EP0549918A1 - Démulsifiant basé sur un alkoxylat et procédé de préparation de cet alkoxytat - Google Patents

Démulsifiant basé sur un alkoxylat et procédé de préparation de cet alkoxytat Download PDF

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Publication number
EP0549918A1
EP0549918A1 EP92120785A EP92120785A EP0549918A1 EP 0549918 A1 EP0549918 A1 EP 0549918A1 EP 92120785 A EP92120785 A EP 92120785A EP 92120785 A EP92120785 A EP 92120785A EP 0549918 A1 EP0549918 A1 EP 0549918A1
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EP
European Patent Office
Prior art keywords
formula
alkyl
alkoxylate
radical
alkylphenol
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EP92120785A
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German (de)
English (en)
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EP0549918B1 (fr
Inventor
Guenther Elfers
Wilfried Dr. Sager
Hans-Henning Dr. Vogel
Knut Dr. Oppenlaender
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BASF SE
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BASF SE
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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 petroleum emulsion breakers containing an alkoxylate of an alkylphenol-formaldehyde resin, an alcohol, a bisphenol or an amine and a process for the preparation of the alkoxylates using a special catalyst.
  • the crude oils differ greatly in their composition depending on their provenance.
  • the natural emulsifiers contained in the crude oils also have a complicated chemical structure, so that in order to overcome their effects, oil demulsifiers (demulsifiers) have to be selectively developed.
  • oil demulsifiers demulsifiers
  • demulsifiers are ethylene oxide / propylene oxide block copolymers, alkoxylated alkylphenyl-formaldehyde resins, as described, for example, in DE-PS 27 19 978, alkoxylated polyamines (see, for example, US 3 907 701 and DE-OS 24 35 713) and Crosslinking products of the above basic classes with multifunctional reagents, such as diisocyanates, dicarboxylic acids, bisglycidyl ethers, di- and trimethylolphenols.
  • the object of the present invention was therefore to provide petroleum emulsion splitters which allow the emulsion to be separated as quantitatively as possible into oil and water in the shortest possible time, i.e. which show good effectiveness even in low doses.
  • the alkoxylate shows the stated polydispersity. This polydispersity is achieved by producing the alkoxylate using a special catalyst.
  • the present invention therefore also relates to a process for the preparation of alkoxylates of the above general formula I, which is characterized in that alkylphenol-formaldehyde resins of the above formula II, bisphenols of the above formula VI, alcohols of the above formula III , Amines of formula IV given above or polyethyleneimines with a molecular weight M ⁇ w reacted from 2000 to 50,000 with ethylene oxide, propylene oxide and / or butylene oxide in the presence of an optionally partially hydrolyzed metal alcoholate as a catalyst, the metal being selected from the metals from Groups IIA, IIIA, IVB, and Zn, Ce and La and the alcoholate group has 1 to 8 carbon atoms.
  • hydroxides of the alkali metals are used as catalysts for the alkoxylation (see e.g. DE-PS 20 13 820, column 5, AII). With these catalysts, as was found in comparative experiments, only polydispersities up to 1.6 are achieved.
  • n is a measure of the molecular weight distribution of polymeric compounds (see, for example, Encyclopedia of Polymer Sci. and Engineering, Vol. 10, p. 4, J. Wiley 1987).
  • the alkoxylates prepared according to the invention this means that they have a broader molecular weight distribution than the known compounds prepared with alkali metal hydroxide as a catalyst.
  • alkylphenol-formaldehyde resins this can also be expressed by the hydroxyl number: while the known alkoxylates have hydroxyl numbers from 130 to 170, the alkoxylates prepared according to the invention have hydroxyl numbers above 170, preferably between 180 and 300.
  • the starting compounds for the preparation of the alkoxylates are alkylphenol-formaldehyde resins of the formula II, alcohols of the formula III, amines of the formula IV, bisphenols of the formula VI or polyethyleneimines with a molecular weight M ⁇ w from 2,000 to 50,000, in particular from 5,000 to 25,000.
  • Alkylphenol-formaldehyde resins, alcohols and polyethyleneimines are preferred.
  • An iso-C8-C12 alkyl radical is particularly preferred.
  • diols such as e.g. Ethylene glycol, diethylene glycol or butylene glycol, or glycol monoesters such as e.g. Ethylene glycol monoacetate used.
