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EP0332002B1 - Utilisation de copolymères sélectionnés d'esters d'acides acryliques ou/et méthacryliques, comme agents modifiant l'écoulement dans des pétroles et fractions (II) de pétroles riches en paraffine - Google Patents

Utilisation de copolymères sélectionnés d'esters d'acides acryliques ou/et méthacryliques, comme agents modifiant l'écoulement dans des pétroles et fractions (II) de pétroles riches en paraffine Download PDF

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Publication number
EP0332002B1
EP0332002B1 EP89103385A EP89103385A EP0332002B1 EP 0332002 B1 EP0332002 B1 EP 0332002B1 EP 89103385 A EP89103385 A EP 89103385A EP 89103385 A EP89103385 A EP 89103385A EP 0332002 B1 EP0332002 B1 EP 0332002B1
Authority
EP
European Patent Office
Prior art keywords
weight
copolymers
methacrylic acid
flow
alcohol
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.)
Expired - Lifetime
Application number
EP89103385A
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German (de)
English (en)
Other versions
EP0332002A3 (en
EP0332002A2 (fr
EP0332002B2 (fr
Inventor
Wolfgang Dr. Ritter
Claudia Meyer
Wolfgang Zöllner
Claus-Peter Dr. Herold
Stephan Dr. Von Tapavicza
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Henkel AG and Co KGaA
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0332002A2 publication Critical patent/EP0332002A2/fr
Publication of EP0332002A3 publication Critical patent/EP0332002A3/de
Publication of EP0332002B1 publication Critical patent/EP0332002B1/fr
Application granted granted Critical
Publication of EP0332002B2 publication Critical patent/EP0332002B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/927—Well cleaning fluid
    • Y10S507/929—Cleaning organic contaminant
    • Y10S507/93—Organic contaminant is asphaltic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/927—Well cleaning fluid
    • Y10S507/929—Cleaning organic contaminant
    • Y10S507/931—Organic contaminant is paraffinic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y10T137/0391—Affecting flow by the addition of material or energy

