Biomass-based epoxy fixing agent as well as preparation method and application thereof
Through the use of biomass-based epoxy fixative, the problems of long pretreatment period and short pollutant fixation time in the drilling solid waste sinking stage are solved, and effective pollutant fixation and resource utilization are achieved.
Patent Information
- Application Number
- CN202311727072.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-15
- Publication Date
- 2025-06-17
AI Technical Summary
In the prior art, technical problems such as long pretreatment period of drilling solid waste during the sinking stage, short pollutant fixation time, and high content of pollutants in the leaching liquid.
Using a biomass-based epoxy fixative, the fixative is prepared by biomass depolymerization, acid anhydride modification and grafting reaction, and contains hydroxyl groups, carboxyl groups, epoxy groups and catechol structures, which can effectively fix oil, polymers, heavy metal ions, etc. in drilling solid waste.
It significantly reduces the pollution of drilling solid waste, reduces the COD, color, and improves the light transmittance, shortens the treatment cycle, and facilitates subsequent resource utilization.
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Figure CN120157774A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a biomass-based epoxy fixing agent, a preparation method thereof and an application thereof, belonging to the technical field of solid waste treatment. Background Art
[0002] Water-based drilling solid waste refers to the solid phase after solid-liquid separation by a solids control system after drill cuttings are brought to the ground by water-based drilling mud. Most of these solid phases are rock debris from the formation, and a small part is the mud adhering to the debris. Water-based drilling solid waste is an inevitable product of conventional drilling operations in oil and gas exploration.
[0003] Generally, a large amount of polymer drilling fluid treatment agents are added to the drilling fluid system, and a large amount of heavy metal ions and the like are contained in the drilling solid waste, resulting in relatively high pollution of the drilling solid waste. In the sedimentation stage before the comprehensive utilization of the drilling solid waste, in case of rain or other situations, a large amount of polluted leachate will be generated, causing harm to the natural environment. Therefore, in the sedimentation stage, pretreatment is required to fix organic matters, heavy metals and other pollutants in the solid waste, and then carry out subsequent centralized treatment to prevent environmental pollution and the like.
[0004] At present, for the pretreatment of the sedimentation stage of drilling solid waste, microbial enhanced treatment is often used. However, there are still a large number of deficiencies in the microbial treatment method, including: a large amount of natural soil needs to be consumed, the treatment cycle is long, the treatment effect is poor, and pollution will also be caused in case of extreme weather during the treatment process.
[0005] Therefore, it is necessary to provide a fixing agent for enhancing the treatment of drilling solid waste, so that pollutants can be directly fixed in the drilling solid waste, reducing the treatment cycle and facilitating subsequent further resource utilization. Summary of the Invention
[0006] The present invention aims to solve the technical problems in the prior art such as long pretreatment cycle, short pollutant fixation time, and high pollutant content in leachate in the sedimentation stage of drilling solid waste, and provides a biomass-based epoxy fixing agent, a preparation method thereof and an application thereof.
[0007] In order to achieve the above technical object, the following technical solutions are proposed:
[0008] The first object of this technical solution is to provide: a biomass-based epoxy fixing agent, which is prepared from biomass as a raw material through depolymerization, acid anhydride modification and grafting reaction;
[0009] The biomass-based epoxy fixing agent includes hydroxyl groups, carboxyl groups, epoxy groups and catechol structures (which can fix oil, polymers, heavy metal ions, etc. in drilling solid waste), and the specific structural formula is as follows:
[0010]
[0011] Among them, the values of X and Y are both greater than 2.
[0012] The second objective of this technical solution is to provide: a preparation method of a biomass-based epoxy fixing agent, and the involved reaction formula is as follows:
[0013]
[0014] It includes the following steps:
[0015] S1: Biomass depolymerization;
[0016] Using biomass as the raw material, drying, pulverizing, and controlling the particle size of the biomass powder to be below 100 mesh; then, calculating based on the mass ratio of biomass powder to phosphoric acid of 1-2:10-20, adding the biomass powder to phosphoric acid, and treating (such as stirring to dissolve and initially hydrolyze cellulose) at 30-80 °C for 0.5-5 h; then, adding a precipitating agent, and cellulose precipitates; filtering and washing to obtain the pretreated biomass, that is, the depolymerized biomass.
