CN111285969A - Hyperbranched amide hydrate kinetic inhibitor and preparation method and application thereof - Google Patents
Hyperbranched amide hydrate kinetic inhibitor and preparation method and application thereof Download PDFInfo
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- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
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- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers
Abstract
The invention provides a hyperbranched amide hydrate kinetic inhibitor and a preparation method and application thereof. The structural formula of the hyperbranched amide hydrate kinetic inhibitor is shown as a formula (1), wherein: the weight average molecular weight of the hyperbranched amide hydrate kinetic inhibitor is 10000-40000, and the molecular weight distribution coefficient is 1-3. The hydrate kinetic inhibitor has the advantages of good solubility and small using amount, can be applied to an oil-gas-water system, and has the advantages of simple production process and controllable production process.
Description
The technical field is as follows:
the invention relates to the technical field of hydrate inhibitors, in particular to a hyperbranched amide copolymer hydrate kinetic inhibitor and a preparation technology and application thereof.
Background art:
the natural gas hydrate is an ice cage-like crystalline compound formed by water and natural gas under high pressure and low temperature conditions, and a pipeline can be quickly blocked after the formation due to condition limitation in the natural gas transportation process. To prevent its formation, the method mainly adopted at present is the addition of natural gas hydrate inhibitors. However, the current common thermodynamic inhibitors such as ethylene glycol have poor effect under low concentration condition, and are large in dosage and not friendly to environment.
Therefore, in order to solve this problem, kinetic inhibitors have been the focus of attention. The kinetic inhibitor has low dosage, good effect and multiple varieties, and can well solve the problems.
At present, the kinetic inhibitors mainly comprise vinyl amide polymers and chain amide polymers, and have different development directions respectively. Among them, patents ZL201610802031.8, CN109764241A and ZL201610238183.x introduce the copolymerization of a second cyclic monomer such as pyrrolidone or lactam, but the cyclic structure is not easily decomposed in nature and has potential harm to the environment. While the patent CN109705246A and ZL201610861462.1 respectively modify the terminal group, the method does not substantially change the spatial structure of the inhibitor, only has the effect on the terminal group, and has limited comprehensive effect. In the existing scheme for changing the spatial structure, such as ZL201210150102.2, the selected comonomer has poor effect, and the synthesis is relatively complex and the yield is low. While the structure is changed, ionic liquid or ethylene glycol and the like are respectively introduced into patents ZL201611238756.5, CN104479660A, CN104388069A and CN105802599A, and the like, so that the comprehensive use is attempted by compounding a double-effect or multi-effect inhibitor, and the environmental protection performance is improved. However, the use condition in the scheme is that each part has an effective range, the actual use situation is limited, and the problem is not solved essentially.
The invention content is as follows:
the invention aims to provide a hyperbranched amide copolymer hydrate kinetic inhibitor and a preparation technology and application thereof, the hydrate kinetic inhibitor has the advantages of good solubility and small using amount, can be applied to an oil-gas-water system, and the preparation method of the hydrate kinetic inhibitor has a simple production process and a controllable production process.
The invention aims to provide a hyperbranched amide hydrate kinetic inhibitor, which has a structural formula shown in formula (1):
wherein: the weight average molecular weight of the hyperbranched amide hydrate kinetic inhibitor is 10000-40000, and the molecular weight distribution coefficient is 1-3.
The synthetic route of the hyperbranched amide hydrate kinetic inhibitor is as follows (formula 2-4):
the invention also aims to provide a preparation method of the hyperbranched amide type hydrate kinetic inhibitor, which takes aspartic acid, propiolic alcohol and the like as monomers, p-toluenesulfonic acid and NaNO under the anaerobic operating condition2And the like as an initiator, obtaining 2-bromosuccinic acid propiolic ester through multi-step reaction in solvent benzene, and then synthesizing the hyperbranched poly (vinylcaprolactam-2-bromosuccinic acid propiolic ester) through reversible addition-fragmentation chain transfer polymerization (RAFT) reaction by using the 2-bromosuccinic acid propiolic ester and 2, 2-bipyridine as initiators and vinylcaprolactam as monomers.
