CN116099504A - Recoverable charcoal bead adsorbent and preparation method and application thereof - Google Patents
Recoverable charcoal bead adsorbent and preparation method and application thereof Download PDFInfo
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- CN116099504A CN116099504A CN202310267803.2A CN202310267803A CN116099504A CN 116099504 A CN116099504 A CN 116099504A CN 202310267803 A CN202310267803 A CN 202310267803A CN 116099504 A CN116099504 A CN 116099504A
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000001179 sorption measurement Methods 0.000 abstract description 65
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 27
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- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J20/20—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
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
-
- 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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- 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
- B01J2220/4812—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
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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
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
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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
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- Hydrology & Water Resources (AREA)
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Abstract
The invention provides a recyclable charcoal bead adsorbent, a preparation method and application thereof, wherein the preparation method of the charcoal bead comprises the following steps: mixing the biomass powder of eggshells and peanut shells in water according to a proportion, adding sodium alginate, heating to dissolve, and naturally cooling to room temperature to obtain precursor slurry; dropping the precursor slurry into CaCl 2 Hardening the hydrogel balls into balls in an aqueous solution, drying the hardened hydrogel balls to constant weight, and calcining the hydrogel balls in a nitrogen atmosphere to obtain the biochar bead adsorbent. The invention mixes eggshell biomass powder and peanut shell biomass powder with specific dosage proportion and specific particle size, hardens into balls, and calcines under specific calcination conditions to obtain biochar beadsThe adsorbent not only can ensure that the spherical structure state is always maintained in the phosphate adsorption process, and the recycling of the biological carbon beads is realized, but also has higher phosphorus removal rate.
Description
Technical Field
The invention relates to the technical field of solid waste recycling and water treatment materials, in particular to a recyclable biochar bead adsorbent, and a preparation method and application thereof.
Background
In general, phosphorus is a nutrient limiting agent for eutrophication in fresh water bodies, so that the control of the phosphorus content in the fresh water bodies is important for preventing and controlling the eutrophication of the water bodies.
A huge amount of agricultural waste is produced each year, and common treatment modes are incineration and landfill treatment. The incineration treatment is expensive, and a large amount of greenhouse gases are generated; the agricultural waste in landfill treatment also produces leachate to pollute the groundwater and generate specific CO 2 More weather-destructive methane.
Although the biochar prepared from common agricultural wastes has a certain adsorption capacity, the adsorption efficiency of the biochar on anions such as phosphate is very low due to electronegativity of the biochar surface. The modification method for improving the adsorption capacity of the biological carbon anions usually adopts a modification method for loading metal ions on the biological carbon, and the eggshell contains up to 94 percent by weight of CaCO 3 Is a green natural source of calcium metal modifier. In addition, peanut hulls contain lignin (36.1%), cellulose (44.8%) and hemicellulose (5.6%), and have sufficient surface area and porosity to be suitable for use as a porous substrate to produce biochar. The highest phosphate adsorption capacity of the eggshell modified peanut shell charcoal powder can reach more than 300 mg/g.
It is worth noting that the common biochar adsorbent is often dispersed in a solution in a powdery form in the adsorption process, and is difficult to recover, and the biochar beads prepared by the sodium alginate crosslinking method are expected to realize the preparation of the biochar beads with stable structures, and are favorable for keeping soil fertility and moisture and slowing down the nitrogen and phosphorus loss degree of the soil. However, even the biochar beads prepared by adopting the sodium alginate crosslinking method cannot be prepared into the biochar beads which are stable in storage and structure under the condition that proper preparation conditions and steps are not found; even if the charcoal beads are manufactured with stable structure and are durable in storage, the charcoal beads can not be maintained in a spherical shape in the adsorption process so as to be convenient for recycling.
Therefore, it is needed to find out a biochar bead adsorbent with high adsorption and dephosphorization performance and a method thereof, which can utilize agricultural wastes to prepare the biochar bead adsorbent with stable structure before and after adsorption.
Disclosure of Invention
The invention provides a recyclable biological carbon bead adsorbent, a preparation method and application thereof, and the biological carbon bead adsorbent not only can ensure that a spherical structure state is always kept in the phosphate adsorption process, so that the biological carbon beads can be recycled, but also has higher phosphorus removal rate.
