents.
For example, the acid is selected from hydrochloric acid or nitric acid; the base is selected from sodium hydroxide; the neutral reagent is selected from sodium chloride or sodium nitrate.
When adjusting the pH, the acid, base or neutral agent may be selected from the form of an aqueous solution thereof.
According to the invention, after the addition of the biosorbent in step b) to the solution containing heavy metal ions of step a), shaking is preferably carried out. The oscillation is preferably in an air bath constant temperature oscillator; the oscillation time may be 5-480 min.
According to the invention, in step c), the concentration of the aqueous nitric acid solution is between 0.1 and 0.5 mol/L.
According to the invention, in step c), the desorption temperature is between 25 and 45 ℃; the desorption time is 5-120 min.
The invention has the beneficial effects that:
1. the raw material of the biological adsorbent prepared by the invention is agricultural waste, and the prepared biological adsorbent is used for removing metal ions, particularly heavy metal ions in wastewater, follows the concept of 'resource, environment, circulation and sustainable development', and achieves the aim of 'treating waste with waste';
2. the raw materials of the biological adsorbent prepared by the invention have almost no cost, the source is rich, and the prepared biological adsorbent has low cost;
3. the method for preparing the biological adsorbent is simple and feasible, saves energy, has high efficiency, is easy to control conditions, does not generate waste water, waste gas and waste, has low requirement on equipment, and is convenient for realizing industrial application;
4. the biological adsorbent prepared by the invention has small influence on the adsorption capacity and efficiency of metal ions, particularly heavy metal ions, by the environmental temperature and the initial concentration, does not need temperature control in the adsorption process, and can efficiently adsorb ions in a larger concentration range;
5. the biological adsorbent prepared by the invention can be used for eluting heavy metal ions by using dilute acid after adsorption, has high concentration degree, can be recycled, and cannot cause secondary pollution;
6. the phosphoric acid adopted in the preparation process is medium strong acid and has dehydration property, and the persimmon peel waste is ground into fine powder and then is soaked in the phosphoric acid, so that phosphoric acid molecules fully penetrate into the raw material and form fine pore passages through dehydration and erosion. In the microwave carbonization treatment process, organic matters in the phosphoric acid catalytic material are dehydrated, and the generation of carbon-containing volatile matters is inhibited, so that a microcrystalline structure with developed micropores is formed. Losing part of water at high temperature to form pyrophosphoric acid, and further dehydrating to obtain metaphosphoric acid. After carbonization, pyrophosphoric acid and metaphosphoric acid are hydrolyzed into orthophosphoric acid, and the phosphoric acid can be recycled.
Drawings
FIG. 1 is a nitrogen adsorption degassing isotherm of a microwave-carbonized persimmon peel biosorbent of example 1 of the present invention.
FIG. 2 is an infrared spectrum of the biosorbent of example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of the biosorbent of example 1 according to the present invention.
FIG. 4 is a graph comparing the effect of the biosorbent of example 2 of the present invention on heavy metal ions of lead, copper and nickel at different pH values.
FIG. 5 is a graph showing the effect of the biosorbent of example 3 on heavy metal ions of lead, copper and nickel under different initial ion concentrations.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
Test materials and instruments
Persimmon peel (persimmon peel waste remaining after persimmon is prepared from Fuping, local astringent persimmon variety Fuping, Shaanxi, Fuping Shao), deionized water (ultrapure water system; Chengyang chemical reagent Co., Ltd.), phosphoric acid, sodium hydroxide (national drug group reagent Co., Ltd.), nitric acid (Xinyang chemical reagent Co., Ltd.), lead nitrate, copper nitrate, nickel nitrate, potassium nitrate, sodium hydroxide and the like (national drug group reagent Co., Ltd.), hydrochloric acid (Xinyang chemical reagent Co., Ltd.).
A constant temperature oscillator (MAXQ-4000, Thermo group, USA), a pH meter (UB-7, Saedodes instruments systems, Beijing), an atomic absorption spectrometer (Spectra AA 220, VARIAN, USA) electronic balance (BL-2200H type; Shimadzu corporation, Japan), a high speed universal pulverizer (FW-100; Tester instruments, Inc., Tianjin), a magnetic stirrer (RCT; Guangzhou laboratories, Inc.), an electric heating constant temperature blast drying box (DHG; Shanghai gold macro laboratory Equipment, Inc.), an atomic absorption spectrometer (Spectra AA 220, VARIAN, USA), and a microwave oven (G70F20CN 1L).
