CN114471479A - Novel chlorella-loaded coconut shell activated carbon adsorbent and preparation method and application thereof - Google Patents

Novel chlorella-loaded coconut shell activated carbon adsorbent and preparation method and application thereof Download PDF

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CN114471479A
CN114471479A CN202210194470.0A CN202210194470A CN114471479A CN 114471479 A CN114471479 A CN 114471479A CN 202210194470 A CN202210194470 A CN 202210194470A CN 114471479 A CN114471479 A CN 114471479A
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chlorella
activated carbon
coconut shell
shell activated
loaded
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王利红
蒋喜艳
尹西翔
田勇
乔国栋
张述习
刘媛媛
邓智文
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Jinan Ecological Environment Monitoring Center Of Shandong Province
Shandong Analysis and Test Center
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Shandong Analysis and Test Center
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
    • C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
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    • 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
    • B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
    • 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
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    • C02F2101/20—Heavy metals or heavy metal compounds

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Abstract

The invention discloses a novel chlorella-loaded coconut shell activated carbon adsorbent, and a preparation method and application thereof, and belongs to the technical field of biology. The coconut shell activated carbon adsorbent is prepared from coconut shell activated carbon and living chlorella, and the preparation method comprises the following steps: (1) preparing coconut shell activated carbon; (2) preparing living chlorella; (3) the novel Chlorella-loaded coconut shell activated carbon adsorbent can be prepared by mixing and oscillating coconut shell activated carbon and living Chlorella, the effect of 1+1 & gt 2 on heavy metals is achieved in different time periods, namely the using effect of the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) is larger than the sum of the effects of independent use of the coconut shell activated carbon and independent use of the Chlorella for adsorbing heavy metals, and the research shows that the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) has a certain removal effect on heavy metal pollutants in wastewater and has the potential of repairing heavy metal polluted wastewater.

