CN102167834A - Method for preparing thick oil demulsifier - Google Patents
Method for preparing thick oil demulsifier Download PDFInfo
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- CN102167834A CN102167834A CN 201110008246 CN201110008246A CN102167834A CN 102167834 A CN102167834 A CN 102167834A CN 201110008246 CN201110008246 CN 201110008246 CN 201110008246 A CN201110008246 A CN 201110008246A CN 102167834 A CN102167834 A CN 102167834A
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Abstract
The invention discloses a method for preparing a thick oil demulsifier. The method comprises the following steps of: adding polyether into an organic reaction solvent and a crosslinking agent respectively for crosslinking the polyether; and adding the polyether into the organic reaction solvent and a sulfonation modifier respectively to modify an end group. According to the high-temperature-resistant thick oil demulsifier provided by the invention, an oil-water interface can be quickly reached in crude oil emulsion, so that strength and viscoelasticity of an interface film are reduced, and the aim of demulsification is fulfilled; in addition, a demulsification effect can be improved by changing HLB (Hydrophile Lipophile Balance) value of molecules of the demulsifier through modification of the end group of the polyether, and temperature resistance performance of the molecules of the demulsifier can be improved.
Description
Technical field
The present invention relates to petroleum industry oil-gas gathering and transportation chemical technical field, particularly a kind of preparation method of thick oil demulsifier.
Background technology
Oil in people's life in occupation of important position more and more, in the process of oil production along with each elephant of China has all entered secondary oil recovery later stage and tertiary phase.For keeping crude production rate, each oil field all big area take to improve oil well output such as increasing water filling, caustic flooding, surfactant flooding, polymer flooding wet goods technique means, many viscous crude that are difficult to exploit, super-heavy oil deposit have also begun exploitation.The complicacy of crude oil extraction liquid milk sap and stability all obviously improve, and this is just to the demands for higher performance of crude oil demulsifier.
Emulsion splitter is one of oil field chemical of consumption maximum in the petroleum industry, the oxyethane that China's most of oil field emulsion splitter is, the block polyether of propylene oxide.Have monohydroxy-alcohol, dibasic alcohol, glycerine, tetramethylolmethane, quadrol, polyamines polyene, resol etc. commonly used are the polyether type demulsifying agent of initiator.But, along with the increase of heavy oil production, the intensified oil reduction The Application of Technology, these emulsion splitters can't satisfy the requirement of viscous crude, the on-the-spot dehydration of special viscous crude.At present, the block polyether multipolymer is the product that demulsification, adaptability and production cost all relatively are fit to, and its key problem in technology is the kind of initiator, the block ratio and the sequential structure of polyethers, the hydrophile-lipophile balance value of pfpe molecule etc.
Since emulsion splitter the earliest in 1914 came into operation, the development and the use of emulsion splitter had had great advance, developed different emulsion splitters at different oil fields with different oil production technology.High temperature resistant emulsion splitter at super-heavy oil deposit SAGD (SAGD) technology does not appear in the newspapers as yet at present.
Summary of the invention
One of purpose of the present invention provides a kind of preparation method who is applicable to the high temperature resistant thick oil demulsifier that super viscous crude high temperature dehydration is used.
According to an aspect of the present invention, provide a kind of preparation method of high temperature resistant thick oil demulsifier to comprise:
Polyethers is added the organic reaction solvent respectively and linking agent carries out the crosslinked of polyethers.
In emulsion of crude oil, can reach water-oil interface according to high temperature resistant thick oil demulsifier provided by the invention rapidly, reduce interface film strength and visco-elasticity, reach the purpose of breakdown of emulsion; In addition, the modification of polyethers end group can improve demulsification by the HLB value that changes the emulsion splitter molecule, can improve the heat resistance of emulsion splitter molecule simultaneously.
Embodiment
The preparation method of a kind of thick oil demulsifier that the embodiment of the invention provides can may further comprise the steps:
Synthesizing of step S1, block polyether, specifically synthetic as follows:
At first, ready phenol-amine resin or polyamines polyene and catalyzer are joined in airtight, as the to fill nitrogen voltage-resistant reactor, under agitation condition, be warmed up to 90～150 ℃.
Secondly, alternately add propylene oxide and oxyethane respectively, controlled temperature is between 90～150 ℃, and pressure range is carried out polyreaction at 0.2-0.6Mpa, polyreaction to the pressure in the reactor no longer descends to being to react and finishes, and obtains many blocks macromole polyethers.Many blocks macromole polyethers comprises polyethers FA or polyethers AE.
Polyethers FA is made of phenol-amine resin, propylene oxide and oxyethane; According to the mass fraction, phenol-amine resin: propylene oxide: oxyethane=1: 5～150: 2～50.Polyethers AE is made of polyamines polyene, propylene oxide, oxyethane; According to the mass fraction, polyamines polyene: propylene oxide: oxyethane=1: 5～200: 2～50.