The specific technical scheme is as follows:
a method for preparing a recyclable charcoal bead adsorbent, comprising the following steps:
(1) Mixing eggshell biomass powder and peanut shell biomass powder in water according to a proportion, adding sodium alginate, heating to dissolve, and naturally cooling to room temperature to obtain precursor slurry;
the mass ratio of the eggshell biomass powder to the peanut shell biomass powder is 1:1-3; the particle size of the eggshell biomass powder is 0.15-0.18 mm; the particle size of the peanut shell biomass powder is 0.15-0.25 mm;
(2) Dropping CaCl into the precursor slurry obtained in the step (1) 2 Hardening the hydrogel ball into balls in aqueous solution, drying the hardened hydrogel ball to constant weight, and calcining the hydrogel ball for 1-2 hours at 700-775 ℃ in nitrogen atmosphere to obtain the charcoal bead adsorbent.
Further, in the step (1), the mass percentage of the eggshell biomass powder and the peanut shell biomass powder in water is 4-6% wt.
Further, in the step (1), the mass percentage of the sodium alginate in the precursor slurry is 1.5-3%wt.
Further, in the step (1), the temperature of heating and dissolving is 55-65 ℃, and the stirring time is 20-35 min.
Further, the steps of(2) In the precursor slurry, caCl is dripped into 2 After the aqueous solution, caCl 2 The mass percent of the epoxy resin is 3 to 7 weight percent, and the hardening time is 16 to 20 hours.
Further, in the step (2), the hardened hydrogel spheres are firstly washed with CaCl by deionized water 2 And then drying the mixture to constant weight.
Further, in the step (2), the temperature rising rate in the calcining process is 4-5 ℃/min.
Further, in the step (1), the mass ratio of the eggshell biomass powder to the peanut shell biomass powder is 1:3; the particle size of the eggshell biomass powder is 0.15mm; the particle size of the peanut shell biomass powder is 0.15-0.25 mm; the calcination temperature is 750-775 ℃, and the calcination time is 1.5h.
The invention also provides application of the biochar bead adsorbent in adsorbing phosphate in water.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the eggshell biomass powder and the peanut shell biomass powder with specific dosage proportion and specific particle size are mixed and then hardened into balls, and the balls are calcined under specific calcining conditions, so that the obtained biochar bead adsorbent can ensure that the spherical structure state is always maintained in the phosphate adsorption process, the recovery of the biochar beads is realized, and the phosphorus removal rate is higher.
Drawings
FIG. 1 is an SEM image of a biochar adsorbent;
wherein a) and b) are E; c) D) is EC 1:1; e) F) is C; f) G) is EC 1:3-750 (b); h) I) is EC 1:1-775 (b).
FIG. 2 is an SEM image of the biochar adsorbent after adsorption;
wherein a) and b) are E; c) D) is EC 1:1; e) F) is C; g) H) 750-1:3 (b); i) J) is 775-1:1 (b).
FIG. 3 is a FTIR spectrum before and after adsorption;
wherein, a) is E, EC 1:1, PS biochar; b) 750-1:3 (b) and 775-1:1 (b).
FIG. 4 is an XRD pattern before and after adsorption;
wherein a) is E; b) EC 1:1; c) Is C; d) 750-1:3 (b); e) 775-1:1 (b).
Detailed Description
The invention will be further described with reference to the following examples, which are given by way of illustration only, but the scope of the invention is not limited thereto.
The method of characterization in the following examples is as follows:
(1) Field emission scanning electron microscope and X-ray energy spectrum instrument sign: the microscopic morphology and structure of the biochar bead surface were analyzed by a field emission Scanning Electron Microscope (SEM), using an acceleration voltage of 5kV. Meanwhile, an X-ray energy spectrometer (EDS) equipped with an SEM is used for analyzing the element composition and the percentage content of the surface of the biochar beads.
(2) Surface, pore volume and pore size analysis
Determination of N of biochar beads by surface Analyzer (BET) at 77.35K 2 Adsorption-desorption isotherms and BET, DFJ and BJH models were used to determine the specific surface area of biochar beads (S BET ) Pore Volume (TPV), and average pore size.
(3) Characterization of X-ray crystallography
The crystal structure of the biochar beads was analyzed by X-ray crystallography (XRD) using Cu ka as the X-ray source, scanning was performed in the range of 5-80 ° with a step size of 0.02 ° and a scanning speed of 0.1s.
(4) Fourier transform infrared spectral features
The biochar beads are dried, and the dried biochar beads and the dried potassium bromide (in spectral grade) are ground and mixed according to the mass ratio of 1:100 and are sieved by a 1mm sieve. The prepared material is then sheeted by tabletting, and the characteristic chemical bonds and functional groups of the biochar beads are then analyzed by Fourier infrared spectroscopy (FTIR) with a scanning range of FTIR wavenumbers of 400-4000cm -1 。
The XRD data was fit using jade 6, and the FTIR data and other adsorption experimental data were fit using Excel and Origin 2021. In addition, excel was used to draw tables and origin 2021.
