EP1658356A1 - Polyglycerols reticules alcoxyles et leur utilisation comme desemulsionneurs biodegradables - Google Patents

Polyglycerols reticules alcoxyles et leur utilisation comme desemulsionneurs biodegradables

Info

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
Application number
EP04734666A
Other languages
German (de)
English (en)
Other versions
EP1658356B1 (fr
Inventor
Dirk Leinweber
Franz Xaver Scherl
Elisabeth Wasmund
Heidi Grundner
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 Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
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 Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP1658356A1 publication Critical patent/EP1658356A1/fr
Application granted granted Critical
Publication of EP1658356B1 publication Critical patent/EP1658356B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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

L'invention concerne des polyglycérols alcoxylés, réticulés avec des composés électrophiles multifonctionnels, ayant un poids moléculaire compris entre 1000 et 100.000 unités. Les polyglycérols selon l'invention comprennent 5 à 100 unités glycérol qui sont alcoxylées avec des groupes oxyde d'alkylène C2-C4 ou un mélange de tels groupes oxyde d'alkylène de sorte que le polyglycérol alcoxylé réticulé présente un degré d'alcoxylation d'1 à 100 unités oxyde d'alkylène par groupe OH libre. L'invention concerne également l'utilisation de ces polyglycérols pour séparer des émulsions huile-eau dans des quantités allant de 0,0001 à 5 % en poids par rapport à la teneur en huile de l'émulsion à séparer.
EP04734666A 2003-06-04 2004-05-25 Polyglycerols reticules alcoxyles et leur utilisation comme desemulsionneurs biodegradables Expired - Lifetime EP1658356B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10325198A DE10325198B4 (de) 2003-06-04 2003-06-04 Verwendung von alkoxylierten vernetzten Polyglycerinen als biologisch abbaubare Emulsionsspalter
PCT/EP2004/005587 WO2004108863A1 (fr) 2003-06-04 2004-05-25 Polyglycerols reticules alcoxyles et leur utilisation comme desemulsionneurs biodegradables

Publications (2)

Publication Number Publication Date
EP1658356A1 true EP1658356A1 (fr) 2006-05-24
EP1658356B1 EP1658356B1 (fr) 2007-07-18

Family

ID=33494818

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04734666A Expired - Lifetime EP1658356B1 (fr) 2003-06-04 2004-05-25 Polyglycerols reticules alcoxyles et leur utilisation comme desemulsionneurs biodegradables

Country Status (5)

Country Link
US (1) US7671098B2 (fr)
EP (1) EP1658356B1 (fr)
DE (2) DE10325198B4 (fr)
NO (1) NO336950B1 (fr)
WO (1) WO2004108863A1 (fr)

Cited By (1)

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CN107519672A (zh) * 2017-10-25 2017-12-29 成都凯米拉科技有限公司 一种用于油田的水处理用破乳剂

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CA2659450A1 (fr) * 2006-08-03 2008-08-07 Dow Global Technologies Inc. Nouvelle compositions de charge et leur procede de fabrication
US7981979B2 (en) * 2006-09-22 2011-07-19 Nalco Company Siloxane cross-linked demulsifiers
DE102009019177A1 (de) 2009-04-28 2010-11-11 Clariant International Ltd. Verwendung biologisch abbaubarer alkoxylierter (Meth)acrylat-Copolymere als Rohöl-Emulsionsspalter
RU2539897C2 (ru) 2009-07-30 2015-01-27 Басф Се Композиция для нанесения металлического покрытия, содержащая подавляющий агент, для беспустотного заполнения субмикронных элементов поверхности
DE102009041983A1 (de) 2009-09-17 2011-04-07 Clariant International Ltd. Alkoxylierte Trialkanolaminkondensate und deren Verwendung als Emulsionsspalter
DE102009042971A1 (de) 2009-09-24 2011-09-15 Clariant International Ltd. Alkoxylierte cyclische Diamine und deren Verwendung als Emulsionsspalter
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
BR112013012214A2 (pt) 2010-11-17 2019-09-24 Dow Brasil Sudeste Ind método para desestabilizar uma emulsão de petróleo bruto/água
DE102012005377A1 (de) 2012-03-16 2013-03-14 Clariant International Ltd. Alkoxylierte Polyamidoamine und deren Verwendung als Emulsionsspalter
DE102012005279A1 (de) 2012-03-16 2013-03-14 Clariant International Limited Alkoxylierte, vernetzte Polyamidoamine und deren Verwendung als Emulsionsspalter
CA2870885C (fr) * 2012-05-31 2019-06-25 Nalco Company Chimie et production de tensio-actifs polymeres a base de glycerol
US9663726B2 (en) * 2014-02-10 2017-05-30 Baker Hughes Incorporated Fluid compositions and methods for using cross-linked phenolic resins
US20160074515A1 (en) 2014-06-20 2016-03-17 Reform Biologics, Llc Viscosity-reducing excipient compounds for protein formulations
US10478498B2 (en) 2014-06-20 2019-11-19 Reform Biologics, Llc Excipient compounds for biopolymer formulations
FR3048975B1 (fr) 2016-03-18 2019-11-29 Oleon Nv Desemulsifiant pour petrole
CA3030422C (fr) 2016-07-13 2021-10-26 Reform Biologics, Llc Excipients stabilisants pour formulations de proteines therapeutiques
WO2019036619A1 (fr) * 2017-08-18 2019-02-21 Reform Biologics, Llc Excipients stabilisants pour formulations de protéines thérapeutiques
WO2020223224A1 (fr) 2019-04-29 2020-11-05 Ecolab Usa Inc. Composés d'aminophénol oxygénés et procédés de prévention de la polymérisation de monomères
US12018130B2 (en) 2020-10-21 2024-06-25 Ecolab Usa Inc. Alkoxylated (hydroxyalkyl)aminophenol polymers and methods of use

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Also Published As

Publication number Publication date
DE502004004384D1 (de) 2007-08-30
EP1658356B1 (fr) 2007-07-18
DE10325198A1 (de) 2005-01-13
WO2004108863A1 (fr) 2004-12-16
US7671098B2 (en) 2010-03-02
NO20056114L (no) 2005-12-21
DE10325198B4 (de) 2007-10-25
US20060281931A1 (en) 2006-12-14
NO336950B1 (no) 2015-11-30

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