CN103642518A - High-water-cut heavy oil demulsifier used for oil fields and preparation method thereof - Google Patents

High-water-cut heavy oil demulsifier used for oil fields and preparation method thereof Download PDF

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CN103642518A
CN103642518A CN201310684263.4A CN201310684263A CN103642518A CN 103642518 A CN103642518 A CN 103642518A CN 201310684263 A CN201310684263 A CN 201310684263A CN 103642518 A CN103642518 A CN 103642518A
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polyether
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high moisture
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epoxidized polyether
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CN103642518B (en
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杜晓杰
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Binzhou Qiankun Chemical Machinery Co.,Ltd.
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Tianjin E Tech Energy Technology Development Co Ltd
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Abstract

The invention relates to a high-water-cut heavy oil demulsifier used for oil fields and a preparation method thereof, belonging to the technical field of crude oil dehydration. The preparation method of the high-water-cut heavy oil demulsifier used for oil fields comprises the following steps: 1. synthesizing an initiator: dropwise adding a formaldehyde solution to polyethylene polyamine and bisphenol S at 30-60 DEG C, heating the materials to 100-150 DEG C to react for 1-5 hours, and freeze-drying a product; 2. synthesizing polyether: carrying out catalytic polymerization on the initiator as well as ethylene oxide and propylene oxide with KOH, neutralizing a product with acetic acid, and carrying out suction filtration and desalination; 3. synthesizing epoxy polyether: after diluting polyether with a xylene solution, reacting polyether with epoxy chloropropane to obtain epoxy polyether A; dropwise adding 2-methyl crotonate to triethylene diamine, and then reacting with epoxy chloropropane to obtain epoxy polyether B; 4. synthesizing a demulsifier: dissolving epoxy polyether A and epoxy polyether B in xylene to obtain the high-water-cut heavy oil demulsifier. The preparation method is simple in process, is convenient to operate and is accessible in raw materials and low in cost. The obtained demulsifier has the advantages of small dosage, high dehydration speed, good demulsification effect and the like.

