EP0084411B1 - Composition et méthode pour l'élimination d'une huile hydrocarbonique des surfaces dures - Google Patents

Composition et méthode pour l'élimination d'une huile hydrocarbonique des surfaces dures Download PDF

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Publication number
EP0084411B1
EP0084411B1 EP83300048A EP83300048A EP0084411B1 EP 0084411 B1 EP0084411 B1 EP 0084411B1 EP 83300048 A EP83300048 A EP 83300048A EP 83300048 A EP83300048 A EP 83300048A EP 0084411 B1 EP0084411 B1 EP 0084411B1
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EP
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Prior art keywords
oil
carbon atoms
foregoing
water
cuttings
Prior art date
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Expired
Application number
EP83300048A
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German (de)
English (en)
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EP0084411A1 (fr
Inventor
Michael Blezard
William H. Mcallister
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Solvay Solutions UK Ltd
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Albright and Wilson Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/068—Arrangements for treating drilling fluids outside the borehole using chemical treatment
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
    • E21B41/005—Waste disposal systems

Definitions

  • the present invention relates to methods of cleaning oil/rock mixtures in oil drilling operations and especially to cleaning of drilling oil from rock cuttings on offshore drilling rigs, removal of oil from the face of newly drilled holes prior to reinforcement with casing, and to the cleaning of oil muds from drilling rigs.
  • drilling fluid or drilling mud In the process of drilling for oil and gas, it is necessary for a number of reasons, to use a drilling fluid or drilling mud.
  • the types of drilling fluid or mud in common use are:
  • Oil based drilling media (b) may also contain water in the form of water in oil emulsion. It is customary in the art to refer to a drilling medium containing up to about 15% aqueous phase by volume as oil based. Those drilling media referred to as invert fluids or muds, (c) generally contain between 15% and 55% water. This patent application is particularly concerned with types (b and c) both of which are included in the term "oil” as used herein, together with crude and refined mineral oils.
  • drilling fluid One of the functions of drilling fluid is to carry drill cuttings from the drill bit to the surface, the cuttings are then removed by physical techniques, for example, by using shale shakers, screens, cyclones, and centrifuges. After removal of the cuttings the drilling fluid is re-used and the cuttings are disposed of. If the drilling is offshore then the cuttings are disposed of into the sea, where in the case of aqueous drilling fluids the cuttings disperse and settle without causing significant problems. However, in the case of oil drilling fluids the cuttings are oil wet and settle rapidly to the sea bed below the drilling rig and form an oily, sticky mass, which can interfere with drilling operations, for example, by hindering the movement of divers involved in sub-sea construction and maintenance work. It is thought that the swelling of clays in the cuttings is responsible for the formation of this mass. In addition, the cuttings cause oil pollution through gradual release of the oil.
  • One technique to remove oil from cuttings is to wash the cuttings with a solvent such as diesel, this has the effect of removing most of the oil but still leaves the surfaces contaminated with hydrocarbons, which can gradually be released to the environment.
  • Another way is to use a water miscible solvent, such as a glycol ether, but these are expensive.
  • Yet another way is to wash the cuttings in sea water using good agitation to dislodge the oil from the surface of the cuttings. This process can be used either as the sole process for removing the drilling oil from the cuttings, or as a second step to remove an oil solvent from cuttings previously washed with a hydrocarbon. This process can be improved by adding a surfactant to the sea water, to lower the oil/water interfacial tension.
  • the cuttings may then be discharged to the sea where they disperse and settle over a wide area of sea bed rather than accumulate directly in the area of the drilling operations.
  • the oil in water emulsion which is formed as a result of washing the cuttings may be discharged to the sea where fine dispersion of the oil will facilitate its breakdown by micro-organisms.
  • a commonly used surfactant for the foregoing purposes is a C9-11 alcohol six mole ethoxylate.
  • alkoxylated non-ionic surfactants are known in the detergent art which are sometimes used as ingredients of detergent or shampoo formulations for various purposes, usually in admixture with anionic or cationic surfactants.
  • Another category of known surfactant comprises the alkyl alkanolamides. These are not normally used as cleaning agents in their own right, but are widely used as minor ingredients of detergent and shampoo formulations to promote foaming.
  • An object of the present invention is to provide more effective methods of cleaning oil from rock cuttings.
  • An object of the present invention is to provide more effective methods of cleaning oil from rock cuttings.
  • a further object of our invention is to provide a method whereby oil can be separated from the emulsion resulting from cleaning of the cuttings.
  • our invention provides a method of removing oil from solid surfaces which comprises contacting the surfaces with an aqueous solution containing at least 0.5% by weight of a mixture of (A) from 5 to 95% by weight of at least one alkoxylated alcohol, carboxylic acid, alkylphenol, or nonionic phosphate ester, having in each case at least one alkyl group with from 6 to 22 carbon atoms and from 1 to 20 ethyleneoxy groups, with (B) from 95 to 5% by weight of at least one alkanolamide of the formula: wherein R is an alkyl group, having from 5 to 17 carbon atoms and x and y are each chosen from 0 and integers from 1 to 12, such that the average value of (x+y) is from 1 to 12.
