WO2002012674A1 - Procede de distribution de produits chimiques dans un puits de petrole ou de gaz - Google Patents

Procede de distribution de produits chimiques dans un puits de petrole ou de gaz Download PDF

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Publication number
WO2002012674A1
WO2002012674A1 PCT/GB2001/003547 GB0103547W WO0212674A1 WO 2002012674 A1 WO2002012674 A1 WO 2002012674A1 GB 0103547 W GB0103547 W GB 0103547W WO 0212674 A1 WO0212674 A1 WO 0212674A1
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WIPO (PCT)
Prior art keywords
chemical
carrier
starch
chemicals
well
Prior art date
Application number
PCT/GB2001/003547
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English (en)
Inventor
Hugh Malcolm Bourne
Stephen Mark Heath
Original Assignee
T R Oil Services Limited
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
Priority claimed from GB0019295A external-priority patent/GB0019295D0/en
Priority claimed from GB0020136A external-priority patent/GB0020136D0/en
Application filed by T R Oil Services Limited filed Critical T R Oil Services Limited
Priority to AU2001278587A priority Critical patent/AU2001278587A1/en
Publication of WO2002012674A1 publication Critical patent/WO2002012674A1/fr

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    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/536—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning characterised by their form or by the form of their components, e.g. encapsulated material

Definitions

  • This invention relates to a method for encapsulating chemicals and particularly to a method for starch and wax encapsulation of aggressive chemicals for applications in the oil industry.
  • the invention relates especially to a method of delivering chemicals to an oil or gas well, in encapsulated form.
  • a deployment method which allowed a reduction in the number of chemical injection lines required to deliver the cocktail of chemicals required at each wellhead would offer significant cost benefits.
  • a method of delivering a chemical to an oil or gas well comprising associating the chemical with a carrier, and delivering the chemical plus carrier to the well.
  • the chemical can be encapsulated by the carrier or otherwise entrapped by the carrier.
  • the carrier preferably comprises a suspension or slurry of particles onto or into which the chemical can be loaded.
  • a typical carrier is particulate starch, but other good carriers can be encapsulating agents conventionally known from e.g.
  • the nano/micro particles can typically contain a high active level of oilfield chemical, typically 5- 90%v/v, and can be dispersed in either an aqueous or oleic medium, and in solution or suspension, depending upon the nature of the encapsulation matrix.
  • the entrapped oilfield chemicals are typically released upon contact with the produced fluids due to the breakdown of the coating or carrier matrix either thermally and/or as a result of mixing with oil or water.
  • the potential to control the rate and extent of release as a function of time can also allow chemicals to be transported and released along different sections of the pipeline, thus alleviating some of the kinetic problems associated with scale, wax and hydrate inhibitors in long subsea tie backs.
  • the oilfield production chemical-entrapped particles could be injected topsides, at sub sea wellheads or elsewhere in the well.
  • the particles could also be applied to deliver oilfield chemicals that cannot be effectively deployed by conventional solvents.
  • Certain embodiments may include the delivery of a single oilfield chemical to a well while associated with a carrier such as the above- mentioned compounds.
  • the chemical is typically injected continuously into the well, typically through a dedicated fluid line.
  • the nano/micro particle entrapment technology can be applied to deliver a wide range and a wide combination of oilfield production chemicals down one injection line or umbilical.
  • oilfield production chemicals down one injection line or umbilical.
  • the oilfield chemicals can be entrapped in either liquid or solid form.
  • the particles can be manufactured using a variety of techniques including complex coacervation, interfacial polymerisation, desolvation, extrusion, agglomeration, emulsion polymerisation, gelation, chemical vapour deposition, fluid bed coating, spray drying and combinations thereof.
  • the particles can be produced over a variable particle size, typically, lnm-850 ⁇ m and can contain a high active level of oilfield chemical, typically l-90%v/v.
  • Nano/micro particles containing different oilfield production chemicals can be dispersed into either an aqueous or oleic carrier fluid, that may or may not contain other oilfield production chemicals, using either ionic or non-ionic surface active agents.
  • the material is preferably stable under injection conditions in both aqueous and non-aqueous environments at the ambient and sub-ambient temperatures that may be encountered in a production environment.