Example 1
A recoverable biochar bead adsorbent (sequence 18 in table 4), which is prepared by the following method:
(1) Uniformly mixing eggshell biomass powder which is sieved by a 100-mesh sieve and peanut shell biomass powder which is sieved by the 100-mesh sieve in water according to the mass ratio of 1:3, adding 2% by weight of sodium alginate, heating the mixed solution to 60 ℃, fully stirring for 30min, and naturally cooling the slurry to room temperature to obtain precursor slurry;
(2) Dropwise adding the mixed slurry obtained in the step (1) to 5wt% CaCl (slowly stirred) 2 Balling and hardening in solution for 18h, drying the hardened hydrogel ball to constant weight in a constant temperature oven at 105 ℃, and calcining the dried hydrogel ball in a tube furnace for 1.5h at a nitrogen flow rate of 0.025L/min and a heating rate of 750 ℃ (5 ℃/min); finally, the finished biochar beads (EC 1:3-750 (b)) can be obtained, and the balls can be basically maintained after phosphorus absorption.
Example 2
A recoverable biochar bead adsorbent (sequence 15 in table 4), which is prepared by the following method:
(1) Uniformly mixing eggshell biomass powder which is sieved by a 100-mesh sieve and peanut shell biomass powder which is sieved by a 60-mesh sieve in water according to the mass ratio of 1:1, adding 2% by weight of sodium alginate, heating the mixed solution to 60 ℃, fully stirring for 15min, and naturally cooling the slurry to room temperature to obtain precursor slurry.
(2) The mixed slurry was dropped into slowly stirred 5wt% CaCl 2 Balling in solution, hardening into balls for 24 hours, cleaning with deionized water after hardening, drying the hardened hydrogel balls in a constant-temperature oven at 60 ℃ to constant weight, and calcining the dried hydrogel balls in a tube furnace for 1.5 hours at a nitrogen flow rate of 0.015L/min and a temperature rising rate of 5 ℃ per minute. Finally, the finished biochar beads (EC 1:1-775 (b)) can be obtained, and the spherical shape can be partially maintained after phosphorus absorption.
Example 3
A recoverable biochar bead adsorbent (sequence 20 in table 4), which is prepared by the following method:
(1) Uniformly mixing eggshell biomass powder which is sieved by a 100-mesh sieve and peanut shell biomass powder which is sieved by the 100-mesh sieve in water according to the mass ratio of 1:1, adding 2% by weight of sodium alginate, heating the mixed solution to 60 ℃, fully stirring for 30min, and naturally cooling the slurry to room temperature to obtain precursor slurry.
(2) The mixed slurry was dropped into slowly stirred 5wt% CaCl 2 Balling and hardening in solution for 18h, drying the hardened hydrogel ball to constant weight in a constant temperature oven at 105 ℃, and calcining the dried hydrogel ball in a tube furnace for 1.5h at a nitrogen flow rate of 0.025L/min and a heating rate of 750 ℃ (5 ℃/min); finally, the finished biochar beads (EC 1:1-750) are obtained, and the balls can be mostly maintained after phosphorus absorption.
Comparative example 1
The preparation method of the eggshell charcoal powder (E) comprises the following steps: washing eggshells with pure water for several times, drying, grinding with a grinder, and sieving with 100 mesh sieve. Placing the sieved eggshell powder sample into a programmable tubular electric furnace, and adding the powder sample into N 2 The material powder was heated to 800 ℃ at a rate of 5 ℃/min under atmosphere and held for 2 hours. And cooling the hearth to room temperature to obtain the finished product of the eggshell biological carbon powder.
Comparative example 2
The preparation method of the peanut shell charcoal powder (C) comprises the following steps: washing peanut shell with pure water for several times, oven drying, grinding with grinder, and sieving with 100 mesh sieve. Placing the sieved peanut shell powder sample into a programmable tubular electric furnace, and adding the peanut shell powder sample into a programmable tubular electric furnace 2 The material powder was heated to 800 ℃ at a rate of 5 ℃/min under atmosphere and held for 2 hours. And cooling the hearth to room temperature to obtain the finished product of the peanut shell charcoal powder.
Comparative example 3
The preparation method of the biochar powder (EC 1:1) mixed by eggshells and peanut shells in a mass ratio of 1:1 comprises the following steps: washing eggshells and peanut shells with pure water for a plurality of times according to the mass ratio of 1:1, drying, grinding by a grinder, and finally sieving by a 100-mesh sieve. SievingThe mixed powder sample of (2) is put into a programmable tubular electric furnace, and is added with the following components in N 2 The material powder was heated to 800 ℃ at a rate of 5 ℃/min under atmosphere and held for 2 hours. And cooling the hearth to room temperature to obtain the finished product of the eggshell and peanut shell mixed biochar powder with the mass ratio of 1:1.
