CN115109612A - Demulsifier with corrosion inhibition performance and synthesis method thereof - Google Patents
Demulsifier with corrosion inhibition performance and synthesis method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of crude oil demulsification, particularly relates to a demulsifier with corrosion inhibition performance, and further discloses a synthetic method of the demulsifier. The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier provided by the invention takes an imidazole ring as a main body structure, and simultaneously keeps four active hydrogens to continuously react with propylene oxide and ethylene oxide to generate a multi-branched polyether structure containing an imidazoline structure. The demulsifier is added with an imidazoline structure on the basis of ensuring a multi-branched-chain structure, so that the demulsification and dehydration of crude oil can be realized, and the demulsifier has certain corrosion inhibition performance.
Description
Technical Field
The invention belongs to the technical field of crude oil demulsification, particularly relates to a demulsifier with corrosion inhibition performance, and further discloses a synthetic method of the demulsifier.
Background
Along with continuous deep oil exploitation, the application of the enhanced oil recovery method is more and more extensive, the components of the crude oil produced liquid are more and more complex, and the water and inorganic salt in the crude oil emulsion are increased, so that the emulsion is more stable, and the crude oil demulsification difficulty is increased. If the crude oil in this state is collected, transported and refined without being treated, it is easy to cause equipment corrosion, scaling, and tower washing in the crude oil refining process, resulting in danger and economic loss. At present, the crude oil demulsification method mainly comprises the following steps: electric demulsification, gravity sedimentation, ultrasonic demulsification, centrifugal demulsification, membrane demulsification, microwave demulsification, biological demulsification, chemical demulsification, etc. The chemical demulsification method is the most common crude oil demulsification method, and mainly comprises the steps of adding a demulsifier into a crude oil emulsion, changing the property of an oil-water interface, reducing the strength of an interface film, changing the emulsion from stable to unstable, and finally achieving the effect of oil-water separation.
The demulsifier is a surfactant capable of separating oil from water of crude oil emulsion, and can be used for realizing oil-water separation by damaging a stable film in a mode of replacing an emulsion stable film so as to ensure that the water output from the crude oil meets the specified requirements. At present, demulsifiers are various in types, and can be classified according to a surfactant classification method: cationic, anionic and nonionic. After being dissolved in water, the cationic demulsifier can form an ionic group with positive charges, mainly quaternary ammonium salts, and the demulsifier generally has poor effect on common thin oil, thickened oil and the like; after being dissolved in water, the anionic demulsifier forms negatively charged ionic groups, mainly carboxylates, sulfonates and sulfates, and the demulsifiers are seriously influenced by the mineralization degree; the nonionic demulsifier has no positive charge or negative charge after being dissolved in water, and the main types of the nonionic demulsifier include phenolic resin polyoxypropylene polyoxyethylene ether, polyalcohol polyoxypropylene polyoxyethylene ether, organic amine polyoxypropylene polyoxyethylene ether and the like, and the nonionic demulsifier is also a product with strongest universality, strongest anti-interference capability and largest application amount at present.
In recent years, most demulsifiers applied to oil fields are mainly compounded, the main direction of the demulsifiers is still in the aspect of the performance of the demulsifiers, and the requirements of other secondary performances such as sterilization, corrosion inhibition and the like are still realized by adopting a compounding mode. Most of the agents used for sterilization and corrosion inhibition are ionic substances, and after being compounded with the demulsifier, the agents can more or less influence the final demulsification performance product. Therefore, the development of the multi-performance demulsifier product has positive significance for the application of the demulsifier product.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide imidazole ring polyoxypropylene polyoxyethylene polyether, an intermediate for synthesizing the imidazole ring polyoxypropylene polyoxyethylene polyether and a synthetic method;
the second technical problem to be solved by the invention is to provide the demulsifier with the corrosion inhibition performance, wherein the demulsifier has a new structure, is endowed with certain corrosion inhibition performance, enhances the protection of pipelines and storage tanks, and overcomes the problem of single aging performance of the demulsifier in the prior art.
