WO2003054348A1 - Utilisation de formaldehydes d'alkylphenol sulfures pour stabiliser des asphaltenes dans du petrole brut - Google Patents

Utilisation de formaldehydes d'alkylphenol sulfures pour stabiliser des asphaltenes dans du petrole brut Download PDF

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Publication number
WO2003054348A1
WO2003054348A1 PCT/EP2002/014127 EP0214127W WO03054348A1 WO 2003054348 A1 WO2003054348 A1 WO 2003054348A1 EP 0214127 W EP0214127 W EP 0214127W WO 03054348 A1 WO03054348 A1 WO 03054348A1
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WO
WIPO (PCT)
Prior art keywords
asphaltenes
crude oil
compounds
ppm
formulas
Prior art date
Application number
PCT/EP2002/014127
Other languages
German (de)
English (en)
Inventor
Ansgar Behler
Wolfgang Breuer
Matthias Hof
Original Assignee
Cognis Deutschland Gmbh & Co. Kg
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 Cognis Deutschland Gmbh & Co. Kg filed Critical Cognis Deutschland Gmbh & Co. Kg
Priority to US10/499,765 priority Critical patent/US20050091915A1/en
Priority to EP02798329A priority patent/EP1458951A1/fr
Priority to CA002471413A priority patent/CA2471413A1/fr
Priority to BR0215153-7A priority patent/BR0215153A/pt
Publication of WO2003054348A1 publication Critical patent/WO2003054348A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes

Definitions

  • the present invention relates to certain sulfonated alkylphenol formaldehydes and their use for stabilizing asphaltenes in crude oil, and to a method for preventing the precipitation of asphaltenes in crude oils.
  • Crude oil is a complex mixture of different paraffinic and aromatic hydrocarbons, whereby the individual components have very different chemical and physical properties. In the distillation of crude oil, therefore, both highly volatile, low-viscosity components and waxy, highly viscous fractions are obtained. This last group includes petroleum resins and predominantly asphaltenes, which are colloidally disperse in the oil phase.
  • the asphaltenes consist of a mixture of different, saturated, unsaturated and aromatic hydrocarbons, especially naphthalene derivatives. There are also heterocyclic hydrocarbons, some of which also contain complexed metal ions. Asphaltenes are also rich in sulfur, nitrogen and oxygen compounds. Due to the complex composition, asphaltenes are generally characterized by their solubility.
  • the heptane or pentane-insoluble but toluene-soluble petroleum fraction is referred to as asphaltenes, the "dissolving" of the asphaltenes being a complex process for which a complete theoretical description has not yet existed (cf. EYSheu, OC Mullins, Asphaltenes - Fundamentals and Applications, Plenum Press, New York, 1995, Chapter I and Chapter III).
  • the micelles have different sizes depending on the temperature and composition of the oil phase. For example, it is known that lighter aromatic hydrocarbons in crude oil stabilize the asphaltene micelles. Under the conditions of oil production or production, however, the asphaltenes often precipitate, which leads to the formation of highly viscous, waxy to solid residues on the surface of the production facilities and the petroleum-containing formation surrounding the borehole leads. The asphalt residues clog the pores of the formation, which leads to a noticeable reduction in production rates and, in the worst case, can make production completely impossible. Asphalt residues on the surfaces of the production plants, for example the conveyor pipe or the walls of the casing of pipelines or separators, can also significantly hinder the production.
  • the object of the present invention was therefore to provide effective alternatives to the stabilizers known in the prior art for asphaltenes in crude oils, even with very different crude oil qualities. It has been found that certain sulfonated alkylphenol formaldehydes accomplish the above object.
  • the present application relates to the use of products obtainable by sulfonating compounds of the formulas (I) or (II) R
  • n is a number from 2 to 12 and R is a C3-C 2 alkyl, C6-C12-A17I or hydroxyaryl or C7-Ci2-aralkyl radical, as a stabilizer for asphaltenes in crude oil.
  • Ph in the formulas (I) and (II) denotes a phenol radical.
  • the sulfonation products used according to the invention are obtained by sulfonating compounds of the general formulas (I) and / or (II) which are known per se. These starting products are known for example from DE 197 09 797 A1. Reference is made here to the formulas (I) and (II) in claim 1 of DE 197 09 797 A1 and to the disclosure on page 2, lines 40 to 44 and the disclosure of page 3 of this document. The disclosure of these passages is expressly made to disclose the present application. The formulas (I) and (II) in DE 197 09 797 are identical to those of the present application. Such compounds are resins which are available, for example, under the name Dowfax DM 645 (Dow Chemicals).
  • the starting materials of the formulas (I) and (II) are sulfonated in a manner known per se using gaseous SO3. However, the sulfonation products are not neutralized according to the invention but are present as free acids.
  • the sulfonation of the starting materials is preferably carried out in a falling film reactor by means of a continuous process.
  • the gaseous sulfur trioxide is generated in situ by pyrolysis of pure sulfur.
  • the polyalkylformaldehyde resin used is preferably reacted in an equimolar ratio with sulfur trioxide.
  • the reaction itself advantageously takes place in a temperature range of 75-80 ° C.
  • the end product is preferably not neutralized.
  • the products according to the invention are obtained as aqueous solutions which can be formulated or used directly as asphaltene dispersants without further steps.
  • the sulfonated according to the invention Products surprisingly show significantly better properties than asphaltene inhibitors or asphaltene stabilizers than the compounds known from the prior art or their mixtures according to the teaching of DE 197 09 797 A1.
  • Crude oils are understood to be the unrefined petroleum that comes directly from the earth. These are complex mixtures of predominantly hydrocarbons with densities in the range from 0.65 to 1.02 g / cm 3 and calorific values from 38 to 46 MJ / kg.
  • the boiling points of the most important crude oil components are in the temperature range from 50 to 350 ° C (see Römpp Chemielexikon, Volume 2, 1997, pages 1210 to 1213).
  • the sulfated alkylphenol formaldehydes according to the invention i.e. their addition to the crude oils effectively prevents the precipitation of asphaltenes or the formation of residues.
  • Another object of the present invention relates to a method for preventing the precipitation of asphaltenes from crude oils, characterized in that sulfated alkylphenol formaldehydes are added to the crude oils as stabilizers in amounts of 100 to 2500 ppm as described above.
  • the present technical teaching also includes the use of the sulfonated -Akylpherrolformaldehyden-in the form of dilute solutions in aromatic solvents, preferably toluene.
  • dilute solutions preferably contain the polyesteramides in amounts of 2 to 50% by weight, in particular in amounts of 2 to 20 and particularly preferably 2 to 15% by weight.
  • Such formulations can also contain other additives, such as corrosion inhibitors or defoamers. Examples
  • the sulfonation of the starting materials was carried out in a falling film reactor by means of a continuous process.
  • the gaseous sulfur trioxide was generated by pyrolysis of pure sulfur in situ.
  • the polyalkyl formaldehyde resin used was reacted in an equimolar ratio with sulfur trioxide.
  • the reaction was carried out in a temperature range of 75-80 ° C.
  • the end product was not neutralized.
  • the active substance content was determined by Epton titration, the molar mass and the acid number as key figures.
  • the test is based on the fact that asphaltenes are soluble in aromatic but not aliphatic hydrocarbons.
  • dispersants can be tested by dissolving the oil or extracted asphaltenes in an aromatic solvent and then adding a non-aromatic solvent to produce a precipitate. Since asphaltenes are dark in color, the extent of the precipitation can be determined by UV spectroscopic measurement of the supernatant.
  • the following table shows the results of the precipitation tests at three concentrations of different formulations A to H according to the invention.
  • the absorption values of the experimental formulations were divided by the corresponding value of the positive sample (pure toluene) (information in the tables as relative absorption). The closer the values are to 1.0, the better the effect of the dispersant formulation. The values are shown in the following table.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne l'utilisation de résines de formaldéhydes d'alkylphénol sulfurés en tant qu'agents de stabilisation de l'asphaltène dans du pétrole brut.
PCT/EP2002/014127 2001-12-21 2002-12-12 Utilisation de formaldehydes d'alkylphenol sulfures pour stabiliser des asphaltenes dans du petrole brut WO2003054348A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US10/499,765 US20050091915A1 (en) 2001-12-21 2002-12-12 Use of sulphonated alkyl phenol formaldehydes in the stabilization of ashphaltenes in crude oil
EP02798329A EP1458951A1 (fr) 2001-12-21 2002-12-12 Utilisation de formaldehydes d'alkylphenol sulfures pour stabiliser des asphaltenes dans du petrole brut
CA002471413A CA2471413A1 (fr) 2001-12-21 2002-12-12 Utilisation de formaldehydes d'alkylphenol sulfures pour stabiliser des asphaltenes dans du petrole brut
BR0215153-7A BR0215153A (pt) 2001-12-21 2002-12-12 Aplicação de alquilfenolformaldeìdos para a estabilização de asfaltenos no óleo bruto

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10163244A DE10163244A1 (de) 2001-12-21 2001-12-21 Verwendung von sulfierten Alkylphenolformaldehyden zur Stabilisierung von Asphaltenen in Rohöl
DE10163244.4 2001-12-21

Publications (1)

Publication Number Publication Date
WO2003054348A1 true WO2003054348A1 (fr) 2003-07-03

