CN102471431A - Alkoxylated trialkanol amine condensates and the use thereof as demulsifiers - Google Patents
Alkoxylated trialkanol amine condensates and the use thereof as demulsifiers Download PDFInfo
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- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
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Abstract
The invention relates to the use of alkoxylated trialkanolamine condensates for separating water from oil emulsions, said condensates being obtained by condensation of trialkanolamines, with alkaline catalysis, and subsequent alkoxylation with at least one C2 to C4 alkylene oxide, having a number-average molecular weight of between 500 and 500,000 g/mol, comprising between 2 and 250 trialkanolamine units, and an average alkoxylation degree of between 1 and 200 alkylene oxide units per free OH group, in quantities of between 0.0001 and 5 wt. %, in relation to the oil content of the emulsion to be split.
Description
The present invention relates to oxyalkylated three alkanolamine condensess; Oxyalkylated three alkanolamine condensess are used for water-fat liquor breakdown of emulsion, especially in the purposes of Oil extraction; With the method that is used for the water-in-oil emulsion breakdown of emulsion, through in emulsion, adding at least a oxyalkylated three alkanolamine condensess.
Crude oil produces with the form with the emulsion of water when it is exploited.Before the crude oil deep processing, must this emulsion of crude oil breakdown of emulsion be become oil part and water section.Usually use so-called demulsifier for emulsion of crude oil or petroleum emulsions emulsion splitter for this reason, perhaps also be called for short " petroleum demulsifier ".Petroleum demulsifier is the polymer-type compound of interfacial activity, and it can cause the separation of the emulsion composition that needs at short notice.
As demulsifying compound, mainly use alkoxylated alkyl group resol, non-ionic type olefin oxide segmented copolymer and with the crosslinked variant of di-epoxide." Something Old, Something New:A Discussion about Demulsifiers ", T.G.Balson; The 226-238 page or leaf, in Proceedings in the Chemistry in the Oil Industry VIII Symposium, 03.-05.11.2003; Manchester; GB, and " Crude-Oil Emulsions:A State-Of-The-Art Review ", S.Kokal; The 5-13 page or leaf, Society of Petroleum Engineers SPE 77497 provides summary.
US-4 032 514 discloses the purposes that alkyl phenolic resin is used for the petroleum emulsions breakdown of emulsion.These resins are by to alkylphenol and aldehyde, normally formaldehyde condensation and obtaining.
Such resin uses with oxyalkylated form usually, and is for example disclosed the sort of among the DE-A-24 45 873.Make free phenol OH-base and olefin oxide reaction for this reason.
Except that free phenol OH-base, can also be with the NH-based alkoxylation of free alcohol OH-base or amine, for example disclosed among the US-5 401 439.
As other petroleum demulsifier, disclose among the US-4 321 146 among olefin oxide segmented copolymer and the US-5 445 765 and disclose oxyalkylated polymine.
Oxyalkylated dendritic polyester (dendrimer) is disclosed among the DE-A-103 29 723 as the petroleum emulsions emulsion splitter of biodegradable (OECD 306).Be disclosed among the DE-A-103 25 198 according to OECD 306 biodegradable emulsion splitters equally.Relate to oxyalkylated, crosslinked poly-glycerol at this.
Said disclosed emulsion splitter can be with single-component, use with the mixture of other emulsion splitter or with the form of crosslinked product.
The polycondensate of alkanolamine, preferred trolamine polycondensate is described to reverse-phase emulsifier (O/w emulsion).Can adopt basic catalyst (for example disclosed among the US-2 407 895) in this case or adopt an acidic catalyst (for example disclosed among US-4 505 839 or the DE-A-40 03 243) to carry out condensation.
WO-2009/060060 discloses the purposes through the oxyalkylated three alkanolamine condensess of the acid catalysis condensation acquisition of three alkanolamines.But acid catalyzed three alkanolamine condensess have shortcoming, and they reach very high molecular weight and condensation reaction poor controllability.
The different character (for example asphalt content, paraffinicity and salts contg, the chemical constitution of natural demulsifier) and the moisture content volume of different crude oils make that indispensable is to further develop existing petroleum demulsifier.Except that the validity of making every effort to reach higher, from economic and ecological angle, the LDR of the petroleum demulsifier that use and widely operability especially be in prominent position.
Therefore the objective of the invention is to research and develop new petroleum demulsifier, said petroleum demulsifier is equivalent to or surpasses known petroleum demulsifier on effect, can use with dosage that also will be low.
