WO2004046498A1 - Apparatus for recycling of oil based drilling fluid contaminated with water - Google Patents

Apparatus for recycling of oil based drilling fluid contaminated with water Download PDF

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Publication number
WO2004046498A1
WO2004046498A1 PCT/US2003/033612 US0333612W WO2004046498A1 WO 2004046498 A1 WO2004046498 A1 WO 2004046498A1 US 0333612 W US0333612 W US 0333612W WO 2004046498 A1 WO2004046498 A1 WO 2004046498A1
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WO
WIPO (PCT)
Prior art keywords
emulsion
tank
fluid
drilling
alkyl
Prior art date
Application number
PCT/US2003/033612
Other languages
French (fr)
Inventor
Frank Mueller
Original Assignee
M-I L.L.C.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by M-I L.L.C. filed Critical M-I L.L.C.
Priority to DE60334238T priority Critical patent/DE60334238D1/en
Priority to EA200500823A priority patent/EA007444B1/en
Priority to DK03777821.4T priority patent/DK1561004T3/en
Priority to CA2506098A priority patent/CA2506098C/en
Priority to EP03777821A priority patent/EP1561004B1/en
Priority to MXPA05005189A priority patent/MXPA05005189A/en
Priority to NZ539951A priority patent/NZ539951A/en
Priority to AT03777821T priority patent/ATE481552T1/en
Priority to AU2003286615A priority patent/AU2003286615B2/en
Publication of WO2004046498A1 publication Critical patent/WO2004046498A1/en
Priority to NO20052551A priority patent/NO330478B1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/06Dewatering or demulsification of hydrocarbon oils with mechanical means, e.g. by filtration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0202Separation of non-miscible liquids by ab- or adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0208Separation of non-miscible liquids by sedimentation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0208Separation of non-miscible liquids by sedimentation
    • B01D17/0214Separation of non-miscible liquids by sedimentation with removal of one of the phases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/0217Separation of non-miscible liquids by centrifugal force
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/041Breaking emulsions with moving devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D17/00Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02Separation of non-miscible liquids
    • B01D17/04Breaking emulsions
    • B01D17/047Breaking emulsions with separation aids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/0012Settling tanks making use of filters, e.g. by floating layers of particulate material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/02Settling tanks with single outlets for the separated liquid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/02Settling tanks with single outlets for the separated liquid
    • B01D21/04Settling tanks with single outlets for the separated liquid with moving scrapers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D21/00Separation of suspended solid particles from liquids by sedimentation
    • B01D21/18Construction of the scrapers or the driving mechanisms for settling tanks
    • B01D21/186Construction of the scrapers or the driving mechanisms for settling tanks with two or more scrapers fixed at different heights on a central rotating shaft
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/682Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of chemical compounds for dispersing an oily layer on water
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/32Non-aqueous well-drilling compositions, e.g. oil-based
    • C09K8/36Water-in-oil emulsions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06Arrangements for treating drilling fluids outside the borehole
    • E21B21/063Arrangements for treating drilling fluids outside the borehole by separating components
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06Arrangements for treating drilling fluids outside the borehole
    • E21B21/068Arrangements for treating drilling fluids outside the borehole using chemical treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/32Hydrocarbons, e.g. oil
    • C02F2101/325Emulsions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/008Originating from marine vessels, ships and boats, e.g. bilge water or ballast water
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/16Regeneration of sorbents, filters
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/04Surfactants, used as part of a formulation or alone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/12Inert solids used as ballast for improving sedimentation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1048Middle distillates
    • C10G2300/1055Diesel having a boiling range of about 230 - 330 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081Recycling aspects
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • Invert emulsion fluids i.e. emulsions in which the non-oleaginous fluid is the discontinuous phase and the oleaginous fluid is the continuous phase, are employed in drilling processes for the development of oil or gas sources, as well as, in geothermal drilling, water drilling, geoscientific drilling and mine drilling.
  • the invert emulsion fluids are conventionally utilized for such purposes as providing stability to the drilled hole, forming a thin filter cake, lubricating the drilling bore and the downhole area and assembly, and penetrating salt beds without sloughing or enlargement of the drilled hole.
  • Oil-based drilling fluids are generally used in the form of invert emulsion muds.
  • An invert emulsion mud consists of three-phases: an oleaginous phase, a non-oleaginous phase and a finely divided particle phase.
  • emulsifiers and emulsifier systems are typically included, weighting agents, fluid loss additives, viscosity regulators and the like, for stabilizing the system as a whole and for establishing the desired performance properties. Full particulars can be found, for example, in the Article by P. A. Boyd et al entitled "New Base Oil Used in Low- Toxicity Oil Muds" in the Journal of Petroleum Technology, 1985, 137 to 142 and in the Article by R. B. Bennet entitled “New Drilling Fluid Technology-Mineral Oil Mud” in Journal of Petroleum Technology, 1984, 975 to 981 and the literature cited therein.
  • the ratio of oleaginous fluid to non-oleaginous fluid is less than optimal.
  • the formation of a difficult to break emulsion occurs and this is often referred to as the "slop".
  • the oil to water ratio in the slop may be 25/75 or 30/70 or similar such numbers.
  • emulsion breaking it is possible to recover say a 60/40 ratio of oil to water fluid. This is then diluted with additional make up oil to achieve the desired ratio typically 80/20.
  • One of the primary difficulties with this system is the use of emulsion breakers and surface tension breakers that are not environmentally friendly.
  • any rig drilling with oil based synthetic oil based drilling mud is likely producing between 20 to 40 cubic meters per day of slop water, also referred to as waste mud or gray water.
  • the slop water usually may not be directly discharged into the sea because of its hydrocarbon content, which is usually higher than regulatory limits. Therefore the slop water needs to be transported in boat tanks to shore for disposal according to the local regulations. A large portion of this slop water may be classified as special waste.
