US20040198618A1 - High stability, high lubricity, low toxicity, high biodegradability drilling fluid - Google Patents

High stability, high lubricity, low toxicity, high biodegradability drilling fluid Download PDF

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Publication number
US20040198618A1
US20040198618A1 US10/785,317 US78531704A US2004198618A1 US 20040198618 A1 US20040198618 A1 US 20040198618A1 US 78531704 A US78531704 A US 78531704A US 2004198618 A1 US2004198618 A1 US 2004198618A1
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drilling fluid
fluid
fischer
product
isoparaffins
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US10/785,317
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Armen Abazajian
Robert Freerks
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REG Synthetic Fuels LLC
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Syntroleum Corp
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Priority to US10/785,317 priority Critical patent/US20040198618A1/en
Assigned to SYNTROLEUM reassignment SYNTROLEUM ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FREERKS, ROBERT, ABAZAJIAN, ARMEN N.
Publication of US20040198618A1 publication Critical patent/US20040198618A1/en
Assigned to REG SYNTHETIC FUELS, LLC reassignment REG SYNTHETIC FUELS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SYNTROLEUM CORPORATION
Abandoned legal-status Critical Current

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    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • 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
    • C09K8/02—Well-drilling compositions
    • C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon

Definitions

  • the present invention relates to drilling fluids derived from the products of a Fischer-Tropsch synthesis. More particularly, the invention relates to base fluids, and drilling fluids produced therefrom, having high stability, lubricity, and biodegradability while also having low toxicity. The invention further relates to processes of producing and using the drilling fluids.
  • Drilling fluids are well known for use in oil and gas well drilling operations.
  • crude, diesel and mineral oils were used as base fluids in formulating drilling fluids.
  • Such oil based drilling fluids however, have unacceptable toxicity and persistence, or non-biodegradability. Toxicity and persistence issues are especially critical in offshore drilling operations.
  • Pseudo-oil based drilling fluids are also well known wherein the base fluids are fatty acid esters or synthetic hydrocarbons.
  • Such synthetic hydrocarbons have included polyalphaolefins, linear alphaolefins, internal olefins, and mixtures thereof as well as linear and branched paraffins and mixtures thereof.
  • Synthetic olefinic and paraffinic base fluids produced by oligomerizing low carbon number hydrocarbons are well known but are expensive to produce. Similarly, ester base fluids are expensive to produce. 161 The cost of drilling fluids may be reduced by use of Fisher-Tropsch synthesis to produce paraffinic base fluids. Paraffinic drilling fluids, however, generally do not have adequate low temperature properties for use in offshore and cold weather drilling operations.
  • One approach to the low temperature issue incorporates multi-methyl branched isoparaffins or isoparaffins with branches of higher carbon number than methyl into the paraffinic base fluid.
  • Such paraffinic base fluids contain C 10 -C 24 n-paraffins and isoparaffins, with an iso to normal ratio ranging from 0.5:1 to 9:1. Greater than 50% of the total isoparaffin content are mono-methyl branched isoparaffins and about 30% are multi-methyl substituted.
  • a similar approach to the low temperature issue involves formulation of a drilling fluid containing a mixture of n-paraffins and isoparaffins wherein at least 90% of the isoparaffins are mono- or poly-methyl branched isomers.
  • a base fluid of a mixture of linear and branched alphaolefins with the linear to branch ratio ranging from 1:1 to 5:1 is used.
  • the olefins may be produced from high temperature Fischer-Tropsch synthesis.
  • High temperature Fischer-Tropsch synthesis results in primarily internal branching of the branched hydrocarbons.
  • drilling fluids are not wholly biodegradable resulting in increased persistence.
  • drilling fluids composed of olefins are easily oxidizable and, therefore, must be stored under a nitrogen blanket to provide a reasonable shelf life. Even with nitrogen padding, olefinic drilling fluids cannot be stored for periods as long as paraffinic drilling fluids. Therefore, the cost of using olefinic drilling fluids is increased by both its special storage requirements and loss of oxidized product.
  • a base fluid which may be used for drilling fluid formulation.
  • the base fluid includes at least about 5 wt % olefins, at least about 5 wt % n-paraffins and between about 2 and 50 wt % branched paraffins wherein substantially all of the branch groups are monomethyl and wherein the ratio of terminal monomethyl branching to internal monomethyl branching is at least about 1:1.5.
  • a drilling fluid is provided wherein the drilling fluid contains between about 2 and about 90 wt % olefins, between about 5 and about 90 wt % n-paraffins and between about 0 and about 10 wt % oxygenates.
  • Yet another embodiment of the invention provides a process for producing a drilling from a light Fischer-Tropsch liquid.
  • C x refers to a hydrocarbon compound having predominantly a carbon number of x.
