Plant polyphenol-based fixing agent as well as preparation method and application thereof

Abstract

The invention discloses a plant polyphenol-based fixing agent and a preparation method and application thereof, and relates to the technical field of drilling solid waste treatment.The plant polyphenol-based fixing agent is obtained by uniformly mixing plant polyphenol with a catalyst and then adding phenyl-containing diglycidyl ether for a reaction, the plant polyphenol contains one or more benzene ring structures and has phenolic hydroxyl functional groups; the catalyst is one or more of sodium methoxide, potassium methoxide, sodium ethoxide and potassium ethoxide, and the addition amount of the catalyst is 1-5wt% of the total mass of the plant polyphenol and the phenyl-containing diglycidyl ether; the mass ratio of the plant polyphenol to the phenyl-containing diglycidyl ether is (2-10): 1. The technical problems that in the prior art, drilling solid waste treatment is high in cost, long in period, short in fixing time, high in leachate pollutant content and the like are solved.

Description

Technical Field

[0001] This invention relates to the field of drilling solid waste treatment technology, specifically to a plant polyphenol-based fixative, its preparation method, and its application. Background Technology

[0002] Water-based drilling solid waste is an inevitable byproduct of conventional drilling operations. It contains large amounts of chemical additives, oil, and heavy metal ions. Without treatment, significant amounts of pollutants will flow into the soil with leachate during open-air storage, polluting the environment. Currently, the main technologies for the pretreatment of drilling solid waste are high-temperature oxidation and microbial enhanced treatment. High-temperature oxidation requires a large amount of energy, while microbial treatment consumes a large amount of natural soil, resulting in high costs, long treatment cycles, and poor treatment effects. Furthermore, extreme weather conditions during the treatment process can also cause pollution.

[0003] Therefore, it is necessary to provide a fixative for the enhanced treatment of drilling solid waste, which can directly fix pollutants in the drilling solid waste, reduce the treatment cycle, reduce treatment costs, and facilitate subsequent resource utilization. Summary of the Invention

[0004] The purpose of this invention is to provide a plant polyphenol-based fixative, its preparation method, and its application. This plant polyphenol-based fixative can be used to directly fix dyes in drilling solid waste, solving the technical problems of high cost, long cycle, short fixation time, and high pollutant content in leachate of existing drilling solid waste treatment.

[0005] This invention is achieved through the following technical solution: A plant polyphenol-based fixative is obtained by mixing plant polyphenols with a catalyst, adding diglycidyl ether containing phenyl groups, and reacting the mixture. The plant polyphenols contain one or more benzene ring structures and have phenolic hydroxyl functional groups; The catalyst is one or more of sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide, and the amount of catalyst added is 1 to 5 wt% of the total mass of plant polyphenols and phenyl diglycidyl ether; the mass ratio of the plant polyphenols to the phenyl diglycidyl ether is 2 to 10:1.

[0006] Furthermore, the plant polyphenols are one or more of tannic acid, anthocyanins, catechins, quercetin, gallic acid, ellagic acid, arbutin, and their polymers.

[0007] Furthermore, the phenyl-containing diglycidyl ether is one or more of bisphenol A diglycidyl ether, bisphenol A propoxylated diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and resorcinol diglycidyl ether.

[0008] The preparation method of the plant polyphenol fixative as described in any of the preceding claims includes the following steps: I. Add the plant polyphenols and catalyst to solvent one, and then dissolve them completely under a nitrogen atmosphere; II. Then add diglycidyl ether containing phenyl groups to carry out a ring-opening polymerization reaction; III. Purify the product from step II to obtain a plant polyphenol fixative.

[0009] Furthermore, in step I, the solvent is one or more of ethyl acetate, isobutanol, dioxane, xylene, butyl acetate, and ethylene glycol dimethyl ether.

[0010] Furthermore, in step II, after adding diglycidyl ether containing phenyl, the reaction temperature is controlled at 80~120℃ and the reaction time is 5~24h.

[0011] Furthermore, in step II, after adding diglycidyl ether containing phenyl groups, the reaction time is 5-24 hours.

[0012] Further, in step III, the purification method is as follows: add solvent II to the product, then place it in an ultrasonic cleaner for ultrasonic treatment for 5-10 minutes, then centrifuge at high speed at 3000 rpm, and freeze-dry for 24 hours to obtain the purified plant polyphenol fixative.

