CN113145068A - Rice straw biochar impregnated with zinc chloride and preparation method thereof - Google Patents
Rice straw biochar impregnated with zinc chloride and preparation method thereof Download PDFInfo
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- CN113145068A CN113145068A CN202110193852.7A CN202110193852A CN113145068A CN 113145068 A CN113145068 A CN 113145068A CN 202110193852 A CN202110193852 A CN 202110193852A CN 113145068 A CN113145068 A CN 113145068A
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- adsorption
- rice straw
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- chloramphenicol
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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
- B01J20/0203—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
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- 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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a rice straw biochar impregnated with zinc chloride and a preparation method thereof, wherein the preparation method comprises the following steps: crushing the naturally air-dried rice straws by a miniature crusher and then sieving to prepare crushed rice straws; in ZnCl2Soaking in the solution, stirring, filtering, drying in oven to constant weight, pulverizing, and sieving; putting the raw materials into a ceramic crucible, heating in a tubular furnace under the protection of nitrogen, and pyrolyzing; and cooling to room temperature, taking out, and preparing the rice straw biochar after being soaked by the zinc chloride. The invention utilizes zinc chloride impregnationThe charcoal adsorbing material prepared from the rice straws can quickly and efficiently remove chloramphenicol from a water body.
Description
Technical Field
The invention belongs to the technical field of development of a reagent for removing antibiotics, and particularly relates to rice straw biochar impregnated with zinc chloride and a preparation method thereof.
Background
Antibiotics are powerful drugs for humans and animals for the treatment of diseases associated with infections, but the phenomenon of antibiotics abuse in human medicine and animal farming is abundant, leading to a surge in antibiotic levels in the environment. Chloramphenicol is a typical spectrum antibiotic, has low cost and perfect technical process, and is the first choice drug in the third world. While treating diseases, chloramphenicol can cause genetic toxicity and other side effects, such as aplastic agranulocytosis, anemia, and leukopenia, which severely compromise ecological safety and human health. After human beings and animals take chloramphenicol, up to 90% of non-metabolic antibiotics are discharged into sewage through urine and feces, resulting in the pollution of surface water, ground water and even drinking water, and therefore it is important to reduce the concentration of chloramphenicol before discharging sewage.
The resource amount of the Chinese rice straws in 2017 is 19.1 hundred million tons, which accounts for 22.81% of the total amount of the national straw resources and is an important source of the Chinese crop straws. The rice straw resource amount is rich, and the organic matter content is up to 80-90%, thus providing wide space and huge development potential for resource utilization. However, the straw resource amount is large, the density is small, the collection and the resource utilization are difficult, and the biochar prepared under the anoxic temperature control condition not only can reduce the volume, but also can be used for sewage restoration, and is a good way for resource utilization.
The removal of antibiotics in water is always the focus of attention of scholars, and common treatment methods comprise biotechnology, chemical technology and physical technology. First, sewage treatment plants often employ biological methods for denitrification, and antibiotics exert inhibitory effects on microorganisms, including inhibition of cell wall synthesis, interference with protein synthesis, disruption of bacterial cell membranes, and inhibition of transcription and replication of nucleic acids. Studies have shown that bioremediation methods cannot completely remove important antibiotics and are time consuming. Second, chemical methods, which mainly degrade antibiotics into small molecular substances by chemical reactions, include chlorination and advanced oxidation. Although the advanced oxidation process has a high treatment efficiency, the complexity of the antibiotic wastewater may inhibit its removal effect due to its low selectivity. The process generates toxic by-products and pH dependence. Third, common physical methods include membrane separation and adsorption, and the membrane separation technology mainly uses pressure as a driving force and uses the pore size of the membrane to intercept antibiotics, mainly including Reverse Osmosis (RO), Nanofiltration (NF), Microfiltration (MF) and Ultrafiltration (UF). Among them, microfiltration and ultrafiltration belong to low-pressure filtration membranes in classification, have low retention rate on antibiotics, and are generally used as pretreatment means for other membrane separation methods. The application of reverse osmosis and nanofiltration is limited by the defects that the membrane is easy to block and the like although the reverse osmosis and nanofiltration are widely applied. Adsorption is a commonly used physical treatment. Physical adsorption exerts its adsorption mainly by van der waals forces, while chemical adsorption exerts its adsorption by chemical bond formation and electron transfer. Currently, most antibiotic adsorbing materials are mainly clay minerals, metal organic framework compounds, carbon materials and modified materials thereof. Clay minerals and metal organic framework raw materials are not easy to obtain, the cost is high, and the preparation process is complicated.
