CN109233897B - Preparation method of crude oil reverse demulsifier for oil-in-water emulsion - Google Patents
Preparation method of crude oil reverse demulsifier for oil-in-water emulsion Download PDFInfo
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- CN109233897B CN109233897B CN201811169345.4A CN201811169345A CN109233897B CN 109233897 B CN109233897 B CN 109233897B CN 201811169345 A CN201811169345 A CN 201811169345A CN 109233897 B CN109233897 B CN 109233897B
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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
Abstract
The invention relates to a preparation method of a crude oil reverse demulsifier for an oil-in-water emulsion. The preparation method comprises the following steps: the star-shaped macromolecular polyamide-amine is prepared by taking ethylenediamine as a core, and the terminal group is subjected to quaternary ammonium modification and then subjected to ring-opening copolymerization with propylene oxide and ethylene oxide to obtain the crude oil reverse demulsifier for the oil-in-water emulsion. The crude oil reverse demulsifier for the oil-in-water emulsion has good reverse demulsification effect on the oil-in-water emulsion in the high water-containing crude oil produced liquid, and can realize the purposes of high dehydration speed and clear dehydrated water under low addition; in addition, the reverse demulsifier of the invention also has the advantages of low addition, fast demulsification, clear dehydrated water and the like.
Description
Technical Field
The invention belongs to the field of oilfield chemicals, and particularly relates to a preparation method of a crude oil reverse demulsifier for an oil-in-water emulsion.
Background
Water-in-oil (W/O) type emulsions and oil-in-water (O/W) type emulsions contained in oilfield produced fluids are the main treatment objects for crude oil dehydration and sewage oil removal. Along with the extension of development time, when oil field development enters the later stage, the water-oil ratio in the produced liquid rises sharply, and the sewage quantity is increased greatly.
At present, most oil production platforms of offshore oil fields enter the later stage of high water content development, the comprehensive water content of oil well produced liquid exceeds 90%, and the comprehensive water content of partial single well produced liquid reaches or even exceeds 95%. In order to improve the recovery efficiency of crude oil, some offshore oil fields also implement a large-scale polymer injection oil displacement technology. Compared with the produced fluids in the initial and middle stages of oilfield development, the properties of the produced fluid in the high water-containing development stage are greatly changed, the oil-water separation speed is obviously slowed down, the water content of emulsified oil is increased, the oil content of sewage is increased, the treatment difficulty of the produced fluid is increased, and the produced fluid is mainly changed from the conventional water-in-oil (W/O) emulsion into an oil-in-water (O/W) emulsion. The prior crude oil demulsifier mainly takes a water-in-oil breaking type emulsion as a main component, and the problems of large dosage, difficult demulsification and dehydration, long demulsification time and the like are often caused when oil-water treatment is carried out on the sea. The currently used oil-in-water reverse demulsifier mainly takes the type of anions and cations, is easy to generate flocs in a water body to influence oil-water treatment, and has fewer types and larger dosage. The offshore oilfield platform has short treatment time and limited space, so the treatment time is shorter, and the sewage in the platform produced liquid is reinjected or directly discharged into the sea after treatment, so the requirement on the oil content (OIW) in the water after sewage treatment is stricter. Therefore, the development of a novel reverse demulsifier aiming at oil-in-water emulsion is of great significance to offshore platforms.
Disclosure of Invention
Aiming at the defects of the prior art and aiming at solving the problem of reverse demulsification of the existing high-water-content oil-in-water type emulsion, the invention provides a preparation method of a reverse demulsifier which has quick demulsification capability on oil-in-water crude oil emulsion, clear dehydration and small using amount.
The invention is realized by the following technical scheme:
the preparation method takes ethylenediamine and methyl acrylate as raw materials to synthesize a star-shaped macromolecular polyamide-amine intermediate, carries out quaternization modification on an end group, and finally carries out alkoxylation with propylene oxide and ethylene oxide to prepare a series of end group modified reverse demulsifiers with multi-branch structures.
