Water-soluble viscosity reducer for deep thickened oil and preparation method of water-soluble viscosity reducer

Abstract

The invention relates to the technical field of thick oil viscosity reduction, and discloses a water-soluble viscosity reducer for deep thick oil and a preparation method thereof.The water-soluble viscosity reducer for the deep thick oil is obtained by adding acrylamide, hexadecyl trimethyl ammonium bromide and a quaternary ammonium salt polymer into a stirrer and stirring the materials. The quaternary ammonium salt-based polymer contains a large number of benzene ring structures, molecules containing the benzene ring structures can better permeate into gaps of an asphaltene accumulation structure to damage the stable asphaltene accumulation structure and loosen the asphaltene accumulation structure, so that the effect of reducing the viscosity of the heavy oil is achieved, and benzene rings have better stability and keep stable in a high-temperature state; the contained quaternary ammonium salt group can improve the flowing property of the thick oil and improve the crude oil recovery rate; and after the 4-aminophenylboronic acid reacts with the intermediate 1, the substitution degree of the quaternary ammonium salt is improved, so that the effect of improving the fluidity of the thick oil is better.

Description

Technical Field

[0001] The invention relates to the technical field of heavy oil viscosity reduction, in particular to a water-soluble viscosity reducer for deep-layer heavy oil and a preparation method thereof. Background Art

[0002] Heavy oil contains a large amount of heavy components such as asphaltene and colloid, which have the characteristics of high viscosity, high density, poor fluidity and difficulty in mining. At present, surfactants are used to emulsify and reduce the viscosity of heavy oil, but their poor temperature resistance limits their application. For example, the Chinese invention patent application with publication number CN115160508A discloses a polycarboxylate viscosity reducer containing a polyether segment and its preparation method and application. The invention is carried out under normal pressure and low temperature reaction, is easy to operate and control, and has a short reaction time. The product has good water solubility, but its high temperature resistance effect needs to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a water-soluble viscosity reducer for deep-layer heavy oil and a preparation method thereof, which has good temperature resistance and viscosity reduction effects.

[0004] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: a water-soluble viscosity reducer for deep heavy oil, comprising the following components by weight: 40-50 parts by weight of acrylamide, 2-6 parts by weight of hexadecyltrimethylammonium bromide, and 3-5 parts by weight of a quaternary ammonium salt-based polymer.

[0005] Furthermore, the preparation method of the quaternary ammonium salt-based polymer is: Step 1: Add 3.905-3.908 mL of dimethylaminopropyl acrylamide to 45-50 mL of anhydrous acetone, and then add 3-chloro-1-propanol thereto, stir and react at 51-55° C., and after reaction, remove the solvent by rotary evaporation, filter, wash, and dry to obtain intermediate 1; Step 2: Add intermediate 1 and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir to dissolve, continue to add anhydrous magnesium sulfate, react at 65-80° C. for 5-6 hours, wash and dry after completion to obtain an olefinated boron-containing quaternary ammonium salt; Step 3: Add olefinated boron-containing quaternary ammonium salt and pyridine catalyst to N,N-dimethylformamide solvent, stir and dissolve, then add 4-vinylbenzoyl chloride, react at 80-90°C for 4-6h, and then distill under reduced pressure and wash to obtain styryl boron-containing quaternary ammonium salt; Step 4: Add diethanol acrylamide, styrene-based boron-containing quaternary ammonium salt, and N-vinyl pyrrolidone into 50-60 mL of deionized water, dissolve, introduce nitrogen for 30-35 minutes under stirring, then add azobisisobutylamidine hydrochloride, stir and react at 56-70°C for 8-10 hours, wash and filter after completion to obtain a quaternary ammonium salt-based polymer.

[0006] Furthermore, the amount of 3-chloro-1-propanol used in step 1 is 6.71-6.75 mL.

[0007] Furthermore, the reaction time in step 1 is 10-13h.

[0008] Furthermore, in the step 2, the usage ratio of the intermediate 1, 4-aminophenylboric acid and anhydrous magnesium sulfate is 1.22-1.35 g: 0.94-1 g: 0.031-0.034 g.

[0009] Furthermore, in the step three, the usage ratio of the olefinated boron-containing quaternary ammonium salt, the pyridine catalyst, and the 4-vinylbenzoyl chloride is 1 g: 0.02-0.024 g: 0.92-1.13 g.

