CN111346602B - Application of calcium lignosulphonate derived carbon in removal of phosphorus in wastewater - Google Patents
Application of calcium lignosulphonate derived carbon in removal of phosphorus in wastewater Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention provides application of calcium lignosulfonate-derived carbon in removing Phosphorus (PO) in wastewater4 3‑). And provides a method for preparing the calcium lignosulfonate-derived carbon, comprising the following steps: and (2) putting the calcium lignosulphonate into a carbonization furnace, keeping a certain heating rate, heating from room temperature to a carbonization temperature of 350-450 ℃ and 800 ℃, keeping the carbonization time for 1-3 h, naturally cooling and cooling to room temperature to obtain the calcium lignosulphonate derived carbon, wherein the carbonization process and the cooling process are both carried out in a nitrogen atmosphere. The application of the invention not only has the advantages of good adsorption effect, simple treatment operation and no need of adjusting pH; the adsorbent used by the invention also has the advantages of simple preparation process, short production period, low carbonization temperature and the like, and is suitable for industrial production and application.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to application of calcium lignosulphonate derived carbon in removal of phosphorus in wastewater.
Background
With the rapid development of society, human activities such as industrial wastewater, farmland irrigation water, domestic sewage and the like are discharged in large quantities, resulting in serious water eutrophication. Eutrophication of water body can cause excessive propagation of algae and other microorganisms and rapid reduction of dissolved oxygen in water, resulting in reduction of water quality and serious damage to the ecological environment of water body. Water eutrophication is a common global water pollution phenomenon, and at least 80% of water bodies are in eutrophication. Excessive nitrogen and phosphorus enter the water body and are the main reasons for eutrophication. Nitrogen is an important factor for controlling eutrophication of lakes and rivers, and phosphorus is the most important limiting factor for eutrophication of water bodies. When the total phosphorus concentration in the water body exceeds 0.02mg/L, the water body is in a eutrophication state. The key for solving the problem of water eutrophication is to reduce the phosphorus content in the water.
At present, Phosphorus (PO) in wastewater is removed4 3-) The method of (3) includes chemical precipitation, ion exchange, biological and adsorption. Among the methods, the adsorption method is a treatment technology which is simple to operate, efficient, rapid and low in cost, and the key point of adsorption and phosphorus removal is to develop an adsorption material which is efficient, low in cost and free of secondary pollution. The adsorbent can be roughly classified into: natural materials, industrial waste residues, carbon adsorption materials and the like, and the materials are modified to improve the adsorption effect and the adsorption capacity, so that the high efficiency and the economical efficiency of phosphorus adsorption and removal are realized. The biochar is widely applied to the aspect of phosphate adsorption due to the characteristics of simple preparation process, environmental protection, large specific surface area, excellent adsorption performance and the like.
However, pure biomass charcoal as an adsorbent generally has a strong adsorption capacity for metal cations and organic pollutants, and has a strong adsorption capacity for anionic pollutants (such as phosphate radical, PO)4 3-) Has a limited adsorption capacity. Chinese patent document CN110652963A (201911059431.4) discloses a method for preparing biochar from lanthanum carbonate modified sludge, which comprises the steps of firstly mixing bamboo sawdust and sludge according to the mass ratio of 1:1, crushing the mixture by a crusher for 5-10 minutes, sieving the crushed mixture by an 80-200-mesh sieve, heating the mixture to 600 ℃ at the temperature rising rate of 10-15 ℃/h, keeping the temperature of the mixture constant for 1 hour at 600 ℃ for pyrolysis to obtain co-pyrolysis sludge biochar, adding the co-pyrolysis sludge biochar into a metal salt solution of lanthanum ions, heating the mixture and adjusting the pH value to 8-9 by using a carbonate solution, standing the mixture at the constant temperature, and separating the mixture to obtain the co-pyrolysis sludge biochar modified by lanthanum carbonate; the co-pyrolysis sludge biochar is prepared by co-pyrolyzing sludge and bamboo dust. However, the above-mentioned preparation method requires the use of lanthanum carbonate, a relatively expensive materialAnd the preparation process is complicated. Therefore, the development of an adsorbent process or technology which has low cost, does not need to independently introduce metal ions and is convenient and fast in preparation process has wide market prospect and academic value.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, biomass charcoal is used as an adsorbent to remove phosphorus in wastewater, the price of the adsorbent is high, and the preparation method is complex, provides the application of calcium lignosulfonate-derived charcoal in removing phosphorus in wastewater, and realizes low-cost and high-value utilization of lignosulfonate.