Example 1: preparation of microwave carbonized persimmon peel biological adsorbent
Cleaning the persimmon peel waste with water, removing impurities such as soil and sand, drying for 6h at 65 ℃ in a constant-temperature drying oven, and pulverizing into granular powder with the size of 60-100 meshes by using a high-speed pulverizer for later use. Weighing 5g of persimmon peel powder, adding 20mL of 50% phosphoric acid aqueous solution, and stirring at room temperature for 2h by using a magnetic stirrer to dehydrate and activate the persimmon peel powder. And (3) heating and carbonizing the dehydrated and activated product in a microwave oven with the power of 800W for 8min, and curing and crosslinking the product to prepare the adsorbent. The crude adsorbent is firstly washed by deionized water for 3 times, then washed by 0.1mol/L NaOH aqueous solution for 1 time, and finally repeatedly washed by deionized water to be neutral; putting the washed adsorbent into an oven, and drying at 65 ℃ for 6 h; pulverizing into particles, and sieving with 60-100 mesh sieve to obtain microwave carbonized persimmon peel biological adsorbent product.
The adsorption and desorption isotherms of the biosorbent prepared in this example measured by a Quantachrome autosorb-1 nitrogen adsorption analyzer are shown in fig. 1. The FTIR spectrogram and SEM image are shown in figure 2 and figure 3 respectively.
It was found from FIG. 1 that the specific surface area thereof was 266.6m2Per g, pore volume 0.242m3(ii)/g; 3417cm can be seen in FIG. 2-1The broad peak is the stretching vibration of phenolic hydroxyl O-H, 1604cm-1The peak was attributed to keto group C ═ O stretching vibration, 1196cm-1The peak is C-O stretching vibration, which is a partial characteristic peak of tannin; from FIG. 3, it can be seen that the adsorbent has a rough, irregular surface with more pores.
Example 2: the microwave carbonized persimmon peel biological adsorbent is used for adsorbing heavy metal ions such as lead, copper, nickel and the like in an aqueous solution, and the comparison of adsorption effects under different pH conditions is examined
Weighing 20mg of the biosorbent prepared in example 1 in a 50mL triangular flask, mixing with 20mL of lead, copper and nickel ion solutions with different pH values (pH values of 2.0, 3.0, 4.0, 5.0 and 6.0 respectively) and initial concentrations of 60mg/L, oscillating for 2h at 200r/min at 25 ℃ in a constant temperature oscillator, filtering, measuring the concentrations of heavy metal ions in the solutions before and after adsorption by using an atomic absorption spectrometer, and calculating the adsorption rate according to the following equation:
the results show that: the adsorption effect of the microwave carbonized persimmon peel biological adsorbent on lead, copper, nickel and the like under different pH conditions is shown in figure 4. As can be seen from FIG. 4, the adsorbent has the best adsorption effect on each metal ion in the pH range of 5.0 to 6.0. The pH of the initial solution has a great influence on the adsorption of metal ions by the adsorbent, almost no adsorption is realized at pH 2.0, the pH is in the range of 3.0-6.0, and the adsorption rate is rapidly increased.
Example 3: the microwave carbonized persimmon peel biological adsorbent is used for adsorbing heavy metal ions such as lead, copper, nickel and the like in an aqueous solution, and the adsorption effect is compared under the investigation of different initial ion concentrations
Weighing 20mg of the biological adsorbent prepared in example 1 into a 50mL triangular flask, mixing with 20mL of lead, copper and nickel ion solutions with initial ion concentrations of 10mg/L, 20mg/L, 30mg/L, 40mg/L and 50mg/L and pH of 5.5 respectively, oscillating for 2h at 200r/min at 25 ℃ in a constant temperature oscillator, filtering, and calculating the adsorption rate:
the results show that: the adsorption effect of the adsorbent on lead, copper, nickel and the like under different initial ion concentrations is shown in figure 5. In the concentration range of 10-50mg/L, the adsorption amount rises linearly as the initial concentration of ions increases. At the maximum initial concentration of 50mg/L, the adsorption rates of the adsorbent to lead, copper and nickel ions respectively reach 99.3%, 94.5% and 88.6%, and at the initial concentration of 30mg/L and below, the adsorption rates of the adsorbent to lead, copper and nickel ions all reach 100%. The microwave carbonized persimmon peel adsorbent has high-efficiency removal capacity on heavy metal ions in micro-polluted wastewater.