  • the amines to be used include, in particular, the polyalkylene polyamines, such as Diethylene triamine, triethylene tetramine or tetraethylene pentamine. Alkanolamines are also suitable.
  • the polyethyleneimines are preferably branched and contain primary, secondary and tertiary amine groups.
  • Bisphenol A should be mentioned in particular as bisphenol.
  • alkoxylation of the alkylphenol-formaldehyde resins, the alcohols, bisphenols, amines and polyethyleneimines takes place with ethylene oxide, propylene oxide and / or butylene oxide. Ethylene oxide and / or propylene oxide are preferably used.
  • the reaction is carried out in an inert solvent such as e.g. Toluene or xylene, usually at 100 to 180 ° C.
  • an inert solvent such as e.g. Toluene or xylene, usually at 100 to 180 ° C.
  • n 3-100, preferably 3 -50, particularly preferably 4-12.
  • the amount of starting compound and alkylene oxide in relation to the solvent is e.g. chosen so that an 80 wt .-% solution results.
  • Me stands for metals of group IIA, in particular Mg, Ca and Ba
  • group IIIA in particular Al
  • group IVB in particular Ti (group name corresponding to CAS up to 1986)
  • Zn, Ce or La 0
  • d and e depend on the valence of the metal.
  • Aluminum tri or titanium tetra alcoholates are preferably used, in particular aluminum tri (isopropylate).
  • the metal alcoholates can also be used in conjunction with Zn-alkylene and small amounts of H2O in hexane (see US 3,384,603).
  • the amount of the catalyst used, based on the end products, is 0.05 to 5% by weight.
  • the starting compounds can also be used in a conventional manner, i.e. catalyzed with alkali metal hydroxides, prepared, partially oxyalkylated compounds are used. It is only essential that the required polydispersity is obtained by subsequent alkoxylation using the above-mentioned metal alcoholates according to the invention.
  • the polydispersity Q must be at least 1.7 in order to achieve the desired effect.
  • Q is preferably 1.7-5, particularly preferably 1.8 to 3.0, in particular 1.8 to 2.8. It can be observed that the differences in the Q values between alkoxylates prepared with conventional catalysts and alkoxylates prepared with the catalysts to be used according to the invention are different, depending on which compound RH one starts from. However, the difference between these Q values, based on the same starting compound RH, should be 0.3 or more.
  • M ⁇ w - and M ⁇ n values were determined by gel permeation chromatography.
  • the feed volume was 20 ul of a 1 wt .-% solutions, solvent THF.
  • the M ⁇ n - and M ⁇ w values were determined using calibration substances (ethoxylates) from the chromatogram using a standard computer program.
  • the petroleum emulsion splitter according to the invention can contain, as further component B, a different alkoxylated polyalkylene polyamine which does not have the Q values according to the invention.
  • additional components are known and e.g. described in more detail in DE-PS 27 19 978, for which reference is made in this patent specification in particular to column 4, B. This additional mixture component is also disclosed in DE-OS 22 27 546.
  • the weight ratio A to B is preferably 60:40 to 40:60% by weight.
  • the splitters are advantageously added to the crude oil emulsions in amounts of 1 to 1000 ppm, preferably 10 to 100 ppm, based on the weight of the emulsion to be split, at temperatures between 20 and 80 ° C.
  • the splitters can be used as solutions because of their better meterability.
  • Mixtures of organic solvents eg methanol
  • organic solvents with boiling points between 50 and 200 ° C. can be used as solvents serve, for example toluene, xylenes, tetrahydrofuran, dioxane, lower alcohols and light petroleum fractions of the boiling point mentioned.
  • solutions are expediently adjusted to an active substance content (splitter content) of 0.5 to 50% by weight.
  • the solutions are preferably added to the crude oils at the probes (in the field).
  • the cleavage then already takes place at the temperature of the freshly pumped water-in-oil emulsion at such a rate that the emulsion can be broken on the way to the processing plant. There it is separated in a possibly heated separator and possibly with the help of an electric field without difficulty into pure oil and salt water.
  • alkoxylates obtained were mixed with an oxalkylated polyalkylene polyamine B, prepared according to DE-PS 27 19 978, column 4, B, in a ratio of 1: 1 and tested for their effectiveness as a petroleum emulsion breaker.
  • Table 3 No. from Tab. 2 Formation water (ml) separated from 100 g emulsion according to: Minutes Hours 10th 20th 30th 45 60 2nd 4th 16 1 0 0 3rd 5 8th 20th 25th 2nd 0 0 1 3rd 5 18th 22 3rd 0 0 4th 24th 28 35 39 4th 0 0 4th 9 15 31 33 5 0 0 1 3rd 9 17th 20th No. from Tab.