Characterization analysis was performed on EC 1:3-750 (b) prepared in example 1, EC 1:1-775 (b) prepared in example 2, and EC 1:1 prepared in comparative example 1, adsorbent E prepared in comparative example 2, and adsorbent C prepared in comparative example 3, with the following results:
1. surface morphology, elemental composition and BET analysis of biochar before and after adsorption
As shown in fig. 1, the eggshell biochar and the peanut shell biochar before adsorption exhibit different microscopic morphologies. The eggshell biochar E shows an obvious nano particle structure and has an agglomeration phenomenon; while the surface of the peanut shell biochar C is in a flat and microporous fiber structure and trace CaCO 3 The crystal structure is represented by a calcite crystal form in a block shape and an aragonite crystal form in a needle shape. The eggshell nano particles can still be observed on the surface of the biochar EC 1:1, the particle number is smaller than E, and the particles are covered on the peanut shell fiber structure. The E and EC 1:1 surface materials are presumably CaCO, which may be predominantly vaterite crystalline 3 And Ca (OH) 2 . The bead adsorbent has more complex surface microstructure due to the hydrogel formation with sodium alginate and the crosslinking process of calcium chloride in the preparation process, and a large number of agglomerates can be observed to be tightly combined together.
Fig. 2 shows an SEM image after adsorption. After the reaction, fine flocculent particles and amorphous particles appeared on the E and EC 1:1 adsorbents. These flocculent precipitates and particles should be newly generated Ca-P compounds in combination with subsequent XRD and FTIR analysis results. The creation of these flocculent precipitates results in a decrease in the EC porosity and the disappearance of the effective active sites, ultimately leading to adsorption saturation of the EC material. The surface of the adsorbent C is full of pore structures, and after the adsorbent C adsorbs phosphorus, the unknown nanoflower microsphere substances are attached to the pores. Obvious hexagonal crystals (HAP) and floc crystals (various Ca-P intermediate compounds in the HAP formation process) were formed after both 750 and 775 reactions in the bead adsorbent.
The change in the morphology of the adsorbent surface after adsorption may be due to the reaction of the adsorbent with the solution, which promotes its local dissolution and causes mechanical abrasion of the adsorbent material surface under stirring conditions.
The physical properties and main chemical composition of the powder and the adsorbent are shown in table 1 below. In physical properties, the specific surface area of the EC powder material tends to decrease as the mass ratio of eggshells to peanut shells increases. In addition, peanut shells possess the highest specific surface area and pore volume, and biochar fired with the addition of peanut shells would possess higher specific surface area and pore volume. The highest specific surface area and the lowest adsorption capacity of C and the lowest specific surface area and the highest adsorption capacity of E indicate that the pore structure of the adsorbent is not the dominant factor in determining the adsorption capacity of the material. The specific surface area of the bead adsorbent is smaller than the corresponding proportion of the powder adsorbent. In terms of chemical components, as the mass ratio of eggshells to peanut shells in the raw materials increases, the content ratio of Ca and O elements also increases, but the content ratio of C elements gradually decreases.
TABLE 1
2. XRD and FTIR analysis of biochar before and after adsorption
From the FTIR and XRD patterns, the conclusion can be made as follows:
E. EC 1:1 consists essentially of Ca (OH) 2 And CaCO (CaCO) 3 Composition, ca (OH) 2 And CaCO (CaCO) 3 Takes part in the dephosphorization process. After adsorbing phosphorus, mainly produce Ca 5 (PO 4 ) 3 (OH). After adsorption of phosphorus by EC 1:1, ca is mainly produced 3 (PO 4 ) 2 And Ca 2 P 2 O 7 And (3) an iso-calcium phosphorus compound. KH was observed in the adsorbed EC 1:1 material 2 PO 4 The reasons for this may be from KH in the material-to-solution 2 PO 4 Which may be related to the doping of the peanut shell, because the peanut is rich inLignocellulose has abundant pore structure characteristics. The characteristic peaks before and after adsorption of C are not significantly changed, and it is possible that the components in C hardly react with phosphate.