Polyamines polyene can comprise tetraethylene pentamine, five ethene hexamines or mix polyamines polyene etc.Catalyzer is a basic catalyst, can comprise potassium hydroxide, tertiary butyl potassium, potassium tert.-butoxide or potassium ethylate etc.Catalyst levels is 0.2～0.8% of a reaction system gross weight.
The terminal groups modification of step S2, polyethers, concrete modification is as follows:
Polyethers AE and FA are put into 1: 0～5 (according to the mass fraction) ratio in the reactor of band whipping appts, add the organic reaction solvent; Temperature is controlled at 5～20 ℃ and slowly adds a certain amount of sulfonation modifying agent, is warming up to 30 ℃-120 ℃ reactions after adding is finished and reacts completely in 0.5 hour-6 hours, steams solvent and gets required product.
The sulfonation modifying agent can comprise the vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid or thionamic acid etc.Add-on is; The organic reaction solvent can comprise chloroform, Virahol, dioxane, hexanaphthene, dimethylbenzene or tetrahydrofuran (THF) etc., and reaction system concentration is 20～60%.
Step S3, polyethers crosslinked, concrete crosslinked as follows:
With the multi-block polyether FA of modification or unmodified mistake and the mixture of AE (polyethers AE: polyethers FA=1 according to the mass fraction: 0～5) put in the reactor of band whipping appts, add organic reaction solvent (for example, dimethylbenzene), system concentration 40%; Temperature control to 5～25 ℃ drip linking agent then, and dosage of crosslinking agent is 2～5% of a polyethers amount, is warming up to 40-60 ℃ after linking agent is added dropwise to complete, and reacts 1 hour, obtains brown heavy-gravity emulsion splitter.Linking agent can comprise tolylene diisocyanate or '-diphenylmethane diisocyanate etc.
Wherein, step S3 available step S2 also can be without the polyethers of terminal groups modification through the polyethers of terminal groups modification.Not only demulsification can be improved with polyethers, but also the heat resistance of emulsion splitter molecule can be improved through terminal groups modification.
Preparation method to thick oil demulsifier proposed by the invention describes below in conjunction with specific embodiment.
Embodiment one,
Take by weighing polyethers AE30g, polyethers FA10g and put into the 500ml four-necked bottle that has stirring rod, prolong, thermometer and application of sample funnel, add chloroform 60ml, stir, be cooled to 0 ℃ with ice-water bath, take by weighing chlorsulfonic acid 5.8g and slowly add in the four-necked bottle with the application of sample funnel, the application of sample process control temp is at 10 ℃.Be warming up to 40 ℃ of reactions 1 hour after dropwising.The pressure reducing and steaming solvent is stand-by.
R(CH
2CH
2O)
nH+HSO
3Cl→R(CH
2CH
2O)SO
3H+HCl；
In the four-necked bottle that boils off solvent, add dimethylbenzene 60ml, stir, be cooled to 0 ℃ with ice-water bath, adding an amount of potassium hydroxide transfers pH value to be about 8, take by weighing tolylene diisocyanate 1.2g, slowly add in the four-necked bottle with the application of sample funnel, the application of sample process control temp is at 5 ℃.Be warming up to 60 ℃ of reactions 1 hour after dropwising.Can call number be the emulsion splitter sample of TY-1.
Embodiment two,
Take by weighing polyethers AE35g, FA5g and put into and have stirring rod, ventpipe and thermometer voltage-resistant reactor, take by weighing thionamic acid 2.0g, urea 1.0g adds in the reactor simultaneously.Nitrogen blowing three times, closed reactor stirs and is warming up to 120 ℃ simultaneously, 120 ℃ of reactions of constant temperature 6 hours.Cooling is taken out stand-by.
R(CH
2CH
2O)
nH+H
2NSO
3H→R(CH
2CH
2O)OSO
3NH
4；
Previous step product 40g adding is had in the 500ml four-necked bottle of stirring rod, prolong, thermometer and application of sample funnel, add dimethylbenzene 60ml, stir, be cooled to 0 ℃ with ice-water bath, adding an amount of potassium hydroxide transfers pH value to be about 8 to take by weighing tolylene diisocyanate 14g, slowly add in the four-necked bottle with the application of sample funnel, the application of sample process control temp is at 10 ℃.Be warming up to 60 ℃ of reactions 1 hour after dropwising.Can call number be the emulsion splitter sample of TY-2.
Embodiment three,
Take by weighing polyethers AE25g, FA15g and put into the 500ml four-necked bottle that has stirring rod, prolong, thermometer and application of sample funnel., add dimethylbenzene 60ml, stir, be cooled to 0 ℃ with ice-water bath, adding an amount of potassium hydroxide transfers pH value to be about 8, take by weighing tolylene diisocyanate 1.2g, slowly add in the four-necked bottle with the application of sample funnel, the application of sample process control temp is at 25 ℃.Be warming up to 60 ℃ of reactions 1 hour after dropwising.The pressure reducing and steaming solvent is stand-by.