In summary, bioremediation cannot completely remove important antibiotics and is time-consuming, chemical removal methods, represented by advanced oxidation methods, generate toxic by-products and pH dependency, and membrane separation methods have high equipment costs and high energy requirements. Compared with the above methods, the adsorption method represented by biochar is simple in operation, low in cost, high in efficiency and free from potential toxicity, and has proved to be a very effective treatment scheme for organic pollutants. The core and key of the adsorption technology lies in preparing an efficient and cheap adsorbent. The biochar is a stable carbon-rich product, is formed by pyrolyzing biomass (such as agricultural and forestry waste) under the anoxic condition, has the superior characteristics of large specific surface area, large pore volume, high dielectric constant and the like, and can effectively realize physical adsorption and chemical adsorption so as to achieve the aim of reducing the concentration of harmful organic matters in water.
Adsorption energy of unmodified rice straw biochar to antibioticsThe force is limited, the specific surface area of the biochar prepared from the activated and modified raw materials is increased, the microporous structure is more complex, and the adsorption of organic matters is facilitated. The preparation of modified biochar by impregnating raw materials with metal ions is a research hotspot at home and abroad, and Yan L et al immerse aerobic granular sludge into 5 mol.L-1ZnCl of2The maximum adsorption amount of tetracycline on Zn-BC is found to be 93.44 mg.g-1Less affected by pH, iron/zinc (Fe/Zn), phosphoric acid (H) are used by Liou et al3PO4) Or Fe/Zn + H3PO4The activated carbon prepared by using the composite modified Sludge Biochar (SBC) as an activating agent is used for adsorbing fluoroquinolone antibiotics, and the adsorption amount of the Fe/Zn + H3PO4-SBC to CIP, NOR and OFL is found to be 20 times of that of the single modified adsorption. The method is characterized in that the biochar prepared by rice straws is deeply researched for tetracycline antibiotics and fluoroquinolone antibiotics at present, the chloramphenicol is not easy to degrade and remove in water due to the stability of the chloramphenicol, the removal of the chloramphenicol is mostly achieved by photocatalytic degradation and advanced oxidation methods at present, the research on the adsorption of the chloramphenicol by the biochar is less, the removal of the chloramphenicol in water is achieved by preparing the biochar by eucalyptus wood by Mohammad BoshirAhmed and the like, and the biochar is modified by phosphoric acid, so that the material is acidic, and the pH needs to be additionally adjusted to achieve the adsorption of the chloramphenicol; mohammad b.ahmed et al adopt nano zero-valent iron particles losing reducibility after use and composite materials thereof to be fixed on biochar to realize the removal of antibiotics in water, although the mode realizes an adsorption effect, the material source is limited, the preparation process is complicated, a large amount of acidic drugs are used in the process of fixing the nano zero-valent iron particles on the biochar, the cost is high, and the nano zero-valent iron particles are not friendly to the environment; although the Fang Yang et al also adopt rice straw as a material to prepare the antibiotic in the removal of the biochar, he needs to adopt a freeze-drying technology, which undoubtedly increases the previous manufacturing cost and equipment cost.
In general, the application of biochar, particularly rice straw biochar, in the adsorption of antibiotics at present has the following problems: the preparation material of the biochar has limited source range, cannot realize industrialized production and has lower yield; the charcoal prepared from unmodified rice straws has low specific surface area and poor adsorption capacity, and cannot realize effective adsorption of antibiotics; the modification and pretreatment modes of the rice straws are complex, and a simple and effective means is lacked to prepare the modified rice straw biochar capable of quickly and efficiently adsorbing antibiotics; in addition, in the adsorption process, the rice straw and modified rice straw biochar have the technical problems of low adsorption rate, long time for reaching adsorption balance, low adsorption capacity, low removal rate and the like.
Disclosure of Invention
In view of the above, the invention provides a rice straw biochar impregnated with zinc chloride and a preparation method thereof, the rice straw modification and biochar preparation process used in the invention is simple, the operation is easy, the preparation period is short, no complex equipment is needed in rice straw pretreatment, only simple impregnation modification is needed, the rice straw is wide in source and easy to collect, the early cost is low, the obtained modified rice straw biochar has stable performance, the high-efficiency adsorption of chloramphenicol can be realized in a short time, and the removal rate is close to 100%.
In order to solve the technical problem, the invention discloses a preparation method of rice straw biochar after zinc chloride impregnation, which comprises the following steps:
Optionally, the mesh number in step 1 is 40-80 mesh.
Optionally, ZnCl in the step 22The concentration of the solution is 1-3 mol.L-1。
Optionally, after the pulverization in the step 2Rice straw and ZnCl2The mass ratio of the solution is 1:2-1: 4.
Optionally, the stirring time in the step 2 is 20-28h, and the oven temperature is 55-65 ℃; the mesh number is 80-120 meshes.
Optionally, the temperature rise rate in the step 3 is 3-10 ℃/min, the pyrolysis temperature is 500-700 ℃, and the pyrolysis time is 1-3 h.