  • the entrapped oilfield chemical can be rapidly released from the encapsulating and/or carrier medium as a result of either thermal degradation of the matrix and/or dissolution in either the oil or water phase, releasing the oilfield chemical under wellhead conditions.
  • the release time of the chemical upon contact with the produced fluids could also be delayed depending upon the nature of the entrapment matrix. This can allow chemicals to be transported and released along different sections of the pipeline, thus enabling the release of chemicals in the right place and alleviating some of the kinetic problems associated with scale, wax and hydrate inhibitors in long sub sea tie backs.
  • the particles containing different production chemicals in either solid or liquid form, can then be mixed together to produce the required blend of oilfield chemicals for dispersion into the fluid carrying medium which may be aqueous or organic based.
  • the solid particles could be dispersed into the fluid-carrying medium by use of a wide range of different types of amphoteric, anionic, cationic and nonionic surface-active agents.
  • Amphoteric surfactants could include acetates such as lauro-, alkyl- and coco-amphoacetates, betaines such as lauryl-, alkyl- and coco-amidopropylbetaines, glycinates, imidazolines and propionates such as lauro-, alkyl- and coco-aminodipropionate .
  • Anionic surfactants could include alkyl- alkylaryl-, alkylether and alkylarylether sulphonates and carbonates, lignin derivatives, olefine and paraffin sulphonates, phosphate esters and sarcosinates .
  • Cationic surfactants could include amides, amines, amidoamines, diamines and quaternaries such as didecyldimethylammonium.
  • Nonionic surfactants could include alkoxylates such as alcohol-, alkylphenol- , amide-, ester-, fatty acid- and glyceride ethoxylates, alkylamides, amine oxides and esters.
  • the required dispersing characteristics could be achieved for example by varying the ratio of a sorbitan ester and a sorbitan ester ethoxylate to achieve the desired hydrophilic - lipophilic balance (HLB) .
  • HLB hydrophilic - lipophilic balance
  • the chemical is typically coated or otherwise associated with a carrier such as starch, flour or wax.
  • a carrier such as starch, flour or wax.
  • the starch can decompose at a given temperature releasing the chemical at a second location where it is needed. Selection of the characteristics of the carrier (e.g. starch) used allows accurate control over the temperature of decomposition. Normally the temperature at the wellhead will be hotter than the surface of the well. The precise temperature at the wellhead will vary from well to well, and typical subsea wellheads may have an ambient temperature of around 110°C (compared with 20°C at surface) .
  • the starch or wax coat can typically be designed to decompose when it crosses a point on the temperature gradient and so release the chemicals.
  • wax carriers can be designed to degrade or dissolve slowly or after a set time has elapsed to release the chemicals continuously over a period of time or after a set interval e.g. in the production fluids.
  • the starch or wax may be modified to decompose at different temperatures as may be necessary for particularly shallow or particularly deep wells or for any other reason in which the temperature of the wellhead may be different from normal.
  • the starch is typically granular starch, and resistant starch made therefrom.
  • the chemical is typically adsorbed onto the starch, typically by simple mixing. Adjuncts useful in controlled release formulations can be added.
  • starch All granular starches and flours (hereinafter “starch”) may be suitable for use herein and may be derived from any native source.
  • a native starch as used herein, is one as it is found in nature.
  • starch derived from a plant grown from artificial mutations and variations of the above genetic composition which may be produced by known standard methods of mutation breeding, are also suitable herein.
  • Typical sources for the starches are cereals, tubers, roots, legumes and fruits.
  • the native source can be corn, pea, potato, sweet potato, banana, barley, wheat, rice, sago, amaranth, tapioca, arrowroot, canna, sorghum, and waxy or high amylose varieties thereof.
  • the term "waxy” is intended to include a starch containing at least about 95% by weight amylopectin and the term "high amylose” is intended to include a starch containing at least about 40% by weight amylose.
  • Conversion products which retain their granular structure may be derived from any of the starches, including fluidity or thin-boiling starches prepared by oxidation, enzyme conversion, acid hydrolysis, heat and or acid dextrinization, and or sheared products may also be useful herein.
  • Particularly useful are granular structures, which have been "pitted” by the action of enzymes or acid, leaving a still organised structure that creates a microporous starch.
  • the enzymatic or acid hydrolysis of the starch granule is carried out using techniques well known in the art.