[0010] Furthermore, in the step 4, the usage ratio of diethanol acrylamide, styrene-based boron-containing quaternary ammonium salt, N-vinyl pyrrolidone, and azobisisobutylamidine hydrochloride is 1.3-1.44 g: 1 g: 0.82-1 g: 0.03-0.04 g.

[0011] Furthermore, the preparation method of the water-soluble viscosity reducer for deep heavy oil is: adding acrylamide, hexadecyltrimethylammonium bromide and quaternary ammonium salt-based polymer into a stirrer, stirring for 5-10 minutes, and obtaining the water-soluble viscosity reducer for deep heavy oil after stirring.

[0012] 3. Beneficial technical effects The invention adds acrylamide, hexadecyltrimethylammonium bromide and quaternary ammonium salt-based polymer into a stirrer and stirs to obtain a water-soluble viscosity reducer for deep thick oil.

[0013] The tertiary amine group in dimethylaminopropyl acrylamide reacts with the chlorine in 3-chloro-1-propanol to generate a quaternary ammonium salt, and an olefinic group and a hydroxyl group are introduced. The hydroxyl group further reacts with the boronic acid group in 4-aminophenylboronic acid to undergo an esterification reaction, and an amine group is introduced. The tertiary amine group is further reacted with the acyl chloride in 4-vinylbenzoyl chloride to introduce an olefinic group to obtain a styrene-based boron-containing quaternary ammonium salt, and finally, the quaternary ammonium salt-based polymer is obtained by polymerization with diethanol acrylamide and N-vinyl pyrrolidone.

[0014] The quaternary ammonium salt-based polymer contains a large number of benzene ring structures. The molecules containing the benzene ring structure can better penetrate into the gaps of the asphaltene stacking structure, destroy the stable stacking structure of the asphaltene, and make it loose, thereby achieving the effect of reducing the viscosity of the heavy oil. The benzene ring has good stability, so that it remains stable under high temperature conditions; the quaternary ammonium salt group contained therein can improve the flow properties of the heavy oil and increase the crude oil recovery rate; and after the reaction of 4-aminophenylboronic acid and intermediate 1, the substitution degree of the quaternary ammonium salt is increased, so that the effect of improving the flow properties of the heavy oil is better. The styrene-based boron-containing quaternary ammonium salt contains a triene structure, which will polymerize with diethanol acrylamide and N-vinyl pyrrolidone to cross-link to obtain a quaternary ammonium salt-based polymer with good high temperature resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 is the reaction formula of intermediate 1. DETAILED DESCRIPTION

[0016] At 0°C, add 300 mL of dichloromethane, 19 mmol of diethanolamine, 67 mmol of pyridine and 57 mmol of acryloyl chloride to a flask, react for 15 h in a nitrogen atmosphere, concentrate the solution, add 30 mL of methanol and 20 mL of a saturated sodium carbonate solution, stir at room temperature for 3 h, then add dichloromethane and water for extraction, and after the reaction of the extract product, separate it by column chromatography, using a solution of chloroform and methanol in a volume ratio of 10:1 as an eluent to obtain diethanolacrylamide. Example 1

[0017] Step 1: Add 3.905 mL of dimethylaminopropyl acrylamide to 45 mL of anhydrous acetone, and then add 6.71 mL of 3-chloro-1-propanol, and stir the reaction at 51°C for 10 h. After the reaction, evaporate the solvent by rotary evaporation, filter, wash, and dry to obtain intermediate 1; Step 2: Add 1.22 g of intermediate 1 and 0.94 g of 4-aminophenylboronic acid to 30 mL of tetrahydrofuran solvent, stir to dissolve, continue to add 0.031 g of anhydrous magnesium sulfate, react at 65° C. for 5 h, wash and dry after completion to obtain an olefinated boron-containing quaternary ammonium salt; Step 3: Add 1 g of olefinic boron-containing quaternary ammonium salt and 0.02 g of pyridine catalyst to 25 mL of N,N-dimethylformamide solvent, stir and dissolve, then add 0.92 g of 4-vinylbenzoyl chloride, react at 80°C for 4 h, and then perform vacuum distillation and washing to obtain styryl boron-containing quaternary ammonium salt; Step 4: Add 1.3 g of diethanol acrylamide, 1 g of styrene-based boron-containing quaternary ammonium salt, and 0.82 g of N-vinyl pyrrolidone into 50 mL of deionized water, dissolve, introduce nitrogen gas for 30 min under stirring, then add 0.03 g of azobisisobutylamidine hydrochloride, stir and react at 56 ° C for 8 h, wash and filter after completion to obtain a quaternary ammonium salt-based polymer; Step 5: Add 40 parts by weight of acrylamide, 2 parts by weight of hexadecyltrimethylammonium bromide and 3 parts by weight of quaternary ammonium salt-based polymer into a stirrer and stir for 5 minutes to obtain a water-soluble viscosity reducer for deep heavy oil. Example 2