  • the present invention is generally directed to an apparatus and method of recycling drilling fluids or muds that have been contaminated with excess water so as to obtain a materials that' is suitable for reuse in the drilling subterranean wells. More particularly, the present invention relates to the separation, on the drilling rig, of the contaminating water from the oleaginous portion of an invert emulsion drilling fluid or mud using a skid-mounted apparatus and a single phase emulsion breaker that is environmentally compatible.
  • the preferred emulsion breaker may include an anionic surfactant, a nonionic surfactant, and an alkyl polyglycoside, or combinations thereof.
  • the invention may be employed to clean industrial wastewater produced during drilling or shipping operations, including bilge water.
  • Fig. 1 is a flow diagram of the overall process
  • Fig. 2 is a detailed view of the mud recycling operation.
  • Fig. 3 is a detailed view of the water flocculation tank and filters.
  • the aim of the mvention is to recycle slop water into oil based / synthetic oil based drilling mud and clean water.
  • the clean water extracted during this process should be of high enough purity to meet the local regulatory limits for allowing discharge from the rig.
  • the invention will reduce the transportation of fluid waste in boat tanks to shore, which in turn will (1) reduce the risk of spills; (2) reduce the need for supply boat tank cleaning and with this cost and time; (3) reduce the need for offshore transport and with this a reduction in CO 2 production; (4) reduce the risk of a possible halting of drilling operations due to unfavorable weather conditions which prevent a supply boat from docking at a drilling rig coupled with the existing storage capacities on the rig being exhausted; (5) reduce the need of the supply of new drilling mud due to losses; and, (6) will reduce the need of special waste disposal onshore.
  • the mobile drilling mud recycling unit may consist of one module, or two or more
  • module 5 separate modules, either skid mounted or containerized, which can be mobile placed on the drilling rig's deck surface.
  • module one will separate the bulk part of the water fraction under use of a chemical reaction from the oil based / synthetic base drilling mud.
  • the oil based mud / synthetic oil based mud will then be transferred back to the shaker house of the rig where it is treated on the rig shaker and directed back into the active mud system.
  • the extracted o water is pumped to the second module where it will be treated with a bentonite based flocculent to eliminate / minimize hydrocarbon, organic and. heavy metal contamination.
  • the produced treatment sludge contaminate loaded bentonite flocculent
  • the cleaned water phase is pumped over an integrated filter package, which will additionally eliminate hydrocarbon contamination.
  • slop water is first sent to an emulsion breaking tank 1,2 with agitator 3 and motor 12.
  • An emulsion breaker from a storage tank 10 and pump 11 is added o to the tank via a distributor 4 during stirring.
  • the water is skimmed 7 with a pump 8 from the top of the emulsion breaking tank to the top 21 of a water treatment tank 20 on Fig. 3.
  • the water treatment tank 20 is vigorously agitated while bentonite based flocculent is added from a venturi powder doser 23 via a venturi nozzle 24
  • a typical dose is between 2 and 4 kilograms per cubic meter of waste water.
  • the usual contaminants in the waste water are hydrocarbons, general organics, and heavy metals.
  • the agitation speed is reduced and the water and bentonite solution is mixed until large, stable bentonite flocculates loaded with the contaminants from the water are observed.
  • the agitation is stopped, and the flocculates are so allowed to settle to the bottom of the mixing tank 29.
  • the water is tapped 27 from the side of the tank above the flocculated material and pumped 28 to a sack filter 34 and a cartridge filter unit 35 for final polishing of any residual hydrocarbons.
  • the produced treatment sludge which contains contaminate loaded bentonite flocculent 29, is directed or pumped 30 to a filter press 31 for de-watering and solidification, eventually accumulating in a dehydrated mud tank 33 for transport and disposal.
  • the water from the filter press 31 may be pumped 32 back
  • the resulting water typically should have below 20 ppm hydrocarbon contamination and no more than 2 ppm of heavy metals, although final purity is determined by the regulatory limits of a particular location. If the hydrocarbon limits are not met by the polished water, it may be reprocessed in the water treatment system until the correct discharge values are achieved.
  • the invention also represents a method of separating contaminating water from the oleaginous portion of invert emulsion drilling fluids or muds using the above described apparatus with a phase emulsion breaker that is environmentally compatible. This method allows the fluids or muds to be recycled for reuse in the drilling of subterranean wells at the well itself.
  • oleaginous liquid such as hydrocarbon oil which serves as a continuous phase
  • non-oleaginous liquid such as water or brine solution which serves as a discontinuous phase
  • emulsifying agent As used herein, emulsifying agent and surfactant are used interchangeably.
  • the emulsifying agent serves to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous o liquid.
  • invert emulsions may be found in Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 328-332, the contents of which are hereby incorporated by reference.
  • invert emulsion is an emulsion in which a non-oleaginous 5 fluid is the discontinuous phase and an oleaginous fluid is the continuous phase.
  • novel invert emulsion fluids of the present invention are useful in a similar manner as conventional invert emulsion fluids which includes utility in preparation for drilling, drilling, completing and working over subterranean wells such as oil and gas wells.
  • Such methods of use of conventional inverse emulsion fluids are described in, for example, Composition and Properties of Drilling 0 and Completion Fluids, 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, the contents which are incorporated by reference, as well as, U.S.
  • Patent No. 5,254,531 and EP 271943 which are incorporated by reference.
  • One of skill in the art should know and understand the standard methods of determining if an invert emulsion has been formed. Examples of two such tests for the formation of an invert emulsion include the Invert Emulsion Test as disclosed herein and the measurement of the electrical stability of the invert
  • oleaginous liquid means an oil which is a liquid at 25 °C and immiscible with water.
  • Oleaginous liquids typically include substances such as diesel oil, mineral oil, synthetic oil, ester oils, glycerides of fatty acids, aliphatic esters, aliphatic ethers, aliphatic acetals, or other such hydrocarbons and combinations of these fluids.
  • the oleaginous liquid is an ester material which provides environmental compatibility to the overall drilling fluid. Such esters are described in greater detail below.
  • the amount of oleaginous liquid in the invert emulsion fluid may vary depending upon the particular oleaginous fluid used, the particular non-oleaginous fluid used, and the particular
  • the amount of oleaginous liquid must be sufficient to form a stable emulsion when utilized as the continuous phase.