The preparation method of the hyperbranched amide hydrate kinetic inhibitor specifically comprises the following steps:
(1) aspartic acid, KBr and NaNO are put in an ice bath under the protection of nitrogen2Adding the mixture into a reaction container, adding distilled water, slowly adding concentrated sulfuric acid, reacting for 2-4 hours, extracting the product by ethyl acetate, and adding anhydrous MgSO4Drying to obtain a target product 2-bromosuccinic acid;
(2) under the oxygen-free operation environment, in 2-bromobutaneAdding a second monomer propiolic alcohol, an initiator p-toluenesulfonic acid and a solvent benzene into diacid, fully mixing, reacting at 80-90 ℃ for 36-48 hours, cooling the solution to room temperature, then drying by rotary evaporation at 40-55 ℃, cooling to room temperature, adding CH2Cl2Redissolving, dropping the solution into mixed solution of ethyl acetate-10 wt% NaOH, washing with distilled water, and MgSO4Drying, and carrying out rotary evaporation drying on the obtained liquid at the temperature of 35-45 ℃ to obtain a target product 2-bromosuccinic acid propiolic ester;
(3) adding 2-bromosuccinic acid propiolic alcohol ester and vinyl caprolactam into a solvent benzene in an oxygen-free operation environment, carrying out low-temperature freezing-vacuumizing-nitrogen-introducing unfreezing circulation for 3 times in liquid nitrogen, then sequentially adding 2, 2-coupling pyridine, CuBr and other initiators, reacting for 3-6 h at 90-120 ℃, cooling to room temperature after the reaction is finished, diluting with tetrahydrofuran, passing through a neutral alumina column, removing metal ions, adding toluene ice to precipitate for 3 times, filtering the obtained product, and then putting the product into a vacuum drying oven to dry at 45 ℃ to obtain the hyperbranched poly (vinyl caprolactam-2-bromosuccinic acid propiolic alcohol ester).
Preferably, the mass ratio of the aspartic acid to the KBr in the step (1) is 1: 3-1: 5, and the total mass of the aspartic acid and the KBr is equal to the mass of NaNO2The mass ratio of (A) to (B) is 4: 1-6: 1; the NaNO2The mass ratio of the distilled water to the concentrated sulfuric acid is 1: 20-1: 40, and the mass ratio of the distilled water to the concentrated sulfuric acid is 10: 1-30: 1.
Preferably, the mass ratio of the 2-bromosuccinic acid to the propiolic alcohol in the step (2) is 1: 2-1: 4, the mass ratio of the total mass of the 2-bromosuccinic acid and the propiolic alcohol to the p-toluenesulfonic acid is 50: 1-85: 1, the mass ratio of the p-toluenesulfonic acid to the benzene is 1: 100-1: 150, and the reaction is carried out at 85 ℃ for 40 hours; the volume ratio of the ethyl acetate to the NaOH solution with the mass fraction of 10 wt% in the mixed solution is 4: 1-5: 1.
In the step (2), the first rotary evaporation temperature is 50 ℃, and the second rotary evaporation temperature is 40 ℃.
Preferably, the mass ratio of 2-propynyl 2-bromosuccinate to vinylcaprolactam in the step (3) is 1: 10-1: 30, the mass ratio of 2-propynyl 2-bromosuccinate to CuBr is 2: 1-1: 1, the mass ratio of CuBr to 2, 2-bipyridine is 1: 2-1: 4, the oil bath temperature is 100 ℃, and the reaction time is 4 hours.
The invention also protects the application of the hyperbranched amide hydrate kinetic inhibitor, and the hyperbranched amide hydrate kinetic inhibitor is applied to the generation of hydrates in an oil-gas-water three-phase system and an oil-water or gas-water two-phase system.
Preferably, when the hyperbranched amide hydrate kinetic inhibitor is used, the concentration of the hyperbranched amide hydrate kinetic inhibitor aqueous solution is 0.5-2 wt%, the applicable pressure is 1-25 MPa, and the temperature is-25 ℃.