In order to achieve the purpose, the invention provides application of calcium lignosulfonate-derived carbon in removing phosphorus in wastewater, wherein the calcium lignosulfonate-derived carbon is used for adsorbing and removing Phosphorus (PO) in the wastewater4 3-)。
Preferably, the pH value of the wastewater is 3-12. Further preferably, the pH is 3-11; more preferably, the pH is 9 to 11.
Preferably, the adsorption time for adsorbing and removing phosphorus in the wastewater by using calcium lignosulphonate derived carbon is 4 hours; PO in the wastewater4 3-The initial concentration is 3-13 mg/L.
Preferably, the application temperature of the calcium lignosulfonate-derived carbon adsorption for removing the phosphorus in the wastewater is 20-50 ℃.
Preferably, the calcium lignosulfonate derived carbon is ground and sieved by a sieve with 80-100 meshes, so that the contact area of the biochar is increased.
Preferably, the screened derivative carbon is washed by deionized water for 3-5 times to remove surface impurities, and dried for 24 hours at 60-100 ℃ to remove the moisture of the biochar.
Preferably, the preparation method of the calcium lignosulfonate-derived carbon comprises the following steps: putting calcium lignosulphonate into a carbonization furnace, keeping a certain heating rate from room temperature to the carbonization temperature of 350-450 ℃ and 800 ℃, keeping the carbonization time for 1-3 h, naturally cooling, and cooling to room temperature to obtain the calcium lignosulphonate derived carbon, wherein the carbonization process and the cooling process are carried out in nitrogen (N)2) The reaction is carried out under an atmosphere.
Further preferably, the temperature rise rate is 5-15 ℃/min. The room temperature in the invention is 25-30 ℃.
Further preferably, the nitrogen gas (N)2) The flow rate of (2) is 400 mL/min.
Further preferably, the carbonization temperature is 350-450 ℃, and further preferably 400 ℃.
Further preferably, the carbonization time is 2 h; the heating carbonization process adopts a tubular carbonization furnace.
One or more technical schemes provided by the embodiment of the invention at least have the following beneficial effects:
(1) according to the invention, the derived carbon prepared from calcium lignosulfonate is applied to removing phosphorus in wastewater, has a good adsorption effect when the pH of the wastewater is within the range of 3-11, is wider in application range, can treat most of phosphorus-containing wastewater, does not need to adjust the pH, and is simple to operate; and the pH value of the wastewater is adjusted, and the pH value of the wastewater after adsorption is 6-8.
(2) The calcium lignosulfonate is used for preparing the derived charcoal, and the calcium lignosulfonate contains metal ion calcium, so that the process of adding metal ions into the carbonized material is reduced, and the process for preparing the calcium-rich biochar adsorbent is simplified.
(3) The process for preparing the calcium lignosulphonate-derived carbon has the advantages of simple operation, short production period, low carbonization temperature, no need of special chemical equipment and easy realization of industrial production.
(4) The prepared adsorbent material takes calcium lignosulphonate as a main raw material, is an environment-friendly material, and has the advantages of recycling waste, reducing environmental pollution and realizing high-value utilization of lignin.