  • the amount of enzyme used is dependent upon the enzyme, i.e., type, source and activity, as well as enzyme concentration, substrate concentration, pH, temperature, the presence or absence of inhibitors, and the degree and type of modification. Types of modifications are described herein, infra . These parameters may be adjusted to optimise the nature and extent of the "pitting" of the starch granule.
  • Resistant starch is commonly known as a starch not likely to be adsorbed in the small intestine of a healthy individual.
  • Granular or particulate starches such as of the RS2-type (a starch granule that resists digestion by pancreatic alpha-amylase) and the RS4-type (a chemically modified starch, such as acetylated, hydroxyalkylated, or cross-linked starch) are particularly suitable.
  • resistant starches of the RS3-type are also suitable for the instant invention due to their high level of retrogradation or crystallisation from the alignment and association of associated amylose.
  • resistant starch are well known in the art and may be exemplified by that disclosed in US Patent Nos. US 5,593,503 which describes a method of making a granular resistant starch; US Patent Nos. 5,281,276 and 5,409,542 which describe methods of making resistant starches of the RS3 type; US 5,855,946 which describes a method of making a resistant starch of the RS4-type; and U.S. Application Serial No. 60/157370, which describes the formation of a very highly resistant starch. The methods for making the resistant starches are described in the preceding references, the disclosures of which are incorporated herein by reference.
  • the starch particulate may be modified by treatment with any reagent or combination of reagents that contribute to the controlled release properties of the starch.
  • Chemical modifications are intended to include crosslinked starches, including crosslinking the particulate starch with reactive polymers.
  • Preferred reactive polymers include starches modified with aldehyde or silanol groups.
  • Other chemical modifications include, without limit, acetylated and organically esterified starches, hydroxyethylated and hydroxypropylated starches, phosphorylated and inorganically esterified starches, cationic, anionic, non-ionic, and zwitterionic starches, and succinate and substituted succinate derivatives of starch.
  • Preferred modified starches are starch acetates having a degree of substitution ( "DS" ) of about up to about 1.5, particularly those disclosed in US 5,321,132, thereby improving compatibility with synthetic hydrophobic materials.
  • DS degree of substitution
  • Such modifications are known in the art, for example in Modified Starches: Properties and Uses, Ed. Wurzburg, CRC Press, Inc., Florida (1986) .
  • the starch is derivatized by reaction with an alkenyl cyclic dicarboxylic acid anhydride by the method disclosed in U.S. Patent Nos. 2,613,206 and 2,661,349, incorporated herein by reference, or propylene oxide, more particularly by reaction with octenylsuccinic anhydride.
  • the encapsulated chemicals can be carried in a liquid-phase inhibitor or other chemical to be delivered to the well that may be incompatible with the encapsulated chemical. All chemicals to be delivered could then be injected through a single umbilical.
  • Two umbilicals could be installed to allow operations to continue in the event of one blocking up. Additionally a third umbilical for methanol could be provided. A total of three umbilicals could therefore provide adequate cover for a well. This represents a significant saving when compared with the prior art, which requires five or six umbilicals for comparable performance.
  • Example 1 Encapsulation of solid material US Patent 4755397 to Eden et al (incorporated herein by reference) describes a process for the starch encapsulation of a solid material, namely, ferric hydroxide, which can be adapted for the encapsulation of oilfield chemicals as follows.
  • the desired oilfield chemical is dissolved in acidified water, dilute sodium hydroxide is added as necessary while stirring to remove from the chemical any trace precipitates.
  • Ammonium sulphate, water and high amylose (70%) cornstarch is added to the chemical slurry to give a slurry of the following composition: Starch 410 grams (19.9%) Ammonium sulphate 610 grams (29.6%) Chemical 41 grams (2.0%) Water 1000 grams (48.5%)
  • This slurry is processed through a jet cooker (Model C-l, National Starch & Chemical Corp) at 150 °C. At this temperature the high amylose starch cooks, despite the presence of a high level of an inhibiting salt, and forms a uniform dispersion.
  • a ball valve attached to the outlet of the jet cooker can be adjusted so that a pressure drop from maximum cooking temperature and pressure to atmospheric pressure occurs as the starch cook passes through the valve. Upstream the pressure is typically 90psig; downstream the pressure is typically Op ' sig.