The invention also discloses the rice straw biochar prepared by the preparation method and impregnated with the zinc chloride.
Compared with the prior art, the invention can obtain the following technical effects:
1) according to the invention, the biochar adsorbing material prepared from the zinc chloride impregnated rice straws can quickly and efficiently remove chloramphenicol in a water body, and the removal rate is as high as more than 95% in 1 h; has better adsorption potential and more adsorption sites; the rice straw as a preparation material is nontoxic and harmless, has low price and is easy to obtain, thereby avoiding the generation of toxic by-products in the removal process and greatly reducing the production cost.
2) Compared with a chemical method, the rice straw used in the invention is non-toxic and harmless, does not produce side products, is proved to have no pH dependence and ion interference resistance by experiments, and has wide application range.
3) Compared with a membrane separation method or using clay minerals and a metal framework as an adsorbent, the method uses rice straws as raw materials, is agricultural and forestry waste, is low in price and easy to obtain, simple in preparation process, stable in structure and good in regeneration performance, can realize efficient adsorption, can realize resource utilization of the agricultural waste, achieves two purposes by one action, saves a large amount of time cost, economic cost and environmental cost, and has good economic benefits and wide development prospects compared with the prior art.
Of course, it is not necessary for any one product to practice the invention to achieve all of the above-described technical results simultaneously.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the best mode contemplated. In the drawings:
FIG. 1 shows that the adsorption kinetics of Zn-BC700 to chloramphenicol with different concentrations is 100 mg.L by using a pseudo first order model, a pseudo second order model and an Elovich model-1(a)，150mg·L-1(b)，200mg·L-1(c) (ii) a (d) Zn-BC700 at different concentrations (100 mg. L)-1，150mg·L-1And 200 mg. L-1) Removal rate in chloramphenicol;
FIG. 2 is a graph showing an intragranular diffusion model (a) and a liquid membrane diffusion model (b) of the present invention in which contact time affects the adsorption of chloramphenicol to Zn-BC 700;
FIG. 3 shows R-BC700, Zn-BC700 and Zn-BC700 after undergoing an adsorption reaction according to the present invention;
FIG. 4 is an XRD pattern of the R-BC700, Zn-BC700 of FIG. 4 according to the present invention;
FIG. 5 is a FT-IR spectrum of Zn-BC700 of the present invention;
FIG. 6 is a nitrogen adsorption-desorption isotherm of Zn-BC700 of the present invention;
FIG. 7 is a pore size distribution of Zn-BC700 of the present invention;
FIG. 8 shows the zero potential of Zn-BC700 according to the present invention;
FIG. 9 is a graph of the effect of pH on chloramphenicol adsorption strength in accordance with the present invention;
FIG. 10 shows the effect of the concentration of salt ions on adsorption in accordance with the present invention, wherein the concentration of chloramphenicol is 100 mg.L-1And reacting at 35 ℃ for 1 h.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the present invention by applying technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
The invention discloses a preparation method of rice straw biochar after zinc chloride impregnation, which comprises the following steps:
The invention also discloses the rice straw biochar prepared by the preparation method and dipped with zinc chloride.
Example 1
The rice straw used was collected from Yingfu city, Sichuan province. 50g of naturally air-dried rice straw is crushed by a miniature crusher (FZ 102, Shanghai Keheng) and then sieved by a 60-mesh sieve, and the crushed material is added into 500mL of 1 mol.L-1ZnCl of2(AR, Chengdu Kellong Chemicals Co., Ltd.) solution was immersed and stirred for 24 hours, filtered, dried in an oven at 60 ℃ to constant weight, pulverized and sieved with a 100-mesh sieve. The rice straws which are not dipped in the zinc chloride are dried in a drying oven at 60 ℃ to constant weight, and are sieved by a 100-mesh sieve after being crushed. Placing the two raw materials in a ceramic crucible in a tube furnace, heating at the speed of 5 ℃/min under the protection of nitrogen, and pyrolyzing for 2h at 700 ℃. And taking out the mixture when the mixture is cooled to room temperature.
Example 2
The rice straw used was collected from Yingfu city, Sichuan province. 50g of naturally air-dried rice straw is crushed by a miniature crusher (FZ 102, Shanghai Keheng) and then sieved by a 60-mesh sieve, and the crushed material is added into 500mL of 1 mol.L-1ZnCl of2(AR, Chengdu Kellong Chemicals Co., Ltd.) solution was immersed and stirred for 24 hours, filtered, dried in an oven at 60 ℃ to constant weight, pulverized and sieved with a 100-mesh sieve. The rice straws which are not dipped in the zinc chloride are dried in a drying oven at 60 ℃ to constant weight, and are sieved by a 100-mesh sieve after being crushed. Placing the two raw materials in a ceramic crucible in a tube furnace, heating at the speed of 5 ℃/min under the protection of nitrogen, and pyrolyzing for 2h at 500 ℃. And taking out the mixture when the mixture is cooled to room temperature.