Drawings
FIG. 1 is a scanning electron micrograph of CLDC400 prior to adsorption;
FIG. 2 is an elemental analysis energy spectrum of CLDC 400;
FIG. 3 is a scanning electron micrograph of CLDC800 prior to adsorption;
FIG. 4 is an elemental analysis energy spectrum of CLDC 800;
FIG. 5 is a scanning electron micrograph of CLDC400 after adsorption of phosphorus;
FIG. 6 is a spectrum of CLDC400 after adsorption of phosphorus;
FIG. 7 is a scanning electron micrograph of CLDC800 after adsorption of phosphorus;
FIG. 8 is a spectrum of CLDC800 after adsorption of phosphorus;
FIG. 9 is a graph of the effect of dosing of derivatized carbon on its phosphorus adsorption performance;
FIG. 10 is a graph showing the effect of contact time on its phosphorus adsorption performance;
FIG. 11 is a graph of the effect of temperature and initial phosphate concentration on its phosphorus adsorption performance;
FIG. 12 is a graph showing the effect of initial pH on the performance of a solution to adsorb phosphorus;
FIG. 13 is a plot of an isotherm fit of CLDC400 for phosphorus adsorption at 50 ℃;
FIG. 14 is a plot of an isotherm fit of CLDC400 for phosphorus adsorption at 30 ℃;
FIG. 15 is a plot of an isotherm fit of CLDC800 adsorbing phosphorus at 50 ℃;
fig. 16 is an isotherm fit plot of CLDC800 adsorbing phosphorus at 30 ℃.
Detailed Description
The present invention is described in further detail below with reference to examples and drawings to ensure that those skilled in the art can practice the invention with reference to the description.
Example 1 preparation of calcium lignosulfonate-derived carbon (CLDC400) comprising the steps of:
(1) the calcium lignosulphonate was placed in a tube furnace at N2Under protection, the temperature rises to the set carbonization temperature of 400 ℃ at the temperature rise rate of 5 ℃/min, the carbonization is kept at 400 ℃ for 2h, and then the calcium lignosulphonate derived carbon is obtained after cooling to the room temperature.
(2) Grinding the derived carbon powder and repeatedly washing the derived carbon powder for 3 times by using deionized water to remove impurities on the surface of the derived carbon.
(3) Drying the surface impurity-removed derived carbon in a vacuum drying oven at 80 ℃ for 24 hours at constant temperature to obtain a calcium lignosulfonate derived carbon labeled as CLDC 400; CLDC400 was stored in a sealed bag for future use.
Example 2 preparation of calcium lignosulfonate-derived carbon (CLDC350) comprising the following steps
(1) Will be provided withThe calcium lignosulphonate is placed in a tubular carbonization furnace in N2Under protection, the temperature rises to 350 ℃ at the heating rate of 10 ℃/min, the obtained product is maintained at 350 ℃ for carbonization for 3h, and then the obtained product is cooled to room temperature to obtain the calcium lignosulphonate derived carbon.
(2) Grinding the derived carbon powder and repeatedly washing the derived carbon powder for 3 times by using deionized water to remove impurities on the surface of the derived carbon.
(3) Drying the surface impurity-removed derived carbon in a vacuum drying oven at 60 ℃ for 24h at constant temperature to obtain a calcium lignosulfonate derived carbon label CLDC 350; CLDC350 is stored in a sealed bag for use.
Example 3 preparation of calcium lignosulfonate-derived carbon (CLDC450) comprising the steps of:
(1) the calcium lignosulphonate was placed in a tube furnace at N2Under protection, the temperature rises to the set carbonization temperature of 450 ℃ at the temperature rise rate of 15 ℃/min, the carbonization is kept at 450 ℃ for 1h, and then the calcium lignosulphonate derived carbon is obtained after cooling to the room temperature.
(2) Grinding the derived carbon powder and repeatedly washing the derived carbon powder for 3 times by using deionized water to remove impurities on the surface of the derived carbon.
(3) Drying the surface impurity-removed derived carbon in a vacuum drying oven at 100 ℃ for 24h at constant temperature to obtain a calcium lignosulfonate derived carbon label CLDC 450; CLDC450 was kept in a sealed bag for future use.
