CN111662745A - Sulfonate demulsifier for crude oil three-recovery produced liquid and preparation method thereof - Google Patents

Sulfonate demulsifier for crude oil three-recovery produced liquid and preparation method thereof Download PDF

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CN111662745A
CN111662745A CN202010348188.4A CN202010348188A CN111662745A CN 111662745 A CN111662745 A CN 111662745A CN 202010348188 A CN202010348188 A CN 202010348188A CN 111662745 A CN111662745 A CN 111662745A
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demulsifier
sulfonate
reaction kettle
formula
polyether
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崔仕章
郭玉玺
张向红
王黎明
宋新旺
于长禄
侯青怡
吴艳青
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Deshi Energy Technology Group Co Ltd
Shandong Deshi Chemical Co Ltd
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Shandong Deshi Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/208—Sediments, e.g. bottom sediment and water or BSW

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention provides a sulfonate demulsifier for crude oil tertiary recovery produced liquid, which is prepared by the following method: (1) adding an initiator and a catalyst into a reaction kettle, and introducing epoxypropane and epoxyethane to prepare polyether A; (2) adding polyether A and maleic anhydride into a reaction kettle, and performing dehydration reaction to obtain an esterified substance B; (3) and adding the esterified substance B and a sulfonating agent into a reaction kettle for sulfonation modification to obtain the sulfonate demulsifier. The sulfonate demulsifier for the crude oil three-recovery produced liquid provided by the invention has higher surface activity, greatly weakens the interfacial tension, adsorbs to an oil-water interface, more covers the original film-forming substances, effectively eliminates the interfacial tension gradient, enables the original oil-water interface film to crack, enables liquid in the film to flow out and gather, realizes oil-water separation, and shows remarkable demulsification performance.

Description

Sulfonate demulsifier for crude oil three-recovery produced liquid and preparation method thereof
Technical Field
The application relates to the technical field of petrochemical industry, in particular to a sulfonate demulsifier for crude oil tertiary recovery produced liquid and a preparation method thereof.
Background
The crude oil demulsifier is an oil field chemical agent for performing oil-water separation on petroleum produced liquid, and is one of important links in petroleum production and processing processes. The demulsifying principle is that the demulsifier goes deep and adheres to the interface of emulsified liquid drops, replaces the original emulsifier, destroys the surface film, releases the liquid drops coated in the film and makes the liquid drops coalesce, thereby separating the oil phase from the water phase. In the process of oil field exploitation, along with the implementation of oil extraction process technologies such as steam flooding, surfactant, polymer and ternary complex flooding, the water content in the crude oil emulsion is increased, the stability is enhanced, and the demulsification difficulty of the crude oil is increased. The water content of crude oil will gradually rise when crude oil is continuously mined, the oil-water mixed liquid gradually forms a stable oil-water emulsion through an oil nozzle and a gathering and transportation pipeline, and a petroleum outlet enters an oil refinery and is reinjected with sewage, which have related requirements on the residual water content of crude oil and the oil content of sewage. Therefore, it is necessary to demulsify and dewater emulsified crude oil.
Demulsifiers for water-in-oil emulsified crude oil have been developed very early, and three generations of demulsifiers have been developed since the 20 th century. In order to solve the problem of demulsification of W/O type crude oil emulsion in 20 to 30 years in the 20 th century, a first-generation anionic demulsifier which is mainly a low-molecular anionic surfactant such as a sulfate type, a sulfonate type and a carboxylate type is developed; its advantages are low cost, high dosage, low effect and easy influence of electrolyte. Second generation low molecular weight non-ionic demulsifiers, such as Peregal, OP and Tween types, were developed in the 40 to 50 s. Although the demulsifier can resist acid, alkali and salt, the dosage of the demulsifier is large. In the 60 s, third-generation high-molecular-weight nonionic demulsifiers such as Dissolvan4411, SP type, AE type, AP type and the like are developed; its advantages are less consumption, high effect, high specificity and low adaptability.
At present, the demulsifiers studied at home and abroad are mainly nonionic polyoxyethylene polyoxypropylene block polymers from the chemical type. In recent years, special surfactants have been synthesized according to newly developed organic synthesis techniques. The wide application of the organic synthesis technology leads the demulsifier to be rapidly developed in variety and quantity, and the application of means such as compounding and copolymerization leads the application range of the demulsifier to be wider and wider.
