CN114130370B - Chitosan and rhamnolipid complex as well as preparation method and application thereof - Google Patents

Chitosan and rhamnolipid complex as well as preparation method and application thereof Download PDF

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CN114130370B
CN114130370B CN202111488439.XA CN202111488439A CN114130370B CN 114130370 B CN114130370 B CN 114130370B CN 202111488439 A CN202111488439 A CN 202111488439A CN 114130370 B CN114130370 B CN 114130370B
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rhamnolipid
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CN114130370A (en
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黄斌艳
李斌
易诚
邓景衡
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Hengyang Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/286Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract

The invention belongs to the field of environment, in particular to the novel technical fields of environment protection functional materials and water treatment, and particularly relates to a chitosan and rhamnolipid compound as well as a preparation method and application thereof. The invention carries out functionalization treatment on chitosan by rhamnolipid, namely, the rhamnolipid is connected with a chitosan matrix through chemical reaction, and finally, the composite particles are obtained through the action of glutaraldehyde. The adsorbent prepared in this way can increase the number of adsorption sites on the surface of chitosan through the modification effect of rhamnolipid on chitosan. The preparation process and the operation of the chitosan and rhamnolipid complex are simple, the preparation is quick, the production period is short, the product recovery rate is high, no special chemical equipment is needed, and the industrial production is easy to realize. The chitosan and rhamnolipid complex disclosed by the invention has high efficiency in removing organic dye in wastewater, is nontoxic and environment-friendly, can be biodegraded, and provides a new way for treating the organic dye in wastewater.