Confirm that surprisingly three alkanolamine condensess oxyalkylated, that obtain through alkaline condensation had demonstrated the excellent effect as crude oil demulsifier already under low-down dosage.
Therefore; To be oxyalkylated three alkanolamine condensess be used for the purposes of water-in-oil emulsion breakdown of emulsion with the amount based on oil content meter 0.0001 to the 5 weight % of the emulsion of treating breakdown of emulsion to theme of the present invention, the base catalysis condensation that said condenses can be through three alkanolamines and adopt at least a C subsequently
2To C
4-olefin oxide alkoxylate and obtaining, said condenses has 500 to 500, and the number-average molecular weight of 000g/mol comprises 2 to 250 three alkanolamine unit, and its average degree of alkoxylation is that each free OH is between 1 and 200 olefin oxide unit.
Another theme of the present invention is the method that is used for the water-in-oil emulsion breakdown of emulsion; Through adding at least a oxyalkylated three alkanolamine condensess to emulsion based on weight meter 0.0001 to the 5 weight % of emulsion, the base catalysis condensation that said condenses can be through three alkanolamines and adopt at least a C subsequently
2To C
4-olefin oxide alkoxylate and obtain and said condenses has 500 to 500, the number-average molecular weight of 000g/mol comprises 2 to 250 three alkanolamine unit, and its average degree of alkoxylation is 1 to 200 oxyalkyl units of each free OH.
Another theme of the present invention is oxyalkylated three alkanolamine condensess, the base catalysis condensation that said condenses can be through three alkanolamines and adopt at least a C subsequently
2To C
4-olefin oxide alkoxylate and obtaining makes average degree of alkoxylation be 1 to 200 oxyalkyl units of each free OH and comprise 2 to 250 three alkanolamine unit and have 500 to 500, the number-average molecular weight of 000g/mol.
In a preferred embodiment, the molecular weight of oxyalkylated three alkanolamine condensess is 1,000 to 350,000g/mol.
The preparation of said three alkanolamine condensess is carried out through the base catalysis condensation of three alkanolamines.Use three alkanolamines of following general formula
N(CH
2CHR
1OH)(CH
2CHR
2OH)(CH
2CHR
3OH)
Wherein, R
1, R
2And R
3Represent H, methyl, ethyl or phenyl independently of one another.
The monomeric instance that can be used for polycondensation is trolamine, tri-isopropanolamine, three (2-hydroxyl butyl) amine, di-alcohol Yi Bingchunan, di-alcohol-2-hydroxyl-2-phenyl-ethyl amine, diisopropanol thanomin and composition thereof.
The temperature of reaction that is used for condensation reaction is usually between 150 and 300 ℃, preferably between 240 and 280 ℃.Reaction is generally under atmospheric pressure carried out.Can for example NaOH or KOH be used as catalyzer.Catalyzer uses in the amount based on weight 0.1 to the 25 weight % of reaction mixture.Condensation needs 1-24 hour usually, preferred 3-16 hour.
The three alkanolamine condensess that so obtain can for example be represented by formula (1)
Wherein, R
1, R
2And R
3Represent H, methyl, ethyl or phenyl independently of one another, and R
4, R
5And R
6The group of the formula (2) of representing OH independently of one another or connecting via the free valency of Sauerstoffatom,
Condition is that three alkanolamine condensess contain 2 to 250 three alkanolamine unit.
Three alkanolamine unit are the unit according to formula (1) or (2).Therefore in formula (1) and (2), be not all radicals R
4, R
5And R
6Represent OH simultaneously, make three alkanolamine condensess comprise 2 to 250 three alkanolamine unit.
Condensation degree, the prolongation along with the reaction times according to the unit number of formula (1) or (2) that promptly in three alkanolamine polycondensates, is contained increases, and calculates through measuring the OH value.
The mensuration of OH value is carried out according to DIN 53240 standards in December, 1971.Preferably, the OH value is between 450-800mg KOH/g material.
Owing to be used for the three-functionality-degree of three alkanolamines of condensation, generation can be by the structural unit of formula (3) (the polycondensate end of the chain), formula (4) (the polycondensate chain link of straight chain) and formula (5) (the polycondensate chain link of branching) expression.Three alkanolamine unit are to be understood that to (1) is through formal excision radicals R from formula at this
4, R
5And R
6The trivalent group that obtains.
