A nanocarbon sphere-methacrylate-alpha-olefin paraffin inhibitor and a preparation method thereof
A highly branched polyolefin anti-wax agent was prepared by polymerizing carbon nanospheres with methacrylate-α-olefin, which solved the problems of high cost and poor environmental performance of existing anti-wax agents and achieved a low-cost and environmentally friendly anti-wax effect.
Patent Information
- Application Number
- CN202510351648.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-24
- Publication Date
- 2025-11-21
- Estimated Expiration
- 2045-03-24
AI Technical Summary
Existing wax inhibitors are expensive, not environmentally friendly, and have poor wax-preventing performance.
A highly branched polyolefin anti-wax agent was prepared by polymerizing carbon nanospheres with methacrylate-α-olefin, and the anti-wax effect was achieved through eutectic reaction and heterogeneous nucleation.
It achieves low-cost and environmentally friendly anti-wax effect, and is suitable for crude oil, diesel and condensate oil, reducing pollution and improving anti-wax efficiency.
Smart Images
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Abstract
Description
Technical fields:
[0001] This invention relates to highly branched polyolefins, specifically to a nano-carbon ball-methacrylate-α-olefin anti-wax agent and its preparation method. Background technology:
[0002] Due to their unique properties, polymers are often used as pour point depressants, wax crystal modifiers, or wax crystal dispersants to improve the fluidity of waxy crude oil. These compounds primarily prevent wax deposition in crude oil by co-crystallizing or co-precipitating with wax crystal molecules through hydrocarbon chains, while the polar groups in their molecular structure repel each other. Although these polymers can effectively improve the cold fluidity of waxy crude oil, they are not an environmentally friendly or cost-effective option because they often require a high heteroatom content or large dosages.
[0003] Nanoparticles are composite materials with nanoscale dimensions, unique size, and ultra-high surface adsorption properties, capable of altering the morphology of wax crystals and achieving a wax-preventing effect. Adding nanoparticles to crude oil reduces the size of wax crystals and hinders their aggregation, thereby lowering the wax precipitation point of the crude oil. Single nanomaterials exhibit poor dispersibility in crude oil; organic modification can improve their dispersion effect. When nanoparticles are used in combination with surfactants, the wax-preventing effect is better than when used alone. Summary of the Invention:
[0004] One objective of this invention is to provide a nano-carbon ball-methacrylate-α-olefin anti-wax agent, which addresses the technical problems of high raw material cost, insufficient environmental friendliness, and poor anti-wax performance of existing anti-wax agents. Another objective of this invention is to provide a method for preparing this nano-carbon ball-methacrylate-α-olefin anti-wax agent.
[0005] The technical solution adopted by this invention to solve its technical problem is: this nano-carbon ball-methacrylate-α-olefin anti-wax agent is a highly branched polyolefin, used in waxy petroleum, diesel, or natural gas condensate, and its structural formula is:
[0006]
[0007] Where R is an alkyl chain.
[0008] The surface of the carbon nanospheres in the above scheme contains hydroxyl groups.
[0009] The diameter of the carbon nanospheres described above is less than or equal to 150 nm.
[0010] The preparation method of the above-mentioned nano-carbon sphere-methacrylate-α-olefin anti-wax agent includes the following steps:
[0011] Step 1: Prepare hydroxyl-containing carbon nanospheres using glucose via a hydrothermal method. Add glucose to deionized water, mix well, and then transfer to a hydrothermal reactor. Heat to 140-190℃ and react for 5-8 hours. Wash with deionized water and dry to obtain hydroxyl-containing carbon nanospheres.
[0012] Step 2: The hydroxyl-containing carbon nanospheres and methacryloyl chloride undergo an esterification reaction to obtain carbon nanosphere-methacrylate.
[0013] Step 3: Polymerize nano-carbon spheres-methacrylate and α-olefin to obtain nano-carbon spheres-methacrylate-α-olefin anti-wax agent.
[0014] In step one of the above scheme, the concentration of glucose and deionized water is 0.1 g / mL.
[0015] Step two in the above scheme is specifically as follows:
[0016] Hydroxyl-containing carbon nanospheres and methacryloyl chloride are added to solvent I, with a mass ratio of hydroxyl-containing carbon nanospheres to methacryloyl chloride of 1:1 to 10. After mixing evenly, a catalyst is added, with a molar ratio of catalyst to methacryloyl chloride of 1.0 to 1.1:1. The temperature is raised to 40-50℃, and the esterification reaction is carried out for 5-10 hours to obtain carbon nanosphere-methacrylate.
[0017] In the above scheme, the catalyst is one or both of anhydrous potassium carbonate and anhydrous sodium carbonate; solvent I is N,N-dimethylformamide or tetrahydrofuran.