  • C x may be modified by reference to a particular species of hydrocarbons, such as, for example, C 5 olefins.
  • the term means an olefin stream comprised predominantly of pentenes but which may have impurity amounts, i.e. less than about 10%, of olefins having other carbon numbers such as hexene, heptene, propene, or butene.
  • C x+ refers to a stream wherein the hydrocarbons are predominantly those having a hydrocarbon number of x or greater but which may also contain impurity levels of hydrocarbons having a carbon number of less than x.
  • C 15+ means hydrocarbons having a carbon number of 15 or greater but which may contain impurity levels of hydrocarbons having carbon numbers of less than 15.
  • C x -C y where x and y are numbers greater than zero, refers to a mixture of hydrocarbon compounds wherein the predominant component hydrocarbons, collectively about 90% or greater by weight, have carbon numbers between x and y inclusive.
  • C 5 -C 9 hydrocarbons means a mixture of hydrocarbon compounds which is predominantly comprised of hydrocarbons having carbon numbers between 5 and 9 inclusive, but may also include impurity level quantities of hydrocarbons having other carbon numbers.
  • high lubricity means having a wear scar of average diameter of about ⁇ 0.46 mm at 60° C. tested in accordance with ASTM Standard D-6079-02 entitled “Standard Test Method for Evaluating Lubricity of Diesel Fuels by the High-Frequency Reciprocating Rig.”
  • high stability and “high oxidative stability” mean having a total solids ⁇ 1.5 mg/100 ml tested in accordance with ASTM Standard D-22-74-Ola entitled “Standard Test Method for Oxidation Stability of Distillate Fuel Oil (Accelerated Method).” Note that these methods are being applied herein to the analysis and characterization of synthetic products although the standards refer expressly to petroleum derived products.
  • Embodiments of the drilling fluid of the invention contain a base fluid having from about 5 to about 90 wt % linear alpha- and internal olefins, from about 5 to about 20 wt % isoparaffins, from about 5 to about 90 wt % n-paraffins and from about 0 to about 10 wt % oxygenates.
  • the base fluid for the drilling fluid of such embodiments may be obtained from a Fischer-Tropsch synthesis using synthesis gas as a feed stock.
  • production of the drilling fluid from a base fluid produced by the Fischer-Tropsch synthesis and subsequent processing as described herein is desirable as it results in a product having the desirable olefin and paraffin contents.
  • the base fluid composition may be otherwise produced while yet retaining the remaining advantages of the invention.
  • some embodiments of the base and drilling fluids of the invention are not produced by Fischer-Tropsch synthesis.
  • a Fischer-Tropsch conversion system for converting hydrocarbon gases to liquid or solid hydrocarbon products using autothermal reforming includes a synthesis gas unit, which includes a synthesis gas reactor in the form of an autothermal reforming reactor (ATR) containing a reforming catalyst, such as a nickel-containing catalyst.
  • a stream of light hydrocarbons to be converted, which may include natural gas, is introduced into the reactor along with oxygen (O 2 ).
  • the oxygen may be provided from compressed air or other compressed oxygen-containing gas, or may be a pure oxygen stream.
  • the ATR reaction may be adiabatic, with no heat being added or removed from the reactor other than from the feeds and the heat of reaction.
  • the reaction is carried out under sub-stoichiometric conditions whereby the oxygen/steam/gas mixture is converted to syngas.
  • Fischer-Tropsch systems are described in U.S. Pat. Nos. 4,973,453; 5,733,941; 5,861,441; 6,130,259, 6,169,120 and 6,172,124, the disclosures of which are herein incorporated by reference.
  • the Fischer-Tropsch reaction for converting syngas which is composed primarily of carbon monoxide (CO) and hydrogen gas (H 2 ) may be characterized by the following general reaction:
  • Non-reactive components such as nitrogen may also be included or mixed with the syngas. This may occur in those instances where air or some other non-pure oxygen source is used during the syngas formation.
  • the syngas is delivered to a synthesis unit, which includes a Fischer-Tropsch reactor (FTR) containing a Fischer-Tropsch catalyst.
  • Fischer-Tropsch catalysts may be used in carrying out the reaction. These include cobalt, iron, ruthenium as well as other Group VIIIB transition metals or combinations of such metals, to prepare both saturated and unsaturated hydrocarbons.
  • a non-iron catalyst may be used.
  • the F-T catalyst may include a support, such as a metal-oxide support, including silica, alumina, silica-alumina or titanium oxides.
  • a Co catalyst on transition alumina with a surface area of approximately 100-200 m 2 /g is used in the form of spheres of 50-150 ⁇ m in diameter.
  • the Co concentration on the support may also be 15-30%.
  • Certain catalyst promoters and stabilizers may be used.