Wherein,
R
1, R
2And R
3Represent independently of one another H, methyl, ethyl or phenyl and
R
4, R
5And R
6The group of representing OH or formula (2) independently of one another.
To use at least a C by the three alkanolamine condensess that the base catalysis condensation obtains then
2To C
4-olefin oxide alkoxylate.Olefin oxide uses with molar excess.That kind as be known in the art is through carrying out alkoxylate with three alkanolamine polycondensates and olefin oxide in 50 to 200 ℃ thermotonus under the elevated pressure that is generally 1.1 to 20 crust.Alkoxylate is carried out on the free OH of three alkanolamine polycondensates.
Use so many olefin oxide, make that average degree of alkoxylation is that each free OH is between 1 and 200 olefin oxide unit.Average degree of alkoxylation is interpreted as the mean number of the oxyalkyl units of addition on each free OH at this.It is preferably 5 to 150, and especially 10 to 100.
Olefin oxide is ethylene oxide, propylene oxide or the mixture be made up of ethylene oxide and propylene oxide preferably.Alkoxy base can block or random arrangement.
Oxyalkylated three alkanolamine polycondensates according to said method preparation can be described by formula (6).
Wherein,
R
1, R
2And R
3Have above-mentioned implication and
R
4, R
5And R
6The group of expression (7) independently of one another
Or the group of formula (8)
-O-(B-O)
m-(A-O)
n-H (8)
Wherein A and B represent the C that differs from one another
2To C
4-alkoxyl group, preferred ethylidene or propylidene group and n and m represent 1 to 100 integer, condition is, is not all radicals R
4, R
5And R
6The group of while expression (8).
Also be suitable for the unitary number of three alkanolamines between 2 and 250 at this.Therefore, radicals R
4, R
5And R
6With such degree group of expression (8) simultaneously not, make that the unitary number of three alkanolamines is 2 to 250.
Olefin oxide unit (AO) is perhaps represented identical olefin oxide unit or is represented the different oxidation olefin unit with (BO).Under latter event, the olefin oxide unit can perhaps be arranged like block form under situation preferred embodiment randomly.
One preferred embodiment in, (AO) with (BO) expression ethylene oxide unit block or (AO) with (BO) expression propylene oxide unit block.
In another preferred embodiment, (AO) expression propylene oxide unit and (BO) expression ethylene oxide unit, perhaps (AO) expression ethylene oxide unit and (BO) expression propylene oxide unit.In the oxyalkylated three alkanolamine polycondensates propylene oxide unit than the ratio of ethylene oxide unit preferably between 40: 1 and 1: 5, more preferably between 30: 1 and 1: 4, especially between 20: 1 and 1: 2.
The oxyalkylated three alkanolamine polycondensates that after condensation and alkoxylate, obtain have 500 to 500,000 units, the especially molecular weight of 1,000 to 350,000 unit.
In preferred embodiment, oxyalkylated three alkanolamine condensess have the water number of 7-22.Water number is nondimensional number and measures according to DIN EN 12836.
Water number has been described the HLB value (hydrophilic-lipophilic balance) of interfacial activity material, and is that oxyalkylated three the alkanolamine condenses is water miscible measures.High water number greater than 15 means good water-solubility, and the low water number less than 10 means good oil soluble.Water number depends on the ratio of EO group and the quantity of PO group.Oxyalkylated three alkanolamine condensess with high water number have the isolated water of oil-contg greatly quickly to emulsion breaking but produce.Breakdown of emulsion carries out slowlyer under low water number, and the oil-contg of isolated water is lower for this reason.
The preferred theme of the present invention is the purposes that the conduct in oil production of oxyalkylated three alkanolamine polycondensates is used for the emulsion splitter of oil/water miscible liquid.
In order to use as petroleum demulsifier, oxyalkylated three alkanolamine polycondensates are added into water-in-oil emulsion, this preferably takes place in solution.As the solvent that is used for oxyalkylated three alkanolamine polycondensates, preferably paraffinic base, aromatics or alcoholic solvent.Oxyalkylated three alkanolamine polycondensates are with the oil content meter based on the emulsion of treating breakdown of emulsion, and 0.0001 to 5, preferred 0.0005 to 2, especially 0.0008 to 1, and particularly the amount of 0.001 to 0.1 weight % is used.