  • the amount of oleaginous liquid is at least about 30, preferably at least about 40, more preferably at least about 50 percent by volume of the total fluid.
  • non-oleaginous liquid mean any substance which is a liquid at o 25 °C and which is not an oleaginous liquid as defined above.
  • Non-oleaginous liquids are immiscible with oleaginous liquids but capable of forming emulsions therewith.
  • Typical non- oleaginous liquids include aqueous substances such as fresh water, sea water, brine containing inorganic or organic dissolved salts, aqueous solutions containing water-miscible organic compounds and mixtures of these.
  • the non-oleaginous fluid is
  • brine solution including inorganic salts such as calcium halide salts, zinc halide salts, alkali metal halide salts and the like.
  • the amount of non-oleaginous liquid in the invert emulsion fluid may vary depending upon the particular non-oleaginous fluid used and the particular application in which the invert emulsion fluid is to be employed.
  • the amount of non-oleaginous liquid is at least o about 1, preferably at least about 3, more preferably at least about 5 percent by volume of the total fluid.
  • the amount should not be so great that it cannot be dispersed in the oleaginous phase. Therefore, typically the amount of non-oleaginous liquid is less than about 90, preferably less than about 80, more preferably less than about 50 percent by volume of the total fluid.
  • surfactants and wetting agents conventionally used in invert emulsion fluids may be incorporated in the fluids of this invention.
  • Such surfactants are, for example, fatty acids, soaps of fatty acids, amido amines, polyamides, polyamines, oleate esters, imidazoline derivatives, oxidized crude tall oil, organic phosphate esters, alkyl aromatic sulfates and sulfonates, as well as, mixtures of the above.
  • surfactants are employed in an amount sufficient to form the invert emulsion. However, due to the cost of such agents, a minimal amount o achieve the desired result is typically used.
  • Viscosifying agents for example, organophillic clays, may optionally be employed in the invert drilling fluid compositions of the present invention.
  • other viscosifying agents such as oil soluble polymers, polyamide resins, polycarboxylic acids and fatty acid soaps may also be employed.
  • the amount of viscosifying agent used in the composition will necessarily vary depending upon the end use of the composition. Usually such viscosifying agents are employed in an amount which is at least about 0.1, preferably at least about 2, more preferably at least about 5 percent by weight to volume of the total fluid.
  • VG-69TM and VG-PLUSTM are organoclay materials and Versa HRPTM is a polyamide resin material manufactured and distributed by M-I L.L.C.
  • the invert emulsion drilling fluids utilized in the practice of the present invention may optionally contain a weight material.
  • the quantity and nature of the weight material depends upon the desired density and viscosity of the final composition.
  • the preferred weight materials include, but are not limited to, barite, calcite, mullite, gallena, manganese oxides, iron oxides, mixtures of these and the like.
  • the weight material is typically added in order to obtain a drilling fluid density of less than about 24, preferably less than about 21, and most preferably less than about 19.5 pounds per gallon.
  • Fluid loss control agents such as modified lignite, polymers, oxidized asphalt and gilsonite may also be added to the invert drilling fluids of this invention. Usually such fluid loss control agents are employed in an amount which is at least about 0.1, preferably at least about 1, more preferably at least about 5 percent by weight to volume of the total fluid.
  • the method of preparing the drilling fluids for use in the present invention is not particularly critical so long as an invert emulsion is formed. Generally, the components may be mixed together in any order under agitation condition in a an emulsion breaking tank 1.
  • a representative method of preparing said invert emulsion fluids comprises mixing an appropriate > quantity of oleaginous fluid and an appropriate quantity of surfactant together with continuous, mild agitation. A non-oleaginous fluid is then added while mixing until an invert emulsion is formed. If weight material, such as those described below, are to be added, then the weight material is typically added after the invert emulsion fluid is formed.
  • the drilling fluid Once used in the drilling process, it is not uncommon for the drilling fluid to encounter a 3 water bearing formation and thus the ratio of oleaginous fluid to non-oleaginous fluid is less than optimal. In some cases, the formation of a difficult to break emulsion occurs and this is often referred to as the "slop".
  • the oil to water ratio in the slop may be 25/75 or 30/70 or similar such numbers.
  • emulsion breaking it is possible to recover say a 60/40 ratio of oil to water fluid. This is then diluted with additional make up oil to achieve the desired 5 ration typically 80/20.
  • One of the primary difficulties with this system is the use of emulsion breakers and surface tension breakers that are not environmentally friendly.
  • alkyl polyglycosides are commercially available substances that are produced by acid-catalyzed o reaction of glycosides and fatty alcohol. Alkyl polyglycosides are environmentally friendly and are utilized in the personal body care and food industries. Alkyl sulfonates and alkyl sulfates are also commercially available substances which are produced by the alkylation of the sulfate ion with long chain alkyl groups.
  • alkyl sulfates of the present invention have the formula: where R- is a linear or branched, saturated or unsaturated C-. 22 alkyl radical and X is an alkali or ammonium ion.
  • alkyl sulfonates of the present invention have the formula:
  • R 3 -SO 3 Y where R 2 is a C ⁇ -18 alkyl radical, R 3 is a linear or branched, saturated or unsaturated C 1-30 alkyl radical, and Y is an alkali or ammonium ion.
  • the nonionic surfactants of the present invention have the formula:
  • alkyl polyglocosides (also sugar surfactants) of the present invention have the formula:
  • R 6 -O-G n where R 6 is a linear or branched, saturated or unsaturated C 1- 2 alkyl radical, G is a glycose unit, and n is a number from 1 to 10.
  • WIGOL EMD 2+2 available from WIGOL of Worms Germany.
  • the method involves taking the slop material, adding the emulsion breaker (i.e. WIGOL EMD 2+2) and allowing the emulsion to settle out in emulsion breaking tank 1. This may take anywhere from less than about one hour to more than about 14 hours.
  • the water phase is then pumped out using skimmer 7 and pump 8.
  • the oleaginous fluid and desired drilling fluid solids are retained and recycled via pump 9.
