CN112662422B - Crude oil demulsifier and preparation method and application thereof - Google Patents
Crude oil demulsifier and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a crude oil demulsifier and a preparation method thereof, wherein the crude oil demulsifier comprises a copolymer which is formed by polymerizing a polyoxyethylene polyoxypropylene ether monomer with a double bond at the end group, a hydrophobic monomer and a hydrophilic monomer through emulsion. The crude oil demulsifier provided by the invention uses the surface active agents such as alkyl sodium sulfonate and the like as the emulsifier, the demulsifier simultaneously contains various structures such as anionic surface active agent, polyether and acrylate, so that the demulsifier has higher surface activity, the copolymer is prepared by adopting a core-shell emulsion polymerization technology, and the emulsion particles have an oleophilic and hydrophilic amphiphilic structure. The novel demulsifier can select the copolymers with different proportions to prepare the corresponding demulsifier according to different crude oil water-in-oil emulsions, thereby improving the broad-spectrum performance of the demulsifier.
Description
Technical Field
The invention belongs to the technical field of crude oil demulsifiers, and particularly relates to a crude oil demulsifier, and a preparation method and application thereof.
Background
In the process of petroleum exploitation and processing, colloid, asphaltic substances, naphthenic acid, fatty acid and salt, crystalline paraffin and various artificially introduced substances with surface activity in crude oil cause the crude oil and water to exist in a water-in-oil or oil-in-water emulsion state, and the oil-water emulsion brings a series of problems to the storage, transportation and processing of the crude oil. The crude oil demulsifier is a surfactant capable of destroying emulsion, and its molecule has both lipophilic and hydrophilic groups, and when it is added into crude oil emulsion, the emulsion is broken, so that it is called chemical demulsification. The demulsifier research started in the 20 th 20 s, and used the first-generation crude oil demulsifier, which mainly comprises anionic surfactant. After the 40 s, second generation crude oil demulsifiers were developed. Since the 60 s, the third generation crude oil demulsifiers mainly based on high molecular nonionic surfactants are researched and applied. After 1990, the amphoteric surfactant research was successful and was in practical use. Since the late 20 th century and 80 s, the research and development of foreign (mainly American) demulsifiers are rapid, and a large amount of novel demulsifier products are researched and developed on the basis of the improvement of third-generation polyether demulsifiers with high relative molecular mass, and the important progress is achieved. Compared with the foreign demulsifiers, the domestic demulsifiers have the following problems: the using amount of the demulsifier is large; small application range, sensitivity to crude oil property change and the like. Therefore, it is necessary to develop a novel efficient demulsifier with wide application range.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a crude oil demulsifier and a preparation method thereof. The novel demulsifier can select the copolymers with different proportions to prepare the corresponding demulsifier according to different crude oil water-in-oil emulsions, thereby improving the broad-spectrum performance of the demulsifier.
To this end, the invention provides a crude oil demulsifier, which comprises a copolymer formed by emulsion polymerization of a polyoxyethylene polyoxypropylene ether monomer with a double bond at the end group, a hydrophobic monomer and a hydrophilic monomer,
wherein the polyoxyethylene polyoxypropylene ether monomer with the terminal group containing double bonds comprises allyl alcohol polyoxyethylene polyoxypropylene ether.
According to some embodiments of the present invention, the polyoxyethylene polyoxypropylene ether monomer having a double bond at an end group has a mass content of 5-80% by weight, for example, 5%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 54%, 55%, 56%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 74%, 75%, 78%, 80% by weight, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at an end group, the hydrophobic monomer, and the hydrophilic monomer, and any value therebetween.
According to some embodiments of the present invention, the polyoxyethylene polyoxypropylene ether monomer having a terminal group containing a double bond has a mass content of 10-60% based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a terminal group containing a double bond, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the hydrophobic monomer is present in an amount of 20 to 95% by mass, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% by mass and any value therebetween, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a terminal group containing a double bond, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the hydrophobic monomer is present in an amount of 35 to 85% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer, and the hydrophilic monomer.