EC 1:3-750 (b) and EC 1:1-775 (b) having CaCO 3 And a small amount of Ca (OH) 2 Other various calcium phosphorus compounds with lower intensity appear after adsorption. Small amounts of Ca (OH) in EC 1:3-750 (b) and EC 1:1-775 (b) 2 With CO 3 2– Forms CaCO 3 With phosphorus, mainly CaCO 3 。
Example 4
A recyclable charcoal bead adsorbent is prepared by the following steps:
(1) Fully mixing eggshell biomass powder (abbreviated as E) and peanut shell biomass powder (abbreviated as C) which are sieved by a 100-mesh sieve according to the mass ratio of 1:1 in deionized water by adopting a magnetic stirrer, then adding sodium alginate, fully stirring for 30min at about 60 ℃, and naturally cooling to room temperature to obtain precursor slurry;
(2) The precursor slurry was dropped into 5% by weight CaCl 2 Balling and hardening in the solution for 18h; after hardening, caCl on the surface of the carbon beads is cleaned by deionized water 2 A solution; drying the hydrogel in a 60 ℃ oven to constant weight; calcining the dried hydrogel beads in a tube furnace at a nitrogen flow rate of 0.025L/min and a temperature rise rate of 700 ℃ (5 ℃/min) for 1.5h, and finally obtaining the finished biochar microbeads.
The prepared 0.03g charcoal beads were placed in 40ml KH with pH=7 at 100mg/L (calculated as P) 2 PO 4 The solution was shaken at 180rpm for 18 hours to determine the phosphorus concentration after adsorption.
The condition test (except that the following conditions are the same as those of the above preparation method of this example) is as follows:
1. CaCl on the surface of the carbon beads after hardening and washing/not washing 2 And the influence of the size of biomass on the structural stability and adsorption capacity of the biochar beads
Setting a process 1 and a process 2; treatment 1: after hardening in the step (2), adopting deionized water to clean CaCl on the surfaces of the carbon beads 2 Solution, setting different particle sizes of eggshells and peanut shells(all passing through 60 mesh, 80 mesh, 100 mesh); treatment 2: caCl on the surface of the carbon beads is not cleaned after hardening in the step (2) 2 A solution. The results are shown in Table 1.
To find the cause and simplify the experimental procedure, caCl on the surface of the carbon beads after hardening with/without water was explored 2 Whether structural stability and adsorption capacity can be influenced or not, and whether the size of biomass can influence the structural stability and adsorption capacity of the prepared biochar beads or not is studied.
TABLE 2 CaCl on the surface of carbon beads after hardening with/without water washing 2 And the influence of the size of biomass on the structural stability and adsorption capacity of the biochar beads
The particle size of the carbon beads which are not washed by water tends to be swelled and powdered after one week, and the surface of the carbon beads is carefully observed to show that the carbon beads are similar to water absorption and moisture absorption, which is probably caused by calcium chloride absorption on the surface of the carbon beads; the swelling phenomenon of different degrees only occurs after one month of the carbon beads are washed by water, but the degree of the carbon beads is light when the carbon beads are not washed by water. In addition, the 100-mesh carbon beads can be kept well in the original state no matter washed with water or not washed with water.
The adsorption capacity of the water-washed carbon beads to P increases along with the reduction of the particle size, but the adsorption capacity of the water-washed carbon beads does not obviously increase to more than 80 meshes; the carbon beads not washed with water show a decrease in adsorption capacity with decreasing particle size.
In conclusion, the eggshell modified peanut shell biochar microbeads prepared by the method are not stable enough in structures of the carbon beads prepared under the particle sizes except for the carbon beads prepared by biomass passing through a 100-mesh sieve. In addition, the adsorption capacity of the biochar beads prepared from biomass passing through a 100-mesh sieve is weak, and the insufficient pyrolysis degree of the biochar beads under the calcination conditions such as the calcination temperature of 700 ℃ and the calcination time of 1.5h is considered. In order to verify this, the pyrolysis degree of the carbon beads is improved, the calcining temperature is increased to 800 ℃, and meanwhile, the influence of different calcining time on the structural stability and the adsorption performance of the prepared biochar balls is explored.
2. Influence of calcination conditions on structural stability and adsorption quantity of biochar beads
The calcination temperature is raised to 800 ℃, and CaCl on the surfaces of the carbon beads is washed off by deionized water after calcination for different time (1 h, 1.5h and 2 h) respectively 2 The E, C particle size is respectively sieved by a 100-mesh sieve; the conditions were the same except that the above conditions were different from the above preparation method of this example. The results are shown in Table 2.
