Preparation method of phenol modified oleic acid adsorption material

Abstract

The invention discloses a preparation method of a phenol modified oleic acid adsorption material. The method comprises the following steps: firstly, blending sulfur, sodium oleate and phenol, and heating to react; and carrying out water washing, acid pickling, water washing and other steps on the product, and drying to obtain the phenol modified oleic acid adsorption material. The material can be used for adsorbing pollutants such as dyes and heavy metal ions, and has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the field of adsorbent preparation, and specifically relates to a preparation method of a phenol-modified oleic acid adsorbent material, belonging to the technical field of functional polymer materials. Background Art

[0002] Regarding the heavy metal pollution problem caused by ore mining, there are currently various treatment methods. Among them, the adsorption method for treating heavy metal pollution has the advantages of simple operation and wide application range compared with chemical precipitation, physical flocculation, bioremediation, etc., and has good application prospects in the field of heavy metal adsorption.

[0003] Phenol or its derivatives widely exist in plants, lakes and soils in nature. The oxygen atom in the phenolic hydroxyl group (-OH) has a lone pair of electrons. Heavy metal ions (such as Cu 2+ , Pb 2+ , Cd 2+ etc.) have empty orbitals and can accept lone pairs of electrons. Therefore, the phenolic hydroxyl group can form a coordination bond with heavy metal ions. One heavy metal ion can coordinate with multiple phenolic hydroxyl groups to form a stable complex, which can "grab" the heavy metal ions like a "grappling hook", thus achieving adsorption. For example, the two phenolic hydroxyl groups of catechol can form a six-membered ring complex with copper ions to enhance the adsorption stability. In some adsorption environments, the surface of the adsorbent material where phenol is located is charged. When heavy metal ions are present, an ion exchange process will occur. For example, the hydrogen ions (H + ) on the surface of the adsorbent material may exchange with heavy metal ions, causing the heavy metal ions to adhere to the adsorbent material and the hydrogen ions to enter the solution, achieving the purpose of adsorbing heavy metal ions. The adsorption surface formed by the aggregation of phenolic compounds may have certain physical adsorption ability. Heavy metal ions will be adsorbed on the surface of phenolic materials due to physical forces such as van der Waals forces. At the same time, the structural characteristics of phenolic compounds may provide more adsorption sites, which helps the aggregation and adsorption of heavy metal ions.

[0004] Sulfur is an important element that constitutes organic matter and is also a rich and inexpensive raw material. As a by-product of petroleum and natural gas refining, there is an annual surplus of approximately 7 million tons of elemental sulfur. Under natural conditions, elemental sulfur mainly exists in the form of cyclic small molecules (S8). The outer electron structure of sulfur atoms enables them to have a strong binding ability with heavy metal ions and can form chemical bonds with heavy metal ions. Moreover, in the physical adsorption process, the structure of the adsorbent material where sulfur is located will provide a large specific surface area to provide a place for the attachment of heavy metal ions, thereby playing an adsorption role.

[0005] Sodium oleate is a white to pale yellow powder or paste, which is a fatty acid salt. Its molecular structure consists of an oleate ion and a sodium ion. Sodium oleate has a hydrophilic carboxylate group and a lipophilic long hydrocarbon chain. It is commonly used in detergents and can also be used as a collector for flotation of ores, etc. When phenol polymerizes, it requires an alkaline condition. However, the double bond in sodium oleate enables phenol to also undergo a polymerization reaction without the need for an alkaline environment.

[0006] When heated to about 120 °C, sulfur begins to melt into a yellow liquid. When the temperature is higher than 159 °C, the molten sulfur ring opens to form chain-like sulfur, which can undergo ring-opening reactions. And the double bond in sodium oleate can cause phenol to undergo a polymerization reaction. By reacting with phenol to prepare a phenol-modified oleic acid adsorbent material, the prepared phenol-modified oleic acid adsorbent material contains a large number of hydroxyl groups and carboxyl groups, improving the adsorption performance and greatly increasing the adsorption capacity. Summary of the Invention

[0007] The present invention aims to provide a preparation method of a phenol-modified oleic acid adsorbent material. This method has a simple process and is easy to control, with mild reaction conditions and less cost investment. The phenol-modified oleic acid adsorbent material prepared by this method not only has a high adsorption capacity but also can achieve a fast adsorption rate, thus showing broad application prospects in the fields of heavy metal and dye treatment of wastewater.

[0008] To achieve the purpose of the present invention, the following technical solutions are provided:

[0009] A preparation method of a phenol-modified oleic acid adsorbent material, characterized by the following steps:

[0010] After mixing phenol, elemental sulfur and sodium oleate, heat and react. After washing the product with water, pickling, washing with water and other steps and then drying, a phenol-modified oleic acid adsorbent material is obtained.

[0011] Further, the phenol for synthesizing the phenol-modified oleic acid adsorbent material is phenol, diphenol, triphenol and their derivatives.

[0012] Further, the phenol for synthesizing the phenol-modified oleic acid adsorbent material is tannic acid.

[0013] Further, the diphenol for synthesizing the phenol-modified oleic acid adsorbent material is resorcinol, hydroquinone, catechol.

[0014] Further, the triphenol for synthesizing the phenol-modified oleic acid adsorbent material is phloroglucinol, resorcinol, hemellitol.

[0015] Further, the molar ratio of the phenol to sulfur for synthesizing the phenol-modified oleic acid adsorbent material is 1 - 20:1.