Example 4 preparation of calcium lignosulfonate-derived carbon (CLDC800) comprising the steps of:
(1) placing calcium lignosulphonate in a tube furnace in N2Under protection, the temperature rises to 800 ℃ at the temperature rise rate of 5 ℃/min, the carbonization is kept at 800 ℃ for 2h, and then the calcium lignosulphonate derived carbon is obtained after cooling to room temperature.
(2) Grinding the derived carbon powder and repeatedly washing the derived carbon powder for 3 times by using deionized water to remove impurities on the surface of the derived carbon.
(3) Drying the surface impurity-removed derived carbon in a vacuum drying oven at 80 ℃ for 24h at constant temperature to obtain a calcium lignosulfonate derived carbon label CLDC 800; CLDC800 was stored in a sealed bag for use.
Comparative example
A method for preparing calcium lignosulfonate-derived carbon (CLDC600) comprises the following steps:
(1) placing calcium lignosulphonate in a tube furnace in N2Under protection, the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min, the mixture is carbonized for 2 hours at the constant temperature of 600 ℃, and the calcium lignosulphonate derived carbon is obtained after cooling to the room temperature.
(2) Grinding the derived carbon powder and repeatedly washing the derived carbon powder for 3 times by using deionized water to remove impurities on the surface of the derived carbon.
(3) Drying the washed derived carbon in a vacuum drying oven at 80 ℃ for 24h at constant temperature to obtain calcium lignosulphonate derived carbon (CLDC 600); CLDC600 was stored in a sealed bag for future use.
CLDC350, CLDC450 and CLDC600 of different masses were added to 50mL of a phosphate solution of 5.07mg/L at pH 7 prepared with potassium dihydrogen phosphate, and adsorbed by shaking at a constant temperature of 30 ℃ for 24 hours. The adsorption amount was measured according to the formula (1), and the results are shown in tables 1 and 2, respectively. Table 1 shows that CLDC350 and CLDC450 have good removal rate of phosphate anion. When the initial phosphate concentration is 5.07mg/L, the addition amount of the derivative carbon required for reaching the adsorption equilibrium state is 1.4 g/L. Table 2 shows that as CLDC600 was added, the removal rate of phosphate anions was substantially unchanged and very low, demonstrating that CLDC600 did not have the ability to effectively adsorb or remove phosphorus.
TABLE 1 influence of the amount of CLDC350 and CLDC450 added on the removal rate of phosphorus
TABLE 2 influence of the amount of CLDC600 added on the phosphorus removal rate
The calcium lignosulfonate derived carbon obtained by the invention is used for PO in wastewater4 3-The adsorption includes physical adsorption, chemical adsorption and chemical reaction, the chemical reaction is lignin sulfonic acidCa release from calcium-derived carbon2+And PO4 3-Precipitation reactions occur to form calcium phosphate, primarily from the chemical elemental composition of the calcium lignosulfonate-derived carbon, while physical adsorption relies primarily on the microstructural features of the calcium lignosulfonate-derived carbon. Among CLDC400, CLDC600 and CLDC800 obtained by the present invention, CLDC400 had the best adsorption effect and CLDC600 had the worst adsorption effect.
One of the possible reasons is that the carbonization temperatures of CLDC400, CLDC600 and CLDC800 are different, resulting in different decomposition rates and precipitation rates of organic matters, which cause differences in the microstructure of the derived carbon, resulting in different attachment sites and amounts of calcium elements on the derived carbon, resulting in different adsorption properties of the derived carbon to phosphorus.
Another possible reason is that, during the carbonization of calcium lignosulfonate, when the carbonization temperature is raised to a certain degree (e.g. 800 ℃), calcium lignosulfonate is partially graphitized, and the higher the crystallinity of the graphite-like microcrystal is, the stronger the ability to fix calcium element is. This results in the adsorption of PO on the calcium lignosulfonate-derived carbon4 3-Can not release enough Ca in the process2+Thus, a better adsorption effect cannot be achieved.
