CN111100288A - Vegetable oil asphalt amide resin, preparation method thereof and application of vegetable oil asphalt amide resin as sand control agent - Google Patents
Vegetable oil asphalt amide resin, preparation method thereof and application of vegetable oil asphalt amide resin as sand control agent Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The invention discloses a vegetable oil asphalt amide resin, which is prepared by the following steps: carrying out salt forming reaction on the vegetable oil asphalt and diamine for 0.5-5 hours at 50-100 ℃ and 0.1-1.5 MPa under the protection of a catalyst and nitrogen; then heating to 180-210 ℃, and carrying out pre-polycondensation reaction for 0.5-10 hours under the pressure of 0-10 MPa; and carrying out reduced pressure reaction for 0.5-10 hours under the pressure of 0-minus 1.0MPa to obtain the product. The diamine is one or more selected from ethylenediamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or other polyethylene polyamine. The catalyst is selected from sodium hypophosphite, hypophosphorous acid and sulfurous acid. When the vegetable oil asphalt amide resin is applied as a sand control agent, a viscous film can be automatically separated out on the pore water-wet surface of a gravel filling layer to keep the stability of a filling sand body, and the problem of rapid reduction of the productivity of an oil well caused by blocking of the gravel filling layer by the migration of reservoir particles is effectively solved.
Description
Technical Field
The invention relates to a vegetable oil asphalt amide resin, a preparation method thereof and application thereof as a sand control agent, belonging to the field of waste resource utilization and the field of petroleum engineering.
Background
The vegetable oil asphalt is residue of vegetable oil residue after extraction of fatty acid by processes of acidification, hydrolysis, distillation and the like, and the appearance of the vegetable oil asphalt is similar to that of petroleum asphalt, so the vegetable oil asphalt is called as vegetable oil asphalt and can also be called as vegetable asphalt. The components of vegetable oil asphalt are fresh and reported, at present, the vegetable oil asphalt is mainly used as waste for combustion treatment, only Chinese patent patents ZL200610038172.3 and ZL200510094457.4 disclose a method for recovering phytosterol and phytosterol acetate from vegetable oil asphalt, a brand new process flow is formed, and the extraction of natural sterol is realized. China is a large oil processing country, and according to incomplete statistics, tens of thousands of tons of vegetable oil asphalt are produced every year in China, so that the development of waste utilization of the vegetable asphalt has important practical significance. The vegetable oil residue should contain unsaturated fatty acids in addition to a large amount of saturated fatty acids, which may form high boiling point poly fatty acids at high temperatures, which may be responsible for the formation of a large amount of vegetable pitch. The poly-fatty acid can form polyamide resin with polyamine, and is an excellent film-forming agent. Based on the thought, the invention provides the vegetable oil asphalt amide resin, the preparation method thereof and the application of the vegetable oil asphalt amide resin as the sand control agent, and the report of the vegetable oil asphalt amide resin, the preparation method thereof and the application of the vegetable oil asphalt amide resin as the sand control agent is not seen at present.
In unconsolidated sandstone reservoir production, one of the major problems often encountered is oil well sand production, which can cause a serious series of problems from the formation to the surface, such as: the capacity of the reservoir decreases rapidly, the sand filter pipe is blocked, the pump is blocked, solid pollutants on the ground are increased, and the like. The cationic polymer sand inhibitor widely used in the prior sand control filling process can not meet the requirements of the prior large pump extract, long-acting sand control and acidification on particle migration control due to the structural and performance limitations, and the main reasons are as follows: firstly, the cationic polymer sand inhibitor is water-soluble, and can be dissolved into formation water again along with the extension of production time, and active ingredients remained on the surface wall of pores can be denatured and broken chains under the influence of formation mineralization and shearing action, and the decrease is rapid, so that the sand inhibiting performance is sharply reduced; secondly, the cationic polymer remained on the surface walls of the pores and the particles is only subjected to electrostatic adsorption and hydrogen bonding, the sand inhibiting performance is weak, and the scouring-resistant discharge capacity is only 900 ml/h; thirdly, the cationic polymer can cause reservoir damage when being improperly used in a hypotonic reservoir. Self-consolidating proppants, although precoated with an organic film, only meet the strength of self-consolidation under subterranean conditions, such precoated organic films do not have viscous properties and therefore cannot adhere to formation fines that invade the pack.