The invention relates to a preparation method of a crude oil reverse demulsifier for an oil-in-water emulsion, which comprises the following steps:
(1) synthesis of Polyamide-amine: adding ethylenediamine and methanol into a reaction container, adding methyl acrylate dropwise after deoxygenation, stirring the mixture to react for 20-24h, and performing rotary evaporation on the product to remove the solvent to obtain a light yellow liquid product, namely 0.5G polyamide-amine; or dripping 0.5G of polyamide-amine into the deoxygenated mixed solution of ethylenediamine and methanol for reaction for 20-24h, and removing the solvent by rotary evaporation to obtain 1.0G of polyamide-amine; the polyamide-amine reacts with methyl acrylate and ethylenediamine in an alternating mode to synthesize 0.5nG of polyamide-amine, wherein n is a natural number of 2-6;
the weight ratio of the raw materials is ethylenediamine: methyl acrylate: methanol is 1:0.1-2: 0.5-10;
(2) modification of the terminal group: dropwise adding halide into the methanol solution of the polyamide-amine and the amine obtained in the step (1), reacting at constant temperature for 6-8h, removing the solvent by rotary evaporation, and precipitating and drying by using ether to obtain modified polyamide-amine;
the weight ratio of the raw materials is polyamide-amine: amine: halide: methanol is 1:0.1-2:0.1-2: 0.5-10;
(3) and (3) synthesizing a reverse demulsifier: putting the modified polyamide-amine obtained in the step (2) into a high-pressure reaction kettle, taking alkali as a catalyst, adding propylene oxide at the temperature of 100 ℃ and 150 ℃, controlling the pressure to be 0.1-0.4MPa, reacting for 4-8h, aging for 1-2h, adding ethylene oxide at the pressure to be 0.1-0.4MPa, reacting for 2-4h, and adding a solvent for aging for 1-2h to prepare a 50% wt solution to obtain a reverse demulsifier;
the raw materials comprise the following components in percentage by mass: propylene oxide: ethylene oxide is 1:0.5-20: 0.5-10.
The amine in the step (2) is ethylenediamine, diethylenetriamine, triethylamine or triethanolamine; the halide is chloroform, chloropropane, chloropropene, epichlorohydrin or benzyl chloride;
the alkali catalyst in the step (3) is one or more of sodium hydroxide, potassium hydroxide and sodium ethoxide; the solvent is one or more of water, methanol, ethanol and xylene.
The raw materials comprise modified polyamide-amine, propylene oxide and ethylene oxide in a mass ratio of 1:0.5-20: 0.5-10;
in the preparation method, preferably, in the step (2), methanol is used as a solvent, 1.0G of polyamide-amine and triethylamine are respectively added, the mixture is reacted at room temperature for 1-1.5h, then the temperature is raised to 50 ℃, epichlorohydrin is slowly added dropwise, the reaction is carried out for 6-7h after the dropwise addition is finished, the methanol solvent is removed by rotary evaporation after the reaction is finished, and the product is precipitated by anhydrous ether and is dried in vacuum to obtain the modified polyamide-amine.
In the preparation method, preferably, in the step (3), after adding the alkali, stirring and heating to 75-85 ℃, vacuumizing the reaction kettle until the vacuum degree is-0.1 MPa, and adding the propylene oxide when the temperature is raised to 100 ℃.
In the above preparation method, in the step (3), the raw materials are preferably modified polyamide-amine, propylene oxide and ethylene oxide in a mass ratio of 1:1-5: 0.5-3.
Compared with the prior art, the preparation method has the following beneficial effects:
the preparation method comprises the steps of taking ethylenediamine and methyl acrylate as raw materials, synthesizing a star-shaped macromolecular polyamide-amine intermediate, carrying out quaternization modification on an end group, and finally carrying out alkoxylation reaction with propylene oxide and ethylene oxide to prepare a series of end group modified reverse demulsifiers with a multi-branch structure. The reverse demulsifier prepared by the preparation method is the modified quaternary ammonium salt reverse demulsifier, can be rapidly dispersed to an oil-water interface when an oil-in-water emulsion is subjected to reverse demulsification, has the characteristics of high dehydration speed, clear dehydrated water and small using amount, and cannot be well demulsified by a common polyether demulsifier aiming at the oil-in-water emulsion. Under the condition of 15mg/L, the dehydration rate can reach more than 90 percent within 15min at the temperature of 80 ℃, and the oil content in water is lower than 100 mg/L.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 Synthesis of reverse demulsifier A
(1)1.0G Synthesis of Polyamide-amine
Adding 4.5G of ethylenediamine and 16G of methanol into a 250mL three-necked bottle, uniformly mixing, introducing nitrogen to remove oxygen, heating to 30 ℃, dropwise adding 51.6G of methyl acrylate, stirring to react for 24 hours after dropwise adding, and performing rotary evaporation on the product to remove the solvent to obtain a light yellow liquid product, namely 0.5G of polyamide-amine.