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  • 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)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polyethers (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP92120785A 1991-12-21 1992-12-05 Démulsifiant basé sur un alkoxylat et procédé de préparation de cet alkoxytat Expired - Lifetime EP0549918B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4142579 1991-12-21
DE4142579A DE4142579A1 (de) 1991-12-21 1991-12-21 Erdoelemulsionsspalter auf der basis eines alkoxylats und verfahren zur herstellung dieses alkoxylats

Publications (2)

Publication Number Publication Date
EP0549918A1 true EP0549918A1 (fr) 1993-07-07
EP0549918B1 EP0549918B1 (fr) 1996-03-27

Family

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Family Applications (1)

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EP92120785A Expired - Lifetime EP0549918B1 (fr) 1991-12-21 1992-12-05 Démulsifiant basé sur un alkoxylat et procédé de préparation de cet alkoxytat

Country Status (6)

Country Link
US (1) US5401439A (fr)
EP (1) EP0549918B1 (fr)
JP (1) JPH05239479A (fr)
CA (1) CA2085414A1 (fr)
DE (2) DE4142579A1 (fr)
NO (1) NO924827L (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995033018A1 (fr) * 1994-05-30 1995-12-07 Basf Aktiengesellschaft Procede permettant de separer l'eau du petrole brut et agent de craquage d'emulsion d'huile brute utilise a cet effet
WO2012068099A1 (fr) 2010-11-17 2012-05-24 Dow Global Technologies Llc Procédé faisant intervenir un dérivé alcoxylé et aminé de bisphénol a en tant que démulsifiant

Families Citing this family (22)

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US5681451A (en) * 1996-01-31 1997-10-28 Betzdearborn Inc. Settling aids for solids in hydrocarbons
ITMI981213A1 (it) * 1998-06-01 1999-12-01 Montell North America Inc Polimeri propilenici adatti per film cast trasparenti
US6106701A (en) * 1998-08-25 2000-08-22 Betzdearborn Inc. Deasphalting process
US6294093B1 (en) 1998-09-04 2001-09-25 Nalco/Exxon Energy Chemicals, L.P. Aqueous dispersion of an oil soluble demulsifier for breaking crude oil emulsions
DE10057043B4 (de) * 2000-11-17 2004-05-06 Clariant Gmbh Alkylphenolglyoxalharze und ihre Verwendung als Emulsionsspalter
WO2002053676A1 (fr) * 2000-12-29 2002-07-11 Halliburton Energy Services, Inc. Diluants pour emulsions inverses
DE10319028B4 (de) * 2003-04-28 2006-12-07 Clariant Produkte (Deutschland) Gmbh Demulgatoren für Mischungen aus Mitteldestillaten mit Brennstoffölen pflanzlichen oder tierischen Ursprungs
DE102004002080B4 (de) * 2004-01-15 2007-03-29 Clariant Produkte (Deutschland) Gmbh Demulgatoren für Mischungen aus Mitteldestillaten mit Brennstoffölen pflanzlichen oder tierischen Ursprungs und Wasser
DE102004024532B4 (de) * 2004-05-18 2006-05-04 Clariant Gmbh Demulgatoren für Mischungen aus Mitteldestillaten mit Brennstoffölen pflanzlichen oder tierischen Ursprungs und Wasser
DE112007000772T5 (de) 2006-04-07 2009-02-05 Akzo Nobel N.V. Umweltfreundliche Öl/Wasser-Demulgatoren
DE102009019179A1 (de) 2009-04-28 2010-11-11 Clariant International Ltd. Alkoxylierte (Meth)acrylat-Polymere und ihre Verwendung als Rohöl-Emulsionsspalter
DE102009019177A1 (de) 2009-04-28 2010-11-11 Clariant International Ltd. Verwendung biologisch abbaubarer alkoxylierter (Meth)acrylat-Copolymere als Rohöl-Emulsionsspalter
DE102009040495B4 (de) 2009-09-08 2014-02-13 Clariant International Ltd. Alkoxylierte Thiacalixarene und deren Verwendung als Rohöl-Emulsionsspalter
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
MX340805B (es) 2011-04-18 2016-06-24 Inst Mexicano Del Petróleo Formulaciones sinergicas de copolimeros funcionalizados y liquidos ionicos para el deshidratado y desalado de aceites crudos medianos, pesados y extrapesados.
DE102012005279A1 (de) 2012-03-16 2013-03-14 Clariant International Limited Alkoxylierte, vernetzte Polyamidoamine und deren Verwendung als Emulsionsspalter
DE102012005377A1 (de) 2012-03-16 2013-03-14 Clariant International Ltd. Alkoxylierte Polyamidoamine und deren Verwendung als Emulsionsspalter
JP6840085B2 (ja) * 2015-02-25 2021-03-10 ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ 汚れた金属表面を洗浄する方法及びそのような方法に有用な物質
WO2016141968A1 (fr) * 2015-03-09 2016-09-15 Amril Ag Désémulsifiant pour émulsions inversées de boue à base d'huile
CN110343545B (zh) * 2019-06-28 2020-06-16 德仕能源科技集团股份有限公司 一种体型原油破乳剂及其制备方法和应用
EP3945126B1 (fr) * 2020-07-31 2024-03-13 Basf Se Compositions de débrumage pour carburants