Description

A kind of high moisture thick oil demulsifier and preparation method thereof for oil field
Technical field
The invention belongs to dehydrating of crude oil technical field, particularly relate to a kind of high moisture thick oil demulsifier and preparation method thereof for oil field.
Background technology
Viscous crude is high viscosity heavy crude, and the division of heavy crude and light crude generally be take its density as foundation, and density is greater than 0.934g/cm 3be mink cell focus.Along with the minimizing year by year of the workable reserve of ordinary crude oils, viscous crude will become the main energy sources of 21 century, but viscous oil recovery is more difficult, has therefore also just increased the difficulty that viscous crude utilizes.Late 1990s, the output in oil field reduces gradually, and in order to maintain crude production rate, each oil field all takes the method that increases water filling to improve crude oil yield, cause oil well produced liquid water ratio to rise rapidly, many oil fields are in the middle and high Water-cut Period development phase.Simultaneously, in various employing processes, the application of a large amount of oil recovery auxiliary agents also makes crude oil, particularly the Produced Liquid of viscous crude composition becomes more complicated, causes the efficient fast emulsion breaking of viscous crude and special viscous crude to become the gordian technique that affects cost for oil production, crude quality, output and the environmental pollution of control oil field.The outstanding feature of viscous crude is that asphaltenes, colloid are more, and colloid, pitch can be adsorbed on water-oil interface, reduces interfacial tension, makes crude oil emulsion become very stable, so the dehydration of viscous crude is more difficult than the dehydration of ordinary crude oils.
There is the technical problems such as raw material is complicated, and preparation cost is high, and product consumption is large, and dehydrating of crude oil process is slow, emulsion splitter weak effect in the high moisture thick oil demulsifier of existing use, therefore synthetic a kind of emulsion splitter for the moisture viscous crude of height also just seems more and more urgent.
Summary of the invention
The present invention provides a kind of high moisture thick oil demulsifier and preparation method thereof for oil field for solving the technical problem existing in known technology.
The object of this invention is to provide and a kind ofly have raw material and be easy to get, with low cost, demulsification is good, and preparation technology is simple, easy to operate, controls easily high moisture thick oil demulsifier for the oil field of production efficiency high.
Oil field of the present invention by the technical scheme that high moisture thick oil demulsifier is taked is:
High moisture thick oil demulsifier for a kind of oil field, be characterized in: the synthesis material of high moisture thick oil demulsifier is polyethylene polyamine, bisphenol S, formaldehyde, KOH catalyzer, oxyethane, propylene oxide, acetic acid, dimethylbenzene, triethylene diamine, 2-butylene acid methyl esters, epoxy chloropropane, takes following technique synthetic:
1) synthetic initiator: polyethylene polyamine and bisphenol S drip formaldehyde solution at 30-60 ℃, and the mol ratio of polyethylene polyamine, bisphenol S and formaldehyde is (0.5-1): (5-7): (3-5), be then warming up to 100-150 ℃ of reaction 1-5h, lyophilize;
2) synthesizing polyether: under 110 ℃-150 ℃, 0.2-0.5MPa condition, initiator and oxyethane and propylene oxide are through KOH catalyzed polymerization, and wherein the mol ratio of oxyethane and propylene oxide is 1:3-3:1, with acetic acid neutralization, suction filtration desalination;
3) synthesizing epoxy polyethers: polyethers is with after xylene solution dilution, under 100-150 ℃, 0.1-0.6MPa, obtains epoxidized polyether A with epichlorohydrin reaction, and wherein the mol ratio of polyethers and epoxy chloropropane is 1:(3-6);
In triethylene diamine, drip 2-butylene acid methyl esters, the mol ratio of triethylene diamine and 2-butylene acid methyl esters is (3-5): (0.5-1), and stirring reaction 0.5-1.5h, be warming up to 70-110 ℃, reaction 12-30h, then with epichlorohydrin reaction, obtain epoxidized polyether B;
4) synthetic emulsion splitter: epoxidized polyether A and epoxidized polyether B are dissolved in dimethylbenzene, obtain high moisture thick oil demulsifier.
Oil field of the present invention can also adopt following technical scheme with high moisture thick oil demulsifier:
High moisture thick oil demulsifier for described oil field, is characterized in: during synthetic emulsion splitter, epoxidized polyether A and epoxidized polyether B are with mol ratio 1:(0.9-1.1) ratio be dissolved in dimethylbenzene.
The preparation method of high moisture thick oil demulsifier for the oil field of the features such as it is simple that two of object of the present invention is to provide a kind of technique, easy to operate, controls easily, with low cost, and product demulsification is good.
Oil field of the present invention by the technical scheme that the preparation method of high moisture thick oil demulsifier takes is:
A preparation method for high moisture thick oil demulsifier for oil field, is characterized in: the preparation method of high moisture thick oil demulsifier comprises following processing step:
1) synthetic initiator: synthetic initiator: polyethylene polyamine and bisphenol S drip formaldehyde solution at 30-60 ℃, the mol ratio of polyethylene polyamine, bisphenol S and formaldehyde is (0.5-1): (5-7): (3-5), then be warming up to 100-150 ℃ of reaction 1-5h, lyophilize;
2) synthesizing polyether: under 110 ℃-150 ℃, 0.2-0.5MPa condition, initiator and oxyethane and propylene oxide are through KOH catalyzed polymerization, and wherein the mol ratio of oxyethane and propylene oxide is 1:3-3:1, with acetic acid neutralization, suction filtration desalination;
3) synthesizing epoxy polyethers: polyethers is with after xylene solution dilution, under 100-150 ℃, 0.1-0.6MPa, obtains epoxidized polyether A with epichlorohydrin reaction, and wherein the mol ratio of polyethers and epoxy chloropropane is 1:(3-6);
In triethylene diamine, drip 2-butylene acid methyl esters, the mol ratio of triethylene diamine and 2-butylene acid methyl esters is (3-5): (0.5-1), and stirring reaction 0.5-1.5h, be warming up to 70-110 ℃, reaction 12-30h, then with epichlorohydrin reaction, obtain epoxidized polyether B;