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PCT/EP2002/014127 WO2003054348A1 (fr) 2001-12-21 2002-12-12 Utilisation de formaldehydes d'alkylphenol sulfures pour stabiliser des asphaltenes dans du petrole brut

Country Status (6)

Country Link
US (1) US20050091915A1 (fr)
EP (1) EP1458951A1 (fr)
BR (1) BR0215153A (fr)
CA (1) CA2471413A1 (fr)
DE (1) DE10163244A1 (fr)
WO (1) WO2003054348A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584641B (zh) * 2011-12-14 2013-12-04 中国日用化学工业研究院 一种制备烷基酚甲醛低聚物磺酸盐的工艺
US9921205B2 (en) 2012-11-13 2018-03-20 Chevron U.S.A. Inc. Method for determining the effectiveness of asphaltene dispersant additives for inhibiting or preventing asphaltene precipitation in a hydrocarbon-containing material subjected to elevated temperature and presssure conditions
US9523054B2 (en) * 2013-08-21 2016-12-20 Baker Hughes Incorporated Asphaltene stabilization in petroleum feedstocks by blending with biological source oil and/or chemical additive
US10513651B2 (en) 2015-11-30 2019-12-24 Bp Corporation North America Inc. Screening methods for asphaltene stabilizers
US10907473B2 (en) 2017-11-14 2021-02-02 Chevron U.S.A., Inc. Low volume in-line filtration methods for analyzing hydrocarbon-containing fluid to evaluate asphaltene content and behavior during production operations
US20240117238A1 (en) 2022-09-28 2024-04-11 Championx Llc Extended release asphaltene inhibitor composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872056A (en) * 1974-01-14 1975-03-18 Ewald Daubach Manufacture of phenol/formaldehyde resins
US4820451A (en) * 1985-11-02 1989-04-11 Henkel Kommanditgesellschaft Auf Aktien Process for the production of mobile pastes of washing-active α-sulfofatty acid ester salts of high solids content
US4954646A (en) * 1988-02-03 1990-09-04 Hoechst Aktiengesellschaft Process for the preparation of sulfated alkanol oxethylates or alkylphenol oxethylates having a lowered content of 1,4-dioxane
US6180683B1 (en) * 1997-03-10 2001-01-30 Clariant Gmbh Synergistic mixtures of alkylphenol-formaldehyde resins with oxalkylated amines as asphaltene dispersants

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US2639227A (en) * 1950-09-02 1953-05-19 Shell Dev Anticlogging fuel oil compositions
US4414035A (en) * 1979-05-21 1983-11-08 Petrolite Corporation Method for the removal of asphaltenic deposits
US20020091069A1 (en) * 1996-11-26 2002-07-11 William F. King Overbased alkyl oxy benzene sulfonates as detergents
US6048904A (en) * 1998-12-01 2000-04-11 Exxon Research And Engineering Co. Branched alkyl-aromatic sulfonic acid dispersants for solublizing asphaltenes in petroleum oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872056A (en) * 1974-01-14 1975-03-18 Ewald Daubach Manufacture of phenol/formaldehyde resins
US4820451A (en) * 1985-11-02 1989-04-11 Henkel Kommanditgesellschaft Auf Aktien Process for the production of mobile pastes of washing-active α-sulfofatty acid ester salts of high solids content
US4954646A (en) * 1988-02-03 1990-09-04 Hoechst Aktiengesellschaft Process for the preparation of sulfated alkanol oxethylates or alkylphenol oxethylates having a lowered content of 1,4-dioxane
US6180683B1 (en) * 1997-03-10 2001-01-30 Clariant Gmbh Synergistic mixtures of alkylphenol-formaldehyde resins with oxalkylated amines as asphaltene dispersants

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ADV CEM RES;ADVANCES IN CEMENT RESEARCH OCT 1993, vol. 5, no. 20, October 1993 (1993-10-01), pages 131 - 138 *
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; BANFILL P F G ET AL: "Superplasticizers for Ciment Fondu. Part 1: Effects on rheological properties of fresh paste and mortar", XP002235820, Database accession no. EIX94071932048 *
DATABASE COMPENDEX [online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; ZHANG XUEXIN ET AL: "STUDIES ON THE SERVICEABLE LIFE BY CHEMILUMINESCENCE METHOD AND ON THE MECHANISM OF HEAT-OXIDATIVE AGING OF SPU", XP002235819, Database accession no. EIX86080114655 *
SHIYOU XUEBAO SHIYOU HUAGONG MAR 1986, vol. 2, no. 1, March 1986 (1986-03-01), pages 81 - 90 *

Also Published As

Publication number Publication date
US20050091915A1 (en) 2005-05-05
DE10163244A1 (de) 2003-07-10
BR0215153A (pt) 2004-10-19
CA2471413A1 (fr) 2003-07-03
EP1458951A1 (fr) 2004-09-22

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