[0013] In actual processing, the duration and number of ultrasonic treatments can be adjusted according to the actual situation. Generally, each ultrasonic treatment lasts 5 to 10 minutes, and 2 to 4 treatments are sufficient. During centrifugation, a high-speed centrifuge speed of 3000 rpm is preferred, but it can also be adjusted according to specific circumstances.

[0014] Furthermore, the solvent two is one or more of methanol, ethanol, water, etc.

[0015] Application of plant polyphenol-based fixatives in drilling solid waste treatment as described in any of the preceding items.

[0016] Furthermore, when treating drilling solid waste, the amount of plant polyphenol-based fixative added is 1-5 wt% of the total material.

[0017] Compared with the prior art, the present invention has the following advantages and beneficial effects: I. In this invention, the plant polyphenol-based fixative uses abundant plant polyphenols found in nature as the main raw material, which can significantly reduce the cost of fixatives and decrease the consumption of petrochemical products. Then, using diglycidyl ether containing phenyl groups as a crosslinking agent, the product is prepared in a one-step process. This preparation method crosslinks the plant polyphenols through covalent bonds and increases the number of phenyl groups in the plant polyphenol-based fixative. When this plant polyphenol-based fixative is applied to drilling solid waste treatment, it can enhance the hydrogen bonding, electrostatic interactions, and π-π interactions between the plant polyphenol-based fixative and pollutants in the drilling solid waste, improving its adhesive, chelating, and fixation capabilities. This allows oil, polymers, heavy metal ions, etc., in the drilling solid waste to be fixed within the solid waste, preventing them from being leached by rainwater, reducing the oil content in the leachate, lowering the COD value, color value, and turbidity value of the leachate, and increasing the transmittance of the leachate. Attached Figure Description

[0018] Figure 1 This is a structural diagram of the plant polyphenol fixative prepared in Example 1. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0020] In this invention, when preparing plant polyphenol fixatives, plant polyphenols containing one or more benzene ring structures and having phenolic hydroxyl functional groups are used as the main raw materials, such as tannic acid, anthocyanins, catechins, quercetin, gallic acid, ellagic acid, arbutin and one or more of their polymers. To facilitate public understanding of this solution, the following examples use tannic acid, ellagic acid, quercetin, anthocyanins, etc. as examples for illustration. The diglycidyl ether containing phenyl groups is one or more of bisphenol A diglycidyl ether, bisphenol A propoxylated diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and resorcinol diglycidyl ether. To facilitate public understanding of this solution, the following examples use bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl ether, and resorcinol diglycidyl ether as examples for illustration. Solvent 1 is one or more of ethyl acetate, isobutanol, dioxane, xylene, butyl acetate, and ethylene glycol dimethyl ether. To facilitate public understanding of this scheme, ethyl acetate, butyl acetate, and isobutanol are used as examples in the following embodiments.

[0021] Example 1 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: Ⅰ. Add 2g of tannic acid and 0.03g of sodium methoxide to 40mL of ethyl acetate, and then mechanically stir under a nitrogen atmosphere until completely dissolved; II. Add 1g of bisphenol A diglycidyl ether and react at 100℃ for 16h to carry out ring-opening polymerization. III. Add methanol to the product of step II and place it in an ultrasonic cleaner (40MHz, 100W) for 5 minutes. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000rpm and freeze dry for 24 hours to obtain plant polyphenol fixative Q1. Figure 1 This is a structural diagram of plant polyphenol fixative Q1.

[0022] Example 2 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: I. Add 2g of ellagic acid and 0.03g of potassium methoxide to 40mL of ethyl acetate, and then mechanically stir under a nitrogen atmosphere until completely dissolved; II. Add 1g of bisphenol S diglycidyl ether and react at 100℃ for 16h to carry out ring-opening polymerization. III. Add methanol to the product of step II and place it in an ultrasonic cleaner (40MHz, 100W) for 5 minutes. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000rpm and freeze dry for 24 hours to obtain plant polyphenol fixative Q2.

[0023] Example 3 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: Ⅰ. Add 2g of quercetin and 0.03g of sodium ethoxide to a 50mL solution of butyl acetate, and then mechanically stir under a nitrogen atmosphere to dissolve it completely; II. Add 1g of bisphenol F diglycidyl ether and react at 90℃ for 18h to carry out ring-opening polymerization. III. Add ethanol to the product of step II and place it in an ultrasonic cleaner (40MHz, 100W) for 5 minutes. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000 rpm and freeze dry for 24 hours to obtain plant polyphenol fixative Q3.