4) synthetic emulsion splitter: epoxidized polyether A and epoxidized polyether B are dissolved in dimethylbenzene, obtain high moisture thick oil demulsifier.
Oil field of the present invention can also adopt following technical scheme by the preparation method of high moisture thick oil demulsifier:
The preparation method of high moisture thick oil demulsifier for described oil field, is characterized in: during synthetic emulsion splitter, epoxidized polyether A and epoxidized polyether B are with mol ratio 1:(0.9-1.1) ratio be dissolved in dimethylbenzene.
Advantage and positively effect that the present invention has are:
Oil field is with high moisture thick oil demulsifier and preparation method thereof owing to having adopted the brand-new technical scheme of the present invention, and compared with prior art, the present invention has the following advantages:
1, there is good demulsification.Under same concentrations, compare with other emulsion splitter, the dehydrating effect of product P RJ-001 of the present invention is best.For emulsion splitter of the same race, when concentration is 10PPM, dehydration rate just can reach 98%.
2, gained emulsion splitter consumption of the present invention is few, and cost is low, and raw material is easy to get.
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples and be described in detail as follows:
Embodiment 1
High moisture thick oil demulsifier for a kind of oil field, its raw material adopting is polyethylene polyamine, bisphenol S, formaldehyde, KOH catalyzer, oxyethane, propylene oxide, acetic acid, dimethylbenzene, triethylene diamine, 2-butylene acid methyl esters, epoxy chloropropane, takes following technique synthetic:
1) synthetic initiator: polyethylene polyamine and bisphenol S drip formaldehyde solution at 30-60 ℃, the mol ratio of polyethylene polyamine, bisphenol S and formaldehyde is 1:5:4, then be warming up to 120 ℃ of reaction 3h, by product lyophilize, obtain homemade phenol amine aldehyde resin initiator.
2) synthesizing polyether: under KOH catalysis, by the oxyalkylated operational condition of preparation, the consumption of KOH catalyzer is 0.22%-0.27%, under 140 ℃, 0.4MPa condition, initiator and oxyethane and propylene oxide are through KOH catalyzed polymerization, and wherein the mol ratio of oxyethane and propylene oxide is 1:1, and product is neutralized to pH=7 with acetic acid, suction filtration desalination, can obtain polyethers.
3) synthesizing epoxy polyethers: polyethers, with after xylene solution dilution, at 120 ℃, under 0.5MPa, obtains epoxidized polyether A with epichlorohydrin reaction, and wherein the mol ratio of polyethers and epoxy chloropropane is 1:3;
In triethylene diamine, drip 2-butylene acid methyl esters, the mol ratio of triethylene diamine and 2-butylene acid methyl esters is 3:1, and stirring reaction 1h, is warming up to 90 ℃, react after 1 day, then with appropriate epichlorohydrin reaction, obtain epoxidized polyether B;
4) synthetic emulsion splitter: epoxidized polyether A and epoxidized polyether B are dissolved in dimethylbenzene with the ratio of mol ratio 1:1, obtain high moisture thick oil demulsifier.
Embodiment 2
A preparation method for high moisture thick oil demulsifier for oil field, preparation method comprises following processing step:
1) synthetic initiator: polyethylene polyamine and bisphenol S drip formaldehyde solution at 50 ℃, and the mol ratio of polyethylene polyamine, bisphenol S and formaldehyde is 1:7:5, is then warming up to 150 ℃ of reaction 3h, by product lyophilize, obtains homemade phenol amine aldehyde resin initiator.
2) synthesizing polyether: under KOH catalysis, by the oxyalkylated operational condition of preparation, the consumption of KOH catalyzer is 0.25%, under 110 ℃, 0.2MPa condition, initiator and oxyethane and propylene oxide are through KOH catalyzed polymerization, and wherein the mol ratio of oxyethane and propylene oxide is 2:1, and product neutralizes with acetic acid, suction filtration desalination, can obtain polyethers.
3) synthesizing epoxy polyethers: polyethers, with after xylene solution dilution, at 150 ℃, under 0.6MPa, obtains epoxidized polyether A with epichlorohydrin reaction, and wherein the mol ratio of polyethers and epoxy chloropropane is 1:6;
In triethylene diamine, drip 2-butylene acid methyl esters, the mol ratio of triethylene diamine and 2-butylene acid methyl esters is 5:1, and stirring reaction 1.5h, is warming up to 100 ℃, react after 1 day, then with appropriate epichlorohydrin reaction, obtain epoxidized polyether B;
4) synthetic emulsion splitter: epoxidized polyether A and epoxidized polyether B are dissolved in dimethylbenzene with the ratio of mol ratio 1:1, obtain high moisture thick oil demulsifier PRJ-001.
Embodiment 3
The dehydrating effect of the high moisture viscous crude of simulation in experiment, experiment adopts the evaluation method of oil and gas industry standard SY-T5281-2000 crude oil demulsifier use properties detection method (bottle examination method) regulation.The high moisture thick oil demulsifier PRJ-001 of embodiment 2 gained.
Experimental temperature is 70 ℃, Water in oil 60.4%, and water oil ratio 70:30, experimental result is as following table:
The demulsification of the different emulsion splitters of table 1
Figure BDA0000438436280000041
Figure BDA0000438436280000051
Wherein, PRO-001--PRO-007 is for the synthetic emulsion splitter of the moisture viscous crude of height.
Embodiment 4
The dehydrating effect of the high moisture viscous crude of simulation in experiment, experiment adopts the evaluation method of oil and gas industry standard SY-T5281-2000 crude oil demulsifier use properties detection method (bottle examination method) regulation.The high moisture thick oil demulsifier PRJ-001 of embodiment 2 gained.
Experimental temperature is 70 ℃, Water in oil 60.4%, and water oil ratio 70:30, experimental result is as following table:
The different adding consistency demulsifications of table 2
Figure BDA0000438436280000052
The present embodiment has described raw material and is easy to get, and with low cost, demulsification is good, and preparation method is simple, simple operation, and it is few that gained emulsion splitter has consumption, and the large and dewatering speed of dehydrating amount the positively effect such as soon.