[0017] S2: Modifying the depolymerized biomass to obtain modified cellulose containing double bonds and carboxyl groups;
[0018] Calculating based on the molar ratio of the depolymerized biomass to the acid anhydride containing double bonds of 1:3-5, mixing the depolymerized biomass and the acid anhydride containing double bonds evenly, reacting at 80-150 °C for 5-10 h, and the degree of substitution of the biomass is 0.5-2; washing and drying to obtain modified cellulose containing double bonds and carboxyl groups.
[0019] S3: Conducting a grafting reaction on the modified cellulose, the glycidyl ether containing double bonds, and the substance containing catechol structure to obtain the biomass-based epoxy fixing agent;
[0020] Calculating based on the molar ratio of the modified cellulose, the glycidyl ether containing double bonds, and the substance containing catechol structure of 1:3-10:3-10, adding the modified cellulose, the glycidyl ether containing double bonds, and the substance containing catechol structure to a solvent, mixing evenly, adding an initiator, reacting at 80-150 °C for 10-24 h, washing and drying to obtain the biomass-based epoxy fixing agent.
[0021] The third objective of this technical solution is to provide: using the above-mentioned biomass-based epoxy fixing agent for solid waste treatment, specifically including using the fixing agent for pretreatment in the sedimentation stage of drilling solid waste.
[0022] Furthermore, in the use of the biomass-based epoxy fixing agent, it is directly added to the solid waste to be treated at a ratio of 1-5 wt%.
[0023] Adopting this technical solution, the beneficial technical effects brought are:
[0024] 1. The present invention uses biomass as a raw material. After depolymerization and anhydride modification treatment, modified cellulose is obtained. Then, epoxy resin and catechol are grafted to obtain a biomass-based epoxy fixing agent. Among them, this fixing agent contains hydroxyl groups, carboxyl groups, epoxy groups and catechol structures, which can enhance its chelating, adhesive and fixing abilities. In drilling waste, it can interact with the waste and make them adhere together. Furthermore, this fixing agent can adsorb oil, polymers, heavy metal ions, etc. in drilling waste and react with them chemically or through hydrogen bond interactions. The catechol structure in the structure has an ability similar to that of mussel adhesion protein, which can further enhance the fixing effect and directly fix the pollutants in drilling waste therein;
[0025] 2. The fixing agent in the present invention can effectively fix organic matter and heavy metal ions, etc. in drilling waste, reduce the pollution of drilling waste, make the leachate of drilling waste have a lower COD, a lower chromaticity and a higher light transmittance, can better connect the pretreatment process in the sedimentation stage of drilling waste, and ensure the smoothness and stability of the drilling waste treatment process;
[0026] 3. In the present invention, first of all, the main raw material is renewable cellulose, which is a biomass-based material and has the characteristics of environmental protection, non-toxicity, low cost, etc. Secondly, depolymerization pretreatment, modification and grafting, etc. further enhance the modification degree of the final product fixing agent and further enhance its fixing ability. Finally, the unique manifestation form of the fixing agent - the mussel-like structure, and the mussel-like structure and epoxy groups, etc. work together to ensure that it has a good curing effect. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1 The spectrum of the biomass-based epoxy fixing agent in the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.
[0029] Example 1
[0030] This example provides: a biomass-based epoxy fixing agent, which is prepared by using biomass as a raw material and through depolymerization, anhydride modification and grafting reaction;
[0031] The biomass-based epoxy fixing agent includes hydroxyl groups, carboxyl groups, epoxy groups and catechol structures (which can fix oil, polymers, heavy metal ions, etc. in drilling waste), and the specific structural formula is as follows:
[0032]
[0033] Among them, the values of X and Y are both greater than 2.