Citations (6)

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US3907701A (en) * 1972-06-07 1975-09-23 Basf Ag Demulsifying crude oil emulsions
EP0055434A1 (fr) * 1980-12-30 1982-07-07 Hoechst Aktiengesellschaft Composés d'addition à partir de blocs de polymères de polyéthers et des bisglycidyléthers, procédé pour leur fabrication et leur application
EP0097897A1 (fr) * 1982-06-25 1984-01-11 Hoechst Aktiengesellschaft Produits de condensation phénol-aldéhyde éthérifiés, modifiés, et leur utilisation pour casser les émulsions à base de pétrole
EP0147743A2 (fr) * 1983-12-28 1985-07-10 BASF Aktiengesellschaft Polyalcènepolyamines oxyalcoylés et réticulés et leur application comme démulsifiants de pétrole brut
EP0174399A1 (fr) * 1983-04-11 1986-03-19 Exxon Research And Engineering Company Désémulsifiant à base d'eau et procédé pour son utilisation dans la déshydratation et la désalination d'huiles d'hydrocarbures
EP0246582A2 (fr) * 1986-05-22 1987-11-25 BASF Aktiengesellschaft Polyéthers qu'on peut obtenir par réaction de bis-(4-hydroxyphényl)-méthanes alkylolés avec des poly(oxyalkylènes) et leur utilisation pour la désémulsification du pétrole brut

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Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907701A (en) * 1972-06-07 1975-09-23 Basf Ag Demulsifying crude oil emulsions
EP0055434A1 (fr) * 1980-12-30 1982-07-07 Hoechst Aktiengesellschaft Composés d'addition à partir de blocs de polymères de polyéthers et des bisglycidyléthers, procédé pour leur fabrication et leur application
EP0097897A1 (fr) * 1982-06-25 1984-01-11 Hoechst Aktiengesellschaft Produits de condensation phénol-aldéhyde éthérifiés, modifiés, et leur utilisation pour casser les émulsions à base de pétrole
EP0174399A1 (fr) * 1983-04-11 1986-03-19 Exxon Research And Engineering Company Désémulsifiant à base d'eau et procédé pour son utilisation dans la déshydratation et la désalination d'huiles d'hydrocarbures
EP0147743A2 (fr) * 1983-12-28 1985-07-10 BASF Aktiengesellschaft Polyalcènepolyamines oxyalcoylés et réticulés et leur application comme démulsifiants de pétrole brut
EP0246582A2 (fr) * 1986-05-22 1987-11-25 BASF Aktiengesellschaft Polyéthers qu'on peut obtenir par réaction de bis-(4-hydroxyphényl)-méthanes alkylolés avec des poly(oxyalkylènes) et leur utilisation pour la désémulsification du pétrole brut

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995033018A1 (fr) * 1994-05-30 1995-12-07 Basf Aktiengesellschaft Procede permettant de separer l'eau du petrole brut et agent de craquage d'emulsion d'huile brute utilise a cet effet
WO2012068099A1 (fr) 2010-11-17 2012-05-24 Dow Global Technologies Llc Procédé faisant intervenir un dérivé alcoxylé et aminé de bisphénol a en tant que démulsifiant

Also Published As

Publication number Publication date
NO924827L (no) 1993-06-22
US5401439A (en) 1995-03-28
JPH05239479A (ja) 1993-09-17
EP0549918B1 (fr) 1996-03-27
NO924827D0 (no) 1992-12-14
DE4142579A1 (de) 1993-06-24
CA2085414A1 (fr) 1993-06-22
DE59205855D1 (de) 1996-05-02

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