Claims (4)

1. a high moisture thick oil demulsifier for oil field, it is characterized in that: the synthesis material of high moisture thick oil demulsifier is polyethylene polyamine, bisphenol S, formaldehyde, KOH catalyzer, oxyethane, propylene oxide, acetic acid, dimethylbenzene, triethylene diamine, 2-butylene acid methyl esters, epoxy chloropropane, takes following technique synthetic:
1) synthetic initiator: polyethylene polyamine and bisphenol S drip formaldehyde solution at 30-60 ℃, and the mol ratio of polyethylene polyamine, bisphenol S and formaldehyde is (0.5-1): (5-7): (3-5), be then warming up to 100-150 ℃ of reaction 1-5h, lyophilize;
2) synthesizing polyether: under 110 ℃-150 ℃, 0.2-0.5MPa condition, initiator and oxyethane and propylene oxide are through KOH catalyzed polymerization, and wherein the mol ratio of oxyethane and propylene oxide is 1:3-3:1, with acetic acid neutralization, suction filtration desalination;
3) synthesizing epoxy polyethers: polyethers is with after xylene solution dilution, under 100-150 ℃, 0.1-0.6MPa, obtains epoxidized polyether A with epichlorohydrin reaction, and wherein the mol ratio of polyethers and epoxy chloropropane is 1:(3-6);
In triethylene diamine, drip 2-butylene acid methyl esters, the mol ratio of triethylene diamine and 2-butylene acid methyl esters is (3-5): (0.5-1), and stirring reaction 0.5-1.5h, be warming up to 70-110 ℃, reaction 12-30h, then with epichlorohydrin reaction, obtain epoxidized polyether B;
4) synthetic emulsion splitter: epoxidized polyether A and epoxidized polyether B are dissolved in dimethylbenzene, obtain high moisture thick oil demulsifier.
2. high moisture thick oil demulsifier for oil field according to claim 1, is characterized in that: during synthetic emulsion splitter, epoxidized polyether A and epoxidized polyether B are with mol ratio 1:(0.9-1.1) ratio be dissolved in dimethylbenzene.
3. a preparation method for high moisture thick oil demulsifier for oil field, is characterized in that: the preparation method of high moisture thick oil demulsifier comprises following processing step:
1) synthetic initiator: synthetic initiator: polyethylene polyamine and bisphenol S drip formaldehyde solution at 30-60 ℃, the mol ratio of polyethylene polyamine, bisphenol S and formaldehyde is (0.5-1): (5-7): (3-5), then be warming up to 100-150 ℃ of reaction 1-5h, lyophilize;
2) synthesizing polyether: under 110 ℃-150 ℃, 0.2-0.5MPa condition, initiator and oxyethane and propylene oxide are through KOH catalyzed polymerization, and wherein the mol ratio of oxyethane and propylene oxide is 1:3-3:1, with acetic acid neutralization, suction filtration desalination;
3) synthesizing epoxy polyethers: polyethers, with after xylene solution dilution, at 100-150 ℃, under 0.1-0.6MPa, obtains epoxidized polyether A with epichlorohydrin reaction, and wherein the mol ratio of polyethers and epoxy chloropropane is 1:(3-6);
In triethylene diamine, drip 2-butylene acid methyl esters, the mol ratio of triethylene diamine and 2-butylene acid methyl esters is (3-5): (0.5-1), and stirring reaction 0.5-1.5h, be warming up to 70-110 ℃, reaction 12-30h, then with epichlorohydrin reaction, obtain epoxidized polyether B;
4) synthetic emulsion splitter: epoxidized polyether A and epoxidized polyether B are dissolved in dimethylbenzene, obtain high moisture thick oil demulsifier.
4. the preparation method of high moisture thick oil demulsifier for oil field according to claim 3, is characterized in that: during synthetic emulsion splitter, epoxidized polyether A and epoxidized polyether B are with mol ratio 1:(0.9-1.1) ratio be dissolved in dimethylbenzene.
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CN105273179A (en) * 2014-12-28 2016-01-27 新疆科力新技术发展有限公司 Preparation method for high-temperature-resistant thick oil demulsifier
CN105348509A (en) * 2015-10-28 2016-02-24 天津亿利科能源科技发展股份有限公司 Preparation method of water clarifier for water quality with high polymer content
CN105861036A (en) * 2016-06-15 2016-08-17 成都高普石油工程技术有限公司 Preparation method of composite demulsifier for crude oil
CN105907420A (en) * 2016-06-15 2016-08-31 成都高普石油工程技术有限公司 Application method of crude oil composite demulsifier
CN105907419A (en) * 2016-06-15 2016-08-31 成都高普石油工程技术有限公司 Using method of sour crude oil emulsion breaker
CN106047398A (en) * 2016-06-15 2016-10-26 成都高普石油工程技术有限公司 Composite demulsifier for crude oil
CN110903661A (en) * 2019-11-20 2020-03-24 江苏中路交通科学技术有限公司 U-pave special modified asphalt and preparation method and application method thereof
CN111778065A (en) * 2020-07-27 2020-10-16 滨州学院 Preparation method of ternary combination flooding crude oil demulsifier
CN111777757A (en) * 2020-07-27 2020-10-16 滨州学院 Preparation method of super heavy oil demulsifier
CN111848943A (en) * 2020-07-31 2020-10-30 安东石油技术(集团)有限公司 Modified polyether, composite crude oil demulsifier, and preparation method and application thereof
CN114214087A (en) * 2021-12-16 2022-03-22 克拉玛依新科澳石油天然气技术股份有限公司 High-efficiency composite demulsifier and preparation method thereof
CN114958412A (en) * 2022-03-25 2022-08-30 中海油(天津)油田化工有限公司 Offshore oilfield demulsification and defoaming comprehensive treatment agent and preparation method thereof
CN115058261A (en) * 2022-07-21 2022-09-16 天津开放大学 Novel modified efficient compound crude oil demulsifier