[0034] The FTIR data are as follows: at 3351 cm -1 there is an absorption peak of N-H, and at 3052 cm -1 there is an absorption peak of hydroxyl group, and at 1710 cm -1 there is an absorption peak of carboxyl group, and at 1594 cm -1 there is an absorption peak of the conjugated structure in the benzene ring, as Figure 1 shown (this data indicates the successful synthesis of the target product).
[0035] Example 2
[0036] This example provides: a preparation method of a biomass-based epoxy fixing agent, and the involved reaction formula is as follows:
[0037]
[0038] It includes the following steps:
[0039] S1: Biomass depolymerization;
[0040] Using biomass as the raw material, drying, pulverizing, and controlling the particle size of the biomass powder to be below 100 mesh (to ensure the subsequent dissolution rate and thus improve the depolymerization efficiency and quality); then, taking the mass ratio of the biomass powder to phosphoric acid as 1-2:10-20, adding the biomass powder to phosphoric acid, and treating it at 30-80 °C (such as stirring to dissolve and initially hydrolyze cellulose) for 0.5-5 h; then, adding a precipitating agent, and cellulose precipitates; filtering and washing to obtain the pretreated biomass, that is, the depolymerized biomass;
[0041] Among them, the main raw material involved is renewable cellulose, which is a biomass-based material. Biomass is materials such as wood and leaves in natural plants, and has the characteristics of environmental protection, non-toxicity, and low cost;
[0042] The concentration of phosphoric acid ≥ 85%. Here, phosphoric acid serves as both a solvent to dissolve biomass and to initially hydrolyze cellulose in the biomass. Other acids such as sulfuric acid and hydrochloric acid can also be used, but considering cost, safety, and hydrolysis degree, etc., phosphoric acid is preferred. It has higher safety and also prevents excessive hydrolysis of cellulose. Phosphoric acid has strong electronegativity and can form hydrogen bonds with the hydroxyl groups in the cellulose macromolecule to form a cellulose-phosphoric acid complex, destroying the cellulose aggregate structure and making cellulose dissolve. That is, the mechanism of the initial hydrolysis of cellulose is the acid hydrolysis mechanism. In addition, the phosphoric acid involved can be reused after distillation, realizing the recycling and reuse of phosphoric acid, thereby effectively saving costs and reducing waste liquid emissions.
[0043] Temperature and time will affect the dissolution rate and the degree of hydrolysis. If the hydrolysis is excessive, it will affect the performance of the final product fixative. Therefore, it is further specified that "treatment is carried out at 30 - 80 °C for 0.5 - 5 h".
[0044] The precipitant is one of water, methanol, and ethanol or a mixture of any two or more of them. First, the target cellulose in this technical solution is insoluble in water and ethanol. The biomass is first dissolved and initially hydrolyzed in phosphoric acid, and then, by adding the precipitant, the cellulose that is insoluble in the precipitant is precipitated.
[0045] S2: Modify the depolymerized biomass to obtain modified cellulose containing double bonds and carboxyl groups.
[0046] Based on the molar ratio of the depolymerized biomass to the acid anhydride containing double bonds being 1:3 - 5, the depolymerized biomass and the acid anhydride containing double bonds are mixed evenly and reacted at 80 - 150 °C for 5 - 10 h. Control the degree of substitution of the biomass to be 0.5 - 2, wash, and dry to obtain modified cellulose containing double bonds and carboxyl groups.
[0047] Among them, the acid anhydride containing double bonds includes one of maleic anhydride, 6 - tetrahydrophthalic anhydride, norbornene dicarboxylic anhydride, and methyltetrahydrophthalic anhydride or a mixture of any two or more of them. The graft modification of the depolymerized biomass mainly involves the esterification reaction between the acid anhydride and the hydroxyl group.
[0048] "Reacting at 80 - 150 °C for 5 - 10 h" can effectively ensure the esterification reaction rate and the reaction degree, that is, control the grafting rate of the obtained modified cellulose, which is suitable for the preparation of the subsequent fixative.