[0016] Further, the molar ratio of oleic acid to phenol for synthesizing the phenol-modified oleic acid adsorbent material is 0.4 - 10:1.

[0017] The reaction conditions further described are a temperature of 80 to 220 °C and a time of 1 to 24 h.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] Through the preparation method of a phenolic acid-modified oleic acid adsorbent material described in the present invention, the prepared phenolic acid-modified oleic acid adsorbent material has the characteristics of low cost, wide source, good adsorption performance, etc., and can be applied to the treatment of dye and heavy metal wastewater, and has good application prospects. Specific embodiments

[0020] The present invention will be further described below through specific embodiments. The following embodiments are intended to illustrate the present invention rather than further limit the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

[0021] Example 1:

[0022] Weigh 6.21 g of sodium oleate, 3.15 g of elemental sulfur and 2.38 g of catechol, mix them and place them in a hydrothermal reaction kettle, then put it into an oven, adjust the oven temperature to 180 °C, and react for 24 h to make the elemental sulfur, sodium oleate and o-phenol react. Use toluene to remove the unreacted sulfur in the product. Then, after steps such as washing with water, pickling, washing with water, and cold drying, cold drying is carried out, and the cold-dried product is subjected to alcoholysis reaction with alcohol to obtain an o-phenol-modified oleic acid adsorbent material.

[0023] Put the generated o-phenol-modified oleic acid adsorbent material into a malachite green solution for adsorption. The adsorption amount increases rapidly with time within the first 60 min, and then the trend slows down and basically remains unchanged after 12 h. At this time, the adsorption amount can reach about 800 mg / g.

[0024] Example 2:

[0025] Weigh 9.16 g of sodium oleate, 4.23 g of elemental sulfur and 2.42 g of hydroquinone, mix them and place them in a three-necked flask, add 20 ml of ethanol for reflux condensation, the oil bath temperature is 180 °C, and react for 12 h to make the elemental sulfur, sodium oleate and o-phenol react fully. Then filter to separate the ethanol to obtain a solid, and use toluene to remove the unreacted sulfur in the solid. Then, after steps such as washing with water, pickling, washing with water, and cold drying, cold drying is carried out, and the cold-dried product is subjected to alcoholysis reaction with alcohol to obtain a hydroquinone-modified oleic acid adsorbent material.

[0026] The generated hydroquinone-modified oleic acid adsorbent was put into a malachite green solution for adsorption. Within the first 60 minutes, the adsorption capacity increased rapidly with time, and then the trend slowed down, remaining basically unchanged after 12 hours. At this time, the adsorption capacity could reach about 650 mg / g.

[0027] Example 3:

[0028] Weighed 6.17 g of sodium oleate, 3.21 g of elemental sulfur and 3.56 g of phloroglucinol, mixed them and placed them in a three-necked flask, added 20 ml of ethanol for reflux condensation, the oil bath temperature was 120 °C, and reacted for 12 hours to make the elemental sulfur, sodium oleate and phloroglucinol react fully. Then, the ethanol was filtered off to obtain a solid, and toluene was used to remove the unreacted sulfur in the solid. Then, the product was washed with water, pickled, washed with water, and dried in the cold, etc., and then dried in the cold. The product after cold drying was subjected to alcoholysis reaction with alcohol to obtain phloroglucinol-modified oleic acid adsorbent.

[0029] The generated phloroglucinol-modified oleic acid adsorbent was put into a cadmium ion solution for adsorption. Within the first 70 minutes, the adsorption capacity increased rapidly with time, and then the trend slowed down, remaining basically unchanged after 12 hours. At this time, the adsorption capacity could reach about 60 mg / g.

Claims

1. A method for preparing a phenol-modified oleic acid adsorbent material, characterized by the following steps: Phenol (including tannic acid), elemental sulfur and sodium oleate are mixed and heated for reaction. The product is washed with water, acid washed, washed with water and dried to obtain a phenol-modified oleic acid adsorption material.

2. The method for preparing a phenol-modified oleic acid adsorbent material according to claim 1, characterized in that The phenol in the phenol-modified oleic acid adsorbent material is phenol, diphenol, triphenol and their derivatives.

3. The method for preparing a phenol-modified oleic acid adsorbent material according to claim 1, characterized in that The phenol in the phenol-modified oleic acid adsorbent material is tannic acid.

4. The method for preparing a phenol-modified oleic acid adsorbent material according to claim 2, characterized in that The diphenols used in the phenol-modified oleic acid adsorbent material are catechol, resorcinol and hydroquinone.

5. The method for preparing a phenol-modified oleic acid adsorbent material according to claim 2, characterized in that The triphenols in the phenol-modified oleic acid adsorbent material are pyrogallol, pyrogallol and pyrogallol.

6. The method for preparing a phenol-modified oleic acid adsorbent material according to claim 1, characterized in that The molar ratio of phenol to sulfur in the phenol-modified oleic acid adsorbent is 1 to 20:

1.

7. The method for preparing a phenol-modified oleic acid adsorbent material according to claim 1, characterized in that The molar ratio of sodium oleate to phenol in the phenol-modified oleic acid adsorbent is 0.4-10:

1.

8. The method for preparing a phenol-modified oleic acid adsorbent material according to claim 1, characterized in that The reaction conditions for phenol-modified oleic acid adsorbent material are a temperature of 80 to 220° C. and a time of 1 to 24 hours.