According to some embodiments of the present invention, the hydrophilic monomer is present in an amount of 1 to 10% by mass, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal, the hydrophobic monomer, and the hydrophilic monomer, for example, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 10%, and any value therebetween.
According to some embodiments of the present invention, the hydrophilic monomer is present in an amount of 3 to 8% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer, and the hydrophilic monomer.
According to some embodiments of the invention, the hydrophobic monomer is selected from at least one of methacrylate compounds and acrylate compounds.
According to some embodiments of the invention, the hydrophobic monomer is selected from at least one of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl methacrylate, ethylhexyl acrylate, isooctyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate and stearyl methacrylate.
According to some embodiments of the invention, the hydrophilic monomer is selected from at least one of an acrylic compound and a methacrylic compound.
According to some embodiments of the invention, the hydrophilic monomer is selected from one or more of methacrylic acid and acrylic acid.
The second aspect of the invention provides a preparation method of the crude oil demulsifier according to the first aspect of the invention, which comprises adopting a core-shell emulsion polymerization mode, and comprises the following specific steps:
s1: mixing a polyoxyethylene polyoxypropylene ether monomer with a double bond at the end group, a hydrophobic monomer, a first part of emulsifier, an auxiliary emulsifier and a buffer agent in a first part of solvent to form a nuclear layer pre-emulsion;
s2: mixing a hydrophilic monomer and a second part of emulsifier in a second part of solvent to form a shell layer emulsion;
s3: dissolving an initiator in the third portion of solvent to form an initiator solution;
s4: and adding a part of initiator solution into the nuclear layer pre-emulsion, preserving heat for the first time, adding the shell layer emulsion and the rest part of initiator solution, and preserving heat for the second time to obtain the crude oil demulsifier.
According to some embodiments of the invention, the emulsifier is selected from one or more of petroleum sulfonate, sodium dodecyl sulfonate, sodium alkyl benzene sulfonate, sodium dodecyl sulfate, and polyoxyethylene alkyl phenol ether.
According to some embodiments of the invention, the co-emulsifier is selected from one or more of methanol, ethanol, ethylene glycol, isopropanol, glycerol, n-butanol and isoamyl alcohol.
According to some embodiments of the invention, the buffer is selected from one or more of sodium hydrogen phosphate, sodium carbonate or sodium bicarbonate.
According to some embodiments of the invention, the initiator is selected from one or more of ammonium persulfate, potassium persulfate, dimethyl 2, 2-azobisisobutyrate, 2-azo [2- (2-imidazolinyl) propane ] dihydrochloride, azobisisobutyramidine hydrochloride.
According to some embodiments of the invention, the solvent is water.
According to some embodiments of the present invention, the polyoxyethylene polyoxypropylene ether monomer having a double bond at an end group has a mass content of 5-80% by weight, for example, 5%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 54%, 55%, 56%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 74%, 75%, 78%, 80% by weight, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at an end group, the hydrophobic monomer, and the hydrophilic monomer, and any value therebetween.
According to some embodiments of the present invention, the polyoxyethylene polyoxypropylene ether monomer having a terminal group containing a double bond has a mass content of 10-60% based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a terminal group containing a double bond, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the hydrophobic monomer is present in an amount of 20 to 95% by mass, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% by weight and any value therebetween, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal, the hydrophobic monomer, and the hydrophilic monomer.
According to some embodiments of the present invention, the hydrophobic monomer is present in an amount of 35 to 85% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the hydrophilic monomer is present in an amount of 1 to 10% by mass, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal, the hydrophobic monomer, and the hydrophilic monomer, for example, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 10%, and any value therebetween.