In the four-necked bottle that boils off solvent, add chloroform 60ml, stir, be cooled to 0 ℃, take by weighing chlorsulfonic acid 5.0g and slowly add in the four-necked bottle, 5 ℃ of application of sample process control temps with the application of sample funnel with ice-water bath.Be warming up to 40 ℃ of reactions 1 hour after dropwising.
R(CH
2CH
2O)
nH+HSO
3Cl→R(CH
2CH
2O)SO
3H+HCl；
Can call number be the emulsion splitter sample of TY-3.
Embodiment four,
The breakdown of emulsion test of Liaohe Oil Field SAGD (SAGD) extraction liquid.Colloid, asphalt content height (50%～54.3%) in the SAGD extraction liquid; Content of impurities height (6 * 104mg/L～1.2 * 105mg/L); Viscosity height (50 ℃ of viscosity 1.2 * 105mPa.s); Emulsion-stabilizing is difficult for dehydration.We utilize pressure vessel to carry out the breaking emulsion and dewatering experiment in the laboratory according to SAGD oil production technology feature.Experiment condition is: oil in water emulsion initial aqueous 45.94%, emulsion splitter add dose 300mg/L, utilize nitrogen pressure to 0.65MP in the container, and 170 ℃ of constant temperature of oil bath 90 minutes are got dehydration back oil sample and surveyed water cut in purified, and experimental result sees the following form:
Table 1: Liaohe Oil Field SAGD crude oil demulsification experiment
Experimental result shows that gained emulsion splitter of the present invention has good breaking emulsion and dewatering effect to super viscous crude, and dehydration rate reaches more than 90%.
The present invention is that the better emulsion splitter of effect crosslinked and that modification obtains is carried out on the basis with macromole polyethers or the polyether mixture with multiple-branching construction, this emulsion splitter can reach water-oil interface rapidly in emulsion of crude oil, reduce interface film strength and visco-elasticity, reach the purpose of breakdown of emulsion, the modification of end group can improve demulsification by the HLB value that changes the emulsion splitter molecule, can improve the heat resistance of emulsion splitter molecule simultaneously.This thick oil demulsifier can be used for the high-efficiency dehydration of different moisture content crude oil in the oil field.Be specially adapted to utilize the high temperature dehydration of the super viscous crude of SAGD (SAGD) technology exploitation.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (17)
1. the preparation method of a thick oil demulsifier is characterized in that, comprising:
Polyethers is added the organic reaction solvent respectively and linking agent carries out the crosslinked of polyethers.
2. preparation method according to claim 1 is characterized in that, describedly polyethers is added organic reaction solvent and linking agent respectively carries out also comprising before or after polyethers crosslinked:
Described polyethers is added the organic reaction solvent respectively and terminal groups modification is carried out in the sulfonation modifying agent.
3. preparation method according to claim 2 is characterized in that, described polyethers can make in the following manner:
At first with phenol-amine resin or polyamines polyene, basic catalyst is added in the voltage-resistant reactor, stirs to heat up;
Alternately add propylene oxide and oxyethane then respectively and carry out polyreaction, thereby obtain many blocks macromole polyethers.
4. preparation method according to claim 3 is characterized in that:
The temperature range of described intensification is at 90～150 ℃; The temperature range of described polyreaction is at 90～150 ℃; The pressure range of described polyreaction is at 0.2-0.6Mpa.
5. preparation method according to claim 3 is characterized in that:
Described many blocks macromole polyethers comprises polyethers FA or polyethers AE;
Wherein, described polyethers FA is made of phenol-amine resin, propylene oxide and oxyethane; According to the mass fraction, phenol-amine resin: propylene oxide: oxyethane=1:5～150:2～50;
Described polyethers AE is made of polyamines polyene, propylene oxide, oxyethane; According to the mass fraction, polyamines polyene: propylene oxide: oxyethane=1:5～200:2～50.
6. preparation method according to claim 3 is characterized in that:
Described polyamines polyene comprises tetraethylene pentamine, five ethene hexamines or mixes polyamines polyene.
7. preparation method according to claim 3 is characterized in that:
Described basic catalyst comprises potassium hydroxide, tertiary butyl potassium, potassium tert.-butoxide or potassium ethylate.
8. preparation method according to claim 5 is characterized in that, describedly polyethers is added organic reaction solvent and linking agent respectively carries out the crosslinked of polyethers and is:
The mixture of described polyethers FA and polyethers AE is put in the reactor of band whipping appts, and added the organic reaction solvent, temperature control drips linking agent then, heats up, and reaction obtains emulsion splitter.