Example 4: adsorption of metal ions in simulated wastewater by using microwave carbonized persimmon peel biological adsorbent
The research is carried out by adopting the simulated industrial wastewater of various coexisting ions. The concentrations of lead, copper, nickel, manganese, magnesium, calcium, potassium and sodium in the wastewater are respectively 25.2mg/L, 18.3mg/L, 8.6mg/L, 15.5mg/L, 34.2mg/L, 9.3mg/L, 350.6mg/L and 80.3mg/L by determination, and the pH value is 5.35. 100mg of the biosorbent prepared in example 1 was mixed with 200mL of the above simulated wastewater solution, shaken at 200r/min for 2 hours at 25 ℃ in a constant temperature shaker, filtered, and the adsorption rate was calculated.
The results show that: the concentration change of the microwave carbonized persimmon peel biological adsorbent before and after adsorption of metal ions in simulated wastewater is shown in table 1. Therefore, the biological adsorbent has high selective adsorption capacity for toxic and harmful heavy metal ions of lead, copper and nickel in the wastewater, the adsorption rate reaches 100%, the biological adsorbent also has certain adsorption capacity for manganese, magnesium and calcium, and the biological adsorbent has no adsorption capacity for potassium and sodium ions. Therefore, the microwave carbonized persimmon peel adsorbent can be used as an adsorbing material with low cost and selective adsorption capacity on metal ions, can be used for removing metal ions such as lead, copper, nickel, manganese, magnesium, calcium and the like in wastewater, and is particularly suitable for removing heavy metal ions such as lead, copper, nickel and the like in wastewater.
Table 1 concentration change before and after adsorption of metal ions in simulated wastewater by the biosorbent of example 4
Example 5: desorbing the persimmon peel adsorbed metal ions in the simulated wastewater by using a nitric acid aqueous solution after microwave carbonization
After the process of adsorbing the metal ions in the simulated wastewater is completed, the biological adsorbent of example 4 is filtered and dried to obtain the adsorbent adsorbed with the metal ions. Mixing 50mg of the adsorbent with 100mL of 0.1mol/L nitric acid aqueous solution, oscillating at 25 ℃ in a constant temperature oscillator at 200r/min, filtering after 30min, measuring the concentration of metal ions, and calculating the static desorption rate.
The results show that: the ion concentration and desorption rate of the adsorbed biosorbent after desorption with an aqueous nitric acid solution are shown in table 2. Therefore, the nitric acid aqueous solution can elute the metal ions attached to the biological adsorbent after adsorption, and the desorption rates of the nitric acid aqueous solution on lead, copper, nickel, manganese and magnesium are all over 93 percent. Therefore, the metal ions can be eluted by nitric acid aqueous solution after the microwave carbonization persimmon peel adsorbent is attached, and the adsorbent can be recycled without causing secondary pollution.
TABLE 2 ion concentration and desorption Rate of the biosorbent of example 5 after desorption with aqueous nitric acid solution
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (25)
1. A microwave carbonization persimmon peel biological adsorbent is characterized in that the biological adsorbent contains crosslinked and cured persimmon tannin, and the mass percentage content of the crosslinked and cured persimmon tannin is 2.0-15.0%;
the specific surface area of the biological adsorbent is 220-460m2Per g, pore volume of 0.200-0.380m3The characteristic peak of the infrared absorption spectrum is 3417cm-1，1604cm-1And 1196cm-1。
2. The biosorbent according to claim 1, wherein the biosorbent has a specific surface area of 266.6m2(ii) the pore volume of the biosorbent is 0.242m3/g。
3. The biosorbent according to claim 1, wherein said biosorbent has an infrared absorption spectrum substantially as shown in figure 2.
4. The preparation method of the microwave carbonization persimmon peel biological adsorbent as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) mixing persimmon peel with a phosphoric acid aqueous solution to obtain a mixture;
(2) and (2) carrying out microwave heating on the mixture obtained in the step (1) to prepare the biological adsorbent.
5. The method as claimed in claim 4, wherein the persimmon peel is selected from persimmon peel granules.
6. The method for preparing persimmon peels as claimed in claim 4, wherein the persimmon peels are further subjected to a pretreatment before being mixed with an aqueous phosphoric acid solution, the pretreatment comprising the steps of:
(1-1) washing and drying the persimmon peel raw material with water;
(1-2) pulverizing dried persimmon peel.
7. The method according to claim 6, wherein the drying is constant temperature drying or vacuum freeze drying;
the temperature of the constant-temperature drying is 50-85 ℃, and the time of the constant-temperature drying is 1-24 h;
the vacuum degree of the vacuum freeze drying is 0-1 MPa; the vacuum freeze-drying time is 4-36 h.