  • any convention method of settling and separation may be used. For quickly separating emulsions a cyclone separator may be used. Otherwise settling tanks or other similar separation devices can be used.
  • the basic test emulsion material utilised the following laboratory tests are drilling fluids as substantially described above with an Oil/Water Ratio (OWR) of approximately 32/68 and OWR 50/50.
  • OWR Oil/Water Ratio
  • Emulsion Clearance Agent The emulsion clearance agents of the prior art serve as basis and standard for tins test. At the same time it is about an industrial flushing agent based on anionic surfactants (RENAX) and a surfactant raw material based on sugar surfactants (6202), being applied as follows: Renax + Sugar surfactant 6202, Concentration: 2 % each, Ratio of mixture: 1:1.
  • RENAX anionic surfactants
  • 6202 a surfactant raw material based on sugar surfactants
  • GSA Emulsion Clearance Agents
  • a measured quantity of process mud i.e 100 g was placed into a beaker together with a measured portions of the emulsion clearance agent. The mixture was agitated for one minute at 300 rpm. The separated water layer was decanted after a settling time of several hours.
  • the composition of the remaining Oil/Water (O/W) emulsion was measured by means of distillation (ROFI). A 50 g sample of the treated drilling mud was added and boiled down to a dry substance. The volume of the separated Oil/Water layer was measured in the distillate. Test with Slop 50/50
  • test results for SLOP 50/50 are presented in Table No. 1.
  • the demulsified quantity of water in the precipitated mud DGW was measured after 2, 4 and 14 hours.
  • EMD 2+2, EMD 8.2, and EMD 8.6, with a concentration of 1 - 4 % performed better than when compared to the existing standard emulsion breaking agent (RENAX)
  • RENAX existing standard emulsion breaking agent
  • the use of EMD 2+2 on Slop 30/70 exhibited an increased efficiency of about 35 % when compared to the prior art emulsion breaking agent (RENAX).
  • the highest oil to water ratio obtained during the laboratory test was 75/25.
  • the applied quantity of a demulsification agent may be reduced by 50 % and still achieve the results of the prior art emulsion breaking agent.

Abstract

A mobile apparatus and method for recycling an invert emulsion based drilling fluid, in which the invert emulsion based drilling fluid includes an oleaginous component and an aqueous component. The apparatus includes an emulsion breaking tank, a water treatment tank, a filter press, and hydrocarbon filters. The method includes: mixing said invert emulsion drilling fluid with an emulsion breaker, wherein the emulsion breaker is a mixture of an alkyl glucoside and an alkane sulfonate; and separating the oleaginous component of the invert emulsion drilling fluid from the aqueous component of the invert emulsion drilling fluid. The method preferably utilizes an emulsion breaker that is a combination of an anionic surfactant, a nonionic surfactant and an alkyl polyglycoside surfactant.

Description

APPARATUS FOR RECYCLING OF OIL BASED DRILLING FLUID CONTAMINATED WITH WATER
BACKGROUND
Invert emulsion fluids, i.e. emulsions in which the non-oleaginous fluid is the discontinuous phase and the oleaginous fluid is the continuous phase, are employed in drilling processes for the development of oil or gas sources, as well as, in geothermal drilling, water drilling, geoscientific drilling and mine drilling. Specifically, the invert emulsion fluids are conventionally utilized for such purposes as providing stability to the drilled hole, forming a thin filter cake, lubricating the drilling bore and the downhole area and assembly, and penetrating salt beds without sloughing or enlargement of the drilled hole.
Oil-based drilling fluids are generally used in the form of invert emulsion muds. An invert emulsion mud consists of three-phases: an oleaginous phase, a non-oleaginous phase and a finely divided particle phase. Also typically included are emulsifiers and emulsifier systems, weighting agents, fluid loss additives, viscosity regulators and the like, for stabilizing the system as a whole and for establishing the desired performance properties. Full particulars can be found, for example, in the Article by P. A. Boyd et al entitled "New Base Oil Used in Low- Toxicity Oil Muds" in the Journal of Petroleum Technology, 1985, 137 to 142 and in the Article by R. B. Bennet entitled "New Drilling Fluid Technology-Mineral Oil Mud" in Journal of Petroleum Technology, 1984, 975 to 981 and the literature cited therein.
During the drilling process, it is not uncommon for the drilling fluid to encounter a water bearing formation and thus the ratio of oleaginous fluid to non-oleaginous fluid is less than optimal. In some cases, the formation of a difficult to break emulsion occurs and this is often referred to as the "slop". The oil to water ratio in the slop may be 25/75 or 30/70 or similar such numbers. Using conventional methods of emulsion breaking it is possible to recover say a 60/40 ratio of oil to water fluid. This is then diluted with additional make up oil to achieve the desired ratio typically 80/20. One of the primary difficulties with this system is the use of emulsion breakers and surface tension breakers that are not environmentally friendly. That is to say the emulsion breakers and surface tension breakers of the prior art are harmful to aquatic life and thus may not be directly discharged without further treatment or disposal. Any rig drilling with oil based synthetic oil based drilling mud is likely producing between 20 to 40 cubic meters per day of slop water, also referred to as waste mud or gray water. The slop water usually may not be directly discharged into the sea because of its hydrocarbon content, which is usually higher than regulatory limits. Therefore the slop water needs to be transported in boat tanks to shore for disposal according to the local regulations. A large portion of this slop water may be classified as special waste.
Thus there exists a continuing need for skid-mounted apparatuses and methods to effectively break emulsions on an offshore rig in an environmental friendly manner thereby reducing the need to transport the slop water onshore.
SUMMARY OF THE INVENTION
The present invention is generally directed to an apparatus and method of recycling drilling fluids or muds that have been contaminated with excess water so as to obtain a materials that' is suitable for reuse in the drilling subterranean wells. More particularly, the present invention relates to the separation, on the drilling rig, of the contaminating water from the oleaginous portion of an invert emulsion drilling fluid or mud using a skid-mounted apparatus and a single phase emulsion breaker that is environmentally compatible. The preferred emulsion breaker may include an anionic surfactant, a nonionic surfactant, and an alkyl polyglycoside, or combinations thereof. The invention may be employed to clean industrial wastewater produced during drilling or shipping operations, including bilge water.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a flow diagram of the overall process
Fig. 2 is a detailed view of the mud recycling operation.
