EP1658356A1 - Alkoxylated, cross-linked polyglycerols and use thereof as biodegradable demulsifier - Google Patents
Alkoxylated, cross-linked polyglycerols and use thereof as biodegradable demulsifierInfo
- Publication number
- EP1658356A1 EP1658356A1 EP04734666A EP04734666A EP1658356A1 EP 1658356 A1 EP1658356 A1 EP 1658356A1 EP 04734666 A EP04734666 A EP 04734666A EP 04734666 A EP04734666 A EP 04734666A EP 1658356 A1 EP1658356 A1 EP 1658356A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkoxylated
- polyglycerols
- diglycidyl ether
- use according
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Definitions
- the present invention relates to the use of alkoxylated crosslinked polyglycerols for splitting water-oil emulsions, in particular in the production of crude oil.
- Crude oil is produced as an emulsion with water.
- Petroleum splitters are surface-active polymeric compounds which are able to bring about the required separation of the emulsion components within a short time.
- US 4,321,146 alkylene oxide block copolymers and US 5,445,765 alkoxylated polyethyleneimines are disclosed as petroleum splitters. These can be used as individual components, in mixtures with other emulsion splitters, or as cross-linked products.
- Crosslinks are carried out, for example, by reacting alkoxylated low molecular weight alcohols (such as glycerol or pentaerythrol) or alkoxylated alkylphenol formaldehyde resins with bifunctional compounds such as diepoxides or diisocyanates.
- alkoxylated low molecular weight alcohols such as glycerol or pentaerythrol
- alkoxylated alkylphenol formaldehyde resins with bifunctional compounds such as diepoxides or diisocyanates.
- Such cross-linked compounds are disclosed in US 5,759,409 and US 5,981,687.
- alkoxylated glycerol as a demulsifying component in lubricating oils has been described in DD-229 006.
- glycerin is reacted with alkylene oxides either to form a block copolymer or a statistical copolymer.
- alkoxylated di- and triglycerols as petroleum emulsion breakers has also been described (US-3,110,737, US-2,944,982 and U.S. 4,342,657).
- Alkoxylated polyglycerols are known per se. They are described in the prior art for various applications. For example, in US 5 502 219 alkoxylated polyglycerols have been esterified to be a low calorie substitute for
- alkoxylated polyglycerols were esterified and used as water-swelling gels.
- Alkoxylated polyglycerols which have been reacted with alpha-olefin epoxides act as defoamers according to WO-98/03243. Sulfation of alkoxylated polyglycerols leads to substances which are used in hair shampoos, as disclosed in US Pat. No. 4,263,178.
- Alkoxylated polyglycerols have been disclosed in DE 101 07880 A1 as effective emulsion breakers.
- alkoxylated crosslinked polyglycerols show an excellent effect as a petroleum splitter even at very low doses.
- they showed significantly better biological Degradability (according to OECD 306) compared to conventional commercial emulsion splitters and alkoxylated non-crosslinked polyglycerols.
- the invention therefore relates to the use of alkoxylated polyglycerols crosslinked with multifunctional electrophilic compounds and having a molecular weight of 1000 to 100,000 units, which comprise 5 to 100 glycerol units which are alkoxylated with C 2 -C 4 -alkylene oxide groups or a mixture of such alkylene oxide groups, so that the crosslinked, alkoxylated polyglycerol has a degree of alkoxylation of 1 to 100 alkylene oxide units per free OH group, for splitting oil / water emulsions in amounts of 0.0001 to 5% by weight, based on the oil content of the emulsion to be split.
- alkoxylated crosslinked polyglycerols can be obtained from crosslinked polyglycerols having 5 to 100 glycerol units by alkoxylating the free OH groups with a C 2 -C 4 alkylene oxide or a mixture of such alkylene oxides in a molar excess, so that the alkoxylated crosslinked polyglycerol has the degree of alkoxylation mentioned.
- the production of the polyglycerol is known in the prior art and is generally carried out by acidic or alkaline-catalyzed condensation of glycerol.
- the reaction temperature is generally between 150 and 300 ° C, preferably 200 to 250 ° C.
- the reaction is usually carried out at atmospheric pressure.
- HCl, H2SO4, sulfonic acids or H3PO 4 may be mentioned as catalyzing acids, and NaOH or KOH as bases, which are used in amounts of 0.1 to 50% by weight, based on the weight of the reaction mixture.