According to some embodiments of the present invention, the hydrophilic monomer is present in an amount of 3 to 8% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the total emulsifier is present in an amount of 1 to 10% by mass, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the total emulsifier is present in an amount of 5 to 9% by mass, based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the co-emulsifier is present in an amount of 1 to 10% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the co-emulsifier is present in an amount of 3 to 6% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the buffer is contained in an amount of 0.5 to 10% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, the buffer is added to adjust the pH of the core layer pre-emulsion, so that the core layer pre-emulsion maintains a slightly alkaline environment, and the specific amount of the buffer can be adjusted according to actual conditions.
In some preferred embodiments of the present invention, the buffer is present in an amount of 3 to 8% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the invention, the ratio of the total solvent to the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer is (1-5): 1.
According to some embodiments of the present invention, the ratio of the total solvent to the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer, and the hydrophilic monomer is (1-3): 1.
According to some embodiments of the invention, the mass ratio of the first portion of emulsifier to the second portion of emulsifier is (4-20): 1.
According to some embodiments of the present invention, the initiator is used in an amount of 0.1 to 1.0 wt% based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer.
According to some embodiments of the present invention, in step S4, a portion of the initiator solution is added to the core layer pre-emulsion heated to 50 to 100 ℃, preferably to 60 to 90 ℃; the first time is 2-4 h; the second time is 2-5 h.
In some preferred embodiments of the present invention, the method for preparing the crude oil demulsifier comprises the steps of:
(1) preparing a nuclear layer pre-emulsion, namely adding 30-50 parts by weight of deionized water into a beaker, starting stirring, adding 0.5-10 parts by weight of an emulsifier, 1-2 parts by weight of an auxiliary emulsifier and 0.5-5.0 parts by weight of a buffering agent at one time, stirring, mixing for 10 minutes, adding 1-30% by weight of allyl alcohol polyoxyethylene polyoxypropylene ether and 5-30% by weight of an acrylate monomer, adjusting the rotation speed to 100-200rpm, and emulsifying at high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
(2) preparing a shell pre-emulsion, namely adding 5-20 parts by weight of deionized water into a beaker, starting stirring, adding 0.1-1 part by weight of an emulsifier, adding 0.5-5 parts by weight of acrylic acid, and stirring for 30 minutes to prepare a shell emulsion for later use;
(3) preparing an initiator solution, namely adding 1-10 parts by weight of deionized water into a beaker, then adding the initiator, uniformly stirring to prepare the initiator solution for later use;
(4) adding the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60-90 ℃, introducing nitrogen to replace air, then beginning to dropwise add 80% of initiator solution for 30min, carrying out heat preservation reaction for 2-4 hours after dropwise adding, then simultaneously dropwise adding the shell layer pre-emulsion and 20% of initiator solution for 30min, carrying out heat preservation reaction for 2-5 hours, then cooling to normal temperature, and discharging.
The crude oil demulsifier provided by the invention uses the surface active agents such as alkyl sodium sulfonate and the like as the emulsifier, the demulsifier simultaneously contains various structures such as anionic surface active agent, polyether and acrylate, so that the demulsifier has higher surface activity, the copolymer is prepared by adopting a core-shell emulsion polymerization technology, the emulsion particles have an oleophilic and hydrophilic amphiphilic structure, and the demulsifier has a long-chain-branch structure due to the introduction of allyl alcohol polyoxyethylene polyoxypropylene ether.
The third aspect of the invention provides an application of the crude oil demulsifier of any one of the first aspects or the crude oil demulsifier prepared by the preparation method of any one of the second aspects in petroleum extraction and processing.
Detailed Description
In order that the invention may be more readily understood, the invention will now be described in detail with reference to the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Allyl alcohol polyoxyethylene polyoxypropylene Ether (manufacturer: Haian petrochemical plant, Jiangsu province, type: polyether F6, hydroxyl value: 45 + -8 mg KOH/g, double bond value: more than or equal to 0.5mmol/g)
The test method or the calculation method provided by the invention is as follows:
water yield (%) at different settling times (water yield (ml) at different times/total water content (ml) in crude oil emulsion) x 100%.