Fig. 3 is a detailed view of the water flocculation tank and filters.
DETAILED DESCRIPTION OF THE INVENTION
The aim of the mvention is to recycle slop water into oil based / synthetic oil based drilling mud and clean water. The clean water extracted during this process should be of high enough purity to meet the local regulatory limits for allowing discharge from the rig.
The invention will reduce the transportation of fluid waste in boat tanks to shore, which in turn will (1) reduce the risk of spills; (2) reduce the need for supply boat tank cleaning and with this cost and time; (3) reduce the need for offshore transport and with this a reduction in CO2 production; (4) reduce the risk of a possible halting of drilling operations due to unfavorable weather conditions which prevent a supply boat from docking at a drilling rig coupled with the existing storage capacities on the rig being exhausted; (5) reduce the need of the supply of new drilling mud due to losses; and, (6) will reduce the need of special waste disposal onshore.
The mobile drilling mud recycling unit may consist of one module, or two or more
5 separate modules, either skid mounted or containerized, which can be mobile placed on the drilling rig's deck surface. For two modules, module one will separate the bulk part of the water fraction under use of a chemical reaction from the oil based / synthetic base drilling mud. The oil based mud / synthetic oil based mud will then be transferred back to the shaker house of the rig where it is treated on the rig shaker and directed back into the active mud system. The extracted o water is pumped to the second module where it will be treated with a bentonite based flocculent to eliminate / minimize hydrocarbon, organic and. heavy metal contamination. The produced treatment sludge (contaminate loaded bentonite flocculent) is directed to a filter press for de- watering and solidification for transport and disposal. The cleaned water phase is pumped over an integrated filter package, which will additionally eliminate hydrocarbon contamination. From
5 there the water can then, after checking that it is within the local regulatory limits, be discharged. An embodiment of the present invention will now be described by way of example and reference to the accompanying drawings.
Referring to Fig. 2, typically the slop water is first sent to an emulsion breaking tank 1,2 with agitator 3 and motor 12. An emulsion breaker from a storage tank 10 and pump 11 is added o to the tank via a distributor 4 during stirring. After the mud has settled out to the bottom 6 of the tank, the water is skimmed 7 with a pump 8 from the top of the emulsion breaking tank to the top 21 of a water treatment tank 20 on Fig. 3.
Using the agitator 25 and motor 26, the water treatment tank 20 is vigorously agitated while bentonite based flocculent is added from a venturi powder doser 23 via a venturi nozzle 24
!5 into the water treatment tank 20. A typical dose is between 2 and 4 kilograms per cubic meter of waste water. The usual contaminants in the waste water are hydrocarbons, general organics, and heavy metals. After the bentonite has been wetted, the agitation speed is reduced and the water and bentonite solution is mixed until large, stable bentonite flocculates loaded with the contaminants from the water are observed. The agitation is stopped, and the flocculates are so allowed to settle to the bottom of the mixing tank 29. After settling, the water is tapped 27 from the side of the tank above the flocculated material and pumped 28 to a sack filter 34 and a cartridge filter unit 35 for final polishing of any residual hydrocarbons. The produced treatment sludge, which contains contaminate loaded bentonite flocculent 29, is directed or pumped 30 to a filter press 31 for de-watering and solidification, eventually accumulating in a dehydrated mud tank 33 for transport and disposal. The water from the filter press 31 may be pumped 32 back
5 into the water treatment tank 20.
The resulting water typically should have below 20 ppm hydrocarbon contamination and no more than 2 ppm of heavy metals, although final purity is determined by the regulatory limits of a particular location. If the hydrocarbon limits are not met by the polished water, it may be reprocessed in the water treatment system until the correct discharge values are achieved. o The invention also represents a method of separating contaminating water from the oleaginous portion of invert emulsion drilling fluids or muds using the above described apparatus with a phase emulsion breaker that is environmentally compatible. This method allows the fluids or muds to be recycled for reuse in the drilling of subterranean wells at the well itself. The components of the invert emulsion fluids utilized in the method of the present invention
5 generally include an oleaginous liquid such as hydrocarbon oil which serves as a continuous phase, a non-oleaginous liquid such as water or brine solution which serves as a discontinuous phase, and an emulsifying agent. As used herein, emulsifying agent and surfactant are used interchangeably. The emulsifying agent serves to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous o liquid. A full description of such invert emulsions may be found in Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 328-332, the contents of which are hereby incorporated by reference.
As used herein, the term "invert emulsion" is an emulsion in which a non-oleaginous 5 fluid is the discontinuous phase and an oleaginous fluid is the continuous phase. The novel invert emulsion fluids of the present invention are useful in a similar manner as conventional invert emulsion fluids which includes utility in preparation for drilling, drilling, completing and working over subterranean wells such as oil and gas wells. Such methods of use of conventional inverse emulsion fluids are described in, for example, Composition and Properties of Drilling 0 and Completion Fluids, 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, the contents which are incorporated by reference, as well as, U.S. Patent No. 5,254,531 and EP 271943 which are incorporated by reference. One of skill in the art should know and understand the standard methods of determining if an invert emulsion has been formed. Examples of two such tests for the formation of an invert emulsion include the Invert Emulsion Test as disclosed herein and the measurement of the electrical stability of the invert
5 emulsion.
As used herein the term "oleaginous liquid" means an oil which is a liquid at 25 °C and immiscible with water. Oleaginous liquids typically include substances such as diesel oil, mineral oil, synthetic oil, ester oils, glycerides of fatty acids, aliphatic esters, aliphatic ethers, aliphatic acetals, or other such hydrocarbons and combinations of these fluids. In one illustrative a embodiment of this invention the oleaginous liquid is an ester material which provides environmental compatibility to the overall drilling fluid. Such esters are described in greater detail below.
