WO2011029528A1 - Alkoxylierte thiacalixarene und deren verwendung als rohöl-emulsionsspalter - Google Patents
Alkoxylierte thiacalixarene und deren verwendung als rohöl-emulsionsspalter Download PDFInfo
- Publication number
- WO2011029528A1 WO2011029528A1 PCT/EP2010/005186 EP2010005186W WO2011029528A1 WO 2011029528 A1 WO2011029528 A1 WO 2011029528A1 EP 2010005186 W EP2010005186 W EP 2010005186W WO 2011029528 A1 WO2011029528 A1 WO 2011029528A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- emulsion
- alkoxylated
- thiacalixarenes
- oil
- alkyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/34—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
- C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
Definitions
- Alkoxylated thiacalixarenes and their use as crude oil emulsion breakers The present invention relates to alkoxylated thiacalixarenes and their derivatives
- Crude oil accumulates in its promotion as an emulsion with water.
- Crude splitters are surface-active polymeric compounds capable of effecting, within a short time, the required separation of the emulsion components.
- demulsifiers are mainly alkoxylated alkylphenol-formaldehyde resins, nonionic alkylene oxide block copolymers and crosslinked with Bisepoxiden variants used.
- demulsifiers are mainly alkoxylated alkylphenol-formaldehyde resins, nonionic alkylene oxide block copolymers and crosslinked with Bisepoxiden variants used.
- TG Balson pp. 226-238 in Proceedings in the Chemistry in the 0/7 Industry VIII Symposium, 3-5-112003, Manchester, UK
- Crude -Oil Emulsions: A State-Of-The-Art Review S. Kokal, pp. 5-13, Society of Petroleum Engineers SPE 77497.
- U.S. 4,321,146 discloses alkylene oxide block copolymers for cleavage of
- Such resins are often used in alkoxylated form, as disclosed, for example, in DE-A-24 45 873.
- the free phenolic OH groups are reacted with an alkylene oxide.
- free OH groups of alcohols or NH groups of amines can also be alkoxylated, as disclosed, for example, in US Pat. No. 5,401,439.
- alkylphenol-formaldehyde resins are disclosed in DE-A-100 57 044 and US-6,646,016.
- DE-A-100 57 044 discloses the use of resins of alkylphenols and glyoxalic acid derivatives as emulsion breakers.
- US 6,646,016 discloses the use of condensation products of benzoic acid esters and amides and aldehydes to cleave crude oil emulsions.
- EP-A-1 264 872 discloses thiacalixarenes and a process for their preparation.
- alkoxylated condensates of alkylphenols and elemental sulfur so-called thiacalixarenes, have an excellent action as petroleum breakers even at very low dosages.
- the invention therefore relates to alkoxylated thiacalixarenes obtainable by the reaction of alkylphenols of the formula (I)
- R is a Cr to C3o alkyl, C 2 - to C 3 o-alkenyl, C - C-is- Aryl or C 7 - to C 30 alkylaryl group, with elemental sulfur and subsequent alkoxylation with C 2 - to C 4 alkylene oxides.
- Another object of the invention are compounds of the formula (II)
- R is a Ci to C3 0 alkyl, C 2 - to C3o alkenyl, C 6 - to de-aryl or C 7 - to C3o-alkylaryl,
- AO is a C 2 - to C 4 -alkoxy group, x for a number from 1 to 50,
- n stands for a number between 4 and 12.
- Another object of the invention is the use of the compounds of formula (II) for the cleavage of oil / water emulsions, in amounts of 0.0001 to 5 wt .-% based on the oil content of the emulsion to be cleaved.
- Another object of the invention is a process for the cleavage of oil water emulsions by the emulsion 0.0001 to 5 wt .-%, based on the weight of the emulsion, of a compound of formula (II) is added.
- the compounds of the formula (I) are essentially chemically uniform compounds.
- the term "essentially” here means that compounds of the formula (I) in commercial purity are used for the preparation of the thiacalixarenes according to the invention. Shares of other compounds covered by the formula (I) may thus be contained in the resins, which means in particular not completely separated position isomers. This does not exclude that phenols substituted with different radicals R can be mixed to form the thiacalixarenes according to the invention.
- the substituents R and OH are preferably in the para position.