The prior art provides some novel demulsifiers, such as a thermochemical settling dehydration method of thickened oil transition zone aging oil disclosed in CN102399577A, wherein the novel demulsifier prepared by esterification of acrylic acid and maleic anhydride is obtained; the novel composite demulsification deoiling agent disclosed in CN104828903A is prepared by esterifying polyether and double bond monomer, adding initiator, and compounding with acid and polyacrylamide; the desalting demulsifier disclosed in CN106832254A is used for preparing a carboxyl-terminated ethylene oxide-propylene oxide block copolymer; CN101891656A provides a binary anionic surfactant for oil displacement, which is a sodium succinate sulfonate type. However, the novel demulsifier is mostly compounded with a multi-element oil displacement agent to displace oil. Therefore, the prior art still has difficulty in demulsifying the stable crude oil emulsion caused by the crude oil tertiary recovery technology.
Disclosure of Invention
The invention aims to provide a novel demulsifier with high dehydration speed and high dehydration rate, which solves the problem of difficult demulsification of stable crude oil emulsion caused by a crude oil three-recovery technology in the prior art.
In one aspect, the present application provides a sulfonate-type demulsifier that is a polymer represented by formula (I):
Figure BDA0002470984490000031
in formula (I), X is selected from one of the following groups: -Na, -NH2or-Cl;
r in the formula (I) is selected from one of three structures of formula (1) to formula (3):
structure (1):
Figure BDA0002470984490000032
wherein: m is m1+m2And m is1＝m2＝(m/2)，n＝n1+n2And n is1＝n2＝(n/2)；
Structure (2):
Figure BDA0002470984490000033
wherein: m is m1+m2+m3+m4And m is1＝m2＝m3＝m4＝(m/4)，n＝n1+n2+n3+n4And n is1＝n2＝n3＝n4＝(n/4)；
Structure (3):
Figure BDA0002470984490000034
wherein: m is m1+m2And m is1＝m2＝(m/2)，n＝n1+n2And n is1＝n2＝(n/2)；
In the formula R, m is 80-110, n is 30-60, and the molecular weight of the polymer represented by the formula (I) is 6000-9000.
Further, the polymer had a density of 0.99g/cm3～1.05g/cm3The viscosity is 2000-3000 mPa.s, the flash point is more than 60 ℃, the condensation point is less than-15 ℃, and the RSN value is 13-17.
The sulfonate demulsifier provided by the application introduces nonpolar groups, increases the contact area with an oil-water interface film, replaces natural active substances in the crude oil interface film, has higher surface activity, can weaken the interface tension to a great extent when being applied to crude oil three-extraction produced liquid, adsorbs on the oil-water interface, covers more original film-forming substances, effectively eliminates the interface tension gradient, enables the original oil-water interface film to be broken, enables the liquid in the film to flow out and gather, and effectively realizes oil-water separation.
On the other hand, the application also provides a method for preparing the sulfonate demulsifier, which comprises the following steps:
(1) adding an initiator and a catalyst into a reaction kettle, and introducing epoxypropane and epoxyethane to prepare polyether A; the initiator is selected from one of propylene glycol, diethylenetriamine and tert-butylphenol formaldehyde resin;
(2) adding polyether A and maleic anhydride into a reaction kettle, and performing dehydration reaction to obtain an esterified substance B;
(3) and adding the esterified substance B and a sulfonating agent into a reaction kettle for sulfonation modification to obtain the sulfonate demulsifier.
Preferably, the preparation method can specifically adopt the following steps:
(1) synthesis of polyether intermediate polyether A:
adding an initiator and a catalyst into a reaction kettle, dehydrating at high temperature, and slowly introducing propylene oxide and ethylene oxide at a certain temperature to obtain polyether intermediate polyether A;
(2) synthesis of ester intermediate ester B:
adding polyether A and maleic anhydride into a reaction kettle, and dehydrating at high temperature and in vacuum for 3 hours until no water is removed to obtain an esterified substance intermediate esterified substance B;
(3) synthesis of a sulfonate demulsifier dry agent C:
and adding the esterified substance B and a sulfonating agent into a reaction kettle, performing high-temperature sulfonation modification, and preserving the heat for a period of time to obtain a sulfonate demulsifier dry agent C.