Example 1
Preparing a core layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl sulfate, 1 g of OP-102 g, 2 g of n-butyl alcohol and 3 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 2 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 20 g of butyl acrylate and 15 g of methyl methacrylate, adjusting the rotating speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a core layer pre-emulsion for later use;
preparing a shell pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl sulfate serving as an emulsifier and 3 g of acrylic acid, and stirring for 30 minutes to prepare a shell emulsion for later use;
preparing an initiator solution, namely adding 10 g of deionized water into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60 ℃, introducing nitrogen to replace air, then beginning to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 60 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 60 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
Example 2
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl benzene sulfonate, 1 g of OP-102 g of sodium dodecyl benzene sulfonate, 2 g of n-butyl alcohol and 2.9 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 4 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 23 g of butyl acrylate and 10.1 g of dodecyl acrylate, adjusting the rotating speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell layer pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl benzene sulfonate serving as an emulsifier and 2.9 g of acrylic acid, and stirring for 30 minutes to prepare a shell layer emulsion for later use;
preparing an initiator solution, namely adding 10 g of deionized water into a beaker, then adding 0.25 g of initiator potassium persulfate, and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 85 ℃, introducing nitrogen to replace air, then beginning to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 85 ℃ after dropwise adding, reacting for 2-4h, then dropwise adding the shell layer pre-emulsion and the rest initiator solution at the same time for 30min, keeping the reaction temperature at 85 ℃, reacting for 2-5h, cooling to normal temperature, and discharging.
Example 3
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl sulfate, 1 g of OP-102 g, 2 g of n-butyl alcohol and 2.72 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 6 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 20 g of butyl acrylate and 11.28 g of methyl methacrylate, adjusting the rotation speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell layer pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl sulfate serving as an emulsifier and 2.72 g of acrylic acid, and stirring for 30 minutes to prepare a shell layer emulsion for later use;
preparing an initiator solution, namely adding 10 g of deionized water into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60 ℃, introducing nitrogen to replace air, then starting to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 60 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 60 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
Example 4
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl benzene sulfonate, 1 g of OP-102 g of sodium dodecyl benzene sulfonate, 2 g of n-butyl alcohol and 2.4 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 10 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 20 g of butyl acrylate and 7.6 g of isooctyl acrylate, adjusting the rotation speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl benzene sulfonate serving as an emulsifier and 2.4 g of acrylic acid, and stirring for 30 minutes to prepare a shell emulsion for later use;
preparing an initiator solution, namely adding deionized water 10 into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 65 ℃, introducing nitrogen to replace air, then beginning to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 65 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 65 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
Example 5
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl sulfate, 1 g of OP-102 g, 2 g of n-butyl alcohol and 2.2 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 12 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 15 g of butyl acrylate and 10.8 g of methyl methacrylate, adjusting the rotation speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl sulfate serving as an emulsifier and 2.2 g of acrylic acid, and stirring for 30 minutes to prepare a shell emulsion for later use;
preparing an initiator solution, namely adding 10 g of deionized water into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60 ℃, introducing nitrogen to replace air, then starting to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 60 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 60 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
Example 6
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl sulfate, 1 g of OP-102 g, 2 g of n-butyl alcohol and 1.6 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 20 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 12 g of butyl acrylate and 6.4 g of methyl methacrylate, adjusting the rotation speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl sulfate serving as an emulsifier and 1.6 g of acrylic acid, and stirring for 30 minutes to prepare a shell emulsion for later use;