In order to solve the technical problems, the imidazole ring polyoxypropylene polyoxyethylene polyether has a structure shown as the following formula (I):
wherein x is an integer of 0 to 2;
R 1 selected from substituted or unsubstituted C 2 -C 20 A saturated fatty chain, a substituted or unsubstituted monounsaturated fatty chain, a substituted or unsubstituted polyunsaturated fatty chain, or a mixed chain of the above at least two fatty chains;
R 2 is a polyoxypropylene polyoxyethylene segment having the structure shown in the following formula (II):
wherein m is 20-100, n is 28-120.
Optionally, the R is 1 Is selected from C 16 H 32 、C 16 H 33 、C 17 H 34 、C 17 H 35 、C 18 H 36 Or C 18 H 37 One or more of them.
The invention also discloses an intermediate for preparing the imidazole ring polyoxypropylene polyoxyethylene polyether, and the intermediate has a structure shown as the following formula (M):
wherein x is an integer of 0 to 2;
R 1 selected from substituted or unsubstituted C 2 -C 20 Saturated fatty chains, substituted or unsubstituted monounsaturated fatty chains, substituted or unsubstituted polyunsaturated fatty chains,alternatively, a mixed chain of the above-mentioned at least two kinds of fatty chains.
The invention also discloses a method for preparing the intermediate, which comprises the steps of slowly dripping organic amine into a mixed solution containing organic acid and a water carrying agent and carrying out heat preservation reaction, and the required intermediate is obtained through the steps of heating, refluxing, dehydrating and removing the solvent in vacuum.
Specifically, the preparation method of the intermediate comprises the following steps:
the organic amine comprises at least one of ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine, and preferably tetraethylene pentamine;
the organic acid is at least one of oleic acid, linoleic acid, palmitic acid, arachidic acid, linolenic acid or stearic acid, and is preferably oleic acid;
the water carrying agent comprises at least one of toluene, xylene, trimethylbenzene, 120# solvent oil, 150# solvent oil or 200# solvent oil.
Specifically, the preparation method of the intermediate comprises the following steps:
the molar ratio of the organic acid to the organic amine is 1: 0.5-2, preferably in a molar ratio of 1 mol: 0.8-1.2 mol;
the dosage of the water carrying agent accounts for 20-90 wt% of the total amount of the reaction substrate, and the preferred dosage is 40 wt%.
The invention also discloses a method for preparing the imidazole ring polyoxypropylene polyoxyethylene polyether, which comprises the step of carrying out polymerization reaction on the intermediate, propylene oxide and ethylene oxide;
the molar ratio of the intermediate to the propylene oxide and the ethylene oxide is 1: 20-200: 20-240, preferably in a molar ratio of 1: 60-90: 30-50.
The invention also discloses application of the imidazole ring polyoxypropylene polyoxyethylene polyether in preparation of a demulsifier with corrosion inhibition performance.
The invention also discloses a demulsifier with corrosion inhibition performance, which comprises the imidazole ring polyoxypropylene polyoxyethylene polyether.
Specifically, the demulsifier further comprises a solvent;
the solvent includes at least one of methanol, ethanol, or water.
The invention also discloses application of the demulsifier with corrosion inhibition performance in demulsification of crude oil in an oil field.
The imidazole ring polyoxypropylene polyoxyethylene polyether provided by the invention takes an imidazole ring as a main structure, and simultaneously keeps four active hydrogens to continuously react with propylene oxide and ethylene oxide, so that a multi-branched polyether structure containing an imidazoline structure is generated. The demulsifier is added with an imidazoline structure on the basis of ensuring a multi-branched-chain structure, the multi-branched-chain structure can ensure the demulsification performance of the demulsifier, can realize the demulsification and dehydration of crude oil, has the characteristics of high dehydration speed and water quality of dehydrated water, and simultaneously endows the demulsifier with certain corrosion inhibition performance through the adsorption effect of nitrogen atoms on the imidazole-branched-chain structure, and can form a layer of protective film on the metal surface to prevent the metal from being corroded by crude oil emulsion.