  • the starch As the starch passes through the valve and the pressure is reduced to atmospheric, its temperature drops to around 104 °C, the boiling point of the salt solution at atmospheric pressure. At this temperature, the starch precipitates essentially instantaneously entrapping the solid oilfield chemical.
  • the product collected at the cooker outlet is typically a slurry of tan particles 5 to 7 microns in diameter. The slurry, by volume, is a third salt solution and two thirds precipitated particles. This product is washed free of salt and dried.
  • the dried particles (40% by weight) containing the various oilfield chemicals are then mixed with a synthetic white oil such as Isopar M (52% by weight) and a polyalkoxylated alkyl phenol based dispersant (5% by weight) using a high shear, UltraTurrax mixer at 5000 rpm for 10 minutes.
  • a clay based thickening agent (3% by weight) is then added to this mix and blended using a high shear, UltraTurrax mixer at 10,000 rpm.
  • This process can be used for the production of encapsulated particles containing a) solid biocides; b) de-oilers ; c) demulsifiers; d) scale inhibitors; e) corrosion inhibitors; f)wax inhibitors; and g) asphaltene inhibitors.
  • the chemical-loaded particles are mixed in various combinations of chemicals and delivered through a single fluid delivery pipeline to a wellhead, where the temperature of around 110°C breaks down the starch particles and releases the chemicals.
  • a liquid chemical such as a corrosion inhibitor is mixed with the carrier fluid conveying the particles to the well.
  • Example 2 Encapsulation of an Active Ingredient WO9901214 to Fester et al (incorporated herein by reference) describes a process for the encapsulation of an active ingredient, namely, solids and water- soluble fluids. This can be adapted for encapsulation of oilfield chemicals as follows.
  • a solution of 0.65g NaOH in 10ml water is subsequently added to the emulsion with stirring, in order to initiate partial gelation and cross- linking. After 30 minutes, the stirrer speed is increased to 1000 rpm. After 4 hours the emulsion is broken by addition of acetic acid.
  • the starch particles collected in the water/acetic acid phase. After separation, the particles are washed with de-ionised water and stored. Examination of the dispersed fluid by light microscopy should indicate that the particles are essentially mono dispersed with a size of 25 ⁇ m containing droplets of oil.
  • This process can be used for the production of encapsulated particles containing solid and/or liquid chemicals, namely, scale and corrosion inhibitors, oxygen and hydrogen sulphide scavengers, demulsifiers, gel breakers, tracers and antifoaming agents.
  • the process could be applicable to any solid or water-soluble chemicals.
  • the particulate- entrapped chemicals are mixed in various combinations of chemicals and delivered through a single fluid delivery pipeline to a wellhead, where the temperature of around 110°C breaks down the starch particles and releases the chemicals. Again the liquid phase of the carrier fluid can incorporate a further chemical to be delivered to the well.
  • Example 3 Encapsulation of a Water Insoluble Liquid
  • a water insoluble liquid namely, peppermint oil
  • this can be adapted for the production of starch encapsulation of hydrophobic oilfield chemicals as follows.
  • a slurry is made of the following composition: High Amylose (70%Corn Starch) 20% Ammonium Sulphate 40% Water 40%
  • the resulting slurry/coarse emulsion is jet-cooked through a C-l cooker as in Example 1.
  • the cooker outlet hose empties below the surface of a slurry of ammonium sulphate and ice in saturated ammonium sulphate solution (-8°C.) to condense and trap any free peppermint oil vapours.
  • the resulting product is typically coarse ( ⁇ 20 mesh) light tan powder in salt solution. The powder is recovered by filtration and dried.
  • a 3% weight aqueous solution of HEC is then prepared by slowly adding the powdered HEC to distilled water and gradually increasing the mixing speed over a five-minute period. Once a solution is formed a sorbitan ester ethoxylate based dispersant (6% by weight) is added to the aqueous HEC mixture and blended at 2000rpm for five minutes. The dried particles (50% by weight) containing the various oilfield chemicals are then mixed with the aqueous solution of HEC and dispersant using a high shear, UltraTurrax mixer at 5000 rpm for 10 minutes.
  • This process is particularly useful for manufacturing encapsulated products containing oil soluble scale and corrosion inhibitors, wax and asphaltene inhibitors, drag reducers, demulsifiers and de-oilers.