Disclosure of Invention
In view of the prior art and the problems, the invention provides a vegetable oil asphalt amide resin capable of forming a film and a preparation method thereof, wherein the vegetable oil asphalt amide resin can be used as a sand control agent, can generate a viscous film on the surface of pores of a reservoir and/or a gravel filling layer, stabilizes a sand filling body, and effectively solves the problem of rapid reduction of the productivity of an oil well caused by blocking of the gravel filling layer by migration of reservoir particles. The invention uses the grease industrial waste-vegetable oil asphalt to prepare the vegetable oil asphalt amide resin, and uses the vegetable oil asphalt as the chemical sand control agent of the oil well, thereby having wide popularization and application prospect.
The invention is realized by the following technical scheme:
a vegetable oil asphalt amide resin is prepared by the following steps: carrying out salt forming reaction on the vegetable oil asphalt and diamine for 0.5-5 hours at 50-100 ℃ and 0.1-1.5 MPa under the protection of a catalyst and nitrogen; then heating to 180-210 ℃, and carrying out pre-polycondensation reaction for 0.5-10 hours under the pressure of 0-10 MPa; then carrying out reduced pressure reaction for 0.5-10 hours under the pressure of 0-minus 1.0MPa to obtain vegetable oil asphalt amide resin, discharging, cooling and granulating; wherein the molar ratio of the functional group amino of the diamine to the functional group carboxyl of the vegetable oil asphalt is 1.0-1.2: 1; the diamine is selected from one or more of ethylenediamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or other polyethylene polyamines; the catalyst is selected from sodium hypophosphite, hypophosphorous acid and sulfurous acid.
Preferably, the purity of the vegetable oil asphalt is more than or equal to 98 percent.
Preferably, the catalyst is used in an amount of 0.05% to 0.5%, more preferably 0.1% to 0.2%, based on the total weight of the reactants.
Preferably, the temperature of the salt forming reaction is 70-100 ℃, and more preferably 90 ℃.
Preferably, the pressure of the pre-polycondensation reaction is 1.0-2.0 MPa.
Preferably, the time of the pre-polycondensation reaction is 1.5 to 2.0 hours.
Preferably, the time for the reduced-pressure reaction is 0.5 to 1.5 hours, more preferably 1.0 hour.
Preferably, the preparation method is as follows: carrying out salt forming reaction on vegetable oil asphalt and ethylenediamine at 90 ℃ and normal pressure for 2 hours under the protection of sodium hypophosphite and nitrogen as catalysts; heating to 180-210 ℃, and carrying out pre-polycondensation reaction for 1.5-2.0 hours under the pressure of 1.0-2.0 MPa; then carrying out reduced pressure reaction for 0.5-1.5 hours under the pressure of 0-minus 1.0MPa to obtain the vegetable oil asphalt amide resin, discharging, cooling and granulating; wherein the molar ratio of the functional group amino of the diamine to the functional group carboxyl of the vegetable oil asphalt is 1: 1; the dosage of the catalyst is 0.1-0.2% of the total weight of the reactants.
The vegetable oil asphalt amide resin is used as a sand control agent. When the vegetable oil asphalt amide resin is applied as a sand control agent, the vegetable oil asphalt amide resin can automatically separate out and generate a viscous membrane on the pore water-wet surface of a gravel filling layer, so that the stability of a filling sand body is kept, and the problem of rapid reduction of the productivity of an oil well caused by blocking of the gravel filling layer by the migration of reservoir particles is effectively solved. The generation of the viscous membrane is promoted by a slug type pump injection process, so that the permeability of an oil layer is not damaged, higher flow conductivity is kept, the stability of the filled sand body is obviously improved, and the construction is convenient.
When in specific application, the vegetable oil asphalt amide resin and the dispersant are mixed to prepare the sand control agent (the concentration of the vegetable oil asphalt amide resin is 2-25 percent, and the weight percentage is higher); the dispersant is selected from one or more of ethanol, methanol, ethylene glycol, pentaerythritol, n-propanol, m-cresol, toluene, xylene, formic acid and acetic acid, preferably xylene, acetic acid and ethanol.