[0018] Step three in the above plan specifically refers to:
[0019] Nano-carbon spheres-methacrylate and α-olefins are added to solvent II at a mass ratio of 0.05 to 2:100. After mixing evenly, an initiator is added at a mass of 0.01% to 1% of the total mass of the reactants. The mixture is heated to 110-150°C under argon atmosphere and polymerized for 8-10 hours to obtain nano-carbon spheres-methacrylate-α-olefin anti-wax agent.
[0020] In the above scheme, solvent II is at least one of toluene, xylene, trimethylbenzene, and C9 aromatic hydrocarbons.
[0021] In the above scheme, the initiator is at least one of azobisisobutyronitrile, dicumyl peroxide, benzoyl peroxide, and tert-butyl peroxide.
[0022] Beneficial effects:
[0023] 1. This invention obtains a novel nano-carbon ball-methacrylate-α-olefin wax inhibitor by grafting and polymerizing environmentally friendly nano-carbon balls with organic matter. This novel nanoparticle-polymer wax inhibitor is a highly branched polyolefin, achieving its wax-inhibiting effect mainly through eutectic reaction and heterogeneous nucleation. Compared with traditional wax inhibitors, this invention has advantages such as small dosage, high wax-inhibiting efficiency, no pollution, inexpensive and readily available raw materials, and less pollution in the wax-inhibiting treatment of crude oil, diesel, and condensate. It solves the technical problems of high raw material cost, insufficient environmental friendliness, and poor wax-inhibiting performance of existing wax inhibitors.
[0024] 2. This invention can effectively inhibit the precipitation of paraffin in natural gas condensate and prevent the aggregation and growth of wax crystals, thereby ensuring that the condensate will not solidify under low temperature conditions and maintain good fluidity. Detailed implementation method:
[0025] The present invention will be further described below:
[0026] Example 1:
[0027] This nano-carbon sphere-methacrylate-α-olefin anti-wax agent is a highly branched polyolefin used for anti-wax treatment of waxy petroleum, diesel, or natural gas condensate. Its structural formula is:
[0028]
[0029] Where R is an alkyl chain.
[0030] This nano-carbon sphere-methacrylate-α-olefin anti-wax agent is obtained through the following steps:
[0031] First, 4g of glucose was dissolved in 40mL of deionized water. Then, the mixture was hydrothermally heated at 190℃ for 5 hours. The prepared product was washed with deionized water until the pH was neutral. Finally, it was dried in a forced-air drying oven to obtain nano-carbon spheres with hydroxyl groups on the surface.
[0032] Dissolve 0.5g of the carbon nanospheres and 0.5g of methacryloyl chloride in 30mL of N,N-dimethylformamide, then add 0.5g of anhydrous sodium carbonate, react at 50℃ for 4h, wash with deionized water, and dry to obtain carbon nanosphere-methacrylate.
[0033] 0.5g of nano-carbon spheres-methacrylate and 20g of α-hexadecene were dissolved in toluene, and 2g of benzoyl peroxide was added. The mixture was reacted at 110℃ for 10h under argon atmosphere. The product was washed several times with methanol and finally dried at 60℃ in a vacuum drying oven to obtain nano-carbon spheres-methacrylate-α-olefin anti-wax agent.
[0034] Example 2:
[0035] The structural formula of the nano-carbon ball-methacrylate-α-olefin anti-wax agent in this embodiment is the same as that in Example 1.
[0036] The nano-carbon sphere-methacrylate-α-olefin anti-wax agent of this embodiment is obtained through the following steps:
[0037] First, weigh 4g of glucose and dissolve it in 40mL of deionized water. Then, heat the solution at 190℃ for 5 hours. Wash the prepared product with deionized water until the pH is neutral. Finally, dry the product in a forced-air drying oven to obtain carbon nanospheres with hydroxyl groups on the surface.
[0038] Dissolve 0.5g of the carbon nanospheres and 0.5g of methacryloyl chloride in 30mL of N,N-dimethylformamide, then add 0.5g of anhydrous potassium carbonate, react at 50℃ for 4h, wash with deionized water, and dry to obtain carbon nanosphere-methacrylate.
[0039] 0.5g of nano-carbon spheres-methacrylate and 20g of α-hexadecene were dissolved in toluene, and 2g of benzoyl peroxide was added. The mixture was reacted at 110℃ for 10h under argon atmosphere. The product was washed several times with methanol and finally dried at 60℃ in a vacuum drying oven to obtain nano-carbon spheres-methacrylate-α-olefin anti-wax agent.
[0040] Example 3:
[0041] The structural formula of the nano-carbon ball-methacrylate-α-olefin anti-wax agent in this embodiment is the same as that in Example 1.