Embodiment
Three alkanolamines of alkali condensation:
50% NaOH in water with 225g trolamine and 0.5mol% in being furnished with the 500ml three-necked flask of contact thermometer, whisking appliance and water trap mixes.The water that the reaction that reacting by heating mixture and continuous still battery under agitation goes out to produce produces.By the carrying out of OH pH-value determination pH following response, and when reaching predetermined OH value, interrupt reaction.
Table 1 has showed the synthetic embodiment according to three alkanolamine condensess of of the present invention, alkali condensation.
Table 1: according to three alkanolamine condensess of the present invention, the alkali condensation
| Embodiment | Monomer | T | Time | The OH value | n |
| 1 | TEA(100％) | 250/270 | 2/2 | 708 | 2-3 |
| 2 | TEA(100％) | 250/270 | 2/3 | 515 | 8-9 |
| 3 | TIPA(100％) | 250/270 | 2/6 | 677 | 3-4 |
| 4 | DEIPA(100％) | 250/270 | 2/4 | 631 | 4-5 |
| 5 | DEPEA(100％) | 250/270 | 2/4 | 625 | 4-5 |
| 6 | TEA∶TIPA1∶1 | 250/270 | 2/6 | 623 | 3-4 |
| 7 | TEA∶DEIPA1∶1 | 250/270 | 2/4 | 588 | 5-6 |
The data of temperature and time are meant as 250/270 and 2/3, keep 2 hours at 250 ℃, keep 3 hours at 270 ℃ then.
Shortenings:
The TEA=trolamine
The TIPA=tri-isopropanolamine
DEIPA=di-alcohol Yi Bingchunan
DEPEA=di-alcohol-2-phenylethanolamine
The T=temperature of reaction [℃]
Time=reaction times [hour]
OH-value=OH value [mg KOH/g material]
The average condensation degree of n=
From correlated purpose, according to the 12nd page of WO2009060060A1, embodiment 1a) and 3a) the trolamine polycondensate of two kinds of sour condensations of preparation.Table 2 has been explained their character.
Table 2: the trolamine polycondensate (comparative example) of sour condensation
| Embodiment | Monomer | ?T | Time | The OH-value |
| V3 | TEA(100％) | ?227 | 3.5 | 733 |
| V4 | TEA(100％) | ?227 | 7 | 476 |
The alkoxylate of three alkanolamine polycondensates
Ethoxylation
The three alkanol polycondensates that will obtain according to general polycondensation rules or its propoxide are introduced the final base number that is adjusted to about 2.5mg KOH/g material in 11 the glass autoclave and with sodium methoxide solution.Autoclave is used the nitrogen inerting, the pressure in the autoclave is adjusted to about 0.8 to 1.0 crust at pressure test post-heating to 135 ℃ and with nitrogen.Measure the ethylene oxide amount of adding expectation down at the highest 140 ℃ then, wherein pressure should not surpass 4.5 crust.After having added, metering continues reaction until constant pressure at the highest 140 ℃.
Propoxylation
The three alkanol polycondensates that will obtain according to general polycondensation rules or its b-oxide are introduced the final base number that is adjusted to about 1.5mg KOH/g material in 11 the glass autoclave and with sodium methoxide solution.Autoclave is used the nitrogen inerting, the pressure in the autoclave is adjusted to about 0.8 to 1.0 crust at pressure test post-heating to 125 ℃ and with nitrogen.Measure the propylene oxide amount of adding expectation down at the highest 130 ℃ then, wherein pressure should not surpass 3.5 crust.After having added, metering continues reaction until constant pressure at the highest 130 ℃.
Following table 3 and 4 has been explained synthetic embodiment, wherein with at first propoxylation and the ethoxylation subsequently of related polycondensate.
Table 3: the polycondensate of propoxylation-ethoxylation
Table 4: from the alkoxide by the sour condensation prepared of trolamine polycondensate of contrast purpose
Following table 5 and 6 has been explained synthetic embodiment, wherein with related polycondensate at first ethoxylation and propoxylation subsequently.
Table 5: ethoxylation-propenoxylated polycondensate
Only three alkanolamine condensess of ethoxylation do not have the water number that can measure, have measured the OH-value as substituting.