Preferably, the sand control agent is prepared by the following method: taking 50g of vegetable oil asphalt amide resin, adding 150mL of dimethylbenzene and 50mL of ethanol, heating, stirring and dissolving, and then diluting with ethanol to the concentration of 2% -10%.
A vegetable oil asphalt amide resin sand control agent is prepared by mixing vegetable oil asphalt amide resin and a dispersing agent; the dispersing agent is selected from one or more than two of ethanol, methanol, glycol, pentaerythritol, n-propanol, m-cresol, toluene, xylene, formic acid and acetic acid.
Preferably, the concentration of the vegetable oil asphalt amide resin is 2 to 25 percent (weight percentage).
Preferably, the sand control agent is prepared by the following method: taking 50g of vegetable oil asphalt amide resin, adding 150mL of dimethylbenzene and 50mL of ethanol, heating, stirring and dissolving, and then diluting with ethanol to the concentration of 2% -10%.
The sand control agent has the scouring discharge capacity of 7000ml/h and the outlet sand content of less than 0.05g/L (4.7 items in Q/SLCG0097-2014 are adopted in the evaluation method), and is suitable for sand control of low-mud common oil wells.
The addition amount of the diamine can be calculated according to the measured acid value (the acid value of the vegetable oil asphalt can be measured by adopting a potentiometric titration method). The vegetable oil asphalt amide resin is dissolved by an organic solvent to prepare a solvent type vegetable asphalt amide resin sand control agent, which automatically precipitates on the water-wet surface of the pore of the gravel filling layer to generate an adhesive film, the film spreading is promoted by the water driving force and the self viscosity of the film forming agent, and after the film forming agent is an ultrathin adhesive film, particles intruding into the filling layer are adhered around the filling sand and cannot migrate to block the pore of the filling layer, so that the high permeability and the stability of the filling layer are maintained for a long time. The method has the characteristics of safety, environmental protection, simple construction, quick film forming, strong scouring resistance and the like, is a new technology for prolonging the stable production period of the sand-proof filling of the oil well in the middle and later stages of oil field development, and has high popularization and application value and strong applicability.
The invention has the following beneficial effects:
1. resource reuse: the plant asphalt is a waste resource, and is applied to the preparation of plant asphalt amide resin and the field of oil well sand consolidation for the first time.
2. The plant asphalt amide resin has a spatial network structure: the plant asphalt is a mixture with a plurality of aliphatic long chains such as poly fatty acid and the like, and can be subjected to polycondensation reaction with diamine at high temperature to form a network integral structure, so that the composite modulus of the plant asphalt amide resin is improved, the elastic behavior of the plant asphalt amide resin is also improved, and the sand control performance of the plant asphalt amide resin can be greatly improved.
3. The asphalt amide film-forming type sand control agent has an excellent molecular structure: the existing sand control agent has low sand control efficiency through single hydrogen bond action, electrostatic coulomb action, physical wrapping action and the like with silicon dioxide. The asphalt amide resin contains strong polar group amido and has partial positive electricity, and can generate affinity action with sand grains through hydrogen bonds and also generate affinity action with the sand grains through electrostatic coulomb action to generate strong physical adsorption; meanwhile, the amide group density of the polymer can be adjusted through structural design, the number of sites of action with sand grains can be controlled, the viscous film forming property of the polymer can be adjusted through structural design, and the polymer is enabled to migrate to the surface of the sand grains and strongly adhere to the surface of the sand grains as a result of multiple actions. The solvent is coated on the surface of sand grains to form a nano-to micron-sized ultrathin polymer film; at the same time, the viscous character of the polymer and the long molecular chains cause the sand grains to aggregate. The strength of the polymer itself and the multiple interactions between the sand grains and the polymer provide the consolidation strength between the sand grains.