Example 3
The rice straw used was collected from Yingfu city, Sichuan province. 50g of naturally air-dried rice straw is crushed by a miniature crusher (FZ 102, Shanghai Keheng) and then sieved by a 60-mesh sieve, and the crushed material is added into 500mL of 1 mol.L-1ZnCl of2(AR, Chengdu Kellong Chemicals Co., Ltd.) solution was immersed and stirred for 24 hours, filtered, dried in an oven at 60 ℃ to constant weight, pulverized and sieved with a 100-mesh sieve. The rice straws which are not dipped in the zinc chloride are dried in a drying oven at 60 ℃ to constant weight, and are sieved by a 100-mesh sieve after being crushed. Placing the two raw materials in a ceramic crucible in a tube furnace, heating at the speed of 5 ℃/min under the protection of nitrogen, and pyrolyzing for 2h at 600 ℃. And taking out the mixture when the mixture is cooled to room temperature.
Example 4
A preparation method of rice straw biochar impregnated with zinc chloride comprises the following steps:
Example 5
A preparation method of rice straw biochar impregnated with zinc chloride comprises the following steps:
The technical effects of the invention are illustrated below with reference to specific experimental data:
the first experiment method comprises the following steps:
1. chloramphenicol adsorption test:
chloramphenicol (C)11H12Cl2N2O598%, MACKLIN) were run in a constant temperature magnetic stirrer, three replicates of each treatment and a control set was set up. The adsorption kinetics experimental process is as follows: weighing 0.25g of biochar sample into a 250mL conical flask, adding 250mL of 50mg & L-1，100mg·L-1And 150 mg. L-1The chloramphenicol solution was reacted for 1 hour in a magnetic stirrer at 35 ℃ in the absence of light. Samples were taken at 3, 5, 7, 10, 15, 20, 25, 30, 35, 40, 50 and 60 minutes, respectively, and the solution concentration was measured by an ultraviolet-visible spectrophotometer (UV-2600, Shimadzu, Japan) and high performance liquid chromatography (LC20A, Shimadzu, Japan) after passing through a 0.22 μm filter.
Chloramphenicol adsorption quantity Q at reaction equilibriume(mg·g-1) Adsorption quantity Q of contact time tt(mg·g-1) And the chloramphenicol solution removal rate N (%) was calculated from the formulas (1) to (3).
In the formula, QeThe adsorption capacity (mg. g) of the biochar to the chloramphenicol-1)，CeAnd C0The initial equilibrium concentration and the experimental equilibrium concentration (mg. g) of chloramphenicol in the solution were measured, respectively-1)，QtIs the adsorption capacity of the biochar to the chloramphenicol at time t, (mg. g)-1) Nt is the adsorption removal rate at time t, C0、 CtAnd CeThe initial and time t and equilibrium chloramphenicol concentrations (mg. L)-1) V is the volume of the solution (L) and m is the mass of the biochar (g).
2. Selecting a pyrolysis temperature:
biochar prepared in examples 1-3 was treated at the same chloramphenicol concentration (100 mg. L)-1) The adsorption capacity of the three materials is shown in table 1, the adsorption capacity of the three materials to chloramphenicol is significant, and is most prominent as Zn-BC700 (example 1, rice straw biochar impregnated with zinc chloride), probably because as the pyrolysis temperature rises, the roughness and the pore structure gradually increase, the internal structure of the biochar gradually decomposes, more pyrolysis gas is separated out from the biochar, a large amount of pore structures are formed gradually, and the large amount of pore structures provide more active sites for the adsorption of chloramphenicol, so that chloramphenicol molecules can enter the inner layer of the biochar more favorably and can be combined with the adsorption sites and active groups on the surface of the inner layer, and the adsorption capacity is further increased. As the rice straw biochar can produce the best adsorption effect when pyrolyzed at 700 ℃. Therefore, the required rice straw biochar is prepared at the pyrolysis temperature of 700 ℃, and is named as Zn-BC 700.
TABLE 1 adsorption capacities of different biochar species
3. Principle of adsorption
Within 0-10 min, the concentration of the chloramphenicol solution is reduced at a fast speed, within the interval of 20-40 min, the reduction speed of the chloramphenicol solution is slow, and the chloramphenicol concentrations at the three concentrations at 40min and 60min are only slightly different, so that 60min is a time point sufficient for achieving adsorption equilibrium. In the early stage of the adsorption reaction, the rapid increase of the Zn-BC700 (example 1) adsorption amount may be caused by the fact that a large number of active adsorption sites on the surface of the Zn-BC700 biochar are almost completely exposed, the concentration of the biochar surface is greatly different from that of a chloramphenicol solution, more chloramphenicol molecules are transferred from the aqueous solution to the biochar surface, and the adsorption amount and the removal rate are rapidly increased. The adsorption quantity is slowly increased along with the increase of the adsorption time, which belongs to the adsorption saturation effect in the later adsorption period, the chloramphenicol occupies most of the active centers on the surface of the biochar and gradually reaches a saturation state, the active sites are reduced, and the adsorption rate is gradually reduced.