Compared with the prior art, the invention has the following advantages: compared with the existing kinetic inhibitor, the synthetic kinetic inhibitor has the advantages of simple synthetic process, high yield, high proportion of effective inhibitor components, only one cyclic structure, controllable molecular weight, small molecular dispersion coefficient, biodegradable part, environment friendliness and wider application range and conditions.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
The experimental procedures described in the following examples can be carried out with reference to conventional techniques for process parameters not specifically noted; the reagents and materials, unless otherwise indicated, are commercially available.
The method for detecting and measuring the inhibition effect of the product prepared by the method comprises the following steps:
the detection equipment is a visual high-pressure stirring experimental device, and the main components of the visual high-pressure stirring experimental device comprise a double-view mirror high-pressure reaction kettle, a magnetic stirrer, a buffer tank, a low-temperature constant-temperature tank, a manual booster pump, a temperature and pressure sensor, a vacuum pump, a gas cylinder, a data acquisition instrument and the like. The highest working pressure of the high-pressure reaction kettle is 30MPa, and the working temperature ranges from minus 30 ℃ to 100 ℃. The pressure in the high-pressure reaction kettle can be freely adjusted through a manual piston type pressure increasing valve, and the maximum pressure of a pump is 30 MPa. The low-temperature constant-temperature tank can provide refrigerant circulating liquid at the temperature of-30-100 ℃ for a jacket of the high-pressure reaction kettle. The data acquisition system acquires the pressure and the temperature in the reaction kettle in real time. The formation of the hydrate can be judged through the temperature or pressure change during the reaction or directly observed through a visual window. After the reaction starts, the point of sudden drop of the pressure in the kettle is the starting point of the generation of the hydrate. The hydrate induction time is the time elapsed from the start of the stirring at the stable initial pressure temperature to the start of the drastic drop in pressure. And detecting the action effect of the inhibitor according to the induction time of the hydrate, wherein the longer the time is, the better the inhibition effect is.
The specific detection process comprises the following steps:
the experimental temperature of the reaction is set to be 0.5 ℃, the experimental pressure is 7.6MPa, and the experimental gas is methane. The equilibrium temperature for the formation of methane hydrate at 7.6MPa is 11 ℃. Before the experiment is operated, the reaction kettle is repeatedly cleaned by deionized water for 3-5 times, and then nitrogen is used for purging the reaction kettle and the experiment pipeline system, so that the system is ensured to be dry. The reaction vessel was evacuated and 30mL of the prepared inhibitor solution was aspirated. 1MPa methane gas is introduced, then the vacuum pumping is carried out, and the process is repeated for three times to remove the air in the kettle. And starting the low-temperature constant-temperature tank to cool the reaction kettle until the temperature in the kettle reaches 0.5 ℃. And when the temperature is stable, opening an air inlet valve, and precooling the methane gas into the buffer tank to reach 7.6 MPa. After the temperature and the pressure in the kettle are stabilized for a period of time, the magnetic stirring is started, and the rotating speed is kept at 800 rpm. Because methane is dissolved in water, the pressure in the kettle is slightly reduced at the beginning of stirring, the change of the pressure-temperature curve is observed, and whether the hydrate is generated or not is judged
Example 1:
a preparation method of a hyperbranched amide hydrate kinetic inhibitor specifically comprises the following steps:
(1) 10.156g of aspartic acid and 42.1g of KBr are taken and added into a three-neck flask, then the three necks of the flask are connected with a thermometer, a condenser tube and a rubber hole plug, and the upper end of the condenser tube is communicated with a gas circuit. And introducing nitrogen after vacuumizing, and preliminarily removing air in the pipeline. 25.8mL of concentrated sulfuric acid was slowly added to 200mL of distilled water under ice bath conditions, cooled, and transferred to a flask. Mixing 9.57g NaNO2Adding 20mL of distilled water, dropwise adding into the flask from the rubber plug hole by using an injector at low temperature, sealing, stopping the reaction after 2h, extracting the product by using ethyl acetate, and performing secondary reactionWith anhydrous MgSO4Drying to obtain 2-bromosuccinic acid;
(2) under the environment of nitrogen gas, 10.64g of 2-bromosuccinic acid, 30g of propiolic alcohol and 0.5g of p-toluenesulfonic acid are sequentially added into a flask, dissolved in 100mL of benzene, fully mixed, reacted at the oil bath temperature of 85 ℃ for 36 hours, cooled to room temperature, then evaporated to dryness at 45 ℃ to obtain benzene, cooled again to room temperature, and added with 100mL of CH2Cl2Redissolved and the solution washed 3 times with a 4:1 by volume mixture of ethyl acetate-10 wt% NaOH and 2 times with distilled water and dried over anhydrous MgSO 4. The obtained liquid is subjected to rotary evaporation and drying at the temperature of 40 ℃ to obtain a target product 2-bromosuccinic acid propiolic ester;
(3) under the condition of introducing nitrogen, 0.517g of 2-bromosuccinic acid propiolic ester and 20g of vinyl caprolactam are added into 100mL of benzene as a solvent, then 0.977g of 2, 2-coupled pyridine and 0.304g of CuBr are sequentially added, low-temperature freezing-vacuumizing-nitrogen-introducing unfreezing circulation is rapidly carried out for 3 times in liquid nitrogen, the mixture is subjected to reaction for 4 hours under an oil bath at 100 ℃ after vacuumizing, the reaction product is cooled to room temperature after the reaction is finished, the reaction product is diluted by 200mL of tetrahydrofuran and then passes through a neutral alumina column, metal ions are removed, then, toluene ice is added for precipitation for 3 times, the obtained product is filtered and then put into a vacuum drying oven to be dried at 45 ℃, and the final product of hyperbranched poly (vinyl caprolactam-2-bromosuccinic acid propiolic ester) is obtained.
Detection and determination: the inhibitor is prepared into 0.5 wt%, 1 wt% and 2 wt% aqueous solution, detection is carried out by a laboratory natural gas hydrate inhibition performance testing device under the conditions that the initial temperature is 0.5 ℃ and the initial pressure is 7.6MPa, the induction time for inhibiting the generation of hydrate by the inhibitor is measured, and the experimental result is shown in table 1.
Example 2:
the same as example 1, except that:
in the step (1), the mass ratio of aspartic acid to KBr is 1:3, and the total mass of aspartic acid and KBr to NaNO2The mass ratio of (A) to (B) is 4: 1; NaNO2The mass ratio of the concentrated sulfuric acid to the distilled water is 1:20, the mass ratio of the distilled water to the concentrated sulfuric acid is 10:1, and the reaction time is 3 hours.
In the step (2), the mass ratio of the 2-bromosuccinic acid to the propiolic alcohol is 1:2, the mass ratio of the total mass of the 2-bromosuccinic acid and the propiolic alcohol to the p-toluenesulfonic acid is 50:1, the mass ratio of the p-toluenesulfonic acid to the benzene is 1:100, the reaction temperature is 80 ℃, and the reaction time is 48 hours; the volume ratio of ethyl acetate to 10 wt% NaOH solution in the mixed solution is 4:1, the first rotary evaporation temperature is 40 ℃, and the second rotary evaporation temperature is 35 ℃.
In the step (3), the mass ratio of 2-bromosuccinic acid propiolic ester to vinyl caprolactam is 1:10, the mass ratio of 2-bromosuccinic acid propiolic ester to CuBr is 2:1, the mass ratio of CuBr to 2, 2-bipyridine is 1:2, the oil bath temperature is 90 ℃, and the reaction time is 6 hours.
Example 3:
the same as example 1, except that:
in the step (1), the mass ratio of aspartic acid to KBr is 1:5, and the total mass of aspartic acid and KBr to NaNO2The mass ratio of (A) to (B) is 5: 1; NaNO2The mass ratio of the concentrated sulfuric acid to the distilled water is 1:40, the mass ratio of the distilled water to the concentrated sulfuric acid is 30:1, and the reaction time is 4 hours.