The amount of oleaginous liquid in the invert emulsion fluid may vary depending upon the particular oleaginous fluid used, the particular non-oleaginous fluid used, and the particular
5 application in which the invert emulsion fluid is to be employed. However, generally the amount of oleaginous liquid must be sufficient to form a stable emulsion when utilized as the continuous phase. Typically, the amount of oleaginous liquid is at least about 30, preferably at least about 40, more preferably at least about 50 percent by volume of the total fluid.
As used herein, the term "non-oleaginous liquid" mean any substance which is a liquid at o 25 °C and which is not an oleaginous liquid as defined above. Non-oleaginous liquids are immiscible with oleaginous liquids but capable of forming emulsions therewith. Typical non- oleaginous liquids include aqueous substances such as fresh water, sea water, brine containing inorganic or organic dissolved salts, aqueous solutions containing water-miscible organic compounds and mixtures of these. In one illustrative embodiment the non-oleaginous fluid is
5 brine solution including inorganic salts such as calcium halide salts, zinc halide salts, alkali metal halide salts and the like.
The amount of non-oleaginous liquid in the invert emulsion fluid may vary depending upon the particular non-oleaginous fluid used and the particular application in which the invert emulsion fluid is to be employed. Typically, the amount of non-oleaginous liquid is at least o about 1, preferably at least about 3, more preferably at least about 5 percent by volume of the total fluid. Correspondingly, the amount should not be so great that it cannot be dispersed in the oleaginous phase. Therefore, typically the amount of non-oleaginous liquid is less than about 90, preferably less than about 80, more preferably less than about 50 percent by volume of the total fluid.
Various surfactants and wetting agents conventionally used in invert emulsion fluids may be incorporated in the fluids of this invention. Such surfactants are, for example, fatty acids, soaps of fatty acids, amido amines, polyamides, polyamines, oleate esters, imidazoline derivatives, oxidized crude tall oil, organic phosphate esters, alkyl aromatic sulfates and sulfonates, as well as, mixtures of the above. Generally, such surfactants are employed in an amount sufficient to form the invert emulsion. However, due to the cost of such agents, a minimal amount o achieve the desired result is typically used.
Viscosifying agents, for example, organophillic clays, may optionally be employed in the invert drilling fluid compositions of the present invention. Usually, other viscosifying agents, such as oil soluble polymers, polyamide resins, polycarboxylic acids and fatty acid soaps may also be employed. The amount of viscosifying agent used in the composition will necessarily vary depending upon the end use of the composition. Usually such viscosifying agents are employed in an amount which is at least about 0.1, preferably at least about 2, more preferably at least about 5 percent by weight to volume of the total fluid. VG-69™ and VG-PLUS™ are organoclay materials and Versa HRP™ is a polyamide resin material manufactured and distributed by M-I L.L.C. which are suitable viscosifying agents. The invert emulsion drilling fluids utilized in the practice of the present invention may optionally contain a weight material. The quantity and nature of the weight material depends upon the desired density and viscosity of the final composition. The preferred weight materials include, but are not limited to, barite, calcite, mullite, gallena, manganese oxides, iron oxides, mixtures of these and the like. The weight material is typically added in order to obtain a drilling fluid density of less than about 24, preferably less than about 21, and most preferably less than about 19.5 pounds per gallon.
Fluid loss control agents such as modified lignite, polymers, oxidized asphalt and gilsonite may also be added to the invert drilling fluids of this invention. Usually such fluid loss control agents are employed in an amount which is at least about 0.1, preferably at least about 1, more preferably at least about 5 percent by weight to volume of the total fluid. The method of preparing the drilling fluids for use in the present invention is not particularly critical so long as an invert emulsion is formed. Generally, the components may be mixed together in any order under agitation condition in a an emulsion breaking tank 1. A representative method of preparing said invert emulsion fluids comprises mixing an appropriate > quantity of oleaginous fluid and an appropriate quantity of surfactant together with continuous, mild agitation. A non-oleaginous fluid is then added while mixing until an invert emulsion is formed. If weight material, such as those described below, are to be added, then the weight material is typically added after the invert emulsion fluid is formed.
Once used in the drilling process, it is not uncommon for the drilling fluid to encounter a 3 water bearing formation and thus the ratio of oleaginous fluid to non-oleaginous fluid is less than optimal. In some cases, the formation of a difficult to break emulsion occurs and this is often referred to as the "slop". The oil to water ratio in the slop may be 25/75 or 30/70 or similar such numbers. Using convention methods of emulsion breaking it is possible to recover say a 60/40 ratio of oil to water fluid. This is then diluted with additional make up oil to achieve the desired 5 ration typically 80/20. One of the primary difficulties with this system is the use of emulsion breakers and surface tension breakers that are not environmentally friendly.
The present invention overcomes these limits by using a combination of alkyl polyglycosides, alkyl sulfonates and alkyl sulfates as the emulsion breaking system. Alkyl polyglycosides are commercially available substances that are produced by acid-catalyzed o reaction of glycosides and fatty alcohol. Alkyl polyglycosides are environmentally friendly and are utilized in the personal body care and food industries. Alkyl sulfonates and alkyl sulfates are also commercially available substances which are produced by the alkylation of the sulfate ion with long chain alkyl groups.
The alkyl sulfates of the present invention have the formula:
Figure imgf000008_0001
where R- is a linear or branched, saturated or unsaturated C-.22 alkyl radical and X is an alkali or ammonium ion.
The alkyl sulfonates of the present invention have the formula:
R2-SO3Y o or
R3-SO3Y where R2 is a Cι-18 alkyl radical, R3 is a linear or branched, saturated or unsaturated C1-30 alkyl radical, and Y is an alkali or ammonium ion.
The nonionic surfactants of the present invention have the formula:
R4-O-(EO)nH or
Figure imgf000009_0001
where R4 is a liner or branched, saturated or unsaturated C1- alkyl radical, R5 is a liner or branched alkyl radical, saturated or unsaturated C1-22 alkyl radical, n is a number from 1 to 5, EO is an ethylene oxide radical, propylene oxide radical, or butylene oxide radical or mixture thereof and m is a number from 1 to 50.