Description

Chitosan and rhamnolipid complex as well as preparation method and application thereof
Technical Field
The invention belongs to the field of environment, in particular to the novel technical fields of environment protection functional materials and water treatment, and particularly relates to a chitosan and rhamnolipid compound as well as a preparation method and application thereof.
Background
With the rapid development of industry, a large amount of highly concentrated organic dye wastewater is discharged from many industries such as textile, paper, leather, paint, cosmetics and medicines. Since most dyes have been identified as toxic, mutagenic and even carcinogenic, the release of organic dye waste water to the environment poses a great threat to human health and to the ecosystem, and it is becoming particularly necessary to explore an economical and efficient way for removal of organic dye waste water prior to discharge. To date, the most effective methods for removing organic dye wastewater include biodegradation, photocatalytic degradation, membrane filtration, and adsorption. Among them, the adsorption method uses the characteristics of the adsorbent such as high porosity, high specific surface area, or active functional groups of the adsorbent, and is a water pollutant removal technology that has been rapidly developed in recent years. Compared with other methods, the adsorption method has the advantages of simple operation, low use cost, wide source of adsorbent materials, mild reaction conditions, short treatment time, no secondary pollution and the like, and is widely applied.
The chitosan is a natural and nontoxic high molecular polymer, is a deacetylated product of chitin, can be produced by a simple process, is rich in raw materials and low in cost, mainly generates a good flocculation effect on pollutants in water through electrostatic action and surface complexation, can form cage-shaped molecules with similar network structures through hydrogen bonds and salt bonds due to the existence of hydroxyl groups, amino groups and other groups in molecules, can be chelated with a plurality of metal ions, and can effectively adsorb heavy metal ions in solution. In recent years, researchers find that chitosan and derivatives thereof have good application effects in the aspects of printing and dyeing wastewater treatment, food processing treatment and municipal sewage treatment. However, chitosan itself is insoluble in water, and thus cannot be directly used for treating dye wastewater. Rhamnolipid is a very good complexing agent, and is also a biological surfactant with biological metabolic properties produced by pseudomonas or burkholderia, and an anionic surfactant belonging to glycolipid can be used for binding with chitosan.
At present, the application of chitosan/rhamnolipid composite materials is rarely reported, and the chitosan/rhamnolipid composite materials are concentrated in the aspects of medicines and emulsifying agents, but the chitosan/rhamnolipid composite materials are not reported for removing organic pollutants, heavy metals and the like in water bodies.
Disclosure of Invention
The innovation point of the invention is that the chitosan and the rhamnolipid are both environment-friendly reagents, are easy to degrade and have no pollution to the environment, thus playing an extremely important role in environmental protection. The invention aims to solve the technical problems that: aiming at the technical problems existing in the prior art, a chitosan and rhamnolipid compound which is low in price and high in efficiency and can be used for adsorbing and treating organic dye wastewater is developed. And a preparation method of the chitosan and rhamnolipid complex, which has simple process and rapid preparation; also provides a method for applying the compound to remove organic dye wastewater.
The preparation method of the chitosan and rhamnolipid complex provided by the invention is characterized in that the rhamnolipid is used for carrying out functionalization treatment on chitosan, so that the prepared adsorbent can increase the number of adsorption sites on the surface of the chitosan through the modification effect of the rhamnolipid on the chitosan.
The invention provides a preparation method of a chitosan and rhamnolipid composite, which is characterized in that a chitosan matrix is used for connecting rhamnolipid on the chitosan matrix through chemical reaction, and finally, the composite particles are obtained through the action of glutaraldehyde.
Specifically, it comprises the following steps: dissolving chitosan and rhamnolipid in acetic acid or methanol respectively, then carrying out chemical reaction through EDC and NHS, and finally separating out the compound through the crosslinking of glutaraldehyde to obtain
More specific steps are as follows: respectively dissolving chitosan in organic solvents such as acetic acid and methanol solution, dissolving rhamnolipid in corresponding organic solvents, respectively performing ultrasonic treatment, and mixing to obtain dispersion solution; then EDC and NHS are added into the dispersion solution and stirred for reaction; then adding glutaraldehyde solution dropwise to the mixture, followed by stirring at 60-90 ℃; after centrifugation, the resulting product is washed sequentially with ethanol and ultrapure water, preferably 2-3 times, and dried in vacuo for use.
Preferably, the mass ratio of chitosan to rhamnolipid in the preparation of the complex is 1:0.8 to 1.2, more preferably 1:1.
in another preferred mode, in the preparation of the composite material, chitosan and rhamnolipid are reacted for 20-28 hours at room temperature, and then 10% glutaraldehyde solution is added dropwise to ensure that the finally synthesized composite is precipitated in a solid form.
In one embodiment, 1g of chitosan is dissolved in 100mL of 2% acetic acid solution, 1g of rhamnolipid is dissolved in 100mL of methanol, and the mixture is mixed after ultrasonic treatment for 20 minutes; then, 1gEDC and 1gNHS were added to the dispersion solution, and the reaction was stirred at room temperature (25 ℃) for 24 hours. 25mL of a 10% glutaraldehyde solution was then added dropwise to the mixture, followed by stirring at 80℃for 1 hour; after centrifugation at 3000rpm for 5 minutes, the resulting product was washed successively with ethanol and ultrapure water, respectively, 2-3 times, and dried under vacuum at 45℃for further use.
The invention also provides the chitosan and rhamnolipid complex obtained by the preparation method.
The invention further provides application of the chitosan and rhamnolipid complex in removing organic dye in wastewater. Preferably, the chitosan and rhamnolipid complex is used in an amount of 0.2-0.6 g/L, preferably 0.4g/L, in the organic wastewater. Preferably, the pH is adjusted to 3.0-10.0 during mixing; after mixing, at 15 ℃ or higher, preferably 25 ℃ or higher, preferably up to 35 ℃; the adsorption equilibrium time is 5-8 hours after mixing. More specifically, the organic dye is an anionic dye such as acid orange 7, methyl orange, congo red, and the like.
Compared with the prior art, the invention has the advantages that: the preparation process and the operation of the chitosan and rhamnolipid complex are simple, the preparation is quick, the production period is short, the product recovery rate is high, no special chemical equipment is needed, and the industrial production is easy to realize. The chitosan and rhamnolipid complex disclosed by the invention has high efficiency in removing organic dye in wastewater, is nontoxic and environment-friendly, can be biodegraded, and provides a new way for treating the organic dye in wastewater.