- the condensation generally takes 3 to 10 hours.
- Polyglycerols can be represented by Formula 1.
- n stands for the degree of condensation, i.e. the number of glycerol units. n increases with increasing reaction time and is determined using the OH number.
- the polyglycerols produced in this way are crosslinked with di- or multifunctional, electrophilic compounds.
- di- or polyglycidyl ethers, di- or polyepoxides, di- or polycarboxylic acids, carboxylic acid anhydrides, di- or polyisocyanates, dialkoxy dialkylsilanes, trialkoxyalkylsilanes and tetraalkoxysilanes are used as crosslinkers.
- the crosslinking is carried out as is known in the prior art.
- crosslinkers are particularly preferred:
- Adipic acid maleic acid, phthalic acid, maleic anhydride
- crosslinking agents or chemically related compounds mentioned are preferably used in the range of 0.1-10, particularly preferably 0.5-5 and especially 1.0-2.5% by weight, based on the polyglycerol.
- the crosslinking step is carried out after the glycerol condensation and before the alkoxylation.
- Crosslinking after glycerol condensation and subsequent alkoxylation can also be carried out according to the invention.
- the crosslinked polyglycerols obtained from glycerol condensation and subsequent crosslinking are then alkoxylated with one or more C 2 -C 4 alkylene oxides, preferably ethylene oxide (EO) or propylene oxide (PO).
- the alkoxylating agent is used in a molar excess.
- alkoxylation is carried out by reacting the polyglycerols with an alkylene oxide under elevated pressure, generally from 1.1 to 20 bar, at from 50 to 200.degree.
- the alkoxylation takes place on the free OH groups of the polyglycerols.
- So much alkylene oxide is used that the average degree of alkoxylation is between 1 and 100 alkylene oxide units per free OH group.
- the average degree of alkoxylation here means the average number of alkoxy units which are attached to each free OH group. It is preferably 2 to 70, in particular 5 to 50, especially 20 to 40.
- the alkoxylation is preferably carried out first with PO and then with EO.
- the ratio of EO to PO in the alkoxylated polyglycerol is preferably between 1: 1 and 1:10. According to the invention, however, the alkoxylation can also take place in the reverse order, first EO then PO or with a mixture of PO and EO.
- the polyglycerol obtained after condensation, subsequent crosslinking and alkoxylation preferably has a molecular weight of 3,000 to 50,000 units, in particular 5,000 to 30,000 units, especially 8,000 to 25,000.
- (AO) k, i, mO stand for the alkoxylated OH radicals, in which AO is a C 2 -C 4
- Alkylene oxide unit and k, I, m represent the degrees of alkoxylation, n stands for
- n is preferably a number from 5 to 50, particularly preferably 8 to 30, especially 10 to 20.
- a preferred subject of the present invention is the use of the alkoxylated polyglycerols as splitters for oil / water emulsions in the
- the crosslinked alkoxylated polyglycerols are added to the water-oil emulsions, which is preferably done in solution. Paraffinic or aromatic solvents are preferred as solvents for the crosslinked alkoxylated polyglycerols.
- the crosslinked alkoxylated polyglycerols are used in amounts of 0.0001 to 5, preferably 0.0005 to 2, in particular 0.0008 to 1 and especially 0.001 to 0.1% by weight, based on the oil content of the emulsion to be split.
- the crosslinked polyglycerols described above were introduced into a 1 liter glass autoclave and the pressure in the autoclave was adjusted to about 0.2 bar excess pressure with nitrogen. The mixture was slowly heated to 130 ° C. and, after this temperature had been reached, the pressure was again set to 0.2 bar gauge pressure. The desired amount of PO was then metered in at 130 ° C. (see Table 1), the pressure should not exceed 4.0 bar. After the PO addition had ended, the mixture was left to react at 130 ° C. for a further 30 minutes.
- the degree of alkoxylation was determined by means of 13 C-NMR.
- the water separation from a crude oil emulsion per time and the dewatering and desalination of the oil were determined.
- 100 ml of the crude oil emulsion were poured into splitter glasses (tapered, screwable, graduated glass bottles), a defined amount of the emulsion splitter was added with a micropipette just below the surface of the oil emulsion and the splitter was mixed into the emulsion by intensive shaking.