[0024] Example 4 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: Ⅰ. Add 2g of anthocyanins and 0.03g of potassium ethoxide to 40mL of isobutanol, and then mechanically stir under a nitrogen atmosphere to dissolve them completely; II. Add 1g of resorcinol diglycidyl ether and react at 100℃ for 18h to carry out ring-opening polymerization. III. Add deionized water to the product of step II and place it in an ultrasonic cleaner (40MHz, 100W) for 5 minutes. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000rpm and freeze dry for 24 hours to obtain plant polyphenol fixative Q4.

[0025] Example 5 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: Ⅰ. Add 4g of tannic acid and 3% sodium methoxide to 60mL of ethyl acetate, and then mechanically stir under a nitrogen atmosphere until completely dissolved; II. Add 1g of bisphenol A diglycidyl ether and react at 100℃ for 16h to carry out ring-opening polymerization. III. Add methanol to the product of step II and place it in an ultrasonic cleaner (40 MHz, 100W) for 5 min. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000 rpm and freeze dry for 24 h to obtain plant polyphenol fixative Q5.

[0026] Example 6 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: Ⅰ. Add 10g of tannic acid and 3% sodium methoxide to 100mL of ethyl acetate, and then mechanically stir under a nitrogen atmosphere until completely dissolved; II. Add 1g of bisphenol A diglycidyl ether and react at 100℃ for 16h to carry out ring-opening polymerization. III. Add methanol to the product of step II and place it in an ultrasonic cleaner (40 MHz, 100W) for 5 min. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000 rpm and freeze dry for 24 h to obtain plant polyphenol fixative Q6.

[0027] Example 7 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: Ⅰ. Add 2g of tannic acid and 1% sodium methoxide to 40mL of ethyl acetate, and then mechanically stir under a nitrogen atmosphere until completely dissolved; II. Add 1g of bisphenol A diglycidyl ether and react at 100℃ for 16h to carry out ring-opening polymerization. III. Add methanol to the product of step II and place it in an ultrasonic cleaner (40MHz, 100W) for 5 minutes. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000rpm and freeze dry for 24 hours to obtain plant polyphenol fixative Q7.

[0028] Example 8 This embodiment provides a plant polyphenol-based fixative, belonging to the field of drilling solid waste treatment technology. The plant polyphenol-based fixative is obtained through the following steps: Ⅰ. Add 2g of tannic acid and 5% sodium methoxide to 40mL of ethyl acetate, and then mechanically stir under a nitrogen atmosphere until completely dissolved; II. Add 1g of bisphenol A diglycidyl ether and react at 100℃ for 16h to carry out ring-opening polymerization. III. Add methanol to the product of step II and place it in an ultrasonic cleaner (40MHz, 100W) for 5 minutes. Repeat the ultrasonic cleaning 3 times. Then, centrifuge at 3000rpm and freeze dry for 24 hours to obtain plant polyphenol fixative Q8.

[0029] Comparative Example 1 This comparative example provides a method for preparing a plant polyphenol-based fixative. The difference from Example 1 is that no catalyst is added, and the resulting fixative is denoted as T1.

[0030] Comparative Example 2 This comparative example provides a method for preparing a plant polyphenol-based fixative. Compared with Example 1, the difference is that bisphenol A diglycidyl ether is replaced with an equal mass of ethylene glycol diglycidyl ether, and the resulting fixative is denoted as T2.

[0031] Comparative Examples 3-5 are commercially available flocculants (CPAM), commercially available flocculants (PAC), and another commercial fixative (S1), which were purchased directly from the market.

[0032] Example 9 In this embodiment, the plant polyphenol-based fixatives Q1-Q8 obtained in Examples 1-8 and the fixatives in Comparative Examples 1-5 were applied to the treatment of drilling solid waste, and the fixation capacity of each fixative was examined. The fixation capacity of the fixative was determined by comprehensively evaluating the COD value and color of the leachate from the drilling solid waste.

[0033] The testing procedure referenced the standard HJ 557—2010 Solid Waste Leaching Toxicity Leaching Method. Test results are shown in Table 1.

[0034] In Table 1 below, the test method for COD value of leachate refers to the rapid digestion spectrophotometric method for the determination of chemical oxygen demand in water quality HJ / T 399—2007. Color determination shall refer to GB 11903—89 Determination of color in water quality and HJ 1182—2021 Determination of color in water quality by dilution ratio method.