Drawings
FIG. 1 is an electron microscopic image of chitosan prepared as a comparison.
FIG. 2 is a schematic diagram of a scanning electron microscope of the chitosan and rhamnolipid complex of example 1 of the present invention.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
Preparation of chitosan and rhamnolipid complex example 1:
0.8 g g chitosan was dissolved in 100mL2% acetic acid solution, sonicated for 20 min, then 1g rhamnolipid was dissolved in 100mL methanol and added to the solution and sonicated until complete dissolution (30 min ultrasound) was continued, then 1g EDC and 1g NHS were added to the dispersion solution and reacted at room temperature with stirring for 24 h. Then 5mL of 10% glutaraldehyde solution was added dropwise to the mixture, followed by stirring at 80 ℃ for 1 hour. Centrifuging the solution, washing the precipitate with ethanol and distilled water for several times, and vacuum drying.
Preparation of chitosan and rhamnolipid complex example 2:
1g chitosan was dissolved in 100mL of 2% acetic acid solution, sonicated for 20 min, then 1g rhamnolipid was dissolved in 100mL methanol and added to the solution and sonication continued until complete dissolution (30 min of sonication), then 1g EDC and 1g NHS were added to the dispersion and stirred at 25℃for 24 h. Then 5mL of 10% glutaraldehyde solution is added dropwise to the mixture, the pH value is adjusted to be 9-10, the mixture is stirred at 80 ℃ for 1 h, the solution is centrifuged, and the precipitate is washed with ethanol and distilled water for several times in sequence and then dried in vacuum for standby.
The appearance of the chitosan and rhamnolipid compound prepared by the invention is yellow brown, and when the chitosan and rhamnolipid compound is observed under a scanning electron microscope, the surface structure is shown as figure 2, and the surface structure is layered, but still has a relatively smooth surface. For comparison, pure chitosan particles were prepared in the same manner as in example 2, except that no rhamnolipid was added. An electron microscope image of chitosan at the same magnification is shown in fig. 1. As can be seen from the comparison of the figures, the chitosan surface is smooth, the rhamnolipid is compounded, the surface is rough, and the specific surface area is also increased.
Application example 1:
the chitosan and rhamnolipid complex prepared in example 2 of the invention is used for treating acid orange 7 in organic dye wastewater, and comprises the following steps:
adding the chitosan and rhamnolipid compound prepared in example 1 into acid orange 7 with initial concentration of 20-250 mg/L of 50 mL, carrying out oscillation adsorption reaction at 25 ℃ by using an air bath constant temperature oscillator at 180rpm for 24 hours, separating the adsorbent from waste water by filtration, measuring the content of the acid orange 7 which is not adsorbed in the waste water at 484nm by using an ultraviolet-visible spectrophotometer, and calculating the adsorption amount, wherein the calculated adsorption amount is shown in table 1:
table 1: adsorption data of chitosan and rhamnolipid complex under different initial concentration conditions of acid orange 7
As is clear from Table 1, the adsorbent had an adsorption amount of 43.14 mg/g at an initial concentration of 20 mg/L and increased with an increase in the initial concentration to 588.41mg/g at 250 mg/L.
Application example 2:
the chitosan and rhamnolipid complex prepared in example 2 of the invention is used for treating acid orange 7 in organic wastewater, and comprises the following steps:
the chitosan and rhamnolipid complex prepared in example 1 was added to a 50 mL initial concentration of 100mg/L acid orange 7 solution, the amount of the adsorbent was 0.02 g, the adsorption reaction was carried out by shaking in an air bath constant temperature shaker at 15, 25 and 35 ℃ respectively, the adsorbent was separated from the waste water by filtration after 24 hours at 180rpm, the content of non-adsorbed acid orange 7 in the waste water was measured at 484nm by an ultraviolet-visible spectrophotometer, and the calculated adsorption amount results are shown in table 2:
table 2: adsorption capacity data of chitosan and rhamnolipid complex on acid orange 7 under different temperature conditions
Reaction temperature (. Degree. C.) 15 25 35
Adsorption quantity (mg/g) 205.47 212.47 229.36
As is clear from Table 2, the adsorption amount of the complex to acid orange 7 was 205.47mg/g at a reaction temperature of 15℃and increased with an increase in the initial temperature, and the adsorption amount reached 229.36mg/g at a temperature of 35 ℃.
Application example 3:
the chitosan and rhamnolipid complex prepared in example 2 of the invention is used for treating acid orange 7 in organic wastewater, and comprises the following steps:
the chitosan and rhamnolipid complex prepared in example 1 was added to a solution of acid orange 7 having an initial concentration of 100mg/L of 50 mL, the amount of the adsorbent was 0.02 g, the adsorption reaction was carried out by shaking at a constant temperature of 25 ℃ in an air bath shaker at a rotation speed of 180rpm, the adsorbent was separated from the wastewater by filtration after 10, 20, 40, 60, 90, 180, 360, 720, 1080 and 1440 minutes from the start of the adsorption reaction, the content of acid orange 7 not adsorbed in the wastewater was measured at 484nm by an ultraviolet-visible spectrophotometer, and the calculated adsorption amount results were shown in table 3:
table 3: adsorption capacity data of chitosan and rhamnolipid complex on acid orange 7 under different reaction time
Reaction time (min) 10 30 60 360 720 1080 1440
Adsorption quantity (mg/g) 141.25 144.25 193.75 226.25 229.75 232.25 233.50
As shown in table 3, the adsorption amount of the chitosan and rhamnolipid complex to the acid orange 7 in the organic wastewater is increased continuously with time, and after 360 minutes, the adsorption amount of the acid orange 7 is stable, namely the adsorption equilibrium time of the chitosan and rhamnolipid complex to the acid orange 7 is 6 h.
Application example 4:
the chitosan and rhamnolipid complex prepared in example 2 of the invention is used for treating acid orange 7 in organic wastewater, and comprises the following steps:
taking 50 mL acid orange 7 solution with initial concentration of 100mg/L, adding the chitosan and rhamnolipid complex prepared in example 1, adjusting pH to 3.0-10.0, using 0.02 g of the adsorbent, carrying out oscillation adsorption reaction by an air bath constant temperature oscillator at 25 ℃, separating the adsorbent from waste water by filtration after rotating at 180rpm for 24 hours, measuring the content of acid orange 7 which is not adsorbed in the waste water at 484nm by an ultraviolet-visible spectrophotometer, and calculating the adsorption amount as shown in Table 4:
table 4: adsorption capacity data of chitosan and rhamnolipid complex on acid orange 7 under different pH conditions
pH value of 3 4 5 6 7 8 9 10
Adsorption quantity (mg/g) 236.55 245.23 250.20 244.83 233.03 243.44 242.53 241.12
The above is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples, but various process schemes without substantial differences from the concept of the present invention are all within the scope of the present invention.