In the step (2), the mass ratio of the 2-bromosuccinic acid to the propiolic alcohol is 1:4, the mass ratio of the total mass of the 2-bromosuccinic acid and the propiolic alcohol to the p-toluenesulfonic acid is 70:1, the mass ratio of the p-toluenesulfonic acid to the benzene is 1:150, the reaction temperature is 90 ℃, and the reaction time is 36 hours; the volume ratio of the ethyl acetate to the NaOH solution with the mass fraction of 10 wt% in the mixed solution is 5:1, the first rotary evaporation temperature is 55 ℃, and the second rotary evaporation temperature is 45 ℃.
In the step (3), the mass ratio of 2-bromosuccinic acid propiolic ester to vinyl caprolactam is 1:30, the mass ratio of 2-bromosuccinic acid propiolic ester to CuBr is 1:1, the mass ratio of CuBr to 2, 2-bipyridine is 1:4, the oil bath temperature is 120 ℃, and the reaction time is 3 hours.
The molecular weight and the molecular weight distribution of the final product hyperbranched poly (vinylcaprolactam-2-bromosuccinic acid propiolic ester) obtained in examples 1-3 are detected by using a GPC-1515 type gel chromatograph manufactured by Waters corporation of America under the detection condition of 28 ℃ and the flow rate of 1mL/min and using a polystyrene standard sample and a DMF solvent as a mobile phase, and the weight average molecular weight of the hyperbranched amide hydrate kinetic inhibitor is 10000-40000, and the molecular weight distribution coefficient is 1-3.
Comparative example 1:
352mg of azodiisobutyronitrile serving as a chain initiator is added into a 250mL three-neck flask, and nitrogen is introduced after vacuum pumping to ensure an anaerobic operation environment. Under nitrogen, 22mL of monomeric vinylpyrrolidone and 100mL of solvent dimethylformamide were mixed and added to the flask. The magnetic stirring and oil bath was turned on and the reaction was carried out at 80 ℃ for 7h at 300 rpm. After the reaction, the mixed solution obtained by polymerization is transferred to a round-bottom flask, and the reaction is stopped when the liquid is viscous by rotary evaporation at 90 ℃. After it had cooled naturally, the product was slowly dropped into 250ml of cold ethyl acetate to give a white viscous solid. After filtering with a glass sand core funnel, the solid product together with the filter paper is transferred to a watch glass, and is dried for 48 hours in a vacuum drying oven at 45 ℃, and then is heated to 105 ℃ to remove water for 1 hour. And finally obtaining the target product polyvinylpyrrolidone (PVP).
Evaluation of inhibition performance: it was prepared as a 1 wt% aqueous solution. The method comprises the steps of detecting through a laboratory natural gas hydrate inhibition performance testing device under the conditions that the initial temperature is 0.5 ℃ and the initial pressure is 7.6MPa, measuring the induction time for inhibiting the generation of hydrate by an inhibitor, and obtaining an experimental result shown in table 1.
Comparative example 2:
20.127g of monomeric vinylcaprolactam are dissolved in 100mL of dimethylformamide as a solvent, sealed, evacuated and then purged with nitrogen, and the operation is repeated 3 times. 0.205g of azodiisobutyronitrile as a chain initiator was weighed into a 250mL three-neck flask under nitrogen protection, and vacuum-nitrogen circulation was performed three times. The magnetic stirring and oil bath was turned on and the reaction was carried out at 80 ℃ for 10h at 300 rpm. After the reaction, the mixture obtained by polymerization was transferred to a round-bottom flask and rotary-evaporated at 75 ℃ until the liquid appeared viscous. After the mixture is naturally cooled, the mixture is dropped into 250mL of cold anhydrous ether to obtain white viscous solid. After suction filtration, the mixture is placed in a vacuum drying oven for drying for 48 hours at the temperature of 40 ℃, and then the temperature is raised to 110 ℃ for drying for 5 hours. Finally obtaining the target product polyvinyl caprolactam (PVCap).
Evaluation of inhibition performance: it was prepared as a 1 wt% aqueous solution. The method comprises the steps of detecting through a laboratory natural gas hydrate inhibition performance testing device under the conditions that the initial temperature is 0.5 ℃ and the initial pressure is 7.6MPa, measuring the induction time for inhibiting the generation of hydrate by an inhibitor, and obtaining an experimental result shown in table 1.