- the split glasses were then placed in a tempering bath (30 ° C and 50 ° C) and the water separation was monitored.
- samples of the oil were taken from the upper part of the splitter glass (so-called top oil) and the water content according to Karl Fischer and the salt content were determined by conductometry. In this way, the new splitters could be assessed after water separation, drainage and desalination of the oil.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10325198A DE10325198B4 (en) | 2003-06-04 | 2003-06-04 | Use of alkoxylated crosslinked polyglycerols as biodegradable emulsion breakers |
PCT/EP2004/005587 WO2004108863A1 (en) | 2003-06-04 | 2004-05-25 | Alkoxylated, cross-linked polyglycerols and use thereof as biodegradable demulsifier |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1658356A1 true EP1658356A1 (en) | 2006-05-24 |
EP1658356B1 EP1658356B1 (en) | 2007-07-18 |
Family
ID=33494818
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04734666A Expired - Fee Related EP1658356B1 (en) | 2003-06-04 | 2004-05-25 | Alkoxylated, cross-linked polyglycerols and use thereof as biodegradable demulsifier |
Country Status (5)
Country | Link |
---|---|
US (1) | US7671098B2 (en) |
EP (1) | EP1658356B1 (en) |
DE (2) | DE10325198B4 (en) |
NO (1) | NO336950B1 (en) |
WO (1) | WO2004108863A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107519672A (en) * | 2017-10-25 | 2017-12-29 | 成都凯米拉科技有限公司 | A kind of water process demulsifier for oil field |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101501440A (en) * | 2006-08-03 | 2009-08-05 | 陶氏环球技术公司 | New fill compositions and method for making the same |
US7981979B2 (en) * | 2006-09-22 | 2011-07-19 | Nalco Company | Siloxane cross-linked demulsifiers |
DE102009019177A1 (en) * | 2009-04-28 | 2010-11-11 | Clariant International Ltd. | Use of biodegradable alkoxylated (meth) acrylate copolymers as crude oil emulsion breakers |
JP5714581B2 (en) | 2009-07-30 | 2015-05-07 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Composition for metal plating containing an inhibitor for satisfying a sub-micrometer mechanism without forming a void |
DE102009041983A1 (en) | 2009-09-17 | 2011-04-07 | Clariant International Ltd. | Alkoxylated trialkanolamine condensates and their use as emulsion breakers |
DE102009042971A1 (en) | 2009-09-24 | 2011-09-15 | Clariant International Ltd. | Alkoxylated cyclic diamines and their use as emulsion breakers |
US20110201534A1 (en) * | 2010-02-12 | 2011-08-18 | Jennifer Beth Ponder | Benefit compositions comprising polyglycerol esters |
US9416490B2 (en) * | 2010-03-10 | 2016-08-16 | Nalco Company | Cross-linked glycerol based polymers as digestion aids for improving wood pulping processes |
US20120059088A1 (en) * | 2010-09-02 | 2012-03-08 | Baker Hughes Incorporated | Novel Copolymers for Use as Oilfield Demulsifiers |
US20130237641A1 (en) | 2010-11-17 | 2013-09-12 | Dow Brasil Sudeste Industiral Ltda Filia Poliestireno | Process using bisphenol a aminated and alkoxylated derivative as demulsifier |
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 |
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 |
PT2855410T (en) * | 2012-05-31 | 2017-01-02 | Nalco Co | Glycerol based polymer surface active chemistry and production |
US9663726B2 (en) * | 2014-02-10 | 2017-05-30 | Baker Hughes Incorporated | Fluid compositions and methods for using cross-linked phenolic resins |
US10478498B2 (en) | 2014-06-20 | 2019-11-19 | Reform Biologics, Llc | Excipient compounds for biopolymer formulations |
WO2015196091A1 (en) | 2014-06-20 | 2015-12-23 | Reform Biologics, Llc | Viscosity-reducing excipient compounds for protein formulations |
FR3048975B1 (en) | 2016-03-18 | 2019-11-29 | Oleon Nv | DESEMULSIFIANT FOR OIL |