Claims (12)

1. A preparation method of a chitosan and rhamnolipid complex is characterized in that a chitosan matrix is used for connecting rhamnolipid on the chitosan matrix through chemical reaction, and finally, the complex particles are obtained through the action of glutaraldehyde;
which comprises the following steps:
dissolving chitosan in an organic solvent solution, dissolving rhamnolipid in a corresponding organic solvent, respectively carrying out ultrasonic treatment, and mixing to obtain a dispersion solution; then EDC and NHS are added into the dispersion solution and stirred for reaction; then adding glutaraldehyde solution dropwise to the mixture, followed by stirring at 60-90 ℃; after centrifugation, the obtained product was washed with ethanol and ultrapure water, respectively, and dried in vacuum for use.
2. The method for preparing a complex of chitosan and rhamnolipid according to claim 1, wherein chitosan is dissolved in acetic acid or methanol solution and rhamnolipid is dissolved in a corresponding organic solvent.
3. The method for preparing the chitosan and rhamnolipid complex according to claim 1, wherein the method comprises the following steps: and respectively cleaning the obtained products with ethanol and ultrapure water for 2-3 times in sequence, and then carrying out vacuum drying for standby.
4. A method for preparing the chitosan and rhamnolipid complex as claimed in claim 3, wherein: the mass ratio of chitosan to rhamnolipid in the preparation of the compound is 1:0.8-1.2.
5. The method for preparing the chitosan and rhamnolipid complex according to claim 2, wherein the method comprises the following steps: in the preparation of the composite material, chitosan and rhamnolipid react for 20-28 hours at room temperature, and then 10% glutaraldehyde solution is added dropwise to ensure that the finally synthesized composite is precipitated in a solid form.
6. The method for preparing the chitosan and rhamnolipid complex according to claim 2, wherein the method comprises the following steps: respectively dissolving 1g of chitosan in 100mL of 2% acetic acid solution, dissolving 1g of rhamnolipid in 100mL of methanol, respectively carrying out ultrasonic treatment for 20 minutes, and mixing; then, 1g of EDC and 1g of NHS were added to the dispersion solution, and the reaction was stirred at room temperature for 24 hours; then 25mL of 10% glutaraldehyde solution was added dropwise to the mixture, followed by stirring at 80℃for 1 hour, centrifuging at 3000rpm for 5 minutes, washing the resulting product with ethanol and ultrapure water, respectively, 2-3 times in sequence, and vacuum drying at 45℃for use.
7. A chitosan and rhamnolipid complex obtainable by the process according to any one of claims 1 to 6.
8. Use of the chitosan and rhamnolipid complex of claim 7 for removing organic dye from wastewater.
9. The use according to claim 8, wherein the chitosan and rhamnolipid complex is used in an amount of 0.2-0.6 g/L in organic waste water.
10. The use according to claim 9, wherein the pH is adjusted to 3.0-10.0 during mixing; mixing, and adsorbing at 15-35 deg.C for 5-8 hr.
11. Use according to claim 10, characterized in that the organic dye is an anionic dye.
12. The use according to claim 11, wherein the organic dye is acid orange 7, methyl orange or congo red.
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CN115403101A (en) * 2022-11-01 2022-11-29 济宁市圣奥精细化工有限公司 Dyeing and printing industrial sewage treatment agent and preparation method thereof
CN116196488B (en) * 2023-01-18 2024-04-26 南京工业大学 Rapidly degradable antibacterial material loaded with enzyme complex and preparation method thereof

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