Wherein, the initiator in the step (1) is selected from propylene glycol, diethylenetriamine and tert-butyl phenol formaldehyde resin.
Further, in the step (1), the reaction mass ratio of the initiator to the propylene oxide to the ethylene oxide is 1: (50-150): (10-40), preferably 1: (60-100): (15-30).
Further, the mass ratio of the total mass of the propylene oxide and the ethylene oxide to the reaction mass of the catalyst in the step (1) is 1000: (2-7).
Further, the catalyst in step (1) is selected from one of potassium hydroxide, sodium hydroxide and potassium methoxide.
Further, the catalyst is prepared by mixing a solute hydrogen oxidant and solvent water, wherein the solute is selected from one of potassium hydroxide, sodium hydroxide and potassium methoxide, and the solvent is selected from one of deionized water, methanol and ethanol. The solute is preferably potassium hydroxide, and the solvent is preferably deionized water. The mass ratio of the solute to the solvent is 1: (1-10), preferably, the mass ratio of the solute to the solvent is 1: 3.
further, in the step (2), the reaction mass ratio of the polyether A to the maleic anhydride is 100: (2-10).
Further, the mass ratio of the esterification product B to the sulfonating agent in the step (3) is 1: (0.3-0.7).
Further, maleic anhydride is preferable in the step (2).
Further, the sulfonating agent in the step (3) is selected from ClSO3H (chlorosulfonic acid), H2NSO3H (sulfamic acid), NaHSO3(sodium bisulfite).
Further, the above method uses an electrically heated reaction vessel and/or polymerization vessel.
In a more preferred embodiment, the above preparation method specifically comprises the steps of:
(1) polyether intermediate polyether A synthesis:
cleaning and drying a stainless steel reaction kettle, pumping an initiator and a catalyst into the dry and clean reaction kettle, heating to 100-120 ℃, stirring for 30min until the state is uniform, starting a vacuum pump at 100-120 ℃ to perform high-temperature vacuum dehydration for 2h until no water is removed, then slowly adding epoxypropane at 120-125 ℃, controlling the temperature to 120-125 ℃ in the reaction process, performing heat preservation reaction for 1h after the feeding is finished, heating to 125-130 ℃, slowly adding ethylene oxide, controlling the temperature to 125-130 ℃ in the reaction process, performing heat preservation reaction for 2h after the feeding is finished, cooling, measuring and discharging after sampling and inspection are qualified to obtain the polyether A.
(2) Synthesis of ester intermediate ester B
Cleaning and drying a stainless steel reaction kettle, pumping polyether A into the dry and clean reaction kettle, adding maleic anhydride, heating to 90 ℃, stirring for 30min until the state is uniform, slowly heating to 170-175 ℃, keeping the temperature, reacting and dehydrating for 2h until no water is removed, starting a vacuum pump, dehydrating for 1h under the condition of 170-175 ℃ in vacuum until no water is removed, cooling, sampling, checking to be qualified, metering and discharging to obtain an esterified substance B.
(3) Synthesis of sulfonate demulsifier and drying agent C
Cleaning and drying a stainless steel reaction kettle, pumping an esterified substance B and a sulfonating agent into the dry and clean reaction kettle, heating to 50-60 ℃, stirring for 30min until the state is uniform, slowly heating to 120-135 ℃, carrying out heat preservation reaction for 5h, cooling, measuring and discharging after sampling and inspection are qualified, and thus obtaining the sulfonate demulsifier C.
The synthetic route for synthesizing the sulfonate demulsifier by adopting the synthetic method is as follows:
(1) synthesis of polyether intermediate polyether A:
polyether intermediate a-1 (propylene glycol as initiator):
Figure BDA0002470984490000061
wherein: m is m1+m2，m1＝m2＝(m/2)
n＝n1+n2，n1＝n2＝(n/2)
Polyether intermediate a-2 (diethylenetriamine as initiator):
Figure BDA0002470984490000071
wherein: m is m1+m2+m3+m4，m1＝m2＝m3＝m4＝(m/4)
n＝n1+n2+n3+n4And n is1＝n2＝n3＝n4＝(n/4)
Polyether intermediate a-3 (tert-butylphenol formaldehyde resin as initiator):
Figure BDA0002470984490000072
wherein: m is m1+m2，m1＝m2＝(m/2)
n＝n1+n2，n1＝n2＝(n/2)
(2) Synthesis of ester intermediate ester B:
Figure BDA0002470984490000073
wherein: r has the following three structures:
structure (1):
Figure BDA0002470984490000074
structure (2):
Figure BDA0002470984490000081
structure (3):
Figure BDA0002470984490000082
(3) synthesis of a sulfonate demulsifier dry agent C:
Figure BDA0002470984490000083
wherein: r has the following three structures:
structure (1):
Figure BDA0002470984490000084
structure (2):
Figure BDA0002470984490000085
structure (3):
Figure BDA0002470984490000091
x has the following structure:
-Na or-NH2or-Cl
On the other hand, the application also provides the application of the sulfonate demulsifier and/or the sulfonate demulsifier prepared by the method in the crude oil tertiary recovery produced fluid.