The effect of the above-mentioned additive effect on the adsorption properties of the product is not predictable. The results of the present invention suggest that chemisorption (chemical reaction) is an absolute advantage in the removal of phosphorus by CLDC 400. While in the process of removing phosphorus by CLDC600 and CLDC800, the specific gravity of physical adsorption increases and the specific gravity of chemisorption (chemical reaction) decreases. And since CLDC800 has a specific surface area greater than CLDC600, the larger the specific surface area is, the more advantageous for physical adsorption. Thus, CLDC800 adsorption effect is higher than CLDC 600. The method also embodies the advantages that the calcium lignosulfonate derived carbon (carbonization temperature is 350-450 ℃) is prepared at low cost, and phosphorus in the wastewater is removed efficiently.
Structure and properties of calcium lignosulfonate-derived carbon
1. The prepared lignin calcium xanthate derived carbon is subjected to surface morphology and element analysis characterization
Fig. 1 and 3 are scanning electron micrographs of calcium lignosulfonate-derived carbon CLDC400 and calcium lignosulfonate-derived carbon CLDC800, respectively, and fig. 3 shows a small amount of graphitic crystallites on the surface compared to fig. 1. FIGS. 2 and 4 are histograms of CLDC400 and CLDC800, respectively; FIGS. 5-8 are scanning electron microscope and energy spectrum images of samples of CLDC400 and CLDC800 after adsorption of phosphorus. Fig. 6 and 8 illustrate that CLDC400 and CLDC800 derived carbons, both of which contain phosphorus elements after adsorbing phosphorus in wastewater, demonstrate that both of these derived carbons can adsorb or remove phosphorus from water bodies.
NO in wastewater3 2-、Cl-The adsorption effect is not basically influenced; SO (SO)4 2-At higher contents, it will react with PO4 3-Compete for adsorption sites and influence the adsorption effect, SO if the wastewater contains more SO4 2-When ionic, the dosage of the calcium lignosulfonate derived carbon can be increased to increase SO4 2-Together with PO4 3-Are removed together.
2. Effect of dosage on adsorption Properties of calcium Lignosulfonate-derived carbon
Calcium lignosulfonate-derived carbon CLDC400 and CLDC800 are applied to adsorption experiments of phosphate in water, the influence of adsorption time on adsorption performance is examined, and the adsorption amount of the derived carbon on phosphorus is calculated by adopting a formula (1).
Wherein q istIs the average adsorption capacity of the adsorbent per unit mass in t time, mg-P/g; coThe concentration of phosphate in the solution before adsorption is mg/L; ctThe concentration of phosphate in the solution after t time of adsorption is mg/L; v is the volume of phosphate solution, L; m is the mass of the adsorbent, g.
0.03, 0.04, 0.05, 0.06, 0.07, 0.08g of CLDC400 was added to 50mL of a 5.07mg/L phosphate solution prepared from potassium dihydrogen phosphate and having a pH of 7, and the mixture was shaken at 30 ℃ for 24 hours. The adsorption amount was measured according to the formula (1), and the results are shown in FIG. 9. Fig. 9 shows that the adsorption of CLDC400 gradually increased with increasing dosage until adsorption equilibrium was reached. When the initial phosphate concentration is 5.07mg/L, the dosage required by the derivatized carbon to reach adsorption equilibrium is 1.2 g/L.
0.05, 0.1, 0.15, 0.2, 0.25, 0.3g of CLDC800 prepared in example 1 were added to 50mL of a 5.07mg/L phosphate solution prepared with potassium dihydrogen phosphate, and shaken at 30 ℃ for 24 hours. The adsorption amount was measured according to the formula (1), and the results are shown in FIG. 9. Fig. 9 shows that the adsorption of CLDC800 gradually increased with increasing dosage until adsorption equilibrium was reached. When the initial phosphate concentration is 5.07mg/L, the addition amount of the derivative carbon required for reaching the adsorption equilibrium state is 3 g/L. Fig. 9 shows that the adsorption of CLDC400 is better than the adsorption of CLDC800 at the same dosage.