4. The fast film-forming property and the excellent mechanical property are as follows: the asphalt amide resin is prepared into a solvent type sand control agent, and when the asphalt amide resin is contacted with a water phase, the asphalt amide resin is quickly replaced to form a film and is separated out, and the asphalt amide resin is crosslinked with the sand surface. Because the molecules have hydrophilic groups with certain affinity with water and have enough long lipophilic fatty chains, the hydrophilic lipid chain has certain effect on reducing the friction force of the membrane and the assembly defect of the membrane. The rigid group and the flexible chain segment of the asphalt amide resin are optimized, the regular arrangement of the rigid group can improve the regularity of the sand-coated film and the binding force with the substrate, the bearing capacity of the sand-coated film is enhanced, and the wear resistance of the sand-coated film is influenced by the charge property of the end group, the hydrophilicity of the end group and the number of the film layers.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
Experiment 1 investigation of the influence of dwelling pressure on number average molecular weight, tensile strength and elongation at break of copolymer
Collecting vegetable oil asphalt (from Yichun far-reaching chemical Co., Ltd., Jiangxi, model No. 1, acid value not less than 57, sterol of about 10% and high-grade fatty acid with specific gravity of 97-98%; the same below) and ethylenediamine (COOH: NH)2The molar ratio is 1: 1) placing the mixture into a reaction kettle, and reacting at 90 ℃ under the protection of nitrogen and under the protection of a catalyst (the catalyst is sodium hypophosphite, the dosage is 0.1 percent of the total amount of the raw materials),Reacting for 2.0 hours under normal pressure (salt forming reaction); heating to 200 ℃, and reacting for 2.0 hours (pre-polycondensation reaction) under set pressure (0MPa, 0.5MPa, 1MPa, 1.5MPa, 3MPa, 5 groups); reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, carrying out reduced pressure reaction for 1 hour to obtain the vegetable oil asphalt amide resin, discharging, cooling and granulating.
The influence of the holding pressure in the prepolycondensation stage on the number average molecular weight and properties of the copolymer was examined, and the results are shown in Table 1. As can be seen from Table 1, the number average molecular weight of the copolymer tends to increase with an increase in the holding pressure, but the change is small. Therefore, the optimum pressure is selected to be 1.0-2.0 MPa.
TABLE 1 Effect of pressure on number average molecular weight, tensile Strength and elongation at Break of copolymer
Experiment 2 investigation of the influence of dwell reaction time on the number average molecular weight, tensile strength and elongation at break of the copolymer
Mixing vegetable oil asphalt and ethylenediamine (COOH: NH)2The molar ratio is 1: 1) placing the mixture into a reaction kettle, and reacting for 2.0 hours (salt forming reaction) at 90 ℃ and normal pressure under the protection of nitrogen under the protection of a catalyst (the catalyst is sodium hypophosphite, and the dosage is 0.1 percent of the total amount of the raw materials); heating to 200 ℃, and reacting (pre-polycondensation) under the pressure of 1.5MPa for 1 hour, 1.5 hours, 2.0 hours and 4.0 hours respectively; reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, carrying out reduced pressure reaction for 1 hour to obtain the vegetable oil asphalt amide resin, discharging, cooling and granulating.
The influence of the dwell reaction time in the prepolycondensation stage on the number average molecular weight and properties of the copolymer was examined, and the results are shown in Table 2. As can be seen from Table 2, the number average molecular weight of the copolymer tended to increase with increasing dwell reaction time, but the change was small. Therefore, the optimum pressure maintaining time is selected to be 1.5 to 2.0 hours.
TABLE 2 Effect of dwell time on number average molecular weight, tensile strength and elongation at break of the copolymer
Experiment 3 investigation of the influence of the salt formation temperature on the number average molecular weight, tensile strength and elongation at break of the copolymer
Mixing vegetable oil asphalt and ethylenediamine (COOH: NH)2The molar ratio is 1: 1.1), placing the mixture into a reaction kettle, and reacting for 2.0 hours (salt forming reaction) at a set temperature (4 groups in total at 70 ℃, 80 ℃, 90 ℃ and 100 ℃) and normal pressure under the protection of a catalyst (the catalyst is sodium hypophosphite, the dosage is 0.1 percent of the total amount of the raw materials) and nitrogen; heating to 200 ℃, and reacting for 2 hours under the pressure of 1.5MPa (pre-polycondensation reaction); reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, carrying out reduced pressure reaction for 1 hour to obtain the vegetable oil asphalt amide resin, discharging, cooling and granulating.