Comparative example 3:
13.92g of monomer vinyl caprolactam and 11mL of monomer vinyl pyrrolidone are added into a 250mL three-neck flask, and nitrogen is introduced after vacuum pumping to ensure an anaerobic operation environment. 0.164g of azobisisobutyronitrile as a chain initiator and 90mL of dimethylformamide as a solvent were weighed, the azobisisobutyronitrile was dissolved in the dimethylformamide and injected into the flask from the hole of the rubber stopper with a syringe to close the hole of the rubber stopper. Then vacuumizing and introducing nitrogen for three times to circulate, and removing oxygen. The condensed water circulation is opened, and after the reaction is carried out for 8 hours at the temperature of 80 ℃ of the oil bath and the rotating speed of 300rpm, the oil bath is closed and stirred. After the solution was cooled to room temperature, the solution was transferred to a round bottom flask. The solution is steamed in a rotary manner at the temperature of 90 ℃ until the precipitation is completely separated out, the solution is cooled to the room temperature, then the solution is dripped into a large amount of cold anhydrous ether for precipitation, and the obtained solid is washed and dried in vacuum at the temperature of 80 ℃ for 24 hours. Finally obtaining the target product poly (vinyl caprolactam-vinyl pyrrolidone) (PVCap-PVP).
Evaluation of inhibition performance: the method comprises the steps of detecting through a laboratory natural gas hydrate inhibition performance testing device under the conditions that the initial temperature is 4 ℃ and the initial pressure is 7.6MPa, measuring the induction time for inhibiting the generation of hydrate by an inhibitor, and obtaining an experimental result shown in table 1.
Comparative example 4:
30mL of deionized water is added into a reaction kettle, detection is carried out by a laboratory natural gas hydrate inhibition performance testing device under the conditions that the initial temperature is 0.5 ℃ and the initial pressure is 7.6MPa, the induction time for inhibiting the generation of hydrate by an inhibitor is measured, and the experimental result is shown in Table 1.
TABLE 1
Through detection, when the initial pressure is 7.6MPa, the temperature is 0.5 ℃, the supercooling degree is more than 10K, and the concentration of the inhibitor is 1 wt%, the product prepared by the invention enables the generation induction time of the methane hydrate to be as long as 270min, and the commonly used kinetic inhibitors PVP, PVCap and PVCap-PVP binary cyclic copolymer have no effect basically under the conditions of the temperature and the pressure.
Meanwhile, the calculation proves that 6.423g of the hyperbranched amide hydrate kinetic inhibitor provided by the invention is purified under the condition of simple production process, the calculated yield is 32.1%, and compared with the similar multi-component inhibitor, the yield is relatively higher, and the implementation process is further improved.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. A hyperbranched amide hydrate kinetic inhibitor is characterized in that the structural formula of the hyperbranched amide hydrate kinetic inhibitor is shown as a formula (1):
wherein: the weight average molecular weight of the hyperbranched amide hydrate kinetic inhibitor is 10000-40000, and the molecular weight distribution coefficient is 1-3.
2. The preparation method of the hyperbranched amide-type hydrate kinetic inhibitor of claim 1, which is characterized by comprising the following steps:
(1) aspartic acid, KBr and NaNO are put in an ice bath under the protection of nitrogen2Adding the mixture into a reaction vessel, adding distilled water, slowly adding concentrated sulfuric acid, reacting for 2-4 hours, extracting the product, and dryingThen, obtaining a target product 2-bromosuccinic acid;
(2) under an oxygen-free operation environment, propiolic alcohol, p-toluenesulfonic acid and benzene are sequentially added into 2-bromosuccinic acid, the mixture is fully mixed, after the mixture reacts for 36 to 48 hours at a temperature of between 80 and 90 ℃, the solution is cooled to room temperature, then the solution is dried at a temperature of between 40 and 55 ℃, cooled to room temperature, CH is added2Cl2Re-dissolving, namely dripping the solution into a mixed solution of ethyl acetate and NaOH with the mass fraction of 10 wt% for washing, washing and drying by using distilled water to obtain a target product 2-propynyl bromosuccinate;
(3) adding 2-bromosuccinic acid propiolic alcohol ester and vinyl caprolactam into benzene in an oxygen-free operation environment, performing low-temperature freezing-vacuumizing-nitrogen-introducing unfreezing circulation in liquid nitrogen, then sequentially adding 2, 2-coupling pyridine and CuBr, reacting at 90-120 ℃ for 3-6 h, cooling to room temperature after the reaction is finished, diluting with tetrahydrofuran, passing through a neutral alumina column, removing metal ions, adding toluene ice for precipitation, filtering the obtained product, and drying to obtain the hyperbranched poly (vinyl caprolactam-2-bromosuccinic acid propiolic alcohol ester).