And (3) fitting experimental data by using a dynamic model (Pseudo-first order model, Pseudo-second order model and Elovich model) to research the adsorption process characteristics of three different initial chloramphenicol concentrations.
The first order modeling assumes that adsorption is diffusion controlled, and the equations and linear relationships are as follows:
lg(qe-qt)＝lgqe-K1t (4)
in the formula, qeAnd q istThe adsorption capacity (mg. g) of the adsorbent at equilibrium and a certain time, respectively-1)，K1To simulate a first order adsorption rate constant (min)-1)。
The pseudo-second order model assumes that chemisorption controls the adsorption rate, including electron transfer and electron sharing between the adsorbate and the adsorbent during the reaction. The equations and linear relationships are as follows:
wherein K2Is a pseudo second order adsorption rate constant (g.mg)-1·min-1)。
The curves and kinetic parameters are shown in Table 2 and FIG. 1a, a graph1b, FIG. 1c, correlation coefficient R at three concentrations2It was shown that the pseudo second order model (0.9595, 0.9814, 0.9820) and the Elovich model (0.9352, 0.9548, 0.9520) fit the experimental data better than the pseudo first order model (0.6090, 0.8599, 0.8414). The pseudo second-order process can be divided into two dynamic steps, chloramphenicol molecules are firstly adsorbed on the surface of the adsorbent to form a monolayer of chloramphenicol molecules, the biochar starts to remove the chloramphenicol through a chemical adsorption mechanism along with the fact that the monolayer physical adsorption is close to a saturated state, and valence exchange or electronic exchange and other chemical adsorption processes start to occur between Zn-BC700 and the chloramphenicol.
TABLE 2 parameters and correlation coefficients of the kinetic model
Since the surface of the Zn-BC700 biochar prepared in example 1 is non-uniform and chemisorption interaction occurs on the surface, solute transfer is usually expressed as external liquid film diffusion of a non-porous medium and adsorption controlled by film diffusion for the solid-liquid adsorption process, and solute is transferred by liquid film external diffusion or liquid film internal diffusion or a combination of both in the solid-liquid adsorption process through analysis of an intra-granular diffusion model and a liquid film diffusion model. The liquid film diffusion model is based on the Fick diffusion second law; assuming that the external resistance only acts at the initial stage of diffusion, the direction of particle diffusion is random, the adsorbate concentration does not change with the particle position, and the intra-particle diffusion coefficient is constant and does not change with time. To further analyze the diffusion mechanism, an intra-particle diffusion model was used, with the following formula:
in the formula, Kt(mg·g-1·min1/2) As an intraparticle diffusion rate constant, C (g. mg)-1) The larger the value of C, the greater the influence of the boundary layer on the adsorption rate, which is a constant related to the thickness and the boundary layer.
To determine whether the actual rate control step is caused by liquid film diffusion or by void diffusion, the kinetic data were analyzed using a liquid film diffusion model, as follows:
in the formula, Kfd(min-1) Is the liquid film diffusion coefficient.
The Elovich model is calculated by equation (8):
where the constant a is related to the chemisorption rate and the constant b is related to the surface coverage.
From FIG. 2a, q can be seentAnd t1/2The curve of (1) consists of three straight line segments, and the adsorption process of the surface of Zn-BC700 prepared in example 1 on chloramphenicol is multistep, and the linear correlation coefficient and K aret、 Ct、KfdThe values of (A) are shown in Table 2. It can be seen that the curves of the first section at the three concentrations all show the same characteristics, the curves are steeper, but have no zero intercept, the correlation coefficient is higher, and the steeper curves indicate that the chloramphenicol migrates from the bulk solution to the surface of the adsorbent, which is controlled by both molecular diffusion and liquid film diffusion, the large intercept surface adsorption mainly occurs at the surface, and the intragranular diffusion and the liquid film diffusion proceed simultaneously. The reaction in the second and third stages is obviously lower than that in the first stage, and the diffusion of the liquid film in the adsorption process in the later stage of the reaction is already in the dominant position of the adsorption. In the later period of the reaction, when the initial concentration of chloramphenicol is increased, although the slope of the intragranular diffusion model is reduced, the curve still shows a relatively steep trend, and the intercept is compared with that of the chloramphenicol with low initial concentrationRelatively reduced but with a higher correlation coefficient. This shows that with the increase of the initial concentration of chloramphenicol, the liquid film diffusion and the intragranular diffusion still present a combined action state in the later stage of the adsorption reaction, and neither diffusion model has a condition of occupying an obvious dominant position. Different dynamic models have important significance for revealing possible mechanisms of adsorption and determining speed-limiting steps of the whole process, and under the experimental conditions, the pseudo second-order model and the Elovich model are well fitted with experimental data, which indicates that chemical adsorption such as valence force exchange or electronic exchange occurs in the adsorption process, and liquid film diffusion and intra-granular diffusion exist simultaneously in the adsorption process.