  • the stabilizers include Group IIA or Group IIIB metals, while the promoters may include elements from Group VIII or Group VIIB.
  • the Fischer-Tropsch catalyst and reaction conditions may be selected to be optimal for desired reaction products, such as for hydrocarbons of certain chain lengths or number of carbon atoms.
  • any of the following reactor configurations may be employed for Fischer-Tropsch synthesis: fixed bed, slurry reactor, ebullating bed, fluidizing bed, or continuously stirred tank reactor (CSTR).
  • CSTR continuously stirred tank reactor
  • a slurry bed reactor is used.
  • the FTR may be operated at a pressure of 100 to 500 psia and a temperature of 375° F. to 500° C.
  • the reactor gas hourly space velocity (“GHSV”) may be from 1000 to 8000 hr ⁇ 1 .
  • Syngas useful in producing a Fischer-Tropsch product useful in the invention may contain gaseous hydrocarbons, hydrogen, carbon monoxide and nitrogen with H 2 /CO ratios from about 1.8 to about 2.4.
  • the hydrocarbon products derived from the Fischer-Tropsch reaction may range from methane (CH 4 ) to high molecular weight paraffinic waxes containing more than 100 carbon atoms.
  • An overhead product stream is recovered from the FTR and may be separated into tail gas and light Fischer-Tropsch liquid (“LFTL”) products in a cold separator. The LFTL stream may then be distilled to yield a hydrocarbon product of primarily C 13 -C 22 olefins and paraffins.
  • the C 13 -C 22 distillation cut may be used directly as the base fluid.
  • Low levels of C 13 ⁇ hydrocarbons may be present in the C 13 -C 22 cut provided such levels do not cause the drilling fluid to exceed current regulatory limits.
  • C 13 ⁇ hydrocarbons may be present in amounts between about 0.01 and 10 wt %. The presence of such small amounts of C 13 ⁇ hydrocarbons permits incorporation of a wider distribution of C 13+ hydrocarbons, particularly C 16+ hydrocarbons, for improved lubricity.
  • the hydrocarbon number distribution is such as to result in a drilling fluid pour point below about 10° C.
  • Embodiments of the base fluid contains from about 5 to about 90 wt % linear alpha- and internal olefins.
  • the olefin content may provide the mixture with lower pour-point, better surface activity, better lubricity and better adherence to metal.
  • the Fischer-Tropsch product will have approximately 5% alpha and internal olefin content.
  • Concentration of olefins may be undertaken, for example, by one or more of the following known techniques: (1) molecular sieve separation of olefins and paraffins, such as UOP's OLEX® process, and (2) distillation of paraffins away from individual C X cuts.
  • the base fluid may contain between about 5 to about 95 wt % paraffins. Of the total paraffin content from about 3 to about 20 wt % are isoparaffins. Substantially all of the isoparaffins are terminal monomethyl species. As used herein, the terminal species include 2- and 3-methyl branched. The presence of monomethyl isoparaffins improves low temperature properties, such as pour point, as well as lubricity and viscosity. Moreover, because the isoparaffins are predominantly terminally branched, the paraffin content of the base fluid is substantially wholly biodegradable. Using the Fischer-Tropsch synthesis described herein, about 5 wt % terminal methyl branched paraffins are produced in the LFTL.
  • Concentration of isoparaffins may be increased by one or more of the following techniques: (1) molecular sieve separation of linear and branched paraffins, such as UOP's OLEX® process, and (2) isomeric distillation of isoparaffin.
  • Embodiments of the base fluid contain between about 0 and about 10 wt % oxygenates.
  • the oxygenates are principally primary alcohols.
  • Other oxygenates, including aldehydes, ketones, carboxylic acids and esters and di-esters of carboxylic acids are also present in small amounts.
  • Oxygenate content in the C 13 -C 22 cut of the Fischer-Tropsch reaction product ranges from between about 0.5 to about 5.0 wt %.
  • Low levels of oxygenates in the drilling fluid from between about 0 and about 10 wt % provide improved lubricity.
  • oxygenates may assist in emulsification in invert drilling muds.
  • Oxygenate control may be used on the C 13 -C 22 cut of the Fischer-Tropsch product stream.
  • a base fluid is produced by vaporizing a product stream and passing the vaporized product over an activated alumina catalysts to dehydrate alcohols to corresponding olefins. The conversion of the alcohol content of the product stream occurs according to the following reaction:
  • the LFTL, C 13 -C 22 or other product stream may be vaporized at a temperature from about 400° F. to about 800° F. and then passed over one or more dehydration beds containing activated treated alumina or silica-alumina.
  • the dehydration beds are packed beds. Essentially all of the primary and internal alcohols present in the vaporized stream are dehydrated to their corresponding olefins, with conversion rates of at least 95%.
  • Dehydration reaction temperature may range from between about 400° and 800° F.