3. Effect of adsorption time on phosphorus adsorption Performance of calcium lignosulfonate-derived carbon
In an experiment to examine the effect of adsorption time on phosphorus removal, 0.06g of CLDC400 was added to 50mL of a phosphate solution of pH 7 and 5.07mg/L in potassium dihydrogen phosphate, and the adsorption performance was tested by shaking at a constant temperature of 30 ℃. A certain volume of sample was taken at regular intervals, and the adsorption amount of the derivative carbon was measured according to the formula (1), and the results are shown in FIG. 10. Fig. 10 illustrates that the adsorption of CLDC400 gradually increased with increasing contact time until adsorption equilibrium was reached. When the initial phosphate concentration was 5.07mg/L, the time required for CLDC400 to reach adsorption equilibrium was 4h, corresponding to an adsorption capacity of 4.2 mg/g.
In experiments to examine the effect of adsorption time on phosphorus removal, 0.15g of CLDC800 was added to 50mL of a 5.07mg/L phosphate solution prepared with potassium dihydrogen phosphate at pH 7, and the adsorption experiments were shaken at a constant temperature of 30 ℃. A certain volume of sample was taken at regular intervals, and the amount of adsorption was measured according to the formula (1), and the results are shown in FIG. 10. Fig. 10 shows that the adsorption of CLDC800 gradually increased with increasing contact time until adsorption equilibrium was reached. When the initial phosphate concentration was 5.07mg/L, the time required for CLDC800 to reach adsorption equilibrium was 5h, corresponding to an adsorption amount of 1.64 mg/g. For convenient measurement, the adsorption time is uniformly adopted for 5 hours.
4. Effect of initial phosphate concentration on phosphorus adsorption Performance of calcium Lignosulfonate-derived carbon
To analyze the effect of initial phosphate concentration on the phosphorus adsorption performance of the derivatized carbon, 0.06g of CLDC400 was weighed into 50mL of phosphate solution prepared from potassium dihydrogen phosphate and having pH 7 and concentrations of 0.51, 2.42, 5.07, 6.89, 9.42, 12.97, 25.97, 39.37, and 50.00mg/L, and after adsorption at 30 ℃ for 5 hours with constant temperature shaking, a liquid sample was taken for analysis and the amount of adsorption was determined according to equation (1), and the results are shown in fig. 11. Fig. 11 illustrates that as the initial phosphate concentration increases, the adsorption capacity of CLDC400 increases, which may lead to increased adsorption performance due to increased phosphate concentration in the system which increases the probability of phosphate coordination to the adsorbent binding site. The maximum theoretical monolayer adsorption of 51.05mg/g (see table 3) was calculated using the Langmuir model (formula 2), indicating that the CLDC400 produced has a better potential in wastewater phosphorous removal.
To examine the effect of initial phosphate concentration on adsorption performance, 0.15g of CLDC800 was weighed into 50mL of phosphate solution prepared from potassium dihydrogen phosphate at pH 7 and concentrations of 0.51, 2.42, 5.07, 6.89, 9.42, 12.97, 25.97, 39.37, and 50.00mg/L, and after adsorption at 30 ℃ for 5 hours with constant temperature shaking, a liquid sample was taken for analysis and the amount of adsorption was measured according to equation (1), and the results are shown in fig. 11. Fig. 11 shows that the adsorption capacity of CLDC800 increases with increasing initial phosphate concentration, which may lead to increased adsorption performance due to increased phosphate concentration in the system, which increases the probability of phosphate coordination to the adsorbent binding sites. The maximum theoretical monolayer adsorption of 15.49mg/g (see table 3) was calculated using the Langmuir model (formula 2), indicating that the CLDC800 produced has a certain potential for removing phosphorus from wastewater.
