Carbon nanosphere-methacrylate-alpha-olefin paraffin inhibitor and preparation method thereof

Abstract

The invention relates to a carbon nanosphere-methacrylate-alpha-olefin paraffin inhibitor and a preparation method thereof, the carbon nanosphere-methacrylate-alpha-olefin paraffin inhibitor is high-branching-degree polyolefin and is used in wax-containing petroleum or diesel oil or natural gas condensate, and the surface of the carbon nanosphere contains hydroxyl; the preparation method of the nano carbon sphere-methacrylate-alpha-olefin paraffin inhibitor comprises the following steps: preparing nano carbon spheres with hydroxyl groups on the surfaces by using glucose through a hydrothermal method; the preparation method comprises the following steps: carrying out esterification reaction on hydroxyl-containing carbon nanospheres and methacryloyl chloride to obtain carbon nanosphere-methacrylate; and polymerizing the nano carbon sphere-methacrylate and alpha-olefin to obtain the nano carbon sphere-methacrylate-alpha-olefin paraffin inhibitor. The natural gas condensate paraffin inhibitor can effectively inhibit precipitation of paraffin in natural gas condensate and prevent aggregation and growth of wax crystals, and has the advantages of small dosage, high paraffin inhibition efficiency, no pollution and cheap and easily available raw materials.

Description

Technical Field:

[0001] The present invention relates to highly branched polyolefins, and specifically to a nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor and a preparation method thereof. Background Art:

[0002] Due to their unique properties, high molecular 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 mainly prevent the deposition of wax in crude oil by co-crystallizing or co-precipitating with wax crystal molecules through hydrocarbon chains, while the polar groups on the molecular structure repel each other. Although these high molecular 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 a large dosage.

[0003] Nanoparticles are a type of composite material with a nanoscale size, having unique sizes and ultra-high surface adsorption properties, which can change the morphology of wax crystals and achieve a paraffin inhibition effect. After adding nanoparticles to crude oil, the size of wax crystals decreases and the aggregation behavior is hindered, thereby reducing the wax precipitation point of crude oil. The dispersion of single nano materials in crude oil is poor, and organic modification can improve their dispersion effect in crude oil. When nanoparticles and surfactants are used in combination, the paraffin inhibition effect is better than that of single use. Summary of the Invention:

[0004] An object of the present invention is to provide a nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor, which is used to solve the technical problems such as high raw material cost, lack of environmental friendliness and poor paraffin inhibition performance in the prior art; another object of the present invention is to provide a preparation method of this nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor.

[0005] The technical solution adopted by the present invention to solve its technical problems is: this nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor is a highly branched polyolefin, which is used in waxy petroleum or diesel or natural gas condensate oil, and its structural formula is:

[0006]

[0007] Wherein R is an alkyl chain.

[0008] In the above solution, the surface of the nano-carbon sphere contains hydroxyl groups.

[0009] In the above solution, the diameter of the nano-carbon sphere is less than or equal to 150 nm.

[0010] The preparation method of the above nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor includes the following steps:

[0011] Step 1: Prepare nanocarbon spheres with hydroxyl groups on the surface by hydrothermal method using glucose. Add glucose to deionized water, mix evenly, then transfer it to a hydrothermal reactor, heat it to 140 - 190 °C and react for 5 - 8 h. After washing with deionized water and drying, nanocarbon spheres containing hydroxyl groups are obtained;

[0012] Step 2: Carry out an esterification reaction between the nanocarbon spheres containing hydroxyl groups and methacryloyl chloride to obtain nanocarbon sphere - methacrylate;

[0013] Step 3: Polymerize the nanocarbon sphere - methacrylate and α - olefin to obtain a paraffin inhibitor of nanocarbon sphere - methacrylate - α - olefin.

[0014] In the above - mentioned step 1, the concentration of glucose and deionized water is 0.1 g / mL.

[0015] Specifically, step 2 in the above - mentioned solution is as follows:

[0016] Add the nanocarbon spheres containing hydroxyl groups and methacryloyl chloride into solvent I. The mass ratio of the nanocarbon spheres containing hydroxyl groups to methacryloyl chloride is 1:1 - 10. Mix evenly, then add a catalyst. The molar ratio of the catalyst to methacryloyl chloride is 1.0 - 1.1:1. Heat it to 40 - 50 °C and carry out an esterification reaction for 5 - 10 h to obtain nanocarbon sphere - methacrylate.

[0017] In the above - mentioned solution, the catalyst is one or two of anhydrous potassium carbonate and anhydrous sodium carbonate; solvent I is N,N - dimethylformamide or tetrahydrofuran.