Definitions

  • auxiliaries which are also referred to as paraffin inhibitors and are generally prepared by polymerizing olefinically unsaturated compounds which contain at least partially unbranched, saturated hydrocarbon chains with at least 18 carbon atoms.
  • DE-A-2 264 328 describes the use of copolymers of acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts with at least 16 carbon atoms in the alcohol residue as additives for crude oils and petroleum fractions to reduce their flow properties.
  • the copolymers of DE-A-2 264 328 obviously do not contain any free acrylic acid or methacrylic acid.
  • Example 1 of DE-A-2 264 328 expressly uses equimolar amounts of alcohol and acrylic acid.
  • DE-PS 30 31 900 describes copolymers of n-alkyl acrylates with at least 16 carbon atoms in the alcohol residue and maleic anhydride with molar ratios of n-alkyl acrylate to maleic anhydride from 20 1 to 1:10. Compounds of this type are said to be used as crystallization inhibitors for crude oils containing paraffin. Examples shown numerically relate to the use of corresponding copolymers in the molar ratio of the acrylic acid ester to maleic anhydride in the range from 1: 1 to 8: 1. Crude oils with intrinsic pour points below 20 ° C. are predominantly used.
  • a table of values deals with India crude oil, which is known to be a particularly paraffin-rich starting material (disruptive paraffin content 15%) and has an intrinsic pour point of 33 ° C.
  • the optimum effectiveness of the copolymers used in this publication with regard to lowering the pour point on this starting material is at the molar ratio of acrylic acid ester / maleic anhydride of 4: 1.
  • the lowest pour points set here are at 12 ° C. If the proportion of maleic anhydride in the copolymer is further reduced, then the pour points of the India crude oil thus added rise again with the addition of the same amount (cf. in particular Table 2 of the cited literature reference).
  • the teaching of the present invention is based on the knowledge that a particularly effective lowering of the hardening temperatures - determined according to the known methods of pour point and / or pour point determination - as well as an effective improvement in the flow behavior also can be obtained just in the temperature range just above the lowered pour points if the copolymer types described below in detail from acrylic and / or methacrylic acid esters of higher alcohols and free acrylic acid and / or methacrylic acid are used in limited amounts as comonomers for the purpose of lowering the pour point.
  • the invention accordingly relates to the use of copolymers of acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts with at least 16 carbon atoms in the alcohol residue and 0.5 to 15% by weight% of free acrylic acid and / or methacrylic acid as additive for paraffins as well as crude oils and petroleum fractions containing asphaltenes to lower their pour point or solidification point and to improve the flow properties, particularly in the temperature range just above the solidification point.
  • copolymers of the type mentioned contain, together with the acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts, 0.5 to 15% by weight of the free acids mentioned, copolymers of the type mentioned having free acid contents in the range of about 1 up to 10% by weight may be particularly suitable.
  • the most important copolymers of the type used according to the invention contain acrylic acid and / or methacrylic acid as comonomers in the copolymers shown above in amounts of about 1.5 to 5.0% by weight. All these percentages by weight relate in each case to the copolymer weight.
  • the additives of the invention which lower the pour point and improve the flow properties of the treated oils or oil fractions can very advantageously be used in general for crude oils or petroleum fractions of any origin. Especially helpful is their use in the above-described problem cases, the paraffin-rich crude oils and / or petroleum fractions with self-pour points above 20 ° C and especially above 25 0 C.
  • the F thoroughlyticiansverticianer invention in only limited quantities, it is possible, even with these feeds, the pour points to values below 15 ° C and preferably to values below 10 0 C lower. This is possible even if the starting or self-pouring points of the oils or oil fractions are at 30 0 C or above.
  • the weight percentages given here relate to the content of C 22 alcohol - and possibly higher alcohols - in the alcohol mixture used for the preparation of the acrylate components.
  • the application concentration of the pour point improvers according to the invention is in the conventional range and is, for example, 20 to 1000 ppm, with amounts in the range from 100 to 500 ppm being preferred.
  • the pour point improvers are expediently used in suitable solvents. Details on this and the preparation of the copolymers can be found in the relevant prior art, for example in DE-PS 30 31 900 already cited.
  • the alcohols or alcohol cuts used for the production of the acrylate components can be of native or synthetic origin. Alcohol cuts with a predominant proportion of components with at least 22 C atoms, but at the same time also minor amounts of alcohol components in the range C 16 to C 20 , are the preferred starting materials.
  • the two acrylate ester mixtures A and B are used, which differ in the C chain distribution of the fatty alcohol mixture used for the acrylic acid esterification.
  • the two types of acrylate are characterized as follows:
  • the monomers, initiator and solvent are weighed into a three-necked flask.
  • the batch is evacuated for 10 ⁇ 1 min and the vacuum is released again with 99.999% nitrogen.
  • the batch is heated to 90 ° C. and kept at this temperature.
  • the entire reaction is carried out under inert conditions.
  • the start of the reaction manifests itself in a temperature rise to 93 to 96 ° C.
  • the mixture is kept at 90 ° C ⁇ 1 ° C for 3 h. After this time, the mixture is cooled to room temperature within 45 minutes and the product is filled.
  • Toluene is used as the solvent here and in the subsequent feed process.
  • the polymerization initiator used is dibenzoyl peroxide or azoisobutyronitrile as indicated below.
  • the mixing ratio of solvent to monomer mixture is 1: 1 (parts by weight).
  • the monomers are dissolved in toluene in the desired mixing ratio at 45 to 50 ° C. and the solution is then cooled to 25 ° C.
  • the initiator is also used in solution in toluene. About 20% of the monomer solution determined per batch is placed in a reactor. The reactor is flushed three times with nitrogen and heated to 90 ° C. with a gentle stream of N 2 with stirring. The initiator solution is now metered in so that the total metering time is 2.5 hours.
  • a temperature increase occurs 20 minutes after the initiator has been added.
  • the temperature is kept at 90 ⁇ 3 ° C by cooling the reactor jacket.
  • the remaining monomer solution is metered into the reactor in such a way that the total metering time is 2 h.
  • the temperature is kept at 90 ⁇ 3 ° C throughout the reaction time.
  • the reaction mixture is then kept at the same temperature for a further 60 min.
  • the reaction product is then cooled and filled at 30 ° C.
  • Examples 1 to 12 according to the invention are summarized in Table 2 below.
  • the type of acrylate monomers A or B used is assigned to the respective example and the percentage (% by weight) of acrylic acid in the monomer mixture for the preparation of the pour point depressant is given.
  • the flow improver was produced by the batch process and in examples 2 to 12 by the feed process.
  • Table 2 finally shows the specific viscosity of the copolymer solutions prepared in each case.
  • the viscosity is measured using an Ubbelohde viscometer, capillary I, ⁇ 0.63 mm.
  • the measured toluene solutions are 3% solutions in toluene. The measurement is carried out at 20 ° C after a temperature adjustment of 10 min.
  • Table 2 contains the pour point values which were obtained when the pour point improvers according to the invention were added to an India crude (Bombay crude oil) in accordance with the following working instructions.
  • the pour point was determined in accordance with ASTM D 97-66 and DIN 51597 as follows:
  • the pour point of the untreated Bombay crude oil is 30 ° C according to this determination method.
  • the yield point for the material according to the invention was 99 N. m- 2 and for the branded product 1990 N ⁇ m- 2 .
  • the technical advantage of the flow improver according to the invention can be seen from this.
  • the pump pressure that has to be applied to start up a pipeline filled with cooled crude oil is 48 times after 2 hours and still 20 times after working according to the teaching of the invention in the market product which has also been tested.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Polymerisation Methods In General (AREA)