Preferably, the water content of the crude oil tertiary recovery produced liquid is 35%, and more preferably, the dehydration temperature is 45 ℃.
More preferably, the sulfonate demulsifier, when used to treat a crude oil tertiary recovery produced fluid, is treated with a sulfonate demulsifier: methanol: the water is prepared and used according to the mass ratio of 2:1: 2. Under the using conditions, the absolute dehydration rate of the sulfonate demulsifier at 50ppm can reach 92.9 percent, and the absolute dehydration rate at 100ppm can reach 96.4 percent.
The following beneficial effects can be brought through the application:
the sulfonate demulsifier for the crude oil tertiary recovery produced liquid provided by the invention has the advantages of simple preparation method, easily available raw materials, easy industrial production, higher surface activity, high dehydration speed, clear removed water quality and uniform oil-water interface, can weaken the interfacial tension to a great extent, adsorb the interfacial tension on the oil-water interface, cover more original film-forming substances, effectively eliminate the interfacial tension gradient, crack the original oil-water interfacial film, flow and gather the liquid in the film, realize oil-water separation and show remarkable demulsification performance, and experiments show that the dehydration rate of the crude oil tertiary recovery produced liquid reaches 92.9% when the chemical concentration of the demulsifier is 50ppm under specific use conditions, and the dehydration rate reaches 96.4% when the chemical concentration is 100 ppm.
Detailed Description
In order to more clearly explain the overall concept of the present application, the following detailed description is given by way of example. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present application. It will be apparent, however, to one skilled in the art, that the present application may be practiced without one or more of these specific details. In other instances, well-known features of the art have not been described in order to avoid obscuring the present application.
Reagents in the following examples, if not specifically indicated, were: propylene glycol (CAS:57-55-6), diethylenetriamine (CAS: 111-40-0), tert-butylphenol formaldehyde resin (CAS: 65733-76-8), maleic anhydride (CAS: 108-31-6), sodium bisulfite (CAS: 7631-90-5), sulfamic acid (CAS:7790-94-5), chlorosulfonic acid (CAS: 5329-14-6) are commercially available; both ethylene oxide and propylene oxide were taken from commercial samples. The purity of the reagents is analytical purity.
Example 1
Example 1 provides a novel sulfonate-based demulsifier which is a polymer having the following formula:
Figure BDA0002470984490000101
wherein:
Figure BDA0002470984490000102
in the formula: m is m1+m2And m is1＝m2＝(m/2)，n＝n1+n2And n is1＝n2(n/2); m is 80-110, n is 30-60, and the molecular weight of the polymer is 6000-9000.
The sulfonate demulsifier is represented by C-1, and the preparation method comprises the following steps:
(1) and (3) synthesizing polyether intermediate polyether A-1:
cleaning and drying a stainless steel reaction kettle, pumping 50kg of propylene glycol and 50kg of potassium hydroxide aqueous solution (potassium hydroxide: deionized water is 12.5kg:37.5kg) into the dry and clean reaction kettle, heating to 100-120 ℃, stirring for 30min till the state is uniform, starting a vacuum pump at 100-120 ℃ to perform high-temperature vacuum dehydration for 2h till no water is removed, then slowly adding 5000kg of propylene oxide at 120-125 ℃, controlling the temperature to 120-125 ℃ in the reaction process, and keeping the temperature for reaction for 1h after the feeding is finished; and continuously heating to 125-130 ℃, slowly adding 1250kg of ethylene oxide, controlling the temperature to 125-130 ℃ in the reaction process, carrying out heat preservation reaction for 2 hours after the feeding is finished, cooling, measuring and discharging after sampling and inspection are qualified, and thus obtaining the polyether A-1.