[0049] S3: Carry out a grafting reaction on the modified cellulose, the glycidyl ether containing double bonds, and the substance containing catechol structure to obtain the biomass - based epoxy fixative.
[0050] Based on the molar ratio of the modified cellulose, the glycidyl ether containing double bonds, and the substance containing catechol structure being 1:3 - 10:3 - 10, add the modified cellulose, the glycidyl ether containing double bonds, and the substance containing catechol structure to the solvent, mix evenly, add the initiator, and react at 80 - 150 °C for 10 - 24 h, wash, and dry to obtain the biomass - based epoxy fixative.
[0051] Among them, it mainly involves the amidation reaction between the substance containing catechol structure and the carboxyl group or the ring - opening reaction with the epoxy group; in addition, the glycidyl ether of the double bond polymerizes with the double bond in the modified cellulose under the action of the initiator.
[0052] The glycidyl ether containing double bonds includes one of allyl alcohol glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and glycidyl 4 - hydroxybutyl acrylate or a mixture of any two or more of them.
[0053] The substances containing catechol structure include one of adrenaline, noradrenaline, dopamine, caffeic acid and the mixture of any two or more of them;
[0054] The solvent includes one of water, methanol, ethanol, xylene, N,N-dimethylformamide and dimethyl sulfoxide and the mixture of any two or more of them. Its main function is to disperse and modify cellulose, dissolve reactants, so that the reaction can occur smoothly and stably;
[0055] The initiator includes one of ammonium persulfate, azodiisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate and diisopropyl peroxydicarbonate and the mixture of any two or more of them;
[0056] Similarly, "reacting at 80-150 °C for 10-24 h" can effectively ensure the reaction rate and reaction degree, that is, maximizing the amidation reaction, ring-opening reaction and polymerization reaction, etc.;
[0057] Example 3
[0058] This example provides: using the biomass-based epoxy fixing agent in Examples 1-2 for solid waste treatment, specifically including using the fixing agent for pretreatment in the sedimentation stage of drilling solid waste.
[0059] More specifically, in the use of the biomass-based epoxy fixing agent, it is directly added to the solid waste to be treated at a ratio of 1-5 wt%.
[0060] Example 4
[0061] This example provides: a biomass-based epoxy fixing agent, which is obtained through the following steps.
[0062] S1: Weigh 3 g of biomass powder and add it to 15 mL of phosphoric acid, stir until completely dissolved, treat it at 50 °C for 1 h, then add 10 mL of ethanol to precipitate the biomass, filter, wash and dry to obtain the depolymerized biomass;
[0063] S2: Weigh 2 g of the depolymerized biomass and 10 g of maleic anhydride, mix them evenly, react at 100 °C for 10 h, then wash and dry to obtain the modified cellulose;
[0064] S3: Add 2 g of the modified cellulose, 8 g of allyl glycidyl ether and 8 g of dopamine to the ethanol aqueous solution, mix them evenly, add 0.05 g of ammonium persulfate, react at 80 °C for 16 h, then filter, wash and dry to obtain the biomass-based epoxy fixing agent.
[0065] Example 5
[0066] This embodiment provides: a biomass-based epoxy fixing agent, which is obtained through the following steps.
[0067] S1: Weigh 3 g of biomass powder and add it to 15 mL of phosphoric acid. Stir until completely dissolved, treat it at 50 °C for 1 h, then add 10 mL of ethanol to precipitate the biomass. Filter, wash, and dry to obtain the depolymerized biomass.
[0068] S2: Weigh 2 g of the depolymerized biomass and 8 g of 6-tetrahydrophthalic anhydride. After mixing evenly, react at 100 °C for 10 h, then wash and dry to obtain the modified cellulose.
[0069] S3: Add 2 g of the modified cellulose, 8 g of allyl glycidyl ether, and 8 g of dopamine to an ethanol aqueous solution. After mixing evenly, add 0.05 g of ammonium persulfate and react at 80 °C for 16 h. Then filter, wash, and dry to obtain the biomass-based epoxy fixing agent.