[0035] Table 1 Table 1 shows that commercially available flocculants PAC, CPAM, and S1 commercial fixative have good effects on reducing the color of the treated drilling wastewater, but their COD reduction capabilities are relatively weak. In contrast, the plant polyphenol-based fixative of this invention exhibits excellent fixation capabilities, significantly reducing the COD value and color of the drilling solid waste leachate. With the fixative provided in Example 1 added at 3%, the COD of the treated wastewater can be reduced to 131 mg / L, and the color reduced by 40 times. This demonstrates significant advantages compared to commercial flocculants and commercial fixatives.

[0036] Compared with other experimental groups, control group 1 shows that without a catalyst, the reaction may not proceed or may be extremely slow. Compared with other experimental groups, control group 2 shows that when the crosslinking agent is replaced with ethylene glycol diglycidyl ether, the fixation capacity of the fixative decreases due to the reduction of the benzene ring structure and the increase of hydrophilicity in the crosslinking product. This product can be used in drilling solid waste treatment. Extensive experiments have proven that when using this plant polyphenol-based fixative, the optimal addition amount is 1-5 wt% of the total material, which is economical, environmentally friendly, and provides good fixation results.

[0037] Extensive experimental studies have demonstrated that when the plant polyphenol-based fixative described in this scheme is applied to the treatment of drilling solid waste, the fixation effect is superior and less likely to cause other adverse effects when the amount of plant polyphenol-based fixative added is 1-5 wt% of the total material, and the cost is relatively low.

[0038] As demonstrated by the above experimental results, the plant polyphenol-based fixative provided by this invention exhibits superior performance compared to other products. Furthermore, a method for preparing this plant polyphenol-based fixative is provided, resulting in a more stable fixative.

[0039] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications or equivalent changes made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A plant polyphenol fixative, characterized in that: After mixing plant polyphenols with a catalyst, diglycidyl ether containing phenyl groups is added, and the reaction yields a plant polyphenol group fixative. The plant polyphenols contain one or more benzene ring structures and have phenolic hydroxyl functional groups; The catalyst is one or more of sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide, and the amount of catalyst added is 1 to 5 wt% of the total mass of plant polyphenols and phenyl diglycidyl ether; the mass ratio of the plant polyphenols to the phenyl diglycidyl ether is 2 to 10:

1.

2. The plant polyphenol fixative according to claim 1, characterized in that: The plant polyphenols are one or more of tannic acid, anthocyanins, catechins, quercetin, gallic acid, ellagic acid, arbutin, and their polymers.

3. The plant polyphenol fixative according to claim 1, characterized in that: The diglycidyl ether containing phenyl is one or more of bisphenol A diglycidyl ether, bisphenol A propoxylated diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and resorcinol diglycidyl ether.

4. The method for preparing the plant polyphenol fixative as described in claim 1, characterized in that, Includes the following steps: I. Add the plant polyphenols and catalyst to solvent one, and then dissolve them completely under a nitrogen atmosphere; II. Then add diglycidyl ether containing phenyl groups to carry out a ring-opening polymerization reaction; III. Purify the product from step II to obtain a plant polyphenol fixative.

5. The method for preparing the plant polyphenol fixative according to claim 4, characterized in that: In step I, solvent one is one or more of ethyl acetate, isobutanol, dioxane, xylene, butyl acetate, and ethylene glycol dimethyl ether.

6. The method for preparing the plant polyphenol fixative according to claim 4, characterized in that: In step II, after adding diglycidyl ether containing phenyl groups, the reaction temperature is controlled at 80~120℃ and the reaction time is 5~24h.

7. The method for preparing the plant polyphenol fixative according to claim 6, characterized in that: In step II, after adding diglycidyl ether containing phenyl groups, the reaction time is 5-24 hours.

8. The method for preparing the plant polyphenol fixative according to claim 4, characterized in that, In step III, the purification method is as follows: add solvent II to the product, then place it in an ultrasonic cleaner for ultrasonic treatment for 5-10 min, then centrifuge at high speed at 3000 rpm, and freeze-dry for 24 h to obtain the purified plant polyphenol fixative.

9. The method for preparing the plant polyphenol fixative according to claim 8, characterized in that: The second solvent is one or more of methanol, ethanol, water, etc.

10. The application of the plant polyphenol-based fixative as described in any one of claims 1-9 in the treatment of drilling solid waste.

11. The application according to claim 10, characterized in that: When treating drilling solid waste, the amount of plant polyphenol-based fixative added is 1-5 wt% of the total material.

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