  • the vaporized feed for the dehydration unit may be superheated prior to being fed into the dehydration beds or alternatively, may be heated within packed beds.
  • the LHSV of packed beds may range from about 0.10 hr ⁇ 1 to about 2.0 hr ⁇ 1 .
  • Reaction pressure may be maintained by the pressure of the accumulator and must be such to vaporize all of the dehydration feed. Typically, the pressure may range from between about 0 psia to about 100 psig.
  • a moving bed of alumina or silica-alumina catalyst may be used. Fluidized beds, slurry beds or ebullating beds may be used with continuous batch or semi-batch catalyst removal and regeneration. The catalyst may be removed by one of these methods and regenerated by passing a mixture of nitrogen and oxygen or air at elevated temperatures over the catalyst.
  • Alumina catalysts useful for the dehydration of alcohols include, for example, gamma-alumina, theta-alumina, pacified alumina, and activated alumina.
  • High surface area aluminas are particularly useful in the invention and include those aluminas having a surface area of about 100 m 2 /gm or greater.
  • alumina useful in the integrated Fischer-Tropsch process include, for example, S-400, which has a surface area of about 335 m 2 /gm, and DD-470, which has a surface area of about 375 m 2 /gm.
  • S-400 ad DD-470 are alumina catalysts made and sold by Alcoa.
  • Alumina catalysts for use in the integrated Fischer-Tropsch process generally contain at least about 90 wt % Al 2 O 3 , oxides of silicon and iron present in amounts of less than about 0 wt %, and oxides of sodium present in an amount of less than about 1 wt %.
  • the alumina catalysts are generally supplied as substantially spherical particles having diameter from about 1 ⁇ 8 to about 1 ⁇ 4 inch.
  • molecular sieve or zeolitic molecular sieve forms of the alumina or silica-alumina catalysts may be used.
  • silico alumino phosphate (“SAPO”) molecular sieves may be used in the packed beds.
  • SAPO molecular sieves contain a 3-dimensional microporous crystal structure having 8, 10, or 12 membered ring structures. The ring structures can have an average pore size ranging from between about 3.5 angstroms to about 15 angstroms.
  • Other silica-containing zeolitic molecular sieve catalysts, such as ZSM-5 may be used in the dehydration bed.
  • the aqueous and organic phases may be separated. Such dehydration process may further be used to increase the olefin content of the product stream to be used to produce the base fluid.
  • Other methods of oxygenate control include, for example, reaction of the alcohol content of the C 13 -C 22 cut of a Fischer-Tropsch product stream with maleic or succinic anhydride or with a carboxylic acid, such as formic acid, acetic acid, or other acids.
  • the carboxylic acid esters may be retained in the stream as they are excellent lubricants which are also highly biodegradable. Both the lubricity and the biodegradability of the base fluid may be improved by converting at least a portion of the alcoholic oxygenate content to carboxylic acid esters.
  • the drilling fluid may optionally include one or more surfactants (e.g., emulsifiers, wetting agents), viscosifiers, weighting agents, fluid loss control agents, and proppants. Because the drilling fluid should be non-toxic, these optional ingredients, like the base fluid, are preferably also non-toxic. Acceptable emulsifiers include, but are not limited to, fatty acids, and fatty acid derivatives including amido-amines, polyamides, polyamines, esters, imidaxiolines, and alcohols.
  • Typical wetting agents include, but are not limited to, lecithin, fatty acids, crude tall oil, oxidized crude tall oil, organic phosphate esters, modified imidazolines, modified amidoamines, alkyl aromatic sulfates, alkyl aromatic sulfonates, and organic esters of polyhydric alcohols.
  • Exemplary weighting agents include, but are not limited to, barite, iron oxide, gelana, siderite, calcium oxide, and calcium carbonate.
  • Acceptable proppants include sand, gravel, and nut shells.
  • Exemplary viscosifiers include, but are not limited to, organophilic clays, non-organophilic clays, oil soluble polymers, polyamide resins, and polycarboxylic acids and soaps.
  • the base fluid constitutes from about 25 to about 85 volume percent of the total drilling fluid.
  • Illustrative fluid loss control agents include, but are not limited to, asphaltics (e.g., asphaltenes and sulfonated asphaltenes), modified lignites, and polymers, such as polystyrene, polybutadiene, polyethylene, polypropylene, polybutylene, polyisoprene, natural rubber, and butyl rubber.
  • the LFTL feed was introduced into a first packed distillation column and C 13 and lighter materials were distilled overhead.
  • the first distillation column was operated at the following conditions: 10 psig, 480° F. feed preheat temperature, 407° F. overhead temperature, 528° F. bottoms temperature.
  • the first distillation column had approximately 98 inches of Sulzer Mellapack 750Y packing.