8. The method as claimed in claim 6, wherein the dried persimmon peel is pulverized into granules.
9. The method according to claim 8, wherein the pulverization is carried out by a high-speed pulverizer.
10. The method of claim 8, wherein the crushed particles are further screened through a 60-100 mesh screen.
11. The method according to any one of claims 6 to 10, wherein the persimmon peel raw material is persimmon peel waste generated in the production of dried persimmons.
12. The production method according to any one of claims 4 to 10, wherein in step (1): the mass percentage concentration of the phosphoric acid aqueous solution is 10-85%;
the mass molar ratio of the persimmon peel to the phosphoric acid is 1 (2-6) g/mol;
mixing the persimmon peel with a phosphoric acid aqueous solution to dehydrate and activate the persimmon peel;
the temperature of dehydration activation is 15-65 ℃; the time for dehydration activation is 30min-24 h;
the dehydration activation is carried out under stirring.
13. The production method according to claim 12, wherein in step (1):
the temperature of dehydration activation is room temperature; the time for dehydration activation is 2 hours;
the dehydration activation is carried out under the condition of magnetic stirring or mechanical stirring.
14. The production method according to any one of claims 4 to 10, wherein in the step (2), the microwave heating time is 5 to 40 min; the microwave power is 600-900W;
and (3) performing curing crosslinking on the persimmon tannin in the carbonization process of the step (2).
15. The method of any one of claims 4-10, further comprising the steps of:
(3) and (3) washing the biological adsorbent obtained in the step (2) with water, a NaOH aqueous solution and water to be neutral, drying, crushing and sieving to obtain the biological adsorbent.
16. The preparation method of claim 15, wherein the washing is performed 1 to 3 times with water, then with an aqueous solution of NaOH, and then with water to neutrality;
the concentration of the NaOH aqueous solution is 0.01-0.50 mol/L;
the drying temperature is 50-85 ℃, and the drying time is 2-24 h;
the crushing and sieving is to pass through a 60-100 mesh sieve after crushing.
17. The method of claim 15, further comprising the steps of:
(4) in the microwave heating process, phosphoric acid loses partial water at high temperature to form pyrophosphoric acid, and metaphosphoric acid is obtained after further dehydration; after the microwave heating is completed, pyrophosphoric acid and metaphosphoric acid are hydrolyzed to produce phosphoric acid.
18. Use of the biosorbent of any one of claims 1 to 3 for adsorbing heavy metal ions;
the heavy metal ions are selected from one or more of lead, copper and nickel.
19. Use of the biosorbent according to claim 18, wherein the pH of the solution comprising heavy metal ions is in the range of 2.0 to 7.0.
20. Use of the biosorbent according to claim 18, wherein the pH of the solution comprising heavy metal ions is in the range of 3.0 to 6.0.
21. Use of the biosorbent according to claim 18, wherein the solution comprising heavy metal ions has a pH of 5.0 to 6.0.
22. A method for removing heavy metal ions, which comprises contacting the biosorbent of any one of claims 1 to 3 with heavy metal ions.
23. The method according to claim 22, characterized in that it comprises the steps of:
a) optionally adjusting or not adjusting the pH of the solution containing heavy metal ions;
b) adding the biosorbent of any one of claims 1 to 3 to the solution containing heavy metal ions of step a) to adsorb the heavy metal ions.
24. The method of claim 23, further comprising the steps of:
c) after the adsorption is finished, mixing the adsorbent adsorbed with the heavy metal ions in the step b) with the nitric acid aqueous solution to desorb the heavy metal ions adsorbed on the adsorbent.
25. The method according to any one of claims 22 to 24, wherein the concentration of heavy metal ions in the solution containing heavy metal ions is 10 to 150 mg/L;
in the step a), the pH value of the solution containing the heavy metal ions is within the range of 5.0-6.0, or after the pH value is adjusted, the pH value of the solution containing the heavy metal ions is within the range of 5.0-6.0;
in the step b), adding a biological adsorbent into the solution containing the heavy metal ions in the step a), and oscillating; the oscillation is oscillated in an air bath constant temperature oscillator; the oscillation time is 5-480 min;
in the step c), the concentration of the nitric acid aqueous solution is 0.1-0.5 mol/L;
in step c), the desorption temperature is 25-45 ℃; the desorption time is 5-120 min.
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