The influence of the salt formation temperature on the number average molecular weight and properties of the copolymer was examined, and the results are shown in Table 3. As can be seen from Table 3, the number average molecular weight of the copolymer is lower at the low salt-forming temperature, which is the temperature at which the vegetable oil asphalt and diamine do not react in equal molar amounts, and the diamine volatilizes during the water removal process, so the polymerization degree is lower and the molecular weight is lower. The molecular weight of the copolymer reaches 38910 g.mol when the salification temperature is 90 DEG C-1The influence of the continuous temperature rise on the number average molecular weight and the performance of the copolymer is small, so that the optimal salt forming temperature is selected to be 90 ℃.
TABLE 3 influence of the salt formation temperature on the number average molecular weight, tensile strength and elongation at break of the copolymers
Experiment 4 investigation of the influence of the amount of catalyst on the number average molecular weight, tensile strength and elongation at break of the copolymer
Extracting vegetable oilCyan and ethylenediamine (COOH: NH)2The molar ratio is 1: 1) placing the mixture into a reaction kettle, and reacting for 2.0 hours (salt forming reaction) at 90 ℃ and normal pressure under the protection of a catalyst (the catalyst is sodium hypophosphite, and the dosage of the catalyst is 0.05 percent, 0.1 percent, 0.2 percent and 0.4 percent of the total amount of the raw materials) and nitrogen; heating to 200 ℃, and reacting for 2 hours under the pressure of 1.5MPa (pre-polycondensation reaction); reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, carrying out reduced pressure reaction for 1 hour to obtain the vegetable oil asphalt amide resin, discharging, cooling and granulating.
The influence of the amount of catalyst used on the number average molecular weight and properties of the copolymer was examined, and the results are shown in Table 4. As can be seen from table 4, when the amount of the catalyst is 0.05 to 0.2% of the total mass of the raw materials, the number average molecular weight of the copolymer gradually increases with the increase of the amount of the catalyst, but when the amount of the catalyst is 0.4%, the number average molecular weight decreases, because the catalytic reaction is incomplete when the amount of the catalyst is small, the selectivity of the main reaction decreases when the amount of the catalyst is too large, and a large number of side reactions occur, thereby decreasing the degree of polymerization of the reaction. Therefore, the optimal catalyst dosage is 0.1-0.2%.
TABLE 4 Effect of catalyst amount on number average molecular weight, tensile strength and elongation at break of the copolymer
Experiment 5 investigation of the Effect of the decompression reaction time on the number average molecular weight, tensile Strength and elongation at Break of the copolymer
Mixing vegetable oil asphalt and ethylenediamine (COOH: NH)2The molar ratio is 1: 1) placing the mixture into a reaction kettle, and reacting for 2.0 hours (salt forming reaction) at 90 ℃ and normal pressure under the protection of nitrogen under the protection of a catalyst (the catalyst is sodium hypophosphite, and the dosage is 0.1 percent of the total amount of the raw materials); heating to 200 ℃, and reacting for 2 hours under the pressure of 1.5MPa (pre-polycondensation reaction); reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, performing reduced pressure reaction for 0.5 hour, 1 hour and 1.5 hours respectively to obtain the vegetable oil asphalt amide resin, discharging, and coolingAnd (6) cutting into granules.
The influence of the reduced-pressure reaction time on the number-average molecular weight and properties of the copolymer was examined, and the results are shown in Table 5. As can be seen from Table 5, the reduced pressure reaction time of 0.5 to 1.0 hour had a significant effect on the number average molecular weight of the product, and the further extension of the reaction time resulted in a decrease in the number average molecular weight of the product due to the side reaction. Therefore, the optimum reaction time under reduced pressure was selected to be 1.0 hour.