TABLE 3 influence of calcination time on structural stability and adsorption amount of biochar beads
As can be seen from table 2, at a calcination time of 1.5 hours, the carbon bead structure became unstable as the calcination temperature increased to 800 ℃, and not only was the carbon beads dispersed into powder during the adsorption process to generate a large amount of floc, but also the unadsorbed carbon beads could be easily crushed during shaking. This is confirmed by the morphological changes of the carbon beads with increasing calcination time, considering the structural instability caused by too high a degree of pyrolysis. As is clear from Table 2, the phosphorus adsorption capacity increased with the increase of the calcination time, and the instability of the carbon bead structure increased, and the carbon beads were easily pulverized and dispersed. It can be speculated on the whole that: the longer the calcination time, the higher the calcination temperature and the higher the eggshell pyrolysis degree. The stability of the eggshell structure is closely related to the pyrolysis degree of the eggshell, the pyrolysis degree is too high, the structure is unstable, the pyrolysis degree is too low, and the adsorption capacity is weak.
3. The above explanation is verified using the OLS model. 38 kinds of biochar beads were prepared by selecting a suitable preparation condition range according to the above conclusion. An OLS regression model is adopted to study whether preparation conditions such as calcination temperature, E particle size, C particle size, water washing step after hardening, EC mass ratio and the like have obvious influence on the stability of the carbon beads and the phosphorus adsorption amount. In order to be able to better utilize the OLS regression model to predict the relationship of structural stability to different preparation conditions, the structural stability was approximated as a continuous variable according to the experimentally observed degree of pulverization of the carbon beads after adsorption of phosphorus and classified into the following five classes:
the structure is stable after adsorption, and no pulverization-1 is basically generated;
the surface of the carbon beads after adsorption is slightly powdered-0.75;
almost half of the carbon beads are powdered after adsorption, and the other half of the carbon beads maintain spherical shape-0.5;
a small amount of carbon beads maintain spherical shape-0.25 after adsorption;
the carbon beads are almost completely dispersed to be 0 after adsorption;
the preparation conditions, adsorption amount and structural stability of the prepared 38 carbon beads are shown in Table 4.
TABLE 4 preparation conditions, adsorption amount and structural stability of 38 carbon beads
Note that: although structurally stable biochar beads can be obtained at a calcination temperature of 700 ℃, the beads are not shelf stable. After one week, the carbon beads are expanded and loosened, the structural stability is reduced, and the carbon beads are scattered after adsorption.
From the comprehensive analysis of table 4, it can be concluded that: the structural stability of the biochar beads may be affected by the specific gravity of eggshells in addition to the calcination conditions and the particle size of the biomass.
The method comprises the following steps:
1) When the EC is calcined for 1.5 hours at the temperature of 700 ℃ in 1:1, the stability of the structure of the biochar beads can be ensured only when the EC is 100 meshes, and the adsorption quantity is low at the moment; 2) However, as the calcination temperature increases to 750 ℃, the eggshell pyrolysis degree in the biochar beads increases, and the EC ratio in the biochar beads can be reduced to 1:3 to ensure the stability of the structure of the biochar beads, because the reduction of the specific gravity of E reduces the amount of eggshells pyrolyzed, thereby counteracting the adverse effect of the increase of the calcination temperature on the structural stability, and finally maintaining the structure of the sphere in a stable state. 3) Even if the weight ratio of EC is below 1:3, the prepared carbon beads are quite fluffy, have certain water absorption and moisture absorption characteristics and are unfavorable for long-term storage as long as the particle sizes of E and C are respectively larger than that of the E and C passing through a 100-mesh sieve and a 60-mesh sieve, especially when the particle sizes of E and C are relatively large. Even though the carbon beads were structurally stable as they were prepared, they were deformed after a period of time. Let alone that the carbon beads maintain a complete sphere after adsorption.
The results of OLS regression of structural stability with respect to the preparation conditions obtained from the data of table 4 are shown in table 5.
TABLE 5 OLS regression results for carbon bead stability
***p<0.01,**p<0.05,*p<0.1
The OLS results of table 5 show that the F statistic shows that the model has significance with an error probability of 0.0 (p value < 0.01). Corrected R 2 A value of 0.545, meaning that the above preparation conditions have an effectiveness of 54.5% in explaining and predicting the structural stability of the carbon beads; the structural stability of the carbon beads is inversely related to the calcination temperature, the particle size of the eggshells, the particle size of the peanut shells and the mass ratio of the eggshells to the peanut shells; for the water washing after the 0-1 type independent variable hardening, the average increment of the stability of the carbon beads washed after the hardening is 0.05 more than that of the carbon beads not washed after the hardening, the p value is larger, the regression coefficient is not obvious, and the influence of the water washing step after the hardening on the structural stability of the carbon beads can be primarily judged to be smaller.