Claims (6)

1. Utilisation de copolymères à base d'esters d'acide acrylique et/ou d'acides méthacryliques et d'alcools supérieurs ou de coupes d'alcools ayant au moins 16 atomes de C dans le radical alcool et de 0,5 à 15 % en, poids - rapporté au poids de copolymère - en acide acrylique libre et/ou acide méthacrylique en tant qu'agent d'addition pour des huiles brutes ou des fractions pétrolières contenant des paraffines et/ou de l'asphaltine, en vue de l'abaissement de leur point de solidification ou d'écoulement et de l'amélioration des propriétés d'écoulement, en particulier dans une zone de températures un peu au-dessus du point de solidification.
2. Utilisation selon la revendication 1, caractérisée en ce que les copolymères du type indiqué avec des teneurs en acides libres dans la zone d'environ 1 à 10 % en poids, de préférence dans la zone de 1,5 à 5 % en poids, rapporté au poids de copolymère, sont utilisés.
3. Utilisation selon les revendications 1 et 2, caractérisée en ce que les agents améliorant l'écoulement dans des huiles ou des fractions d'huile riches en paraffines avec des points d'écoulement particuliers au-dessus de 20 °C, en particulier au-dessus de 25 °C entrent en action et en ce que de préférence avec cela les points d'écoulement sont abaissés à des valeurs en-desous de 15 °C, en particulier en-dessous de 10 °C.
4. Utilisation selon les revendications 1 à 3, caractérisée en ce que des copolymères à base d'esters d'alcools ou de coupes d'alcools ayant principalement 18 à 24 atomes de Carbone sont utilisés, dans lesquels les coupes d'alcool correspondantes sont de préférence des coupes dont la teneur en alcool en C22 et supérieurs, constitue au moins environ 25 % en poids, de préférence au moins environ 35 % en poids et en particulier au moins environ 45 % en poids.
5. Utilisation selon les revendications 1 à 4, caractérisée en ce que l'on met en oeuvre des copolymères à base d'esters d'acide acrylique avec des alcools ou des coupes d'alcools supérieurs du type mentionné et d'acide acrylique libre.
6. Utilisation selon les revendications 1 à 5, caractérisée en ce que l'on met en oeuvre les agents qui améliorent l'écoulement en quantités qui vont d'environ 20 à 1000 ppm et pour cela de préférence dissout dans des solvants.
EP89103385A 1988-03-07 1989-02-27 Utilisation de copolymères sélectionnés d'esters d'acides acryliques ou/et méthacryliques, comme agents modifiant l'écoulement dans des pétroles et fractions (II) de pétroles riches en paraffine Expired - Lifetime EP0332002B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3807395A DE3807395A1 (de) 1988-03-07 1988-03-07 Verwendung ausgewaehlter copolymertypen der acryl- und/oder methacrylsaeureester als fliessverbesserer in paraffinreichen erdoelen und erdoelfraktionen (ii)
DE3807395 1988-03-07

Publications (4)

Publication Number Publication Date
EP0332002A2 EP0332002A2 (fr) 1989-09-13
EP0332002A3 EP0332002A3 (en) 1990-03-28
EP0332002B1 true EP0332002B1 (fr) 1992-04-15
EP0332002B2 EP0332002B2 (fr) 1997-05-02