Description

Novel chlorella-loaded coconut shell activated carbon adsorbent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biology, and particularly relates to a novel chlorella-loaded coconut shell activated carbon adsorbent, and a preparation method and application thereof.
Background
Microalgae is a ubiquitous microorganism in various water bodies, is fast in propagation and strong in adaptability, and can reach the concentration required for sewage treatment only by inoculating a very small amount of microalgae mother liquor in the water body and propagating for a period of time in a suitable environment. The sewage is rich in nitrogen and phosphorus, and provides good inorganic nutrition for the propagation of microalgae. In addition, microalgae can obtain carbon source and energy by photosynthesis, and the growth of microalgae is ensured without additionally providing a carbon source, so that the cost is reduced. Therefore, the microalgae is used for treating the sewage, which is a sewage treatment mode with good effect, economy and practicability.
Research shows that some microalgae have an immobilization effect on heavy metal ions, and the process mainly comprises physical adsorption and chemical adsorption. The microalgae is applied to the fixation of heavy metals in sewage, and meanwhile, the microalgae can reduce the content of nitrogen, phosphorus and other nutrient substances in water and absorb other harmful substances in water, so that the method has multiple purposes, and is an economical and effective sewage treatment method. However, although many microalgae have a certain heavy metal ion adsorption capacity, the adsorption efficiency of microalgae in natural environment to heavy metal ions is limited at present, and the tolerance of many microalgae to heavy metal ions is not good, which greatly limits the application of microalgae in sewage treatment.
Therefore, how to utilize microalgae efficiently becomes an urgent problem to be solved.
Disclosure of Invention
The invention aims to provide a novel chlorella-loaded coconut shell activated carbon adsorbent, which is prepared from coconut shell activated carbon and living chlorella.
Preferably, the mass volume ratio of the coconut shell activated carbon to the living chlorella is (0.02-0.2) g: (10-50) mL, wherein the OD680 value of the living chlorella is 1.
The invention also aims to provide a preparation method of the novel chlorella-loaded coconut shell activated carbon adsorbent.
Preferably, the constant temperature oscillation time is 12 h.
More preferably, the temperature of the constant temperature shaking is 25 ℃.
More preferably, the preparation process of the living chlorella comprises the following steps:
culturing chlorella seeds under weak illumination for 2-3 days;
② adjusting the culture temperature to 22-28 ℃, and the illumination condition is 1000-;
and thirdly, adding the alga liquid obtained in the second step into a BG 11 culture medium to culture for 20-30 days.
More preferably, the irradiation time in the step (c) is 12Hr day/12 Hr night.
More preferably, the preparation process of the coconut shell activated carbon comprises the following steps: washing coconut shells with deionized water, crushing, sieving, drying, carbonizing, and sieving to obtain the coconut shell activated carbon.
More preferably, the carbonization conditions are 900 ℃ for 3 h.
The invention also aims to provide the application of the novel chlorella-loaded coconut shell activated carbon adsorbent in sewage treatment.
Compared with the prior art, the invention has the following beneficial effects:
(1) the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) achieves the effect that 1+1 is larger than 2 to heavy metal in different time periods, namely the using effect of the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) is larger than the sum of the effects of independent use of the coconut shell activated carbon and independent use of the Chlorella to adsorb heavy metal, and the research shows that the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) has a certain removal effect on heavy metal pollutants in wastewater and has the potential of repairing the heavy metal polluted wastewater.
(2) Compared with the common coconut shell activated carbon (Cmac) adsorbent, the Cmac @ Chlorella adsorbent not only can greatly shorten the time for reaching the equilibrium of adsorption, but also can improve the adsorption capacity to heavy metals, so that the fact that the novel Chlorella-loaded coconut shell activated carbon (Cmac @ Chlorella) is a novel adsorbent with the heavy metal pollution remediation potential is inferred.
Drawings
FIG. 1 is a graph showing the adsorption effects of Cd, Cr, Pb and Hg by three adsorbents, namely coconut husk activated carbon alone, Chlorella vulgaris alone and novel Chlorella loaded coconut husk activated carbon in test example 1.
FIG. 2 is a graph showing the effect of common coconut husk activated carbon (Csac) and novel Chlorella-loaded coconut husk activated carbon (Csac @ Chlorella) on the removal of Cd, Cr, Pb and Hg in test example 2.
Detailed Description
Example 1
A preparation method of a novel chlorella-loaded coconut shell activated carbon adsorbent comprises the following steps:
(1) preparation of coconut shell activated carbon
The coconut shell is washed by deionized water, crushed, sieved (100 meshes) and dried in an oven (80 ℃). Placing coconut shell powder in a ceramic crucible, wrapping the coconut shell powder with tinfoil, placing the wrapped coconut shell powder in a muffle furnace, carbonizing the coconut shell powder for 3 hours at 900 ℃, cooling the coconut shell powder to room temperature, taking the coconut shell powder out, and sieving the obtained product with a 100-mesh standard sieve to obtain the coconut shell activated carbon.