- R preferably represents an alkyl radical whose chain length is preferably 1 to 18, more preferably 2 to 14, especially 4 to 12, carbon atoms.
- the alkyl radicals can be both linear and branched.
- R furthermore preferably represents an aryl radical whose ring size
- R is preferably an alkenyl radical whose chain length is preferably
- the alkeno radicals can be both linear and branched.
- the preparation of the precursor thiacalixarenes is preferably carried out under alkaline catalysis according to the prior art, as disclosed in EP-1 264 872.
- ring structures are preferably formed with an equal number of phenol units and sulfur atoms.
- KOH or NaOH which are used in amounts of 0.1 to 50 wt .-%, based on the
- the solvents are high-boiling aprotic ethers, such as. B. Tetraglyme.
- the condensation is carried out between 150 and 300 ° C, preferably 200 and 250 ° C, wherein the condensation time is generally 2 to 8 hours.
- the molar ratio of phenol to sulfur is 1: 1 to 1: 3, preferably 1: 1, 3 to 1: 2.3.
- n for a number from 1 to 9 and
- R is a C to C 3 o-alkyl, C 2 - to C 30 -alkenyl, C 6 - to C 8 -aryl or C 7 - to C 30 -alkylaryl group
- the suitable as a precursor for the alkoxylation Thiacalixarene have
- the thiacalixarenes obtained from the condensation are then alkoxylated with a C 2 -C 4 -alkylene oxide, preferably ethylene oxide and propylene oxide.
- the alkoxylation is carried out on the free phenolic OH groups and can either be random or, as in a preferred embodiment, blockwise. So much alkylene oxide is used that the middle
- phenolic OH group is attached. It is preferably from 2 to 40, in particular from 3 to 30.
- alkoxylated thiacalixarene preferably has a number average molecular weight of from 500 to 50,000 units, in particular from 1,000 to 20,000 units.
- the alkoxylation is carried out, as known in the art, by reacting the Thiacalixarene with an alkylene oxide under elevated pressure of generally 1, 1 to 20 bar at temperatures of 50 to 200 ° C.
- a preferred subject of the present invention is the use of the alkoxylated thiacalixarenes as breakers for oil water emulsions in the
- the alkoxylated thiacalixarenes are added to the water in oil emulsions, preferably in solution.
- solvents for the alkoxylated thiacalixarenes aromatic or alcoholic solvents are preferred.
- the alkoxylated thiacalixarenes 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 wt .-% based on the oil content of the emulsion to be cleaved used.
- Tetraethylene glycol dimethyl ether submitted. With stirring and nitrogen purge, the mixture is slowly brought to 230 ° C over 4 hours and held this temperature for 2 more hours. The resulting from the catalyst water is removed via the orbital, the resulting hydrogen sulfide is passed through a gas washing bottle with alkaline
- Tetraethylene glycol dimethyl ether submitted. With stirring and nitrogen purge, the mixture is slowly brought to 230 ° C over 4 hours and held this temperature for 2 more hours. The resulting from the catalyst water is removed via the orbital, the resulting hydrogen sulfide is passed through a gas washing bottle with alkaline
- Tetraethylene glycol dimethyl ether submitted. With stirring and nitrogen purge, the mixture is slowly brought to 230 ° C over 4 hours and held this temperature for 2 more hours. The resulting from the catalyst water is removed via the orbital, the resulting hydrogen sulfide is passed through a gas washing bottle with alkaline
- the thiacalixarenes described above or their ethoxylates were introduced into a 1 l glass autoclave and the pressure in the autoclave was adjusted to about 0.2 bar overpressure with nitrogen. It was slowly heated to 130 ° C and after reaching this temperature, the pressure is again set to 0.2 bar overpressure. Thereafter, the desired amount of ethylene oxide was added at 130 ° C, wherein the pressure should not exceed 4.0 bar. After completion of ethylene oxide addition was allowed to react for 30 minutes at 130 ° C.