  • a variety of these chemicals can be encapsulated as described above and delivered to a wellhead via a single injection line in various combinations, without interaction between the chemicals in the line during delivery.
  • the starch capsules surrounding the chemicals Upon arrival at the wellhead the starch capsules surrounding the chemicals are broken down by the ambient temperature at the wellhead, and the chemicals are released and activated in situ. Incorporation of incompatible liquid phase chemicals in the carrier fluid does not affect the encapsulated chemical.
  • Example 4 Encapsulation of a solid or oil soluble product.
  • a 20% paraffin or micro-crystalline wax, of defined melting point/80% solid oilfield chemical is prepared by mixing the molten wax with the solid chemical, cooling to form an agglomerate and grinding up the agglomerate to form granules. These granules are optionally further processed to form spheres, using a spheroniser. The size of the spheres is controlled by the granulation process but is typically l-50 ⁇ m in diameter.
  • This process is typically used to produce paraffin or microcrystalline wax-based particles containing solid oilfield production chemicals such as scale, wax and corrosion inhibitors, biocides and other scavengers.
  • the wax particles can be manufactured to entrap oil -based liquids such as corrosion, wax and asphaltene inhibitors, demulsifiers and de-oilers.
  • the nano/micro particles containing different production chemicals are dispersed together to produce the required blend of oilfield chemicals for dispersion into the fluid carrying medium which was either aqueous or organic based.
  • the ' solid particles are dispersed into the fluid-carrying medium by use of a wide range of different dispersants.
  • Suitable dispersants include fatty acid esters and alkoxylated (e.g. methoxylated or ethoxylated) fatty acid esters such as sorbitan ester and sorbitan ester ethoxylate; and PEG esters such as PEG laurate.
  • the encapsulated oil field chemicals are mixed in the desired proportions and delivered via a single fluid delivery line to a wellhead, at which point the wax capsules degrade, releasing the chemical into the wellhead environment.
  • the two or more chemicals that are delivered to the well can be encapsulated by different methods e.g. according to any of the examples herein, so that the different particles release their chemical burdens at different points in the well, in response to different stimuli.
  • Example 5 Encapsulation of a wax inhibitor by starch.
  • a granular starch 150g, starch octenylsuccinate, aluminum salt, commercially available from National Starch and Chemical Company
  • XPC 3147C 50 g, Aldrich
  • the mixture was stirred at ambient temperature and pressure in a high shear disperser (Torrence, #785049) at 2000-4000 rpm.
  • An additional 100 g of the granular starch was added to the mixture and stirred for two more minutes to form a fine, free- flowing powder.
  • a carrier fluid that incorporates a scale inhibitor that is incompatible with the wax inhibitor, without any reaction between the chemicals.
  • the scale inhibitor treats the fluid conduit continuously from the point of entry to the wellhead, and the wax inhibitor is activated only after a longer period of time as a result of the starch encapsulating matrix dissolving in the produced fluids.
  • Example 6 Encapsulation of a water-soluble chemical by starch.
  • Water-soluble solids were formulated with starch at a 1:1 ratio (50% loading on starch) .
  • the oil well chemical was solubilised in ambient water and homogenised for 1-2 minutes at 9000-10000 rpm (Silverson L4RT) .
  • the starch was then added to the solution and the mixture was further homogenised for 2-3 minutes at 9000-lOOOOrpm, 20°C (Silverson L4RT) .
  • the mixture was spray dried (40% solids, 375°F inlet temperature, 225°F outlet temperature with a feed rate of 160ml/minutes and dual wheel atomisation using Bowen Lab Model (30" x 36") to produce a flowable, non-sticky composition.
  • the example was carried out using a scale inhibitor, Scaletreat 2001-28, as the oil well chemical and Vulca 90, a maize starch crosslinked with 1.5% epichlorohydrin on dry starch.
  • the example was carried out using a corrosion inhibitor, Corrtreat 2001-29 as the oil well chemical and a starch acetate (1.5 DS) waxy maize starch.
  • c The example was carried out using a scale inhibitor, Scaletreat 2001-26 as the oil well chemical and a microporous waxy maize starch that was digested using 0.3% glucoamylase on dry starch to achieve 15% digestion.
  • the encapsulated chemicals are mixed as desired and delivered in mixtures of encapsulated particles to the well-head through a single fluid line.