(2) Synthesis of esterified intermediate esterified product B-1:
cleaning and drying a stainless steel reaction kettle, pumping 500kg of polyether A-1 and adding 25kg of maleic anhydride into the dry and clean reaction kettle, heating to 90 ℃, stirring for 30min until the state is uniform, slowly heating to 170-175 ℃, keeping the temperature, reacting and dehydrating for 2h until no water is removed, starting a vacuum pump, dehydrating for 1h under the condition of 170-175 ℃ in vacuum until no water is removed, cooling, sampling, checking to be qualified, metering and discharging to obtain an esterified substance B-1.
(3) Synthesis of a sulfonate demulsifier dry agent C-1:
cleaning and drying a stainless steel reaction kettle, pumping 500kg of esterified substance B-1 into the dry and clean reaction kettle, adding 200kg of sodium bisulfite, heating to 50-60 ℃, stirring for 30min until the state is uniform, then slowly heating to 120-135 ℃, keeping the temperature for reaction for 5h, cooling, sampling, checking to be qualified, metering and discharging to obtain the sulfonate demulsifier C-1.
The sulfonate demulsifier C-1 prepared by the method has the appearance character of deep yellow viscous uniform liquid, no mechanical impurities and solid content of more than or equal to 95 percent; the density of the demulsifier polymer was measured to be 0.99g/cm3～1.05g/cm3The viscosity is 2000-3000 mPa.s, the flash point is more than 60 ℃, the condensation point is less than-15 ℃, and the RSN value is 13-17.
Example 2
Example 2 provides a novel sulfonate-based demulsifier that is a polymer having the following formula:
Figure BDA0002470984490000121
wherein R has the following structure:
Figure BDA0002470984490000122
in the formula: m is m1+m2+m3+m4，m1＝m2＝m3＝m4＝(m/4)；n＝n1+n2+n3+n4And n is1＝n2＝n3＝n4(n/4). m is 80-110, n is 30-60, and the molecular weight of the polymer is 6000-9000.
The sulfonate demulsifier is represented by C-2, and the preparation method comprises the following steps:
(1) and (3) synthesizing polyether intermediate polyether A-2:
cleaning and drying a stainless steel reaction kettle, pumping 65kg of diethylenetriamine and 50kg of potassium hydroxide aqueous solution (potassium hydroxide: deionized water is 12.5kg:37.5kg) into the dry and clean reaction kettle, heating to 100-120 ℃, stirring for 30min until the state is uniform, starting a vacuum pump at 100-120 ℃ to perform high-temperature vacuum dehydration for 2h until no water is removed, then slowly adding 5000kg of propylene oxide at 120-125 ℃, controlling the temperature to 120-125 ℃ in the reaction process, and keeping the temperature for reaction for 1h after the feeding is finished; and continuously heating to 125-130 ℃, slowly adding 1250kg of ethylene oxide, controlling the temperature to 125-130 ℃ in the reaction process, carrying out heat preservation reaction for 2 hours after the feeding is finished, cooling, measuring and discharging after sampling and inspection are qualified, and thus obtaining the polyether A-2.
(2) Synthesis of esterified intermediate esterified product B-2:
cleaning and drying a stainless steel reaction kettle, pumping 500kg of polyether A-2 and adding 25kg of maleic anhydride into the dry and clean reaction kettle, heating to 90 ℃, stirring for 30min until the state is uniform, slowly heating to 170-175 ℃, keeping the temperature, reacting and dehydrating for 2h until no water is removed, starting a vacuum pump, dehydrating for 1h under the condition of 170-175 ℃ in vacuum until no water is removed, cooling, sampling, checking to be qualified, metering and discharging to obtain an esterified substance B-2.
(3) Synthesis of a sulfonate demulsifier dry agent C-2:
cleaning and drying a stainless steel reaction kettle, pumping 500kg of esterified substance B-2 and adding 185kg of sulfamic acid into the dry and clean reaction kettle, heating to 50-60 ℃, stirring for 30min till the state is uniform, slowly heating to 120-135 ℃, carrying out heat preservation reaction for 5h, cooling, sampling, checking to be qualified, and metering and discharging to obtain the sulfonate demulsifier C-2.