- splitters Tapered,
- Demulsifying temperature 50 ° C
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyethers (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10747177A EP2475651A1 (de) | 2009-09-08 | 2010-08-24 | Alkoxylierte thiacalixarene und deren verwendung als rohöl-emulsionsspalter |
CN201080027570.XA CN102471308B (zh) | 2009-09-08 | 2010-08-24 | 烷氧基化的硫代杯芳烃及其作为原油破乳剂的用途 |
US13/394,697 US8722593B2 (en) | 2009-09-08 | 2010-08-24 | Alkoxylated thiacalixarenes and the use thereof as crude oil demulsifiers |
CA2773492A CA2773492A1 (en) | 2009-09-08 | 2010-08-24 | Alkoxylated thiacalixarenes and the use thereof as crude oil demulsifiers |
BR112012005132A BR112012005132A2 (pt) | 2009-09-08 | 2010-08-24 | tiacalixarenos alcoxilados e seu uso como desemulsificadores de óleo cru |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009040495.3 | 2009-09-08 | ||
DE102009040495.3A DE102009040495B4 (de) | 2009-09-08 | 2009-09-08 | Alkoxylierte Thiacalixarene und deren Verwendung als Rohöl-Emulsionsspalter |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011029528A1 true WO2011029528A1 (de) | 2011-03-17 |
Family
ID=43033417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/005186 WO2011029528A1 (de) | 2009-09-08 | 2010-08-24 | Alkoxylierte thiacalixarene und deren verwendung als rohöl-emulsionsspalter |
Country Status (7)
Country | Link |
---|---|
US (1) | US8722593B2 (de) |
EP (1) | EP2475651A1 (de) |
CN (1) | CN102471308B (de) |
BR (1) | BR112012005132A2 (de) |
CA (1) | CA2773492A1 (de) |
DE (1) | DE102009040495B4 (de) |
WO (1) | WO2011029528A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2551277C1 (ru) * | 2014-01-20 | 2015-05-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Новосибирский национальный исследовательский государственный университет" (Новосибирский государственный университет, НГУ) | Производные тиакаликсаренов как средство доставки днк в клетки |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014028193A1 (en) | 2012-08-14 | 2014-02-20 | General Electric Company | Demulsifying compositions and methods of use |
US9260601B2 (en) | 2012-09-26 | 2016-02-16 | General Electric Company | Single drum oil and aqueous products and methods of use |
US10875953B2 (en) | 2017-01-25 | 2020-12-29 | Si Group, Inc. | Solubilized alkoxylated calixarene resins |
BR112019015142A2 (pt) | 2017-01-25 | 2020-03-24 | Si Group, Inc. | Solução de resina, resina, processo para estabilizar ou solubilizar uma mistura de resina fenólica, resina fenólica estabilizada ou solubilizada, e, método para resolver uma emulsão de água em óleo ou de óleo em água. |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2445873A1 (de) | 1974-09-26 | 1976-04-08 | Hoechst Ag | Erdoelspalter |
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 |
EP0264841A2 (de) | 1986-10-18 | 1988-04-27 | BASF Aktiengesellschaft | Copolymerisate aus hydrophoben Acrylsäure-, bzw. Methacrylsäureestern und hydrophilen Comonomeren, Verfahren zu ihrer Herstellung und ihre Verwendung als Erölemulsionsspalter |
EP0541018A2 (de) | 1991-11-07 | 1993-05-12 | BASF Aktiengesellschaft | Erdölemulsionsspalter |
US5401439A (en) | 1991-12-21 | 1995-03-28 | Basf Aktiengesellschaft | Oil-demulsifiers based on an alkoxylate and preparation of this alkoxylate |
DE10057044A1 (de) | 2000-11-17 | 2002-05-29 | Clariant Gmbh | Harze aus Alkylphenolen und Glyoxalsäurederivaten, und ihre Verwendung als Emulsionsspalter |
EP1264872A1 (de) | 2000-03-09 | 2002-12-11 | Cosmo Oil Co., Ltd | Fluoreszierendes material auf der basis von cyklischen phenolsulfiden mit assoziiertem metal und zusammensetzung davon |