[0018] Step 1: Add 3.908 mL of dimethylaminopropyl acrylamide to 50 mL of anhydrous acetone, and then add 6.75 mL of 3-chloro-1-propanol, and stir the reaction at 55°C for 13 hours. After the reaction, remove the solvent by rotary evaporation, filter, wash, and dry to obtain intermediate 1; Step 2: Add 1.35 g of intermediate 1 and 1 g of 4-aminophenylboronic acid to 50 mL of tetrahydrofuran solvent, stir to dissolve, continue to add 0.034 g of anhydrous magnesium sulfate, react at 80° C. for 6 h, wash after completion, and dry to obtain an olefinated boron-containing quaternary ammonium salt; Step 3: Add 1 g of olefinic boron-containing quaternary ammonium salt and 0.024 g of pyridine catalyst to 35 mL of N,N-dimethylformamide solvent, stir and dissolve, then add 1.13 g of 4-vinylbenzoyl chloride, react at 90°C for 6 h, and then distill under reduced pressure and wash to obtain styryl boron-containing quaternary ammonium salt; Step 4: Add 1.44 g of diethanol acrylamide, 1 g of styrene-based boron-containing quaternary ammonium salt, and 1 g of N-vinyl pyrrolidone into 60 mL of deionized water, dissolve, introduce nitrogen gas for 35 min under stirring, then add 0.04 g of azobisisobutylamidine hydrochloride, stir and react at 70°C for 10 h, wash and filter after completion to obtain a quaternary ammonium salt-based polymer; Step 5: Add 50 parts by weight of acrylamide, 6 parts by weight of hexadecyltrimethylammonium bromide and 5 parts by weight of quaternary ammonium salt-based polymer into a stirrer and stir for 10 minutes to obtain a water-soluble viscosity reducer for deep heavy oil. Example 3

[0019] Step 1: Add 3.906 mL of dimethylaminopropyl acrylamide to 47 mL of anhydrous acetone, and then add 6.73 mL of 3-chloro-1-propanol, and stir the reaction at 52°C for 12 h. After the reaction, remove the solvent by rotary evaporation, filter, wash, and dry to obtain intermediate 1; Step 2: Add 1.26 g of intermediate 1 and 0.97 g of 4-aminophenylboronic acid to 45 mL of tetrahydrofuran solvent, stir to dissolve, continue to add 0.032 g of anhydrous magnesium sulfate, react at 70° C. for 5 h, wash after completion, and dry to obtain an olefinated boron-containing quaternary ammonium salt; Step 3: Add 1 g of olefinic boron-containing quaternary ammonium salt and 0.021 g of pyridine catalyst to 30 mL of N,N-dimethylformamide solvent, stir and dissolve, then add 1.12 g of 4-vinylbenzoyl chloride, react at 85°C for 5 h, and then distill under reduced pressure and wash to obtain styryl boron-containing quaternary ammonium salt; Step 4: Add 1.42 g of diethanol acrylamide, 1 g of styrene-based boron-containing quaternary ammonium salt, and 0.94 g of N-vinyl pyrrolidone into 55 mL of deionized water, dissolve, introduce nitrogen gas for 32 min under stirring, then add 0.035 g of azobisisobutylamidine hydrochloride, stir and react at 58 ° C for 9 h, wash and filter after completion to obtain a quaternary ammonium salt-based polymer; Step 5: Add 45 parts by weight of acrylamide, 4 parts by weight of hexadecyltrimethylammonium bromide and 4 parts by weight of quaternary ammonium salt-based polymer into a stirrer and stir for 8 minutes to obtain a water-soluble viscosity reducer for deep heavy oil. Example 4