[0042] The nano-carbon sphere-methacrylate-α-olefin anti-wax agent of this embodiment is obtained through the following steps:
[0043] First, weigh 4g of glucose and dissolve it in 40mL of deionized water. Then, heat the solution at 190℃ for 5 hours. Wash the prepared product with deionized water until the pH is neutral. Finally, dry the product in a forced-air drying oven to obtain carbon nanospheres with hydroxyl groups on the surface.
[0044] Dissolve 0.5g of the carbon nanospheres and 0.5g of methacryloyl chloride in 30mL of N,N-dimethylformamide, then add 0.5g of anhydrous sodium carbonate, react at 50℃ for 4h, wash with deionized water, and dry to obtain carbon nanosphere-methacrylate.
[0045] 0.5g of nano-carbon spheres-methacrylate and 20g of α-dodecene were dissolved in xylene, and 5g of benzoyl peroxide was added. The mixture was reacted at 110℃ for 10h under argon atmosphere. The product was washed several times with methanol and finally dried at 60℃ in a vacuum drying oven to obtain nano-carbon spheres-methacrylate-α-olefin anti-wax agent.
[0046] Example 4:
[0047] The structural formula of the nano-carbon ball-methacrylate-α-olefin anti-wax agent in this embodiment is the same as that in Example 1.
[0048] The nano-carbon sphere-methacrylate-α-olefin anti-wax agent of this embodiment is obtained through the following steps:
[0049] First, weigh 4g of glucose and dissolve it in 40mL of deionized water. Then, heat it at 180℃ for 5 hours. Wash the prepared product with deionized water until the pH is neutral. Finally, dry it in a forced-air drying oven to obtain nano-carbon spheres with hydroxyl groups on the surface.
[0050] Dissolve 0.5g of the carbon nanospheres and 0.5g of methacryloyl chloride in 30mL of N,N-dimethylformamide, then add 0.5g of anhydrous sodium carbonate, react at 50℃ for 4h, wash with deionized water, and dry to obtain carbon nanosphere-methacrylate.
[0051] 0.5g of nano-carbon spheres-methacrylate and 20g of α-hexadecene were dissolved in toluene, and 2g of azobisisobutyronitrile was added. The mixture was reacted at 110℃ for 8 hours under argon atmosphere. The product was washed several times with methanol and finally dried at 60℃ in a vacuum drying oven to obtain nano-carbon spheres-methacrylate-α-olefin anti-wax agent.
[0052] Example 5:
[0053] The structural formula of the nano-carbon ball-methacrylate-α-olefin anti-wax agent in this embodiment is the same as that in Example 1.
[0054] The nano-carbon sphere-methacrylate-α-olefin anti-wax agent of this embodiment is obtained through the following steps:
[0055] First, weigh 4g of glucose and dissolve it in 40mL of deionized water. Then, heat the solution at 190℃ for 5 hours. Wash the prepared product with deionized water until the pH is neutral. Finally, dry the product in a forced-air drying oven to obtain carbon nanospheres with hydroxyl groups on the surface.
[0056] Dissolve 0.5g of the carbon nanospheres and 0.5g of methacryloyl chloride in 30mL of N,N-dimethylformamide, then add 0.5g of anhydrous sodium carbonate, react at 50℃ for 4h, wash with deionized water, and dry to obtain carbon nanosphere-methacrylate.
[0057] 0.5g of nano-carbon spheres-methacrylate and 20g of α-hexadecene were dissolved in trimethylbenzene, and 2g of dicumyl peroxide was added. The mixture was reacted at 140℃ for 8 hours under argon atmosphere. The product was washed several times with methanol and finally dried at 60℃ in a vacuum drying oven to obtain nano-carbon spheres-methacrylate-α-olefin anti-wax agent.
[0058] This invention pertains to a pharmaceutical preparation. The results of indoor testing are as follows:
[0059] The nano-carbon spheres-methacrylate-α-olefin prepared in Examples 1-5 were used as crude oil anti-wax agents. A 10% anti-wax agent solution was prepared using xylene as a solvent. The anti-wax agent solution was added to crude oil, and different concentrations of dosage were obtained by adjusting the amount added. Four groups of experiments were conducted with dosages of 500 ppm, 1000 ppm, 1500 ppm, and 2000 ppm to characterize the anti-wax performance in crude oil. The results were compared with commercially available products and are shown in Table 1. The evaluation of the anti-wax agent was carried out in accordance with the provisions of standard SYT6300-2009 "Technical Conditions for Anti-wax Agents for Oil Production".
[0060] Table 1 shows the anti-wax properties of the nanocarbon spheres-methacrylate-α-olefins prepared in Examples 1-5 in crude oil.
[0061]
[0062]
[0063] As shown in Table 1, the anti-wax agent of the present invention can effectively inhibit the growth and aggregation of paraffin crystals, has good dispersibility for paraffin, and achieves a good anti-wax effect.
