EP2475651A1 - Thiacalixarènes alcoxylés et leur utilisation en tant que désémulsifiants de pétrole brut - Google Patents

Thiacalixarènes alcoxylés et leur utilisation en tant que désémulsifiants de pétrole brut

Info

Publication number
EP2475651A1
EP2475651A1 EP10747177A EP10747177A EP2475651A1 EP 2475651 A1 EP2475651 A1 EP 2475651A1 EP 10747177 A EP10747177 A EP 10747177A EP 10747177 A EP10747177 A EP 10747177A EP 2475651 A1 EP2475651 A1 EP 2475651A1
Authority
EP
European Patent Office
Prior art keywords
emulsion
alkoxylated
thiacalixarenes
oil
alkyl
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.)
Withdrawn
Application number
EP10747177A
Other languages
German (de)
English (en)
Inventor
Stefan Dilsky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of EP2475651A1 publication Critical patent/EP2475651A1/fr
Withdrawn legal-status Critical Current

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

L'invention concerne des composés de formule (II) (II), dans laquelle R désigne un groupe alkyle en C1 à C30, alcényle en C2 à C30, aryle en C6 à C18 ou alkylaryle en C7 à C30, AO désigne un groupe alcoxy en C2 à C4, x désigne un nombre allant de 1 à 50, m désigne un nombre compris entre 4 et 12. L'invention concerne également leur utilisation dans des quantités allant de 0,0001 à 5 % en poids, par rapport à la teneur en pétrole de l'émulsion à séparer, pour la séparation de l'eau dans les émulsions de pétrole.
EP10747177A 2009-09-08 2010-08-24 Thiacalixarènes alcoxylés et leur utilisation en tant que désémulsifiants de pétrole brut Withdrawn EP2475651A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009040495.3A DE102009040495B4 (de) 2009-09-08 2009-09-08 Alkoxylierte Thiacalixarene und deren Verwendung als Rohöl-Emulsionsspalter
PCT/EP2010/005186 WO2011029528A1 (fr) 2009-09-08 2010-08-24 Thiacalixarènes alcoxylés et leur utilisation en tant que désémulsifiants de pétrole brut

Publications (1)

Publication Number Publication Date
EP2475651A1 true EP2475651A1 (fr) 2012-07-18

Family

ID=43033417

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10747177A Withdrawn EP2475651A1 (fr) 2009-09-08 2010-08-24 Thiacalixarènes alcoxylés et leur utilisation en tant que désémulsifiants de pétrole brut

Country Status (7)

Country Link
US (1) US8722593B2 (fr)
EP (1) EP2475651A1 (fr)
CN (1) CN102471308B (fr)
BR (1) BR112012005132A2 (fr)
CA (1) CA2773492A1 (fr)
DE (1) DE102009040495B4 (fr)
WO (1) WO2011029528A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9260601B2 (en) 2012-09-26 2016-02-16 General Electric Company Single drum oil and aqueous products and methods of use
EP2885379B1 (fr) 2012-08-14 2018-02-14 General Electric Company Procédé de résolution d'émulsions
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
US10875953B2 (en) 2017-01-25 2020-12-29 Si Group, Inc. Solubilized alkoxylated calixarene resins
US10889677B2 (en) 2017-01-25 2021-01-12 Si Group, Inc. Compositions and process for stabilizing phenolic resins containing calixarenes

Family Cites Families (10)

* Cited by examiner, † Cited by third party
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
NL178329C (nl) 1974-09-26 1986-03-03 Hoechst Ag Werkwijze voor het bereiden van veretherde fenolaldehyde-condensatie-produkten en een werkwijze voor het daarmede breken van ruwe-olie-emulsies.
US4321146A (en) 1980-05-22 1982-03-23 Texaco Inc. Demulsification of bitumen emulsions with a high molecular weight mixed alkylene oxide polyol
DE3635489A1 (de) 1986-10-18 1988-04-21 Basf Ag Copolymerisate aus hydrophoben acrylsaeure- bzw. methacrylsaeureestern und hydrophilen comonomeren, verfahren zu ihrer herstellung und ihre verwendung als erdoelemulsionsspalter
DE4136661A1 (de) 1991-11-07 1993-05-13 Basf Ag Erdoelemulsionsspalter
DE4142579A1 (de) 1991-12-21 1993-06-24 Basf Ag Erdoelemulsionsspalter auf der basis eines alkoxylats und verfahren zur herstellung dieses alkoxylats
DE19916946C1 (de) 1999-04-15 2000-07-27 Clariant Gmbh Aromatische Aldehydharze und ihre Verwendung als Emulsionsspalter
JP2001254075A (ja) 2000-03-09 2001-09-18 Cosmo Research Inst 環状フェノール硫化物金属会合体の蛍光材料及びその組成物
DE10057044B4 (de) 2000-11-17 2004-05-06 Clariant Gmbh Harze aus Alkylphenolen und Glyoxalsäurederivaten, und ihre Verwendung als Emulsionsspalter
FR2821357B1 (fr) * 2001-02-23 2005-02-25 Univ Claude Bernard Lyon Nouveaux thiacalix[4]arenes et leurs complexes metalliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011029528A1 *

Also Published As

Publication number Publication date
DE102009040495B4 (de) 2014-02-13
CA2773492A1 (fr) 2011-03-17
US20120172270A1 (en) 2012-07-05
CN102471308B (zh) 2014-05-07
DE102009040495A1 (de) 2011-03-24
CN102471308A (zh) 2012-05-23
US8722593B2 (en) 2014-05-13
BR112012005132A2 (pt) 2015-09-08
WO2011029528A1 (fr) 2011-03-17

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