5. Effect of temperature on adsorption Properties of Lignosulfonic acid-derived carbon
In order to examine the influence of adsorption temperature on the phosphorus adsorption performance of the derivatized carbon, 0.06g of CLDC400 was weighed, added to 50mL of phosphate solution prepared from potassium dihydrogen phosphate and having a pH of 7 and concentrations of 0.51, 2.42, 5.07, 6.89, 9.42, 12.97, 25.97, 39.37, and 50.00mg/L, and the solution was subjected to adsorption at 30 ℃ and 50 ℃ for 5 hours with constant temperature shaking, and then the liquid was analyzed and the amount of adsorption was calculated according to the formula (1), and the results were shown in fig. 11. Fig. 11 illustrates that the adsorption capacity of CLDC400 increases with increasing temperature, but the magnitude of the increase is not significant. This may lead to an increase in adsorption performance due to a higher adsorption temperature increasing the probability of phosphate coordination to the adsorbent binding site. The maximum theoretical monolayer adsorption was calculated to be 53.22mg/g using the Langmuir model (equation 2) (see Table 3).
In order to examine the effect of temperature on the phosphorus adsorption performance of the derived carbon, 0.15g of CLDC800 prepared in example 1 was weighed into 50mL of a phosphate solution prepared from potassium dihydrogen phosphate at pH 7 and concentrations of 0.51, 2.42, 5.07, 6.89, 9.42, 12.97, 25.97, 39.37, and 50.00mg/L, and after adsorption at 30 ℃ and 50 ℃ for 5 hours with constant temperature shaking, a liquid sample was taken for analysis and the amount adsorbed was calculated according to equation (1), and the result is shown in fig. 11. As the adsorption temperature increases, the adsorption capacity of CLDC800 also increases, but the increase is not significant. This may lead to an increase in adsorption performance of the derivatized carbon due to the higher adsorption temperature increasing the probability of phosphate coordination to the adsorbent binding site. The maximum theoretical monolayer adsorption was calculated to be 17.77mg/g using the Langmuir model (equation 2) (see Table 3).
6. Adsorption isothermal model
Adsorption isotherms can be used to indicate the relationship between the concentration of adsorbate and the amount adsorbed at the surface interface. The Langmuir and Freundlich equations are currently the two most widely used adsorption isotherms.
The Langmuir adsorption isothermal model assumes that a monolayer on the surface of a material is saturated, adsorption particles do not interact with each other, the adsorption particles are independently adsorbed, and the adsorption capacity of each adsorption site is consistent. When adsorption reaches equilibrium, the adsorption rate is the same as the desorption rate.
In the formula: q. q ofeRepresents the adsorption amount of phosphate in the adsorption equilibrium state, mg/g; ceIndicates the residual phosphorus in the solution at the equilibrium state of adsorptionAcid salt concentration, mg/L; q. q.smaxTheoretical value representing the maximum adsorption of the fit analysis, mg/g; kLRepresents Langmuir constant, L/mg.
The Langmuir adsorption isothermal model can be characterized by a constant dimensionless factor RLExpressed, its equation is as in formula (3):
in the formula: c0Indicates the initial phosphorus concentration, mg/L. When R isL0, adsorption is irreversible; r is more than 0LLess than 1, the adsorption is favorable; rL1, adsorption is linear; rL> 1, adsorption is unfavorable.
The Freundlich adsorption isothermal model can be used to describe adsorption processes where the material surface is heterogeneous. There is an interaction between the adsorbates, whose equation is as follows (4):
in the formula: q. q.seRepresents the adsorption amount of phosphate in the adsorption equilibrium state, mg/g; ceRepresents the concentration of phosphate remained in the solution in the adsorption equilibrium state, mg/L; q. q.smaxTheoretical value representing the maximum adsorption of the fit analysis, mg/g; kFIndicating the Freundlich constant, L/mg.