Table 6: from the alkoxide by the sour condensation prepared of trolamine polycondensate of contrast purpose
The demulsification of petroleum emulsions emulsion splitter is measured
Be to measure the effect of emulsion splitter, the unit time measure from the water sepn of emulsion of crude oil and visual inspection the outward appearance and the phase interface of isolating water.In emulsion splitter glassware (but screwing, be with graduated vial), be respectively charged into the 100mL petroleum emulsions with taper shape ending screw thread for this reason; Respectively quantitative emulsion splitter is added near under the fat liquor surface with the micropipet metering, and emulsion splitter is sneaked in the emulsion through strong jolting.Then the emulsion splitter glassware is put into controlled-temperature bath (50 ℃), and pay close attention to water sepn.
Demulsification is estimated through actual observation.
A) " water " is being represented when being designated as "+" that isolating water is transparent,
, " water " representes that isolating water is muddy when being designated as " 0 ",
" water " is represented when being designated as "-" isolating water because greasy dirt but opaque and
B) " phase interface " represented phase interface clearly when being designated as "+"
, " phase interface " represent slight greasy filth (not having smooth phase interface) when being designated as " 0 "
" phase interface " represented intensive greasy filth (meniscus configurations) when being designated as "-"
The demulsification of said emulsion splitter
Emulsion of crude oil source: Hebertshausen, Germany
The water-content of emulsion: 48%
Emulsion breaking temperature: 50 ℃
Table 7: compare alkoxylate with the polyamine propoxide, three alkanolamine polycondensates are as the effect of emulsion splitter, dose rate 250ppm (commercially available prod V1).
Table 8: compare with the trolamine polycondensate-alkoxide V5-V8 of sour condensation, oxyalkylated three alkanolamine polycondensates are as the effect (dosage interpolation rate 75ppm) of emulsion splitter
Table 9: with the EO-PO block polymer that few amine begins, dose rate 75ppm (V2) compare with the trolamine polycondensate-alkoxide V9-V11 of sour condensation, and oxyalkylated three alkanolamine polycondensates are as the effect of emulsion splitter by the commercially available prod
Claims (11)
1. oxyalkylated three alkanolamine condensess are used for the purposes of water-in-oil emulsion breakdown of emulsion with the amount based on oil content meter 0.0001 to the 5 weight % of the emulsion of treating breakdown of emulsion, the base catalysis condensation that said condenses can be through three alkanolamines and adopt at least a C subsequently
2To C
4-olefin oxide alkoxylate and obtaining, said condenses has 500 to 500, and the number-average molecular weight of 000g/mol comprises 2 to 250 three alkanolamine unit, and its average degree of alkoxylation is that each free OH is between 1 and 200 olefin oxide unit.
2. according to the purposes of claim 1, it is characterized in that three alkanolamine polycondensates contain at least a in the structure of formula (3), (4) or (5) before the alkoxylate,
Wherein
R
1, R
2And R
3Represent independently of one another H, methyl, ethyl or phenyl and
R
4, R
5And R
6The group of representing OH or formula (2) independently of one another,
Condition is, is not all radicals R
4, R
5And R
6Represent OH simultaneously, make three alkanolamine condensess comprise 2 to 250 three alkanolamine unit.
3. according to the purposes of claim 1 and/or 2, it is characterized in that said polycondensate has the number-average molecular weight of 1000 to 350,000 units after alkoxylate.
4. according to one or multinomial purposes in the claim 1 to 3, it is characterized in that olefin oxide unit (AO) and (BO) the two all representes ethylene oxide unit.
5. according to one or multinomial purposes in the claim 1 to 3, it is characterized in that olefin oxide unit (AO) and (BO) the two all representes propylene oxide unit.
6. according to one or multinomial purposes in the claim 1 to 3; It is characterized in that; (AO) expression propylene oxide unit and (BO) expression ethylene oxide unit; Perhaps (AO) expression ethylene oxide unit and (BO) expression propylene oxide unit, wherein in oxyalkylated three alkanolamine polycondensates propylene oxide unit than the ratio of ethylene oxide unit between 40: 1 and 1: 5.
7. according to one or multinomial purposes in the claim 1 to 6, it is characterized in that oxyalkylated three alkanolamine polycondensates are described by formula (6)
Wherein,
R
1, R
2And R
3Represent independently of one another H, methyl, ethyl or phenyl and
R
4, R
5And R
6The group of expression (7) independently of one another
Or the group of formula (8)
-O-(B-O)
m-(A-O)
n-H (8)
Wherein A and B represent that ethylidene and/or propylidene group and n and m represent 1 to 100 integer, and condition is, is not all radicals R
4, R
5And R
6The group of expression (8) makes said oxyalkylated three alkanolamine polycondensates comprise 2 to 250 three alkanolamine unit simultaneously.