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ID=6349042

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EP89103385A Expired - Lifetime EP0332002B2 (fr) 1988-03-07 1989-02-27 Utilisation de copolymères sélectionnés d'esters d'acides acryliques ou/et méthacryliques, comme agents modifiant l'écoulement dans des pétroles et fractions (II) de pétroles riches en paraffine

Country Status (11)

Country Link
US (1) US5039432A (fr)
EP (1) EP0332002B2 (fr)
JP (1) JPH01287393A (fr)
AU (1) AU611265B2 (fr)
BR (1) BR8901034A (fr)
CA (1) CA1327538C (fr)
DE (2) DE3807395A1 (fr)
DK (1) DK110789A (fr)
MX (1) MX171036B (fr)
NO (1) NO176413C (fr)
TR (1) TR24478A (fr)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3830913A1 (de) * 1988-09-10 1990-03-15 Henkel Kgaa Neue waessrige emulsionscopolymerisate, insbesondere in wasser- und oel-verduennbarer form zur verbesserung der fliesseigenschaften und stockpunktserniedrigung von erdoelen und erdoelfraktionen sowie ihre verwendung
US5281329A (en) * 1989-07-14 1994-01-25 Rohm Gmbh Method for improving the pour point of petroleum oils
DE4040317A1 (de) * 1990-12-17 1992-06-25 Henkel Kgaa Mischungen von fettsaeureniedrigalkylestern mit verbesserter kaeltestabilitaet
EP0523672B1 (fr) * 1991-07-18 1996-10-09 Hoechst Aktiengesellschaft Copolymères d'esters d'acides carboxyliques éthyléniquement insaturés et de polyalkylenether d'alcools inférieurs insaturés comme agents modifiant l'écoulement de pétroles contenant de la paraffine
US5759962A (en) * 1992-01-31 1998-06-02 Institut Francais Du Petrole Method for inhibiting reactive argillaceous formations and use thereof in a drilling fluid
AT404137B (de) * 1994-04-08 1998-08-25 Bundesanstalt Fuer Landtechnik Verfahren zur trennung von fettsäureestergemischen
US5663127A (en) * 1994-07-29 1997-09-02 Minnesota Mining And Manufacturing Company Perfluoropolyether lubricating compositions
GB9702238D0 (en) * 1997-02-04 1997-03-26 Bp Chem Int Ltd Compositions
FR2772375B1 (fr) * 1997-12-15 2000-01-14 Atochem Elf Sa Procede de conditionnement d'acrylates d'alkyle a longue chaine
US6313367B1 (en) 1999-02-22 2001-11-06 Baker Hughes Incorporated Inhibition of asphaltene deposition in crude oil production systems
US6403149B1 (en) 2001-04-24 2002-06-11 3M Innovative Properties Company Fluorinated ketones as lubricant deposition solvents for magnetic media applications
US20040058827A1 (en) * 2002-09-24 2004-03-25 Baker Hughes Incorporated Paraffin inhibitor compositions and their use in oil and gas production
US20050049327A1 (en) * 2003-09-02 2005-03-03 Vladimir Jovancicevic Drag reducing agents for multiphase flow
US7541315B2 (en) * 2003-09-11 2009-06-02 Baker Hughes Incorporated Paraffin inhibitor compositions and their use in oil and gas production
US20070284110A1 (en) * 2006-06-08 2007-12-13 Harris William F Downhole flow improvement
US9784414B2 (en) 2006-12-22 2017-10-10 Liquidpower Specialty Products, Inc. Drag reduction of asphaltenic crude oils
US9676878B2 (en) 2011-08-12 2017-06-13 Liquidpower Specialty Products Inc. Monomer selection to prepare ultra high molecular weight drag reducer polymer
WO2009047786A2 (fr) * 2007-06-18 2009-04-16 Dai-Ichi Karkaria Limited Composition polymère permettant d'abaisser le point d'écoulement
US20140093641A1 (en) 2011-03-03 2014-04-03 3Mm Innovative Properties Company Lubricant compositions containing fluorooxiranes
FR2982871A1 (fr) * 2011-11-22 2013-05-24 Univ Sud Toulon Var Polymeres de poly(acrylate de n-alkyle)s et leur utilisation comme abaisseurs de point d'ecoulement de petrole
US10280714B2 (en) 2015-11-19 2019-05-07 Ecolab Usa Inc. Solid chemicals injection system for oil field applications
CA3015143C (fr) 2016-03-10 2023-10-03 Basf Se Dispersions aqueuses de polymeres, procede pour leur preparation et utilisation correspondante comme agents abaissant le point d'ecoulement pour le petrole brut, le petrole et les produits petroliers
US10717918B2 (en) 2017-05-23 2020-07-21 Ecolab Usa Inc. Injection system for controlled delivery of solid oil field chemicals
EP3630341A1 (fr) 2017-05-23 2020-04-08 Ecolab USA, Inc. Patin de dilution et système d'injection pour produits chimiques solides/liquides à viscosité élevée
SG11202002161XA (en) 2017-09-11 2020-04-29 Basf Corp Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products
GB202006908D0 (en) * 2020-05-11 2020-06-24 Croda Int Plc Paraffin inhibitor composition, method and use