II, experimental results:
1. physical and chemical property characteristics of rice straw biochar
Rice straw and stalk ZnCl2The elemental analysis of the rice straw treated by dipping (JY/T017- & 1996 elemental analyzer method general rule) is shown in Table 3. By ZnCl2The content of C in the biochar prepared by the impregnation treatment is obviously increased, and the content of H element is reduced, because H and O can interact with each other and can also react with C to form volatile gas in the pyrolysis process, so that the H element can be released from the surface of the sample. The ratio of H/C, O/C, (N + O)/C can be used to evaluate the aromaticity, hydrophilicity and polarity of the material. Compared with rice straws, the Zn-BC700 prepared in example 1 has the advantages of obviously increased C content and reduced H element content, which means that the Zn-BC700 has enhanced aromatic structure, enhanced stability, reduced polarity and may contain more functional groups. On the other hand, the presence of heteroatoms (e.g., N, O, P or S) on the surface of biochar increases the adsorption capacity of biochar and increases the adsorption selectivity and sensitivity to target antibiotic molecules by enhancing supramolecular interactions, i.e., supramolecular interactions of biochar such as van der Waals forces, pi-electron acceptor interactions, electrostatic and hydrogen bonding interactions.
TABLE 3 elemental analysis of Rice straw and Zn-BC700
2. Structural morphology of rice straw biochar
The surface appearance and microstructure of the material were observed by Scanning Electron Microscopy (SEM), and the image of the original biochar R-BC700 prepared from untreated rice straw is shown in FIG. 3a, wherein the R-BC700 is a layered structure with initial pores of porous, coarse and micro-scale particles on the surface and is composed of closely packed tubular tissues. By ZnCl2As shown in FIG. 3b, the biochar Zn-BC700 (example 1) prepared from the rice straws subjected to impregnation treatment is more disordered in surface morphology compared with R-BC700, the Zn-BC700 prepared in example 1 has a stacking and layering structure, and more cluster structures and porous structures appear, and the ZnCl proves that the biochar Zn-BC700 is subjected to ZnCl treatment2The charcoal prepared by the impregnation treatment is easier to expose the active sites. This is due to the fact that in ZnCl2The carbonization process plays a role in dehydration, so that the carbonization and aromatization of the carbon skeleton are caused, and the formation of a porous structure is facilitated to promote the adsorption. This also remains consistent with the results of elemental analysis and FT-IR analysis. As shown in FIG. 3c, Zn-BC700 subjected to chloramphenicol adsorption reaction has smooth surface, reduced pores, regular structure, and reduced cluster structure. This proves that after the adsorption reaction occurs, a large amount of chloramphenicol occupies the adsorption sites on the surface of the adsorption material, and chloramphenicol molecules fill up the pores of Zn-BC 700.
3. Characterization of rice straw biochar XRD
The X-ray diffraction technology has become the most basic and important structural test means, and is mainly applied to phase analysis, crystallinity measurement and precise measurement of lattice parameters. The X-ray diffraction with CuK as the radiation source can provide the crystal structure and composition information of the biochar. As shown in FIG. 4, the diffraction peaks of the XRD pattern of Zn-BC700 (example 1, rice straw biochar impregnated with zinc chloride) are significantly changed compared to R-BC700, which indicates that ZnCl is passed through2The solution-impregnated rice straw has a large amount of mineral crystals, and the chemical composition formula of the more obvious diffraction peak is marked in the figure. It was found that the Zn-BC700 surface had a large amount of Zn-containing compounds, which proved to be ZnCl2The biochar prepared by solution impregnation successfully loads Zn element on the biochar. The XRD pattern of the Zn-BC700 sample presents a broad peak within the range of 20-30 degrees, and presents a hump within the range of 40-50 degrees, which shows that the crystallinity of the Zn-BC700 is increased, the amorphous material with a certain degree of short-range order can be attributed to the formation of turbine structure microcrystals, so that the carbon compound structure is more stable, and the adsorption performance is enhanced.