The sulfonate demulsifier C-2 prepared by the method has the appearance character of deep yellow viscous uniform liquid, no mechanical impurities and solid content of more than or equal to 95 percent; the density of the demulsifier polymer is 0.99g/cm3～1.05g/cm3The viscosity is 2000-3000 mPa.s, the flash point is more than 60 ℃, the condensation point is less than-15 ℃, and the RSN value is 13-17.
Example 3
Example 3 provides a novel sulfonate-based demulsifier that is a polymer having the following formula:
Figure BDA0002470984490000131
wherein R has the following structure:
Figure BDA0002470984490000132
in the formula: m is m1+m2And m is1＝m2＝(m/2)，n＝n1+n2And n is1＝n2(n/2); m is 80-110, n is 30-60, and the molecular weight of the polymer is 6000-9000.
The sulfonate demulsifier is represented by C-3, and the preparation method comprises the following steps:
(1) and (3) synthesizing polyether intermediate polyether A-3:
cleaning and drying a stainless steel reaction kettle, pumping 80kg of tert-butyl phenol formaldehyde resin and 50kg of potassium hydroxide aqueous solution (potassium hydroxide: deionized water is 12.5kg:37.5kg) into the dry and clean reaction kettle, heating to 100-120 ℃, stirring for 30min until the state is uniform, starting a vacuum pump at 100-120 ℃ to perform high-temperature vacuum dehydration for 2h until no water is removed, then slowly adding 5000kg of propylene oxide at 120-125 ℃, controlling the temperature to 120-125 ℃ in the reaction process, and keeping the temperature for reaction for 1h after the feeding is finished; and continuously heating to 125-130 ℃, slowly adding 1250kg of ethylene oxide, controlling the temperature to 125-130 ℃ in the reaction process, carrying out heat preservation reaction for 2 hours after the feeding is finished, cooling, measuring and discharging after sampling and inspection are qualified, and thus obtaining the polyether A-3.
(2) Synthesis of esterified intermediate esterified product B-3:
cleaning and drying a stainless steel reaction kettle, pumping 500kg of polyether A-3 and adding 25kg of maleic anhydride into the dry and clean reaction kettle, heating to 90 ℃, stirring for 30min until the state is uniform, slowly heating to 170-175 ℃, keeping the temperature, reacting and dehydrating for 2h until no water is removed, starting a vacuum pump, dehydrating for 1h under the condition of 170-175 ℃ in vacuum until no water is removed, cooling, sampling, checking to be qualified, metering and discharging to obtain an esterified substance B-3.
(3) Synthesis of a sulfonate demulsifier dry agent C-3:
cleaning and drying a stainless steel reaction kettle, pumping 500kg of esterified substance B-3 and adding 225kg of chlorosulfonic acid into the dry and clean reaction kettle, heating to 50-60 ℃, stirring for 30min till the state is uniform, slowly heating to 120-135 ℃, carrying out heat preservation reaction for 5h, cooling, sampling, checking to be qualified, and metering and discharging to obtain the sulfonate demulsifier C-3.
The sulfonate demulsifier C-3 prepared by the method has the appearance character of deep yellow viscous uniform liquid, no mechanical impurities and solid content of more than or equal to 95 percent; the density of the demulsifier polymer is 0.99g/cm3～1.05g/cm3The viscosity is 2000-3000 mPa.s, the flash point is more than 60 ℃, the condensation point is less than-15 ℃, and the RSN value is 13-17.