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL103681C (fr) * 1959-05-28
US3926579A (en) * 1968-09-16 1975-12-16 Exxon Research Engineering Co Petroleum crude oils containing polymers comprised of c' 18'+14 c' 40 'alpha-olefins have reduced tendency to deposit wax
GB1285087A (en) * 1969-12-18 1972-08-09 Shell Int Research Oil compositions
US3654994A (en) * 1970-08-06 1972-04-11 Calgon Corp Friction reducing in flowing hydrocarbon fluids
US3669189A (en) * 1970-10-28 1972-06-13 Union Oil Co Method for inhibiting the deposition of wax from a wax-containing oil
US3957659A (en) * 1971-03-05 1976-05-18 Shell Oil Company Crude oil compositions having improved low temperature flow properties
US3758406A (en) * 1971-10-22 1973-09-11 Halliburton Co Flow of hydrocarbon liquids methods and compositions for reducing frictional pressure loss in the
US3748266A (en) * 1971-11-01 1973-07-24 Halliburton Co Methods and compositions for reducing frictional pressure loss in theflow of hydrocarbon liquids
US3735770A (en) * 1972-02-09 1973-05-29 Gulf Research Development Co Method for increasing the mobility of waxy crude oils
US3904385A (en) * 1972-05-08 1975-09-09 Texaco Inc Polyacrylates and waxy residual fuel compositions thereof
US3854893A (en) * 1972-06-14 1974-12-17 Exxon Research Engineering Co Long side chain polymeric flow improvers for waxy hydrocarbon oils
US3853497A (en) * 1972-11-08 1974-12-10 Texaco Inc Low pour vacuum gas oil compositions
US4045360A (en) * 1975-09-22 1977-08-30 Union Oil Company Of California Inhibiting wax deposition from a wax-containing oil
US4068676A (en) * 1976-01-26 1978-01-17 Halliburton Company Method for dissolving polymeric materials in hydrocarbon liquids
US4110283A (en) * 1977-05-10 1978-08-29 Chemische Fabriek Servo B.V. Crystallization inhibitor for paraffin
DE3031900C2 (de) * 1980-08-23 1983-06-09 Chemische Fabriek Servo B.V., 7491 Delden Mischpolymerisate aus n-Alkylacrylaten und Maleinsäureanhydrid und ihre Verwendung als Kristallisationsinhibitoren für paraffinhaltige Rohöle
DE3537769A1 (de) * 1985-10-24 1987-04-30 Basf Ag Verwendung von estern von 1-alken-acrylsaeure-copolymerisaten bzw. von 1-alken-methacrylsaeure-copolymerisaten zur verbesserung der fliesseigenschaften von erdoelen
US4983186A (en) * 1989-07-18 1991-01-08 Petrolite Corporation Methods and compositions for reduction of drag in hydrocarbon fluids

Also Published As

Publication number Publication date
MX171036B (es) 1993-09-27
DE3807395A1 (de) 1989-09-21
BR8901034A (pt) 1989-10-24
EP0332002A3 (en) 1990-03-28
NO890938D0 (no) 1989-03-06
NO176413B (no) 1994-12-19
NO176413C (no) 1995-03-29
CA1327538C (fr) 1994-03-08
NO890938L (no) 1989-09-08
JPH01287393A (ja) 1989-11-20
AU611265B2 (en) 1991-06-06
TR24478A (tr) 1991-10-11
DK110789D0 (da) 1989-03-07
EP0332002A2 (fr) 1989-09-13
EP0332002B2 (fr) 1997-05-02
DE58901132D1 (de) 1992-05-21
DK110789A (da) 1989-09-08
AU3102589A (en) 1989-09-07
US5039432A (en) 1991-08-13

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