preparing an initiator solution, namely adding deionized water 10 into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60 ℃, introducing nitrogen to replace air, then beginning to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 60 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 60 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
Example 7
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl sulfate, 1 g of OP-102 g, 2 g of n-butyl alcohol and 1.3 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 24 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 10 g of butyl acrylate and 4.7 g of methyl methacrylate, adjusting the rotation speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell layer pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl sulfate serving as an emulsifier and 1.3 g of acrylic acid, and stirring for 30 minutes to prepare a shell layer emulsion for later use;
preparing an initiator solution, namely adding 10 g of deionized water into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60 ℃, introducing nitrogen to replace air, then beginning to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 60 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 60 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
Example 8
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl sulfate, 1 g of OP-102 g, 2 g of n-butyl alcohol and 0.6 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 32 g of allyl alcohol polyoxyethylene polyoxypropylene ether, 5 g of butyl acrylate and 2.4 g of methyl methacrylate, adjusting the rotation speed to 100-200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell layer pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl sulfate serving as an emulsifier and 0.6 g of acrylic acid, and stirring for 30 minutes to prepare a shell layer emulsion for later use;
preparing an initiator solution, namely adding 10 g of deionized water into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60 ℃, introducing nitrogen to replace air, then starting to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 60 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 60 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
Comparative example 1
Preparing a nuclear layer pre-emulsion, namely adding 50 g of deionized water into a beaker, stirring, adding 1 g of sodium dodecyl sulfate, 1 g of OP-102 g, 2 g of n-butyl alcohol and 3.2 g of sodium bicarbonate, stirring, mixing for 10 minutes, adding 25 g of butyl acrylate and 11.8 g of methyl methacrylate, adjusting the rotation speed to 100 plus 200rpm, and emulsifying at a high speed for 30 minutes to prepare a nuclear layer pre-emulsion for later use;
preparing a shell layer pre-emulsion, namely adding 20 g of deionized water into a beaker, starting stirring, sequentially adding 0.5 g of sodium dodecyl sulfate serving as an emulsifier and 3.2 g of acrylic acid, and stirring for 30 minutes to prepare a shell layer emulsion for later use;
preparing an initiator solution, namely adding 10 g of deionized water into a beaker, then adding 0.25 g of initiator 2-azo (2-amidinopropane) dihydrochloride (V50), and uniformly stirring to prepare the initiator solution for later use;
wherein the mass contents of the components in the raw materials are listed in table 1 based on the total weight of the allyl alcohol polyoxyethylene polyoxypropylene ether, the hydrophobic monomer and the hydrophilic monomer;
the reaction steps comprise:
adding all the nuclear layer pre-emulsion into a reaction kettle, starting stirring, heating to 60 ℃, introducing nitrogen to replace air, then beginning to dropwise add 8 g of initiator solution for 30min, keeping the reaction temperature at 60 ℃ after dropwise adding, reacting for 2-4 hours, then simultaneously dropwise adding the shell layer pre-emulsion and the rest initiator solution for 30min, keeping the reaction temperature at 60 ℃, reacting for 2-5 hours, cooling to normal temperature, and discharging.
TABLE 1
Comparative example 2
Allyl alcohol polyoxyethylene polyoxypropylene Ether (polyether F6)
Comparative example 3
The demulsifier used on site in Jiangsu oilfield Wei 5 united station is provided by Jiangsu oilfield engineering institute, and the demulsifier uses polyoxyethylene polyoxypropylene ether with polyene polyamine as initiator.
Comparative example 4
The demulsifier is a modified polyether of polyol as an initiator and is provided by Yangli chemical estuary branch company.
Comparative example 5
The demulsifier used on site of Chenzhuang united station of Shengli oil field estuary oil production plant is polyoxyethylene polyoxypropylene ether of phenolic resin as initiator and is provided by Shengli chemical estuary division company.
Example 9
The demulsifier prepared in example 2 and example 4 and the comparative examples 2 to 4 are respectively adopted to evaluate the demulsification performance of the Jiangsu oilfield vir 5 crude oil, the demulsification performance of the crude oil is evaluated by an evaluation method specified by a service performance detection method (bottle test method) of a crude oil demulsifier in a petroleum and natural gas industry standard SY-T5281-2000, and the experimental results are listed in Table 2 China.