Adding 36g of ethylenediamine and 180g of methanol into a 250mL three-necked bottle, uniformly mixing, introducing nitrogen to remove oxygen, and heating to 30 ℃. Uniformly mixing 10.1G of 0.5G polyamide-amine and 32G of methanol, dropwise adding into the three-necked bottle, stirring and reacting for 24 hours after dropwise adding to obtain a product, and performing reduced pressure rotary evaporation on the product to remove the solvent and the ethylenediamine to obtain a light yellow liquid product, namely 1.0G polyamide-amine.
(2)1.0G modification of polyamidoamines
Dissolving 51.6g of 1.0G of polyamide-amine and 40.4g of triethylamine in 60g of methanol, reacting for 1h at room temperature in a three-necked bottle, heating to 50 ℃, dropwise adding 37g of epichlorohydrin, stirring and reacting for 6h after the dropwise adding is finished, removing the solvent by reduced pressure rotary evaporation, and precipitating the product by using anhydrous ether to obtain a white paste, namely the modified polyamide-amine.
(3) Synthesis of reverse demulsifier A
Adding 20g of modified polyamide-amine and 0.16g of potassium hydroxide into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring and heating, vacuumizing the reaction kettle by using a vacuum pump when the temperature is raised to about 80 ℃, and stopping vacuumizing when the vacuum degree in the reaction kettle is-0.1 MPa for about 20 minutes. Continuously stirring and heating, slowly adding 20g of propylene oxide when the temperature is increased to 100 ℃, controlling the reaction temperature at 120-140 ℃, the pressure at 0.2-0.4MPa, and the reaction time for 3 h. After the reaction is finished, aging is carried out for 1h, and the temperature is reduced to 100 ℃. 13g of ethylene oxide is added into a reaction kettle, the reaction temperature is controlled at 120 ℃ and 140 ℃, and the pressure is controlled at 0.2-0.4 MPa. After the reaction time is 1.5h, aging is carried out for 1h, and water is added to prepare a solution with the weight of 50 percent, thus obtaining the reverse demulsifier A.
Example 2 Synthesis of reverse demulsifier B
The reaction was carried out as described in example 1(3) except that KOH was added in an amount of 0.15g and ethylene oxide was added in an amount of 10g to give reverse demulsifier B.
Example 3 Synthesis of reverse demulsifier C
The reaction was carried out as described in example 1(3) except that KOH was added in an amount of 0.24g and propylene oxide was added in an amount of 40g and ethylene oxide was added in an amount of 20g, to obtain a reverse demulsifier C.
Example 4 Synthesis of reverse demulsifier D
The reaction was carried out as described in example 1(3) except that KOH was added in an amount of 0.33g and propylene oxide was added in an amount of 60g and ethylene oxide was added in an amount of 30g, to obtain a reverse demulsifier C.
Bottle test experiment the performance evaluation experiment of the demulsifiers prepared in examples 1 to 4
The bottle test demulsification test is carried out on the crude oil of the south China sea oilfield at the field temperature of 80 ℃, compared with the field demulsifier BP-10, and the test results are shown in Table 1.
The bottle test method refers to the Chinese petroleum and natural gas industry standard SY/T5281-2000 crude oil demulsifier use performance detection method (bottle test method). The oil content in the water phase is measured according to the specification of SY/T5329-2012 'water quality index and analysis method for clastic rock oil reservoir water injection'.
The specific experimental steps are as follows:
mixing oil and water of crude oil extract sample of certain oilfield in south China sea uniformly without obvious free water, pouring into a dehydration test tube, and keeping constant temperature for 10min in 80 ℃ water bath.
A quantity of reverse demulsifiers (A, B, C, D and BP-10) were injected into the dehydrated tubes with a microsyringe. The vibration of the dehydration test tube adopts a manual vibration method. After screwing the bottle cap, the dehydration test tube is turned upside down for 2-5 times, after the bottle plug is loosened slowly and deflated, the bottle plug is screwed again, and the bottle plug is directly oscillated manually. After oscillating for 100 times by the left hand, slowly loosening the bottle stopper and deflating, and screwing the bottle stopper again. And then the right hand is changed for shaking for 100 times, after the mixture is fully mixed, the bottle stopper is loosened, and the dehydration test tube is placed in the constant temperature water bath again for standing and settling.
Recording the dewatering water amount at different time, observing and recording the sewage color and the oil-water interface condition when the dewatering is finished, and measuring the oil content in the water phase after the dewatering is finished. The results of the experiment are shown in table 1.