The alkyl polyglocosides (also sugar surfactants) of the present invention have the formula:
R6-O-Gn where R6 is a linear or branched, saturated or unsaturated C1- 2 alkyl radical, G is a glycose unit, and n is a number from 1 to 10.
As presented in the following examples this combination of components is referred to as
WIGOL EMD 2+2 available from WIGOL of Worms Germany. Generally the method involves taking the slop material, adding the emulsion breaker (i.e. WIGOL EMD 2+2) and allowing the emulsion to settle out in emulsion breaking tank 1. This may take anywhere from less than about one hour to more than about 14 hours. The water phase is then pumped out using skimmer 7 and pump 8. The oleaginous fluid and desired drilling fluid solids are retained and recycled via pump 9. In practicing the present method any convention method of settling and separation may be used. For quickly separating emulsions a cyclone separator may be used. Otherwise settling tanks or other similar separation devices can be used. The following examples are included to demonstrate preferred embodiments of of the emulsion breakers of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the scope of the invention. EXAMPLE 1:
The basic test emulsion material utilised the following laboratory tests are drilling fluids as substantially described above with an Oil/Water Ratio (OWR) of approximately 32/68 and OWR 50/50.
Figure imgf000010_0001
Emulsion Clearance Agent: The emulsion clearance agents of the prior art serve as basis and standard for tins test. At the same time it is about an industrial flushing agent based on anionic surfactants (RENAX) and a surfactant raw material based on sugar surfactants (6202), being applied as follows: Renax + Sugar surfactant 6202, Concentration: 2 % each, Ratio of mixture: 1:1. A variety of Emulsion Clearance Agents (EGA) were tested as shown below:
Figure imgf000010_0002
A measured quantity of process mud (i.e 100 g) was placed into a beaker together with a measured portions of the emulsion clearance agent. The mixture was agitated for one minute at 300 rpm. The separated water layer was decanted after a settling time of several hours.
The composition of the remaining Oil/Water (O/W) emulsion was measured by means of distillation (ROFI). A 50 g sample of the treated drilling mud was added and boiled down to a dry substance. The volume of the separated Oil/Water layer was measured in the distillate. Test with Slop 50/50
The test results for SLOP 50/50 are presented in Table No. 1. The demulsified quantity of water in the precipitated mud DGW was measured after 2, 4 and 14 hours.
s Table No. 1 : Tests with Slo 50/50.
Figure imgf000011_0001
After 14 hours 25 grams of water is separated from both the WIGOL-Formula EMD 2+2 and from the RENAX Formula. One of skill in the art should appreciate that this corresponds to a theoretical OWR of 67/33. Under laboratory conditions, and with 4% additive, one of skill in o the art should also appreciate that a very high degree of water precipitation from the emulsion, even if the maximum amount of precipitated water was reached only after 12 to 24 hours. The additive EMD 8.2 showed the highest volume of precipitated water (OWR 70/30). However, the mix was decanted only after the test was finished. Test with Slop 30/70
5 The test results for SLOP 30/70 are presented in Table No. 2. The demulsified water of the settled mud DGW and the Oil/Water ratio OWR were measured after 14 hours by means of ROFI.
Figure imgf000012_0001
Upon review of the above results, one of skill in the art should appreciate that the EMD 2+2, EMD 8.2, and EMD 8.6, with a concentration of 1 - 4 %, performed better than when compared to the existing standard emulsion breaking agent (RENAX) It should also be appreciated that the use of EMD 2+2 on Slop 30/70 exhibited an increased efficiency of about 35 % when compared to the prior art emulsion breaking agent (RENAX). Further it should be noted by one of skill in the art that the highest oil to water ratio obtained during the laboratory test was 75/25. Thus, in relation to the combination RENAX/6202, one can reasonably conclude that the applied quantity of a demulsification agent may be reduced by 50 % and still achieve the results of the prior art emulsion breaking agent.
While the apparatuses, compositions and methods of the present invention have been described in terms of illustrative embodiments, it will be apparent to those of skill in the art that variations may be applied to the process described herein without departing from the concept and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope and concept of the invention s defined by the following claims.

Claims

CLAIMS:
1. A mobile apparatus for recycling drilling mud or fluid, comprising: an emulsion breaking tank which comprises an agitator, means for the addition of an emulsion breaker, and means for the addition of drilling mud; 5 a water treatment tank which comprises an agitator, means for adding flocculation materials, and means for removing an aqueous phase; a filter press; and, hydrocarbon filters.
2. The apparatus of claim 1, wherein the apparatus is mounted on a skid. o
3. The apparatus of claim 2, wherein the apparatus is mounted on more than one skid.
4. The apparatus of claim 1 wherein the apparatus is sized to fit on a drilling rig.
5. The apparatus of claim 1, further comprising a second emulsion breaking tank.
6. The apparatus of claim 1, further comprising a pump to remove the drilling mud or fluid from said emulsion breaking tank.
5 7. The apparatus of claim 1 further comprising a tank which holds dehydrated mud from said filter press.
8. The apparatus of claim 1 wherein said hydrocarbon filters comprise a sack filters and cartridge filters.
9. The apparatus of claim 1 wherein the means for adding flocculation materials 0 comprises a venturi powder doser.
10. The apparatus of claim 1 wherein the means for the addition of an emulsion breaker comprises a pump and a distribution system comprising multiple nozzles.
11. The apparatus of claim 1 wherein the means for the addition of drilling mud comprises a nozzle at the top of said emulsion breaking tank. 5
12. The apparatus of claim 1 where in the means for removing said aqueous phase comprising a skimming nozzle in said water treatment tank.
13. The apparatus of claim 1 further comprising a waste mud pump on the bottom of said emulsion breaking tank.
14. The apparatus of claim 1 further comprising a filtrate return pump which recycles 0 filtrate to said water treatment tank from said filter press.