  • the bottoms of the first distillation column constituted a C 13-20+ hydrocarbon fraction, the composition of which is shown in Table 2.
  • the overhead stream of the first distillation column was fed into a second packed distillation column operated at 12 psig, 370° F. overhead temperature and 437° F. bottoms temperature.
  • the second distillation column had about 28 inches of Sulzer EX packing.
  • An LFTL feed substantially having the composition shown in Table 1, was hydrotreated at reactor conditions of 800 psig and 550° to 590° F.
  • the resulting hydrotreated stream was distilled under conditions as described in Example 1 forming a hydrotreated analog of the C 10-13 light kerosene product.
  • This hydrotreated light kerosene material was analyzed on a Hewlett Packard Series II gas chromatograph with 60 m RTX 1 column with 0.32 mm diameter and 3 micron film thickness. The isomer content of this product is shown in Table 4. TABLE 5 Component Wt.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US10/785,317 2003-02-24 2004-02-24 High stability, high lubricity, low toxicity, high biodegradability drilling fluid Abandoned US20040198618A1 (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070178339A1 (en) * 2006-02-02 2007-08-02 Syntroleum Corporation Paraffinic hydrocarbon for fuel cell application
US20070213229A1 (en) * 2002-04-30 2007-09-13 Petroleum Oil and Gas Corporation of South Africa (Pty) Ltd. Process for reducing the toxicity of hydrocarbons
WO2008130505A1 (en) * 2007-04-20 2008-10-30 Sasol North America Inc. Compositions for use in well servicing fluids
US20100113847A1 (en) * 2005-01-31 2010-05-06 Kowalik Ralph M Olefin Oligomerization And Biodegradable Compositions Therefrom
US20150126627A1 (en) * 2012-07-16 2015-05-07 Res Usa, Llc Integration of syngas generation technology with fischer-tropsch production via catalytic gas conversion
US9295966B1 (en) 2011-07-19 2016-03-29 Jacob G. Appelbaum System and method for cleaning hydrocarbon contaminated water and converting lower molecular weight gaseous hydrocarbon mixtures into higher molecular weight highly-branched hydrocarbons using electron beam combined with electron beam-sustained non-thermal plasma discharge
WO2019025358A1 (en) * 2017-08-01 2019-02-07 Shell Internationale Research Maatschappij B.V. DRILLING FLUID
US11319474B2 (en) 2017-02-03 2022-05-03 Saudi Arabian Oil Company Oil-based fluid compositions for hydrocarbon recovery applications

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2565592C2 (ru) * 2010-05-03 2015-10-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Отработанная смазочная композиция

Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852207A (en) * 1973-03-26 1974-12-03 Chevron Res Production of stable lubricating oils by sequential hydrocracking and hydrogenation
US3904513A (en) * 1974-03-19 1975-09-09 Mobil Oil Corp Hydrofinishing of petroleum
US4080397A (en) * 1976-07-09 1978-03-21 Mobile Oil Corporation Method for upgrading synthetic oils boiling above gasoline boiling material
US4131568A (en) * 1975-08-14 1978-12-26 Air Products And Chemicals, Inc. Catalytic synthesis of low molecular weight hydrocarbons
US4157294A (en) * 1976-11-02 1979-06-05 Idemitsu Kosan Company Limited Method of preparing base stocks for lubricating oil
US4207424A (en) * 1978-08-09 1980-06-10 Halcon Research & Development Corporation Catalytic process for dehydration of alcohols
US4497968A (en) * 1984-04-11 1985-02-05 Mobil Oil Corporation Multistage process for converting olefins or oxygenates to heavier hydrocarbons
US4513161A (en) * 1984-06-29 1985-04-23 Exxon Research And Engineering Co. Conversion of methanol to hydrocarbons
US4542122A (en) * 1984-06-29 1985-09-17 Exxon Research And Engineering Co. Cobalt catalysts for the preparation of hydrocarbons from synthesis gas and from methanol
US4556752A (en) * 1984-06-29 1985-12-03 Exxon Research And Engineering Co. Preparation of liquid hydrocarbons from methanol
US4568663A (en) * 1984-06-29 1986-02-04 Exxon Research And Engineering Co. Cobalt catalysts for the conversion of methanol to hydrocarbons and for Fischer-Tropsch synthesis
US4579995A (en) * 1984-06-29 1986-04-01 Exxon Research And Engineering Co. Process for the conversion of methanol to hydrocarbons
US4628135A (en) * 1985-09-23 1986-12-09 Mobil Oil Corporation Integrated process for converting oxygenates to liquid hydrocarbons