Example 4 Performance testing
Crude oil demulsification experiment for certain united station of North China oilfield
Four groups of experiments are carried out on a three-extraction produced liquid oil sample of a certain united station of the North China oilfield, wherein the four groups of experiments comprise agents with better indoor evaluation effect and field agents, and each group of agents respectively experiments the demulsification performance under the conditions of the same temperature and different chemical adding amounts. Wherein DS-3106 is a product of C-1 medicament which is not sulfonated; the sulfonate demulsifiers obtained in examples 1 to 3 are represented by symbols C-1, C-2 and C-3, and were calculated as the dry agent C: methanol: preparing a finished product by the ratio of 2:1: 2; the water content of the field oil sample is 35 percent, and the dehydration temperature is 45 ℃. The test results for each agent are shown in table 1:
TABLE 1
Figure BDA0002470984490000151
As can be seen from Table 1, the novel sulfonate demulsifiers provided in examples 1 to 3 had a high dehydration rate, a uniform oil-water interface, and a clear dehydrated water, and the dehydration effect was significantly better than that of the other comparative agents. And the experiment result shows that the dehydration rate of the C-1 demulsifier under the condition of dosing concentration of 50ppm reaches 92.9 percent, is higher than the dehydration rates of 75.0 percent of DS-3106 which is not sulfonated under the same concentration and 85.7 percent of field agent, and is also higher than the performance effects of DS-3106 which is not sulfonated and the field agent under the condition of dosing amount of 100 ppm; the dehydration rate of the C-1 demulsifier under the condition of adding the chemical concentration of 100ppm is more up to 96.4 percent, and the C-1 demulsifier shows remarkable demulsification and dehydration performances.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.

Claims (10)

1. A sulfonate-type demulsifier, wherein the demulsifier has a polymer represented by formula (I):
Figure FDA0002470984480000011
in formula (I), X is selected from one of the following groups: -Na, -NH2or-Cl;
in the formula (I), R is selected from one of three structures of formula (1) to formula (3):
structure (1):
Figure FDA0002470984480000012
wherein: m is m1+m2And m is1＝m2＝(m/2)，n＝n1+n2And n is1＝n2＝(n/2)；
Structure (2):
Figure FDA0002470984480000013
wherein: m is m1+m2+m3+m4And m is1＝m2＝m3＝m4＝(m/4)，n＝n1+n2+n3+n4And n is1＝n2＝n3＝n4＝(n/4)；
Structure (3):
Figure FDA0002470984480000014
wherein: m is m1+m2And m is1＝m2＝(m/2)，n＝n1+n2And n is1＝n2＝(n/2)；
In the formula R, m is 80-110, n is 30-60, and the molecular weight of the polymer represented by the formula (I) is 6000-9000.
2. The sulfonate demulsifier of claim 1, wherein the polymer has a density of 0.99g/cm3～1.05g/cm3The viscosity is 2000-3000 mPa.s, the flash point is more than 60 ℃, the condensation point is less than-15 ℃, and the RSN value is 13-17.
3. The method of preparing the sulfonate demulsifier of claim 1, comprising:
(1) adding an initiator and a catalyst into a reaction kettle, and introducing epoxypropane and epoxyethane to prepare polyether A; the initiator is selected from one of propylene glycol, diethylenetriamine and tert-butylphenol formaldehyde resin;
(2) adding polyether A and maleic anhydride into a reaction kettle, and performing dehydration reaction to obtain an esterified substance B;
(3) and adding the esterified substance B and a sulfonating agent into a reaction kettle for sulfonation modification to obtain the sulfonate demulsifier.
4. The production method according to claim 3, wherein the mass ratio of the initiator, propylene oxide and ethylene oxide in the step (1) is 1: (50-150): (10-40).
5. The process according to claim 3, wherein the mass ratio of the total mass of propylene oxide and ethylene oxide to the catalyst in step (1) is 1000: (2-7).
6. The method according to claim 3, wherein the catalyst in the step (1) is one selected from the group consisting of potassium hydroxide, sodium hydroxide and potassium methoxide.
7. The production method according to claim 3, wherein the mass ratio of polyether A to maleic anhydride in step (2) is 100: (2-10).
8. The preparation method according to claim 3, wherein the mass ratio of the ester B to the sulfonating agent in the step (3) is 1: (0.3-0.7).
9. The method according to claim 3, wherein the sulfonating agent in the step (3) is selected from chlorosulfonic acid, sulfamic acid and sodium bisulfite.
10. Use of the sulfonate demulsifier of any one of claims 1 to 2 and/or the sulfonate demulsifier obtained by the process of any one of claims 3 to 9 in a crude oil tertiary recovery produced fluid; preferably, the water content of the crude oil tertiary recovery produced liquid is 35%; more preferably, the emulsion breaker is a sulfonate type emulsion breaker: methanol: the water is prepared and used according to the mass ratio of 2:1: 2.
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CN116286091B (en) * 2023-05-22 2023-08-11 新疆科力新技术发展股份有限公司 Oil field produced liquid composite treatment medicament and preparation method thereof

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