  • (A) is primary straight or branched chain alcohol having from 6 to 18 carbon atoms and alkoxylated with from 1 to 10 ethylene-oxy groups.
  • a mixture of (A) and (B) is supplied as a concentrate which is dissolved in, or diluted with, water to provide the cleansing solution at the site of the rig.
  • Such concentrates optionally contain a solvent such as water or a water miscible alcohol, glycol or glycol ether, e.g. isopropanol, ethylene glycol, propylene glycol, polyethylene glycol, or any other mono-, di- or trihydroxy alcohol, or alcohol ether, having from 2 to 8 carbon atoms, as required to provide a fluid, pourable composition under the conditions likely to be encountered.
  • the concentrate may, additionally, contain minor proportions of hydrotropes, such as alkaline earth, sodium or potassium mono- di- or tri-alkyl benzene sulphonate salts having less than six aliphatic carbon atoms, e.g. toluene or xylene sulphonates, phosphate esters salts, preservatives, such as formalin, dyes and/or perfumes.
  • Water may be present in any convenient proportion between zero and the final working concentration of the cleaner. Generally, the lower the proportion of the water the greater the convenience for transport and storage of the concentrate. These considerations however must be balanced against the preference for a stable, pourable composition.
  • Organic solvents can add appreciably to the cost of the composition and are preferably, therefore used sparingly e.g. less than 50% and preferably less than 20% of the weight of the concentrate.
  • the concentrate may typically contain from 5 to 95% by weight of (A) and from 95 to 5% by weight of (B).
  • (A) is present in concentrations greater than 10% by weight, most preferably greater than 20% and usually greater than 30%.
  • (B) is also preferably present in concentrations of greater than 10% by weight, more preferably greater than 20% and usually greater than 30%.
  • each of A and B should be present in proportions of greater than 20% by weight, e.g. 20-60% together, optionally with up to 10% water and up to 10% of water miscible, hydroxyl containing solvent.
  • a suitable mixture contains from 40% to 60% of (A), from 60% to 40% of (B) and from 0 to 20% of solvent.
  • the concentrate is dissolved or dispersed in water at the site of application.
  • the concentrate When used at offshore locations, the concentrate may conveniently be dissolved or dispersed in sea water.
  • the concentrate is diluted to from 0.5% to 10% active matter by weight preferably from 1 to 6. We do not exclude higher concentrations, but they are unlikely to prove cost effective.
  • the component (A) in our concentrate may conveniently be an ethoxylated alcohol having from 8 to 14 carbon atoms and from 2 to 7 ethylene oxide groups.
  • the cuttings When used to clean rock cuttings, the cuttings are preferably agitated with the solution of the concentrate in water or brine, for a sufficient time to emulsify a substantial proportion of the oil.
  • the emulsion may then be separated from the cuttings which, when sufficiently clean, are dumped.
  • the emulsion may be discharged.
  • the oil is recovered from the emulsion by moderate heating. Typically temperatures in excess of 40°C e.g. 50 to 70°C are sufficient to break the emulsion and permit recovery of the separated oil phase.
  • the cleaning solution according to our invention may also be injected into bore holes to clean oil from the sides of the rock. This is necessary when a casing is to be bonded with cement to the sides of the bore hole.
  • the solution may also be used according to our invention to clean oil mud from the rigs themselves and generally to remove viscous hydrocarbon oils from hard surfaces.
  • A C9/C11 primary alcohol nominal 6 mole ethoxylate.
  • B coconut monoethanolamide+2 mole ethylene oxide.
  • A C10/C12 primary alcohol nominal 5 mole ethoxylate.
  • A C8 /C10 primary alcohol nominal 4 mole ethoxylate.
  • A nonyl phenol nominal 9 mole ethoxylate.
  • A oleic acid nominal 8 mole ethoxylate.
  • A mixture of mono and di- C8/C10 alkyl phosphate nominal 5.4 mole ethoxylate.
  • step c) The emulsion decanted in step c) and obtained using A (3.75%)+B (1.25%) was heated to 40°C and separated into distinct oil and aqueous phases.
  • a concentrate was prepared for use according to the invention consisting of 45% by weight of C10/C12 fatty alcohol 5 mole ethoxylate, 45% by weight coconut diethanolamide, 5% by weight propylene glycol, 5% by weight water.
  • the product was fluid and stable at temperatures between -5°C and 35°C and readily dispersed in sea water. When evaluated in the above cuttings cleaning test the results were as follows.
  • A C9/C11 primary alcohol nominal 6 mole ethoxylate. This is the surfactant most commonly used for cleaning oil mud cuttings.
  • step c) of the method and obtained using the formulation of Example 7 was heated to 50°C and separated into distinct oil and aqueous phases.
  • test solution used contained 7.5% of a C10/C12 fatty alcohol 5 mole ethoxylate, 7.5% coconut diethanolamide and 85% water.
  • the oil was substantially removed from the surface of the mild steel leaving a clean non-oily surface.
  • test solution was a commercial hydrocarbon solvent based degreaser believed to contain emulsifiers.
  • the mild steel was less thoroughly cleaned and the surface was oily.
  • A C9/C11 primary alcohol nominal 6 mole ethoxylate.
  • surfactant A is the same as A in Example 1.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • Mining & Mineral Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Detergent Compositions (AREA)
  • Earth Drilling (AREA)