(2) Culture of Chlorella (Chlorella)
A chlorella (FACHB-8) is purchased from a freshwater algae seed bank of a Chinese academy of sciences, and the chlorella is cultured and transferred by itself, and the specific method is as follows:
firstly, shaking up algae seeds in a test tube after receiving the algae seeds, directly transferring the algae seeds into a glass triangular flask (25mL-50mL) under aseptic operation, sealing a bottle mouth, and placing the glass triangular flask in a light culture box for 2-3 days under weak light;
adjusting the culture temperature to 25 ℃, setting the illumination condition to be 1000-;
③ preparing a BG 11 culture medium, adding 5-10mL of the algae liquid after the weak light culture into 10-20mL of the fresh BG 11 culture medium, and culturing the algae liquid in a sterile wide-mouth triangular flask for 20-30 days, wherein the growth state of the algae is good, and the biomass is obviously increased. At this time, switching can be performed again, and the ratio 1: 5 (algal solution: BG 11 Medium). When the algae solution is cultured in the volume less than 500mL, the triangular flask is shaken for 2 times every day, and when the algae solution is cultured in the volume more than 500mL, the shaking table is used for auxiliary culture.
Note: the transfer process is performed under completely sterile (uv sterile room) conditions.
The composition of BG 11 medium is shown in Table 1.
TABLE 1
Figure BDA0003526604330000031
(3) Preparation method of novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella)
Firstly, taking a proper amount of chlorella in logarithmic growth phase, centrifuging the chlorella in a 50mL centrifuge tube at 5000rpm/min for 20min, pouring out supernatant, adding equal amount of ultrapure water to suspend the chlorella, and repeating the operation for three times;
weighing a proper amount of granular coconut shell activated carbon into a 250mL conical bottle with a plug, and adding a proper amount of ultrapure water;
and thirdly, pouring the suspended chlorella into the conical flask with the plug, and oscillating the flask in a constant-temperature oscillator for 12 hours to ensure that the chlorella is fully contacted with the coconut shell activated carbon to obtain the novel chlorella-loaded coconut shell activated carbon.
The formulation of the novel Chlorella-loaded coconut husk activated carbon (Csac @ Chlorella) adsorbent is shown in Table 2.
TABLE 2
Figure BDA0003526604330000041
Note: the addition amount of the coconut shell activated carbon is calculated in g; the addition amount of Chlorella was measured as "OD value (OD680) at a wavelength of 680 nm".
Test example 1
In order to explore the difference between the adsorption effects of a Csac adsorbent, a Chlorella adsorbent and a Csac @ Chlorella adsorbent on heavy metals, the Csac @ Chlorella composite adsorbent with different dose ratios is added into a proper amount of heavy metal solution to perform an adsorption experiment, the final reaction system is 100mL, the concentration of Chlorella is measured by OD value with the wavelength of 680nm, wherein the initial concentrations of heavy metals Cd and Pb are both 1mg/L, the initial concentration of Cr solution is 5mg/L, the initial concentration of Hg solution is 100mg/L, the pH of heavy metal Cd solution is adjusted to 8 by using 1mol/LNaOH or HCl, the pH of heavy metal Cr solution is adjusted to 3, the pH of heavy metal Hg solution is adjusted to 4, and the pH of heavy metal Pb solution is adjusted to 5. The adsorption reaction is carried out for different times under the conditions of 25 ℃ and 200rpm/min of rotation speed, the specific addition amount and the reaction time of the adsorbent are listed in Table 3 according to different types of heavy metals, 1mL of homogeneous samples are taken and centrifuged at 5000rpm/min for 20min in different reaction time periods, and ultrapure water is used for diluting corresponding times to the concentration range of the heavy metals measured by an inductively coupled plasma mass spectrometer (ICP-MS) and an Atomic Fluorescence Spectrophotometer (AFS), so that the concentration of the heavy metals in the supernatant is measured.
FIG. 1 is a diagram showing the adsorption effect of three adsorbents, namely, coconut shell activated carbon alone, chlorella vulgaris alone and novel chlorella loaded coconut shell activated carbon, on Cd, Cr, Pb and Hg.
Table 3 shows the test conditions of the test examples.
TABLE 3
Figure BDA0003526604330000051
Table 4 shows adsorption data of Cd, Cr, Pb and Hg by three adsorbents, namely coconut husk activated carbon alone, chlorella vulgaris alone and novel chlorella-loaded coconut husk activated carbon.
TABLE 4
Figure BDA0003526604330000052
From the above data, it can be seen that: (1) the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) has the adsorption effect on Cr and Pb in a short time (1-20 min) which is greater than the sum of the two single effects;
(2) the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) has the adsorption effect on Cd and Hg for a long time (15-20 h) which is greater than the sum of the single effects of the Csac @ Chlorella and the activated carbon;
the data can prove that the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) achieves the effect of 1+1 & gt 2 on heavy metals in different time periods, namely the using effect of the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) is larger than the sum of the effects of independent use of the coconut shell activated carbon and independent use of the Chlorella for adsorbing heavy metals, and the research shows that the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) has a certain removal effect on heavy metal pollutants in wastewater and has the potential of repairing heavy metal polluted wastewater.