TABLE 5 Effect of reduced pressure reaction time on number average molecular weight, tensile strength and elongation at break of the copolymer
EXAMPLE 1 preparation of vegetable oil Bituminamide resin and Sand control agent
Mixing vegetable oil asphalt and ethylenediamine (COOH: NH)2The molar ratio is 1: 1) placing the mixture into a reaction kettle, and reacting for 2.0 hours (salt forming reaction) at 90 ℃ and normal pressure under the protection of nitrogen under the protection of a catalyst (the catalyst is sodium hypophosphite, and the dosage is 0.1 percent of the total amount of the raw materials); respectively heating to 170 ℃ (1), 180 ℃ (3), 190 ℃ (4), 200 ℃ (5)210 ℃, reacting under the pressure of 1.5MPa (pre-polycondensation reaction), reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, carrying out reduced pressure reaction for 1 hour to obtain the vegetable oil asphalt amide resin, discharging, cooling, granulating, detecting the product with the number average molecular weight shown in table 6 (1, 2, 3, 4 and 5 in table 6, respectively corresponding to the different pre-polycondensation reaction temperatures, namely, the product with the number average molecular weight shown in table 1 corresponding to the pre-polycondensation reaction temperature of 170 ℃, and the rest is analogized).
Taking 50g of the prepared vegetable oil asphalt amide resin, adding 150mL of dimethylbenzene and 50mL of ethanol, heating, stirring and dissolving, and then diluting with ethanol to a concentration of 5% (weight percentage), namely the sand control agent.
And (3) filling a proper amount of quartz sand into the rock core pipe, and introducing the sand control agent. And introducing water, pressurizing and displacing. The influence of the resin molecular weight on the amount of sand produced was examined, and the results are shown in Table 6. As can be seen from Table 6, the outlet sand contents are all less than 0.05g/L (the evaluation method adopts the item 4.7 in Q/SLCG 0097-2014).
TABLE 6 data sheet of sand yield and resin molecular weight
Example 2 preparation of vegetable oil Bituminamide resin and Sand control agent
Mixing vegetable oil asphalt and ethylenediamine (COOH: NH)2The molar ratio is 1: 1) placing the mixture into a reaction kettle, and reacting for 2.0 hours (salt forming reaction) at 90 ℃ and normal pressure under the protection of nitrogen under the protection of a catalyst (sodium hypophosphite is used as the catalyst, and the using amounts of the sodium hypophosphite are respectively 0.1 percent of the total amount of the raw materials); heating to 200 ℃, and reacting for 2 hours under the pressure of 1.5MPa (pre-polycondensation reaction); reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, carrying out reduced pressure reaction for 1 hour to obtain the vegetable oil asphalt amide resin, discharging, cooling and granulating. The number average molecular weight is 5.126g & mol-1。
Taking 50g of the prepared vegetable oil asphalt amide resin, adding 150mL of dimethylbenzene and 50mL of ethanol, heating, stirring and dissolving, and then diluting with ethanol to obtain the sand control agent, wherein the concentrations of the vegetable oil asphalt amide resin are respectively 2%, 3%, 4%, 5% and 6% (weight percentage).
And (3) filling a proper amount of quartz sand into the rock core pipe, and introducing the sand control agent. And introducing water, pressurizing and displacing. The influence of the concentration of the sand control agent and the washout amount on the sand production rate of the rock core is examined, and the results are shown in table 7. As can be seen from Table 7, the outlet sand content is still less than 0.05g/L, and when the flushing displacement is higher (more than 6L/h), the outlet sand content is still less than 0.05g/L (4.7 items in Q/SLCG0097-2014 are adopted in the evaluation method).
TABLE 7 influence of Sand control agent concentration on core Sand production
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (10)
1. A preparation method of vegetable oil asphalt amide resin is characterized by comprising the following steps: carrying out salt forming reaction on the vegetable oil asphalt and diamine for 0.5-5 hours at 50-100 ℃ and 0.1-1.5 MPa under the protection of a catalyst and nitrogen; then heating to 180-210 ℃, and carrying out pre-polycondensation reaction for 0.5-10 hours under the pressure of 0-10 MPa; then carrying out reduced pressure reaction for 0.5-10 hours under the pressure of 0-minus 1.0MPa to obtain vegetable oil asphalt amide resin, discharging, cooling and granulating; wherein the molar ratio of the functional group amino of the diamine to the functional group carboxyl of the vegetable oil asphalt is 1.0-1.2: 1; the diamine is selected from one or more of ethylenediamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine or other polyethylene polyamines; the catalyst is selected from sodium hypophosphite, hypophosphorous acid and sulfurous acid.