TABLE 2 evaluation of indoor demulsification Performance
Experiments prove that the single use of the allyl alcohol polyoxyethylene polyoxypropylene ether or the olefin monomer copolymer emulsion has poor demulsification effect on the Jiangsu Wei 5 crude oil, the demulsification effect of the allyl alcohol polyoxyethylene polyoxypropylene ether and the olefin monomer copolymer emulsion is greatly improved, and the demulsification water yield is higher than that of the comparative example 4 under the condition of the addition concentration of 100mg/L under the addition concentration of 50 mg/L.
Example 10
The demulsifier prepared in example 4 and example 6 and the comparative example 4 were used to evaluate the demulsification performance of the crude oil from Chengdong in Shengli oilfield, and the demulsification performance was evaluated by the evaluation method specified in the service performance testing method (bottle test method) of the crude oil demulsifier in the oil and gas industry standard SY-T5281-2000, and the experimental results are listed in Table 3.
TABLE 3 evaluation of indoor demulsification Performance
Experiments prove that the demulsification effect of the copolymer emulsion prepared by the method as the demulsifier on the thick oil emulsion of the ChengDong united station is obviously higher than that of the demulsifier (namely the field demulsifier) prepared by the comparative example 4. And under the condition of adding the drug concentration of 80mg/L, the demulsifying agent of the embodiment 4 has the same demulsifying effect as that of the comparative example 4 under the condition of adding the drug concentration of 100 mg/L.
Example 11
The demulsifier prepared in the examples 1 to 8 and the demulsifier prepared in the comparative example 4 were used to evaluate the demulsification performance of the thick crude oil in the victory oil field, and the demulsification performance was evaluated by the evaluation method specified in the service performance detection method (bottle test method) of the demulsifier for crude oil in the oil and gas industry standard SY-T5281-2000, and the experimental results are shown in table 4.
TABLE 4 evaluation of indoor demulsification Performance
The aged thick oil in the oil production plant at the estuary of the Shengli oil field has high density and viscosity, and is very difficult to demulsify and dewater, and the field demulsification temperature is up to more than 90 ℃. The copolymer emulsion prepared by the method of the invention in example 6 is more suitable for thick oil emulsion of a Chen and village united station, and the demulsification effect is obviously higher than that of the demulsifier (namely, the field demulsifier) of the comparative example 5. The demulsification effect of the copolymer emulsion of the allyl alcohol polyoxyethylene polyoxypropylene ether and the olefin monomer is greatly improved, the mass content of the allyl alcohol polyoxyethylene polyoxypropylene ether monomer is 10-60% by weight of the total monomer, the synthetic demulsifier effect is good, the addition amount is 200mg/L, and the dehydration rate of crude oil can reach more than 70%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A crude oil demulsifier comprises a copolymer which is polymerized by polyoxyethylene polyoxypropylene ether monomer with double bonds at the end group, hydrophobic monomer and hydrophilic monomer through core-shell emulsion,
wherein the polyoxyethylene polyoxypropylene ether monomer with the terminal group containing double bonds comprises allyl alcohol polyoxyethylene polyoxypropylene ether;
the mass content of the polyoxyethylene polyoxypropylene ether monomer with the double bond at the end group is 10-60%, the mass content of the hydrophobic monomer is 35-85%, and the mass content of the hydrophilic monomer is 3-8% based on the total weight of the polyoxyethylene polyoxypropylene ether monomer with the double bond at the end group, the hydrophobic monomer and the hydrophilic monomer;
the hydrophobic monomer is selected from at least one of methacrylate compounds and acrylate compounds;
and/or the hydrophilic monomer is selected from at least one of acrylic compounds and methacrylic compounds.
2. The crude oil demulsifier of claim 1, wherein the hydrophobic monomer is selected from at least one of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl methacrylate, ethylhexyl acrylate, isooctyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, and stearyl methacrylate; and/or the presence of a gas in the gas,
the hydrophilic monomer is selected from one or two of methacrylic acid and acrylic acid.