US4640764A (en) * 1986-02-24 1987-02-03 Shell Oil Company Selective tricyclic hydrogenation and cracking process and catalyst suitable for such hydroconversion
US4670475A (en) * 1984-06-29 1987-06-02 Exxon Research And Engineering Company Improved cobalt catalysts, and use thereof for Fischer-Tropsch synthesis
US4751345A (en) * 1984-06-29 1988-06-14 Exxon Research And Engineering Company Cobalt catalysts, and use thereof for the conversion of methanol to hydrocarbons, and for Fisher-Tropsch synthesis
US4755536A (en) * 1985-12-27 1988-07-05 Exxon Research And Engineering Co. Cobalt catalysts, and use thereof for the conversion of methanol and for Fischer-Tropsch synthesis, to produce hydrocarbons
US4762959A (en) * 1985-12-27 1988-08-09 Exxon Research And Engineering Company Cobalt catalysts, and use thereof for the conversion of methanol and for Fischer-Tropsch synthesis, to produce hydrocarbons
US4795730A (en) * 1984-04-27 1989-01-03 Phillips Petroleum Company Dehydration of alcohols
US4832819A (en) * 1987-12-18 1989-05-23 Exxon Research And Engineering Company Process for the hydroisomerization and hydrocracking of Fisher-Tropsch waxes to produce a syncrude and upgraded hydrocarbon products
US4973453A (en) * 1988-02-05 1990-11-27 Gtg, Inc. Apparatus for the production of heavier hydrocarbons from gaseous light hydrocarbons
US5023389A (en) * 1988-02-22 1991-06-11 Shell Oil Company Process for preparing normally liquid oxygenate and hydrocarbonaceous products from a hydrocarbon feed containing linear- and branched olefins
US5227563A (en) * 1988-12-26 1993-07-13 Mitsui Petrochemical Industries, Ltd. Preparation of propylene by dehydration of isopropanol in the presence of a pseudo-boehmite derived gamma alumina catalyst
US5432152A (en) * 1993-06-01 1995-07-11 Albemarle Corporation Invert drilling fluid
US5475183A (en) * 1991-02-04 1995-12-12 Mitsui Petrochemical Industries, Ltd. Process for producing lower olefins
US5589442A (en) * 1994-02-02 1996-12-31 Chevron Chemical Company Drilling fluids comprising mostly linear olefins
US5635457A (en) * 1995-04-17 1997-06-03 Union Oil Company Of California Non-toxic, inexpensive synthetic drilling fluid
US5741759A (en) * 1994-02-02 1998-04-21 Chevron Chemical Company Skeletally isomerized linear olefins
US5817906A (en) * 1995-08-10 1998-10-06 Uop Llc Process for producing light olefins using reaction with distillation as an intermediate step
US5833839A (en) * 1995-12-08 1998-11-10 Exxon Research And Engineering Company High purity paraffinic solvent compositions, and process for their manufacture
US6096690A (en) * 1996-03-22 2000-08-01 Exxon Research And Engineering Co. High performance environmentally friendly drilling fluids
US6103773A (en) * 1998-01-27 2000-08-15 Exxon Research And Engineering Co Gas conversion using hydrogen produced from syngas for removing sulfur from gas well hydrocarbon liquids
US6110874A (en) * 1995-04-17 2000-08-29 Union Oil Company Of California Non-toxic, inexpensive synthetic drilling fluid
US6121504A (en) * 1998-04-29 2000-09-19 Exxon Chemical Patents Inc. Process for converting oxygenates to olefins with direct product quenching for heat recovery
US6211423B1 (en) * 1999-08-23 2001-04-03 Shell Oil Company Process for separating saturated compounds from olefins
US6262131B1 (en) * 1998-12-07 2001-07-17 Syntroleum Corporation Structured fischer-tropsch catalyst system and method
US6271434B1 (en) * 1999-08-23 2001-08-07 Shell Oil Company Process for separating linear alpha olefins from a crude stream containing saturated hydrocarbons, internal olefins, branched olefins, and linear alpha olefins
US6296757B1 (en) * 1995-10-17 2001-10-02 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US20020006969A1 (en) * 2000-05-30 2002-01-17 O'beck John Timothy System and method for converting light hydrocarbons into heavier hydrocarbons and for treating contaminated water
US6384170B1 (en) * 1997-12-24 2002-05-07 Clariant Gmbh Hydroxyl-containing ethylene copolymers and fuel oils having an improved lubricating action
US6703353B1 (en) * 2002-09-04 2004-03-09 Chevron U.S.A. Inc. Blending of low viscosity Fischer-Tropsch base oils to produce high quality lubricating base oils