For continuous variables such as calcination temperature, eggshell particle size, peanut shell particle size, and eggshell to peanut shell mass ratio, it is generally not strict enough to simply compare the correlation coefficient of the preparation condition variables to obtain the degree of influence of each preparation condition on the structural stability of the carbon beads. In order to more accurately obtain the contribution of each preparation condition to the structural stability of the carbon beads, the influence of independent variables and dependent variable value ranges on the structural stability of the final biochar needs to be considered, and the calculation mode is as follows: each time the independent variable increases by one standard deviation, the dependent variable increases by [ beta standard deviation value ], and the percentage of the increase to the mean value of the dependent variable is calculated.
The results were as follows: for each increase in calcination temperature by one standard deviation, the structural stability of the carbon beads is reduced by 0.202, and the reduction amount accounts for 48.2% of the mean value of the dependent variables; for each increase in eggshell particle size by one standard deviation, the structural stability of the carbon beads is reduced by 0.118, and the reduction amount accounts for 28.1% of the mean value of the dependent variables; for each increase in peanut shell temperature by one standard deviation, the structural stability of the carbon beads is reduced by 0.112, and the reduction amount accounts for 26.6% of the mean value of the dependent variables; for the mass ratio of eggshell to peanut shell, the structural stability of the carbon beads was reduced by 0.186 for each standard deviation increase, which was 44.3% of the mean value of the dependent variable.
The degree of influence of the above-mentioned continuity variables on the structural stability of the carbon beads is ordered within the preparation condition range: the calcination temperature is more than the mass ratio of eggshell to peanut shell is more than the particle size of eggshell and peanut shell. Even the peanut shell particle size with the lowest influence degree is obvious in the level of p <0.05, and the regression coefficient can show that the biomass particle size plays an important role in the structural stability of the prepared carbon beads.
The results of OLS regression of the adsorption amount with respect to the production conditions obtained from the data of table 4 are shown in table 6:
TABLE 6 OLS regression results of carbon bead phosphorus uptake Capacity
***p<.01,**p<.05,*p<.1
The OLS results of table 6 show that the F statistic shows that the model has significance with an error probability of 0.0 (p value < 0.01). Corrected R 2 A value of 0.534 means that the above preparation conditions have an effectiveness of 53.4% in explaining and predicting the structural stability of the carbon beads; the carbon bead phosphorus adsorption amount is inversely related to the particle size of peanut shells, and is related to the calcination temperature, the particle size of eggshells and the EC mass ratioPositive correlation is presented; for the 0-1 type independent variable after-hardening washing step, the average increase of the stability of the carbon beads after hardening washing is 11.5 which is larger than that of the carbon beads without hardening washing, the p value is larger, the regression coefficient is not obvious, and the influence of the after-hardening washing step on the phosphorus absorption of the carbon beads can be judged to be smaller. In addition, for the preparation condition variables of the continuous variable, namely the eggshell particle size and the peanut shell particle size, the p value is larger, the regression coefficient is not obvious, so that compared with the influence caused by the change of other variables with obvious regression coefficients, the influence of the change of the biomass particle size within 0.15-0.4 mm on the phosphorus adsorption amount of the biochar beads is very small, and other continuous variables are further analyzed.
Comparative analysis of the extent of influence of the preparation conditions with significant regression coefficients on the adsorption amount was performed as in table 6, and the results were as follows: for the calcination temperature, the adsorption amount of carbon bead phosphorus is increased by 24.3 for every one standard deviation, and the increase amount accounts for 27.5% of the average value of the dependent variables; for each increase in EC mass ratio, the carbon bead phosphorus adsorption increased by 22.4, which was 25.4% of the mean value of the dependent variable.
Within the preparation condition range, the influence degree of continuous variables on the carbon bead phosphorus adsorption amount is ordered: the calcination temperature is more than the mass ratio of eggshells to peanut shells.
By combining the analysis results of tables 5 and 6, it is possible to obtain: the calcination temperature and EC mass ratio have the greatest influence on the carbon bead phosphorus adsorption capacity and the carbon bead structural stability in the preparation condition range, except that the carbon bead structural stability is inversely related to two variables, and the carbon bead phosphorus adsorption capacity is positively related to two variables, which indicates to a certain extent that the high phosphorus adsorption performance of the carbon beads is replaced by the reduction of the carbon bead structural stability; the biomass particle size has a larger influence on the structural stability of the carbon beads, and the adsorption capacity of the carbon beads can be reduced in the water washing process after the gel beads are hardened.