CA3030422C (en) | 2016-07-13 | 2021-10-26 | Reform Biologics, Llc | Stabilizing excipients for therapeutic protein formulations |
WO2019036619A1 (en) * | 2017-08-18 | 2019-02-21 | Reform Biologics, Llc | Stabilizing excipients for therapeutic protein formulations |
EP3962889A1 (en) | 2019-04-29 | 2022-03-09 | Ecolab USA Inc. | Oxygenated aminophenol compounds and methods for preventing monomer polymerization |
US11767393B2 (en) | 2020-10-21 | 2023-09-26 | Ecolab Usa Inc. | (Hydroxyalkyl)aminophenol polymers and methods of use |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE229006C (en) | ||||
US2944982A (en) | 1954-06-10 | 1960-07-12 | Petrolite Corp | Process for breaking petroleum emulsions employing certain oxyalkylated acyclic diglycerols |
US3110737A (en) | 1958-09-15 | 1963-11-12 | Petrolite Corp | Certain oxyalkylated polyols |
US4061684A (en) | 1976-10-29 | 1977-12-06 | Basf Wyandotte Corporation | Highly branched polyether polyols of high molecular weight |
US4342657A (en) | 1979-10-05 | 1982-08-03 | Magna Corporation | Method for breaking petroleum emulsions and the like using thin film spreading agents comprising a polyether polyol |
US4263178A (en) | 1979-11-26 | 1981-04-21 | The Gillette Company | Hair shampoo composition |
US4321146A (en) | 1980-05-22 | 1982-03-23 | Texaco Inc. | Demulsification of bitumen emulsions with a high molecular weight mixed alkylene oxide polyol |
DE4023834A1 (en) * | 1990-07-27 | 1992-01-30 | Huels Chemische Werke Ag | DEMULGATORS FOR CUTTING PETROLEUM EMULSIONS |
DE4040022A1 (en) | 1990-12-14 | 1992-06-17 | Bayer Ag | Splitting of water-in-oil emulsions |
DE4104610A1 (en) | 1991-02-15 | 1992-08-20 | Basf Ag | ACTION PRODUCTS OF ALKOXYLATES AND VINYLIC MONOMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE AS DEMULGATORS FOR CRUDEOULULULULULAR POWERS |
DE4136661A1 (en) | 1991-11-07 | 1993-05-13 | Basf Ag | PETROLEUM EMULSION SPLITTER |
US5399371A (en) | 1993-06-17 | 1995-03-21 | Henkel Corporation | Low calorie substitute for an edible oil |
DE4418800A1 (en) | 1994-05-30 | 1995-12-07 | Basf Ag | Sepg. water from crude oil |
US5667727A (en) | 1995-06-26 | 1997-09-16 | Baker Hughes Incorporated | Polymer compositions for demulsifying crude oil |
DE19629038A1 (en) | 1996-07-19 | 1998-01-22 | Henkel Kgaa | Use of ethylene oxide / propylene oxide addition compounds of glycerol or polyglycerol reacted with alpha-olefin epoxides as defoamers |
DE10107880B4 (en) * | 2001-02-20 | 2007-12-06 | Clariant Produkte (Deutschland) Gmbh | Alkoxylated polyglycerols and their use as emulsion breakers |
-
2003
- 2003-06-04 DE DE10325198A patent/DE10325198B4/en not_active Expired - Fee Related
-
2004
- 2004-05-25 US US10/559,719 patent/US7671098B2/en active Active
- 2004-05-25 DE DE502004004384T patent/DE502004004384D1/en not_active Expired - Lifetime
- 2004-05-25 WO PCT/EP2004/005587 patent/WO2004108863A1/en active IP Right Grant
- 2004-05-25 EP EP04734666A patent/EP1658356B1/en not_active Expired - Fee Related
-
2005
- 2005-12-21 NO NO20056114A patent/NO336950B1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO2004108863A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107519672A (en) * | 2017-10-25 | 2017-12-29 | 成都凯米拉科技有限公司 | A kind of water process demulsifier for oil field |
Also Published As
Publication number | Publication date |
---|---|
US20060281931A1 (en) | 2006-12-14 |
US7671098B2 (en) | 2010-03-02 |
WO2004108863A1 (en) | 2004-12-16 |
DE502004004384D1 (en) | 2007-08-30 |
EP1658356B1 (en) | 2007-07-18 |
NO336950B1 (en) | 2015-11-30 |
DE10325198A1 (en) | 2005-01-13 |
DE10325198B4 (en) | 2007-10-25 |
NO20056114L (en) | 2005-12-21 |
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