3. A method for preparing the crude oil demulsifier according to claim 1 or 2, which comprises adopting a core-shell emulsion polymerization mode, and comprises the following steps:
s1: mixing a polyoxyethylene polyoxypropylene ether monomer with a double bond at the end group, a hydrophobic monomer, a first part of an emulsifier, a co-emulsifier and a buffer in the first part of a solvent to form a nuclear layer pre-emulsion;
s2: mixing a hydrophilic monomer and a second portion of an emulsifier in a second portion of a solvent to form a shell emulsion;
s3: dissolving an initiator in the third portion of the solvent to form an initiator solution;
s4: and adding a part of initiator solution into the nuclear layer pre-emulsion, preserving the heat for the first time, adding the shell layer emulsion and the rest part of the initiator solution, and preserving the heat for the second time to obtain the crude oil demulsifier.
4. The method of claim 3, wherein the emulsifier is one or more selected from the group consisting of petroleum sulfonate, sodium salt of dodecyl sulfonic acid, sodium salt of alkyl benzene sulfonic acid, sodium lauryl sulfate, and alkylphenol ethoxylates;
and/or the coemulsifier is selected from one or more of methanol, ethanol, glycol, isopropanol, glycerol, n-butanol and isoamyl alcohol;
and/or the buffer is selected from one or more of disodium hydrogen phosphate, sodium carbonate or sodium bicarbonate;
and/or the initiator is selected from one or more of ammonium persulfate, potassium persulfate, dimethyl 2, 2-azobisisobutyrate, 2-azo [2- (2-imidazolinyl) propane ] dihydrochloride and azobisisobutyramidine hydrochloride;
and/or the solvent is deionized water.
5. The preparation method according to claim 3 or 4, wherein the mass content of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group is 10-60% based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal group, the hydrophobic monomer and the hydrophilic monomer;
and/or the mass content of the hydrophobic monomer is 35-85%;
and/or the mass content of the hydrophilic monomer is 3-8%;
and/or the mass content of the co-emulsifier is 3-6%;
and/or the mass content of the buffer is 3-8%.
6. The method according to claim 3, wherein the mass ratio of the first portion of the emulsifier to the second portion of the emulsifier is (4-20): 1.
7. The method according to claim 3, wherein the initiator is contained in an amount of 0.1 to 1.0% by mass based on the total weight of the polyoxyethylene polyoxypropylene ether monomer having a double bond at the terminal, the hydrophobic monomer and the hydrophilic monomer.
8. The method according to claim 3, wherein in step S4, a part of the initiator solution is added to the core layer pre-emulsion heated to 50 to 100 ℃; the first time is 2-4 h; the second time is 2-5 h.
9. The method of claim 8, wherein the core layer pre-emulsion is heated to a temperature of 60-90 ℃.
10. Use of the crude oil demulsifier according to claim 1 or 2 or the crude oil demulsifier prepared by the preparation method according to any one of claims 3 to 9 in petroleum extraction and processing.
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| GB8608438D0 (en) * | 1985-04-16 | 1986-05-14 | Goldschmidt Ag Th | Copolymers |
| CN102311602A (en) * | 2011-06-07 | 2012-01-11 | 江苏大学 | Acrylate copolymer demulsifier with silica sol in-situ compound core-shell structure and preparation method thereof |
| CN105504143A (en) * | 2014-09-26 | 2016-04-20 | 中国石油化工股份有限公司 | Non-polyether demulsifier and preparation method thereof |
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| GB8608438D0 (en) * | 1985-04-16 | 1986-05-14 | Goldschmidt Ag Th | Copolymers |
| CN102311602A (en) * | 2011-06-07 | 2012-01-11 | 江苏大学 | Acrylate copolymer demulsifier with silica sol in-situ compound core-shell structure and preparation method thereof |
| CN105504143A (en) * | 2014-09-26 | 2016-04-20 | 中国石油化工股份有限公司 | Non-polyether demulsifier and preparation method thereof |
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