[0018] Specifically, step 3 in the above - mentioned solution is as follows:

[0019] Add the nanocarbon sphere - methacrylate and α - olefin into solvent II. The mass ratio of the nanocarbon sphere - methacrylate to α - olefin is 0.05 - 2:100. Mix evenly, then add an initiator. The addition amount of the initiator is 0.01% - 1% of the total mass of the reactants. Heat it to 110 - 150 °C under an argon atmosphere and carry out a polymerization reaction for 8 - 10 h to obtain a paraffin inhibitor of nanocarbon sphere - methacrylate - α - olefin.

[0020] In the above - mentioned solution, solvent II is at least one of toluene, xylene, trimethylbenzene and C9 aromatic hydrocarbons.

[0021] In the above - mentioned solution, the initiator is at least one of azobisisobutyronitrile, di - isopropyl peroxide, benzoyl peroxide and tert - butyl peroxybenzoate.

[0022] Beneficial effects:

[0023] 1. The present invention obtains a novel nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor by grafting and polymerizing green and environmentally friendly nano-carbon spheres with organic substances. This novel nano-particle-polymer paraffin inhibitor is a highly branched polyolefin, and mainly achieves the paraffin inhibition effect through eutectic action and heterogeneous nucleation. Compared with traditional paraffin inhibitors, the present invention has the advantages of small dosage, high paraffin inhibition efficiency, no pollution, cheap and easily available raw materials, and less pollution in the paraffin inhibition treatment of crude oil, diesel, and condensate oil, solving the technical problems such as high raw material cost, insufficient environmental protection, and poor paraffin inhibition performance in the prior art.

[0024] 2. The present invention can effectively inhibit the precipitation of paraffin in natural gas condensate oil and prevent the aggregation and growth of wax crystals, thereby ensuring that the condensate oil will not solidify under low-temperature conditions and maintaining good fluidity. Specific embodiments:

[0025] The following further describes the present invention:

[0026] Example 1:

[0027] This nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor is a highly branched polyolefin and is used for the paraffin inhibition treatment of waxy petroleum, diesel, or natural gas condensate oil. Its structural formula is:

[0028]

[0029] Wherein R is an alkyl chain.

[0030] This nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor is obtained through the following steps:

[0031] First, weigh 4 g of glucose and dissolve it in 40 mL of deionized water. Then, carry out hydrothermal treatment at 190 °C for 5 h. Wash the prepared product with deionized water until the pH is neutral, and then dry it in a blast drying oven to obtain nano-carbon spheres with hydroxyl groups on the surface.

[0032] Dissolve 0.5 g of the nano-carbon spheres and 0.5 g of methacryloyl chloride in 30 mL of N,N-dimethylformamide, and then add 0.5 g of anhydrous sodium carbonate. React at 50 °C for 4 h, wash with deionized water, and dry to prepare nano-carbon sphere-methacrylate.

[0033] Dissolve 0.5 g of nano-carbon sphere-methacrylate and 20 g of α-hexadecene in toluene, add 2 g of benzoyl peroxide, react at 110 °C for 10 h in an argon atmosphere, wash the product with methanol several times, and finally dry it in a vacuum drying oven at 60 °C to obtain the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor.

[0034] Example 2:

[0035] In this example, the structural formula of the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor is the same as that in Example 1.

[0036] The nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor in this example is obtained through the following steps:

[0037] First, weigh 4 g of glucose and dissolve it in 40 mL of deionized water. Then, hydrothermal react at 190 °C for 5 h. Wash the prepared product with deionized water until the pH is neutral, and then dry it in a blast drying oven to obtain nano-carbon spheres with hydroxyl groups on the surface.

[0038] Dissolve 0.5 g of the nano-carbon spheres and 0.5 g of methacryloyl chloride in 30 mL of N,N-dimethylformamide, add 0.5 g of anhydrous potassium carbonate, react at 50 °C for 4 h, wash with deionized water, and dry to prepare nano-carbon sphere-methacrylate.

[0039] Dissolve 0.5 g of nano-carbon sphere-methacrylate and 20 g of α-hexadecene in toluene, add 2 g of benzoyl peroxide, react at 110 °C for 10 h in an argon atmosphere, wash the product with methanol several times, and finally dry it in a vacuum drying oven at 60 °C to obtain the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor.

[0040] Example 3:

[0041] In this example, the structural formula of the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor is the same as that in Example 1.

[0042] The nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor in this example is obtained through the following steps:

[0043] First, weigh 4 g of glucose and dissolve it in 40 mL of deionized water. Then, hydrothermal react at 190 °C for 5 h. Wash the prepared product with deionized water until the pH is neutral, and then dry it in a blast drying oven to obtain nano-carbon spheres with hydroxyl groups on the surface.