8. according to one or multinomial purposes in the claim 1 to 7, wherein, oxyalkylated three alkanolamine condensess have the OH value of 25-300mg KOH/g material.
9. according to one or multinomial purposes in the claim 1 to 8, wherein, oxyalkylated three alkanolamine condensess have the water number of 7-22.
10. oxyalkylated three alkanolamine condensess, the base catalysis condensation that they can be through three alkanolamines and adopt at least a C subsequently
2To C
4-olefin oxide alkoxylate and obtaining makes that average degree of alkoxylation is 1 to 200 oxyalkyl units of each free OH, and comprises 2 to 250 three alkanolamine unit and have 500 to 500, the number-average molecular weight of 000g/mol.
11. the breaking method of water-in-oil emulsion; Through in emulsion, adding at least a oxyalkylated three alkanolamine condensess based on weight meter 0.0001 to the 5 weight % of emulsion, the base catalysis condensation that said condenses can be through three alkanolamines and adopt at least a C subsequently
2To C
4-olefin oxide alkoxylate and obtaining, and said condenses has 500 to 500, the number-average molecular weight of 000g/mol and have 2 to 250 three alkanolamine unit, and its average degree of alkoxylation is 1 to 200 oxyalkyl units of each free OH.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009041983A DE102009041983A1 (en) | 2009-09-17 | 2009-09-17 | Alkoxylated trialkanolamine condensates and their use as emulsion breakers |
| DE102009041983.7 | 2009-09-17 | ||
| PCT/EP2010/005321 WO2011032640A2 (en) | 2009-09-17 | 2010-08-31 | Alkoxylated trialkanol amine condensates and the use thereof as demulsifiers |
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| CN102471431A true CN102471431A (en) | 2012-05-23 |
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| CN201080031180XA Pending CN102471431A (en) | 2009-09-17 | 2010-08-31 | Alkoxylated trialkanol amine condensates and the use thereof as demulsifiers |
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| Country | Link |
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| CN (1) | CN102471431A (en) |
| DE (1) | DE102009041983A1 (en) |
| WO (1) | WO2011032640A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650336A (en) * | 2015-02-11 | 2015-05-27 | 胜利油田胜利化工有限责任公司 | Preparation method of novel organic amine demulsifier |
| CN107207722A (en) * | 2015-01-26 | 2017-09-26 | 巴斯夫欧洲公司 | Polyetheramine with low melting point |
| CN112584910A (en) * | 2018-08-29 | 2021-03-30 | 埃科莱布美国股份有限公司 | Multi-charged ionic compounds derived from polyamines, compositions thereof and their use as reverse demulsifiers for oil and gas operations |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012005377A1 (en) | 2012-03-16 | 2013-03-14 | Clariant International Ltd. | Use of alkoxylated polyamidoamine containing polyamine structural units having nitrogen atoms, and reactive groups that are alkoxylated with alkylene oxide, for splitting water-in-oil emulsions in crude oil extraction |
| DE102012005279A1 (en) | 2012-03-16 | 2013-03-14 | Clariant International Limited | Use of crosslinked and alkoxylated polyamidoamine exhibiting reactive groups that are alkoxylated with alkylene oxide, and specific average degree of alkoxylation, for splitting water-in-oil emulsions in crude oil extraction |
| CA2978437C (en) | 2015-03-04 | 2023-09-19 | Ecolab Usa Inc. | Reverse emulsion breaker polymers from poly(triethanolamine) |
| KR20180097668A (en) | 2015-12-18 | 2018-08-31 | 바스프 에스이 | The stoichiometric alkoxylated polyether |
| CN113003633B (en) * | 2021-04-30 | 2022-06-17 | 西南石油大学 | Dendritic water clarifier for polymer-containing oily sewage treatment and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074926A (en) * | 1992-01-29 | 1993-08-04 | 大连石油化工公司有机合成厂 | The preparation method of demulsifier for mixed crude oil |