Claims (9)
1. The preparation method of the recyclable charcoal bead adsorbent is characterized by comprising the following steps of:
(1) Mixing eggshell biomass powder and peanut shell biomass powder in water according to a proportion, adding sodium alginate, heating to dissolve, and naturally cooling to room temperature to obtain precursor slurry;
the mass ratio of the eggshell biomass powder to the peanut shell biomass powder is 1:1-3; the particle size of the eggshell biomass powder is 0.15-0.18 mm; the particle size of the peanut shell biomass powder is 0.15-0.25 mm;
(2) Dropping CaCl into the precursor slurry obtained in the step (1) 2 Hardening the hydrogel ball into balls in aqueous solution, drying the hardened hydrogel ball to constant weight, and calcining the hydrogel ball for 1-2 hours at 700-775 ℃ in nitrogen atmosphere to obtain the charcoal bead adsorbent.
2. The method for producing a recoverable charcoal bead adsorbent according to claim 1, wherein in the step (1), the mass percentage of the eggshell biomass powder and the peanut shell biomass powder in water is 4 to 6% by weight.
3. The method for producing a recoverable charcoal bead adsorbent according to claim 1, wherein in step (1), the mass percentage of sodium alginate in the precursor slurry is 1.5-3% wt.
4. The method for producing a recoverable charcoal bead adsorbent according to claim 1, wherein in the step (1), the temperature of the heating dissolution is 55 to 65 ℃ and the stirring time is 20 to 35min.
5. The method for producing a recoverable charcoal bead adsorbent according to claim 1, wherein in step (2), the precursor slurry is dropped into CaCl 2 After the aqueous solution, caCl 2 The mass percent of the epoxy resin is 3 to 7 weight percent, and the hardening time is 16 to 20 hours.
6. The method of claim 1, wherein in step (2), the hardened hydrogel pellets are washed with deionized water to remove CaCl 2 And then drying the mixture to constant weight.
7. The method for producing a recoverable charcoal bead adsorbent according to claim 1, wherein in step (2), the temperature rising rate during calcination is 4 to 5 ℃/min.
8. The method for producing a recoverable charcoal bead adsorbent according to claim 1, wherein in the step (1), the mass ratio of eggshell biomass powder to peanut shell biomass powder is 1:3; the particle size of the eggshell biomass powder is 0.15mm; the particle size of the peanut shell biomass powder is 0.15-0.25 mm; the calcination temperature is 750-775 ℃, and the calcination time is 1.5h.
9. Use of the biochar bead adsorbent of claim 8 for adsorbing phosphate in a water body.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921384A (en) * | 2012-11-22 | 2013-02-13 | 天津理工大学 | Method for preparing high-efficiency fluorine removal agent from solid wastes |
| CN105854805A (en) * | 2016-05-31 | 2016-08-17 | 浙江大学 | Modified charcoal microballoon, and preparation method and application thereof |
| CN107983314A (en) * | 2017-12-07 | 2018-05-04 | 湖南大学 | A kind of biological carbon composite of sodium alginate-calcium ion modification and preparation method thereof and purposes |
| CN111701568A (en) * | 2020-07-10 | 2020-09-25 | 西安交通大学 | Eggshell straw biochar composite microsphere phosphorus removal adsorbent with high adsorption performance and preparation method and application thereof |
| CN115106063A (en) * | 2022-07-06 | 2022-09-27 | 重庆大学 | Porous biochar prepared from eggshells and orange peels and application of porous biochar in phosphorus removal |
-
2023
- 2023-03-16 CN CN202310267803.2A patent/CN116099504A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921384A (en) * | 2012-11-22 | 2013-02-13 | 天津理工大学 | Method for preparing high-efficiency fluorine removal agent from solid wastes |
| CN105854805A (en) * | 2016-05-31 | 2016-08-17 | 浙江大学 | Modified charcoal microballoon, and preparation method and application thereof |
| CN107983314A (en) * | 2017-12-07 | 2018-05-04 | 湖南大学 | A kind of biological carbon composite of sodium alginate-calcium ion modification and preparation method thereof and purposes |
| CN111701568A (en) * | 2020-07-10 | 2020-09-25 | 西安交通大学 | Eggshell straw biochar composite microsphere phosphorus removal adsorbent with high adsorption performance and preparation method and application thereof |
| CN115106063A (en) * | 2022-07-06 | 2022-09-27 | 重庆大学 | Porous biochar prepared from eggshells and orange peels and application of porous biochar in phosphorus removal |
Non-Patent Citations (1)
| Title |
|---|
| 许跃 等: "牡蛎壳改性花生壳生物炭吸附水体中磷的研究", 《给水排水》, vol. 48, 31 December 2022 (2022-12-31), pages 743 - 748 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116651399A (en) * | 2023-06-08 | 2023-08-29 | 高频(北京)科技股份有限公司 | Spherical modified coffee grounds biochar and preparation method and application thereof |
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