  • the encapsulated particles are degraded by the fluid conditions at the well-head, and/or by temperature, thereby delivering their active reagents at the required position in the wellhead.
  • Example 7 Encapsulation of a water insoluble chemical by starch.
  • Water insoluble solids were formulated with starch at a 1 : 1 ratio (50% loading on starch) .
  • the oil well chemical was added to a waxy maize starch modified with 3% octenyl succinic anhydride and converted to a water fluidity of 40, and the mixture was homogenised for 1-2 minutes at 9000-10000 rpm, 20°C (Silverson L4RT) . Water was added to the emulsion and the mixture was further homogenised, 1 minute at 9000-10000 rpm, 20°C (Silverson L4RT) .
  • the starch was then added to the solution and the mixture was further homogenised, 1-2 minutes at 9000-10000 rpm, 20°C (Silverson L4RT) .
  • the mixture was spray dried (35% solids, 380°F inlet temperature, 230°F outlet temperature, 140- 160ml/minutes with dual wheel atomisation using Bowen Lab Model (30" x 36")) to produce a flowable, non-sticky composition.
  • the example was carried out using a wax inhibitor, Waxtreat 398 as the oil well chemical and a microporous waxy maize which was 30% digested with 0.3% glucoamylase, and modified with 3% octenyl succinic anhydride and crosslinked with 1% aluminium sulphate.
  • the example was carried out using an asphaltene dispersant, Waxtreat 7302 as the oil well chemical and a microporous waxy maize starch modified using 3% octenyl succinic anhydride, enzymatically treated using 0.3% glucoamylase, to achieve 30% digestion.
  • the example was carried out using a hydrogen sulphide scavenger, Scavtreat 1020 as the oil well chemical and a high amylose corn starch, HYLON ® VII starch, commercially available from National Starch and Chemical Company.
  • the example was carried out using a kinetic hydrate inhibitor, Hytreat 569 as the oil well chemical and a microporous (30% enzyme digested) waxy maize starch modified using 3% octenyl succinic anhydride, enzymatically treated using 0.3% glucoamylase.
  • the example was carried out using an anti- agglomerate hydrate inhibitor, Hytreat A560 as the oil well chemical and a cationic starch silanol, 0.3% Nitrogen, 0.4% silanol .
  • Chemicals are delivered through a single delivery line to a wellhead and also to a well bore and formation.
  • the wellhead chemicals are released from their encapsulated particles at the prevailing wellhead conditions and the formation chemicals are only released upon reaching the more aggressive prevailing conditions at the formation.
  • Example 8 Starch was weighed out into a glass container. The oil well chemical was added while mixing for 5 minutes and then mixed for an additional 5 minutes, or until uniform using a Powerstat, Variable Autotransformer set at 80 (3PN168) , Bodine Electric Co, Speed reducer motor (NSE-12R) .
  • Powerstat Variable Autotransformer set at 80
  • Bodine Electric Co Bodine Electric Co
  • Speed reducer motor NSE-12R
  • Starch used was a 50:50 blend of sago and tapioca, DD and the oil well chemical used was Waxtreat 398.
  • the starch: chemical ratio used was 100:40 and the loading was 28.6%.
  • Starch used was a high amylose (70%) maize starch modified by 3% octenyl succinic anhydride and 10% polyvinyl alcohol and the oil well chemical used was Waxtreat 398.
  • the starch: chemical ratio used was 100:80 and the loading was 44.4%.
  • Starch used was enzyme converted (alpha amylase) maltodextrin and the oil well chemical used was Trosquat .
  • the starch: chemical ratio used was 100:38 and the loading was 27.5%.
  • Starch used was enzyme converted (alpha amylase) maltodextrin and the oil well chemical used was Trosquat.
  • the starch: chemical ratio used was 100:38 and the loading was 27.5%.
  • Starch used was a high amylose (70%) maize that was gelatinised, completely enzymatically de- branched and retrograded and the oil well chemical used was Hytreat A560.
  • the encapsulated chemicals are mixed as desired and delivered to production tubing or other well tubulars through a single fluid line. Once reaching the target in the well the chemicals are released through reaction to local conditions.