TABLE 3 Langmuir and Freundlich isothermal adsorption model parameters
Table 3 shows Langmuir and Freundlich isothermal adsorption model parameters for CLDC400 and CLDC800, and fig. 13 to 16 show Langmuir and Freundlich adsorption isotherms for CLDC400 and CLDC 800. Table 3 shows the correlation coefficients R obtained for two Langmuir models of phosphate adsorption on derivatized carbons (CLDC400 and CLDC800) under two adsorption temperature conditions2(0.974, 0.964, 0.979, 0.966) are all less than FreuR of ndlich adsorption isothermal model2The (0.992, 0.987, 0.992, 0.982) values show that the Freundlich adsorption isothermal model can better describe the whole adsorption dephosphorization process. The maximum single-layer adsorption capacities at 30 ℃ and 50 ℃ obtained by Langmuir isothermal model fitting are 52.67, 53.22, 15.49 and 17.77mg/g respectively, and the difference is not obvious, which shows that the adsorption temperature has little influence on the effect of the derivative carbon on adsorbing phosphorus. Calculating to obtain R of Langmuir adsorption isothermal modelLThe values are all in the range of 0 to 1, which indicates that the adsorption process is advantageous.
7. Effect of solution pH on adsorption Properties of calcium Lignosulfonate-derived carbon
In order to evaluate the influence of the initial pH of the solution on the phosphorus adsorption performance of the derivative carbon, a phosphate solution with the concentration of 5.07mg/L is prepared, and the pH of the solution adjusted by 1mol/L hydrochloric acid and sodium hydroxide is 2-12. Then 0.06g of CLDC400 and 0.15g of CLDC800 are respectively weighed and respectively added into phosphate solutions containing 50mL of different pH values, the samples are taken for typing after constant temperature oscillation and adsorption for 5h at 30 ℃, and the adsorption quantity is calculated according to the formula (1), and the result is shown in figure 12. Fig. 12 illustrates that the prepared derived carbon has better adsorption capacity to phosphate under neutral, acidic and alkaline conditions, which indicates that the adsorption process of the calcium lignosulfonate derived carbon to the phosphorus in the wastewater is less influenced by pH.
While embodiments of the invention have been disclosed above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood, therefore, that the invention is not limited to the details shown and described herein without departing from the generic concept as defined by the claims and the equivalents thereof.
Claims (9)
1. The application of calcium lignosulfonate-derived carbon in removing phosphorus in wastewater is characterized in that the calcium lignosulfonate-derived carbon adsorbs PO in the wastewater4 3-The preparation method of the calcium lignosulfonate-derived carbon comprises the following steps of: placing calcium lignosulfonate in a carbonization furnace, and maintaining a certain literAnd (3) raising the temperature from room temperature to the carbonization temperature of 350-450 ℃, maintaining the carbonization for 1-3 h, naturally cooling and cooling to room temperature to obtain the calcium lignosulphonate derived carbon, wherein the carbonization process and the cooling process are both carried out in a nitrogen atmosphere.
2. The use according to claim 1, wherein the wastewater has a pH of 3 to 12.
3. Use according to claim 2, wherein the pH of the waste water is 9 to 11.
4. The use according to any one of claims 1 to 3, wherein the calcium lignosulfonate-derived carbon is ground and sieved through a 80-100 mesh sieve.
5. The use according to any one of claims 1 to 3, wherein the sieved calcium lignosulfonate-derived carbon is washed with deionized water for 3 to 5 times and dried at 60 to 100 ℃ for 24 hours.
6. Use according to any one of claims 1 to 3, wherein N is introduced2The flow rate of (2) is 400 mL/min.
7. Use according to any one of claims 1 to 3, wherein the rate of temperature rise is from 5 to 15 ℃/min.
8. Use according to any one of claims 1 to 3, wherein the carbonation time is 2 hours.
9. The use according to any one of claims 1 to 3, wherein the heating carbonization process adopts a tubular carbonization furnace.
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