The demulsifier with corrosion inhibition performance has good compounding performance, can be compounded and dissolved with alcohols and/or water to form clear and bright solution, can be well compatible with products such as imidazoline quaternary ammonium salt, quaternary ammonium salt bactericide, polymer scale inhibitor and the like, and can be compounded at will according to the formula requirements.
The preparation method of the demulsifier with corrosion inhibition performance provided by the invention takes organic acid and organic amine as main raw materials, obtains an intermediate containing an imidazoline structure through amidation reaction and cyclization reaction in a water carrying agent, and then performs common alkoxylation reaction with propylene oxide and ethylene oxide.
According to the preparation method of the demulsifier with corrosion inhibition performance, the preferable organic acid is oleic acid, the organic amine is tetraethylenepentamine, the carbon chain length of the oleic acid is 18 carbons, the oleic acid has a hydrophobic effect, the oleic acid is convenient to form a film on the metal surface, and the protective effect is enhanced, the tetraethylenepentamine is a multi-branched structure, the tetraethylenepentamine has a plurality of groups capable of being alkoxylated, the multi-branched structure enhances the diffusion of the demulsifier in crude oil emulsion, the water droplet coalescence speed and the separation efficiency are accelerated, and the dehydration speed and the quality of dehydrated water are improved.
Detailed Description
The present invention can be carried out according to the procedures or conditions of the conventional experimental procedures described in the literature in the field, without specifying the specific experimental procedures or conditions in the following examples. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 30 and n is 14.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) at room temperature, 315kg of No. 120 solvent oil and 282kg of oleic acid are added into a reactor, and the temperature is raised to 100 ℃ and the mixture is fully stirred until the state is uniform; slowly dripping 189kg of tetraethylenepentamine at the temperature of 100 ℃, controlling the dripping time to be 60min, after finishing dripping, carrying out heat preservation reaction at the temperature of 100 ℃ for 30min, then starting to slowly heat up for reflux dehydration, taking the temperature of 10 ℃ as a gradient, starting to heat up to the next stage when no water is removed in a receiver, finally heating up to 200-210 ℃, carrying out heat preservation reaction for 2h until no water is removed, then slowly starting vacuum, carrying out vacuum desolventization until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M1;
(2) putting the intermediate M1100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 1600kg of propylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 560kg of ethylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the system pressure is reduced to-0.1 MPa, cooling and discharging to obtain the required demulsifier dry agent, which is marked as M-PE 1.
Example 2
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 30 and n is 24.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) at room temperature, 315kg of No. 150 solvent oil and 282kg of oleic acid are added into a reactor, and the temperature is raised to 100 ℃ and the mixture is stirred until the state is uniform; slowly dripping 189kg of tetraethylenepentamine at the temperature of 100 ℃, controlling the dripping time to be 60min, carrying out heat preservation reaction at the temperature of 100 ℃ for 30min after finishing dripping, then slowly heating up, refluxing and dehydrating, taking the temperature of 10 ℃ as a gradient, heating up to the next stage when no water is removed from the receiver, finally heating up to 200-210 ℃, carrying out heat preservation reaction for 2h until no water is removed, then slowly starting vacuum, carrying out vacuum desolventization until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M2;
(2) putting the intermediate M2100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 1600kg of propylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 960kg of ethylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain the required demulsifier dry agent, which is marked as M-PE 2.
Example 3
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 44 and n is 14.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of 200# solvent oil and 282kg of oleic acid are added into a reactor at room temperature, the temperature is raised to 100 ℃, and the mixture is stirred until the state is uniform; slowly dripping 189kg of tetraethylenepentamine at the temperature of 100 ℃, controlling the dripping time to be 60min, keeping the temperature at 100 ℃ for reaction for 30min after finishing dripping, then slowly heating up, refluxing and dehydrating, taking 10 ℃ as a gradient, starting heating up to the next stage when no water is removed from the receiver, finally heating up to 200-210 ℃, keeping the temperature for reaction for 2h until no water is removed, then slowly starting vacuum, desolventizing in vacuum until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M3;
(2) adding an initiator M3100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 2350kg of propylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 560kg of ethylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain a demulsifier dry agent, wherein the notation is M-PE 3.