Claims (21)

1. Un procédé pour l'élimination d'une huile des surfaces solides, caractérisé en ce que l'on met les surfaces en contact avec une solution aqueuse contenant au moins 0,5% en poids d'un mélange (A) de 5 à 95% en poids d'au moins un alcool, un acide carboxylique, un alkylphénol ou un ester phosphorique non ionique alcoxylé, comportant dans chaque cas un groupe alkyle ou alcényle avec 6 à 22 atomes de carbone et 1 à 20 groupes oxyde d'éthylène, avec (B) 95 à 5% en poids d'au moins un éthylolamide de formule:
Figure imgb0015
dans laquelle R est un groupe alkyle ayant 5 à 17 atomes de carbone et x et y sont choisis chacun parmi 0 et les nombres entiers de 1 à 12 de façon que la valeur moyenne (x+y) se situe entre 1 et 12.
2. Un procédé selon la revendication 1, dans lequel (A) est un alcool primaire à chaîne droite ou ramifiée ayant 6 à 18 atomes de carbone, éthoxylé avec 1 à 10 groupes oxyde d'éthylène.
3. Un procédé selon la revendication 1, dans lequel (A) est un acide alcanoïque ou alcenoïque à chaîne normale ou ramifiée possédant 8 à 20 atomes de carbone, alcoxylé avec 1 à 10 groupes oxyde d'éthylène.
4. Un procédé selon la revendication 1, dans lequel (A) est un alkylphénol à chaîne droite ou ramifiée possédant 6 à 12 atomes de carbone aliphatique, alcoxylé avec 1 à 12 groupes oxyde d'éthylène.
5. Un procédé selon la revendication 1, dans lequel (A) est un ester d'acide phosphorique non ionique comportant au moins un groupe alkyle à chaîne droite ou ramifiée de 6 à 22 atomes de carbone et au moins un groupe alcoxy ou un groupe polyalcoxy possédant jusqu'à 20 unités d'oxyde d'éthylène.
6. Un procédé selon l'une quelconque des revendications précédentes, dans lequel (B) comporte 1 à 4 groupes oxyde d'éthylène.
7. Un procédé selon la revendication 6, dans lequel (B) est un alkyl monoéthanolamide.
8. Un procédé selon la revendication 6, dans lequel (B) est un alkyl diéthanolamide.
9. Un procédé selon l'une quelconque des revendications précédentes, dans lequel (A) et (B) sont présents chacun dans une proportion supérieure à 20% en poids actif total du mélange.
10. Un procédé selon l'une quelconque des revendications précédentes, dans lequel la solution aqueuse est de l'eau de mer.
11. Un procédé selon l'une quelconque des revendications précédentes, dans lequel le mélange est présent dans la solution aqueuse à une concentration de 0,5% à 10%.
12. Un procédé selon l'une quelconque des revendications précédentes, destiné au lavage des débris des installations de forage du pétrole.
13. Un procédé selon l'une quelconque des revendications précédentes, destiné au lavage des structures.
14. Un procédé selon la revendication 13, destiné au nettoyage des surfaces des installations de forage.
15. Un procédé selon l'une quelconque des revendications précédentes, dans lequel la solution aqueuse est récupérée après lavage et est suffisamment chauffée pour provoquer une séparation de l'huile qui y est émulsionnée.