9. preparation method according to claim 8 is characterized in that:
According to the mass fraction, described polyethers AE: described polyethers FA=1:0～5.
10. preparation method according to claim 8 is characterized in that:
Described temperature control is that temperature is controlled at 5～25 ℃; The scope of described intensification is at 40-60 ℃; The described reaction times is 1 hour.
11. preparation method according to claim 8 is characterized in that:
The consumption of described linking agent be described polyethers FA and polyethers AE amount of mixture 2～5%.
12. preparation method according to claim 5 is characterized in that, describedly described polyethers is added organic reaction solvent and sulfonation modifying agent respectively carries out terminal groups modification and is:
Polyethers AE and polyethers FA are put in the reactor of band whipping appts, add the organic reaction solvent, temperature control also slowly adds the sulfonation modifying agent, heats up, and steams the organic reaction solvent after reacting completely.
13. preparation method according to claim 12 is characterized in that:
According to the mass fraction, described polyethers AE: described polyethers FA=1:0～5.
14. preparation method according to claim 12 is characterized in that:
The temperature of described intensification is 30 ℃-120 ℃; The temperature range of described temperature control is at 5～20 ℃; The described reaction times is 0.5-6 hour.
15., it is characterized in that according to each described preparation method of claim 1-14:
Described linking agent comprises tolylene diisocyanate or '-diphenylmethane diisocyanate.
16., it is characterized in that according to each described preparation method of claim 2-14:
Described sulfonation modifying agent comprises the vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid or thionamic acid.
17., it is characterized in that according to each described preparation method of claim 1-14:
Described organic reaction solvent comprises chloroform, Virahol, dioxane, hexanaphthene, dimethylbenzene or tetrahydrofuran (THF).
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293376A (en) * | 2013-07-19 | 2015-01-21 | 中国石油天然气股份有限公司 | Low temperature demulsifier and preparation method thereof |
| CN106335968A (en) * | 2016-10-19 | 2017-01-18 | 中国石油化工股份有限公司 | Demulsifier for sewage high in thickened oil content and preparation method |
| CN106635134A (en) * | 2016-12-14 | 2017-05-10 | 钦州学院 | Crude oil desalting agent and preparation method thereof |
| CN107557055A (en) * | 2017-10-23 | 2018-01-09 | 天津正达科技有限责任公司 | A kind of preparation method of modified polyether crude oil rapid demulsifier |
| CN109135806A (en) * | 2018-08-17 | 2019-01-04 | 滨州市丰泰技术开发有限公司 | A kind of manufacturing method of marine oil field high-efficient demulsifier |
| CN109536201A (en) * | 2018-11-14 | 2019-03-29 | 西安巨力石油技术有限公司 | A kind of preparation method and applications of demulsifier, demulsifier |
| CN110819381A (en) * | 2019-11-22 | 2020-02-21 | 山东益丰生化环保股份有限公司 | Demulsifier and preparation method thereof |
| CN111662745A (en) * | 2020-04-28 | 2020-09-15 | 德仕能源科技集团股份有限公司 | Sulfonate demulsifier for crude oil three-recovery produced liquid and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293376A (en) * | 2013-07-19 | 2015-01-21 | 中国石油天然气股份有限公司 | Low temperature demulsifier and preparation method thereof |
| CN106335968A (en) * | 2016-10-19 | 2017-01-18 | 中国石油化工股份有限公司 | Demulsifier for sewage high in thickened oil content and preparation method |
| CN106335968B (en) * | 2016-10-19 | 2020-05-19 | 中国石油化工股份有限公司 | Demulsifier for high polymer-containing heavy oil sewage and preparation method thereof |
| CN106635134A (en) * | 2016-12-14 | 2017-05-10 | 钦州学院 | Crude oil desalting agent and preparation method thereof |
| CN107557055A (en) * | 2017-10-23 | 2018-01-09 | 天津正达科技有限责任公司 | A kind of preparation method of modified polyether crude oil rapid demulsifier |
| CN109135806A (en) * | 2018-08-17 | 2019-01-04 | 滨州市丰泰技术开发有限公司 | A kind of manufacturing method of marine oil field high-efficient demulsifier |
| CN109536201A (en) * | 2018-11-14 | 2019-03-29 | 西安巨力石油技术有限公司 | A kind of preparation method and applications of demulsifier, demulsifier |
| CN110819381A (en) * | 2019-11-22 | 2020-02-21 | 山东益丰生化环保股份有限公司 | Demulsifier and preparation method thereof |
| CN111662745A (en) * | 2020-04-28 | 2020-09-15 | 德仕能源科技集团股份有限公司 | Sulfonate demulsifier for crude oil three-recovery produced liquid and preparation method thereof |
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| CN102167834B (en) | 2013-03-13 |
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