Example 4
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 44 and n is 24.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of 120# solvent oil and 282kg of oleic acid are added into a reactor at room temperature, the temperature is raised to 100 ℃, and the mixture is stirred until the state is uniform; slowly dripping 189kg of tetraethylenepentamine at the temperature of 100 ℃, controlling the dripping time to be 60min, keeping the temperature at 100 ℃ for reaction for 30min after finishing dripping, then slowly heating up, refluxing and dehydrating, taking 10 ℃ as a gradient, starting heating up to the next stage when no water is removed from the receiver, finally heating up to 200-210 ℃, keeping the temperature for reaction for 2h until no water is removed, then slowly starting vacuum, desolventizing in vacuum until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M4;
(2) adding an initiator M4100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 2350kg of propylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 960kg of ethylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain a demulsifier dry agent, wherein the notation is M-PE 4.
Example 5
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 38 and n is 20.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of dimethylbenzene and 282kg of oleic acid are added into a reactor at room temperature, and the temperature is raised to 100 ℃ and the mixture is stirred until the mixture is uniform. Slowly dripping 189kg of tetraethylenepentamine at the temperature of 100 ℃, controlling the dripping time to be 60min, keeping the temperature at 100 ℃ for reaction for 30min after finishing dripping, then slowly heating up, refluxing and dehydrating, taking 10 ℃ as a gradient, starting heating up to the next stage when no water is removed from the receiver, finally heating up to 200-210 ℃, keeping the temperature for reaction for 2h until no water is removed, then slowly starting vacuum, desolventizing in vacuum until the solvent is completely removed, cooling to 70 ℃ and discharging to obtain an intermediate M5;
(2) and putting the intermediate M5100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 2030kg of propylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 800kg of ethylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain the demulsifier dry agent, and marking as M-PE 5.
Example 6
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 38 and n is 20.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of dimethylbenzene and 282kg of oleic acid are added into a reactor at room temperature, and the temperature is raised to 100 ℃ and the mixture is stirred until the mixture is uniform. Slowly dripping 146kg of triethylene tetramine at the temperature of 100 ℃, controlling the dripping time to be 60min, after finishing dripping, carrying out heat preservation reaction at the temperature of 100 ℃ for 30min, then slowly heating up, refluxing and dehydrating, taking the temperature of 10 ℃ as a gradient, when no water is removed from a receiver, heating up to the next stage, finally heating up to 200-210 ℃, carrying out heat preservation reaction for 2h until no water is removed, then slowly starting vacuum, carrying out vacuum desolventization until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M6;
(2) putting the intermediate M6100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 1690kg of epoxypropane, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120 ℃ -125 ℃, continuously and slowly introducing 670kg of epoxyethane, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain the demulsifier drier, and marking as M-PE 6.
Example 7
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 38 and n is 20.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of dimethylbenzene and 282kg of oleic acid are added into a reactor at room temperature, and the temperature is raised to 100 ℃ and the mixture is stirred until the mixture is uniform. Slowly dripping 103kg of diethylenetriamine at the temperature of 100 ℃, controlling the dripping time to be 60min, keeping the temperature at 100 ℃ for reaction for 30min after finishing dripping, then starting to slowly heat up, refluxing and dehydrating, taking 10 ℃ as a gradient, starting to heat up to the next stage when no water is removed from the receiver, finally heating up to 200-210 ℃, keeping the temperature for reaction for 2h until no water is removed, then slowly starting vacuum, desolventizing in vacuum until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M7;
(2) putting the intermediate M7100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 1260kg of propylene oxide, heating to 130 ℃ after material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 500kg of ethylene oxide, heating to 130 ℃ after material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain the demulsifier drier, and recording as M-PE 7.