[0064] The nano-carbon spheres-methacrylate-α-olefin prepared in Examples 1-5 were used as natural gas anti-wax agents to characterize their anti-wax performance in natural gas condensate. A 10% anti-wax agent solution was prepared by mixing nano-carbon spheres-methacrylate-α-olefin with xylene. This solution was added to the natural gas condensate, cooled to -18°C, and maintained for 2 hours. The flow state of the condensate was observed. Different dosages were obtained by adjusting the dosage. Four sets of experiments were conducted with dosages of 0 ppm, 1000 ppm, 1500 ppm, and 2000 ppm. The results are shown in Table 2.
[0065] Table 2 shows the anti-wax properties of the nano-carbon spheres-methacrylate-α-olefins prepared in Examples 1-5 in natural gas condensate.
[0066]
[0067] As shown in Table 2, this invention effectively inhibits the precipitation of paraffin in natural gas condensate and prevents the aggregation and growth of wax crystals, thus ensuring that the condensate does not solidify at low temperatures and maintains good fluidity. This is because, on the one hand, the long alkyl chains of the anti-wax agent can co-crystallize with paraffin molecules, hindering the stacking of paraffin molecules; on the other hand, the nano-carbon spheres in the anti-wax agent can provide nucleation sites for paraffin molecules, inhibiting their aggregation. The raw materials of this invention are readily available, the preparation process is simple, and the prepared anti-wax agent has the characteristics of low environmental pollution, small dosage, wide applicability, and high anti-wax rate.
Claims
1. A nanocarbon sphere-methacrylate-a-olefin anti-waxing agent, characterized in that: The nano-carbon sphere-methacrylate-alpha-olefin wax inhibitor is used in waxy oil or diesel or natural gas condensate oil, and has the structural formula: R is an alkyl chain; the surface of the nano-carbon sphere contains hydroxyl groups.
2. The nanocarbon sphere-methacrylate-a-olefin wax inhibitor according to claim 1, characterized in that: The diameter of the nano-carbon sphere is less than or equal to 150 nm.
3. A process for the preparation of the nanocarbon sphere-methacrylate-α-olefin paraffin inhibitor as claimed in claim 2, characterized in that The method comprises the following steps: In step one, the nano-carbon sphere containing hydroxyl groups is prepared by using glucose through a hydrothermal method, the glucose is added into deionized water and mixed uniformly, and then transferred into a hydrothermal kettle, heated to 140-190 DEG C and reacted for 5-8 h, washed with deionized water and dried to obtain the nano-carbon sphere containing hydroxyl groups; In step two, the nano-carbon sphere containing hydroxyl groups and methacryloyl chloride are subjected to esterification to obtain the nano-carbon sphere-methacrylate; In step three, the nano-carbon sphere-methacrylate and alpha-olefin are polymerized to obtain the nano-carbon sphere-methacrylate-alpha-olefin wax inhibitor.
4. The method for preparing the carbon nanosphere-methacrylate-α-olefin paraffin inhibitor according to claim 3, characterized in that: The concentration of the glucose and the deionized water in step one is 0.1 g / mL.
5. The method for preparing the carbon nanosphere-methacrylate-α-olefin paraffin inhibitor according to claim 4, characterized in that: In step two, the following is specifically performed: The nano-carbon sphere containing hydroxyl groups and the methacryloyl chloride are added into solvent I, the mass ratio of the nano-carbon sphere containing hydroxyl groups and the methacryloyl chloride is 1:1-10, mixed uniformly, then a catalyst is added, the molar ratio of the catalyst and the methacryloyl chloride is 1.0-1.1:1, heated to 40-50 DEG C, and esterification is performed for 5-10 h to obtain the nano-carbon sphere-methacrylate.
6. The method for preparing the nanocarbon sphere-methacrylate-α-olefin paraffin inhibitor according to claim 5, characterized in that: In step three, the following is specifically performed: The nano-carbon sphere-methacrylate and the alpha-olefin are added into solvent II, the mass ratio of the nano-carbon sphere-methacrylate and the alpha-olefin is 0.05-2:100, mixed uniformly, then an initiator is added, the amount of the initiator is 0.01%-1% of the total mass of the reactants, heated to 110-150 DEG C under an argon atmosphere, and polymerization is performed for 8-10 h to obtain the nano-carbon sphere-methacrylate-alpha-olefin wax inhibitor.
7. The preparation method of the nano-carbon sphere-methacrylate-α-olefin anti-wax agent according to claim 6, characterized in that: The solvent II is at least one of toluene, xylene, trimethylbenzene and C9 aromatic hydrocarbon.
8. The preparation method of the nano-carbon sphere-methacrylate-α-olefin anti-wax agent according to claim 7, characterized in that: The initiator is at least one of azobis isobutyronitrile, dicumyl peroxide, benzoyl peroxide and tert-butyl peroxybenzoate.