2. The method of preparing a vegetable oil asphalt amide resin according to claim 1, wherein: the dosage of the catalyst is 0.05-0.5% of the total weight of the reactants;
or/and: the temperature of the salt forming reaction is 70-100 ℃;
or/and: the pressure of the pre-polycondensation reaction is 1.0-2.0 MPa;
or/and: the time of the pre-polycondensation reaction is 1.5-2.0 hours;
or/and: the time of the reduced pressure reaction is 0.5 to 1.5 hours.
3. The method for preparing a vegetable oil asphalt amide resin according to claim 1 or 2, characterized in that: carrying out salt forming reaction on vegetable oil asphalt and ethylenediamine at 90 ℃ and normal pressure for 2 hours under the protection of sodium hypophosphite and nitrogen as catalysts; heating to 180-210 ℃, and carrying out pre-polycondensation reaction for 1.5-2.0 hours under the pressure of 1.0-2.0 MPa; then carrying out reduced pressure reaction for 0.5-1.5 hours under the pressure of 0-minus 1.0MPa to obtain the vegetable oil asphalt amide resin, discharging, cooling and granulating; wherein the molar ratio of the functional group amino of the diamine to the functional group carboxyl of the vegetable oil asphalt is 1: 1; the dosage of the catalyst is 0.1-0.2% of the total weight of the reactants.
4. The method for preparing a vegetable oil asphalt amide resin according to claim 1 or 2, characterized in that: taking vegetable oil asphalt and ethylenediamine, placing the vegetable oil asphalt and the ethylenediamine in a reaction kettle, and reacting for 2.0 hours at 90 ℃ and normal pressure under the protection condition of a catalyst sodium hypophosphite and nitrogen; heating to 200 ℃, and reacting for 2 hours under the pressure of 1.5 MPa; reducing the pressure in the reaction kettle to normal pressure within 2 hours, vacuumizing to-1.0 MPa, carrying out reduced pressure reaction for 1 hour to obtain vegetable oil asphalt amide resin, discharging, cooling and granulating; wherein the molar ratio of the functional group amino of the diamine to the functional group carboxyl of the vegetable oil asphalt is 1: 1; the amount of catalyst used was 0.1% by weight based on the total weight of the reactants.
5. The vegetable oil asphalt amide resin prepared by the preparation method of the vegetable oil asphalt amide resin according to any one of claims 1 to 4.
6. Use of the vegetable oil asphaltic amide resin of claim 5 as a sand control agent.
7. Use according to claim 6, characterized in that: when in specific application, the vegetable oil asphalt amide resin and the dispersant are mixed to prepare the sand control agent, and the concentration of the vegetable oil asphalt amide resin is 2 to 25 percent (weight percentage); the dispersing agent is selected from one or more than two of ethanol, methanol, glycol, pentaerythritol, n-propanol, m-cresol, toluene, xylene, formic acid and acetic acid.
8. Use according to claim 6 or 7, characterized in that: the sand control agent is prepared by the following method: taking 50g of vegetable oil asphalt amide resin, adding 150mL of dimethylbenzene and 50mL of ethanol, heating, stirring and dissolving, and then diluting with ethanol to the concentration of 2% -10%.
9. A vegetable oil asphalt amide resin sand control agent is characterized in that: the vegetable oil asphalt amide resin of claim 5 is mixed with a dispersant to prepare; the dispersing agent is selected from one or more than two of ethanol, methanol, glycol, pentaerythritol, n-propanol, m-cresol, toluene, xylene, formic acid and acetic acid.
10. The vegetable oil asphaltic amide resin sand control agent of claim 9, wherein: the concentration of the vegetable oil asphalt amide resin is 2 to 25 percent (weight percentage).
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| CN201811254436.8A CN111100288A (en) | 2018-10-25 | 2018-10-25 | Vegetable oil asphalt amide resin, preparation method thereof and application of vegetable oil asphalt amide resin as sand control agent |
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