Example 8
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 38 and n is 20.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of 150# solvent oil and 282kg of oleic acid are added into a reactor at room temperature, the temperature is increased to 100 ℃, and the mixture is stirred until the state is uniform. Slowly dripping 189kg of tetraethylenepentamine at the temperature of 100 ℃, controlling the dripping time to be 60min, keeping the temperature at 100 ℃ for reaction for 30min after finishing dripping, then slowly heating up, refluxing and dehydrating, taking 10 ℃ as a gradient, starting heating up to the next stage when no water is removed from the receiver, finally heating up to 200-210 ℃, keeping the temperature for reaction for 2h until no water is removed, then slowly starting vacuum, desolventizing in vacuum until the solvent is completely removed, cooling to 70 ℃ and discharging to obtain an intermediate M8;
(2) and putting the intermediate M8100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 2030kg of epoxypropane, heating to 130 ℃ after material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 800kg of epoxyethane, heating to 130 ℃ after material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain the demulsifier drier, and recording as M-PE 8.
Example 9
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 38 and n is 20.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of 150# solvent oil and 282kg of oleic acid are added into a reactor at room temperature, the temperature is increased to 100 ℃, and the mixture is stirred until the state is uniform. Slowly dripping 146kg of triethylene tetramine at the temperature of 100 ℃, controlling the dripping time to be 60min, after finishing dripping, carrying out heat preservation reaction at the temperature of 100 ℃ for 30min, then slowly heating up, refluxing and dehydrating, taking the temperature of 10 ℃ as a gradient, when no water is removed from a receiver, heating up to the next stage, finally heating up to 200-210 ℃, carrying out heat preservation reaction for 2h until no water is removed, then slowly starting vacuum, carrying out vacuum desolventization until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M9;
(2) putting the intermediate M9100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 1690kg of propylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 670kg of ethylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain the demulsifier dry agent, and marking as M-PE 9.
Example 10
The imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier disclosed by the embodiment has the following structural formula:
wherein m is 38 and n is 20.
The preparation method of the imidazole ring polyoxypropylene polyoxyethylene polyether demulsifier comprises the following steps:
(1) 315kg of 150# solvent oil and 282kg of oleic acid are added into a reactor at room temperature, the temperature is increased to 100 ℃, and the mixture is stirred until the state is uniform. Slowly dropwise adding 103kg of diethylenetriamine at the temperature of 100 ℃, controlling the dropwise adding time to be 60min, after the dropwise adding is finished, carrying out heat preservation reaction at the temperature of 100 ℃ for 30min, then slowly heating up, refluxing and dehydrating, taking the temperature of 10 ℃ as a gradient, when no water is removed from the receiver, heating up to the next stage, finally heating up to 200-210 ℃, carrying out heat preservation reaction for 2h until no water is removed, then slowly starting vacuum, carrying out vacuum desolventization until the solvent is completely removed, cooling to 70 ℃, and discharging to obtain an intermediate M10;
(2) and putting the intermediate M10100 kg into a high-temperature high-pressure reaction kettle, heating to 125 ℃, carrying out vacuum treatment for 30min, then slowly introducing 1260kg of propylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling to 120-125 ℃, continuously and slowly introducing 500kg of ethylene oxide, heating to 130 ℃ after the material introduction is finished, carrying out heat preservation reaction for 2h until the pressure is reduced to-0.1 MPa, cooling and discharging to obtain the demulsifier dry agent, and marking as M-PE 10.
Comparative example 1
The comparative example scheme is that according to the scheme of the water-soluble non-ionic imidazoline corrosion inhibitor disclosed in Chinese patent document CN103320797B, imidazoline is used as an initiator to be copolymerized with ethylene oxide, propylene oxide and butylene oxide to obtain the water-soluble imidazoline corrosion inhibitor. However, the polyether product synthesized by the scheme is only used as a corrosion inhibitor and does not have demulsification performance. In addition, the scheme has the advantages that the price of the used epoxy butane is high, the toxicity is strong, the application of the epoxy butane in China is not completely developed, and the danger is high.
Examples of the experiments
1. Demulsification experiment
Subject: the Changqing oilfield field crude oil emulsion (with water content of 28 wt%, wax content of about 12 wt%, 50mPa & s viscosity at 50 ℃ and condensation point of about 20 ℃) is prepared.
Preparing a demulsifier solution: 200g of the demulsifier dry agent M-PE prepared in each group of examples is taken, 100kg of methanol and 100g of water are sequentially added, and a series of demulsifier solutions are obtained after uniform mixing.