[0020] Step 1: Add 3.905 mL of dimethylaminopropyl acrylamide to 45 mL of anhydrous acetone, and then add 6.71 mL of 3-chloro-1-propanol, and stir the reaction at 51°C for 10 h. After the reaction, remove the solvent by rotary evaporation, filter, wash, and dry to obtain intermediate 1; Step 2: Add 1.22 g of intermediate 1 and 0.94 g of 4-aminophenylboronic acid to 30 mL of tetrahydrofuran solvent, stir to dissolve, continue to add 0.031 g of anhydrous magnesium sulfate, react at 65° C. for 5 h, wash and dry after completion to obtain an olefinated boron-containing quaternary ammonium salt; Step 3: Add 1 g of olefinic boron-containing quaternary ammonium salt and 0.024 g of pyridine catalyst to 35 mL of N,N-dimethylformamide solvent, stir and dissolve, then add 1.13 g of 4-vinylbenzoyl chloride, react at 90°C for 6 h, and then distill under reduced pressure and wash to obtain styryl boron-containing quaternary ammonium salt; Step 4: Add 1.44 g of diethanol acrylamide, 1 g of styrene-based boron-containing quaternary ammonium salt, and 1 g of N-vinyl pyrrolidone into 60 mL of deionized water, dissolve, introduce nitrogen gas for 35 min under stirring, then add 0.04 g of azobisisobutylamidine hydrochloride, stir and react at 70°C for 10 h, wash and filter after completion to obtain a quaternary ammonium salt-based polymer; Step 5: Add 45 parts by weight of acrylamide, 4 parts by weight of hexadecyltrimethylammonium bromide and 4 parts by weight of quaternary ammonium salt-based polymer into a stirrer and stir for 8 minutes to obtain a water-soluble viscosity reducer for deep heavy oil. Example 5

[0021] Step 1: Add 3.908 mL of dimethylaminopropyl acrylamide to 50 mL of anhydrous acetone, and then add 6.75 mL of 3-chloro-1-propanol, and stir the reaction at 55°C for 13 hours. After the reaction, remove the solvent by rotary evaporation, filter, wash, and dry to obtain intermediate 1; Step 2: Add 1.35 g of intermediate 1 and 1 g of 4-aminophenylboronic acid to 50 mL of tetrahydrofuran solvent, stir to dissolve, continue to add 0.034 g of anhydrous magnesium sulfate, react at 80° C. for 6 h, wash after completion, and dry to obtain an olefinated boron-containing quaternary ammonium salt; Step 3: Add 1 g of olefinic boron-containing quaternary ammonium salt and 0.021 g of pyridine catalyst to 30 mL of N,N-dimethylformamide solvent, stir and dissolve, then add 1.12 g of 4-vinylbenzoyl chloride, react at 85°C for 5 h, and then distill under reduced pressure and wash to obtain styryl boron-containing quaternary ammonium salt; Step 4: Add 1.42 g of diethanol acrylamide, 1 g of styrene-based boron-containing quaternary ammonium salt, and 0.94 g of N-vinyl pyrrolidone into 55 mL of deionized water, dissolve, introduce nitrogen gas for 32 min under stirring, then add 0.035 g of azobisisobutylamidine hydrochloride, stir and react at 58 ° C for 9 h, wash and filter after completion to obtain a quaternary ammonium salt-based polymer; Step 5: Add 40 parts by weight of acrylamide, 2 parts by weight of hexadecyltrimethylammonium bromide and 3 parts by weight of quaternary ammonium salt-based polymer into a stirrer and stir for 5 minutes to obtain a water-soluble viscosity reducer for deep heavy oil.

[0022] Comparative Example 1 Compared with Example 5, this comparative example differs in that a styrene-based boron-containing quaternary ammonium salt is used instead of a quaternary ammonium salt-based polymer.

[0023] Comparative Example 2 Compared with Example 5, this comparative example differs in that Intermediate 1 is used instead of the quaternary ammonium salt-based polymer.

[0024] The products prepared above (Examples 1-5 and Comparative Examples 1-2) were subjected to a simulated mineralization of 2× 10 5The solution with a mass concentration of 0.2% was prepared from formation water with a mass concentration of 0.1% mg / L. The solution was placed in a closed container and placed in a high-temperature thermostat at 150°C for 24 hours. Crude oil with a surface viscosity of 12000mPa·s was mixed with the viscosity reducer after high-temperature treatment. The mixing ratio of crude oil to viscosity reducer solution was 100mL:50mL. The measuring temperature was 50°C, the viscometer speed was 3rpm, and the viscosity was shown in Table 1.