[0044] Dissolve 0.5 g of the nano-carbon spheres and 0.5 g of methacryloyl chloride in 30 mL of N,N-dimethylformamide, add 0.5 g of anhydrous sodium carbonate, react at 50 °C for 4 h, wash with deionized water, and dry to prepare nano-carbon sphere-methacrylate.

[0045] Dissolve 0.5 g of nano-carbon sphere-methacrylate and 20 g of α-dodecene in xylene, add 5 g of benzoyl peroxide, react at 110 °C for 10 h in an argon atmosphere, wash the product with methanol several times, and finally dry it in a vacuum drying oven at 60 °C to obtain the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor.

[0046] Example 4:

[0047] In this example, the structural formula of the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor is the same as that in Example 1.

[0048] The nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor in this example is obtained through the following steps:

[0049] First, weigh 4 g of glucose and dissolve it in 40 mL of deionized water. Then, hydrothermal react at 180 °C for 5 h. Wash the prepared product with deionized water until the pH is neutral, and then dry it in a blast drying oven to obtain nano-carbon spheres with hydroxyl groups on the surface.

[0050] Dissolve 0.5 g of the nano-carbon spheres and 0.5 g of methacryloyl chloride in 30 mL of N,N-dimethylformamide. Then add 0.5 g of anhydrous sodium carbonate and react at 50 °C for 4 h. Wash with deionized water and dry to prepare nano-carbon sphere-methacrylate.

[0051] Dissolve 0.5 g of nano-carbon sphere-methacrylate and 20 g of α-hexadecene in toluene. Add 2 g of azobisisobutyronitrile and react at 110 °C for 8 h in an argon atmosphere. Wash the product with methanol several times, and finally dry it in a vacuum drying oven at 60 °C to obtain the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor.

[0052] Example 5:

[0053] In this example, the structural formula of the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor is the same as that in Example 1.

[0054] The nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor in this example is obtained through the following steps:

[0055] First, weigh 4 g of glucose and dissolve it in 40 mL of deionized water. Then, hydrothermal react at 190 °C for 5 h. Wash the prepared product with deionized water until the pH is neutral, and then dry it in a blast drying oven to obtain nano-carbon spheres with hydroxyl groups on the surface.

[0056] Dissolve 0.5 g of the nano-carbon spheres and 0.5 g of methacryloyl chloride in 30 mL of N,N-dimethylformamide. Then add 0.5 g of anhydrous sodium carbonate and react at 50 °C for 4 h. Wash with deionized water and dry to prepare nano-carbon sphere-methacrylate.

[0057] Dissolve 0.5 g of nano-carbon sphere-methacrylate and 20 g of α-hexadecene in mesitylene. Add 2 g of diisopropylbenzene peroxide and react at 140 °C for 8 h in an argon atmosphere. Wash the product with methanol several times, and finally dry it in a vacuum drying oven at 60 °C to obtain the nano-carbon sphere-methacrylate-α-olefin paraffin inhibitor.

[0058] The present invention is a pharmaceutical invention, and the test results indoors are as follows:

[0059] The nano-carbon spheres-methacrylate-α-olefin prepared in Examples 1-5 were used as paraffin inhibitors for crude oil. Using xylene as a solvent, a paraffin inhibitor solution with a concentration of 10% was prepared. The paraffin inhibitor solution was added to the crude oil, and different dosages were obtained by adjusting the addition amount. Four groups of experiments with dosages of 500 ppm, 1000 ppm, 1500 ppm, and 2000 ppm were conducted to characterize the paraffin inhibition performance in the crude oil; a comparison was made with commercially available products, and the test results are shown in Table 1; the evaluation of the paraffin inhibitor was carried out in accordance with the regulations in the standard SYT6300-2009 "Technical Conditions for Paraffin Removing and Inhibiting Agents for Oil Production".

[0060] Table 1 shows the paraffin inhibition performance of the nano-carbon spheres-methacrylate-α-olefin prepared in Examples 1-5 in crude oil

[0061]

[0062]

[0063] As can be seen from Table 1, the paraffin inhibitor of the present invention can effectively inhibit the growth and aggregation of paraffin crystals, has good dispersibility for paraffin, and achieves a good paraffin inhibition effect.