The experimental method comprises the following steps: and detecting the demulsification effect of the demulsifier on the crude oil emulsion by adopting a bottle test method according to the national standard SY/T5281-2018.
The dosage is 100ppm except for the blank group, and the blank group is naturally demulsified without adding a demulsifier solution.
The test temperature is 50 ℃, the test time is 90min, the water yield of 15min, 30min, 60min and 90min is recorded, and the dehydration rate is calculated.
For aqueous cleanliness, the first order represents: clear water is removed and is transparent or milk white; secondary representation: the dehydrated water is relatively clear and is light yellow; three-level representation: the dehydrated water is turbid and is yellow and brown; the four levels represent: turbid after dehydration, deep brown or black.
The test results are shown in table 1 below.
Table 1 demulsification effect test results of demulsifiers
As can be seen from the data in the table above, the demulsifier with the structure of the invention has better demulsification performance, wherein the performances of the imidazole ring polyoxypropylene polyoxyethylene polyether defined in the examples 5 and 8 are optimal; the comparison of the scheme data in the embodiment 1 and the embodiment 2 shows that the increase of the ethylene oxide content in the polymer can improve the demulsification efficiency of the product, and the demulsification efficiency is characterized by high dehydration speed and high final dehydration rate; the comparison of the example 3 and the example 4 shows that the demulsification performance of the product can be improved by reducing the content of the propylene oxide; comparing examples 5, 6 and 7 with examples 8, 9 and 10, it was found that the solvent used in the synthesis stage of the initiator had no effect on the final product.
In conclusion, the demulsifier with the structure has better demulsification performance, and the proportion of the propylene oxide and the ethylene oxide in the embodiments 5 and 8 is the better proportion for processing the crude oil emulsion, so that the demulsification performance is better.
2. Corrosion inhibition experiment
Subject: changqing oilfield field sewage.
Preparing a demulsifier solution: 200g of the demulsifier dry agent M-PE prepared in each group of examples is taken, 100kg of methanol and 100g of water are sequentially added, and a series of demulsifier solutions are obtained after uniform mixing.
The experimental method comprises the following steps: and detecting the corrosion inhibition effect of the demulsifier according to the technical requirement of the corrosion inhibitor for water treatment of the oil field with the medium petrochemical standard Q/SH CG 0040-2021.
The test steel sheet is A3 steel sheet, and the dosage of the product is 30 ppm.
The test temperature is 50 +/-2 ℃, the time is 7 days, and the corrosion inhibition rate is calculated by a static normal pressure weight loss method.
The test results are shown in table 2 below.
Table 2 corrosion inhibition effect test results of demulsifier
| Product(s) | Dosage/ppm | Weight loss per gram | Corrosion inhibition rate |
| Blank space | 0 | 0.0086 | / |
| Example 1 | 30 | 0.0049 | 43.02％ |
| Example 2 | 30 | 0.0051 | 40.70％ |
| Example 3 | 30 | 0.0046 | 45.51％ |
| Example 4 | 30 | 0.0061 | 29.07％ |
| Example 5 | 30 | 0.0041 | 52.33％ |
| Example 6 | 30 | 0.0041 | 52.33％ |
| Example 7 | 30 | 0.0043 | 50.00％ |
| Example 8 | 30 | 0.0042 | 51.16％ |
| Example 9 | 30 | 0.0042 | 51.16％ |
| Example 10 | 30 | 0.0042 | 51.16％ |
From the above table of corrosion inhibition experimental data, the demulsifier with the structure provided by the invention has good corrosion inhibition performance, wherein the demulsifier schemes in the examples 5 and 8 show good corrosion inhibition performance, and the comparison of the data of the schemes can find that the demulsifier scheme with more ethylene oxide in the components in the examples has relatively poor slow release effect, and the analysis shows that the water solubility of the demulsifier can be enhanced after the ethylene oxide proportion is increased because the ethoxylate is hydrophilic and the propoxylate is lipophilic, so that a stable protective film can not be formed on the metal surface, and the corrosion inhibition effect is influenced.