15. The apparatus of claim 1, wherein said emulsion breaking tank and said water treatment tank comprise a conical bottom.
16. The apparatus of claim 1, wherein the emulsion breaker is a mixture of a non-ionic tensid and an anionic tensid.
5 17. A method of recycling an invert emulsion based drilling fluid, wherein the invert emulsion based drilling fluid includes an oleaginous component and an aqueous component, the method comprising: the use of a mobile apparatus for recycling drilling mud or fluid, comprising: an emulsion breaking tank which comprises an agitator, means for the addition of o an emulsion breaker, and means for the addition of drilling mud; a water treatment tank which comprises an agitator and means for adding flocculation materials; a filter press; and, hydrocarbon filters; 5 mixing said invert emulsion drilling fluid with a emulsion breaker in said emulsion breaking tank, wherein said emulsion breaker is a mixture of a non-ionic tensid and an anionic tensid; separating the oleaginous component of the invert emulsion drilling fluid from the aqueous component of the invert emulsion drilling fluid; mixing said aqueous component in said water treatment tank with said flocculation materials; skimming the aqueous component from o said water treatment tank; and passing said aqueous component through said hydrocarbon filters.
18. The method of claim 17, wherein the emulsion breaker is a mixture of a non-ionic tensid and an anionic tensid.
19. The method of claim 18, wherein the anionic tensid is selected from the group consisting of: an alkyl sulfate with the formula 5 R O-SO3X where R- is a linear or branched, saturated or unsaturated C1-22 alkyl radical and X is an alkali or ammonium ion; an alkyl sulfonate with the formula
R2-SO3Y O or
R3-SO3Y where R2 is a C1-18 alkyl radical, R3 is a linear or branched, saturated or unsaturated Cι-3<* alkyl radical, and Y is an alkali or ammonium ion; and mixtures thereof.
20. The method of claim 17, wherein the emulsion breaking agent is a combination of an anionic surfactant, a non-ionic surfactant and an alkyl polyglycoside surfactant. 5 21. The method of claim 20 wherein the alkyl polyglycoside has the formula:
R6-O-G„ where R6 is a linear or branched, saturated or unsaturated C1-22 alkyl radical, G is a glycose unit, and n is a number from 1 to 10.
22. The method of claim 20 wherein the non-ionic surfactant is selected from the group o consisting of non-ionic surfactants with the formula
R4-O-(EO)nH
where R- is a liner or branched, saturated or unsaturated C1-22 alkyl radical, n is a number 5 from 1 to 5, and EO is an ethylene oxide radical, propylene oxide radical, or butylene oxide radical or mixture thereof; and
R4-O-(EO)mR5 where Rt is a liner or branched, saturated or unsaturated C-.-22 alkyl radical, R5 is a liner 0 or branched alkyl radical, saturated or unsaturated C1-22 alkyl radical, EO is an ethylene oxide radical, propylene oxide radical, or butylene oxide radical or mixture thereof and m is a number from 1 to 50, and mixtures thereof.
23. The method of claim 17, wherein invert emulsion has an oil to water ratio of about 10/90 to about 90/10. 5
24. The method of claim 17, wherein the invert emulsion further contain a weighting material, said weighting material being selected from barite, calcite, mullite, gallena, manganese oxides, iron oxides, and mixtures of these.
25. The method of claim 17, wherein the oleaginous component of the invert emulsion drilling fluid is selected from diesel oil, mineral oil, synthetic oil, C10-C19 alkyl and alkylene 0 hydrocarbons, ester oils, glycerides of fatty acids, aliphatic esters, aliphatic ethers, aliphatic acetals, and combinations of these.
26. A mobile apparatus for recycling drilling mud or fluid, comprising: an emulsion breaking vessel, means for the addition of an emulsion breaker, and means for the addition of drilling mud; a water treatment tank which comprises an agitator, means for adding flocculation 5 materials, and means for removing an aqueous phase; a filter press; and, hydrocarbon filters. >
27. The apparatus of claim 26, wherein said emulsion breaking vessel is a cyclone separator. o
PCT/US2003/033612 2002-11-15 2003-10-24 Apparatus for recycling of oil based drilling fluid contaminated with water WO2004046498A1 (en)

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DE60334238T DE60334238D1 (en) 2002-11-15 2003-10-24 DEVICE FOR RETURING A WATER VER
EA200500823A EA007444B1 (en) 2002-11-15 2003-10-24 Apparatus for recycling of oil based drilling fluid contaminated with water and water contaminated by oil-based drilling fluid
DK03777821.4T DK1561004T3 (en) 2002-11-15 2003-10-24 Apparatus for recycling oil-based drilling fluid contaminated with water
CA2506098A CA2506098C (en) 2002-11-15 2003-10-24 Apparatus for recycling of oil based drilling fluid contaminated with water
EP03777821A EP1561004B1 (en) 2002-11-15 2003-10-24 Apparatus for recycling of oil based drilling fluid contaminated with water.
MXPA05005189A MXPA05005189A (en) 2002-11-15 2003-10-24 Apparatus for recycling of oil based drilling fluid contaminated with water.
NZ539951A NZ539951A (en) 2002-11-15 2003-10-24 Apparatus for recycling of oil based drilling fluid contaminated with water
AT03777821T ATE481552T1 (en) 2002-11-15 2003-10-24 DEVICE FOR RETURNING AN OIL-BASED DRILLING FLUID CONTAMINATED BY WATER.
AU2003286615A AU2003286615B2 (en) 2002-11-15 2003-10-24 Apparatus for recycling of oil based drilling fluid contaminated with water
NO20052551A NO330478B1 (en) 2002-11-15 2005-05-26 Mobile apparatus for recirculating drilling mud or fluid and method for recycling an inverted emulsion-based drilling fluid.

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US7507344B2 (en) 2009-03-24
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US7300578B2 (en) 2007-11-27
DK1561004T3 (en) 2010-12-13
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EP1561004A1 (en) 2005-08-10
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US20050092671A1 (en) 2005-05-05
NO330478B1 (en) 2011-04-26
US7678280B2 (en) 2010-03-16

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