Patent Citations (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852207A (en) * 1973-03-26 1974-12-03 Chevron Res Production of stable lubricating oils by sequential hydrocracking and hydrogenation
US3904513A (en) * 1974-03-19 1975-09-09 Mobil Oil Corp Hydrofinishing of petroleum
US4131568A (en) * 1975-08-14 1978-12-26 Air Products And Chemicals, Inc. Catalytic synthesis of low molecular weight hydrocarbons
US4080397A (en) * 1976-07-09 1978-03-21 Mobile Oil Corporation Method for upgrading synthetic oils boiling above gasoline boiling material
US4157294A (en) * 1976-11-02 1979-06-05 Idemitsu Kosan Company Limited Method of preparing base stocks for lubricating oil
US4207424A (en) * 1978-08-09 1980-06-10 Halcon Research & Development Corporation Catalytic process for dehydration of alcohols
US4497968A (en) * 1984-04-11 1985-02-05 Mobil Oil Corporation Multistage process for converting olefins or oxygenates to heavier hydrocarbons
US4795730A (en) * 1984-04-27 1989-01-03 Phillips Petroleum Company Dehydration of alcohols
US4568663A (en) * 1984-06-29 1986-02-04 Exxon Research And Engineering Co. Cobalt catalysts for the conversion of methanol to hydrocarbons and for Fischer-Tropsch synthesis
US4556752A (en) * 1984-06-29 1985-12-03 Exxon Research And Engineering Co. Preparation of liquid hydrocarbons from methanol
US4542122A (en) * 1984-06-29 1985-09-17 Exxon Research And Engineering Co. Cobalt catalysts for the preparation of hydrocarbons from synthesis gas and from methanol
US4579995A (en) * 1984-06-29 1986-04-01 Exxon Research And Engineering Co. Process for the conversion of methanol to hydrocarbons
US4663305A (en) * 1984-06-29 1987-05-05 Exxon Research And Engineering Company Cobalt catalysts for the conversion of methanol and for Fischer-Tropsch synthesis to produce hydrocarbons
US4670475A (en) * 1984-06-29 1987-06-02 Exxon Research And Engineering Company Improved cobalt catalysts, and use thereof for Fischer-Tropsch synthesis
US4751345A (en) * 1984-06-29 1988-06-14 Exxon Research And Engineering Company Cobalt catalysts, and use thereof for the conversion of methanol to hydrocarbons, and for Fisher-Tropsch synthesis
US4513161A (en) * 1984-06-29 1985-04-23 Exxon Research And Engineering Co. Conversion of methanol to hydrocarbons
US4628135A (en) * 1985-09-23 1986-12-09 Mobil Oil Corporation Integrated process for converting oxygenates to liquid hydrocarbons
US4755536A (en) * 1985-12-27 1988-07-05 Exxon Research And Engineering Co. Cobalt catalysts, and use thereof for the conversion of methanol and for Fischer-Tropsch synthesis, to produce hydrocarbons
US4762959A (en) * 1985-12-27 1988-08-09 Exxon Research And Engineering Company Cobalt catalysts, and use thereof for the conversion of methanol and for Fischer-Tropsch synthesis, to produce hydrocarbons
US4640764A (en) * 1986-02-24 1987-02-03 Shell Oil Company Selective tricyclic hydrogenation and cracking process and catalyst suitable for such hydroconversion
US4832819A (en) * 1987-12-18 1989-05-23 Exxon Research And Engineering Company Process for the hydroisomerization and hydrocracking of Fisher-Tropsch waxes to produce a syncrude and upgraded hydrocarbon products
US4973453A (en) * 1988-02-05 1990-11-27 Gtg, Inc. Apparatus for the production of heavier hydrocarbons from gaseous light hydrocarbons
US5023389A (en) * 1988-02-22 1991-06-11 Shell Oil Company Process for preparing normally liquid oxygenate and hydrocarbonaceous products from a hydrocarbon feed containing linear- and branched olefins
US5227563A (en) * 1988-12-26 1993-07-13 Mitsui Petrochemical Industries, Ltd. Preparation of propylene by dehydration of isopropanol in the presence of a pseudo-boehmite derived gamma alumina catalyst
US5475183A (en) * 1991-02-04 1995-12-12 Mitsui Petrochemical Industries, Ltd. Process for producing lower olefins
US5432152A (en) * 1993-06-01 1995-07-11 Albemarle Corporation Invert drilling fluid
US5589442A (en) * 1994-02-02 1996-12-31 Chevron Chemical Company Drilling fluids comprising mostly linear olefins
US5741759A (en) * 1994-02-02 1998-04-21 Chevron Chemical Company Skeletally isomerized linear olefins
US6110874A (en) * 1995-04-17 2000-08-29 Union Oil Company Of California Non-toxic, inexpensive synthetic drilling fluid
US5635457A (en) * 1995-04-17 1997-06-03 Union Oil Company Of California Non-toxic, inexpensive synthetic drilling fluid
US5817906A (en) * 1995-08-10 1998-10-06 Uop Llc Process for producing light olefins using reaction with distillation as an intermediate step