TABLE 1 results of reverse demulsification experiments on crude oil from south China sea oilfield with reverse demulsifiers from examples 1-4
Claims (5)
1. A preparation method of a crude oil reverse demulsifier for an oil-in-water emulsion comprises the following steps:
(1) synthesis of Polyamide-amine: adding ethylenediamine and methanol into a reaction container, adding methyl acrylate dropwise after deoxygenation, stirring the mixture to react for 20-24h, and performing rotary evaporation on the product to remove the methanol solvent to obtain a light yellow liquid product, namely 0.5G polyamide-amine; or dripping 0.5G of polyamide-amine into the deoxygenated mixed solution of ethylenediamine and methanol for reaction for 20-24h, and performing rotary evaporation to remove methanol to obtain 1.0G of polyamide-amine; the polyamide-amine reacts with methyl acrylate and ethylenediamine in an alternating mode to synthesize 0.5nG of polyamide-amine, wherein n is a natural number of 2-6;
the weight ratio of the raw materials is ethylenediamine: methyl acrylate: methanol is 1:0.1-2: 0.5-10;
(2) modification of the terminal group: dropwise adding halide into the methanol solution of the polyamide-amine and the amine obtained in the step (1), reacting at constant temperature for 6-8h, removing the methanol solvent by rotary evaporation, and precipitating and drying with diethyl ether to obtain modified polyamide-amine;
the weight ratio of the raw materials is polyamide-amine: amine: halide: methanol is 1:0.1-2:0.1-2: 0.5-10;
(3) and (3) synthesizing a reverse demulsifier: putting the modified polyamide-amine obtained in the step (2) into a high-pressure reaction kettle, taking alkali as a catalyst, adding propylene oxide at the temperature of 100 ℃ and 150 ℃, controlling the pressure to be 0.1-0.4MPa, reacting for 4-8h, aging for 1-2h, adding ethylene oxide at the pressure to be 0.1-0.4MPa, reacting for 2-4h, and adding a solvent for aging for 1-2h to prepare a 50% wt solution to obtain a reverse demulsifier;
the raw materials comprise the following components in percentage by mass: propylene oxide: ethylene oxide 1:0.5-20: 0.5-10;
the amine in the step (2) is ethylenediamine, diethylenetriamine, triethylamine or triethanolamine; the halide is chloroform, chloropropane, chloropropene, epichlorohydrin or benzyl chloride;
the alkali catalyst in the step (3) is one or more of sodium hydroxide, potassium hydroxide and sodium ethoxide; the solvent is one or more of water, methanol, ethanol and xylene.
2. The method for preparing the crude oil reverse demulsifier for oil-in-water emulsions according to claim 1, wherein the polyamidoamine prepared in step (1) is 1.0G.
3. The preparation method of the crude oil reverse phase demulsifier for the oil-in-water emulsion according to claim 1, wherein in the step (3), after adding the alkali, stirring and heating to 75-85 ℃, vacuumizing the reaction kettle to the vacuum degree of-0.1 MPa, and adding the propylene oxide when the temperature is raised to 100 ℃.
4. The preparation method of the crude oil reverse phase demulsifier for the oil-in-water emulsion according to claim 1, wherein in step (2), methanol is used as a solvent, 1.0G of polyamide-amine and triethylamine are respectively added, the mixture is stirred and reacted for 1h to 1.5h at room temperature, then the temperature is raised to 50 ℃, epichlorohydrin is slowly added dropwise, and the reaction is carried out for 6h to 7h after the dropwise addition is finished; and (3) after the reaction is finished, removing the methanol solvent by rotary evaporation, precipitating the product by using anhydrous ether, and drying the precipitated product in vacuum to obtain the modified polyamide-amine.
5. The preparation method of the crude oil reverse demulsifier for the oil-in-water emulsion according to claim 1, wherein in the step (3), the raw materials comprise, by mass, the modified polyamide-amine: propylene oxide: ethylene oxide is 1:1-5: 0.5-3.
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| CN112480899B (en) * | 2020-12-11 | 2022-05-24 | 德仕能源科技集团股份有限公司 | Demulsification and cleanup additive for fracturing and preparation method thereof |
| CN112852476B (en) * | 2020-12-26 | 2022-11-15 | 中海油天津化工研究设计院有限公司 | Polymer-containing produced liquid demulsifier and preparation method thereof |
| CN113444237B (en) * | 2021-05-06 | 2023-07-28 | 中海油(天津)油田化工有限公司 | Quaternized polyether reverse demulsifier and preparation method thereof |
| CN114768309A (en) * | 2022-05-12 | 2022-07-22 | 广东粤首新科技有限公司 | Reverse demulsifier and preparation method thereof |
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| CN102234526A (en) * | 2010-04-30 | 2011-11-09 | 中国石油天然气集团公司 | Dendritic reverse demulsifier |
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