4. Analysis of biochar functional groups of rice straws
FT-IR is an important method for qualitatively identifying characteristic functional groups on the surface of a material, and FIG. 5 is an FT-IR spectrogram of Zn-BC700 (example 1, rice straw biochar impregnated with zinc chloride). 2318cm-1The characteristic peak of (A) can be attributed to the stretching vibration of carboxyl, 1064cm-1、1646cm-1The characteristic peaks at (a) may be the presence of C ═ C and C — O bonds, which may be attributed to the presence of phenolic functional groups on the surface, and the formation of hydrogen bonds between phenolic and oxycarboxylic groups also contributes to the occurrence of adsorption reactions. 1862cm-1The characteristic peak at (A) is considered to be the elastic vibration of the C ═ O bond, indicating ZnCl2The impregnation treatment of (2) is likely to inhibit the deoxidation reaction in the biomass pyrolysis carbonization process. 586cm-1The characteristic peaks at (a) correspond to hydrocarbon functions containing C-H bonds. ZnCl in the carbonization process2Dehydration leads to aromatization of the carbon skeleton and also leads to pi-pi conjugation between the aromatic structure in Zn-BC and the aromatic ring structure in chloramphenicol. Therefore, the Zn-BC700 prepared by pyrolysis contains a large amount of oxygen-containing functional groups, and the oxygen-containing functional groups serve as pi-electron acceptors in the reaction process and are beneficial to electron transfer in the adsorption process. 903cm-1The unknown characteristic peak may be due to ZnCl2In the presence of ZnCl2The introduction of the organic carbon can improve the electron-donating capability of the biochar and promote the interaction of the biochar and strong electron acceptor groups (namely benzene rings and nitro groups) in the chloramphenicol, which is beneficial to the progress of adsorption reaction.
5. Analysis of specific surface area and pore characteristics of rice straw biochar
The BET analysis revealed that the specific surface area and the pore distribution of the material, and thus the change in the physical properties of the material, were known, and the nitrogen adsorption/desorption graph (fig. 6) showed that Zn — BC700 (example 1,rice straw biochar impregnated with zinc chloride) can reach 250cm3·g-1The BET adsorption amount of the rice straw biochar prepared by the leaf synergetic Pistan et al at the same pyrolysis temperature is only 14cm3g-1The adsorption capacity of Zn-BC700 is much larger than that, which shows that the adsorption capacity is much larger than that of ZnCl2Zn-BC700 prepared from the soaked rice straws has good adsorption potential. As can be seen from FIG. 7, the pore diameter of Zn-BC700 is between 0-110 nm, mainly concentrated at 20nm or less. When the relative pressure is increased to about 0.5, the isotherm shows a remarkable hysteresis loop, has the characteristic of a mesoporous structure, and is favorable for the adsorption of macromolecules.
The specific surface area of Zn-BC700 is 640.1748m2·g-1The micropore volume is 0.063686cm3·g-1The average adsorption pore diameters were 2.394nm, respectively. Generally speaking, an adsorbent with a large specific surface area and a more developed porous structure has better adsorption performance, according to the adsorption theory, when the pore diameter is 1.7-3 times larger than that of an adsorbent molecule, the adsorbent has the best adsorption performance, the specific surface area of Zn-BC700 is large, micropores develop well, and the pore diameter is far larger than the size (0.463nm) of a chloramphenicol molecule, which indicates that a micropore filling effect may exist in the adsorption process. The large specific surface area and the mesoporous structure of Zn-BC700 provide more contact area and contact conditions for the adsorption of chloramphenicol.
TABLE 3 BET data for Zn-BC700
6. Influence of pH on the adsorption
Different compounds interact with biochar via mechanisms such as potential electron-donor-acceptor (EDA) interaction, nucleophilic addition, electrostatic attraction, cation bridging, cation/anion exchange, pore filling, partitioning to non-carbonized moieties, and formation of Charge Assisted Hydrogen Bonds (CAHB) with surface oxygen groups. Changes in pH affect the surface charge of the adsorbent, the ionic state of the surface functional groups, the morphology of chloramphenicol on the adsorbent surface and in the adsorbent system, and thus affect chloramphenicol and nascentMechanism of action of charcoal. The adsorption effect of the pH value in the range of 2-11 on Zn-BC700 (example 1, rice straw biochar impregnated with zinc chloride) is shown in FIG. 9, and the adsorption capacity is above 90% and has small change along with the change of the pH value, which indicates that the change of the pH value is not enough to influence the electron donating capability of the adsorbent. The maximum adsorption amount occurs at pH 3 to 4, since the observation is made by the zero potential of Zn-BC700 (pH)pzc5.75, see fig. 8) and the possible presence of acidic functional groups on the surface, the acidic condition provides a suitable environmental condition for better binding of biochar to chloramphenicol, and on the other hand the solution concentration is lower than pHpzcIn the process, the surface of the biochar is positively charged, so that adsorption reaction is more favorably carried out. The molecular structure of the chloramphenicol is provided with 3 hydrogen bond donors and 5 hydrogen bond acceptors, the aqueous solution is neutral, the hydrolysis is slow within the pH range of 2-7 at room temperature, and the decrease of the chloramphenicol concentration in the solution is from the adsorption of the biochar rather than the degradation of the solution due to instability. The adsorption mechanism is presumed to be due to the formation of Charge Assisted Hydrogen Bonds (CAHB) on Zn-BC700, primarily EDA interactions. The result also shows that the Zn-BC700 has a wide pH adaptation range when adsorbing chloramphenicol, and can be used for repairing and treating chloramphenicol-containing sewage with different pH values.