16. Un concentré destiné à la préparation de solutions aqueuses pour utilisation selon le procédé de l'une quelconque des revendications précédentes, comportant essentiellement 20% à 60% en poids de (A), 20% à 60% en poids de (B), jusqu'à 10% en poids d'eau et jusqu'à 10% en poids d'un solvant organique hydroxylé miscible à l'eau.
17. Un concentré selon la revendication 16, dans lequel (A) est un alcool éthoxylé possédant 8 à 14 atomes de carbone et 2 à 7 groupes oxyde d'éthylène.
18. Un concentré selon l'une ou l'autre des revendications 16 et 17, dans lequel (B) est un alkyl diéthanolamide.
19. Un concentré selon l'une quelconque des revendications 16 à 18, dans lequel le solvant est un mono-, di- ou trialcool miscible à l'eau ou un alcool éther comptant 2 à 8 atomes de carbone.
20. Solutions aqueuses destinées au procédé de l'une quelconque des revendications 1 à 15, obtenues par dilution d'un concentré selon l'une des revendications 16 à 19 avec de l'eau et qu'elles contiennent au moins 0,5% de matière tensioactive.
21. Eau de mer destinée au procédé de l'une quelconque des revendications 1 à 15, ayant dissous un concentré selon l'une quelconque des revendications 16 à 19 et quelle contient au moins 0,5% de matière tensio-active.
EP83300048A 1982-01-07 1983-01-06 Composition et méthode pour l'élimination d'une huile hydrocarbonique des surfaces dures Expired EP0084411B1 (fr)

Applications Claiming Priority (2)

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GB8200376 1982-01-07
GB8200376 1982-01-07

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EP0084411A1 EP0084411A1 (fr) 1983-07-27
EP0084411B1 true EP0084411B1 (fr) 1985-09-04

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EP (1) EP0084411B1 (fr)
CA (1) CA1203450A (fr)
DE (1) DE3360678D1 (fr)
DK (1) DK3483A (fr)
ES (1) ES8405878A1 (fr)
GB (1) GB2116579B (fr)
GR (1) GR77136B (fr)
IE (1) IE53660B1 (fr)
IN (1) IN158886B (fr)
NO (1) NO830032L (fr)
PH (1) PH19657A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0103779A2 (fr) * 1982-09-20 1984-03-28 John E. Oliver Elimination de dépôts dans des fluides et des systèmes de puits de pétrole
US5326407A (en) * 1992-03-26 1994-07-05 Institut Francais Du Petrole Process for washing solid particles comprising a sophoroside solution
US5501816A (en) * 1994-07-12 1996-03-26 Basf Corporation Aqueous based solvent free degreaser composition
WO2004050790A1 (fr) * 2002-12-02 2004-06-17 Marquis Fluids Inc. Fluide de forage polymere emulsifie et procedes de preparation et d'utilisation de ce dernier
US7192527B2 (en) 2004-08-10 2007-03-20 Halliburton Energy Services, Inc. Processes for removing oil from solid wellbore materials and produced water
US7229952B2 (en) 2002-12-19 2007-06-12 Halliburton Energy Services, Inc. Additive packages for removing oil from solid materials recovered from a well bore

Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
US2480613A (en) * 1944-11-09 1949-08-30 Vernon O Sipe Building wall of angular tile
DE4023334A1 (de) * 1990-07-23 1992-01-30 Henkel Kgaa Fluessiges, giess- und pumpfaehiges tensidkonzentrat
SE468855B (sv) * 1990-08-09 1993-03-29 Eriksson Tord Utveckling Foerfarande foer rengoering och avfettning, komposition avsedd som foerblandning samt vatten- och elektrolythaltig mikroemulsion
SE500534C2 (sv) * 1990-11-12 1994-07-11 Eriksson Tord Utveckling Förfarande för rengöring och avfettning
GB9623823D0 (en) * 1996-11-16 1997-01-08 Reckitt & Colmann Prod Ltd Improvements in or relating to organic compositions
US7951755B2 (en) 2002-12-02 2011-05-31 An-Ming Wu Emulsified polymer drilling fluid and methods of preparation
WO2006010375A1 (fr) * 2004-07-27 2006-02-02 Rhodia Chimie Formulation de degraissage de metal comprenant un agent desemulsionnant, utilisation de cet agent et procede de degraissage de metal

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0018630A1 (fr) * 1979-05-07 1980-11-12 Henkel Kommanditgesellschaft auf Aktien Agent de lavage pour textiles

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NL168553C (nl) * 1951-04-02 Takeda Chemical Industries Ltd Werkwijze voor het langs microbiologische weg bereiden van citroenzuur.
AT179693B (de) * 1951-04-02 1954-09-25 Metallgesellschaft Ag Saure Emulsionsreiniger zum Beizen und Entfetten von Metallen
US2831814A (en) * 1951-12-19 1958-04-22 Poor & Co Acid pickling of metals and compositions therefor
GB1213792A (en) * 1966-11-30 1970-11-25 Diversey Ltd Inhibition of corrosion of metallic surfaces
SE400575B (sv) * 1974-12-13 1978-04-03 Nordnero Ab Bad for betning av koppar och dess legeringar
US4280915A (en) * 1977-06-23 1981-07-28 Nl Industries, Inc. Salt stable lubricant for water base drilling fluids
US4268406A (en) * 1980-02-19 1981-05-19 The Procter & Gamble Company Liquid detergent composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0018630A1 (fr) * 1979-05-07 1980-11-12 Henkel Kommanditgesellschaft auf Aktien Agent de lavage pour textiles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0103779A2 (fr) * 1982-09-20 1984-03-28 John E. Oliver Elimination de dépôts dans des fluides et des systèmes de puits de pétrole
EP0103779A3 (fr) * 1982-09-20 1985-01-09 John E. Oliver Elimination de dépôts dans des fluides et des systèmes de puits de pétrole
US5326407A (en) * 1992-03-26 1994-07-05 Institut Francais Du Petrole Process for washing solid particles comprising a sophoroside solution
US5501816A (en) * 1994-07-12 1996-03-26 Basf Corporation Aqueous based solvent free degreaser composition
WO2004050790A1 (fr) * 2002-12-02 2004-06-17 Marquis Fluids Inc. Fluide de forage polymere emulsifie et procedes de preparation et d'utilisation de ce dernier
US7229952B2 (en) 2002-12-19 2007-06-12 Halliburton Energy Services, Inc. Additive packages for removing oil from solid materials recovered from a well bore
US7192527B2 (en) 2004-08-10 2007-03-20 Halliburton Energy Services, Inc. Processes for removing oil from solid wellbore materials and produced water
US7374690B2 (en) 2004-08-10 2008-05-20 Halliburton Energy Services, Inc. Processes for removing oil from solid wellbore materials and produced water

Also Published As

Publication number Publication date
IE53660B1 (en) 1989-01-04
GB2116579A (en) 1983-09-28
GR77136B (fr) 1984-09-07
DK3483D0 (da) 1983-01-06
ES518812A0 (es) 1984-06-16
EP0084411A1 (fr) 1983-07-27
DK3483A (da) 1983-07-08
DE3360678D1 (en) 1985-10-10
CA1203450A (fr) 1986-04-22
IN158886B (fr) 1987-02-07
PH19657A (en) 1986-06-09
ES8405878A1 (es) 1984-06-16
IE830026L (en) 1983-07-07
GB2116579B (en) 1985-08-29
NO830032L (no) 1983-07-08

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