In conclusion, the demulsifier with the imidazole ring polyoxypropylene polyoxyethylene polyether structure provided by the invention has expected corrosion inhibition performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An imidazole ring polyoxypropylene polyoxyethylene polyether, which is characterized by having a structure shown as the following formula (I):
wherein x is an integer of 0 to 2;
R 1 selected from substituted or unsubstituted C 2 -C 20 A saturated fatty chain, a substituted or unsubstituted monounsaturated fatty chain, a substituted or unsubstituted polyunsaturated fatty chain, or a mixed chain of the above at least two fatty chains;
R 2 is a polyoxypropylene polyoxyethylene segment having the structure shown in the following formula (II):
wherein m is 20-100, n is 28-120.
2. The imidazole ring polyoxypropylene polyoxyethylene polyether according to claim 1, wherein R is 1 Is selected from C 16 H 32 、C 16 H 33 、C 17 H 34 、C 17 H 35 、C 18 H 36 Or C 18 H 37 One or more of them.
3. An intermediate for preparing the imidazole ring polyoxypropylene polyoxyethylene polyether of claim 1 or 2, wherein the intermediate has the structure shown in formula (M):
wherein x is an integer of 0 to 2;
R 1 selected from substituted or unsubstituted C 2 -C 20 A saturated fatty chain, a substituted or unsubstituted monounsaturated fatty chain, a substituted or unsubstituted polyunsaturated fatty chain, or a mixed chain of at least two of the above fatty chains.
4. The method for preparing the intermediate of claim 3, which is characterized by comprising the steps of slowly dropwise adding organic amine into a mixed solution containing organic acid and a water carrying agent, carrying out heat preservation reaction, heating, refluxing, dehydrating and removing the solvent in vacuum to obtain the required intermediate.
5. The process for the preparation of the intermediate according to claim 4, characterized in that:
the organic amine comprises at least one of ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine;
the organic acid is at least one of oleic acid, linoleic acid, palmitic acid, arachidic acid, linolenic acid or stearic acid;
the water carrying agent comprises at least one of toluene, xylene, trimethylbenzene, 120# solvent oil, 150# solvent oil or 200# solvent oil.
6. The process for the preparation of the intermediate according to claim 4 or 5, characterized in that:
the molar ratio of the organic acid to the organic amine is 1: 0.5 to 2;
the dosage of the water carrying agent accounts for 20-90 wt% of the total amount of the reaction substrate.
7. A process for preparing the imidazole ring polyoxypropylene polyoxyethylene polyether of claim 1 or 2, comprising the step of polymerizing the intermediate of claim 3 with propylene oxide and ethylene oxide;
the molar ratio of the intermediate to the propylene oxide and the ethylene oxide is 1: 20-200: 20-240.
8. Use of the imidazole ring polyoxypropylene polyoxyethylene polyether according to claim 1 or 2 for preparing demulsifiers with corrosion inhibiting properties.
9. An emulsion breaker with corrosion inhibition performance, which is characterized by comprising the imidazole ring polyoxypropylene polyoxyethylene polyether in claim 1 or 2.
10. The demulsifier of claim 9, wherein the demulsifier further comprises a solvent; the solvent includes at least one of methanol, ethanol, or water.
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Citations (2)
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| CN103320797A (en) * | 2013-05-30 | 2013-09-25 | 天津科维津宏环保科技有限公司 | Water-soluble non-ionic imidazoline corrosion inhibitor and preparation method thereof |
| CN113480446A (en) * | 2021-05-27 | 2021-10-08 | 佳化化学科技发展（上海）有限公司 | Amine compound, polymer polyol, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103320797A (en) * | 2013-05-30 | 2013-09-25 | 天津科维津宏环保科技有限公司 | Water-soluble non-ionic imidazoline corrosion inhibitor and preparation method thereof |
| CN113480446A (en) * | 2021-05-27 | 2021-10-08 | 佳化化学科技发展（上海）有限公司 | Amine compound, polymer polyol, and preparation method and application thereof |
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| 董国君等: "《表面活性剂化学》", 北京理工大学出版社, pages: 217 * |
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