US6296757B1 (en) * 1995-10-17 2001-10-02 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US5833839A (en) * 1995-12-08 1998-11-10 Exxon Research And Engineering Company High purity paraffinic solvent compositions, and process for their manufacture
US6096690A (en) * 1996-03-22 2000-08-01 Exxon Research And Engineering Co. High performance environmentally friendly drilling fluids
US6455474B1 (en) * 1996-03-22 2002-09-24 Exxonmobil Research And Engineering Company High performance environmentally friendly, low temperature, drilling fluids
US6384170B1 (en) * 1997-12-24 2002-05-07 Clariant Gmbh Hydroxyl-containing ethylene copolymers and fuel oils having an improved lubricating action
US6103773A (en) * 1998-01-27 2000-08-15 Exxon Research And Engineering Co Gas conversion using hydrogen produced from syngas for removing sulfur from gas well hydrocarbon liquids
US6121504A (en) * 1998-04-29 2000-09-19 Exxon Chemical Patents Inc. Process for converting oxygenates to olefins with direct product quenching for heat recovery
US6262131B1 (en) * 1998-12-07 2001-07-17 Syntroleum Corporation Structured fischer-tropsch catalyst system and method
US6211423B1 (en) * 1999-08-23 2001-04-03 Shell Oil Company Process for separating saturated compounds from olefins
US6271434B1 (en) * 1999-08-23 2001-08-07 Shell Oil Company Process for separating linear alpha olefins from a crude stream containing saturated hydrocarbons, internal olefins, branched olefins, and linear alpha olefins
US20020006969A1 (en) * 2000-05-30 2002-01-17 O'beck John Timothy System and method for converting light hydrocarbons into heavier hydrocarbons and for treating contaminated water
US6703353B1 (en) * 2002-09-04 2004-03-09 Chevron U.S.A. Inc. Blending of low viscosity Fischer-Tropsch base oils to produce high quality lubricating base oils

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070213229A1 (en) * 2002-04-30 2007-09-13 Petroleum Oil and Gas Corporation of South Africa (Pty) Ltd. Process for reducing the toxicity of hydrocarbons
US7429553B2 (en) * 2002-04-30 2008-09-30 Petroleum Oil and Gas Corporation of South Africa (Pty) Ltd. Process for reducing the toxicity of hydrocarbons
US20100113847A1 (en) * 2005-01-31 2010-05-06 Kowalik Ralph M Olefin Oligomerization And Biodegradable Compositions Therefrom
US8318994B2 (en) 2005-01-31 2012-11-27 Exxonmobil Chemical Patents Inc. Olefin oligomerization and biodegradable compositions therefrom
US20070178339A1 (en) * 2006-02-02 2007-08-02 Syntroleum Corporation Paraffinic hydrocarbon for fuel cell application
WO2007092734A1 (en) * 2006-02-02 2007-08-16 Syntroleum Corporation Paraffinic hydrocarbon for fuel cell application
WO2008130505A1 (en) * 2007-04-20 2008-10-30 Sasol North America Inc. Compositions for use in well servicing fluids
US9295966B1 (en) 2011-07-19 2016-03-29 Jacob G. Appelbaum System and method for cleaning hydrocarbon contaminated water and converting lower molecular weight gaseous hydrocarbon mixtures into higher molecular weight highly-branched hydrocarbons using electron beam combined with electron beam-sustained non-thermal plasma discharge
US9908094B2 (en) 2011-07-19 2018-03-06 Jacob G. Appelbaum System and method for converting gaseous hydrocarbon mixtures into highly-branched hydrocarbons using electron beam combined with electron beam-sustained non-thermal plasma discharge
US10343133B2 (en) 2011-07-19 2019-07-09 Jacob G. Appelbaum System and method for cleaning hydrocarbon contaminated water
US10933397B2 (en) 2011-07-19 2021-03-02 Jacob G. Appelbaum System and method for cleaning hyrocarbon contaminated water
US20150126627A1 (en) * 2012-07-16 2015-05-07 Res Usa, Llc Integration of syngas generation technology with fischer-tropsch production via catalytic gas conversion
US11319474B2 (en) 2017-02-03 2022-05-03 Saudi Arabian Oil Company Oil-based fluid compositions for hydrocarbon recovery applications
WO2019025358A1 (en) * 2017-08-01 2019-02-07 Shell Internationale Research Maatschappij B.V. DRILLING FLUID
CN110869476A (zh) * 2017-08-01 2020-03-06 国际壳牌研究有限公司 钻井流体
AU2018311027B2 (en) * 2017-08-01 2021-01-14 Shell Internationale Research Maatschappij B.V. Drilling fluid
US11332653B2 (en) 2017-08-01 2022-05-17 Shell Oil Company Drilling fluid

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