3. The preparation method of the hyperbranched amide-based hydrate kinetic inhibitor according to claim 2, wherein the mass ratio of aspartic acid to KBr in the step (1) is 1: 3-1: 5, and the total mass of aspartic acid and KBr to NaNO2The mass ratio of (A) to (B) is 4: 1-6: 1, and the NaNO is2The mass ratio of the distilled water to the concentrated sulfuric acid is 1: 20-1: 40, and the mass ratio of the distilled water to the concentrated sulfuric acid is 10: 1-30: 1.
4. The preparation method of the hyperbranched amide-type hydrate kinetic inhibitor as claimed in claim 2, wherein the mass ratio of the 2-bromosuccinic acid to the propiolic acid in the step (2) is 1: 2-1: 4, and the mass ratio of the total mass of the 2-bromosuccinic acid and the propiolic acid to the p-toluenesulfonic acid is 50: 1-85: 1.
5. The preparation method of the hyperbranched amide-type hydrate kinetic inhibitor according to claim 2, wherein the mass ratio of p-toluenesulfonic acid to benzene in the step (2) is 1: 100-1: 150, and the reaction is carried out at 85 ℃ for 40 hours.
6. The preparation method of the hyperbranched amide-based hydrate kinetic inhibitor according to claim 2, wherein the volume ratio of the ethyl acetate to the NaOH solution with the mass fraction of 10 wt% in the mixed solution in the step (2) is 4: 1-5: 1.
7. The preparation method of the hyperbranched amide type hydrate kinetic inhibitor as claimed in claim 2, wherein the mass ratio of 2-bromosuccinic acid propiolic ester to vinyl caprolactam in the step (3) is 1: 10-1: 30, the mass ratio of 2-bromosuccinic acid propiolic ester to CuBr is 2: 1-1: 1, and the mass ratio of CuBr to 2, 2-bipyridine is 1: 2-1: 4.
8. The use of the hyperbranched amide-based hydrate kinetic inhibitor of claim 1, which is applied to the formation of hydrates in oil-gas-water three-phase systems, oil-water or gas-water two-phase systems.
9. The application of the hyperbranched amide hydrate kinetic inhibitor according to claim 8, wherein when the hyperbranched amide hydrate kinetic inhibitor is used, the concentration of the hyperbranched amide hydrate kinetic inhibitor in water solution is 0.5-2 wt%, the applicable pressure is 1-25 MPa, and the temperature is-25 ℃.
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| PCT/CN2020/135060 WO2021159835A1 (en) | 2020-03-06 | 2020-12-10 | Hyperbranched amide hydrate kinetic inhibitor and preparation method therefor and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111649237A (en) * | 2020-01-16 | 2020-09-11 | 中石化中原石油工程设计有限公司 | Ground gathering and transporting system for exhausted gas reservoir |
| WO2021159835A1 (en) * | 2020-03-06 | 2021-08-19 | 中国科学院广州能源研究所 | Hyperbranched amide hydrate kinetic inhibitor and preparation method therefor and application thereof |
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| WO2021159835A1 (en) * | 2020-03-06 | 2021-08-19 | 中国科学院广州能源研究所 | Hyperbranched amide hydrate kinetic inhibitor and preparation method therefor and application thereof |
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| WO2021159835A1 (en) | 2021-08-19 |
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