Test example 2
Adding a common coconut shell activated carbon (Csac) adsorbent and a novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) composite adsorbent into a proper amount of heavy metal solution to perform an adsorption experiment, wherein the final reaction system is 100mL, and the Chlorella concentration is calculated by OD value with the wavelength of 680 nm. Wherein the initial concentrations of heavy metals Cd, Pb, Cr and Hg are all 100 mug/L, the addition amount of the adsorbent in the heavy metal Cd solution is 0.2g Cdac @0.1Chlorella, the addition amount of the adsorbent in the heavy metal Cr solution is 0.2g Cdac @0.1Chlorella, the addition amount of the adsorbent in the heavy metal Pb solution is 0.2g Cdac @0.3Chlorella, and the addition amount of the adsorbent in the heavy metal Hg solution is 0.2g Cdac @0.5 Chlorella; the pH of the heavy metal solution was not adjusted; the adsorption reaction is carried out for different times under the conditions of 25 ℃ and 200rpm/min of rotation speed, 1mL of homogeneous sample is taken in different time periods and centrifuged for 20min at 5000rpm/min, ultrapure water is used for diluting by corresponding times, and the concentration of heavy metal in the supernatant is measured by an inductively coupled plasma mass spectrometer (ICP-MS) and an Atomic Fluorescence Spectrophotometer (AFS).
FIG. 2 shows the effect of ordinary coconut shell activated carbon (Csac) and novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) on the removal of Cd, Cr, Pb and Hg at an initial concentration of 100 μ g/L, respectively, where the left ordinate is the adsorption rate and the right ordinate is the adsorption capacity. It can be seen that the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) has a much higher removal effect on Cd, Cr, Pb and Hg than that of common coconut shell activated carbon (Csac), and the adsorption reaches a balance in a short time (1 hour).
In conclusion, compared with common coconut shell activated carbon (Csac) adsorbent, the Csac @ Chlorella adsorbent not only can greatly shorten the time for adsorption to reach equilibrium, but also can improve the adsorption capacity to heavy metals, so that the fact that the novel Chlorella-loaded coconut shell activated carbon (Csac @ Chlorella) is a novel adsorbent with the potential of heavy metal pollution remediation is inferred.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. A novel chlorella-loaded coconut shell activated carbon adsorbent is characterized in that the coconut shell activated carbon adsorbent is prepared from coconut shell activated carbon and living chlorella.
2. The novel chlorella-loaded coconut shell activated carbon adsorbent according to claim 1, wherein the mass-to-volume ratio of the coconut shell activated carbon to the living chlorella is (0.02-0.2) g: (10-50) mL, wherein the OD680 value of the living chlorella is 1.
3. A preparation method of a novel chlorella-loaded coconut shell activated carbon adsorbent is characterized in that living chlorella is mixed with coconut shell activated carbon and then vibrated at a constant temperature, so that the chlorella is fully contacted with the coconut shell activated carbon to prepare the novel chlorella-loaded coconut shell activated carbon.
4. The method according to claim 3, wherein the constant temperature shaking time is 12 hours.
5. The method according to claim 4, wherein the constant temperature shaking temperature is 25 ℃.
6. The method of claim 5, wherein the living chlorella is prepared by the steps of:
culturing chlorella seeds under weak illumination for 2-3 days;
② adjusting the culture temperature to 22-28 ℃, and the illumination condition is 1000-;
and thirdly, adding the alga liquid obtained in the second step into a BG 11 culture medium to culture for 20-30 days.
7. The method according to claim 6, wherein the irradiation time in the step (2) is 12Hr day/12 Hr night.
8. The method of claim 7, wherein the coconut shell activated carbon is prepared by the following steps: washing coconut shells with deionized water, crushing, sieving, drying, carbonizing, and sieving to obtain the coconut shell activated carbon.
9. The method according to claim 8, wherein the carbonizing condition is 900 ℃ for 3 hours.
10. Use of the novel chlorella-loaded coconut shell activated carbon adsorbent of claim 1 or 2 in sewage treatment.
CN202210194470.0A 2022-03-01 2022-03-01 Novel chlorella-loaded coconut shell activated carbon adsorbent and preparation method and application thereof Pending CN114471479A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109174026A (en) * 2018-09-18 2019-01-11 浙江海洋大学 A kind of method of chromium in compound microalgae biological adsorption agent microballoon and its absorption waste water
CN112707509A (en) * 2020-11-10 2021-04-27 烟台大学 Method for removing heavy metals in water body by using marine microalgae

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109174026A (en) * 2018-09-18 2019-01-11 浙江海洋大学 A kind of method of chromium in compound microalgae biological adsorption agent microballoon and its absorption waste water
CN112707509A (en) * 2020-11-10 2021-04-27 烟台大学 Method for removing heavy metals in water body by using marine microalgae

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIYAN JIANG ET AL.: "Study on the mechanism of biochar loaded typical microalgae Chlorella removal of cadmium", 《SCIENCE OF THE TOTAL ENVIRONMENT》, vol. 813, pages 1 - 2 *

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