  • the wellhead is the preferred target of the chemicals delivered in order to protect the tie backs etc from corrosion or blockage, but it will be appreciated that the present invention is not in any way limited to the delivery of chemicals to the wellhead, and in certain embodiments the delivery target is another portion of the well, such as the formation, the reservoir, the casing, production tubing or other tubular or conduit.
  • Typical embodiments of the invention mitigate compatibility problems with delivery of mixtures of chemicals to platforms, remote and complex wells through a single injection line. Some embodiments also facilitate the deployment of certain chemicals that are difficult to handle, for example, because they are very corrosive and/or are insoluble in conventional solvents; for example, polyacrylate wax inhibitors, either alone or in combination with other chemicals, where the chemicals or at least one of them cannot be effectively deployed by conventional solvents.
  • Certain embodiments also enable the deployment of oilfield chemicals at high active concentrations, for example, ethylene vinyl acetate (EVA) wax inhibitors that cannot be effectively deployed at >10%v/v by conventional solvents.
  • EVA ethylene vinyl acetate
  • starch is a preferred entrapping or coating medium
  • other materials such as natural gums, cellulose and derivatives, polysaccharides, gelatin, wax, fatty acids, acrylic, carboxyvinyl polymers, polyester, polystyrene, polycaprolactone, polyvinyl acetate, polyamides, polyvinyl alcohol, polylactic acid, polyglycolide, shellac, zein, oil based gels, silica gel and other materials consisting of mixtures, copolymers, terpolymers and hydrophobically and/or hydrophilically modified and cross-linked derivatives of the above.
  • the nano/micro particles can be dispersed in an aqueous or oleic medium depending upon the encapsulation matrix, and can contain one or more soluble or dispersed oilfield production chemicals.

Abstract

L'invention concerne un procédé de distribution de produits chimiques dans un puits tel qu'un puits de pétrole ou de gaz, ledit procédé consistant à encapsuler les produits chimiques dans ou sur une particule de support telle que l'amidon, et à distribuer ledit produit chimique encapsulé dans le support dans le puits.
PCT/GB2001/003547 2000-08-07 2001-08-07 Procede de distribution de produits chimiques dans un puits de petrole ou de gaz WO2002012674A1 (fr)

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AU2001278587A AU2001278587A1 (en) 2000-08-07 2001-08-07 Method for delivering chemicals to an oil or gas well

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GB0019295A GB0019295D0 (en) 2000-08-07 2000-08-07 Method
GB0019295.5 2000-08-07
GB0020136.8 2000-08-17
GB0020136A GB0020136D0 (en) 2000-08-17 2000-08-17 Method

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Cited By (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6461999B1 (en) 2001-03-28 2002-10-08 The United States Of America As Represented By The Secretary Of Agriculture Starch-containing lubricant systems for oil field applications
WO2003106809A1 (fr) 2002-06-13 2003-12-24 Bp Exploration Operating Company Limited Procede de preparation de microparticules
WO2005017313A1 (fr) * 2003-08-05 2005-02-24 Halliburton Energy Services, Inc. Compositions et procedes permettant de reguler la liberation de substances chimiques situees sur des particules
FR2881787A1 (fr) * 2005-02-10 2006-08-11 Inst Francais Du Petrole Methode de traitement des reservoirs petroliers par injection de nanoparticules contenant un additif anti depots mineraux
WO2009003023A2 (fr) 2007-06-27 2008-12-31 H R D Corporation Système et procédé d'injection d'inhibiteurs
EP2059651A1 (fr) * 2006-09-05 2009-05-20 University Of Kansas Complexes polyélectrolyte pour applications de pétrole et de gaz
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CN108822820A (zh) * 2018-05-22 2018-11-16 东莞理工学院 一种隔离型水合物动力学抑制胶囊及其制备方法与应用
US10392887B2 (en) 2015-11-04 2019-08-27 Halliburton Energy Services, Inc Downhole payload release containers, method and system of using the same
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US7674753B2 (en) 2003-09-17 2010-03-09 Halliburton Energy Services, Inc. Treatment fluids and methods of forming degradable filter cakes comprising aliphatic polyester and their use in subterranean formations
US7829507B2 (en) 2003-09-17 2010-11-09 Halliburton Energy Services Inc. Subterranean treatment fluids comprising a degradable bridging agent and methods of treating subterranean formations