US6646016B2 (en) | 1999-04-15 | 2003-11-11 | Clariant Gmbh | Aromatic aldehyde resins and their use as emulsion breakers |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2821357B1 (fr) * | 2001-02-23 | 2005-02-25 | Univ Claude Bernard Lyon | Nouveaux thiacalix[4]arenes et leurs complexes metalliques |
-
2009
- 2009-09-08 DE DE102009040495.3A patent/DE102009040495B4/de not_active Expired - Fee Related
-
2010
- 2010-08-24 US US13/394,697 patent/US8722593B2/en not_active Expired - Fee Related
- 2010-08-24 WO PCT/EP2010/005186 patent/WO2011029528A1/de active Application Filing
- 2010-08-24 EP EP10747177A patent/EP2475651A1/de not_active Withdrawn
- 2010-08-24 CA CA2773492A patent/CA2773492A1/en not_active Abandoned
- 2010-08-24 BR BR112012005132A patent/BR112012005132A2/pt not_active IP Right Cessation
- 2010-08-24 CN CN201080027570.XA patent/CN102471308B/zh not_active Expired - Fee Related
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4032514A (en) | 1971-08-18 | 1977-06-28 | Petrolite Corporation | Oxyalkylated cyclic phenol-aldehyde resins and uses therefor |
DE2445873A1 (de) | 1974-09-26 | 1976-04-08 | Hoechst Ag | Erdoelspalter |
US4321146A (en) | 1980-05-22 | 1982-03-23 | Texaco Inc. | Demulsification of bitumen emulsions with a high molecular weight mixed alkylene oxide polyol |
EP0264841A2 (de) | 1986-10-18 | 1988-04-27 | BASF Aktiengesellschaft | Copolymerisate aus hydrophoben Acrylsäure-, bzw. Methacrylsäureestern und hydrophilen Comonomeren, Verfahren zu ihrer Herstellung und ihre Verwendung als Erölemulsionsspalter |
EP0541018A2 (de) | 1991-11-07 | 1993-05-12 | BASF Aktiengesellschaft | Erdölemulsionsspalter |
US5445765A (en) | 1991-11-07 | 1995-08-29 | Basf Aktiengesellschaft | Petroleum emulsion breakers |
US5401439A (en) | 1991-12-21 | 1995-03-28 | Basf Aktiengesellschaft | Oil-demulsifiers based on an alkoxylate and preparation of this alkoxylate |
US6646016B2 (en) | 1999-04-15 | 2003-11-11 | Clariant Gmbh | Aromatic aldehyde resins and their use as emulsion breakers |
EP1264872A1 (de) | 2000-03-09 | 2002-12-11 | Cosmo Oil Co., Ltd | Fluoreszierendes material auf der basis von cyklischen phenolsulfiden mit assoziiertem metal und zusammensetzung davon |
DE10057044A1 (de) | 2000-11-17 | 2002-05-29 | Clariant Gmbh | Harze aus Alkylphenolen und Glyoxalsäurederivaten, und ihre Verwendung als Emulsionsspalter |
Non-Patent Citations (3)
Title |
---|
OLEG KASYAN ET AL: "Synthesis, Structure and Selective Upper Rim Functionalization of Long Chained Alkoxythiacalix[4]arenes", JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY, KLUWER ACADEMIC PUBLISHERS, DO, vol. 58, no. 1-2, 22 November 2006 (2006-11-22), pages 127 - 132, XP019502842, ISSN: 1573-1111 * |
S. KOKAL: "Crude-Oil Emulsions: A State-Of-The-Art Review", SOCIETY OF PETROLEUM ENGINEERS SPE 77497, pages 5 - 13 |
T. G. BALSON: "Something Old, Something New: A Discussion about Demulsifiers", PROCEEDINGS IN THE CHEMISTRY IN THE OIL INDUSTRY VIII SYMPOSIUM, vol. 3. - 5.1, 2003, pages 226 - 238 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2551277C1 (ru) * | 2014-01-20 | 2015-05-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Новосибирский национальный исследовательский государственный университет" (Новосибирский государственный университет, НГУ) | Производные тиакаликсаренов как средство доставки днк в клетки |
Also Published As
Publication number | Publication date |
---|---|
DE102009040495A1 (de) | 2011-03-24 |
CN102471308B (zh) | 2014-05-07 |
EP2475651A1 (de) | 2012-07-18 |
US20120172270A1 (en) | 2012-07-05 |
CA2773492A1 (en) | 2011-03-17 |
DE102009040495B4 (de) | 2014-02-13 |
CN102471308A (zh) | 2012-05-23 |
BR112012005132A2 (pt) | 2015-09-08 |
US8722593B2 (en) | 2014-05-13 |
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