[0064] The nano-carbon spheres-methacrylate-α-olefin prepared in Examples 1-5 were used as paraffin inhibitors for natural gas, and the paraffin inhibition performance in natural gas condensate oil was characterized. The nano-carbon spheres-methacrylate-α-olefin was mixed with xylene to prepare a paraffin inhibitor solution with a concentration of 10%. The paraffin inhibitor solution was added to the natural gas condensate oil, cooled to -18°C, and maintained for 2 hours. The flow state of the condensate oil was observed, and different dosages were obtained by adjusting the addition amount. Four groups of experiments with dosages of 0 ppm, 1000 ppm, 1500 ppm, and 2000 ppm were conducted, and the results are shown in Table 2.

[0065] Table 2 shows the paraffin inhibition performance of the nano-carbon spheres-methacrylate-α-olefin prepared in Examples 1-5 in natural gas condensate oil

[0066]

[0067] As can be seen from Table 2, the present invention can effectively inhibit the precipitation of paraffin in natural gas condensate oil and prevent the aggregation and growth of wax crystals, thereby ensuring that the condensate oil does not solidify under low-temperature conditions and maintaining good fluidity. This is because on the one hand, the long alkyl chains of the paraffin inhibitor can form eutectic with paraffin molecules and hinder the stacking of paraffin molecules, and on the other hand, the nano-carbon spheres in the paraffin inhibitor can provide nucleation sites for paraffin molecules and inhibit the aggregation of paraffin molecules. The raw materials of the present invention are easily available, the preparation process is simple, and the prepared paraffin inhibitor has the characteristics of less environmental pollution, small dosage, wide application range, and high paraffin inhibition rate.

Claims

1. A nano carbon ball-methacrylate-α-olefin wax inhibitor, characterized in that: This nano carbon ball-methacrylate-α-olefin wax inhibitor is a highly branched polyolefin, which is used in waxy petroleum, diesel or natural gas condensate, and has the structural formula: R is an alkyl chain; the surface of the nanocarbon sphere contains hydroxyl groups.

2. The nano carbon ball-methacrylate-α-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 method for preparing the nano carbon ball-methacrylate-α-olefin wax inhibitor according to claim 2, characterized in that The steps include: Step 1: Prepare nano-carbon spheres containing hydroxyl groups on the surface by using glucose through a hydrothermal method. Glucose is added to deionized water, mixed evenly, and then transferred to a hydrothermal kettle, heated to 140-190° C. for reaction for 5-8 hours, washed with deionized water and dried to obtain nano-carbon spheres containing hydroxyl groups; Step 2: esterifying the nano-carbon spheres containing hydroxyl groups with methacryloyl chloride to obtain nano-carbon sphere-methacrylate; Step 3: polymerize the nano-carbon sphere-methacrylate and α-olefin to obtain the nano-carbon sphere-methacrylate-α-olefin anti-wax agent.

4. The method for preparing the nano carbon ball-methacrylate-α-olefin wax inhibitor according to claim 3, characterized in that: The concentration of glucose and deionized water in step 1 is 0.1 g / mL.

5. The method for preparing the nano carbon ball-methacrylate-α-olefin wax inhibitor according to claim 4, characterized in that: The step 2 is specifically as follows: Add hydroxyl-containing nano-carbon spheres and methacryloyl chloride into solvent I, wherein the mass ratio of the hydroxyl-containing nano-carbon spheres to methacryloyl chloride is 1:1-10, mix them evenly, then add a catalyst, wherein the molar ratio of the catalyst to methacryloyl chloride is 1.0-1.1:1, heat to 40-50°C, and perform esterification reaction for 5-10h to obtain nano-carbon sphere-methacrylate.

6. The method for preparing the nano carbon sphere-methacrylate-α-olefin wax inhibitor according to claim 5, characterized in that: The catalyst is one or two of anhydrous potassium carbonate and anhydrous sodium carbonate; the solvent I is N,N-dimethylformamide and tetrahydrofuran.

7. The method for preparing the nano carbon ball-methacrylate-α-olefin wax inhibitor according to claim 6, characterized in that: The step three is specifically as follows: Add nano-carbon sphere-methacrylate and α-olefin into solvent II, the mass ratio of nano-carbon sphere-methacrylate and α-olefin is 0.05-2:100, mix evenly, then add initiator, the amount of initiator added is 0.01%-1% of the total mass of the reactants, heat to 110-150°C in an argon environment, and perform polymerization reaction for 8-10 hours to obtain nano-carbon sphere-methacrylate-α-olefin wax inhibitor.

8. The method for preparing the nano carbon sphere-methacrylate-α-olefin wax inhibitor according to claim 7, characterized in that: The solvent II is at least one of toluene, xylene, trimethylbenzene and C9 aromatic hydrocarbons.

9. The method for preparing the nano carbon ball-methacrylate-α-olefin wax inhibitor according to claim 8, characterized in that: The initiator is at least one of azobisisobutyl cyanide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.

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