US7833944B2 (en) 2003-09-17 2010-11-16 Halliburton Energy Services, Inc. Methods and compositions using crosslinked aliphatic polyesters in well bore applications
US7963330B2 (en) 2004-02-10 2011-06-21 Halliburton Energy Services, Inc. Resin compositions and methods of using resin compositions to control proppant flow-back
US8017561B2 (en) 2004-03-03 2011-09-13 Halliburton Energy Services, Inc. Resin compositions and methods of using such resin compositions in subterranean applications
US7712531B2 (en) 2004-06-08 2010-05-11 Halliburton Energy Services, Inc. Methods for controlling particulate migration
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US7757768B2 (en) 2004-10-08 2010-07-20 Halliburton Energy Services, Inc. Method and composition for enhancing coverage and displacement of treatment fluids into subterranean formations
US7648946B2 (en) 2004-11-17 2010-01-19 Halliburton Energy Services, Inc. Methods of degrading filter cakes in subterranean formations
US7883740B2 (en) 2004-12-12 2011-02-08 Halliburton Energy Services, Inc. Low-quality particulates and methods of making and using improved low-quality particulates
US8030249B2 (en) 2005-01-28 2011-10-04 Halliburton Energy Services, Inc. Methods and compositions relating to the hydrolysis of water-hydrolysable materials
US8030251B2 (en) 2005-01-28 2011-10-04 Halliburton Energy Services, Inc. Methods and compositions relating to the hydrolysis of water-hydrolysable materials
US8188013B2 (en) 2005-01-31 2012-05-29 Halliburton Energy Services, Inc. Self-degrading fibers and associated methods of use and manufacture
US8598092B2 (en) 2005-02-02 2013-12-03 Halliburton Energy Services, Inc. Methods of preparing degradable materials and methods of use in subterranean formations
WO2006084981A1 (fr) * 2005-02-10 2006-08-17 Institut Francais Du Petrole Methode de traitement des reservoirs petroliers par injection de nanoparticules contenant un additif anti depots mineraux
FR2881787A1 (fr) * 2005-02-10 2006-08-11 Inst Francais Du Petrole Methode de traitement des reservoirs petroliers par injection de nanoparticules contenant un additif anti depots mineraux
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US8613320B2 (en) 2006-02-10 2013-12-24 Halliburton Energy Services, Inc. Compositions and applications of resins in treating subterranean formations
US7665517B2 (en) 2006-02-15 2010-02-23 Halliburton Energy Services, Inc. Methods of cleaning sand control screens and gravel packs
US8235119B2 (en) 2006-03-30 2012-08-07 Canadian Energy Services, Lp Drilling fluid and method for reducing lost circulation
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US8372786B2 (en) 2006-09-05 2013-02-12 University Of Kansas Polyelectrolyte complexes for oil and gas applications
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US8393395B2 (en) 2009-06-03 2013-03-12 Schlumberger Technology Corporation Use of encapsulated chemical during fracturing
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US8607868B2 (en) 2009-08-14 2013-12-17 Schlumberger Technology Corporation Composite micro-coil for downhole chemical delivery
WO2011051850A3 (fr) * 2009-10-30 2011-08-11 Schlumberger Canada Limited Système et procédé de délivrance de produits chimiques en fond de trou
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EA030183B1 (ru) * 2009-10-30 2018-07-31 Шлюмбергер Текнолоджи Б.В. Система и способ подачи химреагента в скважину
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US20130327524A1 (en) * 2010-12-27 2013-12-12 Eni S.P.A. Method for recovering oil from a reservoir by means of micro(nano)-structured fluids with controlled release of barrier substances
US9890623B2 (en) 2012-06-07 2018-02-13 University Of Leeds Method of inhibiting scale in a geological formation
US9816363B2 (en) 2013-05-17 2017-11-14 Superior Energy Services, Llc Polysaccharide delivery unit for wellbore treatment agent and method
WO2014186174A1 (fr) * 2013-05-17 2014-11-20 Superior Energy Services, L.L.C. Unité de distribution de polysaccharide pour un agent de traitement de puits de forage et procédé
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GB2533229B (en) * 2013-06-24 2016-08-31 Inst Energiteknik Mineral-encapsulated tracers
WO2014207000A1 (fr) * 2013-06-24 2014-12-31 Institutt For Energiteknikk Traceurs encapsulés dans de la matière minérale
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