7. Effect of ionic strength on Chloramphenicol adsorption
In practical situations, the sewage contains high-concentration salt ions, which may affect the adsorption of the biochar. Na (Na)+，K+，Ca2+And Cl-Is ions with higher content in sewage, and 0.2-1 mol.L is adopted in the research-1NaCl, KCl and CaCl of2(AR, Kyoko chemical Co., Ltd.) As a background solution, a chloramphenicol concentration was prepared in consideration of the influence of the ionic strength on the adsorption result, and the result is shown in FIG. 10. Compared with the adsorption process without salt ions, the adsorption capacity of the chloramphenicol of Zn-BC700 (example 1, rice straw biochar impregnated with zinc chloride) with the salt solutions as background can still reach 90mg g-1The difference between the adsorption capacity of the adsorption process and the adsorption capacity of the adsorption process without adding the salt solution is less than 10mg g-1. With KCl and CaCl2In contrast, NaCl exerts a slight inhibitory effect, and the inhibitory effect is slightly increased with an increase in NaCl concentration, which is probably due to Na during the adsorption reaction of the Zn-BC700 adsorbent with chloramphenicol+More easily contacted with the adsorbent than other salt ions, Na+The groups on the surface of the adsorbent Zn-BC700 generate electrostatic interaction, occupy adsorption sites on the surface of the adsorbent, reduce the adsorption capacity of the adsorbent and generate a certain competitive inhibition effect. But in general, Na+， K+,Ca2+And Cl-The existence of the Zn-BC700 can not generate great influence on the adsorption process, which proves that the Zn-BC700 has good application prospect and application value in the actual sewage treatment process.
8. Repeatable adsorption of rice straw biochar
Using the mixed solution subjected to the isotherm test at 35 ℃ for the recycling test of chloramphenicol, filtering the mixed solution after reaction after 1h adsorption balance, drying the adsorbent in the collected mixed solution at 60 ℃, putting the dried powder into a dialysis bag and putting the dialysis bag into the dialysis bag in a volume of 0.2 mol.L-1And (3) dialyzing in NaOH, continuously replacing a new NaOH solution during the dialysis, taking the dialyzate, filtering the dialyzate through a 0.45-micron filter membrane, detecting the content of chloramphenicol by using an ultraviolet-visible spectrophotometer, and determining the end point of the dialysis when the chloramphenicol is not detected any more. The adsorbent in the dialysis bag was collected, washed and dried at 60 ℃ and used for the next chloramphenicol adsorption test. The above cycle was repeated three times, and three replicates were performed. In the adsorption tests for 3 times, the average adsorption content of chloramphenicol was 97.3697 mg g-1，97.2473mg·g-1And 67.4447mg g-1The Zn-BC700 is proved to have good regenerability and good application value.
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of rice straw biochar after zinc chloride impregnation is characterized by comprising the following steps:
step 1, crushing and screening naturally air-dried rice straws by a miniature crusher to prepare crushed rice straws;
step 2, in ZnCl2Soaking in the solution, stirring, filtering, drying in oven to constant weight, pulverizing, and sieving;
step 3, placing the raw materials in a ceramic crucible in a tubular furnace, heating under the protection of nitrogen, and pyrolyzing; and cooling to room temperature, taking out, and preparing the rice straw biochar after being soaked by the zinc chloride.
2. The method according to claim 1, wherein the mesh number in step 1 is 40 to 80 mesh.
3. The method according to claim 1, wherein the ZnCl in the step 2 is used2The concentration of the solution is 1-3 mol.L-1。
4. The method according to claim 1, wherein the pulverized rice straw of step 2 is mixed with ZnCl2The mass ratio of the solution is 1:2-1: 4.
5. The preparation method according to claim 1, wherein the stirring time in the step 2 is 20-28h, and the oven temperature is 55-65 ℃; the mesh number is 80-120 meshes.
6. The preparation method according to claim 1, wherein the temperature rise rate in the step 3 is 3-10 ℃/min, the pyrolysis temperature is 500-700 ℃, and the pyrolysis time is 1-3 h.
7. A zinc chloride-impregnated rice straw biochar prepared by the preparation method as claimed in claims 1-6.
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| CN114989843A (en) * | 2022-06-09 | 2022-09-02 | 武汉轻工大学 | Method for co-producing high-quality bio-oil and activated carbon by catalytic pyrolysis of biomass and polyolefin plastic |
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