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Cited By (14)

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Publication number Priority date Publication date Assignee Title
CN105273179A (en) * 2014-12-28 2016-01-27 新疆科力新技术发展有限公司 Preparation method for high-temperature-resistant thick oil demulsifier
CN105348509A (en) * 2015-10-28 2016-02-24 天津亿利科能源科技发展股份有限公司 Preparation method of water clarifier for water quality with high polymer content
CN105861036A (en) * 2016-06-15 2016-08-17 成都高普石油工程技术有限公司 Preparation method of composite demulsifier for crude oil
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CN105907419A (en) * 2016-06-15 2016-08-31 成都高普石油工程技术有限公司 Using method of sour crude oil emulsion breaker
CN106047398A (en) * 2016-06-15 2016-10-26 成都高普石油工程技术有限公司 Composite demulsifier for crude oil
CN110903661A (en) * 2019-11-20 2020-03-24 江苏中路交通科学技术有限公司 U-pave special modified asphalt and preparation method and application method thereof
CN111778065A (en) * 2020-07-27 2020-10-16 滨州学院 Preparation method of ternary combination flooding crude oil demulsifier
CN111777757A (en) * 2020-07-27 2020-10-16 滨州学院 Preparation method of super heavy oil demulsifier
CN111777757B (en) * 2020-07-27 2022-10-04 滨州学院 Preparation method of super heavy oil demulsifier
CN111848943A (en) * 2020-07-31 2020-10-30 安东石油技术(集团)有限公司 Modified polyether, composite crude oil demulsifier, and preparation method and application thereof
CN114214087A (en) * 2021-12-16 2022-03-22 克拉玛依新科澳石油天然气技术股份有限公司 High-efficiency composite demulsifier and preparation method thereof
CN114958412A (en) * 2022-03-25 2022-08-30 中海油(天津)油田化工有限公司 Offshore oilfield demulsification and defoaming comprehensive treatment agent and preparation method thereof
CN115058261A (en) * 2022-07-21 2022-09-16 天津开放大学 Novel modified efficient compound crude oil demulsifier

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