| CN1100735A (en) * | 1993-09-25 | 1995-03-29 | 锦西信达农药化工有限公司 | Ultra high molecular wt. crude polyether emulsion breaker |
| CN101204643A (en) * | 2006-12-21 | 2008-06-25 | 天津科技大学 | Highly efficiency compositional crude oil emulsion splitter |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2407895A (en) | 1944-10-05 | 1946-09-17 | Petrolite Corp | Processes for resolving oil-in-water emulsions |
| US2430004A (en) * | 1945-04-02 | 1947-11-04 | Petrolite Corp | Certain dicarboxy acid esters of oxyalkylated polymerized hydroxyamines |
| US2552534A (en) * | 1950-03-04 | 1951-05-15 | Petrolite Corp | Processes for breaking petroleum emulsions |
| US3782472A (en) * | 1967-03-20 | 1974-01-01 | Petrolite Corp | Steam injection of oil formations |
| US4032514A (en) | 1971-08-18 | 1977-06-28 | Petrolite Corporation | Oxyalkylated cyclic phenol-aldehyde resins and uses therefor |
| US4321146A (en) | 1980-05-22 | 1982-03-23 | Texaco Inc. | Demulsification of bitumen emulsions with a high molecular weight mixed alkylene oxide polyol |
| US4505839A (en) | 1981-05-18 | 1985-03-19 | Petrolite Corporation | Polyalkanolamines |
| DE4003243A1 (en) | 1990-02-03 | 1991-08-08 | Basf Ag | Use of tri:alkanolamine polyether(s) as demulsifiers in o/w emulsions - obtainable by condensing tri:alkanol:amine(s) in presence of (hypo)phosphorous acid |
| DE4136661A1 (en) | 1991-11-07 | 1993-05-13 | Basf Ag | PETROLEUM EMULSION SPLITTER |
| DE4142579A1 (en) | 1991-12-21 | 1993-06-24 | Basf Ag | PETROLEUM EMULSION SPLITTER BASED ON AN ALKOXYLATE AND METHOD FOR PRODUCING THIS ALKOXYLATE |
| DE4435688A1 (en) * | 1994-10-06 | 1996-04-11 | Basf Ag | Process for the preparation of oligoamines or polyamines |
| DE10325198B4 (en) | 2003-06-04 | 2007-10-25 | Clariant Produkte (Deutschland) Gmbh | Use of alkoxylated crosslinked polyglycerols as biodegradable emulsion breakers |
| DE10329723B3 (en) | 2003-07-02 | 2004-12-02 | Clariant Gmbh | Using alkoxylated dendritic polyesters as emulsion breakers, especially in crude oil recovery, are required in only small amounts and are biodegradable |
| MX306402B (en) | 2007-11-09 | 2013-01-04 | Basf Se | Alkoxylated polyalkanolamines. |
| RU2498841C2 (en) * | 2008-03-04 | 2013-11-20 | Басф Се | Using alkoxylated polyalkanolamines to demulsify oil-in-water emulsions |
-
2009
- 2009-09-17 DE DE102009041983A patent/DE102009041983A1/en not_active Withdrawn
-
2010
- 2010-08-31 CN CN201080031180XA patent/CN102471431A/en active Pending
- 2010-08-31 WO PCT/EP2010/005321 patent/WO2011032640A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074926A (en) * | 1992-01-29 | 1993-08-04 | 大连石油化工公司有机合成厂 | The preparation method of demulsifier for mixed crude oil |
| CN1100735A (en) * | 1993-09-25 | 1995-03-29 | 锦西信达农药化工有限公司 | Ultra high molecular wt. crude polyether emulsion breaker |
| CN101204643A (en) * | 2006-12-21 | 2008-06-25 | 天津科技大学 | Highly efficiency compositional crude oil emulsion splitter |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107207722A (en) * | 2015-01-26 | 2017-09-26 | 巴斯夫欧洲公司 | Polyetheramine with low melting point |
| CN104650336A (en) * | 2015-02-11 | 2015-05-27 | 胜利油田胜利化工有限责任公司 | Preparation method of novel organic amine demulsifier |
| CN112584910A (en) * | 2018-08-29 | 2021-03-30 | 埃科莱布美国股份有限公司 | Multi-charged ionic compounds derived from polyamines, compositions thereof and their use as reverse demulsifiers for oil and gas operations |
| CN112584910B (en) * | 2018-08-29 | 2023-03-14 | 埃科莱布美国股份有限公司 | Multi-charged ionic compounds derived from polyamines, compositions thereof and their use as reverse demulsifiers for oil and gas operations |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011032640A2 (en) | 2011-03-24 |
| DE102009041983A1 (en) | 2011-04-07 |
| WO2011032640A3 (en) | 2011-05-12 |
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