[0025] Table 1: Viscosity reducer performance test.

[0026] project Viscosity (mPa·s) Example 1 82.4 Example 2 70.6 Example 3 83.4 Example 4 77.2 Example 5 75.4 Comparative Example 1 104.7 Comparative Example 2 106.5 It can be seen from Table 1 that Examples 1-5 of the present invention have better viscosity reduction effects than Comparative Examples 1-2.

[0027] Table 2: Viscosity reduction test.

[0028] project Viscosity reduction rate (%) Example 1 99.31 Example 2 99.41 Example 3 99.3 Example 4 99.35 Example 5 99.37 Comparative Example 1 99.12 Comparative Example 2 99.11 It can be seen from Table 2 that Examples 1-5 of the present invention have better viscosity reduction rates than Comparative Examples 1-2.

[0029] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well.

Claims

1. A water-soluble viscosity reducer for deep thick oil, characterized in that: The invention comprises the following components by weight: 40-50 parts by weight of acrylamide, 2-6 parts by weight of hexadecyltrimethylammonium bromide, and 3-5 parts by weight of quaternary ammonium salt-based polymer; The preparation method of the quaternary ammonium salt-based polymer is: Step 1: Add 3.905-3.908 mL of dimethylaminopropyl acrylamide to 45-50 mL of anhydrous acetone, and then add 3-chloro-1-propanol thereto, stir and react at 51-55° C., and after reaction, remove the solvent by rotary evaporation, filter, wash, and dry to obtain intermediate 1; Step 2: Add intermediate 1 and 4-aminophenylboronic acid to tetrahydrofuran solvent, stir to dissolve, continue to add anhydrous magnesium sulfate, react at 65-80° C. for 5-6 hours, wash and dry after completion to obtain an olefinated boron-containing quaternary ammonium salt; Step 3: Add olefinated boron-containing quaternary ammonium salt and pyridine catalyst to N,N-dimethylformamide solvent, stir and dissolve, then add 4-vinylbenzoyl chloride, react at 80-90°C for 4-6h, and then distill under reduced pressure and wash to obtain styryl boron-containing quaternary ammonium salt; Step 4: Add diethanol acrylamide, styrene-based boron-containing quaternary ammonium salt, and N-vinyl pyrrolidone into 50-60 mL of deionized water, dissolve, introduce nitrogen for 30-35 minutes under stirring, then add azobisisobutylamidine hydrochloride, stir and react at 56-70°C for 8-10 hours, wash and filter after completion to obtain a quaternary ammonium salt-based polymer.

2. The water-soluble viscosity reducer for deep thick oil according to claim 1, characterized in that: The amount of 3-chloro-1-propanol used in step 1 is 6.71-6.75 mL.

3. The water-soluble viscosity reducer for deep thick oil according to claim 1, characterized in that: The reaction time in step 1 is 10-13h.

4. The water-soluble viscosity reducer for deep thick oil according to claim 1, characterized in that: In the step 2, the usage ratio of the intermediate 1, 4-aminophenylboric acid, and anhydrous magnesium sulfate is 1.22-1.35 g: 0.94-1 g: 0.031-0.034 g.

5. The water-soluble viscosity reducer for deep thick oil according to claim 1, characterized in that: In the step 3, the usage ratio of the olefination boron-containing quaternary ammonium salt, the pyridine catalyst, and the 4-vinylbenzoyl chloride is 1 g: 0.02-0.024 g: 0.92-1.13 g.

6. The water-soluble viscosity reducer for deep thick oil according to claim 1, characterized in that: In the step 4, the usage ratio of diethanol acrylamide, styrene-based boron-containing quaternary ammonium salt, N-vinyl pyrrolidone, and azobisisobutylamidine hydrochloride is 1.3-1.44 g: 1 g: 0.82-1 g: 0.03-0.04 g.

7. A method for preparing a water-soluble viscosity reducer for deep thick oil according to any one of claims 1 to 6, characterized in that: The preparation method of the water-soluble viscosity reducer for deep-layer heavy oil comprises the following steps: adding acrylamide, hexadecyltrimethylammonium bromide and quaternary ammonium salt-based polymer into a stirrer, stirring for 5-10 minutes, and obtaining the water-soluble viscosity reducer for deep-layer heavy oil after stirring.

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