[0070] Example 6
[0071] This embodiment provides: a biomass-based epoxy fixing agent, which is obtained through the following steps.
[0072] S1: Weigh 3 g of biomass powder and add it to 15 mL of phosphoric acid. Stir until completely dissolved, treat it at 50 °C for 1 h, then add 10 mL of ethanol to precipitate the biomass. Filter, wash, and dry to obtain the depolymerized biomass.
[0073] S2: Weigh 2 g of the depolymerized biomass and 8 g of maleic anhydride. After mixing evenly, react at 100 °C for 10 h, then wash and dry to obtain the modified cellulose.
[0074] S3: Add 2 g of the modified cellulose, 8 g of allyl glycidyl ether, and 8 g of adrenaline to an ethanol aqueous solution. After mixing evenly, add 0.05 g of ammonium persulfate and react at 80 °C for 16 h. Then filter, wash, and dry to obtain the biomass-based epoxy fixing agent.
[0075] Example 7
[0076] This embodiment provides: a biomass-based epoxy fixing agent, which is obtained through the following steps.
[0077] S1: Weigh 3 g of biomass powder and add it to 15 mL of phosphoric acid. Stir until completely dissolved, treat it at 50 °C for 1 h, then add 10 mL of ethanol to precipitate the biomass. Filter, wash, and dry to obtain the depolymerized biomass.
[0078] S2: Weigh 2 g of the depolymerized biomass and 12 g of norbornene dianhydride. After mixing them evenly, react at 100 °C for 10 h, then wash and dry to obtain modified cellulose.
[0079] S3: Add 2 g of the modified cellulose, 8 g of 4-hydroxybutyl acrylate glycidyl ether, and 8 g of caffeic acid to an ethanol aqueous solution. After mixing evenly, add 0.05 g of ammonium persulfate, react at 80 °C for 16 h, then filter, wash, and dry to obtain the biomass-based epoxy fixative.
[0080] Comparative Example 1
[0081] This comparative example provides 2 kinds of commercial flocculants (CPAM, Sichuan Shuiyuanqing Environmental Protection Technology Co., Ltd.; PAC, Chongqing Guanxing Chemical Co., Ltd.) and a commercial fixative (Sichuan Qiaoshui Technology Co., Ltd.), all of which are directly purchased from the market and are respectively used for the fixation of drilling solid waste.
[0082] Application Example
[0083] The biomass-based epoxy fixatives obtained in Examples 4 - 7 and the three fixatives provided in Comparative Example 1 are respectively used to characterize the fixation ability of the biomass-based epoxy fixative.
[0084] Among them, the fixation ability of the biomass-based epoxy fixative is determined by evaluating the COD, chromaticity, and transmittance of the leachate of the drilling solid waste (refer to the horizontal oscillation method for the leaching toxicity of solid waste (HJ 557—2010); the dilution multiple method for the determination of water quality chromaticity (HJ 1182—2021); the rapid digestion spectrophotometry for the determination of water quality chemical oxygen demand (HJ / T 399 - 2007)). The results are shown in Table 1.
[0085] Table 1
[0086] Sample COD (mg / L) Transmittance (%) Colority (times) Example 1 119 95.9 40 Example 2 193 91.6 100 Example 3 158 93.4 50 Example 4 253 90.9 80 Commercial Fixative 802 93.1 80 PAC 800 95.6 30 CPAM 462 91.0 40 Blank Control 1204 33.4 600
[0087] It can be seen that the biomass-based epoxy fixative in the present invention has excellent fixation ability, can greatly reduce the COD of the leachate of the drilling solid waste, reduce the chromaticity, and increase the transmittance.
[0088] The above are the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A biomass-based epoxy fixing agent, characterized in that, It is prepared from biomass as raw material through depolymerization, anhydride modification and grafting reaction; The structural formula of the biomass-based epoxy fixing agent is as follows: Among them, the values of X and Y are both greater than 2.
2. A preparation method of a biomass-based epoxy fixing agent, characterized in that, It includes the following steps: Using biomass as raw material, after pretreatment, depolymerization is carried out to obtain depolymerized biomass; The depolymerized biomass is subjected to anhydride modification to obtain modified cellulose containing double bonds and carboxyl groups; The modified cellulose, glycidyl ether containing double bonds and substances containing catechol structures are subjected to grafting reaction to obtain the biomass-based epoxy fixing agent.
3. The preparation method of the biomass-based epoxy fixing agent according to claim 2, characterized in that, The step of using biomass as raw material, after pretreatment, and then carrying out depolymerization includes: Using biomass as raw material, drying, pulverizing, and controlling the particle size of the biomass powder to be below 100 mesh; then, based on the mass ratio of biomass powder to phosphoric acid of 1-2:10-20, the biomass powder is added to phosphoric acid and completely dissolved, and treated at 30-80 °C for 0.5-5 h; then, a precipitating agent is added, and cellulose precipitates; filtering and washing to obtain depolymerized biomass.
4. The preparation method of the biomass-based epoxy fixing agent according to claim 3, characterized in that, The concentration of the phosphoric acid ≥ 85%.
5. The preparation method of the biomass-based epoxy fixing agent according to claim 3, characterized in that, The precipitating agent is one of water, methanol and ethanol and any mixture of two or more of them.
6. The preparation method of the biomass-based epoxy fixing agent according to claim 2, characterized in that, The step of subjecting the depolymerized biomass to anhydride modification includes: Based on the molar ratio of the depolymerized biomass to the anhydride containing double bonds of 1:3-5, the depolymerized biomass and the anhydride containing double bonds are mixed evenly, and reacted at 80-150 °C for 5-10 h, controlling the degree of substitution of biomass to be 0.5-2, washing and drying to obtain modified cellulose containing double bonds and carboxyl groups.
7. The preparation method of the biomass-based epoxy fixing agent according to claim 6, characterized in that, The anhydride containing double bonds includes one of maleic anhydride, 6-tetrahydrophthalic anhydride, norbornene dicarboxylic anhydride and methyltetrahydrophthalic anhydride and any mixture of two or more of them.
8. The preparation method of the biomass-based epoxy fixing agent according to claim 2, characterized in that, The step of carrying out grafting reaction on the modified cellulose, glycidyl ether containing double bonds and substances containing catechol structures includes: Based on the molar ratio of the modified cellulose, glycidyl ether containing double bonds and substances containing catechol structures of 1:3-10:3-10, the modified cellulose, glycidyl ether containing double bonds and substances containing catechol structures are added to a solvent, mixed evenly, an initiator is added, and reacted at 80-150 °C for 10-24 h, then washed and dried to obtain the biomass-based epoxy fixing agent.
9. The preparation method of the biomass-based epoxy fixing agent according to claim 8, characterized in that, The glycidyl ether containing double bonds includes one of allyl alcohol glycidyl ether, methyl methacrylate glycidyl ether, glycidyl acrylate and 4-hydroxybutyl acrylate glycidyl ether and any mixture of two or more of them.
10. The preparation method of the biomass-based epoxy fixing agent according to claim 8, characterized in that, The substances containing catechol structures include one of adrenaline, norepinephrine, dopamine, caffeic acid and any mixture of two or more of them.
11. The preparation method of the biomass-based epoxy fixing agent according to claim 8, characterized in that, The solvent includes one of water, methanol, ethanol, xylene, N,N-dimethylformamide and dimethyl sulfoxide and any mixture of two or more of them.
12. The preparation method of the biomass-based epoxy fixing agent according to claim 8, characterized in that, The initiator includes one of ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate and diisopropyl peroxydicarbonate and any mixture of two or more of them.
13. Applying the substance-based epoxy fixing agent according to any one of claims 1-12 to solid waste treatment.
14. The application according to claim 13, characterized in that,The application includes applying the substance-based epoxy fixing agent to the pretreatment in the sedimentation stage of drilling solid waste.
15. The application according to claim 13, wherein In the use of the substance-based epoxy fixing agent, it is directly added to the solid waste to be treated at a ratio of 1-5 wt%.